Handbook of X-Ray Spectrometry

TM
Marcel Dekker, Inc. New York

Basel
Handbook of
X-Ray Spectrometry
Second Edition, Revised and Expanded
edited by
Ren E. Van Grieken
University of Antwerp
Antwerp, Belgium
Andrzej A. Markowicz
Vienna, Austria
Copyright 2001 by Marcel Dekker, Inc. All Rights Reserved.
Copyright 2002 Marcel Dekker, Inc.
ISBN: 0-8247-0600-5
First edition was published as Handbook of X-Ray Spectrometry: Methods and Techniques
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Preface to the Second Edition
The positive response to the rst edition of Handbook of X-Ray Spectrometry: Methods
and Techniques and its commercial success have shown that in the early 1990s there was
a clear demand for an exhaustive book covering most of the specialized approaches in this
eld. Therefore, some ve years after the rst edition appeared, the idea of publishing
a second edition emerged. In the meantime, remarkable and steady progress has been
made in both instrumental and methodological aspects of x-ray spectrometry. This
progress includes considerable improvements in the design and production technology of
detectors and in capillary optics applied for focusing the primary photon beam. The
advances in instrumentation, spectrum evaluation, and quantication have resulted in
improved analytical performance and in further extensions of the applicability range of x-
ray spectrometry. Consequently, most of the authors who contributed to the rst edition
of this book enthusiastically accepted the invitation to update their chapters. The progress
made during the last decade is reected well in the chapters of the second edition, which
were all considerably revised, updated, and expanded. A completely new chapter on mi-
crobeam x-ray uorescence analysis has also been included.
Chapter 1 reviews the basic physics behind x-ray emission techniques, and refers to
extensive appendices for all the basic and generally applicable x-ray physics constants.
New analytical expressions have been introduced for the calculation of fundamental
parameters such as the uorescence yield, incoherent scattering function, atomic form
factor, and total mass attenuation coecient.
Chapter 2 outlines established and new instrumentation and discusses the perfor-
mances of wavelength-dispersive x-ray uorescence (XRF) analysis, which, with probably
15,000 units in operation worldwide today, is still the workhorse of x-ray analysis. Its
applications include process control, materials analysis, metallurgy, mining, and almost
every other major branch of science. The additional material in this edition covers new
sources of excitation and comprehensive comparisons of the technical parameters of newly
produced wavelength-dispersive spectrometers.
Chapter 3 has been completely reconsidered, modied, and rewritten by a new au-
thor. The basic principles, background, and recent advances are described for the tube-
excited energy-dispersive mode, which is invoked so frequently in research on environ-
mental and biological samples. This chapter is based on a fresh look and follows
a completely dierent approach.
Chapter 4 reviews in depth the available alternatives for spectrum evaluation and
qualitative analysis. Techniques for deconvolution of spectra have enormously increased
the utility of energy-dispersive x-ray analysis, but deconvolution is still its most critical
step. The second edition includes discussions of partial least-squares regression and
modied Gaussian shape proles.
Chapter 5 reviews quantication in XRF analysis of the classical and typical in-
nitely thick samples. In addition to being updated, the sections on calibration, quality
control, and mathematical correction methods have been expanded.
Chapter 6, on quantication for intermediate-thickness samples, now also in-
cludes the presentation of a modied version of the emission-transmission method and
a discussion of both the accuracy and limitations of such methods.
Chapter 7 is a completely original treatment by a new author of radioisotope-in-
duced and portable XRF. It discusses semiconductor detectors, including the latest types,
analyzes in detail the uncertainty sources, and reviews the recent and increasingly im-
portant applications.
Since the appearance of the rst edition, synchrotron-induced x-ray emission ana-
lysis has increased in importance. Chapter 8 was updated and modied by including
a comprehensive review of the major synchrotron facilities.
Although its principles have been known for some time, it is only since the advent of
powerful commercial units and the combination with synchrotron sources that total re-
ection XRF has rapidly grown, mostly now for characterization of surfaces and of liquid
samples. This is the subject of the substantially modied and expanded Chapter 9. The
new authors have taken a radically dierent approach to the subject.
Polarized-beam XRF and its new commercial instruments are treated in detail in
a substantially revised and expanded Chapter 10.
Capillary optics combined with conventional ne-focus x-ray tubes have enabled the
development of tabletop micro-XRF instruments. The principles of the strongly growing
microbeam XRF and its applications are now covered thoroughly in an additional
chapter, Chapter 11.
Particle-induced x-ray emission analysis has grown recently in its application types
and particularly in its microversion. Chapter 12 discusses the physical backgrounds, in-
strumentation, performance, and applications of this technique. The sections dealing with
the applications were substantially expanded.
Although the practical approaches to electron-induced x-ray emission analysis
a standard technique with wide applications in all branches of science and technology
are often quite dierent from those in other x-ray analysis techniques, a treatment of its
potential for quantitative and spatially resolved analysis is given in Chapter 13. The new
and expanded sections deal with recent absorption correction procedures and with the
quantitative analysis of samples with nonstandard geometries.
Finally, the completely updated and revised Chapter 14 reviews the sample pre-
paration techniques that are invoked most frequently in XRF analysis.
The second edition of this book is again a multiauthored eort. We believe that
having scientists who are actively engaged in a particular technique covering those areas in
which they are particularly qualied outweighs any advantages of uniformity and
homogeneity that characterize a single-authored book. The editors (and one coworker)
again wrote three of the chapters in the new edition. For all the other chapters, we were
fortunate to have the cooperation of truly eminent specialists, some of whom are new
contributors (see Chapters 3, 7, 9, 10 and 11). We wish to thank all the contributors for
their considerable and (in most cases) timely eorts.
We hope that novices in x-ray emission analysis will nd this revised and expanded
handbook useful and instructive, and that our more experienced colleagues will benet
from the large amount of readily accessible information available in this compact form,
some of it for the rst time. An eort has been made to emphasize the elds and devel-
opments that have come into prominence lately and have not been covered in other
general books on x-ray spectrometry.
We also hope this book will help analytical chemists and other users of x-ray
spectrometry to fully exploit the capabilities of this powerful analytical tool and to further
expand its applications in material and environmental sciences, medicine, toxicology,
forensics, archeometry, and many other elds.
Rene E. Van Grieken
Preface to the First Edition
Scientists in recent years have been somewhat ambivalent regarding the role of x-ray
emission spectrometry in analytical chemistry. Whereas no radically new and stunning
developments have been seen, there has been remarkably steady progress, both instru-
mental and methodological, in the more conventional realms of x-ray uorescence. For the
more specialized approachesfor example, x-ray emission induced by synchrotron ra-
diation, radioisotopes and polarized x-ray beams, and total-reection x-ray uorescence
and for advanced spectrum analysis methods, exponential growth and=or increasing ac-
ceptance has occurred. Contrary to previous books on x-ray emission analysis, these latter
approaches make up a large portion of the present Handbook of X-Ray Spectrometry.
The major milestone developments that shaped the eld of x-ray spectrometry and
now have widespread applications all took place more than twenty years ago. After
wavelength-dispersive x-ray spectrometry had been demonstrated and a high-vacuum
x-ray tube had been introduced by Coolidge in 1913, the prototype of the rst modern
commercial x-ray spectrometer with a sealed x-ray tube was built by Friedmann and Birks
in 1948. The rst electron microprobe was successfully developed in 1951 by Castaing,
who also outlined the fundamental concepts of quantitative analysis with it. The semi-
conductor or Si(Li) detector, which heralded the advent of energy-dispersive x-ray
uorescence, was developed around 1965 at Lawrence Berkeley Laboratory. Accelerator-
based particle-induced x-ray emission analysis was developed just before 1970, mostly at
the University of Lund. The various popular matrix correction methods by Lucas-Tooth,
Traill and Lachance, Claisse and Quintin, Tertian, and several others, were all proposed in
the 1960s. One may thus wonder whether the more conventional types of x-ray uores-
cence analysis have reached a state of saturation and consolidation, typical for a mature
and routinely applied analysis technique. Reviewing the state of the art and describing
recent progress for wavelength- and energy-dispersive x-ray uorescence, electron and
heavy charged-particle-induced x-ray emission, quantication, and sample preparation
methods is the purpose of the remaining part of this book.
Chapter 1 reviews the basic physics behind the x-ray emission techniques, and refers
to the appendixes for all the basic and generally applicable x-ray physics constants.
Chapter 2 outlines established and new instrumentation and discusses the performances of
wavelength-dispersive x-ray uorescence analysis, which, with probably 14,000 units in
operation worldwide today, is still the workhorse of x-ray analysis with applications in
a wide range of disciplines including process control, materials analysis, metallurgy,
mining, and almost every other major branch of science. Chapter 3 discusses the basic
principles, background, and recent advances in the tube-excited energy-dispersive mode,
which, after hectic growth in the 1970s, has now apparently leveled o to make up ap-
proximately 20% of the x-ray uorescence market; it is invoked frequently in research on
environmental and biological samples. Chapter 4 reviews in depth the available alter-
natives for spectrum evaluation and qualitative analysis; techniques for deconvolution of
spectra have enormously increased the utility of energy-dispersive x-ray analysis, but de-
convolution is still its most critical step. Chapters 5 and 6 review the quantication pro-
blems in the analysis of samples that are innitely thick and of intermediate thickness,
respectively. Chapter 7 is a very practical treatment of radioisotope-induced x-ray ana-
lysis, which is now rapidly acquiring wide acceptance for dedicated instruments and eld
applications. Chapter 8 reviews synchrotron-induced x-ray emission analysis, the youngest
branch, with limited accessibility but an exponentially growing literature due to its extreme
sensitivity and microanalysis potential. Although its principles have been known for some
time, it is only since the advent of powerful commercial units that total reection x-ray
uorescence has been rapidly introduced, mostly for liquid samples and surface layer
characterization; this is the subject of Chapter 9.
Polarized beam x-ray uorescence is outlined in Chapter 10. Particle-induced x-ray
emission analysis is available at many accelerator centers worldwide; the number of annual
articles on it is growing and it undergoes a revival in its microversion; Chapter 11 treats
the physical backgrounds, instrumentation, performance, and applications of this tech-
nique. Although the practical approaches to electron-induced x-ray emission analysis, now
a standard technique with wide applications in all branches of science and technology, are
often quite dierent from those in other x-ray analysis techniques, a separate treatment of
its potential for quantitative and spatially resolved analysis is given in Chapter 12. Finally,
Chapter 13 briey reviews the sample preparation techniques that are invoked most fre-
quently in combination with x-ray uorescence analysis.
This book is a multi-authored eort. We believe that having scientists who are ac-
tively engaged in a particular technique covering those areas for which they are particu-
larly qualied and presenting their own points of view and general approaches outweighs
any advantages of uniformity and homogeneity that characterize a single-author book.
Three chapters were written by the editors and a coworker. For all the other chapters, we
were fortunate enough to have the cooperation of eminent specialists. The editors wish to
thank all the contributors for their eorts.
We hope that novices in x-ray emission analysis will nd this book useful and in-
structive, and that our more experienced colleagues will benet from the large amount of
readily accessible information available in this compact form, some of it for the rst time.
This book is not intended to replace earlier works, some of which were truly excellent, but
to supplement them. Some overlap is inevitable, but an eort has been made to emphasize
the elds and developments that have come into prominence lately and have not been
treated in a handbook before.
Rene E. Van Grieken
Contents
Preface to the Second Edition
Preface to the First Edition
Contributors
1 X-ray Physics
I. Introduction
II. History
III. General Features
IV. Emission of Continuous Radiation
V. Emission of Characteristic X-rays
VI. Interaction of Photons with Matter
VII. Intensity of Characteristic X-rays
VIII. IUPAC Notation for X-ray Spectroscopy
Appendixes
I. Critical Absorption Wavelengths and Critical Absorption Energies
II. Characteristic X-ray Wavelengths (A
) and Energies (keV)

III. Radiative Transition Probabilities
IV. Natural Widths of K and L Levels and K
a
X-ray Lines (FWHM), in eV
V. Wavelengths of K Satellite Lines (A
) 56
VI. Fluorescence Yields and CosterKronig Transition Probabilities
VII. Coefcients for Calculating the Photoelectric Absorption
Cross Sections t (Barns=Atom) Via lnln Representation
VIII. Coefcients for Calculating the Incoherent Collision
Cross Sections s
c
(Barns=Atom) Via the lnln Representation
IX. Coefcients for Calculating the Coherent Scattering
Cross Sections s
R
(Barns=Atom) Via the lnln Representation
X. Parameters for Calculating the Total Mass Attenuation
Coefcients in the Energy Range 0.11000 keV [Via Eq. (78)]
XI. Total Mass Attenuation Coefcients for Low-Energy Ka Lines
XII. Correspondence Between Old Siegbahn and New IUPAC
Notation X-ray Diagram Lines
References
2 Wavelength-Dispersive X-ray Fluorescence
Jozef A. Helsen and Andrzej Kuczumow
I. Introduction
II. Fundamentals of Wavelength Dispersion
III. Layout of a Spectrometer
IV. Qualitative and Quantitative Analysis
V. Chemical Shift and Speciation
VI. Instrumentation
VII. Future Prospects
References
3 Energy-Dispersive X-ray Fluorescence Analysis Using X-ray Tube Excitation
Andrew T. Ellis
I. Introduction
II. X-ray Tube Excitation Systems
III. Semiconductor Detectors
IV. Semiconductor Detector Electronics
V. Summary
References
4 Spectrum Evaluation
Piet Van Espen
I. Introduction
II. Fundamental Aspects
III. Spectrum Processing Methods
IV. Continuum Estimation Methods
V. Simple Net Peak Area Determination
VI. Least-Squares Fitting Using Reference Spectra
VII. Least-Squares Fitting Using Analytical Functions
VIII. Methods Based on the Monte Carlo Technique
IX. The Least-Squares-Fitting Method
X. Computer Implementation of Various Algorithms
References
5 Quantication of Innitely Thick Specimens by XRF Analysis
Johan L. de Vries and Bruno A. R. Vrebos
I. Introduction
II. Correlation Between Count Rate and Specimen Composition
III. Factors Inuencing the Accuracy of the Intensity Measurement
IV. Calibration and Standard Specimens
V. Converting Intensities to Concentration
VI. Conclusion
References
6 Quantication in XRF Analysis of Intermediate-Thickness Samples
Andrzej A. Markowicz and Rene E. Van Grieken
I. Introduction
II. Emission-Transmission Method
III. Absorption Correction Methods Via Scattered Primary Radiation
IV. Quantitation for Intermediate-Thickness Granular Specimens
References
7 Radioisotope-Excited X-ray Analysis
Stanislaw Piorek
I. Introduction
II. Basic Equations
III. Radioisotope X-ray Sources and Detectors
IV. X-ray and g-ray Techniques
V. Factors Affecting the Overall Accuracy of XRF Analysis
VI. Applications
VII. Future of Radioisotope-Excited XRF Analysis
VIII. Conclusions
Appendix: List of Companies that Manufacture Radioisotope-Based
X-ray Analyzers and Systems
References
8 Synchrotron Radiation-Induced X-ray Emission
Keith W. Jones
I. Introduction
II. Properties of Synchrotron Radiation
III. Description of Synchrotron Facilities
IV. Apparatus for X-ray Microscopy
V. Continuum and Monochromatic Excitation
VI. Quantitation
VII. Sensitivities and Minimum Detection Limits
VIII. Beam-Induced Damage
IX. Applications of SRIXE
X. Tomography
XI. EXAFS and XANES
XII. Future Directions
References
9 Total Reection X-ray Fluorescence
Peter Kregsamer, Christina Streli, and Peter Wobrauschek
I. Introduction
II. Physical Principles
III. Instrumentation
IV. Chemical Analysis
V. Surface Analysis
VI. Thin Films and Depth Proles
VII. Synchrotron Radiation Excitation
VIII. Light Elements
IX. Related Techniques
References
10 Polarized Beam X-ray Fluorescence Analysis
Joachim Heckel and Richard W. Ryon
I. Introduction
II. Theory
III. Barkla Systems
IV. Bragg Systems
V. Barkla-Bragg Combination Systems
VI. Secondary Targets
VII. Conclusion
References
11 Microbeam XRF
Anders Rindby and Koen H. A. Janssens
I. Introduction and Historical Perspective
II. Theoretical Background
III. Instrumentation for Microbeam XRF
IV. Collection and Processing of m-XRF Data
V. Applications
References
12 Particle-Induced X-ray Emission Analysis
Willy Maenhaut and Klas G. Malmqvist
I. Introduction
II. Interactions of Charged Particles with Matter,
Characteristic X-ray Production, and
Continuous Photon Background Production
III. Instrumentation
IV. Quantitation, Detection Limits, Accuracy, and Precision
V. Sample Collection and Sample and Specimen Preparation
for PIXE Analysis
VI. Applications
VII. Complementary Ion-Beam-Analysis Techniques
VIII. Conclusions
References
13 Electron-Induced X-ray Emission
John A. Small, Dale E. Newbury, and John T. Armstrong
I. Introduction
II. Quantitative Analysis
III. Microanalysis at Low Electron Beam Energy
IV. Analysis of Samples with Nonstandard Geometries
V. Spatially Resolved X-ray Analysis
References
14 Sample Preparation for X-ray Fluorescence
Martina Schmeling and Rene E. Van Grieken
I. Introduction
II. Solid Samples
III. Fused Specimen
IV. Liquid Specimen
V. Biological Samples
VI. Atmospheric Particles
VII. Sample Support Materials
References
Contributors
John T. Armstrong, Ph.D. National Institute of Standards and Technology,
Gaithersburg, Maryland
Johan L. de Vries, Ph.D.* Eindhoven, The Netherlands
Andrew T. Ellis, Ph.D. Oxford Instruments Analytical Ltd., High Wycombe,
Buckinghamshire, England
Joachim Heckel, Ph.D. Spectro Analytical Instruments, GmbH & Co. KG, Kleve, Ger-
many
Jozef A. Helsen, Ph.D. Catholic University of Leuven, Leuven, Belgium
Koen H. A. Janssens, Ph.D. University of Antwerp, Antwerp, Belgium
Keith W. Jones, Ph.D. Brookhaven National Laboratory, Upton, New York
Peter Kregsamer, Dr. techn., Dipl. Ing. Atominstitut, Vienna, Austria
Andrzej Kuczumow, Ph.D. Lublin Catholic University, Lublin, Poland
Willy Maenhaut, Ph.D. Ghent University, Ghent, Belgium
Klas G. Malmqvist, Ph.D. Lund University and Lund Institute of Technology, Lund,
Sweden
Andrzej A. Markowicz, Ph.D. Vienna, Austria
Dale E. Newbury, Ph.D. National Institute of Standards and Technology, Gaithersburg,
Maryland
Stanislaw Piorek, Ph.D.
{
Niton Corporation, Billerica, Massachusetts
Anders Rindby, Ph.D. Chalmers University of Technology and University of Go tebo rg,
Go tebo rg, Sweden
Richard W. Ryon, B.A. Lawrence Livermore National Laboratory, Livermore, Califor-
nia
Martina Schmeling, Ph.D. Loyola University Chicago, Chicago, Illinois
John A. Small, Ph.D. National Institute of Standards and Technology, Gaithersburg,
Maryland
Christina Streli, Ph.D. Atominstitut, Vienna, Austria
Piet Van Espen, Ph.D. University of Antwerp, Antwerp, Belgium
Rene E. Van Grieken, Ph.D. University of Antwerp, Antwerp, Belgium
Bruno A. R. Vrebos, Dr. Ir. Philips Analytical, Almelo, The Netherlands
Peter Wobrauschek, Ph.D. Atominstitut, Vienna, Austria
1
X-ray Physics
Vienna, Austria
I. INTRODUCTION
In this introductory chapter, the basic concepts and processes of x-ray physics that relate
to x-ray spectrometry are presented. Special emphasis is on the emission of the continuum
and characteristic x-rays as well as on the interactions of photons with matter. In the
latter, only major processes of the interactions are covered in detail, and the cross sections
for dierent types of interactions and the fundamental parameters for other processes
involved in the emission of the characteristic x-rays are given by the analytical expressions
and=or in a tabulated form. Basic equations for the intensity of the characteristic x-rays
for the dierent modes of x-ray spectrometry are also presented (without derivation).
Detailed expressions relating the emitted intensity of the characteristic x-rays to the
concentration of the element in the specimen are discussed in the subsequent chapters of
this handbook dedicated to specic modes of x-ray spectrometry.
II. HISTORY
X-rays were discovered in 1895 by Wilhelm Conrad Ro ntgen at the University of
Wu rzburg, Bavaria. He noticed that some crystals of barium platinocyanide, near a dis-
charge tube completely enclosed in black paper, became luminescent when the discharge
occurred. By examining the shadows cast by the rays. Ro ntgen traced the origin of the rays
to the walls of the discharge tube. In 1896, Campbell-Swinton introduced a denite target
(platinum) for the cathode rays to hit; this target was called the anticathode.
For his work x-rays, Ro ntgen received the rst Nobel Prize in physics, in 1901. It was
the rst of six to be awarded in the eld of x-rays by 1927.
The obvious similarities with light led to the crucial tests of established wave optics:
polarization, diraction, reection, and refraction. With limited experimental facilities,
Ro ntgen and his contemporaries could nd no evidence of any of these; hence, the des-
ignation x (unknown) of the rays, generated by the stoppage at anode targets of the
cathode rays, identied by Thomson in 1897 as electrons.
The nature of x-rays was the subject of much controversy. In 1906, Barkla found
evidence in scattering experiments that x-rays could be polarized and must therefore by
waves, but W. H. Braggs studies of the produced ionization indicated that they were
corpuscular. The essential wave nature of x-rays was established in 1912 by Laue,
Friedrich, and Knipping, who showed that x-rays could be diracted by a crystal (copper
sulfate pentahydrate) that acted as a three-dimensional diraction grating. W. H. Bragg
and W. L. Bragg (father and son) found the law for the selective reection of x-rays. In
1908, Barkla and Sadler deduced, by scattering experiments, that x-rays contained com-
ponents characteristic of the material of the target; they called these components K and L
radiations. That these radiations had sharply dened wavelengths was shown by the
diraction experiments of W. H. Bragg in 1913. These experiments demonstrated clearly
the existence of a line spectrum superimposed upon a continuous (White) spectrum. In
1913, Moseley showed that the wavelengths of the lines were characteristic of the element
of the which the target was made and, further, showed that they had the same sequence as
the atomic numbers, thus enabling atomic numbers to be determined unambiguously for
the rst time. The characteristic K absorption was rst observed by de Broglie and in-
terpreted by W. L. Bragg and Siegbahn. The eect on x-ray absorption spectra of the
chemical state of the absorber was observed by Bergengren in 1920. The inuence of the
chemical state of the emitter on x-ray emission spectra was observed by Lindh and
Lundquist in 1924. The theory of x-ray spectra was worked out by Sommerfeld and
others. In 1919, Stenstro m found the deviations from Braggs law and interpreted them as
the eect of refraction. The anomalous dispersion of x-ray was discovered by Larsson in
1929, and the extended ne structure of x-ray absorption spectra was qualitatively in-
terpreted by Kronig in 1932.
Soon after the rst primary spectra excited by electron beams in an x-ray tube were
observed, it was found that secondary uorescent x-rays were excited in any material ir-
radiated with beams of primary x-rays and that the spectra of these uorescent x-rays were
identical in wavelengths and relative intensities with those excited when the specimen was
bombarded with electrons. Beginning in 1932, Hevesy, Coster, and others investigated in
detail the possibilities of uorescent x-ray spectroscopy as a means of qualitative and
quantitative elemental analysis.
III. GENERAL FEATURES
X-rays, or Ro ntgen rays, are electromagnetic radiations having wavelengths roughly
within the range from 0.005 to 10 nm. At the short-wavelength end, they overlap with
g-rays, and at the long-wavelength end, they approach ultraviolet radiation.
The properties of x-rays, some of which are discussed in detail in this chapter, are
summarized as follows:
Invisible
Propagated in straight lines with a velocity of 3610
8
m=s, as is light
Unaected by electrical and magnetic elds
Dierentially absorbed while passing through matter of varying composition,
density, or thickness
Reected, diracted, refracted, and polarized
Capable of ionizing gases
Capable of aecting electrical properties of liquids and solids
Capable of blackening a photographic plate
Able to liberate photoelectrons and recoil electrons
Capable of producing biological reactions (e.g., to damage or kill living cells and to
produce genetic mutations)
Emitted in a continuous spectrum whose short-wavelength limit is determined only
by the voltage on the tube
Emitted also with a line spectrum characteristic of the chemical elements
Found to have absorption spectra characteristic of the chemical elements
IV. EMISSIONOF CONTINUOUS RADIATION
Continuous x-rays are produced when electrons, or other high-energy charged particles,
such as protons or a-particles, lose energy in passing through the Coulomb eld of a
nucleus. In this interaction, the radiant energy (photons) lost by the electron is called
bremsstrahlung (from the German bremsen, to brake, and Strahlung, radiation; this term
sometimes designates the interaction itself). The emission of continuous x-rays nds a
simple explanation in terms of classic electromagnetic theory, because, according to this
theory, the acceleration of charged particles should be accompanied by the emission of
radiation. In the case of high-energy electrons striking a target, they must be rapidly
decelerated as they penetrate the material of the target, and such a high negative accel-
eration should produce a pulse of radiation.
The continuous x-ray spectrum generated by electrons in an x-ray tube is char-
acterized by a short-wavelength limit l
min
, corresponding to the maximum energy of the
exciting electrons:
l
min
=
hc
eV
0
(1)
where h is Plancks constant, c is the velocity of light, e is the electron charge, and V
0
is the
potential dierence applied to the tube. This relation of the short-wavelength limit to the
applied potential is called the DuaneHunt law.
The probability of radiative energy loss (bremsstrahlung) is roughly proportional to
q
2
Z
2
T=M
2
0
, where q is the particle charge in units of the electron charge e, Z is the atomic
number of the target material, T is the particle kinetic energy, and M
0
is the rest mass of
the particle. Because protons and heavier particles have large masses compared to the
electron mass, they radiate relatively little; for example, the intensity of continuous x-rays
generated by protons is about four orders of magnitude lower than that generated by
electrons.
The ratio of energy lost by bremsstrahlung to that lost by ionization can be
approximated by
m
0
M
0

2
ZT
1600m
0
c
2
(2)
where m
0
the rest mass of the electron.
A. Spectral Distribution
The continuous x-ray spectrum generated by electrons in an x-ray tube (thick target) is
characterized by the following features:
1. Short-wavelength limit, l
min
[Eq. (1)]; below this wavelength, no radiation is
observed.
2. Wavelength of maximum intensity l
max
, approximately 1.5 times l
min
; however,
the relationship between l
max
and l
min
depends to some extent on voltage,
voltage waveform, and atomic number.
3. Total intensity nearly proportional to the square of the voltage and the rst
power of the atomic number of the target material.
The most complete empirical work on the overall shape of the energy distribution
curve for a thick target has been of Kulenkamp (1922, 1933), who found the following
formula for the energy distribution;
I(v) dv = i aZ v
0
v ( ) bZ
2

dv (3)
where I(n) dn is the intensity of the continuous x-rays within a frequency range
(n; n dv); i is the electron current striking the target, Z is the atomic number of the
target material, n
0
is the cuto frequency (=c=l
min
) above which the intensity is zero, and
a and b are constants independent of atomic number, voltage, and cuto wavelength. The
second term in Eq. (3) is usually small compared to the rst and is often neglected.
The total integrated intensity at all frequencies is
I = i(a
/
ZV
2
0
b
/
Z
2
V
0
) (4)
in which a
/
= a(e
2
=h
2
)=2 and b
/
= b(e=h). An approximate value for b
/
=a
/
is 16.3 V; thus,
I = a
/
iZV
0
(V
0
16:3Z) (5)
The eciency E of conversion of electric power input to x-rays of all frequencies is
given by
Eff =
I
V
0
i
= a
/
Z(V
0
16:3Z) (6)
where V
0
is in volts. Experiments give a
/
= (1:2 0:1) 10
9
(Condon, 1958).
The most complete and successful eorts to apply quantum theory to explain all
features of the continuous x-ray spectrum are those of Kramers (1923) and Wentzel
(1924). By using the correspondence principle, Kramers found the following formulas for
the energy distribution of the continuous x-rays generated in a thin target:
I(v) dv =
16p
2
AZ
2
e
5
3
3
_
m
0
V
0
c
3
dv; v < v
0
I(v) dv = 0; v > v
0
(7)
where A is the atomic mass of the target material. When the decrease in velocity of the
electrons in a thick target was taken into account by applying the ThomsonWhiddington
law (Dyson, 1973), Kramers found, for a thick target,
I(v) dv =
8pe
2
h
3
3
_
lm
0
c
3
Z(v
0
v) dv (8)
where l is approximately 6. The eciency of production of the x-rays calculated via
Kramers law is given by
Eff = 9:2 10
10
ZV
0
(9)
which is in qualitative agreement with the experiments of Kulenkamp (Stephenson,
1957); for example,
Eff = 15 10
10
ZV
0
(10)
It is worth mentioning that the real continuous x-ray distribution is described only ap-
proximately by Kramers equation. This is related, inter alia, to the fact that the derivation
ignores the self-absorption of x-rays and electron backscattering eects.
Wentzel (1924) used a dierent type of correspondence principle than Kramers, and
he explained the spatial distribution asymmetry of the continuous x-rays from thin targets.
An accurate description of continuous x-rays is crucial in all x-ray spectrometry
(XRS). The spectral intensity distributions from x-ray tubes are of great importance for
applying fundamental mathematical matrix correction procedures in quantitative x-ray
uorescence (XRF) analysis. A simple equation for the accurate description of the actual
continuum distributions from x-ray tubes was proposed by Tertian and Broll (1984). It is
based on a modied Kramers law and a rened x-ray absorption correction. Also, a strong
need to model the spectral Bremsstrahlung background exists in electron-probe x-ray
microanalysis (EPXMA). First, tting a function through the background portion, on
which the characteristic x-rays are superimposed in an EPXMA spectrum, is not easy;
several experimental tting routines and mathematical approaches, such as the Simplex
method, have been proposed in this context. Second, for bulk multielement specimens, the
theoretical prediction of the continuum Bremsstrahlung is not trivial; indeed, it has been
known for several years that the commonly used Kramers formula with Z directly sub-
stituted by the average
"
Z =
P
i
W
i
Z
i
(W
i
and Z
i
are the weight fraction and atomic number
of the ith element, respectively) can lead to signicant errors. In this context, some im-
provements are oered by several modied versions of Kramers formula developed for a
multielement bulk specimen (Statham, 1976; Lifshin, 1976; Sherry and Vander Sande, 1977;
Smith and Reed, 1981). Also, a new expression for the continuous x-rays emitted by thick
composite specimens was proposed (Markowicz and Van Grieken, 1984; Markowicz et al.,
1986); it was derived by introducing the compositional dependence of the continuum x-rays
already in the elementary equations. The new expression has been combined with known
equations for the self-absorption of x-rays (Ware and Reed, 1973) and electron back-
scattering (Statham, 1979) to obtain an accurate description of the detected continuum
radiation. A third problem is connected with the description of the x-ray continuum gen-
erated by electrons in specimens of thickness smaller than the continuum x-ray generation
range. This problem arises in the analysis of both thin lms and particles by EPXMA.
A theoretical model for the shape of the continuous x-rays generated in multielement
specimens of nite thickness was developed (Markowicz et al., 1985); both composition and
thickness dependence have been considered. Further renements of the theoretical approach
are hampered by the lack of knowledge concerning the shape of the electron interaction
volume, the distribution of the electron within the interaction volume, and the anisotropy of
continuous radiation for dierent x-ray energies and for dierent lm thickness.
B. Spatial Distribution and Polarization
The spatial distribution of the continuous x-rays emitted by thin targets has been in-
vestigated by Kulenkamp (1928). The author made an extensive survey of the intensity at
angles between 22
and 150
to the electron beam in terms of dependence on wavelength

and voltage. The target was a 0.6-mm-thick Al foil. Figure 1 shows the continuous x-ray
intensity observed at dierent angles for voltages of 37.8, 31.0, 24.0, and 16.4 kV ltered
by 10, 8, 4, and 1.33 mm of Al, respectively (Stephenson, 1957). Curve (a) is repeated as a
dotted line near each of the other curves. The angle of the maximum intensity varied from
50
for 37.8 kV to 65
for 16.4 kV. Figure 2 illustrates the intensity of the continuous

x-rays observed in the Al foil for dierent thicknesses as a function of the angle for a
voltage of 30 kV (Stephenson, 1957). The theoretical curve is from the theory of Scherzer
(1932). The continuous x-ray intensity drops to zero at 180
, and although it is not zero at

0
as the theory of Scherzer predicts, it can be seen from Figure 2 that for a thinner foil, a
lower intensity at 0
is obtained. Summarizing, it appears that the intensity of the con-

tinuous x-rays emitted by thin foils has a maximum at about 55
relative to the incident

electron beam and becomes zero at 180
.
The continuous radiation from thick targets is characterized by a much smaller
anisotropy than that from thin targets. This is because in thick targets the electrons are
rarely stopped in one collision and usually their directions have considerable variation.
The use of electromagnetic theory predicts a maximum energy at right angles to the in-
cident electron beam at low voltages, with the maximum moving slightly away from
perpendicularity toward the direction of the elctron beam as the voltage is increased. In
general, an increase in the anisotropy of the continuous x-rays from thick targets is ob-
served at the short-wavelength limit and for low-Z targets (Dyson, 1973).
Figure1 Intensity of continuous x-rays as a function of direction for different voltages. (Curve (a)
is repeated as dotted line.) (From Stephenson, 1957.)
Continuous x-ray beams are partially polarized only from extremely thin targets; the
angular region of polarization is sharply peaked about the photon emission angle
y = m
0
c
2
=E
0
, where E
0
is the energy of the primary electron beam. Electron scattering in
the target broadens the peak and shifts the maximum to larger angles. Polarization is
dened by (Kenney, 1966)
P(y; E
0
; E
n
) =
dsl(y; E
0
; E
n
) ds|(y; E
0
; E
n
)
dsl(y; E
0
; E
n
) ds|(y; E
0
; E
n
)
(11)
where an electron of energy E
0
radiates a photon of energy E
n
at angle y; dsl(y; E
0
; E
n
)
and ds|(y; E
0
; E
n
) are the cross sections for generation of the continuous radiation with
the electric vector perpendicular (l) and parallel (|) to the plane dened by the incident
electron and the radiated photon, respectively. Polarization is dicult to observe, and only
thin, low-yield radiators give evidence for this eect. When the electron is relativistic
before and after the radiation, the electrical vector is most probably in the l direction.
Practical thick-target Bremsstrahlung shows no polarization eects whatever (Dyson,
1973; Stephenson, 1957; Kenney, 1966).
V. EMISSIONOF CHARACTERISTICX-RAYS
The production of characteristic x-rays involves transitions of the orbital electrons of
atoms in the target material between allowed orbits, or energy states, associated with
ionization of the inner atomic shells. When an electron is ejected from the K shell by
electron bombardment or by the absorption of a photon, the atom becomes ionized and
the ion is left in a high-energy state. The excess energy the ion has over the normal state of
the atom is equal to the energy (the binding energy) required to remove the K electron to a
state of rest outside the atom. If this electron vacancy is lled by an electron coming from
an L level, the transition is accompanied by the emission of an x-ray line known as the Ka
line. This process leaves a vacancy in the L shell. On the other hand, if the atom contains
sucient electrons, the K shell vacancy might be lled by an electron coming from an M
level that is accompanied by the emission of the Kb line. The L or M state ions that remain
may also give rise to emission if the electron vacancies are lled by electrons falling from
further orbits.
Figure 2 Intensity of continuous x-rays as a function of direction for different thicknesses of the
A1 target together with theoretical prediction. (From Stephenson, 1957.)
A. Inner Atomic Shell Ionization
As already mentioned, the emission of characteristic x-ray is preceded by ionization of
inner atomic shells, which can be accomplished either by charged particles (e.g., electrons,
protons, and a-particles) or by photons of sucient energy. The cross section for ion-
ization of an inner atomic shell of element i by electrons is given by (Bethe, 1930; Green
and Cosslett, 1961; Wernisch, 1985)
Q
i
= pe
4
n
s
b
s
ln U
UE
2
c;i
(12)
where U = E=E
c;i
is the overvoltage, dened as the ratio of the instantaneous energy of the
electron at each point of the trajectory to that required to ionize an atom of element i, E
c;i
is the critical excitation energy, and n
s
and b
s
are constants for a particular shell:
s = K: n
s
= 2; b
s
= 0:35
s = L: n
s
= 8; b
s
= 0:25
The cross section for ionization Q
i
is a strong function of the overvoltage, which shows a
maximum at U 34 (Heinrich, 1981; Goldstein et al., 1981).
The probability (or cross section) of ionization of an inner atomic shell by a charged
particle is given by (Merzbacher and Lewis, 1958)
s
s
=
8pr
2
0
q
2
f
s
Z
4
Z
s
(13)
where r
0
is the classic radius of the electron equal to 2.818610
15
m, q is the particle
charge, Z is the atomic number of the target material, f
s
is a factor depending on the wave
functions of the electrons for a particular shell, and Z
s
is a function of the energy of the
incident particles.
In the case of electromagnetic radiation (x or g), the ionization of an inner atomic
shell is a result of the photoelectric eect. This eect involves the disappearance of a ra-
diation photon and the photoelectric ejection of one electron from the absorbing atom,
leaving the atom in an excited level. The kinetic energy of the ejected photoelectron is
given by the dierence between the photon energy hn and the atomic binding energy of the
electron E
c
(critical excitation energy). Critical absorption wavelengths (Clark, 1963) re-
lated to the critical absorption energies (Burr, 1974) via the equation l(nm) =1.24=E(ke V)
are presented in Appendix I. The wavelenghts of K, L, M, and N absorption edges can also
be calculated by using simple empirical equations (Norrish and Tao, 1993).
For energies far from the absorption edge and in the nonrelativistic range, the cross
section t
K
for the ejection of an electron from the K shell is given by (Heitler, 1954)
t
K
=
32
2
_
3
pr
2
0
Z
5
(137)
4
m
0
c
2
hv

7=2
(14)
Equation (14) is not fully adequate in the neighborhood of an absorption edge; in this
case, Eq. (14) should be multiplied by a correction factor f(X) (Stobbe, 1930):
f(X) = 2p
D
hv

1=2
e
4X arccot X
1 e
2pX
(15)
where
X =
D
hv D

1=2
(15a)
with
D
1
2
(Z 0:3)
2
m
0
c
2
(137)
2
(15b)
When the energy of the incident photon is of the order m
0
c
2
or greater, relativistic
cross sections for the photoelectric eect must be used (Sauter, 1931).
B. Spectral Series in X-rays
The energy of an emission line can be calculated as the dierence between two terms, each
term corresponding to a denite state of the atom. If E
1
and E
2
are the term values re-
presenting the energies of the corresponding levels, the frequency of an x-ray line is given
by the relation
v =
E
1
E
2
h
(16)
Using the common notations, one can represent the energies of the levels E by means
of the atomic number and the quantum numbers n, l, s, and j (Sandstro m, 1957):
E
Rh
=
(Z S
n;l
)
2
n
2
a
2
(Z d
n;l; j
)
2
n
3
1
l
1
2
3
4n
!
a
2
(Z d
n;l; j
)
4
n
3
j( j 1) l(l 1) s(s 1)
2l(l
1
2
)(l 1)
(17)
where S
n;l
and d
n;l; j
are screening constants that must be introduced to correct for the eect
of the electrons on the eld in the atom, R is the universal Rydberg constant valid for all
elements with Z>5 or throughout nearly the whole x-ray region, and a is the ne-
structure constant given by
a =
2pe
2
hc
(17a)
The theory of x-ray spectra reveals the existence of a limited number of allowed
transitions; the rest are forbidden. The most intense lines create the electric dipole ra-
diation. The transitions are governed by the selection rules for the change of quantum
numbers:
Dl = 1; Dj = 0 or 1 (18)
The j transition 0 ?0 is forbidden.
According to Diracs theory of radiation (Dirac, 1947), transitions that are forbidden
as dipole radiation can appear as multipole radiation (e.g., as electric quadrupole and
magnetic dipole transitions). The selection rules for the former are
Dl = 0 or 2; Dj = 0; 1; or 2 (19)
The j transitions 0 ?0,
1
2
?
1
2
, and 0 1 are forbidden.
The selection rules for magnetic dipole transitions are
Dl = 0; Dj = 0 or 1 (20)
The j transition 0 ?0 is forbidden.
The commonly used terminology of energy levels and x-ray lines is shown in Figure 3.
A general expression relating the wavelength of an x-ray characteristic line with the
atomic number of the corresponding element is given by Moseleys law (Moseley, 1914):
1
l
= k(Z s)
2
(21)
where k is a constant for a particular spectral series and s is a screening constant for the
repulsion correction due to other electrons in the atom. Moseleys law plays an important
role in the systematizing of x-ray spectra. Appendix II tabulates the energies and wave-
lengths of the principal x-ray emission lines for the K, L, and M series with their ap-
proximate relative intensities, which can be dened either by means of spectral line peak
intensities or by area below their intensity distribution curve. In practice, the relative
Figure 3 Commonly used terminology of energy levels and x-ray lines. (From Sandstro m, 1957.)
intensities of spectral lines are not constant because they depend not only on the electron
transition probability but also on the specimen composition.
Considering the K series, the Ka fraction of the total K spectrum is dened by the
transition probability p
Ka
, which is given by (Schreiber and Wims, 1982)
p
Ka
=
I(Ka
1
Ka
2
)
I(Ka
1
Ka
2
) I(Kb
1
Kb
2
)
(22)
Wernisch (1985) proposed a useful expression for the calculation of the transition prob-
ability p
Ka
for dierent elements:
p
Ka;i
=
1:052 4:39 10
4
Z
2
i
; 11 _ Z
i
_ 19
0:896 6:575 10
4
Z
i
; 20 _ Z
i
_ 29
1:0366 6:82 10
3
Z
i
4:815 10
5
Z
2
i
; 30 _ Z
2
i
_ 60
8
<
:
(23)
For the L level, split into three subshells, several electron transitions exist. The transition
probability p
La
, dened as the fraction of the transitions resulting in La
1
and La
2
radiation
from the total of possible transitions into the L
3
subshell, can be calculated by the ex-
pression (Wernisch, 1985)
p
La;i
=
0:944; 39 _ Z
i
_ 44
4:461 10
1
5:493 10
2
Z
i
7:717 10
4
Z
2
i
3:525 10
6
Z
3
i
; 45 _ Z
i
_ 82
8
<
:
(24)
Radiative transition probabilities for various K and L x-ray lines (West, 198283) are
presented in detail in Appendix III. The experimental results, together with the estimated
95% condence limits, for the relative intensity ratios for K and L x-ray lines for selected
elements with atomic number from Z=14 to 92 have been reported by Stoev and Dlouhy
(1994). The values are in a good agreement with other published experimental data.
Because the electron vacancy created in an atom by charged particles or electro-
magnetic radiation has a certain lifetime, the atomic levels E
1
and E
2
[Eq. (16)] and the
characteristic x-ray lines are characterized by the so-called natural widths (Krause and
Oliver, 1979). The natural x-ray linewidths are the sums of the widths of the atomic levels
involved in the transitions. Semiempirical values of the natural widths of K, L
1
, L
2
and L
3
levels, Ka
1
and Ka
2
x-ray lines for the elements 10 _ Z _ 110 are presented in Appendix
IV. Uncertainties in the level width values are from 3% to 10% for the K shell and from
8% to 30% for the L subshell. Uncertainties in the natural x-ray linewidth values are from
3% to 10% for Ka
1;2
. In both cases, the largest uncertainties are for low-Z elements
(Krause and Oliver, 1979).
C. X-ray Satellites
A large number of x-ray lines have been reported that do not t into the normal energy-
level diagram (Clark, 1955; Kawai and Gohshi, 1986). Most of the x-ray lines, called
satellites or nondiagram lines, are very weak and are of rather little consequence in ana-
lytical x-ray spectrometry. By analogy to the satellites in optical spectra, it was supposed
that the origin of the nondiagram x-ray lines is double or manyfold ionization of an atom
through electron impact. Following the ionization, a multiple electron transition results in
emission of a single photon of energy higher than that of the characteristic x-rays. The
majority of nondiagram lines originate from the dipole-allowed deexcitation of multiply
ionized or excited states and are called multiple-ionization satellites. A line where the
initial state has two vacancies in the same shell, notably the K shell, is called a hypersa-
tellite. In practice, the most important nondiagram x-ray lines occur in the K
a
series; they
are denoted as the Ka
3
;a
4
doublet, and their origin is a double electron transition. The
probability of a multiple-electron transition resulting in the emission of satellite x-ray lines
is considerably higher for low-Z elements than for heavy and medium elements. For
instance, the intensity of the AlKa
3
satellite line is roughly 10% of that of the AlKa
1
; a
2
characteristic x-rays.
Appendix V tabulates wavelengths of the K satellite lines. A new class of satellites
that are inside the natural width of the parent lines was observed by Kawai and Gohshi
(1986). The origin of these satellites, called parasites or hidden satellites, is multiple
ionization in nonadjacent shells.
D. Soft X-ray Emission-Band Spectra
In the soft x-ray region, the characteristic emission spectra of solid elements include
continuous bands of width varying from 1 to 10 electron volts (eV); the same element in
vapor form produces only the usual sharp spectral lines. The bands occur only when an
electron falls from the outermost or valency shell of the atom, the levels of which are
broadened into a wide band when the atoms are packed in a crystal lattice. Investigation
of the emission-band spectra is of great signicance in understanding the electronic
structure of solid metals, alloys, and complex coordination compounds.
E. Auger Effect
It has already been stated that the excess of energy an atom possesses after removing one
electron from an inner shell by whatever means may be emitted as characteristic radiation.
Alternatively, however, an excited atom may return to a state of lower energy by ejecting
one of its own electrons from a less tightly bound state. The radiationless transition is
called the Auger eect, and the ejected electrons are called Auger electrons (Auger, 1925;
Burhop, 1952). Generally, the probability of the Auger eect increases with a decrease in
the dierence of the corresponding energy states, and it is the highest for the low-Z
elements.
Because an excited atom already has one electron missing (e.g., in the K shell) and
another electron is ejected in an Auger process (e.g., from the L shell), the atom is left in a
doubly-ionized state in which two electrons are missing. This atom may return to its
normal state by single- or double-electron jumps with the emission of diagram or satellite
lines, respectively. Alternatively, another Auger process may occur in which a third
electron is ejected from the M shell.
The Auger eect also occurs after capture of a negative meson by an atom. As the
meson changes energy levels in approaching the nucleus, the energy released may be either
emitted as a photon or transferred directly to an electron that is emitted as a high-energy
Auger electron (in the keV range for hydrogen and the MeV range for heavy elements).
Measurements of the energy and intensity of the Auger electrons are applied ex-
tensively in surface physics studies (Auger electron spectroscopy).
F. FluorescenceYield
An important consequence of the Auger eect is that the actual number of x-ray photons
produced from an atom is less than expected, because a vacancy in a given shell might be
lled through a nonradiative transition. The probability that a vacancy in an atomic shell
or subshell is lled through a radiative transition is called the uorescence yield. The
application of this denition to the K shell of an atom is straightforward, and the uor-
escence yield of the K shell is
o
K
=
I
K
n
K
(25)
where I
K
is the total number of characteristic K x-ray photons emitted from a sample and
n
K
is the number of primary K shell vacancies.
The denition of the uorescence yield of higher atomic shells is more complicated,
for the following two reasons:
1. Shells above the K shell consist of more than one subshell; the average
uorescence yield depends on how the shells are ionized.
2. CosterKronig transitions occur, which are nonradiative transitions between the
subshells of an atomic shell having the same principal quantum number (Fink,
1974; Bambynek et al., 1972).
In case CosterKronig transitions are absent, the uorescence yield of the ith sub-
shell of a shell, whose principal quantum number is indicated by X(X = L; M; . . .), is
given as
o
X
i
=
I
X
i
n
X
i
(26)
An average or mean uorescence yield " o
X
for the shell X is dened as
" o
X
=
X
k
i=1
N
X
i
o
X
i
(27)
where N
X
i
is the relative number of primary vacancies in the subshell i of shell X:
N
X
i
=
n
X
i
P
k
i=1
n
X
i
;
X
k
i=1
N
X
i
= 1 (28)
The summations in Eqs. (27) and (28) extend over all k subshells of shell X. For the de-
nition of the average uorescence yield, the primary vacancy distribution must be xed;
that is, CosterKronig transitions must be absent. It is noteworthy that " o
X
generally is not
a fundamental property of the atom, but depends both on the atomic subshell uorescence
yields o
X
i
and on the relative number of primary vacancies N
X
i
characteristic of the method
used to ionize the atoms.
In the presence of CosterKronig transitions, which modify the primary vacancy
distribution by the transfer of ionization from one subshell with a given energy to a
subshell with less energy, the average uorescence yields can be calculated by using two
alternative approaches. In the rst, the average uorescence yield " o
X
is regarded as a
linear combination of the subshell uorescence yields o
X
i
with a vacancy distribution
modied by CosterKronig transitions:
" o
X
=
X
k
i=1
V
X
i
o
X
i
;
X
k
i=1
V
X
i
> 1 (29)
where V
X
i
is the relative number of vacancies in the subshell i of shell X, including
vacancies shifted to each subshell by CosterKronig transitions. The V
X
i
values can be
expressed in terms of the relative numbers N
X
i
of primary vacancies and the CosterKronig
transition probability for shifting a vacancy from a subshell X
i
to a higher subshell X
j
,
denoted as f
X
ij
(Bambynek et al., 1972):
V
X
1
= N
X
1
V
X
2
= N
X
2
f
X
12
N
X
1
V
X
3
= N
X
3
f
X
23
N
X
2
( f
X
13
f
X
12
f
X
23
)N
X
1
(30)
In an alternative approach, the mean uorescence yield " o
X
is a linear combination of
the relative numbers of primary vacancies N
X
i
:
" o
X
=
X
k
i=1
N
X
i
n
X
i
(31)
where n
X
i
represents the total number of characteristic x-rays that result per primary
vacancy in the X
i
subshell. The transformation relations between the coecients n
X
i
and
the subshell uorescence yields o
X
i
follow from Eqs. (29) through (31) and are given in
Fink (1974) and Bambynek et al. (1972).
Among the uorescence yield o
X
i
, the Auger yield a
X
i
, and the CosterKronig
transition probabilities f
X
ij
, the following relationship must hold (Krause, 1979):
o
X
i
a
X
i

X
k
i=1
f
X
ij
= 1 (32)
The mean Auger yield " a
X
is given by
" a
x
=
X
k
i=1
V
X
i
a
X
i
(33)
The values of the K, L, and M shell uorescence yields, the CosterKronig transition
probabilities, as well as the Auger yields are given in Appendix VI.
Although, in principle, the K shell uorescence yield o
k
can be calculated theoreti-
cally, experimental data are applied in practice. The following semiempirical equation, due
to Burhop (1952), gives values correct to a few percent between Z = 23 and Z = 57 and
less accurate values outside these limits:
o
K
1 o
K

1=4
= 6:4 10
2
3:40 10
2
Z 1:03 10
6
Z
3
(34)
The uorescence yield for the K series can also be calculated from a dierent equation:
o
K
1 o
K

1=4
= 0:217 0:03318Z 1:14 10
6
Z
3
(35)
which gives quite good agreement with the experimental values for almost all elements.
Based on a critical review of the available experimental and theoretical data, a recom-
mended set of o
K
; " o
L
; and " o
M
values together with the following analytical expressions
were given by Hubbell (1989) and Hubbell et al. (1994):
o
K
(1 _ Z _ 100) =
X
3
i=0
C
i
Z
i
" #
4
1
X
3
i=0
C
i
Z
i
" #
4
8
<
:
9
=
;
1
(36)
with
C
0
= 0:0370 0:0052
C
1
= 0:03112 0:00044
C
2
= (5:44 0:11) 10
5
C
3
= (1:25 0:07) 10
6
" o
L
(3 _ Z _ 36) = 1:939 10
8
Z
3:8874
" o
L
(37 _ Z _ 100) =
X
3
i=0
C
i
Z
i
" #
4
1
X
3
i=0
C
i
Z
i
" #
4
8
<
:
9
=
;
1
(37)
with
C
0
= 0:17765
C
1
= 0:00298937
C
2
= 8:91297 10
5
C
3
= 2:67184 10
7
" o
M
(13 _ Z _ 100) = 1:29 10
9
(Z 13)
4
(38)
Other useful expressions for the calculation of the uorescence yields
o
K
(12 _ Z _ 42) and o
L3
(38 _ Z _ 79) have been proposed by Hanke et al. (1985),
based on literature and experimental data:
o
K
= 3:3704 10
1
6:0047 10
2
Z
3:3133 10
3
Z
2
3:9215 10
5
Z
3
(39)
o
L3
= 4:41 10
2
4:7559 10
3
Z
1:1494 10
4
Z
2
1:8594 10
7
Z
3
(40)
For the N shell, the best source of " o
N
data is a theoretical work of McGuire (1974)
which provides o
N1
; o
N2
, and o
N3
values for 25 elements over the range 38 _ Z _ 103
and o
N4
; o
N5
, and o
N6;7
values for 20 elements over the range 50 _ Z _ 103.
The average uorescence yield " o
N
can be calculated from (Hubbell, 1989)
" o
N
=
X
7
i=1
1
32
N
N
i
o
N
i
(41)
where N
N
i
are the numbers of electrons in each N
i
subshell.
A comparison of the total x-ray yields for bulk samples (including both the prob-
ability of ionization and the uorescence yield) in terms of photons per steradian per
incident quantum for electrons, protons, and x-ray photons is shown in Figure 4.
G. Fine Features of X-ray Emission Spectra (Valence or Chemical Effects)
Because characteristic x-ray emission is a process in which the innermost electrons in the
atom are concerned, it is reasonable to suppose that the external, or valence, electrons
have little or no eect on the x-ray emission lines. However, this is not fully true for K lines
of low-Z elements and L or M lines of higher-Z elements, where the physical state and
chemical combination of the elements aect the characteristic x-rays (Clark, 1955). The
changes in ne features of x-ray emission spectra with chemical combination can be
classied into three groups: (1) shifting in wavelength (Kallithrakas-Kontos, 1996),
(2) distortion of line shape, and (3) intensity changes (Kawai et al., 1993; Rebohle et al.,
1996). Wavelength shifts to both longer and shorter wavelengths result from energy-level
changes due to electrical shielding or screening of the electrons when the valence electrons
are drawn into a bond. Generally, the so-called last or highest-energy member of a given
series is most aected by chemical combination; maximum energy shifts are of the order of
a few electron volts. Distortion of an x-ray emission line shape gives some indication of the
energy distribution of the electrons occupying positions in or near the valence shell. The
changes in the characteristic x-ray intensity are a result of alterations in excitation
Figure 4 Total x-ray yields for excitation by electrons, protons, and primary x-ray photons as a
function of energy of the exciting quantum. (From Birks, 1971a.)
probabilities of the electrons undergoing transitions. Certain x-ray lines or bands appear
or disappear with chemical combinations. In the case of the K series, the most noticeable
chemical eects on x-ray emission are seen in spectra from low-Z elements (4 _ Z _ 17).
The L series shows as large or even larger changes with chemical combination of the
elements than K series. The valence eects in L spectra have been observed for elements of
the rst transition series and others nearby in the periodic table.
Because the ne features of x-ray emission spectra may be applied to determine how
each element is chemically combined in the sample (speciation), the valence eects found
numerous applications in such elds as physics of solids and surface or near-surface
characterization.
VI. INTERACTIONOF PHOTONS WITHMATTER
Interactions of photons with matter, by which individual photons are removed or deected
from a primary beam of x or g radiation, may be classied according to the following:
The kind of target, such as electrons, atoms or nuclei, with which the photon
interacts
The type of event, such as absorption, scattering, or pair production, that takes
place
These interactions are thought to be independent of the origin of the photon (nuclear
transition for g-rays versus electronic transition for x-rays); hence, we use the term
photon to refer to both g- and x-rays here.
Possible interactions are summarized in Table 1 (Hubbell, 1969), where t is the total
photoelectric absorption cross section per atom (t = t
K
t
L
) and s
R
and s
C
are
Rayleigh and Compton collision cross sections, respectively.
The probability of each of these many competing independent processes can be
expressed as a collision cross section per atom, per electron, or per nucleus in the absorber.
The sum of all these cross sections, normalized to a per atom basis, is then the probability
s
tot
that the incident photon will have an interaction of some kind while passing through a
very thin absorber that contains one atom per square centimeter of area normal to the
path of the incident photon:
s
tot
= t s
R
s
C
(42)
The total collision cross section per atom s
tot
, when multiplied by the number of
atoms per cubic centimeter of absorber, is then the linear attenuation coecient m
+
per
centimeter of travel in the absorber:
m
+
1
cm
= s
tot
cm
2
atom
g
cm
3
N
0
A
atoms
g
(43)
where r is the density of the medium and N
0
is Avogadros number (6.02252610
23
atoms=g atom). The mass attenuation coecient m (cm
2
=g) is the ratio of the linear at-
tenuation coecient and the density of the material.
It is worth mentioning that the absorption coecient is a much more restricted
concept than the attenuation coecient. Attenuation includes the purely elastic process in
which the photon is merely deected and does not give up any of its initial energy to the
absorber; in this process, only a scattering coecient is involved. In a photoelectric in-
teraction, the entire energy of the incident photon is absorbed by an atom of the medium.
Table1 Classication of Photon Interactions
Scattering
Type of interaction Absorption Elastic (coherent) Inelastic (incoherent) Multiphoton eects
Interaction with atomic
electrons
Photoelectric effect
a
~Z
4
low energy
t
~Z
5
high energy
Rayleigh scattering
a
s
R
~Z
2
Compton scattering
a
s
C
~Z
Two-photon Compton
scattering
~Z
Interaction with nucleus
or bound nucleons
Nuclear photoelectric effect:
reactions (g, n) (g, p),
photofission
~Z
Nuclear coherent
scattering
(g, g)
~Z
2
Nuclear Compton
scattering
(g, g
/
)
~Z
(E_10 MeV)
Interaction with electrical field
surrounding charged particles
1. Electronpositron pair production
in field of nucleous,
Delbru ck scattering
~Z
4
~Z
2
(E_1.02 MeV)
2. Electronpositron pair production
in electron field
~Z
(E_2.04 MeV)
3. Nucleonantinucleon pair
production
(E_3 GeV)
Interactions with mesons Photomeson production
(E_150 MeV)
Coherent resonant
scattering (g, g)
a
Major effects of photon attenuation in matter, which are of great importance in practical x-ray spectrometry.
Source: From Hubbell, 1969.
In the Compton eect, some energy is absorbed and appears in the medium as the kinetic
energy of a Compton recoil electron; the balance of the incident energy is not absorbed
and is present as a Compton-scattered photon. Absorption, then, involves the conversion
of incident photon energy into the kinetic energy of a charged particle (usually an elec-
tron), and scattering involves the deection of incident photon energy.
For narrow, parallel, and monochromatic beams, the attenuation of photons in
homogeneous matter is described by the exponential law:
I = I
0
e
m
+
t
(44)
where I is the transmitted intensity, I
0
is the incident intensity, and t is the absorber
thickness in centimeters.
If the absorber is a chemical compound or a mixture, its mass attenuation coecient
can be approximately evaluated from the coecients m
i
for the constituent elements
according to the weighted average:
m =
X
n
i=1
W
i
m
i
(45)
where W
i
is the weight fraction of the ith element and n is the total number of the elements
in the absorber. The mixture rule [Eq. (45)] ignores changes in the atomic wave function
resulting from changes in the molecular, chemical, or crystalline environment of an atom.
Above 10 keV, errors from this approximation are expected to be less than a few percent
(except in the regions just above absorption edges), but at very low energies (10100 eV),
errors of a factor of 2 can occur (Deslattes, 1969).
For situations more complicated than the narrow-beam geometry, the attenuation is
still basically exponential, but it is modied by two additional factors. The rst of these,
sometimes called a geometry factor, depends on the source absorber geometry. The other
factor, often called the buildup factor, takes into account secondary photons produced in
the absorber, mainly as the result of one or more Compton scatters, which nally reach the
detector. The determination of the buildup factor, dened as the ratio of the observed
eect to the eect produced only by the primary radiation, constitutes a large part of g-ray
transport theory (Evans, 1963).
In subsequent sections, only major eects of photon attenuation are discussed
in detail.
A. Photoelectric Absorption
In the photoelectric absorption described partially in Sec. V.A, a photon disappears and
an electron is ejected from an atom. The K shell electrons, which are the most tightly
bound, are the most important for this eect in the energy region considered in XRS. If the
photon energy drops below the binding energy of a given shell, however, an electron from
that shell cannot be ejected. Hence, a plot of t versus photon energy exhibits the char-
acteristic absorption edges.
The mass photoelectric absorption coecient tN
0
=A at the incident energy E (keV)
can approximately be calculated based on Walters equations (Compton and Allison,
1935):
tN
0
A
=
30:3Z
3:94
AE
3
for E > E
K
0:978Z
4:30
AE
3
for E
L1
< E < E
K
0:78Z
3:94
AE
3
for E
M1
< E <
L3
8
>
<
>
:
(46)
Based on available experimental and theoretical information for approximately
10,000 combinations of Z and E covering 87 elements and the energy range 1 keV to
1 MeV, the following lnln polynomials for the photoeect cross section t
j
have been tted
in incident photon energy between each absorption-edge region (Hubbell et al., 1974):
ln t
j
=
P
1;2;or 3
i=0
A
ij
ln[E (keV)[
i
(47)
In this polynomial, the total photoeect cross section t
j
represents one of the following
sums:
t
1
= t
M
t
N
t
O
or t
N
t
O
;
E
M1
< E < E
L3
or E < E
M5
t
2
= t
L
t
M
t
N
t
O
; E
L1
< E < E
K
t
3
= t
K
t
L
t
M
t
N
t
O
; E > E
K
(48)
The values of the tted coecients A
ij
for the lnln representation are given in Appendix
VII (McMaster et al., 1969). In multiple-edge regions (e.g., between L
1
and L
3
edge en-
ergies), the photoelectric absorption cross sections are also obtained via Eq. (47) by using
the following constant jump ratios j (t just above an absorption edge divided by t just
below that absorption edge):
j = 1:16 for E
L2
< E < E
L1
j = 1:64 = 1:16 1:41 for E
L3
< E < E
L2
j = 1:1 for E
M2
< E < E
M1
j = 1:21 = 1:1 1:1 for E
M3
< E < E
M2
j = 1:45 = 1:1 1:1 1:2 for E
M4
< E < E
M3
j = 2:18 = 1:1 1:1 1:2 1:5 for E
M5
< E < E
M4
(49)
Simple expressions for calculating the values of the energies of all photoabsorption edges
are given in Sec. VI.D.
The experimental ratio of the total photoelectric absorption cross section t to the
K shell component t
K
can be tted with an accuracy of ~23% by the equation (Hubbell,
1969)
t
t
K
1 0:01481 ln
2
Z 0:000788 ln
3
Z (50)
Based on the tables of McMaster et al. (1969), Poehn et al. (1985) found a useful
approximation for the calculation of the jump ratios (called also jump factors) for the
K shell ( j
K
) and L
3
subshell ( j
L3
):
j
K
= 1:754 10 6:608 10
1
Z 1:427 10
2
Z
2
1:1 10
4
Z
3
for 11 _ Z _ 50
j
L3
= 2:003 10 7:732 10
1
Z 1:159 10
2
Z
2
5:835 10
5
Z
3
for 30 _ Z _ 83
(51)
As already mentioned [Eq. (49)], the values of the jump factors at the L
2
and L
1
ab-
sorption edges are constant for all elements and equal to 1.41 and 1.16, respectively.
Tabulated values for the photoelectric absorption cross sections for the elements
1 _ Z _ 100 in the energy range of 1 keV to 100 MeV are also available in the work of
Storm and Israel (1970), which provides the photon cross sections for all major interaction
processes as well as the atomic energy levels, K and L x-ray line energies, weighted average
energies for the K and L x-ray series, and relative intensities for K and L x-ray lines.
When the apparently sharp x-ray absorption discontinuities are examined at high
resolution, they are found to contain a ne structure that extends in some cases to about a
few hundred electron volts above the absorption edge. The ne structure very close to an
absorption edge (less than or equal to 50 eV above the edge) is generally referred to as the
Kossel structure and is designated as XANES (x-ray absorption near-edge structure).
Peaks and trenches in this region, which can dier by a factor of 2 or more from the
smoothly extrapolated data, can be described in terms of transitions of the (very low en-
ergy) ejected electrons to unlled discrete energy states of the atom (or molecule), rather
than to the continuum of states beyond a characteristic energy (Sandstro m, 1957; Ko-
ningsberger and Prins, 1988; Behrens, 1992b). Superimposed on the Kossel structure is the
so-called Kronig structure [extended x-ray absorption ne structure (EXAFS)], which
usually extends to about 300 eV above the absorption edge (occasionally to nearly 1 keV
above an edge). The Kronig structure can be described in terms of interference eects on
the de Broglie waves of the ejected electrons by the molecular or crystalline spatial ordering
of neighboring atoms (Hasnain, 1991; Behrens, l992a). The oscillations of the absorption
coecient are of the order of 50% in the energy region 5060 eV above an absorption edge
and of the order of 15% in the region beyond 200 eV above the edge.
Modulations of the absorption coecient in the energy region above an absorption
edge can be described theoretically in terms of the electronic parameters (Lee and Pendry,
1975). Through a Fourier transform relationship, the modulations are closely related to
the radial distribution function around the element of interest (Sayers et al., 1970). Be-
cause both the Kossel and the Kronig ne structures can vary in magnitude and in energy
displacement of the features, depending on the molecular, crystalline, or thermal en-
vironment of the atom, they can be applied for local structural analysis of various ma-
terials, including powders, disordered solids, and liquid and amorphous substances
(Lagarde, 1983, Behrens, 1992a, 1992b; Koningsberger and Prins, 1988).
B. Compton Scattering
Compton scattering (Compton, 1923a, 1923b) is the interaction of a photon with a free
electron that is considered to be at rest. The weak binding of electrons to atoms may be
neglected, provided the momentum transferred to the electron greatly exceeds the mo-
mentum of the electron in the bound state. Considering the conservation of momentum
and energy leads to the following equations:
hn =
hn
0
1 g(1 cos y)
(52)
T = hn
0
hn = hn
0
g(1 cos y)
1 g(1 cos y)
(53)
tan j =
1
1 g
cot
y
2

(54)
with
g =
hn
0
m
0
c
2
where hn
0
and hn are the energies of the incident and scattered photon, respectively, y is the
angle between the photon directions of travel before and following a scattering interaction,
and T and f are the kinetic energy and scattering angle of the Compton recoil electron,
respectively.
For f=180
, Eqs. (52) and (53) reduce to

(hn)
min
= hn
0
1
1 2g
(55)
and
T
max
= hn
0
2g
1 2g
(56)
The dierential KleinNishina collision cross section ds
KN
=dO (dened as the ratio of the
number of photons scattered in a particular direction to the number of incident photons)
for unpolarized photons striking unbound, randomly oriented electrons is given by (Klein
and Nishina, 1929)
ds
KN
dO
=
r
2
0
2
hn
hn
0

2
hn
0
hn

hn
hn
0
sin
2
y

cm
2
electron sr
(57)
where sr is an abbreviation for steradian.
Substitution of Eq. (52) for Eq. (57) gives the dierential cross section as a function
of the scattering angle y:
ds
KN
dO
=
r
2
0
2
1 cos
2
y
[1 g(1 cos y)[
2
1
g
2
(1 cos y)
2
(1 cos
2
y)[1 g(1 cos y)[
( )
cm
2
electron sr
(58)
For very small energies hn
0
m
0
c
2
, the expression reduces to the classic Thompson
scattering cross section for electromagnetic radiation on an electron:
ds
Th
dO
=
r
2
0
2
(1 cos
2
y)
cm
2
electron sr
(59)
For low energies of incident photons (approximately less than a few tens of a kiloelectron
volt, the angular distribution of Compton-scattered photons is symmetrical about y =90
; at
higher incident photons energies, the Compton scattering becomes predominantly forward.
The dierential KleinNishina scattering cross section ds
S
KN
=dO for unpolarized
radiation, dened as the ratio of the amount of energy scattered in a particular direction to
the energy of incident photons, is given by
ds
s
KN
dO
=
hn
hn
0
ds
KN
dO
cm
2
electron sr
(60)
The average (or total) collision cross section s
KN
gives the probability of any Compton
interaction by one photon while passing normally through a material containing one
electron per square centimeter:
s
KN
=
Z
p
0
ds
KN
dO
2p sin y dy
= 2pr
2
0
1 g
g
2
2(g 1)
1 2g

ln(1 2g)
g
!
ln(1 2g)
2g

1 3g
(1 2g)
2
( )
cm
2
electron
(61)
Again, at the low-energy limit, this cross section reduces to the classic Thomson cross
section:
s
Th
=
8
3
pr
2
0
= 0:6652 10
24
cm
2
electron
(62)
At extremely high energies hn
0
m
0
c
2
, Eq. (61) reduces to
s
KN
= pr
2
0
1
g
ln 2g
1
2

cm
2
electron
(63)
The average (or total) scattering cross section, dened as the total scattered energy in
photons of various energies hn, is given by
s
s
KN
=
Z
p
0
ds
s
KN
dO
2p sin y dy
= pr
2
0
ln(1 2g)
g
3

2(1 g)(2g
2
2g 1)
g
2
(1 2g)
2

8g
2
3(1 2g)
3
" #
cm
2
electron
(64)
The usual KleinNishina theory that assumes that the target electron is free and at
rest cannot be directly applicable in some cases. Departures from it occur at low energies
because of electron-binding eects and, at high energies, because of the possibility of
emission of an additional photon (double Compton eect) and radiative corrections as-
sociated with emission and reabsorption of virtual photons; these corrections are discussed
in the work of Hubbell (1969).
The total incoherent (Compton) collision cross section per atom s
C
, involving the
binding corrections by applying the so-called incoherent scattering function S(x, Z), can
be calculated according to
s
C
=
1
2
r
2
0
Z
1
1
[1 g(1 cos y)[
2
(
1 cos
2
y
g
2
(1 cos y)
2
1 g(1 cos y)
" #
ZS(x; Z)
)
2pd(cos y)
cm
2
atom
(65)
where x = sin(y=2)=l is the momentum transfer parameter and l is the photon wavelength
(in angstroms).
The values of the incoherent scattering function S(x, Z) and the incoherent collision
cross section s
C
are given by Hubbell et al. (1975). A useful combination of analytical
functions for calculating S(x, Z) has recently been proposed by Szalo ki (1996):
S(x; Z) =
s
1
(x; Z) =
X
3
i=1
d
i
[exp(x) 1[
i
; 0 _ x _ x
i
s
2
(x; Z) = [Z s
1
(x; Z) t
2
[g
1
(x) t
2
g
2
(x) s
1
(x
1
; Z) x
1
< x
8
>
<
>
:
(66)
where
g
1
(x) = 1 exp[t
1
(x
1
x)[
and
g
2
(x) = 1 exp[t
3
(x
1
x)[
The parameters for the calculation of the S(x, Z), including the critical value of x
1
, are
given by Szalo ki (1996) for all elements (Z=1100) and any values of x. The average
deviation between the calculated [Eq. (66)] and tabulated data (Hubbell et al., 1975) is
slightly above 1%.
The incoherent collision cross sections s
C
can also be calculated by using lnln
polynomials already dened by Eq. (47) (by simply substituting t
j
with s
C
and taking
i =3). The values of the tted coecients for the lnln representation for s
C
valid in the
photon energy range 1 keV to 1 MeV are given in Appendix VIII.
To complete this subsection, it is worth mentioning the Compton eect for polarized
radiation. The dierential collision cross section (ds
KN
=dO)
pp
for the plane-polarized ra-
diation scattered by unoriented electrons has also been derived by Klein and Nishina. It
represents the probability that a photon, passing through a target containing one electron
per square centimeter, will be scattered at an angle y into a solid angle dO in a plane
making an angle b with respect to the plane containing the electrical vector of the incident
wave:
ds
KN
dO

pp
=
r
2
0
2
hn
hn
0

2
hn
0
hn

hn
hn
0
2 sin
2
y cos
2
b

cm
2
electron sr
(67)
The cross section has its maximum value for b=90
, indicating that the photon and

electron tend to be scattered at right angles to the electrical vector of the incident
radiation.
The scattering of circularly polarized (cp) photons by electrons with spins aligned in
the direction of the incident photon is described by
ds
KN
dO

cp
= r
2
0
hn
hn
0

2
hn
0
hn

hn
hn
0
sin
2
y

hn
0
hn

hn
hn
0

cos y
!
cm
2
electron sr
(68)
The rst term is the usual KleinNishina formula for unpolarized radiation. The sign
for the additional term applies to right circularly polarized photons.
C. Rayleigh Scattering
Rayleigh scattering is a process by which photons are scattered by bound atomic electrons
and in which the atom is neither ionized nor excited. The incident photons are scattered
with unchanged frequency and with a denite phase relation between the incoming and
scattered waves. The intensity of the radiation scattered by an atom is determined by
summing the amplitudes of the radiation coherently scattered by each of the electrons
bound in the atom. It should be emphasized that, in Rayleigh scattering, the coherence
extends only over the Z electrons of individual atoms. The interference is always con-
structive, provided the phase change over the diameter of the atom is less than one-half a
wavelength; that is, whenever
4p
l
r
a
sin
y
2

< 1 (69)
where r
a
is the eective radius of the atom.
Rayleigh scattering occurs mostly at the low energies and for high-Z materials, in the
same region where electron binding eects inuence the Compton scattering cross section.
The dierential Rayleigh scattering cross section for unpolarized photons is given by
(Pirenne, 1946)
ds
R
dO
=
1
2
r
2
0
(1 cos
2
y) [ F(x; Z)[
2
cm
2
atom sr
(70)
where F(x; Z) is the atomic form factor,
F(x; Z) =
Z
0
r(r)4pr
sin[(2p=l)rs[
(2p=l)rs
dr (71)
where r(r) is the total density, r is the distance from the nucleus, and s = 2 sin(y=2). The
atomic form factor has been calculated for Z<26 using the Hartree electronic distribution
(Pirenne, 1946) and for Z>26 using the FermiThomas distribution (Compton and
Allison, 1935).
At high photon energies, Rayleigh scattering is conned to small angles; at low
energies, particularly for high-Z materials, the angular distribution of the Rayleigh-scat-
tered radiation is much broader. A useful simple criterion for judging the angular spread
of Rayleigh scattering is given by (Evans, 1958).
y
R
= 2 arcsin
0:0133Z
1=3
E(Mev)

(72)
where y
R
is the opening half-angle of a cone containing at least 75% of the Rayleigh-
scattered photons. In the forward direction, [F(x; Z)[
2
= Z
2
, so that Rayleigh scattering
becomes appreciable in magnitude and must be accounted for in any g- or x-ray scattering
experiments.
The total coherent (Rayleigh) scattering cross section per atom s
R
can be calcu-
lated from
s
R
=
1
2
r
2
0
Z
1
1
(1 cos
2
y)[F(x; Z)[
2
2p d(cos y)
=
3
8
s
Th
Z
1
1
(1 cos
2
y)[F(x; Z)[
2
d(cos y)
cm
2
atom
(73)
The values of the atomic form factor F(x, Z) and the coherent scattering cross section s
R
are given in the work of (Hubbell et al., 1975). Recently, Szalo ki (1996) proposed a useful
combination of analytical functions to calculate F(x, Z):
F
1
(x; Z) =
f
11
(x; Z) = a exp(b
1
x) (Z a) exp(cx); 0 _ x _ x
1
f
12
(x; Z) = f
11
(x
1
; Z) exp(b
2
(x
1
x)[; x
1
_ x _ x
2
f
13
(x; Z) = f
12
(x
2
; Z) exp[b
3
(x
2
x)[; x
2
_ x _ x
3
f
14
(x; Z) = f
13
(x
3
; Z)
x
x
3
h i
b
4
; x
3
_ x _ x
4
8
>
>
>
<
>
>
>
:
(74)
where 1 _ Z _ 7
F
2
(x; Z) =
f
21
(x; Z) = a exp(b
1
x) (Z a) exp(cx); 0 _ x _ x
1
f
22
(x; Z) = f
21
(x
1
; Z) exp[b
2
(x
1
x)[; x
1
_ x _ x
2
f
23
(x; Z) = f
22
(x
2
; Z) exp[b
3
(x
2
x)[; x
2
_ x _ x
3
8
<
:
(75)
where 8 _ Z _ 100
The parameters for the calculation of F(x, Z), including the critical values of x
1
, x
2
,
and x
3
, are given by Szalo ki (1996) for all elements (Z=1100) and the momentum
transfer x from 0 to 15 A
71
. The average deviation between the calculated [Eqs. (74) and
(75)] and tabulated data (Hubbell et al., 1975) is less than 2%.
The simplest method for calculating the coherent scattering cross section s
R
consists
in applying the lnln representation [see Eq. (47) with s
R
instead of t
j
and i =3]. The
values of the tted coecients for lnln polynomials for calculating s
R
in the photon
energy range 1 keV to 1 MeV are given in Appendix IX.
D. Total Mass Attenuation Coefficient
An extensive review of current tabulations of x-ray attenuation coecients has been given
by Hubbell (1984). Dierences between various compilations of total mass attenuation
coecients result from uncertainties in our knowledge of partial cross sections for the
interaction of photons with matter as a function of elemental atomic number Z and
photon energy E. Present discrepancies are disturbing, to say the least, frequently
amounting to 510% in the photon energy region below 10 keV and rising to as much as
30% near an absorption edge.
Hubbell (1982) has tabulated mass attenuation coecients and mass energy ab-
sorption coecients for photon energies from 1 keV to 20 MeV for 40 elements ranging
from hydrogen (Z=1) to uranium (Z=92) and for 45 mixtures and compounds of do-
simetric interest.
The uncertainty ranges for the total mass attenuation coecient values in the tabu-
lation of McMaster et al. (1969) have been estimated by Hubbell et al. (1974). These ranges
of uncertainties fall into four categories. Category I (uncertainty below 2%) applies over
the energy region 640 keV (except near absorption edges) for the following elements: C,
Mg, Al, Ti, Fe, Ni, Cu, Zn, Zr, Mo, Pd, Ag, Cd, Sn, La, Gd, Ta, W, Pt, Au, Pb, Th, and U.
In this category, the photon energy region above 100 keV is also included for all elements in
which incoherent scattering comprises more than 90% of the total cross section. Category
II (uncertainty of 25%) applies to the energy region 26 keV for all elements, 640 keV for
all elements not specied in category I, and above 40 keV except for the scattering-domi-
nated region specied in category I. In category III (uncertainty of 515%), the authors
(Hubbell et al., 1974) included (1) the elements hydrogen, helium, and lithium, (2) the energy
region 12 keV for elements, and (3) the regions containing K, L, M, and N absorption
edges, and the ne-structure regions extending from 200 eV to 1 keV above each of these
regions. The experimental uncertainties in cases 1 and 2 greatly exceed 15%. Category IV
(uncertainty above 15%) applies to the photon energy region about 200 eV above an ab-
sorption edge (Kossel and Kronig ne-structure regions) for all elements.
Based on the tables published by McMaster et al. (1969), Wernisch et al. (1984)
developed an algorithm for the calculation of the total mass attenuation coecient valid
for the photon energy range from 1 to 50 keV and for 73 elements (11 _ Z _ 83). The
authors have applied the simple expression
m
cm
2
g
= He
dk ln E
(76)
Values of H, d, and k have been obtained from least-squares ts applied to the data
published by McMaster et al. (1969); they are given in Figure 5.
The values of the edge energies E
K
, E
L1
, E
L2
, E
L3
, E
M1
, E
M2
, E
M3
, E
M4
, and E
M5
can
simply be calculated from (Wernisch et al., 1984)
E
i
= r
i
s
i
Z t
i
Z
2
n
i
Z
3
keV (77)
the parameters r
i
, s
i
, t
i
, and n
i
for various absorption edges i are given in Table 2.
Another exible semiempirical scheme to calculate the total mass attenuation coef-
cient m for a very wide photon energy range (0.11000 keV) has been proposed by Orlic
et al. (1993)
m = exp[ p
1
p
2
(ln l) p
3
(ln l)
2
p
4
(ln l)
3
[ s
KN
ZN
0
A
1
(78)
where s
KN
is the average incoherent collision cross section gives by Eq. (61). The values of
the tting parameters p
1
, p
2
, p
3
, and p
4
are constant for each element and within the energy
regions dened by two adjacent absorption edges or for energies beyond the K absorption
edge; the parameters are given in Appendix X.
The experimental and theoretical values of total interaction cross sections [s
tot
,
Eq. (42)] and the mass attenuation coecients m for the elements (1 _ Z _ 98) in the
energy range 4.924.9 keV have been collected and compared by Arndt et al. (1992).
Most of the available tabulations of x-ray attenuation coecients do not include the
photon energy region below 1 keV that corresponds to the energies of characteristic K
x-rays of light elements (Z<11). Experimental data in this energy region are incomplete
and it should not be assumed that the accuracy of the available tabulated values is better
than ~15% (Veigele, 1974; Appendix XI).
E. Diffraction, Refraction, and Dispersion
When a beam of monochromatic x-rays falls onto a crystal lattice, a regular periodic
arrangement of atoms, a diracted beam only results in denite directions. The phe-
nomenon of x-ray diraction at an ordered array of atoms (or molecules) can also be
Figure 5 Definition of the energy ranges (a) and values of the parameters H, d, and k (b) applied
for the calculation of the total mass attenuation coefficients according to Eq. (76). (From Wernisch
et al., 1984.)
interpreted as a reection of an incident x-ray beam by the interior planes of a crystal
(Bragg reection). By elementary calculation of the dierence in path between two co-
herent rays, W. L. Bragg found the reinforcement condition for reection (known as
Braggs equation or law):
nl = 2d sin
y
n
2

(79)
where n is the order of reection, d is the interplanar spacing, and y
n
=2 is the angle of
reection (or Bragg angle) dened as the angle between the reecting plane of the crystal
and the incident or reected beam. The rst-order reection (n =1) is normally strongest,
and the reected intensity decreases as n increases.
Braggs law as given in Eq. (79) is only a rst approximation, as the refraction in the
crystal interferes with the angle of reection. Because the refractive index of x-rays is
slightly less than unity, the deviations from Braggs law, Eq. (79), were not observed in the
early years until methods were found for precise measurements of x-ray wavelengths. The
refraction is accounted for by ascribing a slightly dierent value d
n
of the lattice constant
to each order of reection; the simple Braggs law [Eq. (79)] can thus be written as
(Sandstro m, 1957)
nl = 2d 1
4d
2
n
2
d
l
2

sin
y
n
2

(80)
where d = 1 n
/
for small photon absorption (l <1 A
) and n
/
is the refractive index for
x-rays. d is a small positive number of the order 10
5
for heavy elements and 10
6
for light
elements at l =1 A
and is proportional to l
2
.
Because the value of d is positive, total reection occurs back into air when an x-ray
beam meets a surface at a large enough angle of incidence. Provided no absorption occurs,
the critical glancing angle y
tr
(tr, total reection) is dened by (Sandstro m, 1957)
sin y
tr
=
2d
_
(81)
Table2 Values of the Parameters r
i
,s
i
,t
i
, and n
i
Applied for Calculating the Energies of Absorption
Edges via Eq. (77)
Applicability range
i r
i
s
i
t
i
n
i
%
a
Z
min
Z
max
K 1.304610
1
2.633610
3
9.718610
3
4.144610
5
3.5 11 63
L
1
4.506610
1
1.566610
2
7.599610
4
1.792610
5
2.2 28 83
L
2
6.018610
1
1.964610
2
5.935610
4
1.843610
5
2.3 30 83
L
3
3.390610
1
4.931610
2
2.336610
3
1.836610
6
1.9 30 83
M
1
8.645 3.977610
1
5.963610
3
3.624610
5
0.4 52 83
M
2
7.499 3.459610
1
5.250610
3
3.263610
5
0.4 55 83
M
3
6.280 2.831610
1
4.117610
3
2.505610
5
0.4 55 83
M
4
4.778 2.184610
1
3.303610
3
2.115610
5
0.4 60 83
M
5
2.421 1.172610
1
1.845610
3
1.397610
5
0.4 61 83
a
Standard deviation of calculated energies [Eq. (77)] relative to the energies from the tables of McMaster et al.
(1969).
Source: From Wernisch et al., 1984.
For l =0.1 nm, the value of y
tr
is of the order 10
3
for light elements and 5610
3
for
heavy elements, increasing in proportion to l
The refractive index n
/
for a medium containing one type of atom can be calculated
from (Hirsch, 1962)
n
/
= 1
Nl
2
2p
e
2
m
0
c
2
F(0) (82)
where N is the number of atoms per unit volume and F(0) is the atomic scattering factor at
zero scattering angle. Equation (82) shows that n
/
depends on the wavelength; this phe-
nomenon is called dispersion.
The anomalous dispersion causes the quantity d=l
2
, Eq. (80), to vary slightly with
the wavelength. The variations become important only in the neighborhood of the ab-
sorption edges of the constituents of the crystal. Dividing the quantity d=l
2
into one
normal part [(d=l
2
)
n
[ and one anomalous part [(d=l
2
)
a
[, the theory of anomalous dis-
persion leads to an expression of Braggs law that can be written as (Sandstro m, 1957)
nl = 2d 1
4d
2
n
2
d
l
2

n
4d
2
n
2
d
l
2

a
!
sin
y
n
2

(83)
Combined with Braggs law in its uncorrected form, Eq. (79), this expression becomes
(Sandstro m, 1957)
l = 2d 1
4d
2
n
2
d
l
2

n
!
sin
y
n
=2
n

4d
2
n
2
d
l
2

a
l (84)
The values of (d=l
2
)
a
giving a correction for anomalous dispersion can be determined
experimentally.
The theory of anomalous dispersion has been applied by Sparks (1974, 1975) to
explain the inelastic angular-independent scattering from elements having an absorption-
edge energy just above the energy of the incident x-rays. The observed intensity of the
inelastically scattered radiation was found to be dependent on the nearness of the energy
of an absorption edge to the energy of the incident x-rays. The energy of the inelastic peaks
is shifted from the incident energy by the binding energy of the most tightly bound shell
from which electrons could be photoejected by the incident radiation.
F. X-ray Raman Scattering
Immediately after the discovery of Raman scattering in the visible-wavelength region,
a similar eect concerning x-ray radiation was experimentally examined (Davis and
Mitchell, 1928; Krishnan, 1928). X-ray Raman scattering appears as a band spectrum
having a short-wavelength edge corresponding to a denite energy loss equal to the K
electron-binding energy E
K
of the element. This inelastic eect was observed, for example,
when CrKa and CuKa radiation was scattered by solids of light elements, such as lithium,
beryllium , boron, and by graphite (Suzuki, 1966; Suzuki et al., 1970; Suzuki and Naga-
sawa, 1975). The shape of the Raman band is similar to that of the soft x-ray K absorption
spectrum of the solids.
Mizuno and Ohmura (1967) have found the following two conditions for x-ray
Raman scattering:
4p" a
l
0
< 1 (85)
and
hv
0
E
K
(86)
where a" is the mean radius of charge distribution of the K electrons and l
0
is the wave-
length of the incident x-rays. The intensity of the x-ray Raman scattering I(y, l) is given by
(Suzuki and Nagasawa, 1975)
I(y; l) (1 cos
2
y) T
1
(l)
4p" a
l
0
sin
y
2
!
2
T
2
(l)
4p" a
l
0
sin
y
2
!
2
( )
(87)
where T
1
(l) and T
2
(l) factors are related to the dipole and multipole transitions, respec-
tively. Although according to this equation a slight displacement of the peak position of
the Raman band is expected with the scattering angle, the peak position does not shift in
most experiments.
In general, x-ray Raman scattering gives information about the unoccupied states
above the Fermi level of the relevant solids. Moreover, this kind of inelastic scattering by
electrons in solids should sometimes be taken into account in x-ray spectrum evaluation.
VII. INTENSITYOF CHARACTERISTICX-RAYS
This section provides some of the necessary background information for subsequent
chapters dealing with quantitative x-ray analysis. Derivation of any relationship between
excitation source intensity and measured characteristic x-rays is sometimes complex and is
presented in detail in many relevant books, such as those by Jenkins et al. (1981) and
Tertian and Claisse (1982) on XRF analysis and by Goldstein et al. (1981) and Heinrich
(1981) on EPXMA.
A. Photon Excitation
When continuous (polychromatic) radiation is used to excite the characteristic x-rays of
element i in a completely homogeneous sample of thickness T (cm) and when enhancement
eects are neglected, the intensity of the uorescent radiation I
i
(E
i
) is described by
I
i
(E
i
) dO
1
dO
2
=
dO
1
dO
2
4p
e(E
i
)
sin C
1
Z
E
max
E
c;i
a
i
(E
0
)
1 exp[rT(m(E
0
) csc C
1
m(E
i
) csc C
2
)[
m(E
0
) csc C
1
m(E
i
) csc C
2
I
0
(E
0
) dE
0
(88)
with
a
i
(E
0
) = W
i
t
/
i
(E
0
)o
i
p
i
1
1
j
i

(89)
where dO
1
and dO
2
are the dierential solid angles for the incident (primary) and emerging
(characteristic) radiation, respectively; e(E
i
) is the intrinsic detector eciency for recording
a photon of energy E
i
; E
c;i
and E
max
are the critical absorption energy of element i and the
maximum energy in the excitation spectrum; r is the density of the specimen (in g=cm
3
);
C
1
and C
2
are the eective incidence and takeo angles, respectively; m(E
0
) and m(E
i
) are
the total mass attenuation coecients (in cm
2
=g) for the whole specimen [Eq. (45)] at
energies E
0
and E
i
, respectively; I
0
(E
0
) dE
0
is the number of incident photons per second
per steradian in the energy interval E
0
to E
0
dE
0
; W
i
is the weight fraction of the ith
element; and t
/
i
(E
0
) is the total photoelectric mass absorption coecient for the ith element
at the energy E
0
(in cm
2
=g).
Because large solid angles O
1
and O
2
are used for the excitation and characteristic
x-rays in practical spectrometers, Eq. (88) should also be integrated over these nite solid
angles. Such calculations can often be omitted; however, and for a given measurement
geometry, an experimentally determined geometry factor G can be applied.
As seen from Eq. (88), the intensity of characteristic x-rays is modied by the eects
of primary [m(E
0
)] and secondary [m(E
i
)] absorption in the specimen; this is a major source
of the so-called matrix eects in XRF analysis.
If the excitationsource is monochromatic (emits only one energy), Eq. (88) simplies to
I
i
(E
i
) = G
e(E
i
)a
i
(E
0
)I
0
(E
0
)
sin C
1
1 exp[rT(m(E
0
) csc C
1
m(E
i
) csc C
2
)[
m(E
0
) csc C
1
m(E
i
) csc C
2
(90)
The enhancement eect, consisting of an extra excitation of the element of interest by the
characteristic radiation of some matrix elements, modies the equations for the intensity
I
i
(E
i
). In the case of monochromatic photon excitation, a factor, 1 H
i
, should be in-
cluded in Eq. (90), where H
i
is the enhancement term dened as
H
i
=
1
2m
i
(E
0
)
X
m
k=1
W
k
o
k
1
1
j
k

m
i
(E
k
)m
k
(E
0
)
ln(1 m(E
0
)=[m(E
k
) sin C
1
[)
m(E
0
)= sin C
1
ln(1 m(E
i
)=[m(E
k
) sin C
2
[)
m(E
i
)= sin C
2
!
(91)
where m
i
(E
0
) and m
i
(E
k
) are the total mass attenuation coecients for the ith element at
the energy of incident radiation (E
0
) and characteristic radiation of the element k (E
k
),
respectively, m
k
(E
0
) is the total mass attenuation coecient for the element k at the
energy E
0
, and m(E
k
) is the total mass attenuation coecient for the whole specimen at
the energy E
k
.
1. Thin-SampleTechnique
If the total mass per unit area of a given sample m = rT is small, Eq. (90) simplies to
I
thin
i
(E
i
) =
G
sin C
1
e(E
i
)a
i
(E
0
)I
0
(E
0
)m (92)
The relative error resulting from applying Eq. (92) instead of Eq. (90) does not exceed 5%
when the total mass per unit area satises the condition
m
thin
_
0:1
m(E
0
) csc C
1
m(E
i
) csc C
2
(93)
A major feature of the thin-sample technique is that the intensity of the characteristic
x-rays, I
thin
i
, depends linearly on the concentration of the ith element (or on its mass per
unit area); it is equivalent to the fact that, in the thin-sample technique, matrix eects can
safely be neglected.
2. Thick-SampleTechnique
By the term thick sample, we mean a sample whose mass per unit area (thickness) is
greater than the so-called saturation mass (thickness). The saturation thickness is dened
as a limiting value above which practically no further increase in the intensity of the
characteristic radiation is observed as the sample thickness is increased.
If the total mass per unit area of a given sample is suciently large, Eq. (90) sim-
plies to
I
thick
i
(E
i
) =
Ge(E
i
)a
i
(E
0
)I
0
(E
0
)
m(E
0
) sin C
1
=(sin C
2
)m(E
i
)
(94)
The relative error resulting from applying Eq. (94) instead of Eq. (90) does not exceed 1%
when the total mass per unit area satises the condition
m
thick
_
4:61
m(E
0
) csc C
1
m(E
i
) csc C
2
(95)
B. Electron Excitation
For a thin foil (dened as a foil of thickness such that the beam electron undergoes only one
scattering act), the intensity of the characteristic x-rays I
tf
i
(in photons per second) is given by
I
tf
i
= K
i
I
0
Q
i
o
i
N
0
1
A
i
rTW
i
(96)
where K
i
is a factor depending on the measurement geometry and detection eciency and
the other symbols have the following dimensions: I
0
=electrons=s, Q
i
=ionizations per
electron for 1 atom=cm
2
, o
i
=photons=ionization. N
0
=atoms=mol, 1=A
i
=mol=g,
r=g=cm
3
, and T=cm.
For a bulk target, Eq. (96) must be integrated over the electron path, taking into
account the loss of energy by the electron beam:
I
bulk
i
= I
0
o
i
K
i
N
0
W
i
A
i
Z
E
c;i
E
0
Q
i
(E)
dE=d(rx)
dE (97)
where dE=d(rx) is the electron energy loss per unit of distance traveled in a material, given
by the Bethe equation (Heinrich, 1981; Bethe and Ashkin, 1953):
dE
d(rx)
= 78; 500
1
E
X
n
j=1
W
j
Z
j
A
j
ln 1:166
E
J
j

keV=g cm
2
(98)
where J
j
is the mean ionization potential of element j(J
j
= 9:76Z
j
58:5Z
0:19
j
eV)
(Goldstein et al., 1981). Strictly speaking, the Bethe equation is only valid for the electron
energy E > 6:3J
j
. Below this limit, the energy loss of the electrons should be described
either by the modication of Rao-Sahib and Wittry (1972) [Eq. (99)] or by the modi-
cation of Love et al. (l978) [Eq. (l00)]:
dE
d(rx)
= 0:6236 10
5
1
E
_
X
n
j=1
W
j
Z
j
A
j
J
j
p keV=g cm
2
(99)
dE
d(rx)
=
X
n
j=1
W
j
Z
j
A
j
J
j
1
1:18 10
5
(E=J
j
)
1=2
1:47 10
6
E=J
j
keV=g cm
2
(100)
However, to describe the intensity of characteristic x-rays emitted, three eects should be
considered additionally (Heinrich, 1981; Goldstein et al., 1981; Love and Scott, 1981):
1. Absorption of characteristic x-rays within the specimen
2. Electron backscattering
3. Secondary uorescence by characteristic x-rays and=or bremsstrahlung con-
tinuum produced by an electron beam
C. Particle Excitation
For a thin, uniform, homogeneous target, the intensity of characteristic x-rays I
tt
i
is given
by the simple formula
I
tt
i
= K
i
I
0
N
0
s
s;i
(E
0
)o
i
1
A
i
m
i
(101)
where m
i
is the areal density of the element with atomic number Z
i
and atomic mass A
i
.
For a thick, homogeneous target, the intensity of characteristic x-rays, I
thick
i
, from
the element i of concentration W
i
can be calculated by (Campbell and Cookson, 1984)
I
thick
i
=
K
i
o
i
N
0
A
i
I
0
W
i
X
0
E
0
s
s;i
(E)T
i
(E)
S(E)
dE (102)
where S(E) is the stopping power and T
i
(E) is the photon attenuation factor. The latter is
given by
T
i
(E) = exp m(E
i
)
sin C
1
sin C
2
Z
E
E
0
dE
S(E)
0
B
@
1
C
A (103)
More details on various x-ray analytical techniques are provided in subsequent chapters.
VIII. IUPACNOTATIONFOR X-RAYSPECTROSCOPY
The nomenclature commonly used in XRS to describe x-ray emission spectra was in-
troduced by M. Sieghahn in the l920s and is based on the relative intensity of lines from
dierent series. A new and more systematic notation for x-ray emission lines and ab-
sorption edges, based on the energy-level designation, was developed by the International
Union of Pure and Applied Chemistry (Jenkins et al. 1991). Because the new notation,
called the IUPAC notation, replaces the Siegbahns notation, some characteristic features
of the new nomenclature must be mentioned. The IUPAC notation prescribes Arabic
numerals for subscripts; the original notation uses Roman numerals (e.g., L
2
and L
3
,
instead of L
II
and L
III
). In the IUPAC notation, states with double or multiple vacancies
should be denoted by, for example, K
2
; KL
1
, and L
n
2;3
, which correspond to the electron
congurations 1s
2
; 1s
1
2s
1
, and 2p
n
, respectively. X-ray transitions and x-ray emission
diagram lines are denoted by the initial (placed rst) and nal x-ray levels separated by a
hyphen. To conform with the IUPAC notation of x-ray spectra, the hyphen separating the
initial and nal state levels should also be introduced into the notation for Auger electron
emission process. The IUPAC notation is compared with the Sieghahn notation in Ap-
pendix XII.
APPENDIXI: CRITICAL ABSORPTIONWAVELENGTHS AND CRITICAL ABSORPTIONENERGIES
Atomic
number
K edge L
1
edge L
2
edge L
3
edge M
4
edge M
5
edge
Element A
keV A
keV A
keV A
keV A
keV A
keV
1 H 918 0.014
2 He 504 0.025
3 Li 226.953 0.055
4 Be 106.9 0.116
5 B 64.6 0.192
6 C 43.767 0.283
7 N 31.052 0.399
8 O 23.367 0.531
9 F 18.05 0.687
10 Ne 14.19 0.874 258 0.048 564 0.022 564 0.022
11 Na 11.48 1.08 225 0.055 365 0.034 365 0.034
12 Mg 9.512 1.303 197 0.063 248 0.050 253 0.049
13 Al 7.951 1.559 143 0.087 170 0.073 172 0.072
14 Si 6.745 1.837 105 0.118 125 0.099 127 0.098
15 P 5.787 2.142 81.0 0.153 96.1 0.129 96.9 0.128
16 S 5.018 2.470 64.2 0.193 75.6 0.164 76.1 0.163
17 Cl 4.397 2.819 52.1 0.238 61.1 0.203 61.4 0.202
18 Ar 3.871 3.202 43.2 0.287 50.2 0.247 50.6 0.245
19 K 3.437 3.606 36.4 0.341 41.8 0.297 42.2 0.294
20 Ca 3.070 4.037 30.7 0.399 35.2 0.352 35.5 0.349
21 Sc 2.757 4.495 26.8 0.462 30.2 0.411 30.8 0.402
22 Ti 2.497 4.963 23.4 0.530 27.0 0.460 27.3 0.454
23 V 2.269 5.462 20.5 0.604 23.9 0.519 24.2 0.512
24 Cr 2.070 5.987 18.3 0.679 21.3 0.583 21.6 0.574
25 Mn 1.896 6.535 16.3 0.762 19.1 0.650 19.4 0.639
26 Fe 1.743 7.109 14.6 0.849 17.2 0.721 17.5 0.708
27 Co 1.608 7.707 13.3 0.929 15.6 0.794 15.9 0.779
28 Ni 1.488 8.329 12.22 1.015 14.2 0.871 14.5 0.853
29 Cu 1.380 8.978 11.27 1.100 13.0 0.953 13.3 0.933
30 Zn 1.283 9.657 10.33 1.200 11.87 1.045 12.13 1.022
31 Ga 1.196 10.365 9.54 1.30 10.93 1.134 11.10 1.117
32 Ge 1.117 11.100 8.73 1.42 9.94 1.248 10.19 1.217
33 As 1.045 11.860 8.107 1.529 9.124 1.358 9.39 1.32
34 Se 0.980 12.649 7.506 1.651 8.416 1.473 8.67 1.43
35 Br 0.920 13.471 6.97 1.78 7.80 1.59 8.00 1.55
36 Kr 0.866 14.319 6.46 1.92 7.21 1.72 7.43 1.67
37 Rb 0.816 15.197 5.998 2.066 6.643 1.865 6.89 1.80
38 Sr 0.770 16.101 5.583 2.220 6.172 2.008 6.387 1.940
39 Y 0.728 17.032 5.232 2.369 5.755 2.153 5.962 2.079
40 Zr 0.689 17.993 4.867 2.546 5.378 2.304 5.583 2.220
41 Nb 0.653 18.981 4.581 2.705 5.026 2.467 5.223 2.373
42 Mo 0.620 19.996 4.298 2.883 4.718 2.627 4.913 2.523
43 Tc 0.589 21.045 4.060 3.054 4.436 2.795 4.632 2.677
44 Ru 0.561 22.112 3.83 3.24 4.180 2.965 4.369 2.837
45 Rh 0.534 23.217 3.626 3.418 3.942 3.144 4.130 3.001
46 Pd 0.509 24.341 3.428 3.616 3.724 3.328 3.908 3.171
47 Ag 0.486 25.509 3.254 3.809 3.514 3.527 3.698 3.351
48 Cd 0.464 26.704 3.085 4.018 3.326 3.726 3.504 3.537
49 In 0.444 27.920 2.926 4.236 3.147 3.938 3.324 3.728
50 Sn 0.425 29.182 2.777 4.463 2.982 4.156 3.156 3.927
51 Sb 0.407 30.477 2.639 4.695 2.830 4.380 3.000 4.131
52 Te 0.390 31.800 2.511 4.937 2.687 4.611 2.855 4.340
53 I 0.374 33.155 2.389 5.188 2.553 4.855 2.719 4.557
54 Xe 0.359 34.570 2.274 5.451 2.429 5.102 2.592 4.780
55 Cs 0.345 35.949 2.167 5.719 2.314 5.356 2.474 5.010
56 Ba 0.331 37.399 2.068 5.994 2.204 5.622 2.363 5.245 15.56 0.7967 15.89 0.7801
57 La 0.318 38.920 1.973 6.282 2.103 5.893 2.258 5.488
58 Ce 0.307 40.438 1.889 6.559 2.011 6.163 2.164 5.727
59 Pr 0.295 41.986 1.811 6.844 1.924 6.441 2.077 5.967 13.122 0.9448 13.394 0.9257
60 Nd 0.285 43.559 1.735 7.142 1.843 6.725 1.995 6.213 12.459 0.9951 23.737 0.9734
61 Pm 0.274 45.207 1.665 7.448 1.767 7.018 1.918 6.466
62 Sm 0.265 46.833 1.599 7.752 1.703 7.279 1.845 6.719 11.288 1.0983 11.552 1.0732
63 Eu 0.256 48.501 1.536 8.066 1.626 7.621 1.775 6.981 10.711 1.1575 11.013 1.1258
Appendix I Continued
Atomic
number
K edge L
1
edge L
2
edge L
3
edge M
4
edge M
5
edge
Element A
keV A
keV A
keV A
keV A
keV A
keV
64 Gd 0.247 50.215 1.477 8.391 1.561 7.938 1.710 7.250
65 Tb 0.238 51.984 1.421 8.722 1.501 8.256 1.649 7.517
66 Dy 0.231 53.773 1.365 9.081 1.438 8.619 1.579 7.848
67 Ho 0.223 55.599 1.317 9.408 1.390 8.918 1.535 8.072
68 Er 0.216 57.465 1.268 9.773 1.338 9.260 1.482 8.361 8.601 1.4415 8.847 1.4013
69 Tm 0.209 59.319 1.222 10.141 1.288 9.626 1.433 8.650 8.487 1.4609
70 Yb 0.202 61.282 1.182 10.487 1.243 9.972 1.386 8.941
71 Lu 0.196 63.281 1.140 10.870 1.199 10.341 1.341 9.239
72 Hf 0.190 65.292 1.100 11.271 1.155 10.732 1.297 9.554
73 Ta 0.184 67.379 1.061 11.681 1.114 11.128 1.255 9.874 6.87 1.804 7.11 1.743
74 W 0.178 69.479 1.025 12.097 1.075 11.533 1.216 10.196 6.59 1.880 6.83 1.814
75 Re 0.173 71.590 0.990 12.524 1.037 11.953 1.177 10.529 6.33 1.958 6.560 1.890
76 Os 0.168 73.856 0.956 12.968 1.001 12.380 1.140 10.867 6.073 2.042 6.30 1.967
77 Ir 0.163 76.096 0.923 13.427 0.967 12.817 1.106 11.209 5.83 2.126 6.05 2.048
78 Pt 0.158 78.352 0.893 13.875 0.934 13.266 1.072 11.556 5.59 2.217 5.81 2.133
79 Au 0.153 80.768 0.863 14.354 0.903 13.731 1.040 11.917 5.374 2.307 5.584 2.220
80 Hg 0.149 83.046 0.835 14.837 0.872 14.210 1.008 12.3 5.157 2.404 5.36 2.313
81 Tl 0.415 85.646 0.808 15.338 0.843 14.695 0.979 12.655 4.952 2.504 5.153 2.406
82 Pb 0.141 88.037 0.782 15.858 0.815 15.205 0.950 13.041 4.757 2.606 4.955 2.502
83 Bi 0.137 90.420 0.757 16.376 0.789 15.713 0.923 13.422 4.572 2.711 4.764 2.603
84 Po 0.133 93.112 0.732 16.935 0.763 16.244 0.897 13.817
85 At 0.130 95.740 0.709 17.490 0.739 16.784 0.872 14.215
86 Rn 0.126 98.418 0.687 18.058 0.715 17.337 0.848 14.618
87 Fr 0.123 101.147 0.665 18.638 0.693 17.904 0.825 15.028
88 Ra 0.645 19.229 0.671 18.478 0.803 15.439
89 Ac 0.116 106.759 0.625 19.842 0.650 19.078 0.782 15.865
90 Th 0.113 109.741 0.606 20.458 0.630 19.677 0.761 16.293 3.557 3.485 3.729 3.325
91 Pa 0.110 112.581 0.588 21.102 0.611 20.311 0.741 16.731 3.436 3.608 3.618 3.436
92 U 0.108 115.610 0.56 21.764 0.592 20.938 0.722 17.160 3.333 3.720 3.497 3.545
93 Np 0.105 118.619 0.553 22.417 0.574 21.596 0.704 17.614
94 Pu 0.102 121.720 0.537 23.097 0.557 22.262 0.686 18.066
95 Am 0.099 124.816 0.521 23.793 0.540 22.944 0.669 18.525
96 Cm 0.097 128.088 0.506 24.503 0.525 23.640 0.653 18.990
97 Bk 0.094 131.357 0.491 25.230 0.509 24.352 0.637 19.461
98 Cf 0.092 134.683 0.477 25.971 0.494 25.080 0.622 19.938
99 Es 0.090 138.067 0.464 26.729 0.480 25.824 0.607 20.422
100 Fm 0.088 141.510 0.451 27.503 0.466 26.584 0.593 20.912
Source: From Clark, 1963 and Burr, 1974.
APPENDIXII: CHARACTERISTICX-RAY WAVELENGTHS (A ) ANDENERGIES (keV)
Table1 K Series Diagram Lines (A
)
a
Line a
1,2
a
1
a
2
b
1
b
3
b
2
b
4
Approximate
intensity 150 100 50 15 5 <1
Li 3 230
B 4 113
B 5 67
C 6 44
N 7 31.603
O 8 23.707
F 9 18.307
Ne 10 14.615 14.460
Na 11 11.909 11.574 11.726
Mg 12 9.889 9.559 9.667
Al 13 8.339 8.338 8.341 7.960 8.059
Si 14 7.126 7.125 7.127 6.778
P 15 6.155 6.154 6.157 5.804
S 16 5.373 5.372 5.375 5.032
Cl 17 4.729 4.728 4.731 4.403
Ar 18 4.192 4.191 4.194 3.886
K 19 3.744 3.742 3.745 3.454
Ca 20 3.360 3.359 3.362 3.089
Sc 21 3.032 3.031 3.034 2.780
Ti 22 2.750 2.749 2.753 2.514
V 23 2.505 2.503 2.507 2.285
Cr 24 2.291 2.290 2.294 2.085
Mn 25 2.103 2.102 2.105 1.910
Fe 26 1.937 1.936 1.940 1.757
Co 27 1.791 1.789 1.793 1.621
Ni 28 1.659 1.658 1.661 1.500 1.489
Cu 29 1.542 1.540 1.544 1.392 1.393 1.381
Zn 30 1.437 1.435 1.439 1.296 1.284
Ga 31 1.341 1.340 1.344 1.207 1.208 1.196
Ge 32 1.256 1.255 1.258 1.129 1.129 1.117
As 33 1.177 1.175 1.179 1.057 1.058 1.045
Se 34 1.106 1.105 1.109 0.992 0.993 0.980
Br 35 1.041 1.040 1.044 0.933 0.933 0.921
Kr 36 0.981 0.980 0.984 0.879 0.879 0.866 0.866
Rb 37 0.927 0.926 0.930 0.829 0.830 0.817 0.815
Sr 38 0.877 0.875 0.880 0.783 0.784 0.771 0.770
Y 39 0.831 0.829 0.833 0.740 0.741 0.728 0.727
Zr 40 0.788 0.786 0.791 0.701 0.702 0.690 0.689
Nb 41 0.748 0.747 0.751 0.665 0.666 0.654 0.653
Mo 42 0.710 0.709 0.713 0.632 0.633 0.621 0.620
Tc 43 0.676 0.675 0.679 0.601 0.590
Ru 44 0.644 0.643 0.647 0.572 0.573 0.562 0.561
Rh 45 0.614 0.613 0.617 0.546 0.546 0.535 0.534
Pd 46 0.587 0.585 0.590 0.521 0.521 0.510
Table1 Continued
Line a
1,2
a
1
a
2
b
1
b
3
b
2
b
4
Approximate
intensity 150 100 50 15 5 <1
Ag 47 0.561 0.559 0.564 0.497 0.498 0.487 0.486
Cs 48 0.536 0.535 0.539 0.475 0.476 0.465
In 49 0.514 0.512 0.517 0.455 0.455 0.445 0.444
Sn 50 0.492 0.491 0.495 0.435 0.436 0.426 0.425
Sb 51 0.472 0.470 0.475 0.417 0.418 0.408 0.407
Te 52 0.453 0.451 0.456 0.400 0.401 0.391
I 53 0.435 0.433 0.438 0.384 0.385 0.376
Xe 54 0.418 0.416 0.421 0.369 0.360
Cs 55 0.402 0.401 0.405 0.355 0.355 0.346
Ba 56 0.387 0.385 0.390 0.341 0.342 0.333
La 57 0.373 0.371 0.376 0.328 0.329 0.320 0.319
Ce 58 0.359 0.357 0.362 0.316 0.317 0.309 0.307
Pr 59 0.346 0.344 0.349 0.305 0.305 0.297
Nd 60 0.334 0.332 0.337 0.294 0.294 0.287
Pm 61 0.322 0.321 0.325 0.283
Sm 62 0.311 0.309 0.314 0.274 0.274 0.267
Eu 63 0.301 0.299 0.304 0.264 0.265 0.258
Gd 64 0.291 0.289 0.294 0.255 0.256 0.249
Tb 65 0.281 0.279 0.284 0.246 0.246 0.239
Dy 66 0.272 0.270 0.275 0.237 0.238 0.231
Ho 67 0.263 0.261 0.266 0.230 0.231
Er 68 0.255 0.253 0.258 0.222 0.223 0.217
Tm 69 0.246 0.244 0.250 0.215 0.216
Yb 70 0.238 0.236 0.241 0.208 0.208 0.203
Lu 71 0.231 0.229 0.234 0.202 0.203 0.197
Hf 72 0.224 0.222 0.227 0.195 0.196 0.190
Ta 73 0.217 0.215 0.220 0.190 0.191 0.185 0.184
W 74 0.211 0.209 0.213 0.184 0.185 0.179 0.179
Re 75 0.204 0.202 0.207 0.179 0.179 0.174 0.174
Os 76 0.198 0.196 0.201 0.173 0.174 0.169 0.168
Ir 77 0.193 0.191 0.196 0.168 0.169 0.164 0.163
Pt 78 0.187 0.158 0.190 0.163 0.164 0.159 0.159
Au 79 0.182 0.180 0.185 0.159 0.160 0.155 0.154
Hg 80 0.177 0.175 0.180 0.154 0.155 0.150 0.150
Tl 81 0.172 0.170 0.175 0.150 0.151 0.146 0.146
Pb 82 0.167 0.165 0.170 0.146 0.147 0.147 0.141
Bi 83 0.162 0.161 0.165 0.142 0.143 0.138 0.138
Po 84 0.185 0.156 0.161 0.138 0.133
At 85 0.152 0.157 0.134 0.135
Rn 86 0.148 0.153 0.131 0.132
Fr 87 0.144 0.149 0.127 0.128
Ra 88 0.144 0.149 0.127 0.128
Ac 89 0.140 0.145 0.124 0.125
Th 90 0.135 0.133 0.138 0.117 0.118 0.114 0.114
Pa 91 0.131 0.136 0.115 0.116
U 92 0.128 0.126 0.131 0.111 0.112 0.108 0.108
a
Conversion equation: E (keV) =12.4=l (A
).
Source: From Clark, 1963.
Table 2 L Series Diagram Lines (A
)
Line a a
1
a
2
b
1
b
2
b
3
b
4
b
5
b
6
b
7
b
9
Approximate
intensity 110 100 10 50 20 6 4 1 <1 <1 <1
Na 11
Mg 12
Al 13
Si 14
P 15
S 16
Cl 17
Ar 18
K 19
Ca 20 36.393 36.022
Sc 21 31.393 31.072
Ti 22 27.445 27.074
V 23 24.309 23.898
Cr 24 21.713 21.323 19.429
Mn 25 19.489 19.158 17.757
Fe 26 17.602 17.290 15.742
Co 27 16.000 15.698 14.269
Ni 28 14.595 14.308 13.167
Cu 29 13.357 13.079 12.115
Zn 30 12.282 12.009 11.225
Ga 31 11.313 11.045
Ge 32 10.456 10.194
As 33 9.671 9.414 8.930
Se 34 8.990 8.735
Br 35 8.375 8.126
Kr 36
Rb 37 7.318 7.325 7.075 6.788 6.821 6.984
Sr 38 6.863 6.870 6.623 6.367 6.403 6.519
Y 39 6.449 6.456 6.211 5.983 6.018 6.094
Zr 40 6.070 6.077 5.836 5.586 5.632 5.668 5.710
Nb 41 5.725 5.732 5.492 5.238 5.310 5.346 5.361
Mo 42 5.406 5.414 5.176 4.923 5.013 5.048 5.048
Tc 43
Ru 44 4.846 4.854 4.620 4.372 4.487 4.532 4.487
Rh 45 4.597 4.605 4.374 4.130 4.253 4.289 4.242
Pd 46 4.368 4.376 4.146 3.909 4.034 4.071 4.016 3.792
Ag 47 4.154 4.162 3.935 3.703 3.834 3.870 3.808 3.605
Cd 48 3.956 3.965 3.739 3.514 3.644 3.681 3.614 3.430
In 49 3.752 3.781 3.555 3.339 3.470 3.507 3.436 3.268
Sn 50 3.600 3.609 3.385 3.175 3.306 3.344 3.270 3.155 3.115
Sb 51 3.439 3.448 3.226 3.023 3.152 3.190 3.115 3.005 2.973
Te 52 3.290 3.299 3.077 2.882 3.009 3.046 2.971 2.863 2.839
I 53 3.148 3.157 2.937 2.751 2.874 2.912 2.837 2.730 2.713
Xe 54
Cs 55 2.892 2.902 2.683 2.511 2.628 2.666 2.593 2.485 2.478
b
10
b
15
b
17
g
1
g
2
g
3
g
4
g
5
g
6
g
8
Z s t
<1 <1 <1 10 1 2 <1 <1 <1 <1 3 1 <1 <1
410
260
180
67.84 67.25
56.212 56.813
47.835 47.325
41.042 40.542
36.671 35.200
31.423 30.942
27.826 27.375
24.840 24.339
22.315 21.864
20.201 19.73
18.358 17.86
16.693 16.304
15.297 14.940
14.081 13.719
12.976 12.620
11.944 11.608
11.069 10.732
10.293 9.959
9.583 9.253
6.045 6.754 8.363 8.042
5.644 6.297 7.836 7.517
5.283 5.875 7.356 7.040
5.384 4.953 5.497 6.918 6.606
5.036 4.654 5.151 6.517 6.210
4.726 4.380 4.387 6.150 5.847
4.182 3.897 4.288 5.503 5.204
3.944 3.685 4.045 5.217 4.922
3.799 3.725 3.489 3.822 4.952 4.660
3.611 3.523 3.307 3.616 4.707 4.418
3.437 3.336 3.137 3.426 4.480 4.193
3.274 3.162 2.980 2.026 3.249 4.269 3.983
3.121 3.001 2.835 2.778 3.085 4.071 3.789
2.979 2.852 2.695 2.639 2.932 3.888 3.607
2.847 2.712 2.567 2.511 2.790 3.716 3.438
2.720 2.582 2.447 2.391 2.657 3.557 3.280
2.492 2.348 2.237 2.233 2.174 2.417 3.267 2.994
Table 2 Continued
Line a a
1
a
2
b
1
b
2
b
3
b
4
b
5
b
6
b
7
b
9
Approximate
intensity 110 100 10 50 20 6 4 1 <1 <1 <1
Ba 56 2.776 2.785 2.567 2.404 2.516 2.555 2.482 2.382 2.376
La 57 2.665 2.674 2.458 2.303 2.410 2.449 2.379 2.275 2.282
Ce 58 2.561 2.570 2.356 2.208 2.311 2.349 2.282 2.180 2.188
Pr 59 2.463 2.473 2.259 2.119 2.216 2.255 2.190 2.091 2.100
Nd 60 2.370 2.382 2.166 2.035 2.126 2.166 2.103 2.009 2.016
Pm 61 2.283 2.081
Sm 62 2.199 2.210 1.998 1.882 1.962 2.000 1.779 1.946 1.856 1.862
Eu 63 2.120 2.131 1.920 1.812 1.887 1.926 1.875 1.788 1.792
Gd 64 2.046 2.057 1.847 1.746 1.815 1.853 1.807 1.723
Tb 65 1.976 1.986 1.777 1.682 1.747 1.785 1.577 1.742 1.659
Dy 66 1.909 1.920 1.710 1.623 1.681 1.720 1.681 1.599
Ho 67 1.845 1.856 1.647 1.567 1.619 1.658 1.622
Er 68 1.785 1.796 1.587 1.514 1.561 1.601 1.567 1.494 1.485
Tm 69 1.726 1.738 1.530 1.463 1.505 1.544 1.515
Yb 70 1.672 1.682 1.476 1.416 1.452 1.491 1.387 1.466 1.395 1.384
Lu 71 1.619 1.630 1.424 1.370 1.402 1.441 1.342 1.419 1.350 1.336
Hf 72 1.569 1.580 1.374 1.327 1.353 1.392 1.298 1.374 1.306 1.291
Ta 73 1.522 1.533 1.327 1.285 1.307 1.346 1.256 1.331 1.264 1.247
W 74 1.476 1.487 1.282 1.245 1.263 1.302 1.215 1.290 1.224 1.204
Re 75 1.433 1.444 1.238 1.206 1.220 1.260 1.177 1.252 1.186 1.165
Os 76 1.391 1.402 1.197 1.169 1.179 1.218 1.140 1.213 1.149 1.126
Ir 77 1.352 1.363 1.158 1.135 1.141 1.179 1.106 1.179 1.115 1.090
Pt 78 1.313 1.325 1.120 1.102 1.104 1.142 1.072 1.143 1.082 1.054
Au 79 1.277 1.288 1.083 1.070 1.068 1.106 1.040 1.111 1.050 1.021
Hg 80 1.242 1.253 1.049 1.040 1.034 1.072 1.010 1.080 1.019 0.986
Tl 81 1.207 1.218 1.015 1.010 1.001 1.039 0.981 1.050 0.990 0.957
Pb 82 1.175 1.186 0.982 0.983 0.969 1.007 0.953 1.021 0.962 0.927
Bi 83 1.144 1.155 0.952 0.955 0.939 0.977 0.926 0.993 0.935 0.898
Po 84 1.114 1.126 0.921 0.929 0.908 0.948 0.900 0.967
At 85
Rn 86
Fr 87 1.030 0.840 0.858
Ra 88 1.005 1.017 0.814 0.836 0.803 0.841 0.807 0.871 0.817 0.769
Ac 89
Th 90 0.956 0.968 0.766 0.794 0.755 0.793 0.765 0.828 0.775 0.723
Pa 91 0.933 0.945 0.742 0.774 0.732 0.770 0.746 0.803 0.755 0.701
U 92 0.911 0.923 0.720 0.755 0.710 0.748 0.726 0.789 0.736 0.681
Np 93 0.890 0.901 0.698 0.735
Pu 94 0.868 0.880 0.678 0.719 0.669 0.707 0.691
Am 95 0.849 0.860 0.658 0.701
b
10
b
15
b
17
g
1
g
2
g
3
g
4
g
5
g
6
g
8
Z s t
<1 <1 <1 10 1 2 <1 <1 <1 <1 3 1 <1 <1
2.387 2.442 2.138 2.134 2.075 2.309 2.222 3.135 2.862
2.290 2.141 2.046 2.041 1.983 2.205 3.006 2.740
2.195 2.048 1.960 1.955 1.899 2.110 2.023 2.892 2.620
2.107 1.961 1.879 1.874 1.819 2.020 1.936 2.784 2.512
2.023 1.878 1.801 1.797 1.745 1.935 1.855 2.675 2.409
1.870 1.726 1.659 1.655 1.606 2.482 2.218
1.800 1.657 1.597 1.591 1.544 1.708 1.632 2.395
1.731 1.592 1.534 1.529 1.485 2.312 2.049
1.667 1.530 1.477 1.471 1.427 2.234
1.473 1.423 1.417 1.374 1.518 2.158 1.898
1.417 1.371 1.364 1.323 1.462 2.086 1.826
1.494 1.364 1.321 1.315 1.276 1.406 2.019 1.757
1.316 1.274 1.268 1.355 1.955 1.695
1.392 1.268 1.228 1.222 1.185 1.307 1.243 1.250 1.894 1.635 1.831
1.343 1.372 1.222 1.185 1.179 1.143 1.260 1.198 1.204 1.836 1.478 1.776
1.299 1.328 1.437 1.179 1.144 1.138 1.103 1.215 1.155 1.161 1.782 1.523 1.663 1.723
1.254 1.287 1.138 1.105 1.099 1.065 1.173 1.114 1.120 1.728 1.471 1.612 1.672
1.212 1.247 1.339 1.098 1.068 1.062 1.028 1.132 1.074 1.081 1.678 1.421
1.172 1.208 1.293 1.061 1.032 1.026 0.993 1.094 1.037 1.044 1.630 1.374
1.133 1.171 1.025 0.998 0.992 0.959 1.057 1.001 1.008 1.585 1.328
1.097 1.137 0.991 0.966 0.959 0.928 1.022 0.967 0.974 1.541 1.285
1.062 1.166 0.958 0.934 0.928 0.897 0.988 0.934 0.941 1.499 1.243
1.028 1.072 1.128 0.927 0.905 0.898 0.867 0.956 0.903 0.010 1.460 1.202 1.352 1.414
0.996 1.041 1.090 0.897 0.876 0.869 0.839 0.925 0.873 0.880 1.422 1.164
0.964 1.012 1.056 0.868 0.848 0.842 0.812 0.895 0.845 0.852 1.385 1.127 1.279 1.342
0.934 0.984 1.022 0.840 0.822 0.815 0.867 0.817 0.824 1.350 1.092 1.244 1.308
0.905 0.957 0.989 0.814 0.796 0.790 0.761 0.840 0.791 0.799 1.317 1.058 1.210
0.931 0.786 0.771 0.764 0.765 1.283
0.716
0.776 0.838 0.844 0.694 0.682 0.675 0.649 0.717 0.673 0.680 1.167 0.908
0.730 0.653 0.642 0.635 0.611 0.675 0.632 0.640 1.115 0.855 1.011 1.080
0.708 0.634 0.624 0.617 0.594 0.655 0.613 1.091 0.830
0.687 0.615 0.605 0.598 0.577 0.635 0.595 0.601 1.067 0.806 0.904 1.035
0.597
0.579
0.562
Table 3 M Series Diagram Lines (A
)
Line a
1
a
2
b g l
K 19 680
Cu 29 170
Ru 44 26.85
Rh 45 25.00
Pd 46
Ag 47 21.80
Cd 48 20.46
In 49
Sn 50 17.94
Sb 51 16.92
Te 52 15.93
Ba 56 12.700
La 57 14.88 14.51 12.064
Ce 58 14.06 13.78 11.534 18.38
Pr 59 10.997
Nd 60 12.675 Band 10.504
Sm 62 Band Band 9.599
Eu 63 Band 10.744 9.211 14.22
Gd 64 Band 10.253 8.844 13.57
Tb 65 Band 9.792 8.485 12.98
Dy 66 Band 9.364 8.144 12.43
Ho 67 Band 8.965 7.865 11.86
Er 68 Band 8.593 7.545 11.37
Tm 69 8.460 8.246
Yb 70 8.139 8.155 7.909 7.023 10.48
Lu 71 7.840 7.600 6.761 10.07
Hf 72 7.539 7.546 7.304 6.543 9.69
Ta 73 7.251 7.258 7.022 6.312 9.32
W 74 6.983 6.990 6.756 6.088 8.96
Re 75 6.528 6.504 5.887 8.63
Os 76 6.490 6.267 5.681
Ir 77 6.261 6.275 6.037 5.501 8.02
Pt 78 6.046 6.057 5.828 5.320 7.74
Au 79 5.840 5.854 5.623 5.145 7.47
Hg 80 5.666 5.452
Tl 81 5.461 5.472 5.250 4.825 6.97
Pb 82 5.285 5.299 5.075 4.674 6.74
Bi 83 5.118 5.129 4.909 4.531 6.52
Th 90 4.138 4.151 3.942 3.679 5.24
Pa 91 4.022 4.035 3.827 3.577 5.08
U 92 3.910 3.924 3.715 3.480 4.95
Table 4 Energies of Principal K and L X-ray Emission Lines (keV)
Atomic
number Element Kb
2
Kb
1
Ka
1
Ka
2
Lg
1
Lb
2
Lb
1
La
1
La
2
3 Li 0.052
4 Be 0.110
5 B 0.185
6 C 0.282
7 N 0.392
8 C 0.523
9 F 0.677
10 Ne 0.851
11 Na 1.067 1.041
12 Mg 1.297 1.254
13 Al 1.553 1.487 1.486
14 Si 1.832 1.40 1.739
15 P 2.136 2.015 2.014
16 S 2.464 2.309 2.306
17 Cl 2.815 2.622 2.621
18 Ar 3.192 2.957 2.955
19 K 3.589 3.313 3.310
20 Ca 4.012 3.691 3.688 0.344 0.341
21 Sc 4.460 4.090 4.085 0.399 0.395
22 Ti 4.931 4.510 4.504 0.458 0.492
23 V 5.427 4.952 4.944 0.519 0.510
24 Cr 5.946 5.414 5.405 0.581 0.571
25 Mn 6.490 5.898 5.887 0.647 0.636
26 Fe 7.057 6.403 6.390 0.717 0.704
27 Co 7.647 6.930 6.915 0.790 0.775
28 Ni 8.328 8.264 7.477 7.460 0.866 0.849
29 Cu 8.976 8.904 8.047 8.027 0.943 0.928
30 Zn 9.657 9.571 8.638 8.615 1.032 1.009
31 Ga 10.365 10.263 9.251 9.234 1.122 1.096
32 Ge 11.100 10.981 9.885 9.854 1.216 1.166
33 As 11.863 11.725 10.543 10.507 1.517 1.282
34 Se 12.651 12.495 11.221 11.181 1.419 1.379
35 Br 13.465 13.290 11.923 11.877 1.526 1.480
36 Kr 14.313 14.112 12.648 12.597 1.638 1.587
37 Rb 15.184 14.960 13.394 13.335 1.752 1.694 1.692
38 Sr 16.083 15.834 14.164 14.097 1.872 1.806 1.805
39 Y 17.011 16.736 14.957 14.882 1.996 1.922 1.920
40 Zr 17.969 17.666 15.774 15.690 2.302 2.219 2.124 2.042 2.040
41 Nb 18.951 18.621 16.614 16.520 2.462 2.367 2.257 2.166 2.163
42 Mo 19.964 19.607 17.478 17.373 2.623 2.518 2.395 2.293 2.290
43 Tc 21.012 20.585 18.410 18.328 2.792 2.674 2.538 2.424 2.420
44 Ru 22.072 21.655 19.278 19.149 2.964 2.836 2.683 2.558 2.554
45 Rh 23.169 22.721 20.214 20.072 3.144 3.001 2.834 2.696 2.692
46 Pd 24.297 23.816 21.175 21.018 3.328 3.172 2.990 2.838 2.833
47 Ag 25.454 24.942 22.162 21.988 3.519 3.348 3.151 2.994 2.978
48 Cd 26.641 26.093 23.172 22.982 3.716 3.528 3.316 3.133 3.127
49 In 27.859 27.274 24.207 24.000 3.920 3.713 3.487 3.287 3.279
50 Sn 29.106 28.483 25.270 25.042 4.131 3.904 3.662 3.444 3.436
Table 4 Continued
Atomic
number Element Kb
2
Kb
1
Ka
1
Ka
2
Lg
1
Lb
2
Lb
1
La
1
La
2
51 Sb 30.387 29.723 26.357 26.109 4.347 4.100 3.543 3.605 3.595
52 To 31.698 30.993 27.471 27.200 4.570 4.301 4.029 3.769 3.758
53 I 33.016 32.292 28.610 28.315 4.800 4.507 4.220 3.937 3.926
54 Xe 34.446 33.644 29.802 29.485 5.036 4.720 4.422 4.111 4.098
55 Cs 35.819 34.984 30.970 30.623 5.280 4.936 4.620 4.286 4.272
56 Ba 37.255 35.376 32.191 31.815 5.531 5.156 4.828 4.467 4.451
57 La 38.728 37.799 33.440 33.033 5.789 5.384 5.043 4.651 4.635
58 Ce 40.231 39.255 34.717 34.276 6.052 5.613 5.262 4.840 4.823
59 Pr 41.772 40.746 36.023 35.548 6.322 5.850 5.489 5.034 5.014
60 Nd 43.298 42.269 37.359 36.845 6.602 6.090 5.722 5.230 5.208
61 Pm 44.955 43.945 38.649 38.160 6.891 6.336 5.956 5.431 5.408
62 Sm 46.553 45.400 40.124 39.523 7.180 6.587 6.206 5.636 5.609
63 Eu 48.241 47.027 41.529 40.877 7.478 6.842 6.456 5.846 5.816
64 Gd 49.961 48.718 42.983 42.280 7.788 7.102 6.714 6.039 6.027
65 Tb 51.737 50.391 44.470 43.737 8.104 7.368 6.979 6.275 6.241
66 Dy 53.491 52.178 45.985 45.193 8.418 7.638 7.249 6.495 6.457
67 Ho 55.292 53.934 47.528 46.686 8.748 7.912 7.528 6.720 6.680
68 Er 57.088 55.690 49.099 48.205 9.089 8.188 7.810 6.948 6.904
69 Tm 58.969 57.576 50.730 49.762 9.424 8.472 8.103 7.181 7.135
70 Yb 60.959 59.352 52.360 51.326 9.779 8.758 8.401 7.414 7.367
71 Lu 62.946 61.282 54.063 52.959 10.142 9.048 8.709 7.654 7.604
72 Hf 64.936 63.209 55.757 54.579 10.514 9.346 9.021 7.898 7.843
73 Ta 66.999 65.210 57.524 56.270 10.892 9.649 9.341 8.145 8.087
74 W 69.090 67.233 59.310 57.973 11.283 9.959 9.670 8.396 8.333
75 Re 71.220 69.298 61.131 59.707 11.684 10.273 10.008 8.651 8.584
76 Os 73.393 71.404 62.991 61.477 12.094 10.596 10.354 8.910 8.840
77 Ir 75.605 73.549 64.886 63.278 12.509 10.918 10.706 9.173 9.098
78 Pt 77.866 75.736 66.820 65.111 12.939 11.249 11.069 9.441 9.360
79 Au 80.165 77.968 68.794 66.980 13.379 11.582 11.439 9.711 9.625
80 Hg 82.526 80.258 70.821 68.894 13.828 11.923 11.823 9.987 9.896
81 Tl 84.904 82.558 72.860 70.320 14.288 12.268 12.210 10.266 10.170
82 Pb 87.343 94.922 74.957 72.794 14.762 12.620 12.611 10.549 10.448
83 Bi 89.833 87.335 77.097 74.805 15.244 12.977 13.021 10.836 10.729
84 Po 92.386 89.809 79.296 76.868 15.740 13.338 13.441 11.128 11.014
85 At 94.976 92.319 81.525 78.956 16.248 13.705 13.873 11.424 11.304
86 Rn 97.616 94.877 83.800 81.080 16.768 14.077 14.316 11.724 11.597
87 Fr 100.305 97.483 86.119 83.243 17.301 14.459 14.770 12.029 11.894
88 Ra 103.048 100.136 88.485 85.446 17.845 14.839 15.233 12.338 12.194
89 Ac 105.838 102.846 90.894 87.681 l8.405 l5.227 15.712 12.650 12.499
90 Th 108.671 105.592 93.334 89.942 18.977 15.620 16.200 12.966 12.808
91 Pa 111.575 108.408 95.851 92.271 19.559 16.022 16.700 13.291 13.120
92 U 114.549 111.289 98.428 94.648 20.163 16.425 17.218 13.613 13.438
93 Np 117.533 114.181 101.005 97.023 20.774 16.837 17.740 13.945 12.758
94 Pu 120.592 117.146 103.653 99.457 21.401 17.254 18.278 14.279 14.082
95 Am 123.706 120.163 106.351 101.932 22.042 17.667 18.829 14.618 14.411
96 Cm 126.875 123.235 109.098 104.448 22.699 18.106 19.393 14.961 14.743
97 Bk 130.101 126.362 111.896 107.023 23.370 18.540 19.971 15.309 15.079
98 Cf 133.383 129.544 114.745 109.603 24.056 18.980 20.562 15.661 15.420
99 Es 136.724 132.781 118.646 112.244 24.758 19.426 21.l66 16.018 15.764
100 Fm 140.122 136.075 120.598 114.926 25.475 19.879 21.785 16.379 16.113
APPENDIXIII: RADIATIVE TRANSITIONPROBABILITIES
Table1 Radiative Transition Probabilities for K X-ray Lines
Atomic
number Element Ka
2
=Ka
1
Kb
3
=Kb
1
(Kb
1
Kb
3
)=Ka
1
Kb
e
a
1
=Ka
1
Kb
e
b
2
=Ka
1
Kb
c
=Ka
d
20 Ca 0.505 0.116 0.116 0.069
22 Ti 0.505 0.137 0.137 0.095
24 Cr 0.506 0.155 0.156 0.114
26 Fe 0.506 0.172 0.171 0.128
28 Ni 0.507 0.189 0.187 0.133
30 Zn 0.509 0.202 0.202 0.137
32 Ge 0.511 0.215 0.215 0.142
34 Sc 0.513 0.225 0.225 0.006 0.153
36 Kr 0.515 0.235 0.235 0.013 0.164
38 Sr 0.518 0.244 0.244 0.022 0.175
40 Zr 0.520 0.251 0.252 0.034 0.185
42 Mo 0.523 0.258 0.259 0.043 0.193
44 Ru 0.526 0.264 0.265 0.048 0.201
46 Pd 0.528 0.270 0.271 0.051 0.209
48 Cd 0.531 0.275 0.277 0.054 0.216
50 Sn 0.533 0.516 0.280 0.282 0.056 0.222
52 Te 0.536 0.517 0.285 0.287 0.060 0.226
54 Xe 0.537 0.518 0.290 0.292 0.064 0.232
56 Ba 0.542 0.519 0.294 0.297 0.670 0.240
58 Ce 0.545 0.521 0.298 0.301 0.076 0.244
60 Nd 0.549 0.522 0.303 0.306 0.082 0.247
62 Sm 0.551 0.523 0.307 0.311 0.085 0.250
64 Gd 0.556 0.525 0.310 0.314 0.088 0.253
66 Dy 0.560 0.526 0.314 0.318 0.089 0.256
68 Er 0.565 0.527 0.317 0.322 0.090 0.259
70 Yb 0.568 0.529 0.320 0.325 0.090 0.261
72 Hf 0.572 0.531 0.324 0.329 0.091 0.263
74 W 0.576 0.532 0.326 0.332 0.092 0.267
76 Os 0.580 0.534 0.330 0.336 0.094 0.270
78 Pt 0.585 0.535 0.333 0.339 0.097 0.274
80 Hg 0.590 0.537 0.336 0.343 0.100 0.277
82 Pb 0.595 0.539 0.339 0.346 0.103 0.282
84 Po 0.600 0.541 0.342 0.350 0.106 0.285
86 Rn 0.605 0.542 0.345 0.353 0.110 0.288
88 Ra 0.612 0.544 0.348 0.356 0.113 0.291
90 Th 0.619 0.546 0.351 0.360 0.118 0.295
92 U 0.624 0.548 0.354 0.363 0.123 0.299
94 Pu 0.631 0.550 0.356 0.366 0.125 0.301
96 Cm 0.638 0.552 0.359 0.370 0.130 0.305
98 Cf 0.646 0.554 0.362 0.374 0.134 0.309
100 Em 0.652 0.556 0.364 0.377 0.138 0.312
a
Kb
e
1
= KM
2
KM
3
KM
4;5
:
b
Kb
e
2
= KN
2;3
KO
2;3
:
c
Kb = Kb
e
1
Kb
e
2
:
d
Ka = Ka
1
Ka
2
:
Source: From West, 198283.
Table 2 Radiative Transition Probabilities for L
1
X-ray Lines Normalized to Lb
3
=100
Atomic
number Element Lb
3
Lb
4
Lg
3
Lg
2
36 Kr 100 10.8
38 Sr 100 14.7
40 Zr 100 18.1
42 Mo 100 71.0 21.0
44 Ru 100 64.9 23.4
46 Pd 100 61.9 25.5
48 Cd 100 61.0 27.2
50 Sn 100 61.4 28.5
52 Te 100 62.6 29.5
54 Xe 100 64.1 30.3
56 Ba 100 65.5 30.8
58 Ce 100 66.7 31.2
60 Nd 100 67.5 31.4
62 Sm 100 69.7 31.5
64 Gd 100 68.0 31.5
66 Dy 100 67.8 31.4
68 Er 100 67.6 31.4
70 Yb 100 67.5 31.4 18.5
72 Hf 100 67.6 31.4 20.0
74 W 100 68.3 31.6 21.5
76 Os 100 69.6 31.9 23.2
78 Pt 100 71.7 32.3 25.0
80 Hg 100 74.8 33.0 26.9
82 Pb 100 78.8 34.0 28.8
84 Po 100 83.9 35.2 30.9
86 Rn 100 89.8 36.8 33.1
88 Ra 100 95.0 38.7 35.3
90 Th 100 102.0 41.0 37.7
92 U 100 110.0 43.8 40.2
94 Pu 100 120.0 47.5 44.0
Table 3 L
2
X-ray Lines Normalized to Lb
1
=100
Atomic
number Element Lb
1
LZ Lg
1
Lg
6
30 Zn 100 12.3
32 Ge 100 10.4
34 Se 100 8.75
36 Kr 100 7.40
38 Sr 100 6.25
40 Zr 100 5.25 0.91
42 Mo 100 4.35 6.71
44 Ru 100 3.63 10.6
46 Pd 100 3.0 13.1
48 Cd 100 2.6 14.5
50 Sn 100 2.35 15.3
52 Te 100 2.25 15.4
54 Xe 100 2.2 15.6
56 Ba 100 2.16 15.6
58 Ce 100 2.12 15.7
60 Nd 100 2.10 15.8
62 Sn 100 2.10 15.9
64 Gd 100 2.10 16.1
66 Dy 100 2.10 16.5
68 Er 100 2.10 17.0
70 Yb 100 2.12 17.6
72 Hf 100 2.13 18.4
74 W 100 2.16 19.2 0.375
76 Os 100 2.20 20.1 1.73
78 Pt 100 2.23 20.9 2.42
80 Hg 100 2.28 21.7 2.98
82 Pb 100 2.33 22.3 3.45
84 Po 100 2.40 22.8 3.88
86 Rn 100 2.45 23.2 4.29
88 Ra 100 2.50 23.4 4.74
90 Th 100 2.60 23.7 5.25
92 U 100 2.80 24.0 5.88
94 Pu 100 2.30 24.2 6.65
Table 4 L
3
X-ray Lines Normalized to La
1
=100
Atomic number Element La
1
Lb
2,15
La
2
Lb
5
Lb
6
Ll
22 Ti 100 40.37
24 Cr 100 26.13
26 Fe 100 15.35
28 Ni 100 10.29
30 Zn 100 7.56
32 Ge 100 5.96
34 Se 100 4.98
36 Kr 100 4.36
38 Sr 100 3.98
40 Zr 100 2.43 3.75
42 Mo 100 6.40 12.5 3.65
44 Ru 100 9.55 12.2 3.58
46 Pd 100 12.1 12.1 3.55
48 Cd 100 13.9 11.9 3.56
50 Sn 100 15.4 11.7 5.59
52 Te 100 16.4 11.5 3.62
54 Xe 100 17.2 11.3 3.67
56 Ba 100 17.8 11.2 3.73
58 Ce 100 18.2 11.1 3.79
60 Nd 100 18.5 11.1 3.86
62 Sm 100 18.8 11.0 3.92
64 Gd 100 19.2 11.1 3.99
66 Dy 100 19.6 11.1 4.07
68 Er 100 20.0 11.2 4.15
70 Yb 100 20.5 11.2 4.23
72 Hf 100 21.2 11.3 1.15 4.32
74 W 100 21.9 11.3 0.242 1.28 4.42
76 Os 100 22.7 11.4 0.873 1.38 4.53
78 Pt 100 23.5 11.4 1.74 1.46 4.65
80 Hg 100 24.4 11.5 2.62 1.55 4.78
82 Pb 100 25.3 11.5 3.24 1.59 4.93
84 Po 100 26.2 11.4 3.85 1.65 5.09
86 Rn 100 26.8 11.4 4.28 1.70 5.27
88 Ra 100 27.3 11.3 4.69 1.75 5.46
90 Th 100 27.5 11.1 4.94 1.80 5.69
92 U 100 27.5 11.0 5.20 1.85 5.93
94 Pu 100 27.0 10.5 5.40 1.89 6.18
Source: From West, 198283.
APPENDIXIV: NATURALWIDTHS OF K ANDL LEVELS ANDK
a
X-RAYLINES
(FWHM), INeV
Level X-ray line
Element K L
1
L
2
L
3
Ka
1
Ka
2
10 Ne 0.24 ( <0.1) (0.000) (0.000) 0.24 0.24
11 Na 0.30 (0.2) (0.000) (0.000) 0.30 0.30
12 Mg 0.36 0.41 0.00l 0.001 0.36 0.36
13 Al 0.42 0.73 0.004 0.004 0.43 0.43
14 Si 0.48 1.03 0.015 0.014 0.49 0.49
15 P 0.53 1.26 0.032 0.033 0.57 0.56
16 S 0.59 1.49 0.054 0.054 0.65 0.64
17 Cl 0.64 1.58 0.083 0.087 0.72 0.72
18 Ar 0.68 1.63 0.126 0.128 0.81 0.80
19 K 0.74 1.92 0.152 0.156 0.89 0.89
20 Ca 0.81 2.07 0.17 0.17 0.98 0.98
21 Sc 0.86 2.21 0.19 0.19 1.05 1.06
22 Ti 0.94 2.34 0.24 0.22 1.16 1.18
23 V 1.01 2.41 0.26 0.24 1.26 1.28
24 Cr 1.08 2.54 0.29 0.27 1.35 1.37
25 Mn 1.16 2.62 0.34 0.32 1.48 1.50
26 Fe 1.25 2.76 0.37 0.36 1.61 1.62
27 Co 1.33 2.79 0.43 0.43 1.76 1.76
28 Ni 1.44 2.89 0.52 0.48 1.94 1.96
29 Cu 1.55 3.06 0.62 0.56 2.11 2.17
30 Zn 1.67 3.28 0.72 0.65 2.32 2.39
31 Ga 1.82 3.38 0.83 0.76 2.59 2.66
32 Ge 1.96 3.53 0.95 0.82 2.78 2.92
33 As 2.14 3.79 1.03 0.94 3.08 3.17
34 Se 2.33 3.94 1.13 1.00 3.33 3.46
35 Br 2.52 4.11 1.21 1.08 3.60 3.73
36 Kr 2.75 4.28 1.31 1.17 3.92 4.06
37 Rb 2.99 4.44 1.43 1.27 4.26 4.92
38 Sr 3.25 4.67 1.54 1.39 4.63 4.79
39 Y 3.52 4.71 1.65 1.50 5.02 5.18
40 Zr 3.84 4.78 1.78 1.57 5.40 5.62
41 Nb 4.14 3.94 1.87 1.66 5.80 6.01
42 Mo 4.52 4.25 1.97 1.78 6.31 6.49
43 Tc 4.91 4.36 2.08 1.91 6.82 6.99
44 Ru 5.33 4.58 2.23 2.00 7.33 7.56
45 Rh 5.77 4.73 2.35 2.13 7.90 8.12
46 Pd 6.24 4.93 2.43 2.25 8.49 8.67
47 Ag 6.75 4.88 2.57 2.40 9.16 9.32
48 Cd 7.28 4.87 2.62 2.50 9.79 9.91
49 In 7.91 5.00 2.72 2.65 10.56 10.63
50 Sn 8.49 2.97 2.84 2.75 11.2 11.3
51 Sb 9.16 3.13 3.00 2.87 12.0 12.2
52 Te 9.89 3.32 3.12 2.95 12.8 13.0
53 I 10.6 3.46 3.25 3.08 13.7 13.8
Appendix IV Continued
Level X-ray line
Element K L
1
L
2
L
3
Ka
1
Ka
2
54 Xe 11.4 3.64 3.40 3.13 14.6 14.8
55 Cs 12.3 3.78 3.51 3.25 15.6 15.8
56 Ba 13.2 3.92 3.57 3.32 16.5 16.8
57 La 14.1 4.06 3.68 3.41 17.6 17.8
58 Ce 15.1 4.21 3.80 3.48 I8.6 18.9
59 Pr 16.2 4.34 3.89 3.60 19.8 20.1
60 Nd 17.3 4.52 3.97 3.65 20.9 21.3
61 Pm 18.5 4.67 4.06 3.75 22.2 22.5
62 Sm 19.7 4.80 4.15 3.86 23.6 23.8
63 Eu 21.0 4.91 4.23 3.91 24.9 25.2
64 Gd 22.3 5.05 4.32 4.01 26.4 26.7
65 Tb 23.8 5.19 4.43 4.12 27.9 28.2
66 Dy 25.2 5.25 4.55 4.17 29.4 29.8
67 Ho 26.8 5.33 4.66 4.26 31.1 31.5
68 Er 28.4 5.43 4.73 4.35 32.7 33.1
69 Tm 30.1 5.47 4.79 4.48 34.6 34.9
70 Yb 31.9 5.53 4.82 4.60 36.5 36.7
71 Lu 33.7 5.54 4.92 4.68 38.4 38.7
72 Hf 35.7 5.63 5.02 4.80 40.5 40.7
73 Ta 37.7 5.58 5.15 4.88 42.6 42.9
74 W 39.9 5.61 5.33 4.98 44.9 45.2
75 Re 42.1 6.18 5.48 5.04 47.2 47.6
76 Os 44.4 7.25 5.59 5.16 49.6 50.0
77 Ir 46.8 8.30 5.69 5.25 52.1 52.5
78 Pt 49.3 9.39 5.86 5.31 54.6 55.2
79 Au 52.0 10.5 6.00 5.41 57.4 58.0
80 Hg 54.6 11.3 6.17 5.50 60.1 60.8
81 Tl 57.4 12.0 6.32 5.65 63.1 63.8
82 Pb 60.4 12.2 6.48 5.81 66.2 66.8
83 Bi 63.4 12.4 6.67 5.98 69.4 70.1
84 Po 66.6 12.6 6.83 6.13 72.7 73.4
85 At 69.8 12.8 7.01 6.29 76.1 76.8
86 Rn 73.3 13.1 7.20 6.41 79.7 80.5
87 Fr 76.8 13.3 7.47 6.65 83.4 84.2
88 Ra 80.4 13.4 7.68 6.82 87.2 88.1
89 Ac 84.1 13.6 7.95 6.98 91.1 92.0
90 Th 88.0 13.7 8.18 7.13 95.2 96.2
91 Pa 91.9 14.3 8.75 7.33 99.3 100.7
92 U 96.1 14.0 9.32 7.43 103.5 105.4
93 Np 100 14.0 9.91 7.59 108 110
94 Pu 105 13.5 10.5 7.82 113 115
95 Am 109 13.3 10.9 8.04 117 120
96 Cm 114 13.6 11.4 8.26 122 125
97 Bk 119 13.8 11.8 8.55 127 130
98 Cf 124 14.0 12.2 8.75 132 136
99 Es 129 14.3 12.7 9.04 138 141
APPENDIXIV Continued
Level X-ray line
Element K L
1
L
2
L
3
Ka
1
Ka
2
100 Fm 135 14.4 13.1 9.33 144 148
101 Md 140 14.8 13.6 9.61 150 153
102 No 145 15.1 14.0 9.90 155 159
103 Lr 150 15.9 14.4 10.1 161 165
104 156 16.2 14.9 10.5 167 171
105 162 16.5 15.5 10.8 173 177
106 168 16.8 15.9 11.2 179 184
107 174 17.0 16.4 11.6 185 190
108 181 17.2 17.0 12.0 193 198
109 187 17.6 17.5 12.3 200 205
110 193 18.1 18.1 12.7 206 211
Source: From Krause and Oliver, 1979.
APPENDIXV: WAVELENGTHS OF KSATELLITE LINES (A )
Atomic
number Element a
II
a
I
a
3
a
3
I
a
3
II
a
4
a
4
I
a
5
a
6
a
7
b
0
b
I
11 Na 11.860 11.830 11.810 11.742 11.711
12 Mg 9.845 9.820 9.804 9.749 9.724
13 Al 8.302 8.283 8.267 8.226 8.206
14 Si 7.100 7.095 7.082 7.073 7.069 7.035 7.017 7.026 6.816
15 P 6.140 6.131 6.117 6.109 6.075 6.063 6.838
16 S 5.370 5.354 5.341 5.339 5.344 5.334
17 Cl 4.725 4.415
18 Ar
19 K 3.739 3.728 3.721 3.718 3.724 3.717 3.496
20 Ca 3.356 3.347 3.340 3.338 3.343 3.337 3.133 3.101
21 Sc 3.029 3.021 3.015 3.013 3.018 3.013 2.819 2.789
22 Ti 2.747 2.740 2.733 2.731 2.737 2.731 2.551 2.522
23 V 2.502 2.496 2.491 2.489 2.493 2.490 2.320 2.291
24 Cr 2.282 2.279 2.277 2.280 2.278 2.118 2.090
25 Mn 2.095 2.093 2.091 2.094 2.091 1.914
26 Fe 1.930 1.928 1.926 1.929 1.927 1.783 1.760
27 Co 1.784 1.782 1.780 1.783 1.781 1.645 1.623
28 Ni 1.653 1.651 1.650 1.652 1.650 1.522 1.502
29 Cu 1.536 1.535 1.533 1.534 1.394
30 Zn 1.431 1.430 1.428 1.429 1.296
31 Ga 1.138 1.335 1.334 1.335 1.209
32 Ge 1.250 1.250 1.248 1.249
33 As 1.173 1.172 1.170 1.171 1.061
34 Se 1.101 1.100 1.101 0.9958
35 Br 1.036 1.035 1.036 0.9367
36 Kr 0.8832
37 Rb 0.8835
38 Sr 0.8727 0.8646 0.8721 0.7881
39 Y 0.7457
40 Zr 0.7836 0.7828 0.7832 0.7056
41 Nb 0.7432 0.7436 0.6706
42 Mo 0.7065 0.7070 0.6369
43 Tc
44 Ru 0.5766
45 Rh 0.5493
46 Pd 0.5833 0.5837
47 Ag 0.5007
b
1x
b
x
b
V
b
II
b
II
III
b
III
b
IV
b
5
b
6
b
7
b
8
b
9
b
10
6.753
5.800 5.792 5.712 5.691
5.028 5.023
4.400 4.395
3.882
3.449 3.441 3.412 3.404
3.087 3.082 3.054 3.048
2.772 2.749 2.744
2.506 2.489
2.277 2.262
2.078 2.066
1.895
1.749 1.742
1.614 1.607
1.494 1.487
1.391 1.380
1.295 1.282
1.207
1.128 1.116
1.042 1.044 1.064 1.050 1.054 1.047
0.9770 0.9786 0.9996 0.9854 0.9889
0.9177 0.9194 0.9403 0.9629 0.9297 0.9228
1.8745
0.8135 0.8155 0.8365 0.8234 0.8259 0.8193
0.7681 0.7699 0.7911 0.7778 0.7802 0.7736
0.7261 0.7218 0.7492 0.7362 0.7382 0.7315
0.6870 0.6890 0.7105 0.6973 0.6993 0.6924
0.6510 0.6531 0.6741 0.6619 0.6636 0.6568
0.6288 0.6303 0.6235 0.6256 0.6519
0.5589 0.5808 0.5693 0.5708 0.5639 0.5607
0.5427 0.5439 0.5374 0.5399 0.5452
0.5189
0.4943 0.4954 0.4902 0.4920
APPENDIXVI: FLUORESCENCE YIELDS AND COSTER^KRONIGTRANSITION
PROBABILITIES
Table1 K Shell Fluorescence Yield o
K
Atomic number Element o
K
K
6 C 0.0009 45 Rh 0.81
7 N 0.0015 46 Pd 0.82
8 O 0.0022 47 Ag 0.83
10 Ne 0.0100 48 Cd 0.84
11 Na 0.020 49 In 0.85
12 Mg 0.030 50 Sn 0.86
13 Al 0.040 51 Sb 0.87
14 Si 0.055 52 Te 0.875
15 P 0.070 53 I 0.88
16 S 0.090 54 Xe 0.89
17 Cl 0.105 55 Cs 0.895
18 Ar 0.125 56 Ba 0.90
19 K 0.140 57 La 0.905
20 Sc 0.165 58 Ce 0.91
21 Ca 0.190 59 Pr 0.915
22 Ti 0.220 60 Nd 0.92
23 V 0.240 61 Pm 0.925
24 Cr 0.26 62 Sm 0.93
25 Mn 0.285 63 Eu 0.93
26 Fe 0.32 64 Gd 0.935
27 Co 0.345 65 Tb 0.94
28 Ni 0.375 66 Dy 0.94
29 Cu 0.41 67 Ho 0.945
30 Zn 0.435 68 Er 0.945
31 Ga 0.47 69 Tm 0.95
32 Ge 0.50 70 Yb 0.95
33 As 0.53 71 In 0.95
34 Se 0.565 72 Hf 0.955
35 Br 0.60 73 Ta 0.955
36 Kr 0.635 74 W 0.96
37 Rb 0.665 75 Re 0.96
38 Sr 0.685 76 Os 0.96
39 Y 0.71 77 Ir 0.96
40 Zr 0.72 78 Pd 0.965
41 Nb 0.755 79 Au 0.965
42 Mo 0.77 80 Hg 0.965
43 Tc 0.785 82 Pb 0.97
44 Ru 0.80 92 U 0.97
Source: From Birks, 1971b and Fink, 1974.
Table 2 Experimental L Subshell Fluorescence Yields o
i
1
o
2
o
3
54 Xe 0.10 0.01
56 Ba 0.06 0.05 0.01
65 Tb 0.18 0.165 0.018 0.188 0.016
67 Ho 0.22 0.03
0.170 0.055 0.169 0.030
68 Er 0.21 0.03
0.185 0.060 0.172 0.032
70 Yb 0.20 0.02
0.188 0.011 0.183 0.011
71 Lu 0.22 0.03
0.251 0.035
72 Hf 0.22 0.03
0.228 0.025
73 Ta 0.25 0.02 0.27 0.01
0.257 0.013 0.25 0.03
0.191
0.228 0.013
0.254 0.025
74 W 0.207
0.272 0.037
75 Re 0.284 0.043
76 Os 0.290 0.030
77 Ir 0.244
0.262 0.036
78 Pt 0.331 0.021 0.262
0.31 0.04
0.317 0.029
0.291 0.018
79 Au 0.276
0.31 0.04
0.317 0.025
80 Hg 0.39 0.03 0.40 0.02
0.319 0.010 0.32 0.05
0.367 0.050
0.300 0.010
81 Tl 0.07 0.02 0.319 0.010 0.37 0.07
0.373 0.025 0.386 0.053
0.306 0.010
0.330 0.021
82 Pb 0.07 0.02 0.363 0.015 0.337
0.09 0.02 0.315 0.013
0.32
0.35 0.05
0.354 0.028
83 Bi 0.12 0.01 0.32 0.04 0.367
0.095 0.005 0.38 0.02 0.36
0.37 0.05
0.362 0.029
0.40 0.05
Table 2 Continued
1
o
2
o
3
0.340 0.018
90 Th 0.42
0.517 0.042
91 Pa 0.46 0.05
92 U 0.44
0.500 0.040
96 Cm 0.28 0.06 0.552 0.032 0.515 0.034
0.55 0.02 0.63 0.02
Source: From Bambynek et al., 1972.
Table 3 Measured L Shell CosterKronig Yields
Atomic number Element f
12
f
13
f
23
56 Ba 0.66 0.07
65 Tb 0.41 0.36 0.43 0.28 0.066 0.014
67 Ho 0.205 0.034
68 Er 0.255 0.025
70 Yb 0.142 0.009
73 Ta <0.14 0.19 0.148 0.010
<0.36 0.20 0.04
74 W 0.27 0.03
75 Re 0.30 0.04
77 Ir 0.46 0.06
78 Pt 0.50 0.05
79 Au 0.25 0.13 0.51 0.13 0.22
0.61 0.07
80 Hg 0.74 0.04 0.22 0.04
0.08 0.02
0.188 0.010
81 Tl 0.17 0.05 0.76 0.10 0.25 0.13
0.14 0.03 0.57 0.10 0.169 0.010
0.56 0.07 0.159 0.013
0.56 0.05
82 Pb 0.15 0.04 0.57 0.03 0.164 0.016
0.17 0.05 0.61 0.08 0.156 0.010
83 Bi 0.19 0.05 0.58 0.05 0.14
0.06
70.06
0.18 0.02 0.58 0.02 0.164
92 U 0.23 0.12
93 Np 0.10 0.04 0.55 0.09 0.05
0.02
70.02
94 Pu 0.22 0.08
0.24 0.08
96 Cm 0.038 0.022 0.68 0.04 0.188 0.019
Table 4 Theoretical L Subshell Fluorescence Yields o
i
and CosterKronig Yields f
ij
a
1
o
2
o
3
f
12
f
13
f
12
f
13
f
23
13 Al 3.05-6 2.40-3 0.982
14 Si 9.77-6 1.08-3 0.975
15 P 2.12-5 4.1-4 0.971
16 S 3.63-5 2.9-4 0.968
17 Cl 5.60-5 2.3-4 0.964
18 Ar 8.58-5 1.9-4 0.965
19 K 1.15-4 2.1-4 0.962
20 Ca 1.56-4 2.1-4 0.955
22 Ti 2.80-4 1.18-3 0.313 0.629
24 Cr 2.97-4 3.29-3 0.317 0.636
26 Fe 3.84-4 1.43-3 5.59-3 0.302 0.652 7.24-2
1.49-3
28 Ni 4.63-4 2.69-3 8.02-3 0.325 0.622 9.97-2
29 Cu 3.57-3 3.83-3 0.109
30 Zn 5.23-4 1.08-2 0.322 0.624
32 Ge 7.70-4 7.72-3 1.44-2 0.266 0.671 2.49-2
33 As 1.40-3 8.85-3 9.74-3 0.282 0.547 4.13-2
34 Se 1.30-3 9.94-3 1.78-2 0.302 0.616 5.95-2
35 Br 1.09-2 7.64-2
36 Kr 1.85-3 2.20-2 2.36-2 0.230 0.686 8.97-2
2.19-3 1.19-2 1.23-2 0.225 0.585 9.22-2
37 Rb 1.32-2 0.107
38 Sr 3.00-3 2.24-2 2.43-2 0.249 0.646 0.115
40 Zr 3.97-3 2.94-2 2.95-2 0.236 0.648 0.118
3.96-3 1.89-2 2.01-2 0.271 0.522 0.123
42 Mo 5.75-3 3.50-2 3.73-2 0.166 0.689 0.124
6.34-3 2.45-2 2.59-2 0.048 0.692 0.126
44 Ru 7.74-3 4.18-2 4.50-2 0.057 0.779 0.136
47 Ag 1.02-2 5.47-2 6.02-2 0.052 0.786 0.152
1.01-2 4.30-2 4.49-2 0.064 0.695 0.130
50 Sn 1.30-2 6.56-2 7.37-2 0.052 0.784 0.162
1.30-2 5.67-2 0.072 0.693 0.136
51 Sb 3.11-2 6.16-2 6.33-2 0.164 0.316 0.138
54 Xe 5.84-2 9.12-2 9.70-2 0.179 0.274 0.173
56 Ba 4.46-2 9.07-2 8.99-2 0.168 0.336 0.151
60 Nd 7.46-2 0.133 0.135 0.207 0.303 0.141
6.00-2 0.120 0.120 0.165 0.332 0.142
65 Tb 0.166 0.160 0.131
67 Ho 0.112 0.203 0.201 0.202 0.309 0.138
0.094 0.178 0.317
70 Yb 0.112 0.180 0.316
74 W 0.115 0.287 0.268 0.195 0.332 0.123
0.138 0.271 0.253 0.160 0.324 0.117
79 Au 0.105 0.357 0.327 0.083 0.644 0.132
80 Hg 0.098 0.352 0.321 0.101 0.618 0.108
83 Bi 0.120 0.417 0.389 0.069 0.656 0.101
85 At 0.129 0.422 0.380 0.082 0.612 0.100
90 Th 0.197 0.529 0.461 0.069 0.575 0.102
93 Np 0.460 0.472 0.209
a
Figures following a sign indicate powers of 10. For example, 3.05-6 means 3.05610
76
.
Source: From Bambynek et al., 1972. Copyright 2002 Marcel Dekker, Inc.
Table 5 Measured M Shell Fluorescence Yields and CosterKronig Probabilities
Atomic
number Element " o
M
o
LM
a
o
LM
b
o
1
f
12
o
2
n
i
o
i
76 Os 0.013 0.0024 0.016 0.003
79 Au 0.023 0.001
79 Au 0.024 0.005 0.030 0.006
82 Pb 0.029 0.002
82 Pb 0.026 0.005 0.032 0.006
83 Bi 0.037 0.007
83 Bi 0.035 0.002
83 Bi 0.030 0.006 0.037 0.005
92 U 0.06
93 Np 0.003 n
1
=0.065 0.014
0.002
70.002 n
2
=0.0080 0.029
n
3
=0.062 0.005
n
4
=0.065 0.012 o
5
=0.06 0.012
n
4
=0.065 0.012
96 Cm 0.0089 n
4,5
=0.081 0.016
0.0075 0.0051
70.0075 n
1
=0.068 0.023 o
2
=0.0046
n
2
=0.062 0.019 70.0046
n
3
=0.080 0.006
n
4,5
=0.075 0.012
o
5
=0.075 0.012
a
Corrected for a 20% contribution from double M shell vacancies.
b
Uncorrected values.
Table 6 Adopted Values of Fluorescence and Coster-Kronig Yields
a
Z o
k
o
1
o
2
o
3
f
1
f
12
f
13
f
23
5 B 1.7E-03
6 C 2.8E-03
7 N 5.2E-03
8 O 8.3E-03
9 F 0.013
10 Ne 0.018
11 Na 0.023
12 Mg 0.030 2.9E-05 1.2E-03 1.2E-03 0.962 0.32 0.64
13 Al 0.039 2.6E-05 7.5E-04 7.5E-04 0.965 0.32 0.64
14 Si 0.050 3.0E-05 3.7E-04 3.8E-04 0.959 0.32 0.64
15 P 0.063 3.9E-05 3.1E-04 3.1E-04 0.951 0.32 0.63
16 S 0.078 7.4E-05 2.6E-04 2.6E-04 0.944 0.32 0.62
17 Cl 0.097 1.2E-04 2.4E-04 2.4E-04 0.939 0.32 0.62
18 Ar 0.118 1.8E-04 2.2E-04 2.2E-04 0.934 0.31 0.62
19 K 0.140 2.4E-04 2.7E-04 2.7E-04 0.929 0.31 0.62
20 Ca 0.163 3.1E-04 3.3E-04 3.3E-04 0.920 0.31 0.61
21 Sc 0.188 3.9E-04 8.4E-04 8.4E-04 0.912 0.31 0.60
22 Ti 0.214 4.7E-04 1.5E-03 1.5E-03 0.902 0.31 0.59
23 V 0.243 5.8E-04 2.6E-03 2.6E-03 0.894 0.31 0.58
24 Cr 0.275 7.1E-04 3.7E-03 3.7E-03 0.885 0.31 0.57
25 Mn 0.308 8.4E-04 5.0E-03 5.0E-03 0.877 0.30 0.58
26 Fe 0.340 1.0E-03 6.3E-03 6.3E-03 0.868 0.30 0.57
27 Co 0.373 1.2E-03 7.7E-03 7.7E-03 0.856 0.30 0.56
28 Ni 0.406 1.4E-03 8.6E-03 9.3E-03 0.847 0.30 0.55 0.028
29 Cu 0.440 1.6E-03 0.010 0.011 0.839 0.30 0.54 0.028
30 Zn 0.474 1.8E-03 0.011 0.012 0.831 0.29 0.54 0.026
31 Ga 0.507 2.1E-03 0.012 0.013 0.822 0.29 0.53 0.032
32 Ge 0.535 2.4E-03 0.013 0.015 0.815 0.28 0.53 0.050
33 As 0.562 2.8E-03 0.014 0.016 0.809 0.28 0.53 0.063
34 Se 0.589 3.2E-03 0.016 0.018 0.804 0.28 0.52 0.076
35 Br 0.618 3.6E-03 0.018 0.020 0.800 0.28 0.52 0.088
36 Kr 0.643 4.1E-03 0.020 0.022 0.797 0.27 0.52 0.100
37 Rb 0.667 4.6E-03 0.022 0.024 0.794 0.27 0.52 0.109
38 Sb 0.690 5.1E-03 0.024 0.026 0.790 0.27 0.52 0.117
39 Y 0.710 5.9E-03 0.026 0.028 0.785 0.26 0.52 0.126
40 Zr 0.730 6.8E-03 0.028 0.031 0.779 0.26 0.52 0.132
41 Nb 0.747 9.4E-03 0.031 0.034 0.713 0.10 0.61 0.137
42 Mo 0.765 0.010 0.034 0.037 0.712 0.10 0.61 0.141
43 Tc 0.780 0.011 0.037 0.040 0.711 0.10 0.61 0.144
44 Ru 0.794 0.012 0.040 0.043 0.709 0.10 0.61 0.148
45 Rh 0.808 0.013 0.043 0.046 0.705 0.10 0.60 0.150
46 Pd 0.820 0.014 0.047 0.049 0.700 0.10 0.60 0.151
47 Ag 0.831 0.016 0.051 0.052 0.694 0.10 0.59 0.153
48 Cd 0.843 0.018 0.056 0.056 0.688 0.10 0.59 0.155
49 In 0.853 0.020 0.061 0.060 0.681 0.10 0.59 0.157
Table 6 Continued
Z o
k
o
1
o
2
o
3
f
1
f
12
f
13
f
23
50 Sn 0.862 0.037 0.065 0.064 0.439 0.17 0.27 0.157
51 Sb 0.870 0.039 0.069 0.069 0.448 0.17 0.28 0.156
52 Te 0.877 0.041 0.074 0.074 0.495 0.18 0.28 0.155
53 I 0.884 0.044 0.079 0.079 0.461 0.18 0.28 0.154
54 Xe 0.891 0.046 0.083 0.085 0.466 0.19 0.28 0.154
55 Cs 0.897 0.049 0.090 0.091 0.470 0.19 0.28 0.154
56 Ba 0.902 0.052 0.096 0.097 0.474 0.19 0.28 0.153
57 La 0.907 0.055 0.103 0.104 0.478 0.19 0.29 0.153
58 Ce 0.912 0.058 0.110 0.111 0.482 0.19 0.29 0.153
59 Pr 0.917 0.061 0.117 0.118 0.485 0.19 0.29 0.153
60 Nd 0.921 0.064 0.124 0.125 0.488 0.19 0.30 0.152
61 Pm 0.925 0.066 0.132 0.132 0.490 0.19 0.30 0.151
62 Sm 0.929 0.071 0.140 0.139 0.492 0.19 0.30 0.150
63 Eu 0.932 0.075 0.149 0.147 0.493 0.19 0.30 0.149
64 Gd 0.935 0.079 0.158 0.155 0.493 0.19 0.30 0.147
65 Tb 0.938 0.083 0.167 0.164 0.493 0.19 0.30 0.145
66 Dy 0.941 0.089 0.178 0.174 0.492 0.19 0.30 0.143
67 Ho 0.944 0.044 0.189 0.182 0.490 0.19 0.30 0.142
68 Er 0.947 0.100 0.200 0.192 0.487 0.19 0.30 0.140
69 Tm 0.949 0.106 0.211 0.201 0.483 0.19 0.29 0.139
70 Yb 0.951 0.112 0.222 0.210 0.478 0.19 0.29 0.138
71 Lu 0.953 0.120 0.234 0.220 0.472 0.19 0.28 0.136
72 Hf 0.955 0.128 0.246 0.231 0.465 0.18 0.28 0.135
73 Ta 0.957 0.137 0.258 0.243 0.457 0.18 0.28 0.134
74 W 0.958 0.147 0.270 0.255 0.447 0.17 0.28 0.133
75 Re 0.959 0.144 0.283 0.268 0.485 0.16 0.33 0.130
76 Os 0.961 0.130 0.295 0.281 0.552 0.16 0.39 0.128
77 Ir 0.962 0.120 0.308 0.294 0.603 0.15 0.45 0.126
78 Pt 0.963 0.114 0.321 0.306 0.640 0.14 0.50 0.124
79 Au 0.964 0.107 0.334 0.320 0.672 0.14 0.53 0.122
80 Hg 0.965 0.107 0.347 0.333 0.690 0.13 0.56 0.120
81 Tl 0.966 0.107 0.360 0.347 0.696 0.13 0.57 0.118
82 Pb 0.967 0.112 0.373 0.360 0.696 0.12 0.58 0.116
83 Bi 0.968 0.117 0.387 0.373 0.694 0.11 0.58 0.113
84 Po 0.968 0.122 0.401 0.386 0.689 0.11 0.58 0.111
85 At 0.969 0.128 0.415 0.399 0.685 0.10 0.59 0.111
86 Rn 0.969 0.134 0.429 0.411 0.682 0.10 0.58 0.110
87 Fr 0.970 0.139 0.443 0.424 0.677 0.10 0.58 0.109
88 Ra 0.970 0.146 0.456 0.437 0.672 0.09 0.58 0.108
89 Ac 0.971 0.153 0.468 0.450 0.664 0.09 0.58 0.108
90 Th 0.971 0.161 0.479 0.463 0.660 0.09 0.57 0.108
91 Pa 0.972 0.162 0.472 0.476 0.664 0.08 0.58 0.139
92 U 0.972 0.176 0.467 0.489 0.652 0.08 0.57 0.167
93 Np 0.973 0.187 0.466 0.502 0.642 0.07 0.57 0.192
94 Pu 0.973 0.205 0.464 0.514 0.605 0.05 0.56 0.198
Table 6 Continued
Z o
k
o
1
o
2
o
3
f
1
f
12
f
13
f
23
95 Am 0.974 0.218 0.471 0.526 0.595 0.05 0.55 0.203
96 Cm 0.974 0.228 0.479 0.539 0.587 0.04 0.55 0.200
97 Bk 0.975 0.236 0.485 0.550 0.580 0.04 0.54 0.198
98 Cf 0.975 0.244 0.490 0.560 0.573 0.03 0.54 0.197
99 Es 0.975 0.253 0.497 0.570 0.565 0.03 0.54 0.196
100 Fm 0.976 0.263 0.506 0.579 0.556 0.03 0.53 0.194
101 Md 0.976 0.272 0.515 0.588 0.548 0.02 0.53 0.191
102 No 0.976 0.280 0.524 0.596 0.540 0.02 0.52 0.189
103 Lr 0.977 0.282 0.533 0.604 0.538 0.01 0.53 0.185
104 0.977 0.291 0.544 0.611 0.531 0.01 0.52 0.181
105 0.977 0.300 0.553 0.618 0.522 0.01 0.51 0.178
106 0.978 0.310 0.562 0.624 0.513 0.51 0.174
107 0.978 0.320 0.573 0.630 0.505 0.50 0.171
108 0.978 0.331 0.584 0.635 0.497 0.50 0.165
109 0.978 0.343 0.590 0.640 0.488 0.49 0.163
110 0.979 0.354 0.598 0.644 0.477 0.48 0.158
a
Note: 1.7E-03 =1.7610
73
; designation for L shell is omitted, read, for example, o
1
= o
L1
; f
1
= f
12
f
13
.
Source: From Krause, 1979.
5 B 0.998
6 C 0.997
7 N 0.995
8 O 0.992
9 F 0.987
10 Ne 0.982
11 Na 0.977
12 Mg 0.970 0.038 0.999 0.999
13 Al 0.961 0.035 0.999 0.999
14 Si 0.950 0.041 1.000 1.000
15 P 0.937 0.049 1.000 1.000
16 S 0.922 0.056 1.000 1.000
17 Cl 0.903 0.061 1.000 1.000
18 Ag 0.882 0.066 1.000 1.000
19 K 0.860 0.071 1.000 1.000
20 Ca 0.837 0.080 1.000 1.000
21 Sc 0.812 0.088 0.999 0.999
22 Ti 0.786 0.098 0.999 0.999
23 V 0.757 0.105 0.997 0.997
24 Cr 0.725 0.114 0.996 0.996
25 Mn 0.692 0.122 0.995 0.995
26 Fe 0.660 0.131 0.994 0.994
27 Co 0.627 0.143 0.992 0.992
28 Ni 0.394 0.152 0.963 0.991
29 Cu 0.560 0.159 0.962 0.989
30 Zn 0.526 0.167 0.963 0.988
31 Ga 0.493 0.176 0.956 0.987
32 Ge 0.465 0.183 0.937 0.985
33 As 0.438 0.188 0.923 0.984
34 Se 0.411 0.193 0.908 0.982
35 Br 0.382 0.196 0.894 0.980
36 Kr 0.357 0.199 0.880 0.978
37 Rb 0.333 0.201 0.869 0.976
38 Sr 0.310 0.205 0.859 0.974
39 Y 0.290 0.209 0.848 0.972
40 Zr 0.270 0.214 0.840 0.969
41 Nb 0.253 0.278 0.832 0.966
42 Mo 0.235 0.278 0.825 0.963
43 Tc 0.220 0.278 0.819 0.960
44 Ru 0.206 0.279 0.812 0.957
45 Rh 0.192 0.282 0.807 0.954
46 Pd 0.180 0.286 0.802 0.951
47 Ag 0.169 0.290 0.796 0.948
48 Cd 0.157 0.294 0.789 0.944
49 In 0.147 0.299 0.782 0.940
50 Sn 0.138 0.524 0.778 0.936
51 Sb 0.130 0.513 0.775 0.931
52 Te 0.123 0.504 0.771 0.926
53 I 0.116 0.495 0.767 0.921
54 Xe 0.109 0.488 0.763 0.915
55 Cs 0.103 0.481 0.756 0.909
56 Ba 0.098 0.474 0.751 0.903
57 La 0.093 0.467 0.744 0.896
58 Ce 0.088 0.460 0.737 0.889
59 Pr 0.083 0.454 0.730 0.882
60 Nd 0.079 0.448 0.724 0.875
61 Pm 0.075 0.444 0.717 0.868
62 Sm 0.071 0.437 0.710 0.861
63 Eu 0.068 0.432 0.702 0.853
64 Gd 0.065 0.428 0.695 0.845
65 Tb 0.062 0.424 0.688 0.836
66 Dy 0.059 0.419 0.679 0.826
67 Ho 0.056 0.416 0.669 0.818
68 Er 0.053 0.413 0.660 0.808
69 Tm 0.051 0.411 0.650 0.799
70 Yb 0.049 0.410 0.640 0.790
71 Lu 0.047 0.408 0.630 0.780
72 Hf 0.045 0.407 0.619 0.769
73 Ta 0.043 0.406 0.608 0.757
74 W 0.042 0.406 0.597 0.745
75 Re 0.041 0.371 0.587 0.732
76 Os 0.039 0.318 0.577 0.719
77 Ir 0.038 0.277 0.566 0.706
78 Pt 0.037 0.246 0.555 0.694
79 Au 0.036 0.221 0.344 0.680
80 Hg 0.035 0.203 0.533 0.667
81 Tl 0.034 0.197 0.522 0.653
82 Pb 0.033 0.192 0.511 0.640
83 Bi 0.032 0.189 0.500 0.627
84 Po 0.032 0.189 0.488 0.614
85 At 0.031 0.187 0.474 0.601
86 Rn 0.031 0.184 0.461 0.589
87 Fr 0.030 0.184 0.448 0.576
88 Ra 0.030 0.182 0.436 0.563
89 Ac 0.029 0.183 0.424 0.590
90 Th 0.029 0.179 0.413 0.537
91 Pa 0.028 0.174 0.389 0.524
92 U 0.028 0.172 0.366 0.511
93 Np 0.027 0.171 0.342 0.498
94 Pu 0.027 0.190 0.338 0.486
Table 7 Auger Yields for K, L
1
, L
2
and L
3
Levels
a
Z a
K
a
1
a
2
a
3
Z a
K
a
1
a
2
a
3
Table 7 Continued
Z a
K
a
1
a
2
a
3
Z a
K
a
1
a
2
a
3
95 Am 0.026 0.167 0.326 0.474
96 Cm 0.026 0.185 0.321 0.461
97 Bk 0.025 0.184 0.317 0.450
98 Cf 0.025 0.183 0.313 0.440
99 Es 0.025 0.182 0.307 0.430
100 Fm 0.024 0.181 0.300 0.421
101 Md 0.024 0.180 0.294 0.412
102 No 0.024 0.180 0.287 0.404
103 Lr 0.023 0.180 0.282 0.396
104 0.023 0.178 0.275 0.389
105 0.023 0.178 0.269 0.382
106 0.022 0.177 0.264 0.376
107 0.022 0.175 0.256 0.370
108 0.022 0.172 0.251 0.365
109 0.022 0.169 0.247 0.360
110 0.021 0.169 0.244 0.356
a
Designation for L shell is omitted; read, for example, a
1
=a
L1
.
Source: From Krause, 1979.
APPENDIXVII: COEFFICIENTS FOR CALCULATINGTHE PHOTOELECTRIC
ABSORPTIONCROSS SECTIONS (BARNS=ATOM) VIA ln^ln REPRESENTATION
Table1 E>E
K
a
Atomic
number Element
Atomic
weight A
0
A
1
A
2
A
3
1 H 1.008 2.44964 73.34953 74.71370-2 7.09962-3
2 He 4.003 6.06488 73.29055 71.07256-1 1.44465-2
3 Li 6.940 7.75370 72.81801 72.41738-1 2.62542-2
4 Be 9.012 9.04511 72.83487 72.10021-1 2.29526-2
5 B 10.811 9.95057 72.74173 72.15138-1 2.27845-2
6 C 12.010 1.06879 1 72.71400 72.00530-1 2.07248-2
7 N 14.008 1.12765 1 72.65400 72.00445-1 2.00765-2
8 O 16.000 1.17130 1 72.57229 72.05893-1 1.99244-2
9 F 19.000 1.20963 1 72.44148 72.34461-1 2.19537-2
10 Ne 20.183 1.24485 1 72.45819 72.12591-1 1.96489-2
11 Na 22.997 1.26777 1 72.24521 72.74873-1 2.50270-2
12 Mg 24.320 1.28793 1 72.12574 72.99392-1 2.67643-2
13 Al 26.970 1.31738 1 72.18203 72.58960-1 2.22840-2
14 Si 28.086 1.32682 1 71.98174 73.16950-1 2.73928-2
15 P 30.975 1.33735 1 71.86342 73.39440-1 2.88858-2
16 S 32.066 1.37394 1 72.04786 72.73259-1 2.29976-2
17 Cl 35.457 1.36188 1 71.71937 73.54154-1 2.90841-2
18 Ar 39.944 1.39491 1 71.82276 73.28827-1 2.74382-2
19 K 39.102 1.37976 1 71.54015 73.94528-1 3.23561-2
20 Ca 40.080 1.42950 1 71.88644 72.83647-1 2.26263-2
21 Sc 44.960 1.39664 1 71.40872 74.14365-1 3.34355-2
22 Ti 47.900 1.43506 1 71.66322 73.31539-1 2.62065-2
23 V 50.942 1.47601 1 71.88867 72.71861-1 2.15792-2
24 Cr 51.996 1.48019 1 71.82430 72.79116-1 2.17324-2
25 Mn 54.940 1.48965 1 71.79872 72.83664-1 2.22095-2
26 Fe 55.850 1.43456 1 71.23491 74.18785-1 3.21662-2
27 Co 58.933 1.47047 1 71.38933 73.86631-1 3.03286-2
28 Ni 58.690 1.42388 1 79.67736-1 74.78070-1 3.66138-2
29 Cu 63.540 1.45808 1 71.18375 74.13850-1 3.12088-2
30 Zn 65.380 1.44118 1 79.33083-1 74.77357-1 3.62829-2
31 Ga 69.720 1.36182 1 73.18459-1 76.11348-1 4.58138-2
32 Ge 72.590 1.39288 1 74.79613-1 75.72897-1 4.31277-2
33 As 74.920 1.34722 1 77.73513-2 76.60456-1 4.92177-2
34 Se 78.960 1.30756 1 1.83235-1 76.94264-1 5.02280-2
35 Br 79.920 1.32273 1 1.37130-1 76.83203-1 4.95424-2
36 Kr 83.800 1.35927 1 73.05214-2 76.51340-1 4.77616-2
37 Rb 85.480 1.30204 1 3.82736-1 77.32427-1 5.29874-2
38 Sr 87.620 1.35888 1 2.20194-3 76.38940-1 4.60070-2
39 Y 88.905 1.34674 1 1.91023-1 76.86616-1 4.97356-2
40 Zr 91.220 1.27538 1 6.97409-1 77.89307-1 5.64531-2
41 Nb 92.906 1.33843 1 2.81028-1 76.86607-1 4.86607-2
42 Mo 95.950 1.39853 1 71.17426-1 75.91094-1 4.17843-2
43 Tc 99.000 1.28214 1 7.51993-1 77.87006-1 5.58668-2
44 Ru 101.070 1.26658 1 8.85020-1 78.11144-1 5.73759-2
45 Rh 102.910 1.21760 1 1.19682 78.66697-1 6.06931-2
Table1 Continued
Atomic
number Element
Atomic
weight A
0
A
1
A
2
A
3
46 Pd 106.400 1.39389 1 1.64528-1 76.62170-1 4.76289-2
47 Ag 107.880 1.33926 1 4.41380-1 76.93711-1 4.82085-2
48 Cd 112.410 1.15254 1 1.07714 78.31424-1 5.79120-2
49 In 114.820 1.18198 1 1.45768 78.88529-1 6.05982-2
50 Sn 118.690 1.30323 1 7.90788-1 77.62349-1 5.27872-2
51 Sb 121.760 9.06999 3.28791 71.26203 8.53470-2
52 Te 127.600 1.16656 1 1.71052 79.48281-1 6.53213-2
53 I 126.910 1.21075 1 1.43635 78.82038-1 6.03575-2
54 Xe 131.300 1.10857 1 2.08356 71.01209 6.90310-2
55 Cs 132.910 1.13757 1 1.94161 79.83232-1 6.7l986-2
56 Ba 137.360 1.02250 1 2.67835 71.12648 7.62669-2
57 La 138.920 1.09780 1 2.23814 71.03549 7.02339-2
58 Ce 140.130 1.02725 1 2.74562 71.14174 7.74162-2
59 Pr 140.920 1.10156 1 2.22056 71.02216 6.90465-2
60 Nd 144.270 1.17632 1 1.79481 79.36661-1 6.35332-2
61 Pm 147.000 1.13864 1 2.05593 79.88180-1 6.69106-2
62 Sm 150.350 1.19223 1 1.79546 79.42902-1 6.44202-2
63 Eu 152.000 1.16168 1 1.97533 79.70901-1 6.58459-2
64 Gd 157.260 9.91968 3.03111 71.17520 7.86751-2
65 Tb 158.930 1.13818 1 2.14447 79.99222-1 6.75569-2
66 Dy 162.510 1.14845 1 2.10451 79.89870-1 6.69382-2
67 Ho 164.940 8.75203 3.71822 71.29273 8.55026-2
68 Er 167.270 1.20195 1 1.84815 79.39582-1 6.38106-2
69 Tm 168.940 1.25613 1 1.57523 78.90467-1 6.09779-2
70 Yb 173.040 7.42791 4.28955 71.35167 8.66136-2
71 Lu 174.990 1.26387 1 1.55476 78.81094-1 6.02036-2
72 Hf 178.500 7.58160 4.47037 71.42808 9.39044-2
73 Ta 180.950 8.65271 3.73117 71.26359 8.23539-2
74 W 183.920 7.57541 4.28874 71.34998 8.65200-2
75 Re 186.200 1.36944 7.79444 71.99822 1.26225-1
76 Os 190.200 1.37534 1 1.02122 77.77126-1 5.38811-2
77 Ir 192.200 1.25506 1 1.63090 78.75676-1 5.92011-2
78 Pt 195.090 1.27882 1 1.63605 78.98523-1 6.18550-2
79 Au 197.200 4.96352 5.79212 71.61842 1.02911-1
80 Hg 200.610 1.97594 1 71.97990 72.76981-1 2.68856-2
81 Tl 204.390 1.52879 1 2.73664-1 76.38890-1 4.57495-2
82 Pb 207.210 8.63374 3.69400 71.21312 7.74601-2
83 Bi 209.000 9.44293 3.44965 71.19886 7.83484-2
86 Rn 222.000 1.51782 1 3.49021-1 76.37638-1 4.51377-2
90 Th 232.000 1.34336 1 1.34805 78.13282-1 5.55664-2
92 U 238.070 1.37951 1 1.23983 78.01545-1 5.53596-2
94 Pu 239.100 1.82787 1 71.17371 73.68344-1 2.98738-2
a
Notation abbreviated as in Appendix VI, Table 4.
Table 2 E
L1
<E<E
K
a
Atomic
number Element
Atomic
weight A
0
A
1
A
2
11 Na 22.997 1.02355 1 72.55905 71.19524-1
12 Mg 24.310 1.05973 1 72.89818 2.34506-1
13 Al 26.970 1.08711 1 72.77860 1.75853-1
14 Si 28.086 1.12237 1 72.73694 1.27557-1
15 P 30.975 1.15508 1 72.92200 2.54262-1
16 S 32.066 1.18181 1 72.64618 79.68049-2
17 Cl 35.457 1.20031 1 72.41694 72.40897-1
18 Ar 39.944 1.22960 1 72.63279 77.36600-2
19 K 39.102 1.24878 1 72.53656 71.04892-1
20 Ca 40.080 1.27044 1 72.55011 79.43195-2
21 Sc 44.960 1.28949 1 72.40609 71.77791-1
22 Ti 47.900 1.31075 1 72.53576 79.57177-2
23 V 50.942 1.32514 1 72.49765 7 1.06383-1
24 Cr 51.996 1.34236 1 72.51532 71.01999-1
25 Mn 54.040 1.35761 1 72.49761 71.05943-1
26 Fe 55.850 1.36696 1 72.39195 71.37648-1
27 Co 58.933 1.38699 1 72.50669 78.69945-2
28 Ni 58.690 1.39848 1 72.48080 78.88115-2
29 Cu 63.540 1.42439 1 72.58677 76.67398-2
30 Zn 65.380 1.43221 1 72.62384 72.64926-2
31 Ga 69.720 1.44795 1 72.54469 77.57204-2
32 Ge 72.590 1.46813 1 72.69285 72.08355-2
33 As 74.920 1.46431 1 72.48397 77.96180-2
34 Se 78.960 1.47048 1 72.38853 71.05877-1
35 Br 79.920 1.48136 1 72.42347 79.14590-2
36 Kr 83.800 1.49190 1 72.42418 78.76447-2
37 Rb 85.480 1.49985 1 72.39108 79.59473-2
38 Sr 87.620 1.50114 1 72.28169 71.26485-1
39 Y 88.905 1.51822 1 72.38946 78.81174-2
40 Zr 91.220 1.52906 1 72.38703 79.12292-2
41 Nb 92.906 1.52088 1 72.20278 71.36759-1
42 Mo 95.950 1.53494 1 72.26646 71.16881-1
43 Tc 99.000 1.55086 1 72.33733 79.87857-1
44 Ru 101.070 1.54734 1 72.23080 71.19454-1
45 Rh 102.910 1.55757 1 72.24976 71.13377-1
46 Pd 106.400 1.55649 1 72.17229 71.27652-1
47 Ag 107.880 1.56869 1 72.22636 71.12223-1
48 Cd 112.410 1.59668 1 72.38363 78.01104-2
49 In 114.820 1.62101 1 72.51838 75.49951-2
50 Sn 118.690 1.58638 1 72.19010 71.13539-1
51 Sb 121.760 1.57557 1 72.04460 71.40745-1
52 Te 127.600 1.61087 1 72.27876 79.29405-2
53 I 126.910 1.64086 1 72.48214 75.07179-2
54 Xe 131.300 1.63098 1 72.31679 78.54498-2
55 Cs 132.910 1.65418 1 72.46363 75.42849-2
56 Ba 137.360 1.66217 1 72.48972 74.49623-2
57 La 138.920 1.63134 1 72.20156 79.80569-2
58 Ce 140.130 1.65862 1 72.36288 76.54708-2
Table 2 Continued
Atomic
number Element
Atomic
weight A
0
A
1
A
2
59 Pr 140.920 1.67179 1 72.40326 76.12619-2
60 Nd 144.270 1.65964 1 72.26073 78.72426-2
61 Pm 147.000 1.68368 1 72.38881 76.45041-2
62 Sm 150.350 1.68725 1 72.39051 76.01080-2
63 Eu 152.000 1.70692 1 72.48046 74.47055-2
64 Cd 157.260 1.71159 1 72.47838 74.37107-2
65 Tb 158.930 1.71499 1 72.45507 74.71370-2
66 Dy 162.510 1.73446 1 72.54821 73.17606-2
67 Ho 164.940 1.76583 1 72.72523 78.19409-4
68 Er 167.270 1.77988 1 72.74671 72.87580-3
69 Tm 168.940 1.74250 1 72.51103 73.29454-2
70 Yb 173.040 1.69795 1 72.22577 77.32557-2
71 Lu 174.990 1.72638 1 72.37189 74.95994-2
72 Hf 178.500 1.64329 1 71.82851 71.32268-1
73 Ta 180.950 1.72410 1 72.30313 75.91006-2
74 W 183.920 1.72533 1 72.23874 77.27338-2
75 Re 186.200 1.78750 1 72.61051 71.36093-2
76 Os 190.200 1.73525 1 72.28550 75.88047-2
77 Ir 192.200 1.65270 1 71.76315 71.35232-1
78 Pt 195.090 1.73636 1 72.21112 77.30934-2
79 Au 197.200 1.74240 1 72.23911 76.63720-2
80 Hg 200.610 1.71857 1 72.08470 78.53294-2
81 Tl 204.390 1.77379 1 72.37745 74.33223-2
82 Pb 207.210 1.77963 1 72.37691 74.55883-2
83 Bi 209.000 1.75348 1 72.23353 75.96161-2
86 Rn 222.000 1.75028 1 72.13876 77.24638-2
90 Th 232.000 1.85481 1 72.61281 77.90574-3
92 U 238.070 1.75258 1 72.07237 77.23932-2
94 Pu 239.100 1.75519 1 72.02162 78.22940-2
a
Table 3 E
M1
< E < E
L3
a
Atomic number Element Atomic weight A
0
A
1
31 Ga 69.720 1.22646 1 72.68965
32 Ge 72.590 1.24133 1 72.53085
33 As 74.920 1.25392 1 72.41380
34 Se 78.960 1.26773 1 72.39750
35 Br 79.920 1.27612 1 72.37730
36 Kr 83.800 1.28898 1 72.26021
37 Rb 85.480 1.30286 1 72.38693
38 Sr 87.620 1.31565 1 72.36655
39 Y 88.905 1.32775 1 72.43174
40 Zr 91.220 1.34508 1 72.50201
41 Nb 92.906 1.35434 1 72.50135
42 Mo 95.950 1.36568 1 72.48982
43 Tc 99.000 1.37498 1 72.44737
44 Ru 101.070 1.38782 1 72.48066
45 Rh 102.910 1.40312 1 72.61303
46 Pd 106.400 1.41392 1 72.57206
47 Ag 107.880 1.41673 1 72.48078
48 Cd 112.410 1.43497 1 72.52756
49 In 114.820 1.44115 1 72.49401
50 Sn 118.690 1.45572 1 72.56792
51 Sb 121.760 1.46268 1 72.55562
52 Te 127.600 1.47125 1 72.54324
53 I 126.910 1.47496 1 72.48179
54 Xe 131.300 1.47603 1 72.45068
55 Cs 132.910 1.49713 1 72.53145
56 Ba 137.360 1.50844 1 72.56341
57 La 138.920 1.51863 1 72.58287
58 Ce 140.130 1.52693 1 72.58174
59 Pr 140.920 1.53379 1 72.57086
60 Nd 144.270 1.54353 1 72.59006
61 Pm 147.000 1.55131 1 72.59623
62 Sm 150.350 1.56006 1 72.61328
63 Eu 152.000 1.57063 1 72.63481
64 Gd 157.260 1.57159 1 72.60843
65 Tb 158.930 1.58415 1 72.64040
66 Dy 162.510 1.59225 1 72.65289
67 Ho 164.940 1.60140 1 72.67903
68 Er 167.270 1.60672 1 72.67587
69 Tm 168.940 1.61269 1 72.67886
70 Yb 173.040 1.61794 1 72.67715
71 Lu 174.990 1.62289 1 72.67128
72 Hf 178.500 1.62758 1 72.66622
73 Ta 180.950 1.63068 1 72.66148
74 W 183.920 1.62613 1 72.60672
75 Re 186.200 1.63564 1 72.62453
76 Os 190.200 1.64233 1 72.63163
77 Ir 192.200 1.65144 1 72.64832
78 Pt 195.090 1.67024 1 72.71631
79 Au 197.200 1.64734 1 72.57834
Table 3 Continued
0
A
1
80 Hg 200.610 1.65903 1 72.60670
81 Tl 204.390 1.66564 1 72.61593
82 Pb 207.210 1.67131 1 72.61538
83 Bi 209.000 1.67078 1 72.58648
86 Rn 222.000 1.69000 1 72.60945
90 Th 232.000 1.70483 1 72.58569
92 U 238.070 1.70353 1 72.56903
94 Pu 239.100 1.72953 1 72.62164
a
Notation abbreviated in Appendix VI, Table 4.
Table 4 E < E
M5
a
0
A
1
61 Pm 147.000 1.55131 1 72.59623
62 Sm 150.350 1.56006 1 72.61328
63 Eu 152.000 1.57063 1 72.63481
64 Gd 157.260 1.57159 1 72.60843
65 Tb 158.930 1.58415 1 72.64040
66 Dy 162.510 1.59225 1 72.65289
67 Ho 164.940 1.60140 1 72.67903
68 Er 167.270 1.60672 1 72.67587
69 Tm 168.940 1.61269 1 72.67886
70 Yb 173.040 1.39111 1 72.40380
71 Lu 174.990 1.39813 1 72.40841
72 Hf 178.500 1.40548 1 72.42829
73 Ta 180.950 1.41313 1 72.47214
74 W 183.920 1.42536 1 72.32582
75 Re 186.200 1.42392 1 72.35326
76 Os 190.200 1.42795 1 72.21971
77 Ir 192.200 1.43422 1 72.40183
78 Pt 195.090 1.43785 1 72.34834
79 Au 197.200 1.44398 1 72.32838
80 Hg 200.610 1.45195 1 72.33016
81 Tl 204.390 1.45473 1 72.26773
82 Pb 207.210 1.45771 1 72.25279
83 Bi 209.000 1.46832 1 72.30940
86 Rn 222.000 1.47243 1 72.12905
90 Th 232.000 1.47730 1 71.91192
92 U 238.070 1.49036 1 72.12148
94 Pu 239.100 1.48535 1 71.87733
a
Source: From McMaster et al., 1969.
APPENDIXVIII: COEFFICIENTS FOR CALCULATINGTHE INCOHERENT
COLLISIONCROSS SECTIONS
C
(BARNS=ATOM) VIATHE ln^ln
REPRESENTATION
Atomic Number Element A
0
A
1
A
2
A
3
1 H 72.l5772 1.32685 73.05620-1
a
1.85025-2
2 He 72.56357 2.02536 74.48710-1 2.79691-2
3 Li 71.08740 1.03368 71.90377-1 7.79955-3
4 Be 76.90079-1 9.46448-1 71.71142-1 6.51413-3
5 B 77.91177-1 1.21611 72.39087-1 1.17686-2
6 C 79.87878-1 1.46693 72.93743-1 1.56005-2
7 N 71.23693 1.74510 73.54660-1 1.98705-2
8 O 71.73679 2.17686 74.49050-1 2.64733-2
9 F 71.87570 2.32016 74.75412-1 2.80680-2
10 Ne 71.75510 2.24226 74.47640-1 2.55801-2
11 Na 79.67717-1 1.61794 72.87191-1 1.31526-2
12 Mg 75.71611-1 1.35498 72.22491-1 8.30141-3
13 Al 74.39322-1 1.30867 72.11648-1 7.54210-3
14 Si 74.14971-1 1.34868 72.22315-1 8.41959-3
15 P 74.76903-1 1.46032 72.51331-1 1.07202-2
16 S 76.56419-1 1.65408 72.98623-1 1.42979-2
17 Cl 77.18627-1 1.74294 73.19429-1 1.58429-2
18 Ar 76.82105-1 1.74279 73.17646-1 1.56467-2
19 K 73.44007-1 1.49236 72.54135-1 1.07684-2
20 Ca 79.82420-2 1.32829 72.13747-1 7.73065-3
21 Sc 71.59831-1 1.39055 72.25849-1 8.51954-3
22 Ti 72.30573-1 1.45848 72.39160-1 9.38528-3
23 V 73.08103-1 1.52879 72.52768-1 1.02571-2
24 Cr 73.87641-1 1.59727 72.66240-1 1.11523-2
25 Mn 72.47059-1 1.49722 72.38781-1 8.93208-3
26 Fe 73.42379-1 1.57245 72.53198-1 9.85822-3
27 Co 74.28804-1 1.64129 72.66013-1 1.06512-2
28 Ni 75.04360-1 1.70040 72.76443-1 1.12628-2
29 Cu 75.70210-1 1.75042 72.84555-1 1.16930-2
30 Zn 74.20535-1 1.63400 72.53646-1 9.27233-3
31 Ga 73.58218-1 1.60050 72.44908-1 8.61898-3
32 Ge 73.34383-1 1.60237 72.45555-1 8.71239-3
33 As 73.39189-1 1.62535 72.50783-1 9.09103-3
34 Se 74.32927-1 1.72833 72.77138-1 1.11735-2
35 Br 74.48001-1 1.76082 72.85099-1 1.17865-2
36 Kr 73.91810-1 1.73010 72.76824-1 1.11280-2
37 Rb 71.28039-1 1.53044 2.27403-1 7.39033-3
38 Sr 7.99161-2 1.38397 71.92225-1 4.78611-3
39 Y 6.29057-2 1.41577 71.99713-1 5.33312-3
40 Zr 3.66697-2 1.45207 72.08122-1 5.95139-3
41 Nb 2.02289-4 1.49347 72.17419-1 6.62245-3
42 Mo 75.62860-2 1.55778 72.33341-1 7.85506-3
43 Tc 7.57616-2 1.44950 72.04890-1 5.64745-3
44 Ru 74.24981-2 1.54639 72.26470-1 7.18375-3
45 Rh 71.60399-1 1.64861 72.50238-1 8.93818-3
46 Pd 72.67564-1 1.73740 72.69883-1 1.03248-2
Appendix VIII Continued
Atomic Number Element A
0
A
1
A
2
A
3
47 Ag 71.66475-1 1.65794 72.48740-1 8.66218-3
48 Ce 75.16701-2 1.57426 72.27646-1 7.05650-3
49 In 78.17283-2 1.55865 72.24492-1 6.85776-3
50 Sn 1.42151-2 1.55754 72.24736-1 6.91395-3
51 Sb 1.56362-2 1.57175 72.28753-1 7.26386-3
52 Te 74.07579-2 1.64267 72.47897-1 8.80567-3
53 I 74.04420-2 1.65596 72.51067-1 9.04874-3
54 Xe 72.82407-3 1.64039 72.47642-1 8.82144-3
55 Cs 1.84861-1 1.50030 72.13333-1 6.24264-3
56 Ba 3.44376-1 1.38742 71.86356-1 4.24917-3
57 La 4.09104-1 1.33075 71.70883-1 3.04111-3
58 Ce 4.39881-1 1.30925 71.64548-1 2.52641-3
59 Pr 4.49124-1 1.30351 71.61841-1 2.27394-3
60 Nd 4.37283-1 1.31370 71.62866-1 2.29377-3
61 Pm 4.05823-1 1.33837 71.67229-1 2.55570-3
62 Sm 3.55383-1 1.37733 71.74941-1 3.06213-3
63 Eu 2.80316-1 1.44016 71.88641-1 4.01226-3
64 Gd 2.73133-1 1.43842 71.86137-1 3.75240-3
65 Tb 2.57539-1 1.45064 71.87591-1 3.79932-3
66 Dy 2.42685-1 1.46266 71.89102-1 3.85628-3
67 Ho 2.28493-1 1.47438 71.90559-1 3.90903-3
68 Er 2.15233-1 1.48545 71.91908-1 3.95645-3
69 Tm 2.02656-1 1.49625 71.93234-1 4.00233-3
70 Yb 2.02248-1 1.48804 71.89143-1 3.62264-3
71 Lu 1.97176-1 1.50264 71.92474-1 3.85751-3
72 Hf 1.99469-1 1.50233 71.91385-1 3.74011-1
73 Ta 1.96871-1 1.50623 71.91396-1 3.70889-3
74 W 1.91015-1 1.51240 71.91922-1 3.71450-3
75 Re 1.89644-1 1.50867 71.89570-1 3.49584-3
76 Os 1.16448-1 1.57615 72.05532-1 4.66731-3
77 Ir 7.19908-2 1.61204 72.13186-1 5.20497-3
78 Pt 4.20186-2 1.63611 72.17964-1 5.52670-3
79 Au 1.56916-2 1.65406 72.20982-1 5.70751-3
80 Hg 1.14587-1 1.58076 72.02968-1 4.35692-3
81 Tl 1.47052-1 1.56695 72.00347-1 4.20901-3
82 Pb 1.82167-1 1.54661 71.95793-1 3.90772-3
83 Bi 1.89860-1 1.56125 72.00932-1 4.36768-3
86 Rn 1.96619-1 1.60080 72.13800-1 5.51717-3
90 Th 1.70890-1 1.65561 72.29702-1 6.92516-3
92 U 1.08277-1 1.74158 72.54104-1 8.95056-3
94 Pu 3.88791-2 1.82229 72.76009-1 1.07392-2
a
Notation as in Appendix VI, Table 4.
APPENDIXIX: COEFFICIENTS FOR CALCULATINGTHE COHERENT SCATTERING
CROSS SECTIONS
R
(BARNS/ATOM) VIATHE ln^ln REPRESENTATION
Atomic number Element A
0
A
1
A
2
A
3
1 H 71.19075-1
a
79.37086-1 72.00538-1 1.06587-2
2 He 1.04768 78.51805-2 74.03527-1 2.69398-2
3 Li 1.34366 1.81557-1 74.23981-1 2.66190-2
4 Be 2.00860 74.61920-2 73.37018-1 1.86939-2
5 B 2.61862 72.07916-1 72.86283-1 1.44966-2
6 C 3.10861 72.60580-1 72.71974-1 1.35181-2
7 N 3.47760 72.15762-1 72.88874-1 1.51312-2
8 O 3.77239 71.48539-1 73.07124-1 1.67303-2
9 F 4.00716 75.60908-2 73.32017-1 1.87934-2
10 Ne 4.20151 4.16247-2 73.56754-1 2.07585-2
11 Na 4.26374 1.34662-1 73.70080-1 2.14467-2
12 Mg 4.39404 1.37858-1 73.59540-1 2.02380-2
13 Al 4.51995 1.40549-1 73.52441-1 1.93692-2
14 Si 4.64678 1.62780-1 73.58563-1 1.96926-2
15 P 4.76525 1.68708-1 73.60383-1 1.97155-2
16 S 4.92707 1.65746-1 73.59424-1 1.95505-2
17 Cl 5.07222 1.49127-1 73.52858-1 1.89439-2
18 Ar 5.21079 1.35618-1 73.47214-1 1.84333-2
19 K 5.25587 1.88040-1 73.59623-1 1.93085-2
20 Ca 5.32375 2.06685-1 73.61664-1 1.93328-2
21 Sc 5.43942 2.00174-1 73.59064-1 1.91027-2
22 Ti 5.55039 1.97697-1 73.57694-1 1.89866-2
23 V 5.65514 1.99533-1 73.57487-1 1.89691-2
24 Cr 5.77399 2.03858-1 73.59699-1 1.92225-2
25 Mn 5.84604 2.13814-1 73.59718-1 1.91459-2
26 Fe 5.93292 2.25048-1 73.61748-1 1.93024-2
27 Co 6.01478 2.37959-1 73.64056-1 1.94754-2
28 Ni 6.09204 2.52277-1 73.66568-1 1.96586-2
29 Cu 6.17739 2.73123-1 73.72360-1 2.01638-2
30 Zn 6.23402 2.84312-1 73.72143-1 2.00525-2
31 Ga 6.28298 2.91334-1 73.69391-1 1.97029-2
32 Ge 6.33896 2.91512-1 73.65643-1 1.92895-2
33 As 6.39750 2.88866-1 73.61747-1 1.88788-2
34 Se 6.45637 2.86737-1 73.58794-1 1.85618-2
35 Br 6.51444 2.86324-1 73.57027-1 1.83557-2
36 Kr 6.57129 2.87711-1 73.56311-1 1.82470-2
37 Rb 6.59750 3.02389-1 73.56755-1 1.81706-2
38 Sr 6.62203 3.24559-1 73.61651-1 1.84800-2
39 Y 6.67096 3.25075-1 73.60613-1 1.83325-2
40 Zr 6.72275 3.23964-1 73.59463-1 1.81890-2
41 Nb 6.79013 3.11282-1 73.55233-1 1.78231-2
42 Mo 6.84600 3.02797-1 73.51131-1 1.74403-2
43 Tc 6.87599 3.26165-1 73.58969-1 1.80482-2
44 Ru 6.93136 3.34794-1 73.63497-1 1.84429-2
45 Rh 6.97547 3.46394-1 73.67794-1 1.87885-2
46 Pd 7.03216 3.49838-1 73.70099-1 1.89983-2
47 Ag 7.06446 3.63456-1 73.73597-1 1.92478-2
Appendix IX Continued
Atomic number Element A
0
A
1
A
2
A
3
48 Cd 7.09856 3.72199-1 73.75345-1 1.93481-2
49 In 7.12708 3.82082-1 73.76855-1 1.94151-2
50 Sn 7.16085 3.85512-1 73.76481-1 1.93305-2
51 Sb 7.19665 3.85543-1 73.75054-1 1.91608-2
52 Te 7.23464 3.82493-1 73.72715-1 1.89194-2
53 I 7.27415 3.77223-1 73.69728-1 1.86280-2
54 Xe 7.31469 3.70315-1 73.66280-1 1.83025-2
55 Cs 7.33490 3.76825-1 73.65713-1 1.81843-2
56 Ba 7.35812 3.79361-1 73.64099-1 1.79817-2
57 La 7.39532 3.69895-1 73.59376-1 1.75406-2
58 Ce 7.44255 3.71328-1 73.59642-1 1.75852-2
59 Pr 7.48347 3.68431-1 73.57689-1 1.74099-2
60 Nd 7.52334 3.66462-1 73.56048-1 1.72620-2
61 Pm 7.56222 3.65055-1 73.54511-1 1.71214-2
62 Sm 7.60020 3.64134-1 73.53086-1 1.69894-2
63 Eu 7.63711 3.63957-1 73.51909-1 1.68783-2
64 Gd 7.66938 3.59752-1 73.48899-1 1.65890-2
65 Tb 7.70798 3.65345-1 73.50031-1 1.66927-2
66 Dy 7.74188 3.67107-1 73.49433-1 1.66273-2
67 Ho 7.77470 3.69722-1 73.49132-1 1.65862-2
68 Er 7.80643 3.73226-1 73.49147-1 1.65710-2
69 Tm 7.83711 3.77547-1 73.49441-1 1.65780-2
70 Yb 7.86662 3.82933-1 73.50126-1 1.66173-2
71 Lu 7.89137 3.86034-1 73.49756-1 1.65480-2
72 Hf 7.91803 3.87021-1 73.48881-1 1.64406-2
73 Ta 7.94534 3.87299-1 73.47926-1 1.63299-2
74 W 7.97266 3.87704-1 73.47155-1 1.62372-2
75 Re 7.99940 3.88739-1 73.46726-1 1.61751-2
76 Os 8.02574 3.90458-1 73.46658-1 1.61455-2
77 Ir 8.05150 3.93143-1 73.47052-1 1.61573-2
78 Pt 8.08084 3.95790-1 73.48032-1 1.62345-2
79 Au 8.10524 4.00576-1 73.49340-1 1.63264-2
80 Hg 8.12542 4.05858-1 73.50329-1 1.63772-2
81 Tl 8.14399 4.08692-1 73.49802-1 1.62888-2
82 Pb 8.15996 4.18031-1 73.52330-1 1.64660-2
83 Bi 8.17489 4.27916-1 73.55068-1 1.66601-1
86 Rn 8.22553 4.51478-1 73.62056-1 1.71556-2
90 Th 8.27843 4.79056-1 73.67657-1 1.74621-2
92 U 8.33010 4.78314-1 73.67250-1 1.74129-2
94 Pu 8.38174 4.77085-1 73.66556-1 1.73422-2
a
APPENDIXX: PARAMETERSFORCALCULATINGTHE TOTALMASSATTENUATIONCOEFFICIENTSINTHEENERGYRANGE
0.1^1000 keV [VIAEQ. (78)]
Table1 Parameters for Calculating the Total Mass Attenuation Coefcients for Photon Energies Above the K Absorption Edge (k
1
, k
2
, k
3
, k
4
) and for
Energies Between L
1
and E
K
Absorption Edge (l
1
, l
2
, l
3
, l
4
); Z=Atomic Number, Sy =Symbol of Corresponding Element
E
L1
<E<E
K
E>E
K
Z Sy E
L1
l
1
l
2
l
3
l
4
E
K
k
1
k
2
k
3
k
4
1 H 76.48071 3.27538 0.04385 70.00866
2 He 73.51566 2.60589 0.26361 70.03787
3 Li 72.36523 2.88866 0.15389 70.02935
4 Be 71.38914 3.05349 0.07919 70.02484
5 B 70.58244 3.07947 0.05871 70.02647
6 C 77.00266 5.19086 70.34413 0.2838 0.11476 3.09245 0.03213 70.02494
7 N 72.38938 3.24818 70.11121 0.4016 0.63927 3.08731 0.01587 70.02538
8 O 72.50341 3.43696 70.12806 0.5320 1.08730 3.07389 0.00035 70.02438
9 F 72.03564 3.43789 70.13520 0.6854 1.42132 3.06182 70.00946 70.02708
10 Ne 72.91417 4.13834 70.22931 0.8669 1.81194 3.04034 70.02320 70.02568
11 Na 0.15632 2.00149 0.32080 70.04820 1.0721 2.07992 3.04059 70.02978 70.03575
12 Mg 2.10634 0.28244 0.92539 70.11707 1.3050 2.39196 3.00737 70.04492 70.02734
13 Al 3.34768 70.83777 1.34549 70.16880 1.5596 2.62043 2.99387 70.05681 70.03063
14 Si 3.81364 71.04042 1.42378 70.17980 1.8389 2.88077 2.96887 70.06174 70.02724
15 P 3.05305 70.24003 1.25060 70.17486 2.1455 3.06672 2.95078 70.07943 70.03227
16 S 0.2292 2.76125 0.29160 1.09998 70.16451 2.4720 3.28801 2.92821 70.08514 70.03094
17 Cl 0.2702 3.00797 0.19834 1.11670 70.16546 2.8224 3.42667 2.90289 70.09061 70.02881
18 Ar 0.3200 2.62786 0.68939 1.01331 70.16625 3.2029 3.53219 2.88277 70.10191 70.03142
19 K 0.3771 0.68453 3.86200 70.43637 0.04226 3.6074 3.75863 2.85955 70.09992 70.02689
20 Ca 0.4378 2.44853 1.46227 0.69759 70.12878 4.0381 3.93329 2.83775 70.11226 70.02972
21 Sc 0.5004 2.03061 2.27680 0.31534 70.07434 4.4928 4.00179 2.81618 70.11678 70.02898
22 Ti 0.5637 2.33976 1.88017 0.55084 70.11829 4.9664 4.11127 2.79692 70.11885 70.02784
23 V 0.6282 2.38673 1.99445 0.50415 70.11481 5.4651 4.21463 2.77190 70.13140 70.03049
24 Cr 0.6946 2.53782 1.85115 0.62868 70.14231 5.9892 4.35405 2.75878 70.13335 70.03142
25 Mn 0.7690 2.65431 1.83552 0.65972 70.15525 6.5390 4.44148 2.72589 70.14641 70.03205
26 Fe 0.8461 2.41689 2.80062 70.00696 70.01904 7.1120 4.56600 2.70395 70.15515 70.03352
27 Co 0.9256 2.60591 2.55718 0.18669 70.06696 7.7089 4.64390 2.67587 70.16255 70.03403
28 Ni 1.0081 2.69756 2.72893 0.04244 70.03220 8.3328 4.77308 2.65503 70.16936 70.03476
29 Cu 1.0961 2.75840 2.72647 0.04391 70.03423 8.9789 4.81074 2.62267 70.18383 70.03729
30 Zn 1.1936 2.87225 2.72029 0.04441 70.03527 9.6586 4.89850 2.60534 70.18393 70.03594
31 Ga 1.2977 2.93846 2.73406 0.03264 70.03438 10.3671 4.93990 2.57045 71.19961 70.03856
32 Ge 1.4143 3.02673 2.74409 0.01747 70.03117 11.1031 5.00743 2.55814 70.19972 70.03827
33 As 1.5265 3.12353 2.74414 0.01165 70.03096 11.8667 5.07635 2.53376 70.20666 70.03872
34 Se 1.6539 3.19106 2.76121 70.01683 70.02249 12.6578 5.11759 2.50569 70.21581 70.03969
35 Br 1.7820 3.30117 2.73599 0.01398 70.03428 13.4737 5.19474 2.48145 70.22156 70.04024
36 Kr 1.9210 3.36926 2.74007 0.00224 70.03125 14.3256 5.23284 2.44844 70.23505 70.04200
37 Rb 2.0651 3.46256 2.74320 70.10161 70.02723 15.1997 5.29354 2.41378 70.24899 70.04399
38 Sr 2.2163 3.54696 2.73914 70.00741 70.03104 16.1046 5.34695 2.38309 70.25992 70.04534
39 Y 2.3725 3.63965 2.73646 70.01290 70.03036 17.0384 5.41166 2.37364 70.25521 70.04393
40 Zr 2.5316 3.71677 2.73020 70.01273 70.03038 17.9976 5.45290 2.33638 70.26879 70.04558
41 Nb 2.6977 3.79880 2.72885 70.01869 70.02896 18.9856 5.50180 2.30251 70.28165 70.04737
42 Mo 2.8655 3.86387 2.72657 70.02278 70.02881 19.9995 6.47503 3.03067 70.04965 70.03050
43 Te 3.0425 3.93865 2.72262 70.02487 70.03004 21.0440 5.57355 2.24202 70.29909 70.04910
44 Ru 3.2240 3.99914 2.70967 70.02706 70.03l74 22.1172 5.60095 2.21314 70.30745 70.04983
45 Rh 3.4119 4.07189 2.71531 70.02854 70.03173 23.2199 5.63478 2.17349 70.32262 70.05195
46 Pd 3.6043 4.12607 2.71194 70.03442 70.02941 24.3503 5.65532 2.14514 70.32915 70.05230
47 Ag 3.8058 4.19974 2.70350 70.03661 70.02694 25.5140 5.68392 2.05134 70.34706 70.05473
48 Cd 3.0180 4.24309 2.70139 70.04152 70.02776 26.7112 5.68137 2.09840 70.36341 70.05665
49 In 4.2375 4.30447 2.69926 70.04319 70.03320 27.9399 5.72030 2.04363 70.36014 70.05573
50 Sn 4.4647 4.35252 2.69160 70.04781 70.02689 29.2001 5.76598 2.05890 70.34949 70.05406
51 Sb 4.6983 4.40598 2.68835 70.04963 70.03001 30.4912 5.74957 1.98639 70.37446 70.05693
52 Te 4.9392 4.43690 2.68323 70.05424 70.03161 31.8138 3.74700 1.96282 70.37979 70.05738
53 I 5.1881 4.51763 2.67963 70.05663 70.03296 33.1694 5.79401 1.93222 70.38924 70.05845
54 Xe 5.4528 4.53737 2.66911 70.05780 70.02658 34.5614 5.80690 1.91476 70.39242 70.05865
55 Cs 5.7143 4.61780 2.66299 70.06277 70.02884 35.9846 5.82191 1.87715 70.040213 70.05948
56 Ba 5.9888 4.65770 2.65946 70.07172 70.03577 37.4406 5.84551 1.87466 70.39966 70.05904
57 La 6.2663 4.71490 2.65505 70.07121 70.03442 38.9246 5.85321 1.82364 70.41682 70.06098
58 Ce 6.5488 4.77277 2.64710 70.07113 70.03077 40.4430 5.87476 1.79700 70.42193 70.06126
59 Pr 6.8348 4.83442 2.64088 70.07717 70.03325 41.9906 5.90293 1.77311 70.42727 70.06168
60 Nd 7.1260 4.87359 2.63355 70.07273 70.02815 43.5689 5.90905 1.74652 70.43341 70.06218
Table1 Continued
E
L1
<E<E
K
E>E
K
Z Sy E
L1
l
1
l
2
l
3
l
4
E
K
k
1
k
2
k
3
k
4
61 Pm 7.4279 4.93318 2.62474 70.08002 70.02998 45.1840 5.92214 1.70715 70.44407 70.06326
62 Sm 7.7368 4.95712 2.61647 70.07625 70.02487 46.8342 5.92934 1.69904 70.44407 70.06312
63 Eu 8.0520 5.00931 2.61226 70.08680 70.03205 48.5190 5.94975 1.67827 70.44795 70.06335
64 Gd 8.3756 5.03443 2.60481 70.08912 70.03162 50.2391 5.92827 1.64215 70.45629 70.06402
65 Tb 8.7080 5.08055 2.60115 70.07597 70.02286 51.9957 5.95498 1.63471 70.45467 70.06359
66 Dy 9.0458 5.11495 2.59238 70.08230 70.02541 53.7885 5.95991 1.61100 70.46029 70.06408
67 Ho 9.3942 5.15537 2.58071 70.08885 70.02644 55.6177 5.94804 1.55826 70.47717 70.06595
68 Er 9.7513 5.19648 2.57148 70.09459 70.02802 57.4855 5.96408 1.54243 70.47949 70.06606
69 Tm 10.1157 5.23938 2.56466 70.09047 70.02454 59.3896 5.88779 1.43854 70.50808 70.06870
70 Yb 10.4864 5.26855 2.55541 70.10174 70.03012 61.3323 6.04546 1.57974 70.45878 70.06334
71 Lu 10.8704 5.31163 2.55490 70.09208 70.02484 63.3138 6.07395 1.57891 70.45631 70.06301
72 Hf 11.2707 5.34305 2.54268 70.10077 70.02734 65.3508 6.00771 1.48367 70.48598 70.06608
73 Ta 11.6815 5.37806 2.53595 70.09548 70.02359 67.4164 6.05159 1.50856 70.47273 70.06439
74 W 12.0998 5.41320 2.53128 70.10036 70.02631 69.5250 6.00250 1.43225 70.49552 70.06672
75 Re 12.5267 5.44913 2.52042 70.10577 70.02724 71.6764 6.03030 1.43738 70.48952 70.06580
76 Os 12.9680 5.47715 2.52666 70.09007 70.02154 73.8708 6.11400 1.50446 70.46496 70.06309
77 Ir 13.4185 5.50865 2.50428 70.10492 70.02495 76.1110 6.09889 1.45990 70.47717 70.06429
78 Pt 13.8799 5.54158 2.50551 70.09847 70.02303 78.3948 6.15378 1.53187 70.44176 70.05974
79 Au 14.3528 5.57564 2.48980 70.10793 70.02561 80.7249 6.15303 1.47494 70.46441 70.06253
80 Hg 14.8393 5.60041 2.47759 70.11241 70.02570 83.1023 6.19862 1.50676 70.45079 70.06097
81 Tl 15.3467 5.62415 2.46173 70.12251 70.02850 85.5304 6.17641 1.46912 70.46009 70.06183
82 Pb 15.8608 5.65349 2.45575 70.12044 70.02698 88.0045 6.17648 1.45115 70.46277 70.06196
83 Bi 16.3875 5.69400 2.47086 70.10349 70.02277 90.5259 6.30427 1.55736 70.42520 70.05792
84 Po 16.9393 5.73466 2.46840 70.09608 70.01973 93.1050 6.21512 1.43087 70.46426 70.06195
85 At 17.4930 5.76863 2.45600 70.10153 70.02099 95.7299 6.18945 1.38290 70.47598 70.06300
86 Rn 18.0490 5.74682 2.43686 70.11031 70.02272 98.4040 6.24492 1.47699 70.43939 70.05879
87 Fr 18.6390 5.78319 2.43220 70.10993 70.02259 101.1370 6.31471 1.51865 70.42408 70.05721
88 Ra 19.2367 5.80588 2.41932 70.11330 70.02255 103.9219 6.26760 1.45136 70.44373 70.05917
89 Ac 19.8400 5.83228 2.39643 70.12322 70.02407 106.7553 6.32123 1.48583 70.42883 70.05744
90 Th 20.4721 5.85156 2.40038 70.11549 70.02204 109.6509 6.39823 1.55418 70.40447 70.05479
91 Pa 21.1046 5.87741 2.35466 70.14418 70.02817 112.6014 6.28773 1.41526 70.44597 70.05907
92 U 21.7574 5.88224 2.34307 70.15054 70.03027 115.6061 6.30701 1.44776 70.43028 70.05716
Source: From Orlic et al., 1993. Reprinted with kind permission from Elsevier Science NL, Sara Burgehartstraat 25, 1055 KV Amsterdam, The Netherlands.
Table 2 Parameters for Calculating the Total Mass Attentuation Coefcients for Photon Energy Between L
1
, L
2
, and L
3
Absorption Edges and for
Energies Between L
3
and Lower Energy Limit E
0
or M Absorption Edge
E
0
<E<E
L3
E
L3
< E < E
L2
E
L2
< E < E
L1
Z Sy E
0
=E
edge
m
1
m
2
m
3
m
4
E
L3
l
31
l
32
E
L2
l
21
l
22
E
L1
16 S 0.1 3.98381 71.96207 1.29140 70.13371 0.2292
17 Cl 0.1 72.71337 2.78307 0.23822 70.05767 0.2702
18 Ar 0.1 2.07772 70.84611 1.21097 70.14523 0.3200
19 K 0.1 8.53825 74.62277 1.97295 70.19719 0.3771
20 Ca 0.1 5.10006 71.85097 1.29907 70.14560 0.4378
21 Sc 0.1 7.28382 73.26298 1.60507 70.16673 0.5004
22 Ti 0.1 6.39592 72.45282 1.38399 70.14698 0.5637
23 V 0.1 2.83998 0.44991 0.61932 70.08033 0.6282
24 Cr 0.1 77.38556 8.17416 71.29292 0.07794 0.6946
25 Mn 0.1 2.13747 1.11467 0.46032 70.06687 0.7690
26 Fe 0.1 2.21508 1.10224 0.47160 70.06697 0.8461
27 Co 0.1 4.76476 71.05687 1.09423 70.12565 0.9256
28 Ni 0.1 4.28916 70.66344 1.02071 70.12207 1.0081
29 Cu 0.1 2.32551 1.22642 0.45413 70.06650 1.0961
30 Zn 0.1 4.23694 70.64439 1.08840 70.13570 1.0197 77.206 727.639 1.0428 9.4520 70.2320 1.1936
31 Ga 0.1 2.60598 0.84383 0.68376 70.10262 1.1154 47.827 716.433 1.1423 6.2330 1.1180 1.2977
32 Ge 0.1 4.27624 70.65284 1.15806 70.15244 1.2167 20.461 75.2040 1.2478 5.4560 1.4580 1.4143
33 As 0.1 5.14580 71.51272 1.47391 70.19017 1.3231 6.9330 0.6640 1.3586 5.1580 1.6080 1.5265
34 Se 0.1 6.74588 73.03410 1.98313 70.24674 1.4358 0.0065 3.8833 1.4762 3.9491 2.1968 1.6539
35 Br 0.1 7.26941 73.69837 2.28437 70.28824 1.5499 74.6062 6.2403 1.5960 3.8764 2.2734 1.7820
36 Kr 0.1 11.95287 78.69443 4.04104 70.48832 1.6749 75.6370 6.9490 1.7272 3.4100 2.5440 1.9210
37 Rb 0.1 15.89070 712.8788 5.51561 70.65735 1.8044 3.2959 2.4609 1.8639 4.0979 2.2097 2.0651
38 Sr 0.1085 11.09104 78.15432 4.08776 70.52451 1.9396 2.0366 3.1926 2.0068 3.9355 2.3328 2.2163
39 Y 0.1487 5.18978 71.99566 2.09278 70.32184 2.0800 1.9840 3.2996 2.1555 3.9621 2.3596 2.3725
40 Zr 0.2122 6.15438 72.90381 2.42622 70.36813 2.2223 2.2290 3.2290 2.3067 3.9270 2.4170 2.5316
41 Nb 0.2118 5.83085 72.56434 2.36756 70.37176 2.3705 2.724 2.999 2.4647 3.981 2.425 2.6977
42 Mo 0.2370 6.35098 73.21302 2.67445 70.41914 2.5202 2.813 2.999 2.6251 3.996 2.447 2.8655
43 Tc 0.2631 5.57003 72.03397 2.13536 70.33831 2.6769 3.044 2.907 2.7932 4.051 2.452 3.0425
44 Ru 0.2901 9.99349 78.27969 5.01647 70.76636 2.8379 3.320 2.770 2.9669 4.303 2.302 3.2240
45 Rh 0.3180 6.55219 73.56318 2.98931 70.48554 3.0038 3.653 2.586 3.1469 4.091 2.502 3.4119
46 Pd 0.3425 6.32821 73.29827 2.95809 70.49645 3.1733 4.146 2.250 3.3303 4.344 2.337 3.6043
47 Ag 0.3766 5.65378 72.26740 2.49736 70.43066 3.3511 4.111 2.321 3.5237 4.217 2.487 3.8058
48 Cd 0.4129 3.12801 1.54731 0.70511 70.16236 3.5375 3.971 2.454 3.7270 4.328 2.420 3.0180
49 In 0.4530 2.78289 2.29146 0.30064 70.09544 3.7301 4.293 2.217 3.9380 4.620 2.196 4.2375
50 Sn 0.4946 2.57173 2.70219 0.11208 70.07092 3.9288 4.834 1.753 4.1561 4.592 2.238 4.4647
51 Sb 0.5379 2.52338 2.80299 0.07373 70.06562 4.1322 4.637 1.940 4.3804 4.584 2.279 4.6983
52 Te 0.5827 4.98562 71.29951 2.27938 70.44589 4.3414 4.618 1.955 4.6120 4.554 2.323 4.9392
53 I 0.6293 3.00387 2.36374 0.26067 70.09483 4.5571 4.577 2.048 4.8521 4.625 2.318 5.1881
54 Xe 0.6775 3.00203 2.56894 0.10775 70.06179 4.7822 4.572 2.073 5.1037 4.599 2.375 5.4528
55 Cs 1.2171 3.16785 2.42799 0.12755 70.05218 5.0119 4.215 2.528 5.3594 4.563 2.482 5.7143
56 Ba 1.2928 3.19080 2.48392 0.08776 70.04429 5.2470 4.363 2.384 5.6236 4.601 2.470 5.9888
57 La 1.3613 3.23265 2.53710 0.05145 70.03744 5.4827 4.401 2.397 5.8906 4.698 2.404 6.2663
58 Ce 1.4346 3.29411 2.53524 0.05465 70.03926 5.7234 4.449 2.402 6.1642 4.702 2.470 6.5488
59 Pr 1.5110 3.35891 2.54117 0.04839 70.03842 5.9642 4.469 2.438 6.4404 4.757 2.467 6.8348
60 Nd 1.5753 3.41765 2.51947 0.05777 70.04029 6.2079 4.463 2.500 6.7215 4.778 2.490 7.1260
61 Pm 1.6540 3.45084 2.59000 0.00563 0.02894 6.4593 4.500 2.528 7.0128 4.854 2.449 7.4279
62 Sm 1.7228 3.49847 2.55440 0.02671 70.03367 6.7162 4.536 2.502 7.3118 4.861 2.469 7.7368
63 Eu 1.8000 3.54762 2.56798 0.01585 70.03181 6.9769 4.553 2.556 7.6171 4.924 2.428 8.0520
64 Gd 1.8808 3.58135 2.57591 0.00022 70.02718 7.2428 4.583 2.543 7.9303 4.927 2.467 8.3756
65 Tb 1.9675 3.61719 2.61430 70.03278 70.01918 7.5140 4.633 2.537 5.2516 4.985 2.423 8.7080
66 Dy 2.0468 3.67219 2.57359 70.00002 70.02988 7.7901 4.655 2.572 8.5806 5.014 2.420 9.0458
67 Ho 2.1283 3.72181 2.55757 0.010760 70.03537 8.0711 4.695 2.558 8.9178 5.047 2.426 9.3942
68 Er 2.2065 3.77845 2.52004 0.05588 70.04817 8.3579 4.727 2.581 9.2643 5.086 2.414 9.7513
69 Tm 2.3068 3.82800 2.53261 0.03019 70.03886 8.6480 4.767 2.592 9.6169 5.128 2.398 10.1157
70 Yb 2.3981 3.86458 2.50726 0.06374 70.05192 8.9436 4.802 2.569 9.9782 5.082 2.815 10.4864
71 Lu 2.4912 3.91793 2.48402 0.08777 70.06146 9.2441 4.847 2.560 10.3386 5.181 2.431 10.8704
72 Hf 2.6009 3.94527 2.52598 0.03404 70.04239 9.5607 4.866 2.629 10.7394 5.214 2.377 11.2707
73 Ta 2.7080 3.99165 2.50855 0.05734 70.05289 9.8811 4.911 2.584 11.1361 5.237 2.468 11.6815
74 W 2.8196 4.02988 2.51689 0.04574 70.05071 10.2068 4.940 2.624 11.5440 5.276 2.318 12.0998
75 Re 2.9317 4.07043 2.52499 0.03041 70.04512 10.5353 4.979 2.629 11.9687 5.302 2.373 12.5267
76 Os 3.0485 4.10244 2.53312 0.01448 70.03948 10.8709 5.006 2.661 12.3850 5.323 2.314 12.9680
77 Ir 3.1737 4.14636 2.52893 0.01458 70.04009 11.2152 5.050 2.673 12.8241 5.355 2.361 13.4185
78 Pt 3.2960 4.18356 2.53390 0.00520 70.03783 11.5637 5.084 2.666 13.2726 5.375 2.278 13.8799
Table 2 Continued
E
0
<E<E
L3
E
L3
< E < E
L2
E
L2
< E < E
L1
Z Sy E
0
=E
edge
m
1
m
2
m
3
m
4
E
L3
l
31
l
32
E
L2
l
21
l
22
E
L1
79 Au 3.4249 4.22770 2.52409 0.01426 70.04262 11.9187 5.125 2.690 13.7336 5.406 2.303 14.3528
80 Hg 3.5616 4.26093 2.51954 0.02092 70.04665 12.2839 5.156 2.643 14.2087 5.430 2.337 14.8393
81 Tl 3.7041 4.29302 2.51974 0.01369 70.04376 12.6575 5.184 2.630 14.6979 5.451 2.323 15.3467
82 Pb 3.8507 4.32934 2.51778 0.00460 70.03614 13.0352 5.220 2.644 15.2000 5.512 2.502 15.8608
83 Bi 3.9991 4.36991 2.52184 70.01213 70.02654 13.4186 5.257 2.642 15.7111 5.536 2.453 16.3875
84 Po 4.1494 4.41866 2.52158 70.00971 70.03298 13.8138 5.301 2.625 16.2443 5.555 2.387 16.9393
85 At 4.3170 4.46126 2.51394 0.00640 70.04593 14.2135 5.347 2.642 16.7847 5.574 2.335 17.4930
86 Rn 4.4820 4.45433 2.51411 70.00666 70.03871 14.6194 5.334 2.637 17.3371 5.535 2.281 18.0490
87 Fr 4.6520 4.49562 2.51108 70.01358 70.02823 15.0312 5.376 2.647 17.9065 5.650 2.494 18.6390
88 Ra 4.8220 4.52666 2.50733 0.00692 70.05016 15.4444 5.410 2.653 18.4843 5.644 2.411 19.2367
89 Ac 5.0020 4.56932 2.50607 70.01644 70.03124 15.8710 5.454 2.662 19.0832 5.761 2.594 19.8400
90 Th 5.1823 4.59153 2.50190 70.00815 70.03948 16.3003 5.490 2.696 19.6932 5.883 2.800 20.4721
91 Pa 5.3669 4.63772 2.49776 70.00936 70.03490 16.7331 5.525 2.666 20.3137 5.798 2.534 21.1046
92 U 5.5480 4.65216 2.49170 70.02703 70.01144 17.1663 5.541 2.672 20.9476 5.829 2.571 21.7574
Table 3 Parameters for Calculating the Total Mass Attenuation Coefcients for Photon Energies Between M
1
, M
2
, . . ., M
5
Absorption Edges and for Energies
Between M
5
and Lower Energy Limit E
0
E
0
<E<E
edge
E
M5
<E<E
M4
E
M4
<E<E
M3
E
M3
<E<E
M2
E
M2
<E<E
M1
Z E
0
n
1
n
2
n
3
n
4
E
M5
m
42
m
41
E
M4
m
32
m
31
E
M3
m
22
m
21
E
M2
m
12
m
11
E
M1
41 0.1085 115.013 769.4208 14.9364 71.0543
42 0.1085 106.662 767.3126 15.2602 71.1408
43 0.1085 3.5107 2.3889 70.4178 0.0324
44 0.1085 89.5750 757.9740 13.8424 71.1025
45 0.1085 80.5898 757.4238 15.0813 71.3052
46 0.1328 76.3873 1.0408 1.9749 70.3214
47 0.1328 29.0389 718.5282 5.5664 70.5470
48 0.1487 11.0289 76.3556 2.6658 70.3046
49 0.1717 174.946 7138.963 38.3880 73.5077
50 0.1717 42.9485 731.1679 9.1280 70.8669
51 0.1511 39.8331 730.6663 9.5340 70.9502
52 0.1511 37.0196 728.3109 8.8955 70.8939
53 0.1511 14.2756 79.7352 3.9179 70.4554
54 0.1833 23.1086 718.4405 6.7995 70.7732
55 0.2122 32.5527 727.5567 9.7373 71.0874 0.7330 2.364 2.621 1.0650 3.983 2.072 1.2171
56 0.2770 31.6390 728.1233 10.4351 71.2218 0.7905 0.7961 3.768 2.088 1.0622 3.897 2.098 1.1367 3.957 2.097 1.2928
57 0.1926 28.6047 724.1290 8.8027 71.0079 0.8473 0.8485 3.554 2.190 1.1234 3.870 2.132 1.2044 3.970 2.114 1.3613
58 0.2122 3.9181 70.9835 1.6398 70.2735 0.8861 0.9013 3.194 2.376 1.1854 3.852 2.162 1.2728 4.007 2.120 1.4346
59 0.3117 4.6993 0.0130 0.6969 70.0975 0.9349 0.9511 3.317 2.355 1.2422 5.314 1.551 1.3774 2.489 2.863 1.5110
60 0.3117 20.5246 716.5997 6.5042 70.7721 0.9843 0.9999 5.484 1.419 1.2974 3.879 2.193 1.4028 3.993 2.167 1.5753
61 0.2770 16.9684 713.1825 5.4255 70.6587 1.0269 96.373 735.542 1.0515 6.609 0.921 1.3569 3.845 2.234 1.4714 4.039 2.170 1.6540
62 0.2770 11.8798 77.7898 3.5371 70.4381 1.0802 89.021 733.267 1.1060 6.352 1.023 1.4198 3.825 2.255 1.5407 3.986 2.206 1.7228
63 0.2770 5.6437 71.4828 1.4474 70.2096 1.1309 83.564 731.660 1.1606 6.316 1.039 1.4806 3.825 2.278 1.6139 4.005 2.220 1.8000
64 0.2770 6.6183 72.4260 1.7586 70.2443 1.1852 76.154 729.235 1.2172 8.597 0.048 1.5440 3.792 2.308 1.6883 4.032 2.217 1.8808
65 0.1717 75.6112 10.4330 72.6765 0.2602 1.2412 73.753 728.683 1.2750 6.289 1.062 1.6113 3.863 2.296 1.7677 4.027 2.242 1.9675
66 0.2122 1.4535 3.1211 70.1907 70.0138 1.2949 69.682 727.456 1.3325 6.096 1.157 1.6756 3.809 2.342 1.8418 4.060 2.243 2.0468
67 0.2770 4.077 0.1743 0.9232 70.1528 1.3514 65.046 725.898 1.3915 5.446 1.471 1.7412 3.811 2.363 1.9228 4.092 2.245 2.1283
68 0.2122 1.6315 2.7196 0.0767 70.0607 1.4093 60.848 724.477 1.4533 5.353 1.523 1.8118 3.847 2.368 2.0058 4.087 2.269 2.2065
Table 3 Continued
E
0
<E<E
edge
E
M5
<E<E
M4
E
M4
<E<E
M3
E
M3
<E<E
M2
E
M2
<E<E
M1
Z E
0
n
1
n
2
n
3
n
4
E
M5
m
42
m
41
E
M4
m
32
m
31
E
M3
m
22
m
21
E
M2
m
12
m
11
E
M1
69 0.1926 75.0355 9.4382 72.1146 0.1726 1.4677 63.572 726.240 1.5146 5.841 1.257 1.8845 3.889 2.370 2.0998 4.114 2.278 2.3068
70 0.1085 71.8380 6.2849 71.0736 0.0593 1.5278 54.494 722.411 1.5763 5.900 1.222 1.9498 3.916 2.373 2.1730 4.125 2.287 2.3981
71 0.1085 70.3276 4.8522 70.6175 0.0113 1.5885 57.769 724.531 1.6394 6.893 0.681 2.0236 3.876 2.422 2.2635 4.129 2.309 2.4912
72 0.1085 70.1868 4.8402 70.6304 0.0127 1.6517 55.928 724.196 1.7164 7.170 0.527 2.1076 3.916 2.420 2.3654 4.158 2.311 2.6009
73 0.1085 71.9405 6.5977 71.1795 0.0672 1.7351 53.589 723.567 1.7932 6.974 0.627 2.1940 3.957 2.420 2.4687 4.146 2.343 2.7080
74 1.1085 71.1407 5.9151 70.9671 0.0439 1.8092 50.662 722.588 1.8716 6.894 0.671 2.2810 4.019 2.408 2.5749 4.178 2.344 2.8196
75 0.1085 70.3842 5.1929 70.7225 0.0155 1.8829 30.913 712.446 1.9489 6.854 0.666 2.3673 4.063 2.405 2.6816 4.214 2.346 2.9317
76 0.1085 71.8806 6.8129 71.2684 0.0733 1.9601 54.605 725.802 2.0308 6.900 0.581 2.4572 4.032 2.445 2.7922 4.228 2.356 3.0485
77 0.1085 72.9368 7.9106 71.6078 0.1054 2.0404 48.393 722.958 2.1161 7.249 0.343 2.5507 4.126 2.410 2.9087 4.307 2.327 3.1737
78 0.1328 1.5113 3.4177 70.1106 70.0581 2.1216 45.233 721.695 2.2019 7.209 0.344 2.6454 4.166 2.408 3.0265 4.323 2.338 3.2960
79 0.1511 3.5698 1.1260 0.7499 70.1652 2.2057 43.502 721.199 2.2911 7.102 0.393 2.7430 4.199 2.414 3.1478 4.317 2.370 3.4249
80 0.2122 3.6427 1.0962 0.7581 70.1655 2.2949 40.458 719.895 2.3849 6.847 0.540 2.8471 4.187 2.445 3.2785 4.382 2.344 3.5616
81 0.1926 3.6296 1.1014 0.7912 70.1770 2.3893 31.751 715.013 2.4851 6.055 1.064 2.9566 4.191 2.467 3.4157 4.314 2.419 3.7041
82 0.1717 4.6393 70.1055 1.2868 70.2451 2.4840 20.254 78.092 2.5856 5.339 1.574 3.0664 4.259 2.443 3.5542 4.453 2.332 3.8507
83 0.1926 5.7697 71.3933 1.7810 70.3078 2.5796 9.171 71.075 2.6876 4.475 2.212 3.1769 4.277 2.459 3.6963 4.383 2.420 3.9991
84 0.2122 5.6131 71.3279 1.8314 70.3245 2.6839 70.200 5.161 2.7980 3.586 2.895 3.3019 4.327 2.459 3.8541 4.460 2.395 4.1494
85 0.3117 5.1757 70.6452 1.5552 70.2925 2.7867 74.893 8.501 2.9087 3.141 3.276 3.4260 4.372 2.457 4.0080 4.494 2.402 4.3170
86 0.3924 4.2011 0.6074 1.0490 70.2281 2.8924 77.059 10.172 3.0215 3.222 3.251 3.5280 4.382 2.442 4.1590 4.500 2.386 4.4820
87 0.3924 4.5198 0.1763 1.2693 70.2654 2.9999 72.615 7.198 3.1362 3.649 2.961 3.6638 4.405 2.458 4.3270 4.523 2.398 4.6520
88 0.3924 5.5170 71.1906 1.9034 70.3623 3.1049 0.627 4.924 3.2484 3.982 2.716 3.7918 4.391 2.501 4.4895 4.511 2.442 4.8220
89 0.3924 6.3317 72.2638 2.3875 70.4354 3.2190 2.581 3.529 3.3702 4.255 2.525 3.9098 4.460 2.475 4.6560 4.599 2.387 5.0020
90 0.2770 4.1761 0.8164 1.0031 70.2383 3.3320 3.793 2.621 3.4908 4.355 2.455 4.0461 4.495 2.462 4.8304 4.576 2.437 5.1823
91 0.2770 4.3146 0.8409 0.9488 70.2273 3.4418 3.639 2.790 3.6112 4.369 2.484 4.1738 4.526 2.477 5.0009 4.603 2.457 5.3669
92 0.2770 3.9954 1.2801 0.7662 70.2038 3.5517 3.662 2.788 3.7276 4.409 2.460 4.3034 4.527 2.492 5.1822 4.614 2.458 5.5480
APPENDIX XI: TOTAL MASS ATTENUATIONCOEFFICIENTS FOR LOW-ENERGYKLINES
Absorber Emitter wavelength (A
) energy (keV)
B C N O F Ne Na Mg Al
Atomic 6.67 1
a
4.48 1 3.16 1 2.36 1 1.83 1 1.46 1 1.19 1 9.89 0 8.34 0
number Element 1.83 71 2.77 71 3.92 71 5.25 71 6.77 71 8.49 71 1.04 0 1.25 0 1.49 0
1 H 1.81 3 4.89 2 1.51 2 5.85 1 2.62 1 1.22 1 6.32 0 3.76 0 2.23 0
2 He 1.20 4 4.06 3 1.25 3 5.07 2 2.23 2 1.06 2 5.58 1 3.15 1 1.77 1
3 Li 2.98 4 1.08 4 3.67 3 1.60 3 7.57 2 3.84 2 2.09 2 1.20 2 6.82 1
4 Be 5.82 4 2.29 4 8.40 3 3.78 3 1.86 3 9.59 2 5.44 2 3.26 2 1.89 2
5 B 3.93 3 3.75 4 1.53 4 7.22 3 3.63 3 1.93 3 1.10 3 6.73 2 3.94 2
6 C 7.32 3 2.75 3 2.44 4 1.22 4 6.29 3 3.43 3 1.98 3 1.21 3 7.22 2
7 N 1.19 4 4.71 3 1.83 3 1.73 4 9.23 3 5.14 3 3.02 3 1.90 3 1.14 3
8 O 1.74 4 6.90 3 2.68 3 1.27 3 1.21 4 6.94 3 4.17 3 2.67 3 1.63 3
9 F 2.45 4 9.73 3 3.73 3 1.79 3 9.12 2 8.54 3 5.23 3 3.44 3 2.11 3
10 Ne 3.72 4 1.36 4 5.70 3 2.71 3 1.39 3 7.54 2 7.11 3 4.55 3 2.84 3
11 Na 4.25 4 1.80 4 7.26 3 3.52 3 1.83 3 1.01 3 5.93 2 5.65 3 3.53 3
12 Mg 5.62 4 2.44 4 1.00 4 4.89 3 2.55 3 1.42 3 8.37 2 5.06 2 4.39 3
13 Al 6.44 4 2.92 4 1.23 4 6.10 3 3.22 3 1.80 3 1.07 3 6.63 2 4.07 2
14 Si 7.48 4 3.47 4 1.58 4 7.93 3 4.22 3 2.37 3 1.41 3 8.93 2 5.52 2
15 P 7.49 4 4.19 4 1.93 4 9.74 3 5.19 3 2.92 3 1.74 3 1.09 3 6.78 2
16 S 8.18 4 4.95 4 2.38 4 1.21 4 6.52 3 3.69 3 2.21 3 1.39 3 8.64 2
17 Cl 7.44 3 5.17 4 2.67 4 1.39 4 7.50 3 4.27 3 2.57 3 1.63 3 1.01 3
18 Ar 9.51 3 5.24 4 3.00 4 1.59 4 8.59 3 4.89 3 2.93 3 1.85 3 1.15 3
19 K 1.14 4 5.92 3 3.51 4 1.94 4 1.07 4 6.13 3 3.71 3 2.36 3 1.47 3
20 Ca 1.31 4 7.15 3 3.49 4 2.21 4 1.24 4 7.19 3 4.38 3 2.75 3 1.74 3
21 Sc 1.43 4 7.80 3 3.97 3 2.34 4 1.34 4 7.79 3 4.74 3 2.99 3 1.90 3
22 Ti 1.54 4 8.45 3 4.35 3 2.20 4 1.45 4 8.59 3 5.27 3 3.34 3 2.13 3
23 V 1.68 4 9.22 3 4.77 3 1.66 4 1.57 4 9.40 3 5.81 3 3.70 3 2.36 3
24 Cr 2.09 4 1.11 4 5.61 3 3.13 3 1.58 4 1.09 4 6.75 3 4.30 3 2.74 3
25 Mn 2.23 4 1.20 4 6.13 3 3.46 3 1.68 4 1.16 4 7.27 3 4.67 3 3.00 3
26 Fe 2.61 4 1.40 4 7.10 3 4.00 3 2.31 3 1.31 4 8.22 3 5.31 3 3.42 3
27 Co 2.86 4 1.54 4 7.85 3 4.41 3 2.58 3 1.22 4 8.84 3 5.73 3 3.71 3
Appendix XI Continued
) energy (keV)
Atomic 6.67 1
a
4.48 1 3.16 1 2.36 1 1.83 1 1.46 1 1.19 1 9.89 0 8.34 0
number Element 1.83 71 2.77 71 3.92 71 5.25 71 6.77 71 8.49 71 1.04 0 1.25 0 1.49 0
28 Ni 3.34 4 1.81 4 9.19 3 5.25 3 3.01 3 1.80 3 1.02 4 6.58 3 4.26 3
29 Cu 3.65 4 1.96 4 9.96 3 5.94 3 3.20 3 2.01 3 9.47 3 7.04 3 4.52 3
30 Zn 4.03 4 2.26 4 1.17 4 6.56 3 3.73 3 2.25 3 5.26 3 7.51 3 4.96 3
31 Ga 4.18 4 2.42 4 1.26 4 7.10 3 4.08 3 2.47 3 1.52 3 6.92 3 5.23 3
32 Ge 4.41 4 2.64 4 1.40 4 7.89 3 4.56 3 2.75 3 1.70 3 4.72 3 5.63 3
33 As 4.41 4 2.86 4 1.55 4 8.80 3 5.10 3 3.08 3 1.95 3 1.30 3 5.32 3
34 Se 4.49 4 3.03 4 1.69 4 9.64 3 5.61 3 3.38 3 2.17 3 1.53 3 4.86 3
35 Br 4.19 4 3.22 4 1.86 4 1.07 4 6.28 3 3.97 3 2.44 3 1.68 3 1.01 3
36 Kr 3.94 4 3.28 4 2.05 4 1.19 4 6.98 3 4.23 3 2.66 3 1.72 3 1.14 3
37 Rb 3.52 4 3.56 4 2.17 4 1.28 4 7.57 3 4.63 3 2.92 3 1.89 3 1.25 3
38 Sr 2.83 4 3.47 4 2.29 4 1.37 4 8.21 3 5.04 3 3.20 3 2.08 3 1.38 3
39 Y 2.04 4 3.10 4 2.34 4 1.51 4 9.06 3 5.58 3 3.55 3 2.32 3 1.52 3
40 Zr 6.41 3 3.06 4 2.46 4 1.61 4 9.77 3 6.03 3 3.86 3 2.53 3 1.66 3
41 Nb 4.28 3 2.96 4 2.67 4 1.78 4 1.08 4 6.69 3 4.27 3 2.80 3 1.84 3
42 Mo 4.66 3 2.23 4 2.29 4 1.85 4 1.14 4 7.09 3 4.55 3 2.99 3 1.97 3
43 Tc 4.99 3 1.41 4 2.29 4 1.78 4 1.19 4 7.45 3 4.90 3 3.57 3 2.12 3
44 Ru 5.49 3 4.18 3 2.47 4 1.95 4 1.30 4 8.16 3 5.37 3 3.92 3 2.32 3
45 Rh 5.87 3 4.64 3 2.48 4 1.94 4 1.38 4 8.79 3 5.80 3 4.23 3 2.51 3
46 Pd 6.09 3 5.22 3 2.21 4 1.80 4 1.46 4 9.42 3 6.23 3 4.54 3 2.69 3
47 Ag 6.34 3 5.48 3 1.10 4 1.91 4 1.47 4 1.00 4 6.66 3 4.86 3 2.90 3
48 Cd 6.45 3 5.75 3 4.10 3 2.01 4 1.47 4 1.04 4 7.09 3 5.84 3 4.48 3
49 In 6.61 3 6.06 3 4.42 3 2.23 4 1.36 4 1.10 4 7.51 3 6.20 3 4.75 3
50 Sn 6.64 3 6.27 3 4.70 3 9.12 3 1.38 4 1.08 4 7.88 3 6.50 3 4.99 3
51 Sb 6.71 3 6.50 3 4.94 3 3.36 3 1.48 4 1.13 4 8.26 3 6.82 3 5.25 3
52 Te 6.65 3 6.58 3 5.09 3 3.53 3 1.75 4 1.13 4 8.35 3 6.90 3 5.32 3
53 I 5.77 3 6.99 3 5.52 3 3.88 3 1.18 4 1.02 4 8.24 3 6.93 3 5.39 3
54 Xe 5.79 3 7.27 3 5.88 3 4.17 3 2.84 3 1.08 4 8.72 3 6.75 3 5.30 3
55 Cs 5.91 3 7.52 3 6.13 3 4.40 3 3.02 3 1.15 4 9.79 3 6.67 3 5.29 3
56 Ba 4.09 3 7.64 3 6.21 3 4.52 3 3.13 3 1.16 4 7.51 3 6.36 3 5.21 3
57 La 3.76 3 7.74 3 6.32 3 4.66 3 3.26 3 4.21 3 7.89 3 6.56 3 5.22 3
58 Ce 6.79 3 7.98 3 7.14 3 5.16 3 3.57 3 2.45 3 8.81 3 7.12 3 5.43 3
59 Pr 8.74 3 8.77 3 7.60 3 5.45 3 3.77 3 2.59 3 9.49 3 6.10 3 5.26 3
60 Nd 1.05 4 9.43 3 7.92 3 5.64 3 3.89 3 2.68 3 8.29 3 6.19 3 5.47 3
61 Pm 1.26 4 1.04 4 8.40 3 5.92 3 4.07 3 2.79 3 2.51 3 6.59 3 5.73 3
62 Sm 1.48 4 1.13 4 8.95 3 6.26 3 4.27 3 2.93 3 2.01 3 6.94 3 5.84 3
63 Eu 1.58 4 1.20 4 9.42 3 6.58 3 4.49 3 3.08 3 2.12 3 7.32 3 4.88 3
64 Gd 1.49 4 1.12 4 9.39 3 6.60 3 4.53 3 3.12 3 2.17 3 4.57 3 5.01 3
65 Tb 1.87 4 1.24 4 9.93 3 7.38 3 4.99 3 3.39 3 2.34 3 1.61 3 5.49 3
66 Dy 2.04 4 1.37 4 1.06 4 7.83 3 5.26 3 3.56 3 2.47 3 1.73 3 5.68 3
67 Ho 2.16 4 1.47 4 1.13 4 8.29 3 5.56 3 3.76 3 2.61 3 1.87 3 5.70 3
68 Er 2.32 4 1.60 4 1.21 4 8.86 3 5.94 3 4.00 3 2.77 3 2.01 3 2.84 3
69 Tm 2.43 4 1.72 4 1.29 4 9.49 3 6.36 3 4.27 3 2.96 3 2.14 3 1.56 3
70 Yb 2.28 4 1.79 4 1.35 4 9.94 3 6.67 3 4.47 3 3.10 3 2.32 3 1.47 3
71 Lu 2.15 4 1.75 4 1.36 4 1.01 4 6.86 3 4.62 3 3.22 3 2.42 3 1.54 3
72 Hf 2.13 4 1.80 4 1.27 4 9.96 3 7.20 3 4.86 3 3.38 3 2.54 3 1.62 3
73 Ta 2.04 4 1.82 4 1.32 4 1.04 4 7.54 3 5.11 3 3.53 3 2.45 3 1.77 3
74 W 1.93 4 1.85 4 1.37 4 1.09 4 7.90 3 5.36 3 3.70 3 2.57 3 1.86 3
75 Re 1.76 4 1.84 4 1.39 4 1.12 4 8.18 3 5.57 3 3.87 3 2.69 3 1.95 3
76 Os 1.58 4 1.67 4 1.39 4 1.12 4 8.36 3 5.74 3 4.02 3 2.92 3 1.99 3
77 Ir 1.38 4 1.61 4 1.44 4 1.15 4 8.36 3 6.09 3 4.27 3 3.11 3 2.12 3
78 Pt 1.13 4 1.57 4 1.50 4 1.12 4 8.83 3 6.43 3 4.51 3 3.28 3 2.24 3
79 Au 9.09 3 1.49 4 1.51 4 1.16 4 9.23 3 6.74 3 4.68 3 3.28 3 2.29 3
80 Hg 6.62 3 1.47 4 1.50 4 1.17 4 9.30 3 6.95 3 4.77 3 3.31 3 2.36 3
81 Tl 5.42 3 1.29 4 1.40 4 1.21 4 9.55 3 7.24 3 5.13 3 3.88 3 2.50 3
82 Pb 4.19 3 1.14 4 1.38 4 1.23 4 8.93 3 7.10 3 5.34 3 4.04 3 2.61 3
83 Bi 3.17 3 1.01 4 1.35 4 1.26 4 9.23 3 7.35 3 5.55 3 4.20 3 2.72 3
84 Po 2.54 3 8.62 3 1.34 4 1.33 4 9.68 3 7.72 3 5.82 3 4.42 3 2.88 3
85 At 2.28 3 6.67 3 1.31 4 1.23 4 1.02 4 8.14 3 5.70 3 4.57 3 3.04 3
86 Rn 2.52 3 4.13 3 1.21 4 1.16 4 1.02 4 8.26 3 5.72 3 4.46 3 3.04 3
87 Fr 2.69 3 3.02 3 1.10 4 1.17 4 1.05 4 7.52 3 5.99 3 4.57 3 3.18 3
88 Ra 2.66 3 2.42 3 9.31 3 1.17 4 1.04 4 7.75 3 6.22 3 4.68 3 3.30 3
89 Ac 2.49 3 2.59 3 8.17 3 1.15 4 1.01 4 7.88 3 6.35 3 4.49 3 3.40 3
90 Th 1.99 3 2.12 3 6.44 3 1.11 4 8.83 3 7.85 3 6.22 3 4.64 3 3.48 3
Appendix XI Continued
) energy (keV)
Atomic 6.67 1
a
4.48 1 3.16 1 2.36 1 1.83 1 1.46 1 1.19 1 9.89 0 8.34 0
number Element 1.83 71 2.77 71 3.92 71 5.25 71 6.77 71 8.49 71 1.04 0 1.25 0 1.49 0
91 Pa 2.34 3 2.38 3 3.44 3 1.13 4 9.45 3 8.35 3 5.96 3 4.97 3 3.71 3
92 U 2.57 3 2.30 3 2.70 3 1.09 4 9.39 3 8.36 3 6.03 3 4.96 3 3.76 3
93 Np 2.93 3 2.41 3 2.62 3 9.65 3 9.74 3 8.59 3 6.34 3 5.21 3 3.74 3
94 Pu 3.73 3 2.39 3 2.72 3 6.59 3 1.01 4 8.24 3 6.66 3 5.40 3 3.89 3
a
Source: From Veigele, 1974.
APPENDIX XII: CORRESPONDENCE BETWEENOLD SIEGBAHNANDNEWIUPAC
NOTATIONX-RAYDIAGRAMLINES
Siegbahn IUPAC Siegbahn IUPAC Siegbahn IUPAC
Ka
1
K-L
3
La
1
L
3
-M
5
Lg
1
L
2
-N
4
Ka
2
K-L
2
La
2
L
3
-M
4
Lg
2
L
1
-N
2
Kb
1
K-M
3
Lb
1
L
2
-M
4
Lg
3
L
1
-N
3
Kb
I
2
K-N
3
Lb
2
L
3
-N
5
Lg
4
L
1
-O
3
Kb
II
2
K-N
2
Lb
3
L
1
-M
3
Lg
/
4
L
1
-O
2
Kb
3
K-M
2
Lb
4
L
1
-M
2
Lg
5
L
2
-N
1
Kb
I
4
K-N
5
Lb
5
L
3
-O
4,5
Lg
6
L
2
-O
4
Kb
II
4
K-N
4
Lb
6
L
3
-N
1
Lg
8
L
2
-O
1
Kb
4x
K-N
4
Lb
7
L
3
-O
1
Lg
/
8
L
2
-N
6(7)
Kb
I
5
K-M
5
Lb
/
7
L
3
-N
6,7
LZ L
2
-M
1
Kb
II
5
K-M
4
Lb
9
L
1
-M
5
Ll L
3
-M
1
Lb
10
L
1
-M
4
Ls L
3
-M
3
Lb
15
L
3
-N
4
Lt L
3
-M
2
Lb
17
L
2
-M
3
Lu L
3
-N
6,7
Lv L
2
-N
6(7)
Ma
1
M
5
-N
7
Ma
2
M
5
-N
6
Mb M
4
-N
6
Mg M
3
-N
5
Mz M
4,5
-N
2,3
Source: From Jenkins et al., 1991.
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2
Wavelength-Dispersive X-ray Fluorescence
Jozef A. Helsen
Catholic University of Leuven, Leuven, Belgium
Andrzej Kuczumow
Lublin Catholic University, Lublin, Poland
I. INTRODUCTION
Moseleys law, formulated soon after the discovery of x-rays by Ro ntgen (Ro ntgen, 1896),
represented the direct and denite onset of the use of x-ray spectrometry in chemistry. The
rst successful period was completed in the beginning of the 1920s by creating order in the
periodic table of the elements and by the discovery of the missing elements (Weebs and
Leicester, 1967). X-ray uorescence (XRF) spectrometry has some unique features so that
it became an irreplaceable tool for the analyst. Not may techniques had such a brilliant
start to their analytical careers!
gThe rst commercial instrument became available around 1940 and was derived
from the x-ray goniometer of a diraction instrument. A reasonable estimation of the
number of wavelength-dispersive (WDXRF) instruments working today is 15000, of
which some 20% are multichannel spectrometers. In addition, about 3000 instruments
working in this mode are attached to the electron microprobes, mainly in Japan. Some
3000 energy-dispersive (EDXRF) instruments are working independently, and some
15002000 others are attached to electron and other [e.g., proton (Uda et al., 1987,
Folkmann and Frederiksen, 1990)] microprobes; a few hundred instruments are con-
nected to synchrotrons as excitation sources. About 300 instruments are working now in
total reection (TRXRF) and several in grazing emission modes (Klockenka mper, 1997).
The average price of a new WDXPF instrument in 1998 is of the order of magnitude of
$250,000, $100,000 for EDXRF, and $200,000 for TRXRF (Claes et al., 1997) and this is
not expected to rise much in the coming years. The calculation of the total money in-
volved in the x-ray instrument market made hereafter was based on the 50% amortization
estimate per instrument. We consider in our account only these parts of Particle-induced
x-ray emission (PIXE), electron microscope, and synchrotron arrangements which can be
treated as x-ray attachments. An auxiliary market was created also around the main
equipment business, covering the spare parts, recent supplements, and service connected
with the maintenance. Then, the commercial value of the instruments running today may
be estimated at some US$4 billion (Markowicz and Van Grieken, 1986; Van Grieken
et al., 1986). An important body of scientic literature relates to x-ray spectrometry
(Markowicz and Van Grieken, 1986; van Grieken et al., 1986; Jenkins, 1984; de Vries,
1986; Klockenka mper, 1987; Kikkert, 1983; Potts and Webb, 1992; To ro k et al., 1996,
To ro k et al., 1998; Szalo ki et al., 2000; Brill, 1996; Ellis et al., 1997 and Quiset, 1996).
Literature about essentially diraction and scattering problems can also be very useful for
the researchers working in the eld of XRF (Fewster, 1996).
About 10% of the WDXRF instruments are applied in geological research and
prospecting (sequential and simultaneous spectrometers). Most of the simultaneous in-
struments are installed in industry, and the sequential instruments are distributed over
industry, analytical laboratories, and research institutes at universities and public services.
X-ray uorescence spectrometry is unique in element analysis of inanimate matter:
In qualitative analysis, it has unrivaled selectivity for all elements between beryllium and
uranium and also for transuranium elements and an extremely wide dynamic range in
quantitative analysis (ppm to 100%). Although the plasma emission spectrometry [Direct
Current Plasma (DCP) or Inductively Coupled Plasma (ICP)], atomic absorption spec-
trometry (AAS), neutron activation analysis (NAA), and dierent kinds of mass spec-
trometry (MS) have lower or much lower detection limits, the wide dynamic range remains
a unique feature of XRF (over ve decades). Moreover, it possesses the scarce virtue
among spectral methodsthe upper useful limit reaches the concentration of several tens
of percent of the total concentration for the main component. The detection limits at the
ppm level without preconcentration and the limits of precision and accuracy that can be
obtained (connected, in turn, to sample homogeneity and counting statistics) determine
the boundaries of its application.
Earlier books describing the techniques are mentioned in the reference list (Compton
and Allison, 1935; Jenkins and De Vries, 1967; Birks, 1969; Dyson, 1973; Jenkins, 1974;
Bertin, 1975; Tertian and Claisse, 1982; Lachance and Claisse, 1995, Jenkins et al., 1995;
Buhrke et al., 1998the latter is a kind of a guide for sample preparation in XRF and
XRD, but is cited here, because the problem is very important and nontrivial). The
purpose here is to describe the basic principles that allow wavelength dispersion of x-rays
and to describe all the components of a spectrometer.
The phenomenon of x-ray uorescence is only a small part of a much wider problem
of the interaction of charged particles or photons with matter (Feldman and Mayer,
1986). Dierent kinds of secondary particles are then emitted (Fig. 1a). Various combi-
nations of exciting=emitted particles are possible, giving birth to dierent analytical
techniques, with the combination photons as exciting particles=emitted photons as a
base for the x-ray uorescence. The angles the trajectories of the exciting or emitted
particles create with the surface of the sample dene normal XRF and PIXE methods and
total reection versions: TXRF (Chapter 9) and TRPIXE (Vis and van Langevelde, 1991;
van Kan and Vis, 1996a, 1996b, 1997). In addition, for the x-ray uorescence, a grazing-
emission method can be mentioned (GEXRF) (Sasaki, 1990; Becker et al., 1983; de Bokx
and Urbach, 1995; Urbach and de Bokx, 1996; Tsuji et al., 1995; Pe rez and Sa nchez,
1997) (Fig. 1b).
Insofar as the fundamental principles are concerned, we may recall the law of
Moseley (Moseley, 1913, 1914), which is the basis of the qualitative application of XRF:
n
p

c
l
_
kZ s 1
where n is the frequency (in Hz), c is the speed of light (in m=s), l is the wavelength (in m),
k is the constant for a given series, and s is the screening constant. The relationship
Figure 1 Phenomena accompanying the interaction of x-rays with matter: (a) different
applications for analytical purposes (abbreviations of methods coupled with the use of particular
phenomena are mentioned; (b) different versions according to the incidence and emergence angles
(Itotal reflection XRF or PIXE; IIgrazing emission XRF; IIIgrazing incidencegrazing
emission XRF).
between the wavelength of the lines belonging to the same spectral series and the atomic
number is illustrated by Figure 2.
For high-Z elements, the XRF spectra become more complex and full exploitation
for qualitative analysis of mixtures is not always simple. Practical unraveling of spectra is
dealt with in Chapter 4.
The intensity of any spectral line is proportional to the number of atoms emitting
photons of energies attributed to this line. However, a simple linear proportionality is not
the rule. From the concepts of mass attenuation coecients introduced in Chapter 1,
it should be clear that the intensity of an analyte line of one species is attenuated by atoms
of the same species and by any other atoms present in the matrix. Matrix refers to all
elements present in a sample except the analyte element. Attenuation by absorption re-
presents a rst complication compromising the proportionality.
If the matrix contains elements with absorption edges of slightly lower energy than
the energy of the characteristic line of the analyte, strong absorption can occur. On the one
hand, this results in further attenuation of the analyte line and, on the other hand, in
enhancement of the spectral line related to the said absorption edge of the other matrix
element. This phenomenon is known as secondary uorescence. The process may be re-
peated with respect to all matrix elements with an absorption edge with a lower energy
than the energy of a uorescence line emitted by another matrix element. Secondary and
higher-order uorescence is the major complication deteriorating the simple proportion-
ality between intensity and concentration.
In Figure 3, three typical kinds of relationship between the relative intensity (mea-
sured intensity divided by the intensity obtained for the pure element) and concentration
(expressed as weight fraction) are represented. Curve I is obtained when the analyte line
undergoes absorption only. If enhancement occurs, the analyte line intensity is higher than
expected from primary excitation only and the curve is situated above the diagonal.
A similar curve, however, can be obtained when the mass attenuation coecient of the
matrix is lower than the related coecient of the element for its own radiation, as shown in
the case for Fe in FeO (curve II). In a special case, the mutual relation between attenuation
Figure 2 Representation of Moseleys law of K and L spectral lines.
and enhancement coecients may be balanced such that both eects cancel precisely and
then the diagonal is approximated (curve III).
The eects just discussed are all energy (wavelength) dependent. This means that any
calculations converting intensities into concentration should include the attenuation and
higher-order uorescence eects and also integrate over all energies present in the exciting
primary beam above the value of the absorption edge and over all uorescence lines. This
is an ab initio approach for conversion of intensities into concentration implemented by
several authors. We mention here the articles by Gillam and Heal (1952), Sherman (1954,
1955), Shiraiwa and Fujino (1966, 1967), who in the 1950s and the 1960s proposed suitable
equations. Sparks (1976) and Li-Xing (1984) implemented small corrections and rene-
ments concerning the details of these expressions, and de Boer (1990) and de Boer and
Brouwer (1990) gave solutions to some dicult exponential integrals related to the en-
hancement. Important contributions to the numerical side of quantitative XRF are due to
Fernandez (1989), Fernandez and Molinari (1990), Rousseau et al. (1996), and Mantler
(1984). The rst two authors prepared commercial, customer-oriented versions of the
numerical programs XRFPc and CiROU, CiLAC, CiLT, and CiREG, respectively, and
Mantler paved the way for the analyses of multilayers. It should be emphasized that
Fernandez solved the transport equations for x-ray beams, the very general and powerful
but dicult tool for the description of particle beams. Likewise, Gardner and Hawthorne
(1975) obtained similar results by Monte Carlo simulation of x-ray excitation. A specic
approach was presented by Dane et al. (1996). These authors solved the problem of
quantication in situations where either an incomplete data set is available or where a
reasonable assumption about composition and=or depth prole cannot be done. Then, the
idea of processing whole sets of solutions (populations or strings or generations) has been
introduced, instead of processing the particular concentration values in consecutive
iterations.
In the fundamental parameter methods, the incidence and takeo angles are the
important parameters. As a rule, they are kept constant during the traditional run of
the analysis. However, there have been signicant eorts to use the angle-resolved version
Figure 3 Absorption phenomena in a heavy matrix (curve I), in a light matrix (curve II), and in a
neural matrix (curve III).
of x-ray XRF spectrometers for depth proling of the samples (Gries, 1992; Schmitt
et al., 1994).
For a complete treatment of equations deriving the line intensities in x-ray uor-
escence spectrum from the elemental sample composition, the reader referred is to
Chapter 5.
II. FUNDAMENTALS OF WAVELENGTHDISPERSION
The crystal monochromator is the heart of a wavelength-dispersive spectrometer. Wave-
length dispersion of electromagnetic radiation in the x-ray region cannot be performed, as
a rule, by normal gratings but only by diraction on crystals or, for the long-wavelength
regions, on multilayers. We briey explain the principles because the construction features
of the monochromator are directly derived from them.
Consider a monochromatic beam of x-rays of wavelength l with their electrical
vectors of equal amplitude in phase along any point of the direction of propagation.
Assume further that the beam is parallel and is incident on a crystal at an angle W between
a given crystal plane (and all the planes parallel to this rst) and the incident beam di-
rection. The beam is scattered and diracted rays of equal l result but interfering con-
structively only in those directions for which the phase relationship is conserved. This
happens at an angle W for scattered rays 1 and 2 (Fig. 4), for which the path dierence
ABC of ray 2 with ray 1 is equal to an integral number n of wavelengths. From Figure 4, it
is clear that ABBCd sin Wd sin Wnl or, according to Bragg and Bragg (1913),
who rst formulated this relation, written as
nl 2d sin W 2
where n denotes the number of wavelength dierences between the rays scattered by the
adjacent planes. Following the recommendation of the IUPAC (Freiser and Nancollas,
1987), n is the order of diraction. If n 1, the dierence is one wavelength and the
diraction is said to be of rst order. If n 2, the dierence is two wavelengths and the
diraction is second order, and so on.
All x-rays emitted at angles dierent than W cancel because they are out of phase and
destructive interference occurs. From Figure 4, one can note that in the Bragg scattering,
Figure 4 Derivation of the Braggs law. ABC is the path difference.
the incident and exit angles are equal and, in this sense, there is some analogy to mirror
reection in the classical optics. However, diraction is by no means equal to reection in
classical optics, because the diraction is a volume not a surface process. It is less ecient
(with a great loss of intensity) and is performed only under particular angular conditions;
that is, according to Braggs law. Full analogy between the reection of x-rays and the
reection of optical rays happens only at grazing incident angles (i.e., smaller than the
critical Snells angle). This is intrinsically a consequence of the refraction index, which is
slightly smaller than 1 for x-rays. There are continuous eorts to construct a real mirror
on the basis of multilayers, which would eciently reect x-rays under large incident
angles, at least for soft x-rays (Kearney et al., 1991).
Thus, the static condition for obtaining diraction of a monochromatic x-ray beam
in some direction in the volume surrounding the analyzing crystal is given. What happens
in the case of a polychromatic beam of x-rays? For a crystal, one set of planes is selected
(for dierent reasons) and d is constant. If only rst-order diraction is considered and
constructive interference must be realized for all l present in the incident beam, then W is
the only variable:
l constantsin W 2a
The signal arriving from the diraction angle W is detected by a detector placed on a
goniometer arm. The detector rotates around an axis through the macroscopic plane of the
analyzing crystal. For a source at a xed position, the detector rotates over an angle 2W.
The wavelength is calculated from constant 2d and sin W. Note that this holds only for
the rst-order diraction. If the second-order diraction is used, the wavelength is equal to
half of that value. The maximum wavelength l
max
that can be diracted in the rst-order
diraction by a crystal is equal to 2d because sin W1.
Because wavelength and energy are related, one more equations must be given, al-
lowing us to convert wavelengths into energy units:
E
12398:5
l
3
where the energy E is in electron volts (eV) and l is in angstroms (A
). It is a common
practice that the units used by x-ray spectroscopists are still electron volts or kiloelectron
volts for energy and angstroms for wavelength. When joules and nanometers are used, as
required by the international rules, the numerical value of the conversion constant be-
comes 1.98645610
16
(nm=J).
The presence of dierent wavelengths of dierent order on the same goniometer
position has a particular consequence for wavelength-dispersive spectrometry. For a given
position of the goniometer (and detector), one may have a rst-order wavelength, say
0.6 A
, second-order diraction of l 0.3 A
, third-order diraction of l 0.2 A
, or values
of energy 20.66, 41.32, or 61.98 keV, respectively. Figures 5 and 6, reproduced from the
work of Arai (1987) demonstrate a practical situation and Table 1 reprints a fragment
from x-ray tables by Cauchois and Senemaud (1978). Similar compendia of spectral lines
and attenuation coecients are easily available (Birks, 1974), as a rule covering the range
of elements between lithium (Z 3) to plutonium (Z 94). Much more controversial are
the values of the mass attenuation coecients for low energies and for low-Z elements at
the same time (Henke et al. 1982, 1988). If necessary, one can have access to the calcu-
lation for even heavier elements (So et al., 1977). It is easy to understand the practical
value of such calculations for the analysis. However, it is much more dicult to estimate
the accuracy of numerical calculations for transuranium elements. To sort out x-rays with
wavelengths belonging to dierent spectral orders, a pulse-amplitude selector or detector is
needed that can make the distinction between energy levels. A detector is a device of which
the principle can be most easily explained by assuming the particle character of electro-
magnetic radiation. This is one reason that the characteristic of the impacting photons is
often expressed in terms of energy, not wavelength.
Figure 5 Higher-order overlapping of L series x-rays of Cr, Fe, and Ni to Ka of carbon. (From
Arai, 1987.)
Figure 6 Overlapping of CKa by higher-order x-rays of Ni, Fe, and Cr. (From Arai, 1987.)
The dierences between wavelength-dispersive (WD) and energy-dispersive (ED)
XRF are due not only to the dierent detectors but also to other factors:
1. The brightness of a WD spectrometer is very low, the attenuation in a crystal
being responsible for an important part of losses. This problem may be
overcome by the use of radiation sources of signicant intensity, the synchrotron
being the best known but bound to the availability of this large facility.
2. The crystal is only the dispersive device, not the detecting device. The situation is
dierent in EDXRF, for which detectors play a double role: as the dispersive
device and as the detector at the same time.
Table1 Fragment of Detailed Tables of X-ray Lines
l (uX) l (mA
) Element Transition
Notation
usuelle Ordre E (keV) n=R n=R
1=2
1251.56 1254.19 42 Mo KM
IV
Kb
II
5
2
1251.64(
a
) 1254.27 58 Ce KM
IV
Kb
II
5
4
1252.192 1254.824 62 Sm KL
II
Ka
2
4
1252.58 1255.21 73 Ta abs. L
III
1 9.8776 725.99 26.9441
1252.6 1255.2 90 Th L
I
N
IV
2
1252.82 1255.45 73 Ta L
III
O
IV,V
Lb
5
1 9.8758 725.85 26.9416
1255.17 1257.81 73 Ta L
III
N
VI,VII
Lb
7
1 9.8573 724.49 26.9163
1255.43 1258.07 32 Ge KL
II
Ka
2
1 9.8552 724.34 26.9135
1255.50 1258.14 69 Tm KL
I
5
1256.60 1259.24 75 Re L
I
M
II
Lb
4
1 9.8460 723.66 26.9010
1256.71 1259.35 73 Ta L
III
O
III
1 9.8452 723.60 26.8998
1257.1(
a
) 1259.7 71 Lu L
II
N
I
Lg
4
1 9.842 723.4 26.8956
1257.12 1259.76 90 Th abs. L
II
2
1257.66 1260.30 73 Ta L
III
O
II
1 9.8377 723.05 26.8897
1258.74 1261.39 54 Xe KL
II
Ka
2
3
1259.210 1261.856 68 Er KL
III
Ka
1
5
1259.8 1262.4 90 Th L
II
P
II,III
2
1260.30 1262.95 74 W L
I
M
III
Lb
3
1 9.8171 721.54 26.8615
1260.6 1263.2 90 Th L
II
P
I
2
1260.620(
a
) 1263.269 58 Ce KM
III
Kb
1
4
1261.15(
a
) 1263.80 64 Gd KM
IV,V
Kb
5
5
1261.23 1263.88 73 Ta L
III
O
I
Lb
7
1 9.8099 721.01 26.8516
1261.956 1264.608 42 Mo KM
III
Kb
1
2
1262.68 1265.33 90 Th L
II
O
IV
Lg
6
2
1263.086 1265.741 42 Mo KM
II
Kb
3
2
1263.428(
a
) 1266.083 58 Ce KM
II
Kb
3
4
1264.6 1267.3 74 W L
III
N
III
1 9.784 719.1 26.8158
1264.99(
a
) 1267.65 70 Yb L
II
N
IV
Lg
1
1 9.7807 718.86 26.8116
1265.0 1267.7 91 Pa L
II
N
IV
Lg
1
2
1265.24(
a
) 1267.90 69 Tm L
I
N
III
Lg
3
1 9.7788 718.72 26.8090
1268.520(
s
) 1271.186 92 U L
II
N
I
Lg
5
2
1268.66 1271.33 90 Th L
I
N
III
Lg
3
2
1268.68(
a
) 1271.35 68 Er L
I
O
IV,V
1 9.7523 716.77 26.7726
1270.2 1272.9 74 W L
II
M
V
1 9.741 715.9 26.7566
1270.35(
a
) 1273.02 64 Gd KM
III
Kb
1
5
Source: From Cauchois and Senemaud, 1978.
3. Because Braggs law is geometric in character, the angular conditions for the
collimation of primary and secondary beams are very severe for WDXRF (8
25 msr), not the same as for EDXRF (150 msr) (Wollman et al., 1997). This
restriction on the geometrical eciency still makes the overall photon collection
eciency of a wavelength-dispersive spectrometer worse.
4. An attractive aspect of EDXRF is the simultaneous collection of the whole
spectrum, whereas a typical WDXRF device is exclusively sequential.
However, the maximum count rate for an EDXRF instrument is 30 kcps
for the whole spectrum, which severely limits the total number of accumulated
counts and, consequently, limits the precision (counting statistics). Similarly,
the limitation on the total count rate leaves a small margin for trace element
analysis. From the assumption, the trace element, if present in a sample, can
emit only a very small part of the total radiation emitted by a whole sample
(and there is also the background, participating in the total amount of
counts).
Simultaneous WD instruments are composed of a series of individual crystal spectrometer
(channels) operating simultaneously, but the number of channels is limited.
A comparison of wavelength- and energy-dispersive versions of x-ray spectrometers
is performed in a recent publication by Brill (1996).
III. LAYOUT OFASPECTROMETER
The main parts of a spectrometer can be represented in the simplest form by Figure 7. The
analyzing crystal is the central point of the wavelength-dispersive instrument. On the left-
hand side of the crystal, we nd (1) the source of excitation, (2) the lters and devices for
shaping the exciting radiation (collimators and masks), and (3) the sample. On the right-
hand side, we nd (4) devices for shaping the diracted beam (collimators) and (5) the
detector. Signals from the detector are fed into the electronic circuitry where they are
shaped to be processed by the computer software for data analysis. This arrangement can
be reduced or made more complicated according to the demand. However, all possible
reductions lead to less exible devices, and complication does not necessarily enhance the
quality of the instrument.
Figure 7 A wavelength-dispersive spectrometer: FCproportional flow counter; SDscintilla-
tion detector. (Reprinted with permission of Siemens AG.)
A. Sources
A variety of radiation sources, emitting either charged particles or g- or x-rays of sucient
energy, are used for excitation of some or all elements of the periodic table and some or
most of the spectral lines of analytical interest. Other chapters deal with excitation by
protons [proton-induced or sometimes particle-induced x-ray emission (PIXE) (Chapter
12)], by electrons [electron microprobe (Chapter 13)], or by x-rays emitted from secondary
targets or from a synchrotron (Chapter 8). Excitation by x-rays or soft g-rays from
radioisotopes and x-rays from low-power tubes is mainly restricted to energy-dispersive
spectrometers (Chapter 3). The ideal excitation source would be a tunable x-ray laser
(monochromatic and intense, allowing the best choice of exciting wavelength and often
selective excitation), but this cannot be expected in the near future. Nevertheless, it is
worth reading some treatises about recent and future progress in the eld (Nagel, 1982;
Jamelot, 1995; Fill, 1995; Crasemann, 1994; London, 1993). There are serious reasons for
the slow progress in x-ray laser construction. The primary reason is that the population
inversion of electrons means a much larger deviation from the energetical equilibrium if
done between the levels, allowing the emission of x-rays. Consequently, it demands an
excessive pumping power, turning the pumped matter into a plasma. One must be aware
that the x-ray laser would be even much more useful in the elds of x-ray microscopy,
holography, litography, or for the research of time-resolved phenomena than as a source
for XRF analysis on a routine basis.
The synchrotron is another modern source of x-ray radiation, but it cannot be
considered as a tabletop instrument and a device for easy, inexpensive, and routine-based
applications. From a practical point of view, vacuum x-ray tubes are the overwhelming
choice among other potential excitation sources. High-power tubes are the only ones dealt
with in detail in this chapter; low-power tubes are discussed in Chapter 3.
All modern tubes owe their existence to Coolidges hot-cathode x-ray tube as pre-
sented in Physical Review some 85 years ago (Coolidge, 1913). They essentially consist of
a sealed glass tube containing a hot tungsten lament for the production of electrons, a
cooled anode, and a beryllium window. From a variety of modications proposed over
more than three-quarters of the century, two geometries have emerged as the most sui-
table for all practical purposes [the end-window tube (EWT) and the side-window tube
(SWT)], but now the preponderance of the EWT pushes the SWT out of the market.
Perhaps, a future deeper orientation of the WDXRF toward the microprobe applications
will renew the interest in SWT, which is much better in deriving parallel x-ray beams.
The general requirements of the x-ray tube as a source are as follows:
1. Sucient photon ux over a wide spectral range, with increasing emphasis on
the intensity of the long-wavelength tail of the white spectrum. The actual vivid
interest in low-Z element analysis will certainly activate research in this
direction.
2. Good stability of the photon ux (<0.1% at least). Long-term stability reduces
the frequency of recalibration in routine analyses; short-term stability is an
absolute requirement for obtaining an acceptable precision.
3. Switchable tube potential (10100 kV), allowing the creation of the most
eective excitation conditions for each element. Still, in more high-power
constructions available on the market, putting a lter in the beam path is an
easier solution than switching the voltage (Shimadzu XRF-1700). For sure, the
selection of the spectral region for the targeted excitation by the use of a single
x-ray tube will never be as good as in dedicated synchrotron beam lines with
monochromators of the adequate quality, but the low cost of tube operation is
an obvious advantage. The intensity of the analyte lines varies considerably with
excitation conditions. An extreme example is given by Vrebos and Helsen
(1985a, 1985b) for simulated AlMo alloys.
4. Freedom from too many interfering lines from the characteristic spectrum of the
tube anode.
Freedom from interfering lines is important. The scattered characteristic lines of
the anode may spectroscopically interfere with analyte lines, disturbing the qualitative
recognition, the peak intensity estimation for the line of interest, and the accuracy of
subsequent conversion of intensity to concentration. This is found in the results obtained
after correction by some algorithms as well as by fundamental parameter calculations.
Although there is some kind of a remedy by the use of more ecient spectral decon-
volution methods (Remond et al., 1993; 1996), it occurs at the expense of a greatly
increased computational eort and depends heavily on the assumptions made a priori.
An x-ray tube is characterized by its anode element (a single element or two
elements as in dual-anode tubes), its input power [expressed in watts (W) or kilowatts
(kW), typically between 0.2 and 5 kW for high-power tubes], the voltage range between
anode and cathode (10100 kV for a SWT; limited to 60 kV for an EWT for the ma-
jority of commercial instruments), tube current [milliampere (mA), typically up to
60 mA or sometimes to 150 mA for high-power tubes], and an open (SWT) or closed
(EWT) anode cooling circuit. The photon output of the tube or, more importantly, the
photon ux hitting the sample (expressed in counts per second per watt of input power)
is determined by a, the incidence angle of an electron beam on the anode, the takeo
angle b (for SWT), the distance t to the beryllium window, the thickness d of the
beryllium window, and the distance between window and sample, t
0
(Fig. 8). The ra-
diation output power is rather poor with respect to the input power and is of the order
of 1%, making the device a very inecient transformer of electron current to electro-
magnetic radiation. For an energy balance, see Bertin (1975) and some remarks by
Wollman et al. (1997).
The impact of the electrons creates an excitation volume from which the white and
the characteristic radiation of the target escape. This phenomenon represents the rst
distinct dierence between a SWT and an EWT. As shown in Figure 9a, the escape path
of the photons in SWT geometry is, on average, less than in the EWT geometry. An
immediate consequence of this characteristic is that dual anodes are used only in a SWT,
where a light element (e.g., scandium) covers a heavier element (e.g., molybdenum). By
switching the excitation voltage, x-rays are produced either in the upper (lighter) element
layer or in the substrate (higher-Z element), resulting in two distinct tube spectra with
dierent yields in the low- and high-wavelength regions (Fig. 9b). The popular dual-target
tube arrangements are now Rh=Cr and Rh=W.
The smaller the distance t, the higher the output. A decrease of t to half of the
original value increases the intensity roughly by a factor of 4. However, the reduction of
t in the classical setup is limited. The smaller the value of t, the more intense the bom-
bardment by the electrons and subsequent heating of the window by the scattered elec-
trons (Fig. 8). In a SWT, this bombardment is rather intensive because both the anode and
the window are in this geometry at ground potential. In a EWT, to the contrary, the -
lament and the window are both at ground potential, and heating of the window is neg-
ligible. For an EWT, however, t can be reduced to a certain extent only because it faces the
anode at high potential (Fig. 10).
1. Alternative Congurations
To overcome the absorption of the low-wavelength tail of the continuum, a windowless
conguration was considered. This is an obvious solution, but it requires that the whole
spectrometer with sample, collimators, crystals, and ow counter be evacuated to the low
pressure suitable for securing an acceptably long life for the tube lament and conducting
analyses in the required range of the soft x-rays.
Nordfors (1956) advocated a dual-anode tube with two anodes physically separated.
They were excited by deviating the electron beam to either of the two anodes (Fig. 11).
Lack of stability prevented this solution from gaining commercial interest. Probably, a
modied version of this idea was introduced in the series 2000 x-ray spectrometers of
Diano (dual target dual lament; see Section VI).
Tubes with exchangeable anodes are another possibility for solving the problem of
comfortable switching between dierent anodes. To the best of our knowledge, this
solution is not commercially available because of the tedious exchange operation and
diculties in rigorous repeating of previous conditions of the tube action.
Using the sample as an anode is another solution, but then the application is
bound to conducting materials. In a modied form, this solution is implemented in
scanning electron microprobes. Because this anode cannot be adequately cooled, the
input power must be restricted to very low values, entailing low count rates and,
consequently, reducing the precision that can be obtained within reasonable counting
times.
Another possibility is to apply an existing 18-kW rotating anode x-ray tube gene-
rator. Sucient intensity is obtained. Part of this gain can be sacriced and Boehme (1987)
and Nichols et al. (1987) introduced the microdiraction beam collimator into the beam
Figure 8 Details of the geometry of a side-window x-ray tube and sample.
derived from such a high-power tube. This collimates the beam to about 30 mm and allows
microuorescence. Squeezing the beam to more or less the same diameter is possible when
applying the polycapillary lens, even more so with the single capillary. These solutions are
very restrictive for the beam intensity; thus, a reasonable device conguration includes an
energy-dispersive detector instead.
2. Optimization
Because the takeo angle is a very important parameter, the surface of the anode can be
formed in steps in such a way that the yield of low-wavelength radiation is optimized. As is
clear from Figure 12, the step-shaped surface decreases the escape depths.
In a conventional EWT, the reduction of the anode to window distance t is limited
(Fig. 10). According to an old idea of Thordarson (1939), Botden et al. (1952) developed
an x-ray tube with a gold anode evaporated directly on the beryllium window. The tube
was used for surface radiotherapy. After many years, Phillips returned to Botdens
construction and again reduced t to zero by sputtering the anode target element directly
on the beryllium window (Fig. 13). In a SWT, the anode is at ground potential, which
Figure 9 (a) Principle of excitation in a side-window tube. (b) Principle of excitation in a dual-
anode x-ray tube (side window); Mo, W, or Au (for A) and Sc, Rh, or Cr (for B) are commercially
available anode components. The spectral feature of the tube spectrum depends on the energy of the
incident electrons.
considerably facilitates and simplies the safety requirements. This geometry enhances
the intensity by an order of magnitude, allowing a much lower input power: 200 W for
an intensity equivalent to the earlier 3-kW EWT. As a result of the low input power, the
heat produced in the target by the electron beam is easily dissipated and no supple-
mentary water cooling is required. The tube construction is reduced and only the most
basic components are left. The commercial name for this development is T
3
or TTT
(target transmission tube; Fig. 14c). It is used exclusively in simultaneous WDXRF
instruments, especially in the new version of the PW1660 (Philips Technical Materials
Simultaneous X-Ray Spectrometer System PW 1660) (see Section VI).
Figure10 Principle of end-window x-ray tubes.
Figure 11 X-ray tube with two separate anodes: (1) anodes: (2) filaments; (3) cooling;
(4) separating brass wall; (5) insulator. (After Norfords, 1956.)
Figure12 X-ray tube with stepwise configuration of the anode.
3. End-WindowTube
The essential parts of an EWT are displayed in Figure 14a. The ring-shaped cathode and
the cooling circuit of the anode are typical features of EWT construction. The latter
consists of a closed circuit lled with deionized water. Deionized water is necessary to
reduce the conductivity and enhance the safety because the circuit is at anode potential!
Electrons are diverted to the anode surface by electron-optics elements. Because the la-
ment and window are at equal potential, no electrons hit the window. Heating is mainly by
radiation from the anode, and an external cooling circuit is provided, which may be
connected to normal water supplies because it is not in contact with a voltage source.
Although the construction just described is in a common use now, it cannot be
considered as an ideal source of x-rays. Recently, van Sprang and Bekkers (1998) and
Kuczumow et al. (2000) have discussed the deviations from the homogeneity in the end-
window x-ray tube output. The geometry of the excitation system, as described by an
angle supported on the tube axis the sample point the goniometer entrance axis,
deviates from the formal geometry (about 83
). The real, not formal, geometry of the

device can be read out from the shift in the Compton-scatter energy. It creates the
special demands for all the constructors of microprobes and milliprobes. They must
avoid using the conventional end-window tube. There are also the consequences for the
normal analysis: The uniformity of the samples and spinning operation are essential for
getting reproducible results. Otherwise, particular spots on a surface of the sample can
be irradiated in a dierent manner.
4. Side-WindowTube
An expanded view of a SWT is shown in Figure 14b. The essential dierences from an
EWT are the distance between cathode and anode, an earthed anode, and a single cooling
circuit for the anode only. This circuit may be directly connected to the normal water
supply because it is at ground potential. The geometric arrangement of the cathode
supports higher potentials of the cathode with respect to the anode. This is the basic
reason that tube potentials of 100 kV are allowed. Side-window tubes with ne-focus
anodes are used in many microprobe constructions. They are appreciated for their photon
output, easy to transform into a parallel, collimated beam. A consequence of the regulated
anode potentials is the possibility of use of dual anodes. The available dual-anode tubes
are summarized later in Table 10.
5. Tubeswith Rotating Anode
The electrical input in an x-ray generator is high; however, a nal output of about 1% of
primary power is not very impressive. This must be due to the low eciency of conversion
of the electrical energy into the energy of x-ray photons. One should remember that
photon losses are even much greater in further parts of the spectrometer (especially
Figure13 Anode elements deposited on the beryllium window.
Figure14 Different types of construction of commercial x-ray tubes: (a) end-window tube (EWT)
(courtesy of Siemens AG); (b) side-window tube (SWT) (courtesy of Philips Analytical); (c) target
transmission tube (TTT) (courtesy of Philips Analytical); (d) tube with a rotating anode (Vekemans
2000 courtesy of B. Vekemans).
in collimators and crystals). The desparate need for more ecient excitation sources
emerges with many more subtle applications of x-rays: the microprobe constructions,
(micro)diraction experiments with organic or biochemical materials, research on the ne
structure of the absorption edge, focusing of x-rays, or the application of the total
reection, for example. If one does not have access to the synchrotron, no patience to wait
for the beam time or no money for paying great sums for simple analyses, then the tube
with a rotating anode seems to be the best solution.
Figure14 Continued
According to our knowledge, three companies, Rigaku, Siemens, and Enraf-Nonius,
constructed high-power tubes with a rotating anode. The anode, in the shape of a wide
cylinder placed on a narrower cylindrical rotary shaft, can rotate with a speed of 100 rps.
Mo, Cu, and Ag are the materials most frequently applied for the construction of the
anodes. The sides of the anode are under intensive electron bombardment, but the high
heat load is dissipated by the intensive rotation coupled with cooling by water, owing
inside the anode with a rate of 815 L=min. The system is evacuated by a prevacuum oil-
rotary pump followed by a turbo-molecular pump. It enables one to work with a voltage
of 60 kV and a current of 300 mA, sometimes even greater. It gives a power of the order of
2030 kW. Recently, the most powerful generator available is the Ru-1500 by Rigaku with
a 90-kW load. The application of power of the order of 2030 kW means roughly a 10-fold
increase in the intensity as compared to the conventional x-ray tubes. When coupled with a
Kumakhov lens, rotating anode tubes can be used as a powerful microfocusing source.
6. Compact Flash X-Ray Sources
An x-ray tube is a very conventional x-ray source, dating back to the times of Ro ntgen and
Coolidge. The eorts described earlier aimed at a better and more ecient construction of
the x-ray tube. Dierent versions of the tube were by no means the only solution for
constructing a better and more convenient source. The most pronounced progress of the
last decades is the synchrotron, but it is still far from an ideal device in terms of price and
size. Much more promising for most XRF laboratories seems to be a compact ash x-ray
source (Germer, 1979). Such sources are now being developed intensively, giving, for
example, a ux of photons with energies between a few kiloelectron volts to 200 keV, in
pulses lasting between 10 and 50 ns, with a repetition frequency up to 50 Hz. Doses are
very intensive, up to several roentgens per shot (Pouvesle et al., 1996). Primary x-rays from
Figure14 Continued
such sources can be used for the excitation of x-ray uorescence, being especially useful for
real-time monitoring of kinetics of fast processes in ballistics and in the simulation of
accidents. It seems that the polycapillary x-ray focusing waveguide would be an ideal
supplement to this kind of x-ray source, giving the impetus for the development of a new
generation of pulse x-ray spectrometer. This device would combine the time resolution of
the source with the spatial resolution of the focusing polycapillary semilens.
7. High-Voltage Generator
A high-voltage generator supplying up to 60 kV for an EWT or up to 100 kV for a SWT
and an output power of 34 kW (or much lower, 0.2 kW for TTT tubes) is required. A
special generator is needed if one wants the high-power rotating anode tube. The con-
ventional power supplies were very cumbersome because of the size of the transformer.
The new generation belongs to the so-called switched power supplies. Such a power supply
is basically a dc=dc converter in which a dc voltage is electronically switched at high
frequencies (several kilohertz) and fed into an inductancecapacitance network. The
output power is not continuously regulated but is controlled through pulse-width mod-
ulation. One possible scheme of a switched power supply is given in Figure 15. The mains
are rectied (a), high-frequency switched (b), transformed (c), and rectied and smoothed
(d). The output voltage is sensed (e) and compared to a reference voltage (f), and this
signal monitors the pulse-width modulator (g), which, in turn, commands the switching
circuit (b). In the high-frequency transformer, a ferrite core is used; this is a lightweight
component. The whole setup allows the size of the generator to be reduced to a fraction of
the volume of classical generators.
The whole system is generally monitored by microprocessor. Power switching of the
tube is done preferentially along the isowatt curve (constant input power), all under
microprocessor control. The system has a number of safety switches on ow and tem-
perature controllers of cooling water with microswitches on all panels, which when
Figure15 Principle of switched power supply: dc=dc convertor.
removed could expose the customer either to the electrical circuitry (high voltage of the
tube supply or the mains voltage) or to unacceptable radiation levels.
B. X-rayTube Spectrum
The rst attempts to propose a quantitative description of the tube intensity as a function
of wavelength were made by Kulenkamp (1922) and Kramers (1923). The quantitative
treatment of intensities of uorescent x-rays (obtained by polychromatic excitation) by
fundamental parameter programs requires knowledge of the intensity function of the
exciting beam. This explains the continuous interest in the rigorous functional or nu-
merical description of the tube spectrum.
The description of the tube spectrum is divided into two parts, the rst concerning
the continuum spectrum [bremsstrahlung; see Seltzer and Berger (1985)] and the second
concerning the characteristic lines of the anode material superimposed on the con-
tinuum. The relative importance of these two contributions depends on the target ele-
ment: For a tungsten target, the characteristic L lines constitute the minority of the
emitted radiation, about 24%, and the K lines from the copper tube represent about
60% of the emitted radiation at 45 kV. The most popular Rh x-ray tube derives about
4% of the emitted x-rays as RhK and 20% as RhL photons; the rest is emitted as
bremsstrahlung (45 kV). The positive side of the latter tube is its relatively good output
of the low-energy photons, with a possibility of the excitation of the lines of heavier
elements by RhK lines.
In the continuum research, the main eort was focused on the accuracy of Kramers
law. Some deviations of this law from experimental results were corrected by the
introduction of a nonintegral exponent m in the wavelength-dependent term in Kramers
law (Brunetto and Riveros, 1984):
N
l
/
Z
r
l
2
l
l
0
1
_ _
Kramers law 4a
N
l
/
Z
r
l
2
l
l
0
1
_ _
m
Brunettos result 4b
where l
0
is the wavelength at the short-wavelength (high energy) end of the continuum and
r and m are constants related to the power-dependent terms: atomic number Z and energy
function, respectively. The constants were determined by tting the theoretical curves to
the experimental results. Brunetto and Riveros result was conrmed later by Tertian and
Broll (Tertian and Broll, 1984). By no means does it exhaust the solutions; Many other
descriptions of bremsstrahlung spectra have also been published; to mention only the best
known, there are those by Rao-Sahib and Wittry (1972), Reed and Ware (1973), Fiori et al.
(1976), and Statham (1976a, 1976b). Finally, the reader can nd the interesting articles by
Small et al. (1987) and Trincavelli et al. (1998) summarizing the state of the art in this area.
Other corrections must be added to Eqs. (4): the absorption correction [often that of
Philibert; see Pella et al. (1985) and Markowicz and Van Grieken (1984)] and the ex-
ponential correction term including the absorption of the beryllium window.
Furthermore, in the article by Pella et al. (1986), an interesting algorithm was pro-
posed for taking the characteristic line intensities into account. For this purpose, these
authors made use of the equation proposed by Green and Cosslett (1961). The ratio of
peak to background intensity was found to be a function of overvoltage U
0
and atomic
number Z:
N
char
N
con
exp 0:5
U
0
1
1:17U
0
3:2
_ _
2
_ _
a
b Z
4
d
_ _
U
0
ln U
0
U
0
1
1
_ _
5
Overvoltage U
0
is the ratio of the initial electron energy E
0
to the excitation energy of
a given shell E
ex
. The symbols a, b, and d are experimentally determined constants. The
intrinsic merit of this formula is its dependence on the physical parameter U
0
and on Z [see
also the work by Murata and Shibahara (1981) with Monte Carlo estimations of the
penetration depth of electrons].
Recently, a series of papers on the numerical description of the tube output has been
published by Ebel et al. (1989) and Schomann et al. (1995, 1997). The solutions were
derived from the dierent depth distribution functions approximating the electron pene-
tration in anode materials.
Apart from all eorts concentrating on the numerical estimation of x-ray tube
emission, experimentally recorded spectra may always be used [collected in Gilfrich and
Birks (1968), Gilfrich et al. (1971), Gilfrich (1974), Brown et al. (1975), and Loomis and
Keith (1976)].
The same kind of calculation as for the spectral x-ray tube output is very helpful
for the description of the background in wavelength-dispersive XRF analysis. The
background is mainly determined by the scattered bremsstrahlung radiation from the
tube. The theoretical estimation of the continuous radiation should always be helpful
for solving background problems (Arai and Omote, 1988; Omote and Arai, 1989; Arai
and Shoji, 1990; Arai, 1991). Sometimes, the knowledge of background can be applied
for analytical aims (Kuczumow et al., 1992). In this case, a selected bremsstrahlung
channel provides quantitative (but not qualitative!) information about the sample
contents.
A similar approach has been applied in an article by Kuczumow et al. (1995) for the
extraction of the information included in the coherently scattered signal in the energy-
dispersive mode on the capillary version of x-ray spectrometry. A similar extraction of the
information from the Rayleigh signal in wavelength-dispersive XRF and from the selected
bremsstrahlung channel in the electron microprobe is possible as well (Kuczumow et al.,
1999). It concerns special samples (e.g., the biological ones) and the information obtained
is connected with the description of the matrix. It brings additional knowledge about the
density of matrix, which is sometimes of essential signicance in data evaluation. The
articles just mentioned described the analysis of tree rings and other similar periodic
structures, where the variability of the density of the matrix was, by far, more important
than the variability in the chemical composition.
C. Collimators and Masks
The wavelength-dispersive mode of operation depends strongly on rigorous geometric
constraints on goniometer construction and analyzing crystal. Ideally, only a parallel
beam of uorescence radiation should be diracted and stray radiation should be absent.
Stray radiation enhances the background. Diverging beams result in worsening of the
spectral resolution. Converging beams act in the same direction, but the latter are often
necessary for making microanalysis. If applied in such conditions, they demand a special
numerical treatment to obtain analytical results with a given level of condence. Useful
versions of fundamental parameter calculations for converging beams are now available
(Chang and Wittry, 1994).
Masks, which reduce the size of the uorescent beam in front of the collimator, cut
o x-rays emitted or scattered by an area larger than the sample area.
Three positions for collimators in the optical path of the spectrometer are possible:
(1) between the sample and the crystal, (2) between the crystal and the detector, and
sometimes (3) an auxiliary position between two detectors working in tandem. Collimators
are not the ideal devices because they deliver a divergent photon beam with the angle of
divergence a given by
a arctan
_
a
l
_
6
where a is the spacing between the blades and l is the length of the blades. In addition to
divergence, there is also a substantial loss of counts while passing the collimator; for ex-
ample, for a radiation of about 10 keV passing by a typical 10060.25 mm Soller colli-
mator, the transmission is close to 10
5
. On the bonus side of the use of collimators, it
must be said that the resolution is improved very substantially (see Fig. 16). Thus, one
needs to nd a compromise between better resolution and higher brightness. In the deter-
mination of light elements, for which the intensity is relatively low (because poor excita-
tion and ecient attenuation) but relatively well-spaced spectral lines exist, the demand for
intensity prevails over resolution and, whenever possible, a coarse collimator (or none at
all) is usually sucient. Further considerations on this topic are in Section III.D.2. related
to multilayers. In all focusing spectrometers (with curved crystals), the use of collimators is
superuous and the role of collimators is taken over by pinholes or slits.
D. Dispersive Elements
Both the primary photon beam derived from the x-ray tube (or another source of radia-
tion) and the secondary or uorescence beam derived from the sample can be mono-
chromatized. The monochromatization of the primary beam is not essential but can be
made for more ecient excitation of the selected elements by photons of chosen wave-
lengths or for radical simplication of calculation procedures (the fundamental parameter
calculation is then transformed to simple LachanceTraillTertian correction). Mono-
chromatization may be compared to the action of a narrow bandpass lter by which only a
small band of the whole spectrum is transmitted. The width of the bandpass is related to
the spectral resolution. A number of parameters characterizes this process.
Figure 16 Two spectra from the same sample demonstrate how an auxilliary collimator reduces
line overlap when measuring heavy elements (a) without and (b) with auxillary collimator. (Courtesy
of Phillips Analytical. From Phillips Materials.)
The ratio DE=E, where DE denotes the energy width of transmitted radiation band
and E the energy of photons to be transmitted (the mean energy in case of a wide band), is
called the relative spectral resolution of the monochromator. DE is generally expressed as
full width at half-maximum (FWHM) of the transmitted band (a peak in intensityenergy
representation). The reciprocal of spectral resolution, E=DE, is called the resolving power.
The same can be expressed in wavelength units as Dl=l by transformation through Eq. (3).
Both expressions are numerically equivalent but of opposite sign. For the wavelength-
dispersive spectrometer, the angular dispersion (Braggs dispersion) is important and is
obtained by dierentiation of Braggs law:
dW
dl

n
2d cos W
7
The monochromatization of the primary beam, if required, is made by the use of
lters or secondary targets. The absorption edges of the elements present in the lter
should be at lower wavelengths than the wavelength domain to be transmitted. Sec-
ondary targets emit their own characteristic radiation without a white background
(except the scattered part of the primary beam) and with a population density of peaks
depending on the atomic number of the secondary target. In both of these cases,
the monochromatization is far from being perfect. A relatively simple application of
double total reection from the quartz plates was proposed with success for mono-
chromatization in TXRF (Schwenke and Knoth, 1982). The criteria for the mono-
chromatization of the primary beam dier substantially, depending on the application.
They become very sharp in some methods of research [photoelectron spectroscopy, ex-
tended x-ray absorption ne structure (EXAFS)]. Then, the methods of mono-
chromatization of the beam are dierent also, depending very much on new discoveries
in x-ray and related optics. In general, the strong monochromatization of the beam is
associated with a great intensity loss and can be made for the very ecient sources of
x-rays as synchrotrons.
The eorts for the virtual numerical monochromatization of the real exciting beam
by the introduction of the so-called equivalent wavelength concept failed. A new
equivalent wavelength is needed for each analytical situation (e.g., change in composition).
The gain from the simplication of the spectrum is doubtful as compared with the great
increase in the numerical eort.
The monochromatization of the secondary beam is the key problem. Dispersion of
radiation is needed for the specic detection of characteristic lines. There are, however, a
number of analytical problems in which the requisite dispersion is low. In limited cases, it
may be sucient to subdivide the spectrum into two spectral windows, from which one is
to be detected. In other cases, the cutting o of a relatively wide spectral window may be
sucient, as is done in the Philips MiniMate device, where only a sealed gas proportional
counter is applied for the photon energy discrimination. In practice, this selection of wide
spectral domains is easily performed by energy-dispersive systems and pulse-height se-
lection, by lters or by a set of balanced lters. A spectrometer for general use over the
widest range of elements, however, should be equipped with monochromators of sucient
overall resolution, as is obtained by crystal diraction.
1. Crystals
According to the orientation to the possible crystallographic planes of the crystal, dierent
values for d are preferentially diracting and, coupled with it, a dierent resolution results
for a given wavelength. A few values has been calculated for LiF in dierent orientations
and these are listed in Table 2. From the dispersion, it can be expected that the Ka line of
manganese can be separated from the chromium Kb by LiF (220), not by LiF (200). The
values in Table 2 are calculated for ideal crystals and a parallel beam. For real crystals, the
dispersion and resolving power are less favorable; some real values for a complete spec-
trometer are provided later. In Table 3, a list is presented for crystals currently available
for spectrometers: lithium uoride (LiF), silicon (Si), germanium (Ge), pyrolytic graphite
(PG), indium antimonide (InSb), pentaerythritol (PE or PET), ethylenediamine-d-tartrate
(EDDT), ammonium dihydrogen phosphate (ADP), thallium hydrogen phosphate
(TlAP), and multilayers with their commercial designations. Important characteristics
other than the interplanar distances codetermine the ultimate usefulness of an analyzing
crystal: spectral resolution, mosaicity, reectivity, stability, the thermal expansion coe-
cient, and the spectral range.
a. Resolution
The spectral resolution DE=E of the crystals oscillates about the value 10
2
, with few
exceptions. The data for the resolution of dierent crystals are included later in
Figure 26a, a summarizing gure on resolution [see also Kuczumow and Helsen (1989)].
The spectral resolution for the crystals is, generally speaking, better than that of other
dispersive devices, such as detectors or lters, but the dierence with respect to the
energy-dispersive spectrometers becomes less favorable for the short wavelengths. The
progress in superconducting tunnel junctions detectors (Finkbeiner et al., 1991; De
Korte, 1992; Le Grand et al., 1993) and microcalorimeter detectors (Lessyna et al., 1993;
McCammon et al., 1993; Silver et al., 1996) during the last decade shows that these
devices would have even better spectral resolution in the medium energy range (i.e.,
above 45 keV) than the crystals (see Fig. 26b). However, it is a question of compromise
among price, necessity to work at liquid-helium temperatures, the very value of spectral
resolution necessary for a given analysis, and the loss of intensity in crystals on one
hand and the poor count rates allowed in the newest detectors on the other hand, which
decides what kind of resolving device will be the future choice for commercial appli-
cations.
b. Mosaicity and Reectivity
Real crystals have all kinds of imperfections, and mosaicity is one of them. Mosaicity
refers to the existence of blocks within the crystal with sizes of the order of magnitude
of 100 A
, which have slightly dierent orientations and lead to widening the diracted
peaks. This happens to widely diering degress: topaz, EDDT, ADP, and gypsum exhibit
low mosaicity, quartz and LiF a little higher mosaicity, and PET a signicantly higher
Table 2 LiF: d Spacings for Different Orientations and Angular
Dispersion
Crystal 2d (A
) Dispersion
LiF (422) 1.652
LiF (420) 1.800
LiF (220) 2.848 0.5154
LiF (200) 4.027 0.2902
Note: Calculated for W angles corresponding to MnKa (2.102 A
) and n 1.
mosaicity. A result is a slight angular widening of the diracted peak on one hand, but on
the other hand, the intensity of the peak is generally enhanced. Widening is smaller than
widening due to other geometric factors of the whole spectrometer and the loss can be
tolerated while compensated by the increase in intensity. Some mechanical treatments
enhance the mosaicity, and LiF crystals are easily improved in that way. The angular
intensity distribution of a diracted peak, the rocking curve, can be determined by double-
crystal spectrometer. In Figure 17, the peak height of the represented curve obtained by a
high-resolution spectrometer is determined by atomic scatter factors and the space group
of the analyzing crystal, whereas the width at half-maximum is determined by the mo-
saicity of the analyzing crystal and the divergence of the incident and diracted beams.
The surface under the curve is the integral reection or, when the curve is normalized to
the intensity of the incident beam, the integral reection coecient. This coecient is very
much dependent on mosaicity. Abraded LiF has a 10-fold increase in the reection
coecient compared to freshly cleaved LiF (3610
5
to 4610
4
rad), measured by using
CuKa radiation (Birks, 1969). LiF crystals have also the great advantage of low ab-
sorption by their constituting atoms. Topaz and quartz, otherwise good crystals, have
Table 3 Currently Available Crystals
Crystal 2d (nm) Element range Remarks
LiF(420) 0.180 NiU High resolution, special applications for
heavy-element K lines
LiF(220)
a
0.2848 VU High resolution, good intensity
LiF(200)
a
0.4027 KU General purpose, wide range, best diffracted
intensity
Si(111) 0.6271 P, S, Cl Supresses even orders
Ge(111)
a,b
0.6532 P, S, Cl Supresses even orders, good for
intermediate- and low-Z elements
PG(002)
a
0.6708 P, S, Cl Good intensity, poor resolution
InSb(111)
a,b
0.784 Si
PET(002)
b
0.8742 AlCl Good intensity, low spectral contamination,
soft
EDDT(020) 0.8808 AlCl Lower intensity than PET, problems with
stability
ADP(101) 1.064 Mg Still lower intensity
TIAP(100) 2.575 OMg Especially F, Na, Mg, poisonous
PbSt 10.0 F, C Good resolution, low intensity
LTC 15.6 Up to Be Longest wavelengths known for
semicrystals structures
PX-1
a
4.93 OMg Low resolution, good intensity
PX-3
a
19.5 B Low resolution, good intensity
PX-4
a
12.2 C Low resolution, good intensity
OVO 55 5.5 Mg, Na, F Low resolution, good intensity
OVO 100 10.0 C, O Low resolution, good intensity
OVO 160 16.0 B, C Low resolution, good intensity
OVO H300 30.0 Be, B One of the largest 2d available up to now
PX6
a
Also available as curved in simultaneous instruments.
b
Also available as transversely curved for sequential instruments.
poor reectivity properties, whereas PET is very good in this respect. Reection constants
as a function of wavelength are given in Figure 18.
c. Stability and Temperature
The mechanical stability of most crystals is satisfactory, but there are exceptions. Gypsum
can eoresce (especially in a high vacuum); PET has a tendency to change phases on aging
Figure 17 Rocking curve that would be obtained from a real crystal-diffracting parallel
monochromatic radiation (rocking curves are actually measured on double-crystal spectrometers):
Pthe peak diffraction coefficient; Rthe integral reflection coefficient. (From Birks, 1969.)
Figure18 Single-crystal integral reflection coefficients of graphite, LiF (200), LiF (220), and KAP.
[From Gilfrich et al., 1971). Reprinted by permission of Analytical Chemistry. Copyright #
American Chemical Society.]
and it is soft so that it is easily damaged when manipulated. The temperature inside the
measuring chamber of a spectrometer is kept as constant as necessary (<1 or <0.01
C if
chemical peak shifts have to be measured). In these circumstances, damage of the organic
crystals by high temperature is not likely to occur. When very precise measurements of
peak position are to be made for speciation purposes, the thermal-expansion coecient is
important. PET is very disadvantageous in this respect; topaz is in the opposite situation.
It should be noted that the characteristic spectral lines of the crystal can be super-
imposed on the spectrum, making it obscure or even unt to use, especially when it
suggests the presence of some elements in a false way. Crystals of excellent resolving
features, Be and Ge (111), have their own lines in the soft x-ray region.
d. Spectral Range
The useful spectral range covered by one crystal is limited. The maximum wavelength is of
trigonometric origin and is imposed by Braggs law, namely by the condition that sin W < 1
and l
max
< 2d. In practice, the goniometer is scanned for values of 2W varying from a few
degrees to about 150
. However, for higher values of 2W, an angular dispersion widens the

peak proles. On the contrary, in the low-2W range, only a small fraction of x-rays emitted
by the sample is intercepted unless the analyzing crystal is very long. The surface of the
crystal projected on a plane perpendicular to the x-ray beam may be smaller than the
width of the beam emerging from the collimator. Thus, 2W values as well as the macro-
scopic dimension determine the useful spectral range of a crystal.
For x-rays of low energies, the interplanar distances of real crystals become too
small. Some substances, namely salts of heavy metals with organic acids with long chains
(otherwise the soaps of heavy metals), can take over the role of dispersive structures if their
organic chains are regularly arranged. There are special techniques for making such
quasicrystals. The individual layers are called LangmuirBlodgett lms. The ends of hy-
drophobic chains of adjacent layers join each other, and the heavy metal ends are con-
nected to the next heavy-atom ends from the next molecules. Many features of such lms
depend on the length of the chain. A great number of similar structures with a wide variety
of interplanar distances 2d (up to 156 A
in the case of lead melissate) have been synthe-

sized. LangmuirBlodgett structures have dierent negative properties: for example, they
are soft and not very stable, strongly hydrophobic, and of low reectivity. Some of them,
like thallium adipate, are highly poisonous substances.
e. Curved Crystals and Other Focusing Systems
Not only are at crystals used in the goniometer. Some focusing systems, such as the
Johann, Johansson, and Cauchois arrangements, may be used (Fig. 19). Then, the crystal
must be curved, with the curvature radius equal to the diameter of the Rowland circle and,
at the same time, to the Bragg curvature, being half that of the Rowland circle. Three-
dimensional crystals can sometimes meet both of these conditions. The focusing arrange-
ments are extremely useful in all cases in which the sample area is small, losses of intensity
are prohibitive, and scanning over large angles is not necessary. In these arrangements,
x-rays are collected in one point by focusing on the detector. An obvious virtue of such an
arrangement is found in the analysis of small sample areas and by a using focused exciting
beam, as in electron or proton microprobes. In such situations, the curved crystal geometry
allows the collection of x-rays from a relatively large solid angle of diverging x-rays to a
small spot (Fig. 20). A consequence is that the collimators normally placed between the
sample and the crystal, and the crystal and the detector must be replaced by slits and
pinholes. The focusing geometry is a very economical arrangement for saving intensity (the
brightness of such a device is estimated to be up to two orders of magnitude greater than
that of conventional at geometry). The curved crystal geometry is applied in simultaneous
instruments in which scanning is not used and an optimized arrangement is chosen for each
wavelength (element) implemented. Then, logarithmically curved crystals are used. In a
new version of the sequential instrument (Venus), Philips used the reverted channels taken
from the simultaneous instrument. Crystals applied in that construction are curved as in a
simultaneous device and their position is additionally adjusted by a screw to trap as much
intensity as possible. In general, during the last two decades, great progress took place in
the planning and construction of the optical elements based on curved reecting or dif-
fracting surfaces of crystals and multilayers; most of the developments were in the syn-
chrotron version of x-ray spectroscopy (Ice and Sparks, 1984).
The curved crystal version of the x-ray microprobe is not the only known solution. The
progress in x-ray optics during last decades enabled the easy concentration of x-rays while
being transmitted through a single capillary (Rindby, 1986; Carpenter 1989; Thiel et al.,
1989) or even through a semilens based on the bundle of capillaries (Kumakhov and Ko-
marov, 1990; Yiming et al., 1994; Dagabov et al., 1995; Xunliang et al., 1995; X-Ray Optical
Systems Inc., 1997, 1998). This rst possibility, due to the great loss of intensity resulting
from a poor interception of the primary beam by the narrow inlet of a single capillary, is
limited to the energy-dispersive version of x-ray spectrometry (Attaelmanan et al., 1994).
The second version is more interesting from the point of view of WDXRF. A properly
curved capillary bundle can serve as a kind of semifocusing lens with a well-dened
Figure19 Curved crystal x-ray arrangements in (a) Johann, (b) Cauchois (in transmission), and (c)
Johansson version. S entrance slit of radiation; Dexit slit of diffracted radiation; d crystal
lattice spacing.
Figure 20 Focusing of x-rays by a logarithmically curved crystal. (Courtesy of Siemens AG.)
curvature and moderately-dened focus (Fig. 21). The intensity of the beam leaving the
lens is, of course, lower than the intensity derived from the x-ray tube, but still sucient
for many applications. Moreover, the primary collimator is removed in this system and the
gain from this removal is partially balancing the loss resulting from the bundle construction
and operation. One can estimate the focal distance f of such a lens as
df d
0
2 f y
cr
8
where d is the spot size, d
0
is the diameter of the capillary end, and y
cr
is the critical angle
of the total reection. As a rule, the polycapillary array is introduced to concentrate the
primary beam, but it can also be used for the collection of secondary x-rays outgoing from
the sample, before reaching the curved crystals in nonconventional arrangements.
2. Multilayers
The limitation of XRF analysis in the region of soft x-rays is one of the most serious
limitations of crystal monochromators, although none of the rst principles constituting
the background of XRF method puts this limitation explicitly. Moseleys law determines
the rules for qualitative analysis of any element except hydrogen and helium, and the
Shiraiwa and Fujino equations govern quantitative analysis. Irresolvable problems oc-
curred until the late eighties because of troublesome absorption, lack of an adequate
dispersive device, and bad detection while passing to longer wavelengths. The concept of
multilayers or, strictly speaking, layered synthetic microstructures (LSMs) or multilayer
interference mirrors (MIMs) solved at least part of the problems.
Two approaches to the idea of a suitable analyzing device in the soft x-ray domain
have been applied from the very beginning (Underwood and Barbee, 1981). The rst re-
sulted from consideration of Braggs equation [Eq. (2)]. This indicates that if any crystal of
a longer interplanar distance is found, it will be possible to disperse longer wavelengths in
the soft x-ray range. The potential candidates for long-period crystals or quasicrystals,
such as clay minerals of the chlorite (14 A
) or illitemontmorillonite (2530 A
) type, are
not suciently ordered in this respect (Weaver and Pollard, 1973). Unfortunately, natural
crystals, irrespective of their dierent crystallographic planes, oer only limited possibi-
lities in this spectral range; specically, their reectivity is very low. The class of structures
called LangmuirBlodgett lms was more promising, but the reectivity and thermal,
mechanical, and chemical stabilities were rather poor.
Figure 21 Cross section of a typical multicapillary lens: (a) focusing configuration, from wide
spot (divergent source) to another spot (semifocus); (b) configuration transforming the divergent
into the parallel beam. (Courtesy of X-Ray Optical Systems Inc., Albany, NY. and personally from
Dr. J. P. Bly.)
A correct solution resulted from generalization of Braggs law, namely that dif-
fraction also occurs in media consisting of layers of dierent refraction coecientsin
other words, in sites of dierent periodically changing electron densities. Such structures
may be formed in an articial way. They may be treated as crystallike substances ordered
along the c axis (i.e., spacing d or 2d), but with uncontrolled arrangement within the
ab plane. The structure in the ab plane can be amorphous, provided that the optical and
mechanical properties are uniform in these directions.
The rst eort of synthesis was made in 1940, but the AuCu multilayer of Du
Mond and Youtz (1940) did not survive more than a few days because of deterioration by
interdiusion. The problems of thermal, radiative, diusional, and chemical instabilities
of multilayers have recently been solved. Signicant progress in this eld has taken place
in the last three decades, hence some years before the application of multilayers in
WDXRF.
The second approach was the result of an increasing interest in x-ray optics. As a
branch of physics, x-ray optics is nearly as old as the discovery by Ro ntgen, but because of
the specic properties of x-rays, its progress has been slow. All existing substances exhibit
complex refractive indices:
m 1 d ib 9
where m is the refraction index, d is the so-called unit decreament, a real number, and the
imaginary term b is related to absorption. The refraction indices in the x-ray region are all
below but very close to 1. This makes all eorts of x-ray focusing by lenses in a traditional
sense an impractical task. Franks (1977) gives an example of a lens with a curvature radius
of 10 mm built of a material with d 5 10
5
. The focal length of this lens is 100 m. In
such a situation, only glancing, grazing, and diracting features of materials have been of
practical interest for a long time. Otherwise, the grazing optics conditions for x-rays are
extremely severe. However, the need for mirrors, monochromators, and focusing devices
for the x-ray region is increasing rapidly in the elds of synchrotron radiation, plasma
research and diagnostics, x-ray microscopy, x-ray uorescence analysis, diraction, thermo-
nuclear fusion, x-ray laser, x-ray astronomy, and even x-ray waveguides. The invention of
multilayers dened this time as a complex set of particular layers consisting of materials of
periodically dierent refractive indices gave great impetus to progress in this branch of
optics. Some important properties of the materials used to produce the multilayers are
discussed in the next section.
a. Nature of Materials
In principle, three kinds of material are necessary for the synthesis of multilayers. First,
there must be a support (sometimes called a substrate), such as a piece of at or curved
silica layer, with an ideally polished surface. This condition is very important because the
roughness of the surface is translated to the deposited layers, correctable almost ex-
clusively when one of the layers consists of amorphous materials such as carbon. After
years of progress in the eld, when the roughness of the interfaces have probably reached
the limit of about 2 A
, the most important contribution in it is from the deviations of the

substrate from atness (Kortright, 1996). Two sources of relatively inexpensive and pre-
cisely polished supports were found: silicon wafers as used in microelectronics (curved)
and glass or fused-silica optical elements for low-scatter mirrors (at or curved). The
additional polishing is the last step in the preparation of the substrate for further manu-
facturing of the multilayer. An even more complicated role for the substrate is described
by Nicolosi et al. (1986) in whole coal analysis. The authors determined the contents of
C, N, O, and F using multilayered microstructure PX2 and the contents of P, S, K, and Ca
by taking advantage of diracting properties of the supporting wafer of silicon (111) on
which the multilayer was settled.
Heavy metals (Hf, Pb, W, Mo, Pt, Ir, Ru, Rh, Os, Ni, Co, Fe, and Cr) and light
elements or compounds [Al, B, B
4
C (Ovonic Synthetic Materials Co., 1987), BN, Be, C, Si,
SiO
2
, SiC, Ti and Scthe last with the high reection] may be used as materials for al-
ternating high and low optical densities, at the same time being strong and weak scatterers,
respectively. Sometimes, materials from the rst group are called absorbers, and those
belonging to the second group are called spacers. The reactive materials and substances
with a low melting point are excluded from the list. Both components of the multilayer
should not share a common crystalographic structure, to avoid the epitaxial growth. The
selection rule for the materials can easily be understood from Figure 22 for boron. The
mass attenuation coecients for the boron K line, as presented versus the atomic number
of the absorber, have several minima. One falls in the region of boron (weak self-ab-
sorption) and carbon, and the next very deep minimum is in the region of nio-
bium=molybdenum. It puts the constraints on the materials, which can be used for the
determination of boron. The rst, a low-density material, can be carbon or even better
B
4
C; the second, a high-density material, should be niobium or molybdenum. Indeed,
Philips made the structure PX3, composed of Mo=B
4
C, with a period of 195 A
, adviced
for the determination of boron. However, when a new multilayer should be synthesized
Figure 22 Mass attenuation coefficient for the BKa line drawn against the possible absorbers in
the periodic table. Arrows show the deep minima in coefficient value. (Courtesy of Bruno Vrebos
inspiration.)
with high reectivity in mind, then the attention is put, instead, on a pair of materials with
a small value of the scattering DebyeWallner factor [see Eq. (10)]. Here, the W=B
4
C
tandem is a very good one. As a rule, the low-electron-density compounds are selected
from the elements with K absorption edges above the energy of spectral lines to be
measured. In that sense, boron and carbon are selected for multilayers of spacing above
50 A
and beryllium and carbon for spacings above 120 A
.
b. Smoothness
This parameter is of great importance on each level, starting from the supporting
substrate to the last upper layer. All rough places, uneven layers, disturbances in in-
terfaces, interdiusion, and chemical interaction regions or defects, act in a manner
analogous to the thermal motions in classical diraction analysis. During synthesis, the
extent of roughness can vary in a dierent manner: In some cases, it tends to
smoothness, in others to further growth. The use of amorphous materials to form some
layers favors smoothing. The greater interplanar distances are, the more pronounced
the roughness is. On the other hand, the smoothness probably has its limits, even in
the case of multilayers with relatively small interplanar distances, with the Debye
Wallner parameter s tending to reach a value of about 2 A
. It probably results from

the smoothness level obtained during the substrate production. Finally, it puts some
domination of the DebyeWallner parameter over other possible factors inuencing the
quality of multilayers in the region where the interplanar distance is not very long (say,
a few tens of angstroms).
c. Reectivity and Thickness of a Multilayer
Classical dispersive crystals exhibit low reectivity in the soft x-ray range. The situation
was greatly improved in multilayer reectors in which a single layer at normal in-
cidence angles exhibits a reection coecient of the order of 10
4
rad. This coecient
is, however, proportional to the square of the electrical eld amplitude (i.e., to a value
of the order of 10
2
for the amplitude reection coecient). Thus, a multilayer con-
sisting of 100 single layers may provide almost the maximum reectivity if the ab-
sorption can be neglected (Underwood and Atwood, 1984; Underwood, 1986,
http:==www-cxro.lbl.gov==multilayer=survey.html, 1998). For long wavelengths, the re-
sults are not so impressive; for example, in the very important region of the so-called
water window (284530 eV), the reection coecient was lower than 3% (Kozhevnikov
et al., 1994). The region is of essential signicance for the construction of an x-ray
microscope based on zone plates for biological research (Kirz et al., 1995). These re-
sults are in accordance with the calculations by Rosenbluth concerning numbers of
layers necessary for saturation of reectivity [data cited by Barbee (1986)]. Peak
reectivities of some commercially available multilayers [e.g., Philips materials PX1,
PX2 and PX3 (Nicolosi et al., 1986; Van Eenbergen and Volbert, 1987) and the
OVONYX line of multilayers [(Ovonic Synthetic Materials Co., 1987)] are often
compared to classical pseudocrystal dispersive structures, like lead octodecanate and
thallium acid phthalate. The predominance of the multilayer structures over classical
structures is striking, and spectral resolution is the only parameter in which the classic
crystals are better (Van Eenbergen and Volbert, 1987; Henke et al., 1986). Still, when
using multilayers, one must remember the weak points inherently coupled with those
devices: great refraction eects (Martins and Urch, 1992; Luck et al., 1992), deviating
the eective 2d value of the structure from the real value by as much as 5%, and
poorly shaped background with ghost lines in some cases.
d. Quality of Layers and Boundaries
The structure of the multilayer ought to exhibit geometric features. This condition is very
strict. Thus, at layers or gured structures must be uniform, the latter with controlled
curvature, without defects but with clearly dened optical parameters. All deviations
from an ideal model, easy to estimate by the reectivity characteristics, are, as a rule,
coupled by the use of the DebyeWaller factor into the eective roughness parameter s
e
,
including both thickness errors and imperfect boundaries (Spiller and Rosenbluth, 1986).
The DebyeWaller factor DW is the Gaussian-type term describing the reduction of re-
ected amplitude at a boundary:
DW exp 2
2ps cos a
l
_ _
2
_ _
10
where s is the width of a smooth transition layer and a is the propagation angle of
electromagnetic radiation, measured from the normal to the boundary between a medium
with one refractive index to another.
The question arises, however, whether the errors result from a rapid or from a mild
change of the optical features on the boundaries. Any roughness of a given layer decreases
its reectivity (Payne and Clemens, 1993), but a random distribution of roughness may
bear higher reectivities of the higher-order peaks. Moreover, many other physical factors
can inuence the uniformity and expected layer characteristics: Both the support and the
particular monolayers can have dierent slopes, densities are subject to uctuations, the
elements can diuse, or some chemical elements can mutually react (e.g., W with C or Mo
with Si) (Rosen et al., 1993). It should be emphasized that despite of so many obstacles,
the magnitude of the roughness in such a totally articial structure can be kept in the range
of an atom radius (Barbee, 1986).
The numerical description of multilayers is based on the matrix method (a matrix
expresses the features of a layer or interlayer region, and for the characteristics of a
multilayer, the product of matrices is written) or on the recursive use of layerreection
transmission characteristics. Deviations of empirical results (mainly reectivity measure-
ments) from the model predictions are associated with roughness. In this case, s
e
, the
roughness parameter, results from the best t of empirical data to the model.
The selection of an adequate method of synthesis and subsequent control of pro-
duction and quality is a key question. Many methods were checked, and the aim of all
these processes was the deposition in which one atom follows another. The physical vapor
condensation, chemical vapor deposition, electrochemical covering, and sequential ad-
sorption of lms are the most promising methods. However, for the time being, the rst
method prevails. Two basic versions of physical vapor deposition are usedwith thermal
and sputter sources. In the thermal source technique, the covering materials are evapo-
rated by electron beam or laser evaporation. The vapor source and samples are in a xed
position. The time of evaporation is a parameter controlled by shutters or by pulsed laser
irradiation. An in situ monitoring system was used as a feedback system for controlling the
shutter. Spiller (1981) invented a system for thermal deposition. He used a soft x-ray re-
ectometer (a source plus a detector), placed in an evaporation chamber to register the
reectivity of successive layers. The open loop is set according to the indications of
maximum reectivity for a given layer.
It is possible by this method to obtain a multilayer with an area up to 25 cm
2
.
The rates of deposition vary in the range of 2100 A
=s and must be carefully con-

trolled because the successive layers must be commensurate. Sometimes, especially
when multilayers of large surface are produced, a special motion of the substrate in the
evaporation chamber may be necessary to guarantee the same evaporation rate for all
points of the surface. Other diculties arise from this type of deposition: the high
vacuum required in the evaporation chamber (<10
2
Pa), radiation heating of the
deposited lm, and the problems with thermal sources (alloys may segregate during
melting).
The sputter source systems (Barbee, 1981) belong to another processing method. The
glow discharge, magnetron, electron cyclotron, ion beam, and triode devices may serve as
sputter sources. The plasma discharge is always the rst step of the process. The plasma
ux is directed by the electrical potential dierence to the cathode surface, where the ions
and atoms dislodge the maternal atoms. The secondary atoms and ions establish the
proper ux (Sigmund, 1981), which passes to the substrate to deposit a layer on it. Samples
are placed on a special rotatory table, appearing at xed intervals under the secondary ux
courses. The rotation speed, precisely controlled, is the regulating factor for a designated
thickness of the layer. The purity of secondary uxes and their energies also inuence the
quality of the multilayer. The main errors in this method result from the ion and atom
inclusion into layer (there are high-energy tails in the uxes) and from heating caused by
ux energy deposition in thin layers. However, substrate rotation may overcome many of
these defects. Sputter rates range from 1 to 20 A
=s; the covered surfaces may be quite

large. Today, the magnetron sputtering is the most common method, with the best results
obtained as far as the reectivity of the products is concerned.
After presenting two basic methods of layer formation, some attention must be paid
to methods of control. As mentioned earlier, reectivity estimations are of fundamental
importance in multilayer quality determination, both experimentally and in theory
(Spiller, 1981). A comparison of reectivity predicted and obtained in an experiment is
instructive, allowing, at least, understanding the source of the roughness (Henke et al.,
1986; Luck et al., 1992). Dierent peak, absolute, and integrated reectivities were mea-
sured with the use of both laboratory x-ray sources and synchrotron facilities. These re-
sults conrmed the layered structures of the synthesized materials; as a rule, reectivity
was smaller than predicted, but the results show that the optical parameters estimated
until now (Henke et al., 1982, 1988) are reasonably correct, with the shorter the wave-
length concerned, the better.
The methods just discussed only allow the deduction of an indirect image of the
multilayer structure. Other methods give direct insight into the structure. Thus, the dif-
fraction data may be very useful, but they require large sample volumes. Progress in ca-
pillary version of the diractometer (Bilderback et al., 1994), allowing the observation of
the samples as small as 5610
3
mm
3
, may bring a solution to the structural problems.
Very small samples are needed for obtaining the structural information by electron mi-
croscopy, especially in combination with a special technique of sample preparation, so-
called microcleavage (Lepe tre et al., 1986). Wedge-shaped strips of materials are placed in
the electron beam in such a manner that the planes of particular layers are parallel to the
beam direction. Both the transmission image and the diraction pattern can be obtained.
The in-depth and lateral variations, the roughness, and the visual image of the structure
are in the eld of observation. High-resolution electron microscopy can give even better
results, and electron energy loss spectroscopy (EELS) may provide the complementary
chemical information on the subsequent layers (Lepe tre et al., 1986).
Requirements for the application of multilayers in XRF may be summarized as
follows: They should satisfy Braggs law for the assumed wavelength domain within
permissible goniometer angles, have a high reectivity and a good spectral resolution,
suppress diraction peaks of higher order, and do not absorb soft radiation too in-
tensively. Flat or curved multilayers can be used. Dedicated designs are described in the
literature for the application of curved multilayer optics (Van Eenbergen and Volbert,
1987; Gilfrich et al., 1982). The geometric requirements imposed on the curvature of
multilayers for XRF are modest in comparison with their applications in other elds of
x-ray optics. The increasing spectral distance between K lines of the neighboring elements
when going to lower-Z elements may require a dedicated multilayer for each element.
Sometimes, great dierences in the mass attenuation coecients for the lines of neigh-
bouring elements of interest exist for a given materialattenuator. Then, one can con-
struct a multilayer eciently diracting the radiation of one element while deeply
suppressing it for other elements. The dedicated multilayers are the preferable choice for
the simultaneous WDXRF instrument, with an optimized channel for each element.
Multilayers can be also applied in a special version of WDXRF analysis, called grazing
emission x-ray analysis (de Bokx and Urbach, 1995). Curved multilayers are also used in
electron microprobes (Ovonic Synthetic Materials Co., 1987).
From what has just been described, it may be concluded that in order to analyze a
useful range of soft x-rays, at least three dierent multilayers have to be selected. Such
combinations are currently available commercially (e.g., for example from Osmic, Philips,
Siemens, Rigaku, and Shimadzu) (Ovonic Synthetic Materials Co., 1987; Van Eenbergen
and Volbert, 1987; D. K. G. de Boer, personal communication, 1998):
PX1 2d 49:3 A
oxygen to magnesium
PX3 2d 195 A
boron and possibly for beryllium (Nicolosi et al., 1987)

PX4 2d 122 A
carbon
PX5 2d 112 A
nitrogen
PX6 2d 300 A
beryllium
and from the Ovonic Synthetic Materials Company (1987):
OV-040A 2d 40 A
fluorine to silicon
with multilayers changing 2d spacing every 20 A
up to
OV-140B 2d 140 A
carbon to oxygen
and also the MoB
4
C structure:
OV-H series 2d 244 A
beryllium to boron
up to
OV-300H 2d 300 A
Probably, materials with even greater interplanar distances can also be supplied. However,
recent scientic (except the XRF eld) interest in multilayers is centered, instead, more on
multilayers with periods of 1020 A
for their excellent reectivity or for their polarizing

abilities (Scha fers et al., 1998).
These materials are described in the current literature as completely thermally stable;
thus, they do not need temperature stabilization when used in x-ray spectrometers
(Nicolosi et al., 1986; Barbee, 1986; Van Eenbergen and Volbert, 1987). Some sensitivity
to the damaging inuence of intense radiation [above 0.15 J=cm
2
(Kohler et al., 1985)],
conrmed later in an article by Kortright et al. (1991) and by a comprehensive report by
MacGowan et al. (1993), may limit the application of the multilayer for mono-
chromatization of dense ux of x-rays, which usually happens in synchrotron, plasma,
or laser research. Perhaps, the more important conclusion from the latter study is that,
after the impact of high power on multilayers, the amorphous carbon layer transforms
partially into a graphite form. It improves the reectivity but greatly deteriorates the
stability and changes the interplanar distances. The phenomenon of ultrafast graphitiza-
tion ( $40 ps) can, in the future, be applied for the construction of x-ray switches. These
data can be compared with the results cited in a report by Barbee (1986). He claims that
during the sputtering process of multilayer synthesis, very high temporary doses of energy
can be deposited in the layers (power density 10
5
W=cm
3
=s
1
), which involves a sig-
nicant increase in local temperatures (50180
C).
The relative spectral resolution of dispersive devices is often expressed in the form of
the important parameter DE=E or Dl=l, which is the basis for their choice in XRF ap-
plications. Unfortunately, this is the weakest point of the multilayer. In a commercially
available specimen, the relative spectral resolution changes from about 0.025 to over 0.1
while passing from structures with 2d 40 A
to those with 2d 244 A
, respectively, for
dierent measured lines (Ovonic Synthetic Materials Co., 1987), and for the structure with
2d 75 A
, it changes from 0.025 to 0.04 in the wavelength range 775 A
(Henke et al.,
1988), which is about three times worse (Ovonic Synthetic Materials Co., 1987) or even
more (Henke et al., 1986) than for a good classical pseudocrystal. The comparison of
spectra of the same sample by using multilayers with dierent spacings, as in Figure 23, is
very instructive (Van Eerbergen and Volbert, 1987). Relatively broad internal bandpasses
of multilayers diminish the resolution of the whole spectrographic device, seriously in-
creasing the detection limits. This is of special importance to the analysis of the L or M
series, and avoids the eorts to search the chemical shifts in x-ray spectra [although see
Habulibaz et al. (1996), where chemical shift is investigated for the SiL spectrum, dif-
fracted on a multilayer with an interplanar distance 300 A
]. The relatively wide bandpass

of the multilayer can be used in a constructive way. As proven by Vrebos (personal
communication, 1997; see Fig. 24), the imminent width of the BKa peak is so great that
the contribution from the secondary beam collimation to the total width of the signal is
negligible. In that situation, the analyst can remove the ne or medium collimation or
Figure 23 Comparison of sensitivity and resolution for layered synthetic microstructures with 2d
values of 5, 12, and 16 nm from bottom to top, respectively. Increased sensitivity together with
decreased resolution on the drop in 2d is evident. (From Van Eenbergen and Volbert, 1987.)
even the collimation completely. The gain is double. It results from the greater intensity
given by the multilayer as such, as well as from the lack of the collimator, which is always
one of the most intensity-restrictive parts of the WD spectrometer. This kind of work with
a limited collimation is possible only in the region of soft x-rays, where the population of
lines is rare and in the absence of the very soft L and M lines of heavier elements.
The suppression of higher-order diraction peaks gives better spectral purity and
may at least partially compensate for the poorer resolution of multilayers. The isolation of
the weak MgKa line from the dominant CaKa line is possible by the use of PX1 structure
for the analysis of cement (Fig. 25). This is an extreme example of the superiority of
multilayers over a classical crystal in particular cases (Nicolosi et al., 1986). Another great
advantage of multilayers is their great reectivity. It should be added that the peak re-
ectivity is 310 times greater than that of corresponding classical crystals.
Multilayers were frequently used in the routine determination of light elements.
Many examples can be cited, including carbon (Nicolosi et al., 1986, 1987; Van Eenbergen
and Volbert, 1987; Philips Application Note No. 745) and boron determination (Van
Eenbergen and Volbert, 1987; Nicolosi et al., 1987; Adamson et al., 1991; Philips Appli-
cation Note No. 737 and No. 803; Uhlig and Mu ller, 1991; van Sprang and Bekkers,
1998), and beryllium detection (Nicolosi et al., 1987; Siemens Lab Report X-ray Analysis,
1994; Anonymous article, The Rigaku J., 1997). In the analysis, advocated by Rigaku, the
application of the high-power 4-kW generator was the additional factor, enhancing the
detection power for beryllium determination. The detection limit for that element was
found to be in the region of a few tenths of a percent. Determinations of light elements
were made using both at optics sequential spectrometers and curved optics in simulta-
neous instruments (Van Eenbergen and Volbert, 1987). After overcoming the technical
diculties, the results obtained from such analyses may seem quite trivial (Nicolosi et al.,
1987; Bonvin et al., 1995). However, not always are things going in that usual way. Van
Sprang and Bekkers, (1998) emphasized the number of problems, coupled with light-ele-
Figure 24 Comparison of the spectra of the boron K line, obtained by a multilayer PX-3 with a
fine, medium, and coarse collimator. (Courtesy of Bruno Vrebos and Philips Analytical.)
ment determination. For the analysis of boron in glass, only the combination of methods
gave good results in a whole range of the detectable concentrations: The fundamental
parameter method using the uorescent signals for the low B concentrations and the use of
the incoherently scattered radiation as a measure of the light-element fraction above 4%.
One should note some special features of x-ray spectrometry in the soft x-ray range: The
type of analysis changes from bulk to surface measurements; the inuence of the chemical
state and the subsequent wavelength shifts on the analysis can be signicant; the wave-
length of soft x-rays is comparable to the surface roughness; and the problem of the
surface quality becomes extremely important.
Considering the so-called total information depth of x-rays [see Sec.IV.G.1, Eq. (19)],
it can be calculated that in the case of iron determination in a steel sample, the eective
energy of exciting photons being 20 keV, the secondary x-rays arriving at the detector
emerge from depths up to 62 mm. A carbon signal, emitted by a coal sample excited in the
same manner, emerges from depths of only 8.3 mm. The problem looks even more dra-
matic if carbon is determined in a steel sample: In this case, signals emerge from depths as
small as 0.45 mm! This means that the analytical volume for iron is about 140 times greater
than that for carbon and the information on both constituents really refers to totally
diering volumes of the steel sample. Moreover, the method of excitation is also critical in
this case: The excitation of light elements is most ecient if made with relatively
soft x-rays, the energy of which does not substantially exceed the value of the absorption
edge. Excitation by use of hard radiation is not protable in this case, as photons are
mainly stopped inside the sample. The most restricting stage is the very short escape path
of the characteristic photons for low-Z elements.
The eect of the chemical state can be observed during the analysis of some elements
using soft x-rays. The wavelengths of La
1,2
lines of chromium and manganese are 0.573
and 0.637 A
, respectively, and should be analyzed in the region otherwise reserved for the
Figure 25 2W scans for Mg in cement using TlAP and PX1. (From Nicolosi et al., 1986.)
K series of oxygen and uorine, hence by the use of the PX-1, PX-4 or OV-120B pseudo-
crystals. The question is whether the limited spectral resolution of multilayers is sucient
to show such subtle eects as chemical shifts and to separate the mentioned lines of metals
from the disturbing lines of oxygen or uorine if present in the sample.
The wavelengths of characteristic x-rays in the K series are longer than atomic radii
starting from Ga (GaKa 1.337 A
; atomic radius of Ga 1.26 A
) and passing to the

lighter elements. Radiation with a wavelength comparable to the dimensions of an ob-
stacle always result in surface problems, with scattering and diraction at the head. One
should take into account that even the most perfectly polished sample has a surface
roughness of the order of at least one atomic radius and that the best layers in multilayer
structures have a roughness, expressed as the eective roughness s
e
, on the order of one
to several atomic radii (Barbee, 1986; Kortright, 1996).
These latter remarks are not intended to weaken interest in multilayer optics and its
application in XRF, but only to evoke a special awareness of potential problems.
3. Spectral Resolution
Figure 26a shows the features of commonly used dispersive devise (Heinrich, 1981;
Caciuo et al., 1987; Plotnikow and Pszenicznyj, 1973; Fitzgerald and Gantzel, 1971;
Burkhalter and Campbell, 1967; Gohshi et al., 1982a, 1982b; Potts et al., 1985; Sparks,
1980; Salem and Lee, 1976; Bent, 1970; Bandas et al., 1978; Gilfrich, 1987). The width of
the bandpass DE (expressed as FWHM whenever possible) is plotted versus the energy of
radiation E; the parameter is relative to the spectral resolution DE=E. A line of given
value of DE=E is called the isoresolving line. These lines divide the whole gure into two
zones of dierent resolutions (or bandpasses). Note that both the typical dispersing
devices and typical detectors are collected in Figure 26a. Only a few detecting devices
with no resolving power (the reciprocal of the relative spectral resolution) at all exist
(e.g., Geiger-Mu ller counter), and no detector exists with perfect, innite resolving
power. Real dispersive devices exhibit very contrasting features, with the parameter
DE=E varying from almost 1 (scintillator counter or semiconductor photocathode) to
systems with DE=E as small as 10
4
[Ge (111) crystals and two- or three-crystal spec-
trometers]. Even better dispersive devices are needed, for example, for x-ray inelastic
scattering spectroscopy in which relative energy resolution near 10
7
is wanted. Indeed,
we can cite here some exemplary articles announcing the achievement of similar values:
1:14 10
7
at a level of $14:4 keV (Chumakov et al., 1996) or 2 10
8
for $ 25:7 keV
(Verbeni et al., 1996). XRF spectrometry has rather modest demands for resolution. We
see that for introducing the characteristics of the devices with spectral resolution on a
level of 10
8
in our diagram, the scale of Figure 26a should be prolonged by approxi-
mately four orders of magnitude at the bottom!
Another interesting conclusion can be drawn from Figure 26a. Nearly all dispersive
structures exhibit variable relative spectral resolution, but only KAP, topaz, and Ge
(111) crystals and, to some extent, also multilayer structures can be considered as iso-
resolving systems. The microcalorimeters show rather unusual behavior, compared with
other detectors. They have more or less the same absolute spectral resolution in the
whole useful range (220 keV). As we can see from the shape of the DK and DL curves,
nature does not demand isoresolving behavior from the dispersive structures. Rather,
these structures, with resolution curves parallel to the curves mentioned, would be op-
timal for spectrometric aims: The SiLi detector seems to have the better features.
Generally speaking, a bandpass range of 10
1
10
3
is considered analytically useful.
Systems with bandpasses below 10
3
are used only in spectrophysical work. For making
a proper choice of the dispersive structure for study of chemical shifts, one has to take
into account the curves DW and Ka
1
7Ka
2
(or even La
1
7La
2
) from Figure 26b. Figure
26b shows the spectral characteristics, extracted from Figure 26a, as a better demon-
stration of the immanent features of x-ray spectra. Depending on what matters in
analysis, the adequate choice of the resolving system should be made. The regions
occupied in the diagram by the most common [SiLi and crystal (e.g., LiF)] or most
promising (microcalorimeter) detectors are shown in Figure 26c for easier comparison
with data from Figure 26b. Figure 27 represents some example of the parallel analysis of
the same sample, based on spectra from the electron microprobe acquired by the
WDXRF system (TLAP), EDXRF system with Si(Li), and EDXRF system with the
Figure 26 (a) Spectral resolution of different devices: DZspectral difference between analogous
lines of adjacent elements; DWwidth of spectral line; Ka
1
7Ka
2
difference between Ka
1
and Ka
2
lines; (b) the imminent features of x-ray spectra extracted from (a) for better characterization of the
analytical demands; (c) characteristics of new microcalorimeter detectors as compared with typical
SiLi and LiF (200) dispersive structures.
microcalorimeter. For the time being, some preponderance of the LiF detector is ob-
served for light element determinations (below 4 keV) (Wollman et al., 1997), but even
this was endangered when Wollman announced the energy resolution of 2.0=0.1 eV
at 1.5 keV level (Wollman et al., 2000).
Spectral resolution is only one parameter determining the selection of a spectro-
meter. Other parameters, however, such as speed of measurement, count rate capability,
geometrical collection eciency, and ease of operation may aect the choice of the most
suitable instrument.
E. The Goniometer
The goniometer is basically a very simple construction and is the analog of a dif-
fractometer as used in x-ray diraction (the crystallographic research preceded the x-ray
uorescence method). The essential features are shown in Figure 7. The sample is posi-
tioned in front of the tube window. To account for possible heterogeneities, the sample is
Figure 26 Continued
spun about its axis at 30 rotations per minute. The analyzer crystal is positioned in the
center of the diractometer circle, rotates around an axis perpendicular to the plane of the
drawing, and passes through the macroscopic plane of the crystal. The detector moves
along the diractometer circle supported by the goniometer arm. As imposed by the Bragg
condition, the crystal rotates over an angle 2W, realizing equal angles of incidence and
diraction with respect to the crystal plane. The crystal is diracting the incident uor-
escent beam of the opening angle determined by the slit width and length of the collimator.
Rotation of crystal and detector are either mechanically coupled through gears with a
ratio of 1 : 2 or mechanically decoupled but moved by separate computer-controlled
stepping motors, but both arrangements are still implemented (cf. Tables 810 in Sec. VI).
The idea of mechanical decoupling and optical position control was rst introduced by
Applied Research Laboratories (see Sec. VI). This technique oers a number of ad-
vantages:
Alignment of crystals is no longer necessary. They can be positioned on a known
spectral line and the osets are memorized by the computer.
Figure 26 Continued
The detectors can be juxtaposed on the goniometer arm and brought into position as
required by the program. Tandem arrangement of ow and scintillation is no
longer necessary.
Slewing and scanning speed range is virtually unlimited.
Optical position control (Moire fringes or optical encoder) allows very high angular
precision and accuracy.
Low-energy radiation is strongly attenuated by air. The Ka radiation of a pure
copper sample (sample 1 2, measured on a Philips 1410 sequential spectrometer, SWT
with chromium anode, 45 kV and 60 mA) produces 67800, 33200, and 2660 cps, respec-
tively, in vacuum and 48000, 16800, and 890 cps, respectively, in air. The results mentioned
are not easily repeated on recent computer-monitored instruments (e.g., Philips 2400)
which do not routinely allow working under air at normal pressure. To decrease the ab-
sorption of photons, all wide-range spectrometers operate in a controlled atmosphere
(vacuum or helium). The vacuum cabinet contains the entire spectrometer, except for some
instruments such as the scintillator detector. Attenuation of the high-energy radiation is
low, and to reduce the size of the vacuum chamber, the scintillation detector was and still
is placed by some producers outside the chamber. A long rectangular window of a me-
chanically strong low-density polymer (Mylar) along the diractometer circle allows the
high-energy photons to reach the detector.
High angular precision and accuracy is required for positioning the goniometer arm;
therefore, severe mechanical constraints are imposed on its construction. Typical is an
Figure 27 (a) NIST microcalorimeter spectrum of AlGaAs (solid line) compared to parallelly
determined EDS spectrum [with commercial Si(Li) detector]; (b) WDS spectrum of the same sample
(with TLAP applied as a crystal), spectrum transformed from wavelength into energy representation.
Observe still a little better performance of the WDS spectrometer for the considered energy region
11.6 keV. (From Wollman et al., 1997.)
angular reproducibility of 0.001
or less and a mechanical resolution of a few thousands of

a degree or less (cf. Sec. VI). In most modern designs, 2W and W axes are decoupled.
Scanning (step size can be software selected) or measuring at preprogrammed positions
(e.g., element line, background left and right of the line for many elements) is possible.
Typical angular scan speeds (2W) are in the range from 0.1 to 180
=min and slewing speeds

can be up to 4800
=min. The slewing speed is the maximum rotation speed of the goni-
ometer arm for passing from one position to another without recording. The 2W range
covered is from 4
to 152
, with slight dierences between manufacturers. Because of the

high slewing speeds and full automation, the analysis time is severely reduced compared to
the older intsruments and, when not too many elements have to measured, is often not
prohibitively long.
Jenkins et al. (1984) and Croke and Nicolosi (1987) announced a dual-channel se-
quential spectrometer. A twin primary collimator was installed consisting of an upper, ne
collimator and a lower, coarse collimator. The beam is divided into two parts, each
striking its own crystal. Two crystals are mounted close together but with a 15
inclination
dierence. The diracted beams are detected by two detectors 30
apart. This xed angle

between both detectors, however, limits the benets of a dual-channel instrument.
Two alternative constructions should be discussed here. Simultaneous or multi-
channel instruments are equipped with monochromators set by the manufacturer (or by the
customer) at a xed position for the detection of a single element. Usually, curved crystal
optics are used, and the whole setup is optimized for that specic element with an ap-
propriate curved crystal, entrance and exit slits, and detector. The crystals are logarith-
mically or logarithmically and cylindrically curved as explained in Sec. III.D.1.e, see also
Figure 20. To give some more exibility to multichannel instruments, one or two channels
can be equipped with a scanner. The optics are either focusing (e.g., Bruker) or nonfocusing
(e.g., Philips). The at crystal arrangement is principally a reduced size of the normal
monochromator. The focusing arrangement is complicated by the fact that crystal and
detector must be moved to focus the diracted beam on the detector at any position. The
scan range of 2W for the Bruker scanner is 30
120
and 10
100
for the Philips scanner.

Full details of typical construction dierences are given in Sec. VI on instrumentation.
Two hybrid, dicult-to-classify spectrometers are discussed in this section:
MDX1000 (Oxford) and the Venus 100 (Philips). The so-called exi-channel of
MDX1000 is an energy-dispersive spectrometer. The Venus 100 has only xed channels,
but they are sequentially presented to the uorescent beam. Moreover, manufacturers are
focusing more and more on dedicated hyphenated instruments combining x-ray uores-
cence with diraction measurements, such is an ARL 8600S and Philips CubiX.
F. Detectors
The objective of a detector is the transformation of photon energy into an electrical pulse.
Pulses are counted over a period of time, and the count rate, expressed in counts per
second or any other unit of time, is a measure of the intensity of the detected x-ray beam.
From the theoretical point of view, the interaction of photons with matter is explained by
the particle character of electromagnetic radiation, not by its wave nature. Four main
classes of detectors may be distinguished for use in x-ray spectrometry according to the
medium responsible for the energy transformation: gas detectors, scintillation detectors,
semiconductor detectors, and recently introduced detectors supported on superconductive
elements (tunnel junctions and microcalorimeters). They dier in the eciency of detecting
photons of a given energy, determining the range of energy or wavelength for which they
are suited. The width of distribution of pulse amplitudes as a result of impact of photons
of the same energy determines the spectral resolution. Until recently, the best performance
in energy discrimination has been obtained with semiconductor detectors and the full
width at half-maximum (FWHM) is for the typical XRF domain in the range of 130 eV.
This allows electronic pulse-height selection discriminating the energy of the impacting
photons (at the expense of count rate, a maximum of 30 kcps). In WD spectrometers,
pulse-height discrimination is required for removal of noise of low amplitude and of
higher-order peaks of other elements interfering with the analytical line. It is a dis-
advantage typical for diraction spectrometers. High-resolution detectors are not required
in WD spectrometers because the interfering photons dier so substantially in energy that
moderate discrimination is sucient (a few hundred electron volts).
High-resolution detectors constitute the heart of energy-dispersive devices and are
discussed extensively in Chapter 3. Now, it is obvious that new types of device, super-
conductive junction detectors and microcalorimeters, exhibit energy discrimination an
order of magnitude better. Of course, in the future they might be the obvious choice in
applications demanding better spectral resolution, but the availability of the super-
conductive detectors is still a problem, as well as the maximum count rates they can
manage and their routine maintenance and price.
Only gas-lled and scintillation detectors will be discussed here as the devices sup-
plementing crystal dispersive operation. Some attention will be paid also to the micro-
calorimeter counters, because the stormy period in their development and because of the
prospects for the construction of the future generation of XRF (see Sec. VII).
1. Gas-Filled Detectors
In this type of detector, the energy-exchange process occurs between photons and gas
atoms or molecules in a strong electric eld. When a photon strikes an atom, there is a
given probability that the quantum of energy hn of the photon is imparted completely to
an orbital electron of the atom. As a result of this gain in energy, the electron emerges
from the atom with a kinetic energy of E
kin
hn W (Einsteins photoelectric equation).
W is the work function of the electron for leaving its orbital and is a specic constant of
the atom. In the case of argon,
Ar !
hn
Ar
The electron imparts its kinetic energy to other atoms, creating a series of electroncation
pairs on its path through the gas in a number equal to E
kin
divided by the energy needed to
expel an electron. Values for dierent gaseous and solid detector media are included in
Table 4 Effective Ionization Potentials (eV)
He 27.8
Ne 27.4
Ar 26.4
Kr 22.8
Xe 20.8
NaI (Tl) 50
Si (Li) 3.8
Ge 3
Table 4. Subsequently, the cations and electrons are accelerated toward the cathode and
anode of the detector by the gradient of the electrical eld between both electrodes,
forming the avalanches of new ion pairs on their way to the electrodes. The discharge at
the electrodes gives rise to a current pulse in the external electrical circuit. For a range of
electrode potentials, the current pulse is proportional to the energy of the photon, and in
spectrometers, the gas-lled detectors are exclusively used in this range. This is why these
detectors are called proportional counters. Above this potential, in the GeigerMu ller
plateau (Fig. 28), any photon entering the detector gives rise to a pulse of maximum
amplitude without relation to the initial photon energy. The ratio of the number of ion
pairs discharged at the electrodes to the ion pairs originally formed is called the ampli-
cation factor, generally denoted A. It is a complex exponential function of ionization
potential of the gas, anode potential, radii of detector chamber and anode wire, and the
mean free path of the electron. It implies that stability of applied potential and gas
pressure is very important for reducing statistical errors on pulse amplitude.
The basic parts of a gas-lled detector are a metal rectangular housing as cathode, a
thin wire passing through the central axis as an anode isolated from the cathode, a lling
gas, and a window either on one side or on two opposite sides of the housing. This gas
ows through or is enclosed in the housing (Fig. 29). The diameter of the anode wire
should be small. Realistic diameters are in the range of 4080 mm.
a. Flow-Proportional Counters
These detectors cover the widest wavelength range and are used in sequential spec-
trometers exclusively for long wavelength ( >2 A
) and also in simultaneous instru-

ments. The windows are made of thin foils of Mylar or polyester of 0.6, 1.5, 2 or 6 mm
or polypropylene 1, 2, or 6 mm thick. On the inner side, windows are coated with gold
or aluminum to create a homogeneous electrical eld inside the detector. Because of
these very thin windows, there is a leak of the lling gas that is compensated by a
Figure 28 Region of proportionality for gas detectors.
constant ow of gas through the counter (Fig. 29a). This is called a ow-proportional
counter. The gas is Ar with CH
4
at a concentration of 10%, and the ow is about
0.5 dm
3
=h. For detectors in simultaneous instruments, helium is also used, or 88%
He 12% CO
2
. For very specic applications, other combinations of gases may be
useful. The gas is stabilized for pressure, ow, and temperature. This is of signicance
because a 1% change in gas pressure or temperature introduces a much more serious
67% change in pulse amplitude, which can discredit the results of the analysis (Short,
1991). The amplication factor in the proportional range is between 10
2
and 10
6
. The
current pulse is conducted over a resistor by which it is converted into a voltage pulse
that is amplied, shaped, possibly discriminated in height, and counted. The count rate
is a maximum of 2610
6
cps. The operating voltages range from 1000 to 3000 V.
b. Sealed Proportional Detector
Basically, the construction is the same as in the ow-proportional detector but the win-
dows are thicker and no constant ow compensation for a leak is needed (Fig. 29b). The
gases used are Ne, Kr, and Xe with Al, Be, mica, Mylar, or polypropylene windows.
According to the element for which the radiation is to be detected, the most suitable
combination of crystal, gas, and windows is chosen; for example, a PET crystal with a Ne
detector with Al (for the determination of magnesium!) or a LiF (100) crystal with an Ar
or Kr detector and a Be window for the detection many of medium-Z elements. If the
lament is 80 mm thick, it is sti and easy to install, has a long lifetime, and is easily
exchanged.
Because the proportional counter is often used in tandem with a scintillation
counter, two windows are present on both sides of the main body. The absorption
Figure 29 Construction of proportional counters: (a) flow counter; (b) sealed counter.
probability of photons decreases with photon energy; the high-energy photons pass to the
scintillation counter through the proportional counter without being essentially absorbed.
The sealed detectors are applied in simultaneous instruments on their own and are not
used in tandem with a scintillation counter. There is no need for a tandem arrangement
because each channel is optimized for one element with the best-suited combination of
detector and crystal.
c. Pulse-Height Distribution
In the detector, a photon generates a number of ion pairs proportional to the pulse am-
plitude. The formation of ion pairs is subject to statistical uctuations, which means that
the number of pairs formed oscillates around the most probable value. A record of pulses
and their amplitudes as they emerge from the detector as a function of time is represented
in Figure 30. When these pulses are collected according to amplitude, a distribution
emerges as shown on the right side of Figure 30. The width of the distribution is measured
at half-maximum and is designated FWHM. This determines the energy resolution of the
detector. It is small for semiconductor detectors, such as Si(Li) (about 130150 eV for the
5.9-keV MnKa lines from a standard
55
Fe source; see Chapter 3), about 900 eV for gas
proportional counters, and 3500 eV for a scintillation counter, all measured for the same
photon energy. Note that this distribution diers from a distribution in intensity for
a normal spectral line (intensity versus wavelength) because of natural and instrumental
line broadening.
d. Escape Peak
As mentioned in the beginning of this section, a very probable method of energy exchange
between a photon and an atom of the counter gas is the removal of an outer-shell electron.
The probability of removal of inner-shell electrons is not zero, however, and this phe-
nomenon happens in a number of interactions, in which case the specic K or L radiation
is emitted. Because the wavelength of this radiation is on the long-wavelength side of the
absorption edge, the mass attenuation coecient is low and this characteristic photon has
a good chance of escaping from the detector. The remainder of the photon energy is
transferred to the electron of which the kinetic energy is generating a number of ion pairs
but necessarily in a smaller number as an electron having received the whole photon en-
ergy. Thus, a number of pulses is created, distributed around an amplitude proportional to
the energy of this electron. The absorption edge for ArK is 3203 eV; the energy of the
FeKa line is 6403 eV. Pulses centered around 6403 73203 3200 eV are generated, and
Figure 30 Amplitudetime record of impulses from the detector (left) and transformation of it
into a pulse-height distribution (right).
about 3200=26 123 ion pairs are formed, 26 eV being the energy needed per creation of
electronion pair. These pulses are present in the pulse-amplitude distribution as a second
maximum on the low-energy side of the iron peak position. For Ne, Kr, or Xe, photon
energies greater than 0.87, 14.32, or 35.58 keV, respectively, are needed to excite the K
radiation. For lower energies, only L radiation is excited, resulting in an escape peak closer
to the main pulse distribution. Due to the constant distance of escape peaks in relation to
their parent uorescence peaks and high intensity in some cases, they can be used
sometimes instead of the originals.
e. Pulse-Height Discrimination
The energy resolution of a proportional counter, a few hundred electron volts at least, is
not sucient for use in energy-dispersive spectrometers (but see the simplied MiniMate
construction by Philips). The spectral line separation in wavelength-dispersive spectro-
meters is done by the crystal monochromator. As is obvious from Braggs law, however,
higher-order lines of other elements and the continuum radiation of the tube may be
present in the same spectral window (angular position) of the crystal monochromator. In
spectrometry in the ultraviolet or visible region, the higher-order diractions of the
gratings are removed by lters. This is not easily done with x-rays. For the same angle 2W,
a second-order line has a substantially dierent wavelength or energy and is far enough
apart to give two distinct pulse-amplitude distributions at the exit of the counter. For
x-rays, electronic pulse-height selection or discrimination fullls the role of lters in the
optical region. The pulse-height analysis constitutes a necessary attribute to the wave-
length-dispersive systems. Within an interval of 0.1
around 2W 37
for LiF (200) as

analyzer crystal, we nd AuLa
1
in rst order, E 1:2764 keV, ThLg
8
in second order
E 0:6390 keV, SnKb
2
in third order, E 0:4259 keV, and LaKb2 in fourth order,
E 0:3201 keV. The energy dierence with the second-order line is 0.6374 keV and the
energy resolution of a proportional counter is about 0.3 keV. The electronic circuits of all
commercial instruments are able to discriminate between the pulses of both lines and,
consequently, also the other higher-order lines.
2. Scintillation Detectors
The energy exchange occurs in this type of detector in a medium of higher density and
with high-Z elements in the matrix, namely a thallium-doped sodium iodide [NaI(Tl)],
and as can be expected, this detector is only ecient for high-energy photons (<2 A
or >6 keV). The outer orbital electron for an iodide ion requires about 30 eV to be
knocked out. Hence, the originally ejected electron is imparted with almost all the
initial energy of the photon. The ejected electron dissipates its energy by promoting
valence-band electrons to an excited state 3 eV above ground level, an energy emitted
on deexcitation as a photon of 3 eV or l 410 nm. The intensity of the emitted light
pulse is proportional to the number of electrons excited by the x-ray photon
( hv=3 eV). The pulses are detected by a photomultiplier in which the light pulse
produces a few photoelectrons from the cathode material (e.g., indium antimonide).
These electrons are accelerated inside the vacuum tube between the cathode and the
rst intermediary anode, called a dynode (Fig. 31). They gain kinetic energy and
generate, in turn, a higher number of electrons from the dynode. This process is most
often repeated 10 times, resulting in a substantial multiplication of the original number
of electrons. The multiplication depends on the potential dierences between the suc-
cessive dynodes (100150 V), and the order of magnitude of this multiplication is 10
6
,
which is called the amplication factor A. In general, the photomultiplier is a front-end
tube, and the iodide crystal is in close contact with the tube window. The crystal itself
has on its outer faces a reective coating (but transparent for the photons above
6 keV) and a coating against moisture. In the external electronic circuit, the electrons
provoke a current pulse of which the amplitude is ultimately proportional to the energy
of the photon captured in the crystal. The conversion of the x-ray photons into a
current pulse occurs over dierent steps: the initial formation of a photoelectron
(I
!I
0
e
), the quantied dissipation of the kinetic energy of this electron in 3-eV

steps, emission of 410-nm light photons, the production of photoelectrons from the
photocathode of the photomultiplier, and the multiplication of electrons. Although the
production of the number of light photons in the crystal (hn=3 eV) is higher than the
number of ion pairs created in a ow counter (hv=30 eV), the subsequent conversion
into electrons is inecient and roughly 1 electron is produced for every 10 light
photons! The statistical errors of each process, particularly in the photomultiplier tube,
propagate into the error of the output current pulse, thus substantially widening the
distribution of pulse amplitudes and, consequently, reducing the spectral resolution.
The DE is approximately two to three times worse than for a ow-proportional counter
(see Fig. 26a), making a scintillation counter unsuitable for ED spectrometry. However,
the resolution is still sucient for a discrimination of higher-order spectra.
Hardware for pulse amplifying, shaping, and counting are much the same as for the
proportional counters. Also, an escape peak is present, with its energy equal to the initial
photon energy minus the energy at the iodine K absorption edge.
As already discussed, in many sequential spectrometers, ow-proportional and
scintillation detectors are used in tandem, coupled in dierent ways. In another
arrangement, both detectors are shifted over 30
. A secondary collimator is placed in front

of the scintillation detector but inside the vacuum chamber; the scintillation counter
is outside the chamber, but close to the exit window. According to the manufacturer
(Rigaku), this allows a gain in count rate of 15%.
3. Alternative Congurations
Some interesting modications of the detector have been proposed in the article by Ebel
et al. (1983). These authors considered the possibility of reducing count losses between
Figure 31 Layout of a scintillation counter.
analyzer crystal and detector (see Fig. 32) by removing the secondary collimator and al-
lowing the detector to collect a divergent beam and, at the same time, by using a position-
sensitive wire detector (with an energy resolution of 100 eV for detected photons with
energies of about 10 keV). Position-sensitive constructions are popular in many physical
applications, unfortunately not in the XRF eld. Potentially, it may lead to new solutions
for WDXRF.
Another interesting eort is the use of a scintillation gas instead of the scintillation
crystal (Kikkert, 1983; Palicarpo, 1978). This is the so-called gas-scintillation propor-
tional counter (GPSC). As is clear from Figure 26a, the resolution is substantially better
than that of its parents. The production of avalanches of ion pairs by the expelled
electrons is the same as described previously. The discharge currents at the electrodes are
not measured, however, but, rather, the scintillation pulses in the ultraviolet part of the
optical spectrum are detected by a photomultiplier as in other scintillation counters. An
essential dierence with conventional gas proportional counters is that the space charge
during the passage of a photon is avoided. The freedom-of-charge-related phenomena
enable using higher counting rates (up to 2.5610
4
cps; Dos Santos et al., 1993). The
lifetime of a GPSC can be quite long, up to several years, if there is no gas leakage in the
meantime. The ability to use counters with large windows positively dierentiates this
kind of construction from room-temperature solid-state detectors, such as HgI
2
. Their
pulse amplitude is also proportional to the energy of the incident photon. The counter
can be supplied with a digital rise-time discrimination analyzer to suppress the pulses
Figure 32 Geometry with position-sensitive detector: Tx-ray tube; specimen with point P
irradiated by primary x-rays; crystal; mp mirror plane; Mmirror point of P; PSDposition-
sensitive detector; l distance between mirror point and detector wire. (From Ebel et al., 1983.)
forming the background (Simo es et al., 1997). This results in a much better performance
of the counter.
4. Calorimetric X-ray Detectors
Calorimetric detectors operate in extreme conditionsat temperature of liquid helium.
The essential part of the device is a low-temperature, high-Z superconducting material
with a minimal heat capacity. X-rays, even single photons, are absorbed and their energy is
transferred to phonons. The detector is thermally coupled to a cold bath. The increase in
temperature, which results from the absorption, is measured and is proportional to the
energy of the photon. The temperature is measured by a doped semiconductor thermistor,
as small as possible to minimize its heat capacity. It converts the experienced temperature
change into a change in resistance. The thermalization time of the detector is in the range
of 150 ms, and the time necessary to equalize the temperature of the detector to that of the
cooling device is 100500 ms. There is an analogy to the dead time of gas-lled and gas-
scintillation detectors. Still, there is a possibility for that type of device to allow count rates
as high as 10
4
cps. Now, in more modern constructions (Irvin et al., 1996), the semi-
conductor thermistor is substituted by a superconducting transition-edge sensor (TES)
thermometer. It is a strip of superconductor material biased within the transition range
from the normal to superconductive state. The greater thermal sensitivity of the device
allows the use of normal metal absorbers as a rst stage of the detector. Unlike semi-
conductors and superconductors, metals can dissipate the absorbed energy into free-
electron excitations, not phonon ones. The free-electron deexcitation process is quick and
ecient. The use of TES leads to a change in the amplier: A less noisy superconducting
quantum-interference-device current amplier is introduced. As a whole, this new com-
binations exhibits a surprising feature: The energy resolution of the detector, as measured
for the MnKa line, is better than the thermodynamic energy uctuations in the micro-
calorimeter (7.2 eV in comparison with 10.4 eV). The total spectrometer eciency
obtained up to now is reaching 80% in some low-energy regions below 5 keV and can still
be improved.
Among all the detectors mentioned in the present chapter, this one does not make
use of the ionization phenomenon. Strictly speaking, this type of detectors can measure
energy transfers even in these processes, in which no ionization takes place. It has been
recently demonstrated for, e.g., particle detection and impact energy measurements in
time-of-ight mass spectrometry of single biomolecules (Hilton et al., 1998). The quantum
eciency of such an x-ray detector can be very good ( $95%) and the absolute spectral
resolution is $7 eV in the range 0.220 keV; see Figure 26b (Silver et al., 1997). The
expected absolute spectral resolution can potentially be even better than 1 eV in the
mentioned range (Moseley, 1984). Of course, we are fully aware that this type of detector
is not intended to compete with wavelength-dispersive systems, but we must emphasize
here that the time of unbeaten behavior of crystals over all other spectral-resolving devices
has gone. It seems to be a good place to present the comparison between wavelength and
most modern energy-dispersive detectors at their present status.
5. Dead Timeand Shift of MaximumPulse Amplitude
At high count rates (from a few thousand counts per second on!), the recorded count
rate deviates proportionally from the real count rate. The reason for this discrepancy is
the slow decay of the anode charge. Cation sheaths screen the cathode. This reduces the
eective voltage between the electrodes, resulting in a lower acceleration of the electrons
and, consequently, in a smaller number of ion pairs formed. Fouling of the anode wire
by impurities in the counter gas has the same eect. This phenomenon shifts the
maximum of the pulse-amplitude distribution to pulses from apparently lower-energy
photons. Moreover, when a photon is detected, the detector is, for a short time, unable
to detect the next incident photon. This period of time is called the dead time. The
value of the dead time is about 12 ms for scintillation counters, about 0.2 ms for
proportional counters, and $200 ms for a GeigerMu ller detector. To overcome this
problem, one can either choose another detector (but the choice is very limited), lower
the intensity of the exciting beam by masks or absorbers, change the geometry and the
optical arrangement (as is done in the case of synchrotron radiation), or use electronic
anticoincidence circuits or appropriate mathematical corrections. Now, after the in-
troduction of the high-power 4-kW option to the modern spectrometers, masks can be
inserted for the analysis of the major elements (e.g., in Shimadzu instruments). The
mask avoids problems with too great a count rate and its introduction is probably
easier than tube power change during the analysis.
The relation between the real and recorded count rate is
N
r

N
m
1 N
m
t
d
11
where N
r
is the real count rate (count=s or cps), N
m
is the measured count rate (cps), and
t
d
is the dead time (s).
If we allow a given level of discrepancy, say a%, then the following equation is valid:
a
100 a
N
r
t
d
12
The real count rate and dead time are thus connected by a hyperbolic relation. If the
allowed value of discrepancy must be kept constant, the left-hand side of the hyperbolic
equation is constant.
However, this is only part of the problem. As already stated, a photon, arriving just
at the end of the dead time, is registered with reduced amplitude. It is only after the so-
called recovery time that a new photon is registered with normal amplitude.
An improved method for calculation of the dead time was proposed by Bonetto and
Riveros (1984). These authors used the well-known fact that the second-order peaks are
signicantly less intensive than their rst-order analogs, but the ratio of the intensities
should be constant. If it is not constant, the deviation results fully from dead-time losses in
the rst-order signal. They derived the relation
N
m1
N
m2
B AN
m1
13
where B N
r1
=N
r2
and A Bt
d
. The indices 1 and 2 refer to the order of the spectrum.
A summary of the constituting parts of spectrometers and the wavelength ranges in
which they are used is given in Figure 33. Note that dierent excitation sources are used in
dierent branches of XRF, namely radioisotopes for EDXRF and tubes for WDXRF;
there are also examples of synchrotron radiation. The x-ray laser is mentioned, but its
appropriate version for XRF applications does not yet exist.
Figure 33 Review of different elements serving the construction of a spectrometer: optimal range
(crossed area), feasible range (hatched area), and possible range (open area). (Adapted from Bertin,
1975.)
IV. QUALITATIVE AND QUANTITATIVE ANALYSIS
In this section, we review a number of items important to both qualitative and quantitative
analyses. The qualitative application of XRF spectrometry is obvious. In simple cases,
quite unequivocal assignments of spectral lines can be made based on a library of Ka or La
lines or, in case of doubt, when an overlap exists, Kb or other L or M lines are checked to
conrm or reject a line assignment. A few more complex situations are discussed.
Quantitative analysis may also be simple. In the low-concentration range, quasilinear
relationships are found between intensity and concentration. The same holds for de-
terminations of higher concentrations but in a very narrow range for samples with quite
comparable matrices. Interpolation on standard curves, obtained on suitable standard
samples, allows a quick and suciently accurate quantitative determination. Another
intensityconcentration relation, valid for binary samples, is based on the relative in-
tensities of Ka and Kb lines in the case that the absorption edge of another element is
located in between these two lines. In these boundary cases, matrix eects are negligible or
interbalanced but always exist. In normal practice, they compromise the conversion of
intensity into concentration in such a way that more or less complicated mathematical
methods must be used for obtaining any accurate quantitative determination. The ap-
proach by fundamental parameter programs or correction algorithms is dealt with in
Chapter 5. Between simple qualitative work and rigorous quantitative work, however, an
area of applications is situated in which knowledge of the exact concentration or the
complete qualitative composition is less important than the overall aspect of a spectrum
for recognizing classes of samples (i.e., pattern recognition). An introductory discussion of
this aspect is given in this section. Another point of interest in qualitative as well as to
quantitative work is the measurement of the background. A good estimation of the
background is necessary for obtaining net count rates, but decreasing the background
allows lowering the detection limits. The origin and magnitude of the background is
bound to the physical processes involved in the method of excitation and, thus, indirectly
to the type of spectrometer. This aspect is also treated in this section. Finally, the said
disturbing phenomena associated with the excitation of uorescence radiation, as
bremsstrahlung and the scattered radiation, can be used to increase the total analytical
information and they also have some interesting applications.
A. Background
The background in WDXRF has four main sources: (1) the coherent and incoherent
scattering of source radiation, (2) the presence of characteristic radiation of other than
sample origin (materials of sample cup masks, sample cups, collimators, spectrometer
housing, for example), (3) the detector, and (4) environmental noise (i.e., resulting from
the threshold natural radiation of materials and even from a cosmic origin). The back-
ground from characteristic radiation from construction materials of the spectrometer can
be minimized by careful construction and geometric arrangement of the device. Scattering
from sample cup masks can eciently be reduced by masks in front of the primary col-
limator. This contribution is especially great when small samples are analyzed. The beam
mask reduces the irradiated area and may totally eliminate scatter from sample cup masks.
Higher-order scatter increases with increasing wavelength. Pulse-height selection, as ex-
plained earlier, supresses counts from higher-order diraction, but this technique is most
ecient in the long-wavelength region and is decreasingly ecient toward the short-wa-
velength end. The short-wavelengths contribution to the background can be reduced by
installing adequate lters. A 100-mm titanium foil removes the characteristic lines of
chromium from a chromium anode tube, signicantly improving the conditions for the
detection of Cr, Mn, Fe, Co, and Cu (Tertian and Claisse, 1982).
For Cr tube radiation and a LiF (200) analyzer crystal, removal of scattered chro-
mium radiation may be necessary when detecting the neighboring rst-order lines. As
Table 5 shows, not very many common elements are interfering. For steel analysis, only
manganese really represents a problem. Because chromium is present in prevailing con-
centrations in the environment (tube anode!), manganese determination is also dicult
with an aluminum lter. The simplest solution in such a case is the use of a LiF (220)
crystal with better resolution in this region (but also with lower intensity). If tubes with
other targets are used, tables are similar to Table 5 but with even more complex inter-
ference if targets like Mo and Rh are applied. The other elements listed in Table 5 refer
mostly to less common elements and less intense lines. Other higher-order lines may in-
terfere as well if the concentration of elements, from which the lines are derived, is high.
For special cases, a convenient combination of tube targets, analyzer crystals, and lters
can almost always be selected. Let us look at an example for the rhodium target tube. In
the determination of palladium, PdKa
1
overlaps with the Compton peak of RhKb
(Fig. 34). A molybdenum lter in the primary beam reduces this peak to a very small level,
allowing a perfect estimation of the location of the maximum and the determination of the
intensity of the palladium line.
Another ecient solution for background suppression is the use of linearly polarized
x-rays. An excellent example was given by Kno chel et al. (1983) and it is reproduced in
Figure 35. The analysis of nitrogen with a small concentration of xenon was made by a
synchrotron excited XRF. Some special geometries allowing the use of polarized x-rays
have been proposed by Wobrauschek and Aiginger (1980, 1983, 1985, 1986) for the more
conventional XRF spectrometers. For EDXRF systems, a special commercial polarizing
design is available (SPECTRO A.I. Gmbh). The subject is of great signicance to syn-
chrotron-based XRF and discussed as such in Chapter 8.
A careful estimation of the background is apparently the simplest way to take the
background into account! A rst approach, but with limited application, is measurement
on blankssimple at rst glance, but the adequate blank is often a rarity. Moreover, the
blank ought to have the same scattering properties. Intensive eorts for mathematical
modeling of background were performed but frequently for other purposes.
The most common method of background evaluation is the linear (or even non-
linear) interpolation from background countings at a suitable angle above and below the
peak position (suitable means not too far away for an easy linear interpolation, outside the
tailings of the peak, and not at the position of an adjacent peak). Consequently, a good
Table 5 Interfering Lines for CrKa and CrKb with LiF 200 crystal
CrKa DE (eV) D (
2W) CrKb DE (eV) D (
2W)
Pm La
2
10 0.05 Ho Ll <10 0.04
La Lb
2
30 0.31 Pr Lb
7
20 0.24
Ba Lg
5
40 0.60 Mn Ka 50 0.61
La Lb
7
30 0.23 Pm Lb
1
10 0.17
Ce Lb
6
20 0.31 Ba Lg
4
30 0.30
Pm La
1
20 0.31
V Kb 10 0.56
spectral resolution of the system is essential because only in this case are peaks very
narrow and do not overlap, and the background level is easily reached in the intervals
between peaks.
Finally, we refer to a method based on the relationship of uorescent and scattered
radiation intensities versus the value of attenuation coecients. No measurements of back-
ground for the estimation of net line intensities is required in this case (Bougault et al., 1977).
If we cannot overcome the background problem, it would be advantageous to use the
background or scattered tube lines for increasing the information about the sample. There
are very interesting examples of such work and they will be shown in Sec. IV.C.
Figure 34 Spectra of Pd excited by a Rh tube and recorded with and without a primary beam
molybdenum filter (0.1 mm Mo). The peaks are labeled PdKa, PdKb, RhKa, and RhKb with their
respective order indices. (Courtesy of ARL.)
B. Qualitative Spectrometry
Although the number of spectral lines is very limited compared to atomic emission
spectra in the ultraviolet or visible region, overlapping of lines in x-ray spectra does
exist. A classic example can be found in the works of Gentry et al. (1976), Sparks et al.
(1978), and Sparks (1980), and an example is reproduced in Figure 36. At energies at
which K lines of elements between palladium and cesium (about 22 and up to 30 keV)
can be present, additionally the tails of L lines of uranium and thorium are found, and
also the theoretically calculated M lines of the superheavy elements of Z110 [in the
time which passed since 1976 this element has been discovered (Hofmann et al., 1994)]
and 126 should be expected. The erroneous attribution of some lines to these hy-
pothetical elements was the subject of extended research and long discussions (Sparks
et al., 1978; Sparks, 1980). In the software of modern spectrometers, special searching
blocks exist for the assignment of lines: The detected line is compared with data com-
piled in the program. After the initial assignment, other lines of the element are iden-
tied according to data from the library. The initial assignment is eventually rejected if
not conrmed by other lines (Fig. 37). Multichannel wavelength-dispersive instruments
are not suited for this type of work, except for elements implemented on the spectro-
meter (maximum 28 elements). Sequential instruments can cover all elements (from
beryllium on). The spectra can be displayed on the monitor screen of all modern
spectrometers, documented, memorized as les, and printed. Particular parts of the
spectrum can be scanned occasionally with higher resolution and sensitivity (step
scanning) according to the time available for the analysis and the information required.
Parts of particular interest can be displayed separately with a linear intensity axis or
rescaled to square root or logarithmic scales. The peaks can be identied on the display
by the angle 2W, by element name, either by wavelength or energy.
Figure35 Synchrotron-excited spectra of gaseous nitrogen with a small amount of xenon taken in
the direction of polarization and perpendicular to the orbit plane. Counts normalized to stored
electron current are integrated over the lifetime of the detection system. DORIS was operated at
3.3 GeV and about 55 mA. (From Kno chel et al., 1983. Reprinted by permission of the author and
Elsevier Science Publishers.)
Figure 36 Fluorescence spectrum from a monazite particle excited with 37-keV synchrotron
radiation (ORNL DATA) shows an improved signal-to-background ratio over that excited with
5.7-MeV protons (FSU DATA). Data points every 20 eV in ORNL spectrum and every 61.8 eV in
FSU spectrum. (From Sparks, 1980.)
Figure 37 Example of qualitative analysis by rejection. The suspected MoLa peak in the lower
spectrum was rejected after comparison with the standard containing molybdenum (upper
spectrum). (Courtesy of Phillips Analytical.)
The spectrum can be scanned linearly with respect to 2W or in a more optimal way. If
Braggs and Moseleys laws are combined, the following relationship among Z, the atomic
number, and W is found:
Z
m
k2d sin W
_
s 14
Z is proportional to the inverse square root of sin W. Jenkins et al. (1979) proposed
computer monitoring of the scan speed according to this equation. It optimizes the scan
speed, which represents a high gain in time especially in the low-Z range where the angular
distances between the lines are long.
The newest applications of WDXRF softwares try to avoid the old-fashioned treat-
ment of data. One such traditional manual estimation was that concerning the possible
spectral interferences. Normally, the analyst has to decide which place in a spectrum is
relatively empty of disturbing peaks and compromising background contributions. This job
was rather time-consuming, with the wide use of spectral tables and other datasets con-
cerning, for example, intensity ratios. The results were not always encouraging. Now,
virtual synthesis of wavelength-dispersive spectra is in progress (Reed and Buckley, 1996),
in the Internet demonstration version also (Buckley, 1998). The expected pure-element
spectra are loaded from the memory and installed in a region of interest of the anticipated
spectrum. Those partial spectra are apparently corrected for the expected concentrations of
the sample constituents. From the result shown on a screen of the computer, one can easily
estimate whether the region of interest is suitable for a given analysis or should be excluded.
Such a procedure makes the selection of lines for the qualitative analysis much easier, as
well as the estimation of the background and also the assessment of the detection limits.
C. Special Quantitative Applications
Although the main quantitative treatment of XRF has been left to Chapter 5, still there are
some special and nonconventional applications which proved to have potential practical
meaning. Their signicance becomes obvious when, considering the excitation process, one
wonders how great a part of the radiation is transformed into the scattered form and how it
can supplement the essential quantication based on characteristic signals.
As stated earlier, monochromatic excitation simplies the quantitative treatment of
spectral data considerably, but this case is only seldom met in WDXRF. The most
common excitation source is the x-ray tube, in which a set of characteristic lines super-
imposed on a white spectrum is generated. For this reason, only the fundamental coe-
cient method can be considered as rigorous and somewhat simplied in comparison with a
complete fundamental parameter method. How the correction terms can be derived in a
rigorous manner for the case of monochromatic excitation was shown in an article by
Kuczumow (1982). In its original formulation, the LachanceTraill equation is (Lachance
and Traill, 1966)
W
i
R
i
1
j6i
a
ij
W
j
_ _
15
with a
ij
dened as a constant written as
a
ij

m
jC
1
E m
jC
2
E
i
m
iC
1
E m
iC
2
E
i

m
iC
1
E m
iC
2
E
i

15a
where m denotes the mass absorption coecients for primary or secondary photons of
energy E or E
i
, respectively, corrected for the incident C
1
and takeo C
2
angles. It has
been proved (Claisse and Quintin, 1967) that this expression is valid only for boundary
conditions: monochromatic excitation and absence of enhancement. In all other condi-
tions, as are not constant, as experimentally shown (Tertian and Claisse, 1982; Lachance,
1981). It is impossible to derive a more exible algorithm with constant coecients directly
from Shiraiwa and Fujinos equation (Kuczumow, 1982; Rousseau and Claisse, 1974).
Other algorithms similar to that of Tertian (Rousseau, 1974) and Lachance COLA
(Lachance, 1981) are not recognized as fundamental. An algorithm that can be considered
partially fundamental is that of Claisse and Quintin (1967), but it suers from inaccuracies
in the approximations introduced. Later, Rousseau (1984, 1987) and Kuczumow and
Holland (1989) gave examples of algorithms derived from fundamental assumptions.
Kuczumow and Holland describe the change in a when enhancement is included
(monochromatic excitation) as follows:
W
i
R
i
1
j6i;k
a
ij
W
ij
Da
ik
W
k
_ _
16
where all as are dened as previously but Da is dened as
Da
ik

m
0
kC
2
E
i
m
kC
2
E
i
m
iC
1
E m
iC
2
E
i
16a
The new term m
0
kC
2
E
i
was introduced in Eq. (16). Although dependent on the excitation
condition E and composition, this new term has the great advantage of being dependent
on the latter in a simple way. The possibility of deriving the LachanceTraill equation
directly from the Shiraiwa and Fujino equation under the conditions applicable to Eq. (16)
is also well established (Kuczumow and Holland, 1989).
The next interesting case concerns scattered radiation as a source of analytical al-
gorithms. Similar to the derivation made by Kuczumow (1982), an expression on the basis
of coherently scattered radiation is obtained (Kuczumow, 1988):
W
i
R
coh
i

j6i
R
coh
i
a
coh
ij
b
coh
ij
_ _
W
j
17
where
a
coh
ij

m
jC
1
E
0
m
jC
2
E
0
m
iC
1
E
0
m
iC
2
E
0
m
iC
1
E
0
m
iC
2
E
0
17a
b
coh
ij

s
coh
j
E
0
s
coh
i
E
0
17b
and R
i
coh
results from the comparison of a coherently scattered line from the sample and
from the pure element i and s
coh
is the mass coherent scatter coecient (for the set of
incident and takeo angles, as always in the conditions of the analysis). For Compton-
scattered radiation, analogous expressions are obtained:
W
i
R
com
i

j6i
R
com
i
a
com
ij
b
com
ij
_ _
W
j
18
with
a
com
ij

m
jC
1
E
0
m
jC
2
E
com
m
iC
1
E
0
m
iC
2
E
com
m
iC
1
E
0
m
iC
2
E
com
18a
b
com
ij

s
com
j
E
0
s
com
i
E
0
18b
R
i
com
is the ratio of the Compton peak intensity of the sample to that of the pure ele-
ment. Equations (17) and (18) may be called LachanceTraill equations for scattered
radiation by their general appearance as well as by the way they have been derived.
These equations are less sensitive to the type of components and changes in composi-
tions than their analogs for uorescent radiation, which otherwise is an advantage in
analyses of samples widely varying in composition. From assumption, they include only
the terms for strictly dened energy values, even if the analysis is carried out with a
polychromatic source! In Table 6, the coecients a and b from Eqs. (15)(18) are col-
lected, calculated for the K lines of La and Sm, the main components of samples con-
sisting of La
2
O
3
Sm
2
O
3
excited by 60-keV photons at the incidence and emergence
angles equal to 80
and 70
, respectively (the example is taken from EDXRF, but it is

also instructive here).
When applied to nonhomogeneous samples, also the as are proved to be dependent
not only on the composition and the energy but also on particle size for dispersions or
layer thickness for piles of layers of dierent composition (Helsen and Vrebos, 1984a,
1984b).
Kuczumow et al. (1992) have proved that parallely with the conventional analysis of
binary AuCu alloys by uorescent lines (Fig. 38), it is possible to get similar information
using coherently or incoherently scattered tube radiation. Sometimes, the results are even
better than for the direct uorescence analysis.
Still other possibilities of using the scattered lines exist. Kuczumow et al. (1995) have
proved, by a proper mathematical transformation of the scattered Rayleigh signal, that for
light, chemically homogeneous matrices (as biological materials, e.g., wood), this new
function of scattered radiation, called the corrected scattered intensity, strictly follows the
density changes in the analyzed material (Fig. 39). The use of Rayleigh signals eliminates
the necessity of transmission measurements and brings important auxiliary information
(e.g., about the density). Although the method just described has been applied up to now
for x-ray capillary-microprobe-type measurements only, it may be used generally (Luggar
and Gilboy, 1994).
Table 6 a and b Coefcients for Fluorescent and Scattered Signals
La
2
O
3
Sm
2
O
3
a
f
(La
2
O
3
Sm
2
O
3
) 0.292 (Sm
2
O
3
La
2
O
3
) 1.009
Da
f
0.895
a
coh
0.285 0.222
b
coh
1.153 0.867
a
com
0.281 0.219
b
com
1.000 1.000
D. Pattern Recognition
The spectrum of a sample of complex composition is characterized by a set of lines,
documented by their position and intensity. If we imagine an n-dimensional space with the
intensities on the coordinate axes, the set of intensities determines a point in this space.
Such an intensity space is convertible into an n-dimensional space of concentrations, and
the point in the intensity representation has its equivalent in the concentration space
(Klimasara and Berry, 1987). The aim of pattern recognition is to attribute a sample to a
given class. A class is in a discrete way a set of points of similar features in the intensity or
concentration space or, in a continuous way, a subspace inside a complete n-dimensional
space. This subspace is restrained by a closed hyperplane, which can be approximated by a
number of hyperplanes of smaller dimensionality. Inherent to all experimental determi-
nations, the determination of intensity is also bound to a certain degree of uncertainty.
This implies that a point, as such, cannot be determined, only a small subspace of limited
size, limited by the assumed condence levels. Equally ill-dened for the same reasons is
the boundary hyperplane surrounding the subspace occupied by a class of samples. The
thickness of this space ring surrounding the subspace is determined in relation to each
Figure38 Analytical curves in the system R=W-1 versus w w
0
for the CuKa line in AuCu alloys.
The solid line with open circles denotes the authors fluorescence measurements; the solid line with
crosses denotes Rayleigh measurements, and the solid line with solid square denotes Compton
measurements. R is the intensity relative to the intensity measured for the pure element and W is the
composition expressed as weight ratio; w represents the ratio of the mass attenuation coefficient of
the sample to the sine of the takeoff angle C
2
. The subscript O refers to the values for the pure
element o. (Modied from Kuczumow et al., 1992.)
coordinate axis by the appropriate multiplicity of the projection of standard deviation on
this axis.
1. Delimitationof Classes
If we consider classes as separate subspaces in n-dimensional conguration space, it is
obvious that each of these classes has its own boundary hyperplane or closed space ring.
If these hyperplanes can be determined in an analytical way, we are able to know the
boundaries of classes. In simple cases, a class can be delimited by construction of a low-
dimensional hyperplane that closely approximates the real boundary. The simplest ex-
ample is the trivial division of the whole conguration space on two categories; occupied
spaceempty space (zeroone decision). It can be done by assuming the limiting surface
(wall) inbetween the mentioned subspaces. If classes are separated by empty spaces, the
dierentiation of classes is even easier.
2. Methodof Nearest Neighbours
Here, the classes are considered as small subsets of points. The classication of each new
point relies on a comparison with its nearest neighbors. Knowledge of the distance
between the sample and the nearest neighbors is essential. The accuracy of the method
depends on the way the distance is determined and the degree of complexity of the
boundaries between classes, although it can be simplied by imposing proper statistical
weights on learning samples. The method of the nearest neighbors has further implications.
Figure 39 Line scans from x-ray microprobe measurements that show the correspondence
between transmission (dotted) and corrected scattered (solid) data, and the sequence of tree rings of
Silesian Pinus silvestris. The linear scan was made using a 89-mm capillary and a step size of 89 mm.
(Modified from Kuczumow et al., 1995.)
Once the sample is placed in relation to the nearest neighbors, which are nothing but the
standards, a separate program can draw the average from the composition of standards,
taking the distances from the neighbors as the statistical weights for the estimation of the
inuence of each standard on the nal result (Klimasara and Berry, 1987). However, this
way of using pattern-recognition methods is the same as very conventional method of
comparison with standards! Of course, standards are no longer considered in a conven-
tional sense as some numerical values in relation to some elements, but rather as the full
patterns [compare also the genetic algorithm by Dane et al. (1996)].
3. Reductionin Number of Dimensions
All points and classes are included in the multidimensional space generated by the number
of elements present in the sample; however, some variables may be less dependent on the
related coordinates, and then the number of variables necessary to dierentiate the sample
may be reduced. The number of dimensions may also be reduced if some variables are
correlated; the most obvious way of coupling the elements is by joining them in a chemical
compound.
4. Pattern Grammar Approach
Another version of pattern recognition is also possible. The full spectra for dierent
standards and=or samples can be collected and treated as some analytical claims (sen-
tences), with peaks considered to be analogs of single words, and the whole set of spectra
as a constituent of a spectral language. At the same time, we have the complete chemical
knowledge of the same standards, with standard composition treated as the sentences,
their particular components as the single words, and such second system is the part of
another, chemical language. The task of the chemist is to translate sentences from
spectral to chemical language while working with the real samples. Even more, the
translation from one language to another can be treated as mapping (rather linear than
nonlinear!).
5. Examples
Samples may be classied into groups according to their origin. A primitive version of
such x-ray methods was demonstrated by Lagarde et al. (1984). They observed the
characteristic features of spectra of ceramics samples from western Africa and then put the
samples in order by the naked eye according to their origin. A classic reference here is
the work of Kowalski et al. (1972), which was followed by many other articles on arch-
eology. Kowalski recognized the origin of obsidian artifacts by studying a set of intensities
of 10 trace elements and projected the image of this set from 10-dimensional conguration
space into a 2-dimensional space (nonlinear mapping). Similar applications in geology are
obvious. Lo I Yin et al. (1989a, 1989b) proposed the application of the pattern-recogni-
tion-supported XRF to the initial selection and analysis of Mars Rover geological sam-
ples. They discovered on this occasion that it is not necessary to use sophisticated
detection systems. On the contrary, they applied probably the most primitive version of an
x-ray spectrometer with a proportional counter as detector. The resolving power of such a
detecting system belongs to the worst among the existing ones (compare Fig. 26a), but
even in these conditions, the results of the sample-selection procedure are good. In such
classication procedures, putting emphasis on advanced data analysis can be a substitute
for using a sophisticated high-resolution spectrometer for special analyses in dicult
conditions.
If only a limited amount of data is available, samples can only be subdivided in
groups. Discrimination of the alloys 663, B-1900, and 1455 can be done on the basis of
their zirconium content (Kevex Material Analyzer Mode 6500 brochure). Nickelcobalt
alloys were subdivided on the basis of a logical analysis of successive spectral responses: Is
the ratio contents of elements A=contents of element B greater than some assumed level
X: A=B>X (Fig. 40)? Complete analysis of the alloy was not necessary. The same is often
done when samples can be compared to standards [e.g., the framing action by software
(description of Siemens software)].
An important application of pattern recognition may be found in two-stage
analysis. For complex samples with nonlinear dependence of intensity on concentration,
the analysis can be broken down in steps with a smaller number of dimensions (lower
degree of complexity) or the samples may rst be subdivided in classes before applying
correction algorithms. The appropriate sets of dierential equations exist: they establish
the relation between the value of relative intensities [ClaisseThinh systems (Claisse and
Thinh, 1979)] or between increments of intensities [Kloyber et al. (1980) and Kuczumow
(1984) systems] and increments of concentrations. These increments are calculated with
respect to a central standard that represents the origin of a local system of coordinates. In
Figure 40 Selective procedure of the KEVEX Material Analyzer Model 6500 based on successive
analysis of the element ratios. (Courtesy of KEVEX Corp.)
this local system, a certain set of dierential equations is valid and is of linear character (if
not, it is not protable to use it in such a restricted space). After attributing the samples to
given classes, the right set of dierential equations may be used for accurate determination
of composition. The origin of the local system of coordinates may, at the same time, be the
central point of a given class.
When the delimitation of classes becomes problematical, a point in the conguration
space may be designated and a set of dierential equations, valid about this point, may be
determined. From this, the boundaries of classes can be found and determined by some
leading vectors introduced in the central points of the classes.
Yap (1987) and Yap and Tang (1984, 1985) posed the reciprocal question in relation
to pattern recognition: how to extract some number of dierentiating features from the
known classes, diering them by time and place of origin. This was used to analyze pottery
samples. Another name for this method is the training phase of the analysis.
E. Analysis on the Basis of Neural Networks
The pattern-recognition method leads us to quite dierent levels of reasoning. The most
popular recent way of working with a spectrum is to transform it numerically and show it
in two-dimensional intensitywavelength or equivalent intensity2W or intensityenergy
diagrams. Some logical artifacts result from the numerical transformation of the original
sets of signals. The interesting comparison between functioning of the electronic chip
in the binary system of information and the biological cell in the complex system of
information was presented by Cholewa during 15 ICXOM, Antwerp (Cholewa, 1998)
(see Fig. 41).
At the same time, without such a numerical presentation, a common naked-eye
observation allows one to compare a fresh spectrum to other similar pictures compiled in
our memory. Our way of reasoning is not numerical at all, but resembles some procedures
of pattern recognition. It is simply a process of attributing a sample to some class. In a
happy case, one can recall the same pattern in memory and then classify the sample as a
part of existing and well-described objects.
One of the possible ways of reasoning similar to the ways of functioning of the
human brain is by applying so-called fuzzy logic. In that type of logic, the object can
belong to the proper set with some probability, not necessary equal to 1 (belongs) or 0
(does not belong). The spectrum can be recognized in this manner, with some articial
probabilistic rules set in the very beginning of the process. An instructive example is taken
from an article by Otto et al. (1992). For the qualitative estimation of an x-ray spectrum,
the following rule is very useful: If the Ka line is supposed to be in a spectrum, then the Kb
line should be associated with it, being about 5-fold weaker.
Neural networks open another approach to the problem. They imitate the action of
neurons joined by synapses in the human brain. The articial network has a layer of input
cells and a layer of output cells. The cells from layers just mentioned are connected, some
of them directly and the majority indirectly, by the additional cells, grouped in one or
more additional, hidden layers. Each middle cell collects one or more signals from pre-
vious cells, gives those signals the proper statistical weight (e.g., according to previously
imposed rules), and sums them up. Next, the modied signal is sent from the middle cell
into one or many cells in the next hidden layer or, nally, to the output layer. The initial
information (e.g., spectrum) given to the input layer is transformed into a useful
set of information (e.g., about the chemical composition) in the output layer (Otto et al.,
1992; Larsen et al., 1992; Bishop, 1992; Bos and Weber, 1991; Luo et al., 1997). Otherwise,
Figure41 Drawing showing the different degrees of complicacy involved in the action of (left) the
electronic chip and (right) the single biological cell, also from the informatic point of view. The
electronic chip includes only one bit of the binary information; the cell is an incomparably more
complicated system. It is a basis for the differences in computing and brain thinking. (Courtesy of
Dr. Marian Cholewa.) Copyright 2002 Marcel Dekker, Inc.
it resembles the pattern grammar method previously described. The method can be
applied for the classication of very complex spectra, for clustering the datasets, for
coupling the sets of spectra to the groups of compounds, and for nonlinear data trans-
formation between sets with dierent dimensionalities.
F. Detection Limits
The importance of the correct determination of detection limits has been acknowledged by
many chemists, especially those involved in environmental regulation. The accepted de-
nition is as follows: The limit of detection is the lowest concentration level that can be
determined to be statistically signicant from an analytical blank (Nomenclature, 1978).
The limit of detection is expressed as a concentration c
L
or an amount q
L
and is derived
from the smallest measure I
L
, I being the instrument reading. How the data are treated in
the statistics is described in Chapter 5. For a thorough discussion we may refer to the
article by Long and Winefordner (1983). This article also contains interesting references to
articles of Kaiser, Boumans, and others, which are therefore not repeated here. For the
derivation of some simple statistical dependencies, the small, almost forgotten book of
Beers (1958) is instructive. Finally, we can recommend the excellent discussion of the
physical origin of background sources and detection limits in PIXE and synchrotron-ex-
cited XRF given by Sparks (1980), which is also valid for WDXRF.
Here, we only invoke that according to the International Union of Pure and Applied
Chemistry (IUPAC) recommendation, the characteristic signal is statistically attributed to
the element when it is elevated not less than 3s(s standard deviation) above the back-
ground level. It makes the condence level equal to 99.86%. The detection limit is then
calculated for the standard deviation multiplicity k 3 and is expressed as a function of
intensity in a unit of time (RN=t) with t as the counting time and with the sensitivity m
expressed in cps=% or cps=ppm.
In Table 7 a series of values for c
L
are given for randomly chosen elements collected
from manufactures documents. No general list can be included because detection limits as
well as sensitivities depend heavily on matrix composition and on the experimental con-
ditions. Instead, this is intended as an indication of order of magnitude.
Each discussion of detection limits provides methods for deciding whether a signal
value I
U
for a unknown was greater than background reading I
B
with a given level of
condence. Another important approach is advocated and applied by Clayton et al.
(1987). They state that traditional techniques for determining detection limits have been
concerned only with providing protection against type I errors, or false positive conclu-
sions (i.e., reporting an analyte as present when it is not). They have not considered type II
errors, or false negative assertions (i.e., reporting an analyte as not present when it is).
In their article, they discuss a test of the null hypothesis c 0 versus alternatives that c >0,
where c denotes the true but unknown concentration of an analyte in a medium and for
two models of calibration curves with known or with unknown parameters. The test is
applied to chromatographic data. Their theory can certainly be applied to XRF data, but
the attempt has not yet been reported.
G. Limits of XRF
Compared to ultraviolet (UV)visible emission spectra, x-ray spectra are oligoline ones
and very convenient with respect to the resolution of the spectrometers. The UV-visible
emission spectrum of iron contains some 2000 lines between 200 and 800 nm; its
complete x-ray counterpart has a dozen important lines between 1.757 A
(Kb
1
) and
0.615 A
(Lg)! For everyday work, however, only two lines, 1.936 and 1.940 A
(Ka
1,2
)
and 1.757 A
(Kb), play a role. The densely populated L series spectrum such as that of
gold has a set of about 20 lines between 0.9 and 1.5 A
, a spectrum that can be

managed by a spectrometer with a relative spectral resolution of 10
2
. The prospects
for the x-ray spectrometric range should be bright, but what are the limits to this
method?
1. Application Limits
All elements from beryllium on can be detected and=or quantitatively determined. On the
high-Z element or low-l side, the spectral resolution may be a problem for pure
spectroscopic studies, but seldom or never for qualitative or quantitative applications.
Because the emitted energy of photons is high and the attenuation coecients are low,
the critical depth is great and, consequently, the analyzed volume is very representative
of the composition of the bulk. The critical depth is the thickness d
crit
of a layer parallel
to the surface, from which 99% of the intensity sensed by the detector is recruited.
Table 7 Detection Limits
a
Matrix Element c
L
Data source
Terephthalic acid Fe 0.15 Philips
Co 0.18
Low-alloy steel C 80, 240 Philips, Siemens
Al 4, 4.5
Si 2.1, 4.1
Cr 2, 1.7
AlMg alloy Mg 7 Philips
Si 5
Ti 3
Mn 2
Cu 1
Aluminum Mg 10.5 Siemens
P 1.3
Glass powder B 1% Broll, 1985
Phosphosilicate glass B
2
O
3
0.4% Philips
Cement Na
2
O 36 Siemens
b
MgO 27
Al
2
O
3
22
SiO
2
50
SO
3
24
P
2
O
5
32
Copper alloys Be 0.2% Philips
Source: Data from Philips Analytical X-Ray Spectrometry Applica-
tion Notes nos. 504, 622, 623, 737, 808, 913, 916; Siemens SRS
Awendung 84=8, 86=1, 86=5, 86=6; and Broll, 1985.
a
ppm (unless otherwise specied) for 100 s counting time and k 3.
b
With use of multilayer OVO 55.
It is a function of the takeo angle C
2
, the linear absorption coecient mr of the matrix,
and the density:
d
crit
lim
ln 1
I
t
I
1
_ _
" mr=sinC
2
!
ln10
2
" mr=sinC
2
%
4:61
" mr=sinC
2
19
where I
t
is the intensity emitted by a thin foil and I
1
is the intensity emitted by an in-
nitely thick sample.
For long wavelengths, mr becomes high while d
crit
and analyzed volume become
low. If the sampled volume is low, the analysis may be called a near-surface determi-
nation, not representative for the bulk (see discussion in Sec. III.D.2.d). In that sense,
the results of the determination of heavy and light elements in the sample including
dierent kinds of elements can be nonequivalent. The heavier elements are then de-
termined in the bulk, whereas the light ones are determined on the surface only. This can
lead to surprising results if the process of surface segregation is occurring. Moreover,
during recent density determinations (Tsuji and Wagatsuma, 1996) of coating layers by a
similar method, Grazing emission x-ray uorescence, striking dierences have been re-
vealed between surface and bulk densities; for example, the density of a 27-nm-thick
coating lead layer was equal to hardly 35% of the normal, the bulk value of the lead
density (Tsuji et al., 1997). It is a true limit by the force of nature, although it may be
exploited for near-surface determination of light elements. From the concept of critical
depth, it is obvious that coatings can be analyzed up to certain thicknesses depending on
the absorption (and enhancement!) characteristics of the coating and substrate; the
overall thickness range is from 0.01 mm to a few hundred micrometers for the normal
angle versions of XRF.
Apart from the analysis of macrosamples, WD spectrometers may also be t to
electron microprobes, where they supplement the ED spectrometer for better spectral
resolution of light elements. Curved crystal optics is generally used because of optimum
eciency (compare the quantum eciency of a classical WD spectrometer 10
8
, curved
crystal WD 10
6
, and ED spectrometer 10
4
). WD spectrometers are also needed for
heavy-particle-induced emission; because of the presence of many satellite lines, good
resolution is required (Watson et al., 1977; Chapter 12).
The dynamic range of analysis covers about ve orders of magnitude, from 10
3
to
100%. Below 10
3
%, preconcentration procedures must be used.
The intensity and uniformity of exciting beams delivered by conventional end-win-
dow tubes were not sucient to allow spot analysis. However, Boehme (1987) and Nichols
et al. (1987) published the results of two-dimensional mapping executed with small beams
from high-power sources (rotating anode tubes), allowing lateral resolution of about
30 mm. This osets the boundaries to a new domain: high-spatial-resolution x-ray spec-
trometry. Still, the possibilities of the tube-excited, slit-based WDXRF microprobe are
relatively poor in comparison with an x-ray capillary-based EDXRF system or especially
proton and electron microprobes (Chapters 1113). However, for many applications, the
lateral resolution mentioned earlier is quite sucient and this technique is time-saving.
Moreover, the tube can be coupled with the polycapillary device. Note, that, for example,
the diameter of the spot obtained from the polycapillary lens is in a range 50500 mm, but
the careful work with such a beam can give a somewhat better spatial resolution. In
Sec. VI.B.3, we will discuss the milliprobes, a new solution which seems to be the most
suitable for the wavelength-dispersive mode of operation.
2. Limits of Precisionand Accuracy
An analyst is always threatened by errors in the analysis outliers, random, and systematic
errors. When a given operation or measurement provokes an oset between the true and
measured values, a systematic error is said to be introduced. This oset may be due to a
wrong calibration of any kind or to a wrong standard. Such errors can only be detected by
analyzing a sample from the same batch with other techniques. Random errors and
outliers can be dealt with by statistical methods. One example of such a method is de-
scribed by Plesch (1981) and implemented in the software package Spectra 310 (Siemens).
A calibration with n standards is assumed to give a standard deviation. The standard
deviation s
s
is calculated according to
s
s

C
0
i
C
i
2
n p
20
where C
i
is the true weight fraction and C
0
i
the result obtained; p is the number of para-
meters used in the t: p 2 for a linear and p 3 for a parabolic t. If the concentration C
a
of an element in one specimen diers considerably from C
0
a
, the presence of an outlier is
suspected. The suspected value is eliminated, and a new standard deviation is calculated.
C
a
is an outlier with a probability of P% according to the inequality (F-test) (S
1
=S
2
)
2
>F
p
.
The threshold values for F
p
are listed in the current statistical literature. Application of the
F-test in fact checks whether a statistically signicant dierence exists between the stan-
dard deviation calculated with and without the suspected result. Possible causes of outliers
are numerous, including all kinds of human mistake, temporary instrument failure, and
heterogeneity of specimens. Recently, the numerical programs helping to segregate the
data on the true ones and outliers are available. They are based on the Grubbs test
(Grubbs, 1969; Rousseeuw and Leroy, 1987).
A measurement of uorescent radiation is, as in any other experimental determi-
nation, subject to minimal error. The standard deviation of a radiation measurement is
equal to the square root of the number of accumulated counts N. The real standard de-
viation is greater than
N
p
because of errors of instrumental origin. Another source of
error is the conversion of intensity into concentration and, last but not least, inherent to
the sample, microheterogeneity, which is dicult to foresee and to quantify and is present
even when all normal precautions for careful sample preparation are taken.
Heterogeneities caused by sample preparation are dealt with elsewhere. These arti-
facts should be absent here. Segregation, however, which is the origin of what we call
microheterogeneity, is a bulk (or sometimes surface) phenomenon of crystallographic
origin: solid solutions of compounds or elements that are not perfectly soluble in each
other, segregating into multiphase components. The degree of heterogeneity in the
composition of the segregated phase as well as in the size of the phases depends on the
history of the solution (thermal, chemical, or mechanical treatment). It is not easily
mastered and is dicult to quantify. Its importance for XRF analysis has been ac-
knowledged by several authors; Examples are tin and lead in solders (Glade and Post,
1970), silicates in fused beads (Novosel-Radovic et al., 1984), and silicon in SiAl alloys
(Michaelis and Kilday, 1962). The rst report we are aware of is an article by Claisse
(1957) on the determination of FeS in a sulfur matrix. A systematic study has been devoted
to this phenomenon by Helsen and Vrebos (1984a, 1984b, 1986a, 1986b) and Vrebos and
Helsen (1983, 1985a, 1985b, 1986), both by Monte Carlo simulation on hypothetical
mixtures and by measurements on samples of known segregation. It was found by si-
mulation on a (hypothetical) dispersion of spherical particles of iron in a chromium matrix
that even for a particle diameter of 1 mm, an error is introduced in the relative intensity of
FeKa of 6% (on the level of c
Fe
0.5) with respect to the perfectly homogeneous solution.
The eect was proved experimentally on alloys of AlSi, AlMo, and AlZn. The extent of
the eect changes with time, as in fused beads. This was demonstrated by the determi-
nations of Novosel-Radovic et al. (1984) on uxed silicates and also by Monte Carlo si-
mulations by Vrebos and Helsen (1985a, 1985b). Microsegregation imposes a true physical
limit to the accuracy obtainable by XRF spectrometry on quite a substantial number of
samples, including minerals and alloys.
3. High-ZLimit
We already insisted on the low-Z limit in Secs. III.D.1 and III.D.2, but what about the
high-energy end of the spectrum?
Commercially available generators and side-window tubes allow working at high
voltages up to 100 kV, bringing even the K line of bismuth into the potential analytical
spectrometric range. If a tungsten target is used, however, characteristic lines represent
only a minority of the integrated emitted intensity, thus, excitation is bound mostly to
continuous radiation, the maximum of which lies at 50 keV. Thus, only elements with K
absorption edges below this value can be eciently excited (Eu, Z63, and all elements
below). The above remark is even more valid for the spectrometers with end-window
tubes, most commonly used in present-day instruments, of which the high voltage is
limited to 60 kV. Possible excitation of K lines for all the elements from the periodic table
by the tubes operating in voltages up to 160 kV is bound to metalceramic low-power
tubes, cooperating with EDXRF systems and is outside the scope of this chapter. Thus,
the available voltage limitation is the rst one.
If we return to Figure 26b and compare the spectral resolution of the LiF spectro-
meter to spectral distances between analogous lines in the K series, it is obvious that spectral
resolution is worse above 35 keV (for K lines of Pr, Z59). This is a second limitation.
Most of goniometers have their optimal 2W range between 10
15
and 70
: At the
higher 2W end, the angular dispersion becomes insucient; at the lower 2W end, the in-
tensity becomes very low. If we choose LiF (420) with the shortest interplanar distance,
2d 1.802 A
, useful measurements can be made at 10.0
corresponding to photons of
39.6 keV (Sm, Z62 in the rst-order spectrum). This is a third limitation.
Studying Figure 26 further, we note that the spectral resolution of the LiF spec-
trometer is below the spectral resolution of the semiconductor SiLi detector for photons
of energy exceeding 17 keV, which corresponds to MoKa, Z42. This is the fourth and
most serious limitation in the K series. For analysis in the L series, there is no such
limitation because the whole energy range lies within the capabilities of wavelength-dis-
persive devices. However, using the new microcalorimetric detectors with extraordinary
and relatively constant spectral resolution, one can anticipate the preponderance of the
spectral resolution factor for wavelength-dispersive crystals only in a region below
45 keV, which means the Ka line of V, Z23 (see Fig. 27). Then, the ability to make the
ecient trace analysis (because of higher count rates) and the availability of the device are
still the advantageous sides of application of the crystal dispersion in the future.
The wide voltage range of generators should not be used without some awareness of
inherent drawbacks. For example, the K absorption edge of Mo is 20 keV. Thus, each
x-ray tube with characteristic lines above 20 keV and working above twice this 20 kV for
the maximum of bremsstrahlung generation is quite good for the excitation of Mo. The
potential, however, should not exceed this value substantially much because the maximum
of the white radiation would shift more and more away from the molybdenum absorption
edge and even the spectral characteristics do not improve. If we divide the mass coecient
of photoelectron excitation by the sum of mass coecients for Compton and coherent
scatters (this is a kind of measure of peak-to-background ratio), we obtain the values 76
and 18 for tube-excitation potentials of 40 and 100 kV, respectively! This is a substantial
loss in peak-to-background ratio while passing to higher voltages.
The discussion in this section shows that the advantage of high-energy photons
(generated by very high voltages in SWT) does not compensate for the drawbacks and this
probably explains why most manufacturers t EWT tubes to the instruments. During the
last years, manufacturers rather resigned from high-voltage generators and tubes, even in
high-power 4-kW constructions. The use of a higher current is now a preferred option.
Thus, we expect that only spectrometers with a high voltage up to 60 kV will dominate the
market in the future. The eective spectral range above 3040 keV should probably be left
for typical energy-dispersive detectors.
In the preceding paragraphs, we tried to show that although the spectrometers are
almost perfect, there are limits to precision and accuracy due to the nature of the sample
and to the mathematical conversion of intensity to concentration. These uncertainties are
generally greater than those introduced by instrumental parameters.
V. CHEMICAL SHIFTANDSPECIATION
The photoelectric excitation of atoms and subsequent specic deexcitation by emission of
x-rays is the basis of all qualitative and quantitative uses of XRF. The deexcitation process
was considered to take place between unique excited and ground quantum states. If these
states were always stable, x-ray emission lines were to be found at strictly determined
wavelengths or energies. However, electron density and quantum states are inuenced by
the environment of the atom with consequent wavelength shifts, or so-called chemical
shifts, of the emitted lines. Such techniques as nuclear magnetic resonance or Mo ssbauer
spectroscopy collect their spectroscopic information essentially from measurement of
chemical shifts. As a matter of fact, all kinds of spectral lines of electromagnetic radiation
are subject to chemical shifts. All these shifts are small and detectable only if the spectral
linewidths are suciently small and the instrument has the required spectral resolution.
For x-rays, the line shift is at most a few electron volts. An angular error DW 0.02
on the
determination of a peak position at l 1 A
corresponds to 5 eV. Moreover, small tem-

perature changes of the analyzing crystal already shifts the position over similar values.
The sensitivity of peak position to the chemical environment of the atom was ob-
served at the very beginning of x-ray spectrometry by Lindh and Lundquist (1924). The
following characteristics of lines are sensitive to changes: line position (chemical shift)
(Sumbaev et al., 1968; Sumbaev, 1970; 1976), line shape (Urch and Wood, 1978), and
mutual ratios of line intensities (Asada et al., 1975). A detailed summary of the eect can
be found in the book by Agarwal (1979), for example. In spectrometers with limited
resolution, such as dierent energy-dispersive systems, most spectral shifts are hardly
detectable.
Chemical shift research has been done on high-resolution spectrometers. Gohshi
et al. (1982a, 1982b) constructed an excellent two-at-crystal instrument for studying
chemical shifts. Asada et al. (1975) and Haycock and Urch (1978) improved the use of
commercially available instruments for this purpose: by Fourier transform and iterative
procedures for peak position detection or by using ner collimators. When analyzing
crystals with large thermal expansion coecients, such as PET, are used, a temperature
variation of 1
C gives rise to peak shifts greater than the chemical shifts. Helsen and
Wijnhoven (1972) solved this problem by inserting standards at regular intervals and by
using statistical techniques for the determination of the peak position. Sumbaev and Co-
workers (1968, 1970, 1976) made experiments with an instrument in a Cauchois ar-
rangement. In an article by Kataria et al. (1986), it was proved that even using a common
solid-state SiLi detector with moderate energy resolution, it was possible to detect che-
mical eects. Similarly, Habulibaz et al. (1996) performed experiments with a multilayer
with an exact 2d spacing of 300 A
, which means with poor spectral resolution. They

managed to register SiL spectra for dierent compounds, clearly showing the inuence of
the chemical environment.
Theoretically, chemical shifts can be calculated by the self-consistent eld approach
for the four quantum states involved (Manne, 1981). Unfortunately, the calculations are
largely dependent on initial assumptions, the choice of which is dicult and somewhat
random and the results are far from unequivocal. The experimental results of Sumbaev
seem to be more spectacular. He connected the chemical shift DE
KL
to Pauling ionicity, i,
valency m, and the parameter p, which was determined by lifetime ratios of electrons on
the levels K or L:
DE
KL
im p
K
DE
K;Z:Z1
p
L
DE
L;Z:Z1
21
He achieved an even more surprising result by presenting chemical shifts per unit ionicity
versus valence (Fig. 42). This dependence is linear and may serve as proof of both the
importance of chemical shift and the accuracy of Paulings scale. The shift can be related
to the character of the bond in the molecule or the crystal. During the formation of
a chemical bond, a rearrangement of electrons occurs, thus the formation of ions or bonds
of varying degree of ionicity, the inuence of which is reected on all electron energy
levels, sometimes more on the K level than on others levels. An example may be the shift
between the Ka position of metallic aluminum and aluminum in dierent coordination
states (IV and VI) (Helsen and Wijnhoven, 1972).
Asada and Co-workers (1973, 1975, 1976) also made measurements in which the
resulting chemical shift was attributed to the ionic bond character. They investigated the
Figure 42 Chemical shift as a function of valence. The energy shift divided by the ionicity is
plotted (solid line). The dotted curve illustrates the uncorrected values of DE. (From Sumbaev, 1970.
Reprinted with permission of J. B. Adashko.)
changes in the ratio of some spectral lines, such as those for the Kb
5
and Kb
1
satellite line,
and they connected them to the oxidation number of the analyte element. The results are
again surprisingly elegant (Fig. 43). Clear proof for the dependence between the shape of
lines and the oxidation number was given for manganese (Urch and Wood, 1978) and also
between the chemical shift and the coordination number for dierent elements (Gohshi,
1981). The shift of AlKa for coordination states 0, IV, and VI was given by Helsen and
Wijnhoven (1972).
The application of the determination of chemical shift to chemical speciation is
obvious. In geological samples, sulfur can be distinguished according to its dierent
oxidation states (sulfur, sulde, sulte, sulfate, and hyposulfate). Birks and Gilfrich
(1978) made measurements for sulfur using a portable low-power WDXRF instrument.
In environmental and biological samples, the oxidation state of chromium is important:
Cr(III) does not pass the cell wall, but Cr(VI) does and is suspected of being carcino-
genic. Iwatsuki and Fukasawa (1987) reported the determination of chemical states of
arsenic, selenium, and bromine. The determination of the valence of iron in welding
fumes by measuring the energy shift and the intensity ratio of Kb
0
to Kb
1,3
has yielded
very ne results (Fig. 44) (Tanninen et al., 1985). Kataria et al. (1986) managed to
measure the varying ratio between the total line intensities of Kb and Ka as due to
Figure 43 Satellite peak intensity ratio Kb
5
=Kb
1
versus oxidation number. (From Asada et al.,
1975.)
dierent oxidation states of manganese using an instrument of very moderate resolving
power.
This discussion of other than elemental or quantitative information from x-ray
spectra has been intentionally restricted to x-ray spectrometry. A counterpart exists in the
spectrometry of the ejected electrons, but that discussion belongs to the domain of
spectrometry of Auger electrons or primary ejected electrons, for which higher resolutions
are available or better speciation is possible. Another and sometimes severe drawback of
these techniques is the required high vacuum and surface charging for nonconducting
specimens. It should also be mentioned that Raman spectrometry is possible in the x-ray
domain, but this eld of research is only really accessible when synchrotron radiation is
available (Sparks, 1974; Eisenberger et al., 1976a, 1976b), although performance on
conventional instruments is feasible (Suzuki et al., 1970). In analytical determinations by
synchrotron radiation, the Raman signals are often viewed as an additional disturbance
(Jaklevic et al., 1988).
Not many researchers are working in the eld of speciation by WDXRF; never-
theless, it is a eld of increasing importance, with theoretical as well as practical interest. It
gives more than simple elemental information. Moreover, the shift of lines aects the
intensity measurements for quantitative analysis, and stresses the use of the right stan-
dards for specic cases. In extreme cases, it may even be compulsory for quantitative
determinations to scan over the peak maximum for each determination and locate in each
case the intensity at the maximum for good precision and accuracy. If ultimate accuracy
should be required, correction for peak heights may be involved. The few examples given
point out that for studying the chemical shift, shape, and intensity measurements of
spectral lines, the use of dedicated instruments is indicated, although a certain amount of
useful work can be performed on commercially available instruments. A very interesting
discussion of the problems immanently connected with the analytical application of soft
x-rays can be found in the work by van Sprang and Bekkers (1998). These remarks have
the obvious implications for the speciation analysis.
Figure 44 Relative chemical shift DE and the average valence of iron in standard samples and
four welding fumes. The squares indicate the statistical uncertainties: SS stainless steel; MS mild
steel; MMAmanual metal arc technique; MIGmetal inert gas technique. (From Tanninen et al.,
1985.)
VI. INSTRUMENTATION
The physical principles of a WD spectrometer do not allow dramatic dierences in the
general layout of the spectrometer. A practical instrument unites a number of construction
compromises for speed, versatility, resolution, intensity, cost, user friendliness, and other
factors, and all combinations have their own merits and their own drawbacks. Buying an
instrument is a decision that in itself is a compromise because all benets wanted by a
customer are seldom or never united within a single instrument. In this section, the main
features of the most important commercially available instruments are juxtaposed without
formulating a global or nal judgment.
A. Electrical and Electronic Features
In modern instruments, all or almost all functions are controlled by a computer. As the
electronic conguration is subject to continuous change, no details will be given here.
Mentioned here are a few aspects which were dicult to automate or, when feasible, were
hardly automated in older instruments:
High voltage generators: The costly electromechanical control of conventional
generators is replaced by computer-controlled solid-state generators, switched
or high frequency. An example of exploitation of this exible control is the
switching of the tube along the isowatt curve, modifying the high voltage but
keeping the power constant, an interesting feature if dierent intensities of the
primary x-ray beam are required for dierent elements in the analysis of a
complex sample (major, minor elements) by a sequential spectrometer.
A consequence of the mechanical decoupling of W and 2W axes lifts the necessity of
manual alignment of the crystals by giving (and memorizing) a correcting oset
angle to the W axis for each crystal. A tandem disposition for gas and
scintillation counters is no longer a necessity. The one or the other is brought
into the right position under software control.
The sin W potentiometer for continuous adjustment of the manual setting of the
lower level and window of the pulse-height discriminator is replaced by
the multichannel analyzer and electronic and electro-optical detection of the
position of the goniometer.
Automatic digital gain control corrects for pulse shrinking. Dead time is
automatically corrected. This feature ensures linear response in most
instruments to 2 Mcps for a gas-ow-proportional counter and to 1 or more
Mcps for a scintillation counter.
The main remaining electromechanical parts are the motor(s) of the goniometer in
the sequential spectrometer (dc or stepper) or alignment motors for the crystals
in the simultaneous spectrometers, the vacuum pumps, the electrovalves for gas
ow (He, N
2
, counter gas), cooling water and compressed air, temperature
control and fans, safety switches, sample lock and changer (internal and
external), crystal turret, collimators, diaphragms, attenuator, and primary
beam lters.
An aspect totally absent in the older instruments was remote servicing. The full
computer control allows remote servicing over a modem which substantially
reduced the mean service time, especially in situations, where the service
engineer is not close to the users facility.
B. Spectrometer Layout
Commercially available spectrometers are classied according to the x-ray tube used, the
position of the sample, sequential or simultaneous acquisition of the uorescent radiation,
hybrid forms, and some special dedicated designs. They will be discussed in the following
order:
Sequential instruments with EWT or SWT, sample down or sample up
Simultaneous instruments with sample surface up or down
Hybrid or dedicated designs
1. Sequential Spectrometerswith EWTor SWT
A typical example of geometry with sample surface down (i.e., the x-ray tube positioned
under the sample) is represented in Figure 45 (layout of the Siemens-Bruker SRS-3400).
The merit of the sample-surface-down geometry is in the analysis of solutions, not easily
feasible with a sample-surface-up geometry. The positions of primary beam lters,
sample=spectrometer seal, collimator masks or diaphragms, and spectrometer optics are
clearly shown. The front end of the x-ray tube and all other parts except the scintillation
counter are enclosed in a vacuum chamber. The sample=spectrometer seal is inserted in
order to isolate the sample lock from the goniometer during sample loading. The sample
lock and goniometer are evacuated by their own vacuum pump. The aim of this parti-
cularity is the maintenance of a monochromator atmosphere of constant composition,
Figure 45 A spectrometer layout with EWT and sample-surface-down geometry. (Siemens
SRS3400. Courtesy of Bruker.)
which may contribute to the reproducibility of the determination of light elements and
prevent the contamination of the monochromator, particularly the collimator, from
contamination by powdery samples. A drawback is the x-ray absorption when light ele-
ments are to be determined. Philips recently introduced a spectrometer with the same
geometry (PW 2400 or 2404; Fig. 46) with an end-window x-ray tube, called the Super
Sharp Tube (SST). The sux super sharp points to the angle of conical nose of the tube,
allowing a decrease of the sample distance to the window. The duplex detector (replacing
the classical tandem fpc=sc construction) is a combination of a ow counter and a sealed
xenon detector (improved performance for Ka for Ti to Cu and for La to W). The scin-
tillation counter is giving an oset angle with respect to the gas counters. By this, the
scintillation counter can be enclosed in the vacuum chamber without increasing the vol-
ume of the chamber. The selection of the detector is software controlled and became
possible by the decoupling of the W and 2W axes.
Shown in Figure 47 is the method by which one or two additional xed channels can
be added. Fixed channel(s) reduce(s) the analysis time for routine analysis of samples with
one or two elements constantly present or for samples with an internal standard. ARL
Figure46 Spectrometer with EWT and sample-surface-down position but with the addition of a fixed
channel. This channel is the similar to the ones used in simultaneous spectrometers. (Philips PW2404)
(Philips Technical Materials. Sequential X-Ray Spectrometer System PW 2404. Courtesy of Philips.)
realizes the simultaneous determination of more than one element by enclosing within the
vacuum chamber a complete second monochromator of their unique extremely compact
design as represented in Figure 47. It is characterized by the complete absence of gears and
a positioning system by counting Moire fringes resulting from interference of two grating
systems.
A development of the last few years is the substitution of diaphragms by a small-
diameter aperture allowing analysis of an area as small as approximately 1 mm
2
(see
Sec. VI.A.3 about milliprobes). An appropriate mechanism is moving the sample, which
allows element mapping. This feature is realized in the XRF-1700 or 1500 series of Shi-
madzu (Fig. 48). It is an instrument with sample-surface-up geometry and tted with an
attenuator, reducing the intensity by a factor of 10 (for a major element determination);
the merit of this is that no tube power switching is required for major and minor element
determination.
Figure 47 Heart of the ARL 9400 spectrometer (EWT, sample surface down). Two such
monochromators, operating simultaneously, are integrated in one spectrometer, model, ARL 8420S.
(Courtesy of ARL.)
Only one manufacturer still produces an instrument with SWT. A number of in-
struments of a former generation are still in use and the tubes are still available. Diano
Corporation continues the production of a spectrometer with sample-surface-up geometry
and SWT (cf. Table 10). The merits and disadvantages of EWT or SWT were previously
discussed. However, if a good homogeneity of the beam is required, a ne-focus SWT is by
far a better solution.
Sample holders of slightly dierent design for solids and liquids, for sample surface
up or down, are oered by the manufacturers. The holders for instruments with sample-
surface-up geometry are tted with a spring mechanism to press the sample against the
sample mask, both for sequential and simultaneous instruments. The holders adapting
insert for liquids have a shape that can be recognized automatically and will not be ac-
cepted if the spectrometer is not under a He atmosphere (or eventually switches auto-
matically from vacuum to He).
2. Simultaneous Instruments
All simultaneous instruments are equipped with end-window tubes with very similar con-
struction features. Up to 30 monochromators may be arranged radially around the tube
head, with alternating high and low takeo angles. One or more monochromators may be
replaced by programmable goniometers of the at (a normal at crystal goniometer of re-
duced size) or curved crystal type. The latter is small but limited in angular range; the former
has a large angular range but is large and occupies at least two positions otherwise taken by
xed monochromators. As already mentioned, Philips oers a small, low-power target
transmission tube (TTT tube) used in the spectrometer PW 1660 (Philips Technical
Figure 48 Sample-surface-up spectrometer, fitted with small-aperture collimator diaphragms and
an attenuator; all parts are enclosed in the vacuum chamber (Shimadzu XRF-1700). (Courtesy of
Shimadzu.)
Materials. Simultaneous X-ray Spectrometer System PW 1660) or X
0
CEM capable of si-
multaneous determination of only 14 xed elements or 12 elements when equipped with a
programmable goniometer. In most instruments the samples are placed in the surface-up
position. Some instruments (e.g., Oxford and PW2600 from Philips) irradiate in the sample-
down position. The monochromators can be tted to the outside of the vacuum cabinet, in
which case they need not be vacuum tight. Figure 49 shows a generally used geometry.
In the ARL sequential instruments, xed channels (up to eight) or a complete second
monochromator can be added. In Philips sequential spectrometer (PW 2400), an optional
two xed channels may be installed, making this instrument partly simultaneous. This is
made feasible by the use of the special x-ray front end tube, the model Super Sharp Tube.
3. Milliprobes
In an obvious eort toward the new elds of application, two companies introduced
options, which seem to be restricted up to now to the very special, laboratory-made in-
struments. Rigaku and Shimadzu independently constructed the analytical systems with
special masks: nonmovable (Rigaku) and scanning type (Shimadzu). In both versions, the
diameter of the opening is 1 mm. Coupled with a 4-kW generator and high-power tube, it
can carry out the analysis of the small pieces of a sample. In the Shimadzu version,
Figure 49 Layout of a simultaneous spectrometer with sample-surface-up geometry, typical for
Bruker MRS4000 or Philips 1606 and with the arrangement at two levels with different takeoff
angles. (Courtesy of Bruker.)
the opening is scanned before a front of the sample, thus enabling the elemental mapping
of the sample. The suggested application would be for the spot composition and density
tracing of the sample, as it has been checked elsewhere (Kuczumow et al., 1995; Luggar
and Gilboy, 1994). The construction of the milliprobe requires special attention con-
cerning the x-ray tube used. The conventional end-window tube, due to its output in-
homogeneouity, might be used only in the Rigaku arrangement, with a constant mask and
the sample moving in front of the tube. Otherwise, the relatively small output of such tubes
prevents their use as a radiation source for the milliprobes.
C. Intercomparison of Instruments
Only a limited number of manufacturers produce x-ray spectrometers. Hereafter, we will
discuss the instruments of seven manufacturers subdivided in three classes: sequential and
simultaneous instruments and a third class that we called hybrid spectrometers, because
they have characteristics belonging to both former classes. The series numbers together
with the names of the manufacturer are given in Table 8. In Tables 911, the numbers in
the top row of the third, fth, and last column refer to the manufacturer and series number
of Table 8. The reader will nd the actual addresses of the manufacturers headquarters at
the end of this subsection.
1. Sequential Instruments
In Table 9, a summary is given of the main characteristics of the current instruments as a
guide to the market for the interested reader and for those who are considering buying a
new instrument or replacing an older instrument.
a. General Remarks and Items Common to All Instruments
A question mark in the table means that the data were not available in the
brochures. When nothing is marked, it means that the given item is not
applicable.
Table 8 Available Wavelength-Dispersive Spectrometers
Sequential Simultaneous Hybrid
Manufacturer Series Table 9 Series Table 10 Series Table 11
ARL 9400 1 8600S 1
Diano 2000 2
Oxford MDX1000 1
Philips PW2400 3 PW1606 2 Venus 100
PW2404 3
0
PW2600 3 PW4100=20 2
X-CEM 4 PW4120=20 2
0
PW4110=10 3
Rigaku RIX2100 4
RIX3100 4
0
Siemens SRS3400 5 MRS 4000 5
Shimadzu XRF1700 6
XRF1500 6
0
Table 9 Presentation of Sequential Instruments
Manufacturer
1 2 3, 3
0
4, 4
0
5 6, 6
0
Generator
Power (kW) 3 3 3, 4 3 or 4 3 or 4 3 or 4
Voltage range=step
(kV=step)
?60=? (opt.: ?70=?) 1560=1 2060=1 60=? 1060=1 60=?
Current range=step (mA) ?100 080=0.1 10125=1 100 or 150=? 5150=1 100 or 140=?
Switch time (s) ? ? <2,5 ? Fast
Switch mode ? ? Isowatt curve ?
Stability D%/% mains 0.0001 0.0005 0.0005 0.0005 0.0001 0.0002
Source
X-ray tube: geometry,
load (kW)
EWT, 3 SWT EWT, 3 EWT, 3 or 4 EWT, 3 or 4
Anode, type, Be window
thickness (mm)
Rh, 3GN, 75 Cr, EA-75, 250 Rh, SS, 75 or 125 Rh Rh, AGRh66G,
75 or 125
Rh
Option other anodes W, Mo, 125 W,Pt,W=Cr,
Pt=Cr,Mo=Cr
Others on request Rh=Cr,Rh,=C,
Rh=W
Mo, W, Au, Cr Rh=Cr, Rh=W
Primary beam filters
number
3 None 5 1 or 5 10 4
Elements Cu, Al, Fe Al, Cu Zr, Ti, Al, Cu Cu, Al Al, Ti, Ni, Cr
Sample
Sample surface Down Up Down Up Down Up
Sample turret: number
of positions
2 4 2 6 2 8 or 2
Sample=spectrometer seal
(yes, no)
y n n n y n
Optics
Diaphragms: number of
positions
3 4 6 4 5
Collimators: selectable
(yes, no), number
y, 4 1 y, 3 y, 2 or 3 y, 4 3
Attenuator (yes, no) n n n y n y
Crystal changer:
number of positions 9 4 or 6 8 10 8 10
Detectors: extra (yes, no) n Sealed Xe Sealed Xe, Ne,
Kr
n n n
Goniometer angular range (
2y) 17152 0146 13148 8148 4150 7148

fpc angular range (
2y) 0115 8104 5118 4112 0118

sc and 2 axes dec c dec ? dec dec
(coupled=decoupled)
Positioning technology Moire fringe ? Optical sector ? Stepper motor Stepper motor
Continuous scanning
(
2y=min)
0.25128 0.110 0.006120 0.1240 1200 0.01180
Step scanning (
2y=min) 0.0011.00 0.01? 0.00012 0.0050.1 0.0021

Slewing speed (
2y=min) 4800 600 2400 1000 1000 1200

Angular accuracy (
2y,
y) 0.001 0.001 0.0025 ? 0.00001 ?

Angular reproducibility
(
2y,
y)
0.0002 ? 0.0001 0.0005 0.001 0.0003
Temperature stabilization
(
C)
0.1 None <0.05 ? 0.01 0.3
Additional fixed channels
(yes, no, or number)
y None 2 None None None
Parts included in vaccum All All All All except sc All except sc All
Counting electronics
Count rate (kcps): fpc 2000 ? 2000 2000 2000 2000
sc 1500 ? 1500 1000 2000 1000
Sealed 1500 4000
Duplex 3500
Pulse-shift correction Automatic Graphical display Automatic,
dynamic
Pulse-height
discrim.
Automatic Automatic
Dead-time correction Automatic Graphical display Automatic Automatic Automatic Automatic
Computer instrument
monitoring peripherals
Full Partly Full Full Full Full
Remote servicing (yes, no) y n y ? y n
Sample changer: type (x, y),
positions
xy, 1298 x, 4 or 10 xy, 6, 24168 x(?), 50, 100 xy, 8, 58, 100,
110, 138
?
Table 9 Continued
Manufacturer
1 2 3, 3
0
4, 4
0
5 6, 6
0
Installation
Instrument dimensions:
H
*
W
*
D (mm)
920
*
1080
*
760 1400
*
860
*
1346 1092
*
1410
*
920 1400
*
1420
*
1054 1070
*
1890
*
880 1350
*
1770
*
1080
Weight (kg) 450 590 580 750 700 780
Electricity supply (V, kVA) 220, 6 208480, 10 200240, 8, 5 200220, 10 115400, 8 200220, 8 or 9
Cooling water: bar, max.
temp. (
C), flow (L=min)

>2, 20, 0.55 > 1, 29, 19 >3.58, 20, 611 ?, <30, 3.511 46, , 1.5 >1.53, 30, 310
Compressed air: bar,
flow (L=min)
45, ? None 610, 20
The analyzing range of all instruments goes from Be to U and the
transuranians, except for Diano 2000, for which the range is limited to BU.
The mains power requires a stability from 10% to 10%, exceptionally from 15%
to 10%. A single phase is required, except for Rigaku, which requires three
phases.
Most commonly oered by all manufacturers are rhodium anodes for x-ray tubes.
Primary beam lters are used to remove interfering lines from the tube target element
and=or to improve signal-to-background ratio:
Al: improves peak-to-background ratio for Pb and As in light matrices;
removes RhKa line and the CrK lines
Cu: determination of Ru, Rh, Pd, Ag, and Cd; removal of interfering lines
from Rh
Fe: removes the Ka line of Rh
Ti: determination of Cr, Co, Fe, Zn; improves peak-to-background ratio
Zr: measurement of CdKa, removes the Ka line of Rh
Most manufacturers supply other lters on request.
Sample dimensions: Most instrument allow a sample size about 52 mm in diameter
(Diano: 63 mm) and about 30 mm in height (Bruker: 57 mm).
To cope with small heterogeneities, the samples are spun at 30 rpm (or 60 rpm for
Shimadzu) on most instruments (for Diano, the spinner is only available on the
sample changer with 10 positions).
The collimators are quoted in most brochures as extra-coarse, coarse, medium, ne
(high intensity to high resolution). Only Bruker mentions the divergence
angles: 0.077
, 0.15
, 0.46
, 0.93
, 1.0
, 1.90
, and 1.54
.
Crystals: All sequential spectrometers make use of at crystals.
Counters: A gas-ow-proportional counter (fpc) and a scintillation counter (sc) are
standard on all instruments, except Diano, in which the sealed Xe detector is
standard and a scintillation counter is an option. The gas ow (Ar 10%
CH
4
) is 12 L=min.
The electronic counters are all based on a multichannel analyzer (Shimadzu and
Rigaku probably still use a pulse-height discriminator) with an automatic pulse
shift and dead-time correction.
Available on all spectrometers is the choice of vacuum or He as the spectrometer
atmosphere, with nitrogen as option for many.
All companies supply the control unit by personal computer in more or less
sophisticated versions with software for monitoring the instrument, for
qualitative analysis, and for a number of possibilities for conversion of
intensity to concentration. All of these items are subject to change and not
discussed in detail here. The conversion algorithms are discussed in detail in
Chapter 5. The software systems supplied by Bruker, ARL, Rigaku, and
Shimadzu are all very user friendly.
Installation data are added to give the potential buyer an idea of the required space
and infrastructure. The dimensions and weight of the instruments are given
without an external sample changed t.
b. Remarks About the Individual Instruments (in Alphabetical Order as in Table 8)
ARL 9400: As far as we are aware, ARL was the rst manufacturer (and still the only
one) to use counting Moire fringes for its goniometer positioning. The
goniometer is a complete gearless construction and it has the highest slew rates
Table10 Presentation of Simultaneous Instruments
Manufacturer
1 2 3 4 5
Generator
Power (kW) 3 3 3 0.2 3
Voltage (kV), step (kV) ?60=? ?60=? 560=1 (a) 50 2060=1
Current (mA), step (mA) ?100=? ?75=? 5125=1 4 5150=1
Stability D%/% mains 0.0001 0.0005 0.0005 0.0005 0.0001
Source
X-ray tube:
Load (kW) 3 3 3 TTT
*
Rh 66 G
Anodes Rh, W Rh, Cr, Mo Rh, other on
request
Cr Rh, Mo, W,
Au, Cr
Be windows (mm) 125, 75 125, 75 125, 75 125, 75
Primary beam filters 4 (a) 10 3
positions
Elements Cu, Al, Fe
Primary beam attenuators y, 14 y
(Yes, No)
Samples
Sample surface Up Up Down (b)
Size: diameter, height (mm) 75, 50 51, 40 51, 40 40, ? 52, 57
Sample changer (positions) 11, 32, or 8 (b) 6, 72, 300 8, 58, 100, 138
Monochromator (fixed
channels)
Takeoff angle (
) ? 29, 44 29, 44 25, 39, 5 26, 24 (a)

Maximum number 30, 20, 11 (c) 28 (a) 28 14 28
Crystals Curved x Log. curved
Detectors Gas counter, sc Gas (Ar flow, Ne,
Kr sealed)
fc, sc
Element range BeU BeU BeU
Goniometer
Maximum number 1 (d) (a) 2 (c) 2 (d) 8 2 (a)
Collimators 3 1 Slits
Crystals number 9 1 (LiF 200,
220, Ge)
4 (PE, InSb, Ge,
LiF 200, 220)
Up to 4
Type Flat Flat Cyl. curved
Scan speed (
2y=min) 0.25128 0.0676 0.0676 0.0676

Step scan (
2y=step) 0.0011 0.01 0.01 0.01

Slewing speed (
y=min) 4800 1000 480 480

Angular accuracy (
2y) (LiF) 0.015 ? ? ?

Angular resolution (
2y) 0.001 ? ? ?
Angular reproducibility (
) 0.0002 0.003 <0.01 <0.005

Angular range gas counter
(
2y)
17155 5120 10100 8547
sc (
2y) 0115 5120

Detector sc, Kr-sealed fpc
Element range BU BU FU
Spectrometer environment Vac Vac, He, air Vac, other on
request
Vac, other on
request
Vac, air
XRD channel (yes, no) y n
Installation
Dimensions:
H
*
W
*
D (mm)
1350
*
1400
*
950 1804
*
1232
*
877 1190
*
815
*
1230 1800
*
1810
*
950
Weight (kg) 1000 900 580 900
Water supply(bar, max.
C, L=min)
>3, <18, 5 3058, <20,
610
38, 20, 3
Compressed air (bar, L=min) ? 45, ? 610, 20
of all spectrometers. In the series 9420S, two goniometers or additional xed
channels can be tted, adaptable to a great variety of analytical situations,
excellent for rapid nonroutine industrial control, reducing the analysis time by a
factor of 2 with respect to a conventional sequential spectrometer. Separate
vacuumpumps support the vacuumfor the sample lockandthe monochromator.
Diano 2000: This oers dual-target tubes. The targets are push-button selected and
no moving parts are present (dual lament). Two collimators are oered: a
0.032-in. spacing beam tunnel or a 0.010-in.-spacing diracted beam soller
slit. The instrument is not temperature stabilized because the 45-kg bronze
bull gear goniometer has a suciently high thermal capacity, avoiding rapid
temperature changes. It is, however, not sucient when one wants to measure
peak shifts. The crystal in the turret must be individually tuned. The W and 2W
axes are coupled but with a bisector arrangement and moved by a dc motor.
The standard detectors are a ow-proportional counter and sealed Xe, the
scintillation counter is an option. The counting is also by a pulse-height
selector. Diano oers a xed-sample and xed-element mode for analysis.
Table11 Hybrid Instruments
Manufacturer
1 2, 2
0
3
Generator
Voltage (kV)=current
(mA)=power (W)
4050=4=200 50=4=200 id.
Stability D%=%mains 0.007 0.0005 id.
Max. mains
variation (V)
210250 180264 id.
X-ray source
Tube Similar (a) Target transmission id.
Anode Rh Sc Cr
External Cooling None None id.
Sample
Sample surface up, down Down Down id.
Spinning (rpm) 30
Dimension (diameter,
height in mm)
48, 40 2647, 40 id.
Sample changer ? Single, 10 Single
Spectrometer chamber Vac, He optional Vac, He Vac
Monochromator (fixed)
Element covered FU S, S-bg., Zr, Ni,
Ni-bg., Mn,
Mn-bg., V, V-bg
Al, Si, Na, Mg,
Ti, Mn, K, Ca,
P, S, Fe
Crystals Flat, curved optional Curved id.
Additional
spectrometers
Flexi-channel
(EDXRF)
None id.
Dimensions
(H
*
W
*
D in mm)
1090
*
800
*
800 id. 1200
*
750
*
960
Weight (kg) 160 id. 180
Philips PW 2400, 2404: Both types dier only in the power output of the generator.
The tube power is switched along the isowatt curve (i.e., by keeping the power
constant when either the voltage or current is changed). The xed channels
that can be added have as the detector either a ow-proportional counter
(3000 kcps), Xe-sealed (1000 kcps), Kr-sealed (2000 kcps), Ne-sealed
(2000 kcps) proportional counters, or a scintillation counter (1500 kcps). The
positioning of the goniometer is done by optical disk, a sophisticated high-
performance system, giving the highest angular accuracy and reproducibility.
The goniometer is driven by dc motors. The external sample changer accepts
samples of nonuniform size.
Rigaku 2100, 3100: Both types dier only in power output of 3 and 4 kW. The
collimators are either standard=high resolution or standard high resolu-
tion=ultralight elements. The attenuator in front of the monochromator crystal
reduces the intensity by a factor 10. The advantage should be that it avoids
power switching of the x-ray tube. The sample-surface-up geometry makes it
dicult, if not impossible, to analyze solutions. A diaphragm of 1 mm
diameter allows small-spot analysis. A built-in cleaning system removes the
impurities of the wire in seconds in this instrument because the ow-counter
eciency deteriorates by contamination of the wire electrode.
Siemens (Bruker) SRS 3400: The instrument is rather conventional and easy to
service. The positioning of the decoupled arms of the goniometer is done by
stepper motors. The positioning of the sample holders is very reproducible. The
external sample changer accepts nonuniform samples also. An excellent
software SPECTRA PLUS is supplied for qualitative, semiquantitative, and
quantitative analyses. The instrument was formerly sold under the name of
Siemens but is taken over by Bruker Analytical X-Ray Systems (Bruker AXS).
Shimadzu XRF 1700, 1500: The dierence between both instruments is that the
selection of lters, diaphragms, attenuator, and crystals is automated in the
1700 model. A special feature of this instrument is the presence of diaphragms
of diameter 1, 3, 10, 20, and 30 mm. The 1-mm diaphragm together with an
appropriate sample positioning system allows element mapping.
2. Simultaneous Instrumentswith Sample Surface Up or Sample Surface Down
A summary of the characteristics of the instruments capable to determine simultaneously a
number of the elements is given in Table 10. The instruments are composed by a few till
maximum 30 small-size high-eciency spectrometers as discussed earlier, optimized for
one particular element. The set of spectrometers is dedicated to a particular series of
samples as used in, for example, the cement or steel industry. To attribute some exibility
to these instruments, one or more scanning goniometers are added.
a. Remarks and Features Common to All Instruments
All manufacturers use x-ray tubes with either a 75- or 125-mm-thick Be window.
The detectors oered are ow-proportional gas counter (Ar), sealed gas counters
lled with Kr, Ne, or Xe, and a scintillation counter.
The linearity of the photon count rate is equal or similar to the one given for
sequential instruments.
Temperature stabilization is either individual for each spectrometer or for the
ensemble.
Electricity power supply is single phase, 1015 kVA.
ARL oers the possibility of adding an additional x-ray diraction device within the
uorescence spectrometer.
Other manufacturers oer integrated sample transport from the spectrometer to an
x-ray diraction instrument. The CubiX XRF from Philips is a simultaneous
spectrometer for up to 14 elements, similar to the XCem. It is integrated in the
same module with an x-ray diraction instrument; both can be juxtaposed,
allowing a rapid sample transport from one instrument to another. Both devices
are operated by a single personal computer. Cubix represents a modular concept
for integrated analysis, including elemental and crystallographic determination.
b. Remarks About the Individual Instruments (in Alphabetical Order as in Table 8)
APR 8600S
1. The primary beam lter takes the place of three monochromators and cannot be
t alongside an XRD channel.
2. Eight positions for cassettes for large samples (75 mm and height of 50 mm);
11 and 32 positions for small samples (52 mm and height of 30 mm).
3. Thirty monochromators can be tted or 20 plus 1 goniometer, or 11 plus an
XRD channel.
4. The goniometer is the same as the module of the sequential instrument.
Philips PW1600: Maximum two xed channels can be substituted by a program-
mable goniometer (with at crystals and parallel beam collimation). One
programmable channel occupies space as for one xed channel.
Philips PW2600
1. Switching time of the generator is 2 s and the tube is switched along the
isowatt curve.
2. Particular feature of this instrument is that it allows liquid samples to be handled
also.
3. Two dierent goniometers can be tted: (1) one with a at crystal and parallel
beam collimation and it takes the space of one xed channel; (2) one with a
cylindrically curved crystal (logarithmic spiral optics) and two slits and it takes
the space of three xed channels. Optional beam attenuators can be tted,
enabling all channels to handle concentrations from ppm levels up to 100%.
Philips X9 Cem: The x-ray tube is a low-power Target Transmission Tube (TTT),
(Sec. IIIA). Because of the low power (200W), this instrument does not need
external water cooling.
Siemens MRS 4000: High power (4 kW) and high speed instrument.
3. Hybrid Instruments
The instrument from Oxford MDX1000 is classied as hybrid because it combines a WD xed
channel with what is called a Flexi channel, an EDXRF unit. The x-ray tube is similar to the
target transmission tube, produced by Philips, but no other details are given in their brochures.
The instrument series Venus 100 from Philips are called hybrid because Philips uses
xed channels, which are, however, switched sequentially in front of the sample. The in-
struments are delivered for specic purposes: The PW4110=10 is provided for the analysis
of industrial minerals, particularly for the ceramic industry, and the PW4100=20 and
PW4120=20 for the determination of, for example, nickel, sulfur, and vanadium in pet-
roleum products. The element range can be adapted to specic purposes.
Both instruments from Oxford and Philips are simple, low-cost, but high-perfor-
mance devices which can be used in harsh industrial environments; they are simple to
install and are characterized by small dimensions, light weight, no water cooling, no
compressed air, and no severe requirements for the stability of the mains.
Hybrid instruments are presented in Table 11.
4. Instruments Dedicated to Special Applicationsand Supplements
Two manufacturers, Siemens and Philips, supply for the semiconductor industry trans-
formed versions of their sequential spectrometers SRS 3300 (power up to 4 kW, mapping
possible) and PW 2800, respectively. The main feature is the sample area which must
accept silicon disks as large as 10 in. in diameter. The sample introduction system is au-
tomated and meets the standards for working in a cleanroom environment.
The manufacturers also provides as many auxiliary devices as possible. Advanced
analysis lines are available from Rigaku, Philips, and Siemens, which oer a complete
set of the mills, uxers, and polishing devices for the XRF and XRD laboratory.
Worth noting is that, on the other hand, during the last years, some new companies
appeared on the market, oering not whole instruments as such but only some specialized
parts of instrumentation. Among the most important participants in this kind of activity,
the following should be mentioned:
Advance Hivolt, oering x-ray generators, especially with 4 kW power
X-Ray Optical Systems Inc., supplying x-ray focusing and collimating polycapillary
optical devices plus designing the optical systems with x-ray semilens
Osmic Inc., the main producer of multilayers
Corporation Scientique Claisse Inc., producing uxers for sample preparation
Contact with these producers can be very meaningful alternative in case of constructing
new, home-made, and dedicated version of an instrument.
We conclude this subsection on the intercomparison of instruments with a list of the
addresses of the headquarters of the manufacturers:
ARL Applied Research Laboratories S.A., En Vallaire Ouest C, case postale, CH-
1024 Ecublens, Switzerland
Diano Corporation, 271 Salem Street, Woburn, MA 01801, USA
Oxford Instruments, 19=20 Nueld Way, Abingdon, Oxon OX14 1 TX, England
Philips Analytical X-Ray BV, Lelyweg 1, 7602 EA Almelo, The Netherlands
Rigaku International Corporation, 3-9-12, Matsubara-cho, Akishima-shi, Tokyo
196, Japan
Shimadzu Corporation, International Marketing Division, 3, Kanda-Nishikicho
1-chome, Chiyoda-ku, Tokyo 101, Japan
Siemens, A.G., now: Bruker AXS GMBH, Oestliche Rheinbrueckenstr. 50, D-76187,
Karlsruhe, Germany
VII. FUTURE PROSPECTS
The time passed since the rst edition of this handbook has been one of the most stormy
periods in research and applications of x-rays since their discovery! It is well known how
much Ro ntgen was confused, although totally convinced, by the impossibility to de-
monstrate the electromagnetic nature of x-rays through reection, diraction, or inter-
ference experiments! For many years, it remained impossible and further progress was very
slow and tedious. Recent years have brought the real breakthrough. We know of three
recent realizations of x-ray lenses:
Two diractive:
1. Zone plates (in other words, Fresnel diracting structures), earlier restricted to
the very soft x-rays. They are very important for the construction of the x-ray
microscopes and for the observation of living biological objects in the so-called
water window. But now, by combining the Fresnel diraction patterns with
Braggs phenomenon, the special BraggFresnel lens was constructed, well
suited for focusing hard synchrotron radiation (Aristov et al., 1986; Snigirev,
1995; Snigirev et al., 1995; Chevallier and Dhez, 1997).
2. Snigirev refractive lens (Snigirev et al., 1996; 1998; Elleaume, 1998; Hastings,
1996; Eskildsen, et al., 1998), consisting of one or two mutually perpendicular
arrays of holes drilled in low-Z dense material (Be, Al). Depending on the
number and shape of the holes, they can focus hard x-ray beams,
One version using total reection:
1. Kumakhov polycapillary lenslike device, which might be somewhat poor in
focusing capability (spot is $50500 mm wide) but very ecient with respect to
the fraction of the primary input power turned into a small spot on the analyzed
surface. Interesting products were announced by X-Ray Optical Systems Inc.,
Advertising Materials.
In parallel, great progress was realized in the construction of energy-dispersive de-
tectors with increasingly better spectral resolution. The most promising device seems to be
the microcalorimeter detector, a device with very good spectral resolution parameters.
Moreover, its spectral resolution is more or less constant over the whole spectral range
covered (120 keV). With such a device, the spectrum deconvolution problems, so char-
acteristic for devices with poor spectral resolution, should vanish. Potentially, it lowers the
detection limits, by narrowing the energy region in which the very sharp peak is placed.
Only a very restricted number of background counts is detected in that region, thus im-
proving the peak-to-background count rate ratio. However, the detection limit depends on
the maximum count rate allowed for these detectors, which is, at the moment, very re-
stricted. Recent discussions show (Ladbury, 1998) that intensive work is going on to
overcome this shortcoming in the nearest future. The aim is to get the device with an area
of 40 mm
2
, with count rates up to 10
5
cps.
Another progress took place in the construction of time-resolved excitation sources.
The classic radiation generator for the purpose is synchrotron. Probably much more
convenient, the portable and switchable version of a time-resolved x-ray source will be a
compact-ash source. Furthermore, the construction of the x-ray laseran old dream!is
also progressing, maybe slowly, but in a promising direction.
Collected together, all available information about this progress justies hope on the
construction of new versions of existing instruments as well as the advent of new ones. It is
worth noting that in the present chapter we considered an XRF spectrometer mainly as a
device used for the determination of elemental composition. What is now discussed tes-
ties that future instruments will give both compositional and spatial resolution (mi-
croprobe) and time resolution (kinetic probe). New kinds of lenses and normal incidence
mirrors give an impetus to the construction of x-ray microscopes also in the hard part of
the x-ray spectrum. One can easily imagine a microscope (but one easily construct!)
working in the hard x-rays regime supported by two dierent x-ray lensesone acting as
an ocular lens and one as an objective lens.
The new version of the microprobe could then eciently concentrate x-rays (e.g., by
Kumakhov polycapillary) on the conned areas and then record the uorescent radiation
with the excellent spectral resolution of a microcalorimeter as the energy-dispersive de-
tector with the whole spectrum completed in one operation. Such a device is now under
construction in the National Institute of Standards and Technology (Wollman et al.,
1997a, 1997b; Anonymous, 1997). The microcalorimeter detector, attached to a scanning
electron microscope, has, for the time being, a spectral resolution of 7.2 eV0.4 eV,
calculated in the standard way for the MnKa line, or 2.0 eV for 1.5 keV (Wollman et al.,
2000). Count rates are below 150 cps, but it is, by far, not the last word in this matter.
A newcomer in the generation of possible applications of the classical WDXRF,
rather unexpectedly brought to the awareness of scientists, was that the extended ne
structure of uorescent spectra emitted by solid samples can be observed (Hayashi et al.,
1997; Kawai et al., 1998). Up to now, this eld was reserved for the absorption mode,
mostly in combination with synchrotron radiation. The discovery of the extended ne
structure in experiments performed under normal laboratory conditions opens a new eld
in the study of local structure in condensed matter and makes this method available to
lower-budget laboratories.
ACKNOWLEDGMENTS
All manufacturers of instruments are gratefully acknowledged for supplying documents
about their instruments. Mr. P. Van der Aa, Dr. B. Volbert, and Dr. ir. B. A. R. Vrebos
from Philips Analytical and Mr. S. Ornigg, Dr. K. E. Mauser, and Dr. N. Broll from
Siemens (Bruker) AG deserve our gratitude for invaluable advice and critical reading of
the manuscript. Dr. D. de Boer is acknowledged for supplying us with his knowledge on
the most recent progress in multilayer research. A. Kuczumow thanks the Catholic Uni-
versity of Leuven for a fellowship that enabled him to participate in the rst edition of this
work and the Flemish Government for a fellowship helpful in the present revised version.
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3
Energy-Dispersive X-ray Fluorescence
Analysis Using X-ray Tube Excitation
Andrew T. Ellis
Oxford Instruments Analytical Ltd., High Wycombe, Buckinghamshire, England
I. INTRODUCTION
The scope of this chapter is laboratory and industrial x-ray uorescence (XRF) analysis
systems in which x-ray tubes are used for excitation and energy-dispersive (ED) semi-
conductor detectors, as opposed to Bragg-diraction (wavelength) dispersion devices,
are used. Such ED detectors directly measure the energy of the x-rays by collecting the
ionization produced in a suitable semiconductor material. The coverage of this chapter
specically excludes the following topics, which are covered in other chapters: on-line
EDXRF systems (see Chapter 7), total-reection XRF (TXRF) (see Chapter 9), polarized
beam XRF (see Chapter 10), and x-ray microuorescence (XRMF) (see Chapter 11).
Early approaches to EDXRF used gas proportional counters or scintillation de-
tectors to determine directly the energy of the x-rays. Such systems were limited in their
application because of the inherently poor energy resolution, which precluded the se-
paration of characteristic x-rays of adjacent elements in the periodic table. The limited
actual energy resolution of such detectors led them to be known as nondispersive, but this
drawback has been eectively countered in some benchtop instruments through the use of
novel arrangements of primary and secondary beam lters (Ross, 1928; Kirkpatrick, 1939;
Kirkpatrick, 1944; Field, 1993). The real breakthrough in EDXRF came in the late 1960s
(Bertolini et al., 1965; Bowman et al., 1966; Elad and Nakamura, 1966; Aitken, 1968) with
the arrival of solid-state semiconductor diode detectors and their associated pulse pro-
cessing circuits. These detection systems were developed through the early 1970s, often in
electron microscopes, to the point at which practical x-ray spectrometry with an energy
resolution of 200 eV or less became possible (Frankel and Aitken, 1970; Landis et al.,
1971; Heath, 1972). Although the energy-resolution capability of semiconductor detectors
remained greatly inferior to that achieved by wavelength-dispersive (WD) XRF systems,
the increased eciency inherent in the energy-dispersive method compensated in many
analytical applications and permitted the use of a multiplicity of experimental geometries
not practical with WDXRF. A wide variety of EDXRF analytical systems based on
radioisotopoe sources, x-ray tubes, charged-particle accelerators, microprobe electron
beams, and synchrotron light sources have been developed in recent years.
Within the scope of this chapter, only EDXRF systems in which x-ray tubes are used
for excitation will be considered further. The material in this chapter discusses the in-
strumental aspects of the energy-dispersive method, with particular emphasis on the use of
low-power, compact x-ray tubes in combination with semiconductor detectors.
The basic components of an EDXRF instrument within the scope of this chapter are
depicted schematically in Figure 1. Each of the main subsystems of such an instrument is
covered in detail in the following sections.
II. X-RAY TUBE EXCITATIONSYSTEMS
In EDXRF spectrometry, there is no physical discrimination of the secondary radiation
that leaves the sample and enters the detector. This means that all photons of all energies
in this secondary beam interact with the detector. The detector and its associated signal
processing chain have a limited capacity to process these events and this is typically in the
range 150 kcps. As a direct consequence, EDXRF has a limited total counting capacity
Figure1 Basic components of a tube-excited EDXRF instrument.
for all element x-ray emissions and it is, therefore, essential that the content of the incident
spectrum be optimized for its useful information. This may require that more than one
acquisition be made under dierent excitation conditions in order to control the range of
energies needing to be collected in the detection system. Alternatively, the excitation
system may be optimized to increase the intrinsic peak-to-background ratio through the
use of alternative geometries such as TXRF or polarization EDXRF. In both these cases,
however, higher-power x-ray tubes are typically required and there is still the need to apply
some type of selectivity to the excitation system. This selectivity can be achieved in TXRF
using more than one tube target materialtypically Mo and W. In the case of polarization
EDXRF, more than one tube high voltage or polarizing element is likely to be applied.
This selectivity of excitation employed in EDXRF is completely the reverse of
conventional WDXRF practice. In WDXRF, the high discrimination power of the dis-
persion and detection process and its associated losses coupled with very simple detection
and counting systems allow very high count rates to be processed for each narrow wa-
velength band. Thus, the detection process is highly selective and the count rates in an
individual element channel with a modern WDXRF system can be well in excess of 10
6
CPS. Typically, the simple rule of thumb in WDXRF would be to use twice to three times
the kilovoltage (kV) of the absorption edge of the highest element of interest and then to
apply the maximum allowed current at that setting. In summary, we may regard the es-
sential operational dierence between EDXRF and WDXRF spectrometry as follows:
WDXRF uses broad-band excitation and selective detection.
EDXRF uses selective excitation and broad-band detection.
There are various ways in which selective excitation is achieved in EDXRF spec-
trometry. The use of TXRF and polarization is covered elsewhere in this volume and will
not be considered further here. The most important modes in which selective excitation is
realized in EDXRF are as follows:
Selection of tube anode material
Variation of tube voltage (kV)
Use of primary beam lters
Use of secondary targets (and associated lters)
The selection of tube anode material is typically a once-o decision made at the time of
purchase in view of the intended application. The high purchase cost of x-ray tubes
generally precludes operational changes and low-power dual or multiple (Kis-Varga, 1988)
anode x-ray tubes are not commercially available.
The types of x-ray excitation arrangements are shown schematically in Figure 2.
The following subsections describe typical arrangements for excitation and describe
how optimum excitation conditions can be determined. Earlier work on this subject may
be found in the XRF literature (Sandborg and Shen, 1984; Vane and Stewart, 1980;
Gedcke et al., 1977).
A. Direct and Filtered Direct Excitation
In Figure 2, the beam(1) represents the conguration used for direct excitation of the sample
by the x-rays emitted fromthe anode. Aprimary x-ray beamlter can be used to modify the
spectrum from the x-ray tube that is nally used to excite the elements in the sample.
The optimum selection of kV and primary beam lter are critically important for
obtaining the best data from an EDXRF system. As with all spectrometry methods, the
principal driver for best precision and detection limits is peak-to-background (P/B) ratio.
However, as mentioned earlier, the limited total counting capacity of the EDXRF system
and the analysis of multielement samples are added complications in deriving optimum
excitation conditions. In general, the kV governs the sensitivity and the primary beam
lter governs the background.
The energy distribution of the spectrum arriving at the sample governs the eec-
tiveness of excitation for element XRF lines. In order to excite x-ray uorescence, it is
necessary to have incident x-ray energies above the absorption edge for the elements line
series to be excited. In order to have adequate excitation, there needs to be a high intensity
of x-rays with energies higher than the edge and conventional wisdom has suggested that
the tube kV should be 1.52 times the absorption edge of interest. This overvoltage en-
sures that there is a substantial proportion of the x-ray tube output spectrum available for
excitation of the element line(s) of interest. Figure 3 shows the unltered x-ray tube
spectrum scattered from a thin-polymer-lm sample when the x-ray tube is operated at
5, 10, and 15 kV. The observed scatter spectrum is a reasonable representation of the
spectrum striking the sample and clearly shows the following:
Figure 2 An x-ray tube and typical excitation geometries. The high-energy electron beam strikes
the anode to produce x-rays. (1) Direct or direct filtered: the flux (1) is used directly to strike sample
(1) or is first passed through a primary beam x-ray filter. (2) Secondary target: the primary flux (1)
strikes a secondary target 2, which generates a flux of x-rays (2), which strikes the sample at 2.
(3) Transmission geometry: the beam (3) is directed through the anode to the sample.
The high-energy cuto at the operating kV. This is also known as the DuaneHunt
limit.
The bremsstrahlung hump.
The intense characteristic AgLlines (around 3 keV) fromthe tube anode. The intensity
of the AgL lines increases with the kV (i.e., as the overpotential increases).
The tube L lines of Ag and Rh are particularly eective for exciting the light elements in
the range 12.5 keV. Once higher-energy lines (e.g., FeK at 6.4 keV) are sought, the L
lines provide no excitation, as they are lower in energy than the absorption edge (FeK at
7.11 keV) and the bremsstrahlung hump provides the excitation. Despite the highest in-
tensity of the bremsstrahlung being lower than AgL lines, it is the integrated excitation
spectrum, higher in energy than the absorption edge, which is important. When the x-ray
tube kV exceeds the energy of the K edge of the tube anode material, the characteristic K
lines will begin to dominate the excitation spectrum. This is shown in Figure 6, which
depicts the scattered excitation spectrum with the tube operated at 35 kV, at which the
AgK characteristic lines are strongly excited.
The basic sensitivity for analysis is governed by the kV applied to the x-ray tube and
an example of this is seen in Figure 4. The sample was a pressed pellet and the kV was set
in the range 616 kV using a vacuum path in the spectrometer and no primary beam lter.
At each kV, the rhodium-target x-ray tube current was adjusted to give 50% deadtime.
The K-series line intensities were used and the sensitivity for each element has been nor-
malized to the value at 10 kV. From the plots, the following are clear:
The Si intensity falls o as the kV increases. This is due to the increasing distance of
the tube main spectrum from the SiK absorption edge and to the increased relative
contribution of the other elements to the total counts in the spectrum. This latter
Figure 3 Scattered, unfiltered excitation spectrum provided by a silver target x-ray tube operated
at (1) 5, (2) 10, and (3) 15 kV.
factor is important and derives from the limited total count rate for the whole
spectrum.
The FeK lines are not excited until at least 8 kV is applied. The FeK absorption edge
is at 7.111 keV and the maximum sensitivity for Fe is at approximately twice this
value.
The general rule of thumb in which the kV is set to twice the highest absorption-edge
energy is a reasonable place to start. However, as more elements are sought across a wider
energy range, there usually comes a point at which the balance of the spectrum is un-
favorable for the analytical problem being solved. When this happens, split the spectrum
into two or more areas of interest and apply a kV to best suit each of these element ranges.
In any event, as the kV and the number of elements increase, the importance of using a
primary beam lter and splitting the spectrum into optimized energy regions increases.
B. Primary BeamFilter Selection
A primary beam lter acts as an x-ray absorber and it is placed between the x-ray tube and
the sample to modify the x-ray tube output spectrum to which the sample is exposed. In
general, the kV is selected rst to ensure high excitation sensitivity and then an appropriate
lter is chosen. The lter acts to reduce scattered background in the region of interest and
to reduce the excited intensity of lower-energy peaks. The characteristics of the lter are
dened by its x-ray absorption curve, which is controlled by selecting the material and its
thickness. Filters are typical thin, pure metal foils of thickness in the range 10500 mm.
Some typical lters, the range of kV used with each, and the applicable optimum element
range (K lines) are shown in Table 1.
Figure 4 Effect of kV on sensitivity for the major elements in a geological sample (see text for
details).
The x-ray tube spectrum provided by unltered radiation can be seen in Figure 3.
The eect on the x-ray tube spectrum of applying a thin and thick aluminum lter is seen
in Figure 5, where a tube voltage of 15 kV is used.
The aluminum acts as a simple absorption lter, having a single absorption edge at
1.56 keV. From the plots, it is clear that the aluminum lters both completely absorb the
AgL lines as a consequence of the high-mass-absorption coecient of around 700 cm
2
=g.
The hump at lower energy provided by the spectrum ltered though thin Al yields good
P=B ratios for elements in the S to V range (2.35 keV). The absence of the AgL (or RhL,
MoL) lines from the tube removes their spectral interference and avoids the need for these
x-rays to consume counting capacity. The thick aluminum lter pinches the low-energy
side of the bremsstrahlung hump, providing high P=B ratios for the elements with lines in
the range 38 keV.
The combination of kV and an absorption lter provides an energy region in which
the P=B ratio is optimal. On the low-energy side of this region, the excitation is suppressed,
which allows more of the systems counting capacity to be used in the region itself. On the
high-energy side of the region, the excitation from the tube is tuned to provide a high
integrated intensity above the energy of the absorption edges of the element lines of in-
terest. The use of a thick copper lter with maximum kV is another example of this type of
lter. The copper lter used is generally thick enough to completely absorb the x-ray tube
anode K lines, which are of high energy (AgKa is 22.1 keV). Such an arrangement provides
for the eective determination of Ag and Cd using a silver anode x-ray tube. At the other
end of the energy scale, a cellulose lter is a weakly absorbing lter which suppresses the
AgL lines.
The so-called Regenerative Monochromatizing Filter (RMF) is a particularly im-
portant lter in tube-excited EDXRF spectrometry. The lter acts on the x-ray tube anode
K lines so the kV must be suciently high above the K absorption edge of the
anode material to generate intense K characteristic emission. The same element as the
anode material is used to preferentially transmit the characteristic K x-rays generated in
the anode. The lter takes its benet from the fact that an element has a low-mass-
Table1 Typical Primary Beam Filters and Their Range of Use
Filter Thickness kV range Elements Comments
No filter N=A 450 All, NaCa Optimum for light elements
with 48 kV excitation
a
Cellulose Single sheet 510 SiTi Suppresses tube L lines
a
Thin aluminum 2575 mm 812 SV Removes tube L lines
a
Thick aluminum 75200 mm 1020 CaCu Good for transition element
metal alloys
Thin anode element 2575 mm 2540 CaMo RMF
b
, wide range and good
trace analysis
Thick anode element 100150 mm 4050 CuMo RMF
b
, good for trace analysis
of heavy-element L lines.
Copper 200500 mm 50 >Fe Suppresses tube K lines
a
Needs to be used in conjunction with vacuum or He path to remove the air in the spectrometer that would
severely attenuate the low-energy lines and result in ArK lines in the detected spectrum.
b
Regenerative monochromatizing lter (RMF). The same element as the anode material is used as the lter
material to preferentially transmit the characteristic K x-rays generated in the anode.
absorption coecient for its own characteristic lines, as these lie immediately below the
absorption-edge jump. In the case of Ag, the AgKa
1,2
lines are at 22.1 keV and the
absorption coecient of Ag for this energy is only 14 cm
2
=g.
The eect of two silver primary lters, of dierent thickness, on the spectrum from a
silver anode x-ray tube operated at 35 kV is shown in Figure 6. The unltered 35-kV
excitation (curve 1) provides equally intense AgL and AgK characteristic lines and a broad
bremsstrahlung hump centered on 1215 keV. Any element in the 515 keV range will
have the benet of excitation by both the AgK characteristic lines and the bremsstrahlung.
However, there exists the disadvantage of sitting on scattered background derived from
the radiation in the bremsstrahlung hump. With the thin Ag lter in place (curve 2), the
AgL characteristic lines are completely absorbed and the bremsstrahlung hump is reduced
to a low-energy tail on the AgK characteristic lines. The resulting excitation yields high
P=B ratios for lines in the energy range 412 keV. Use of the thicker Ag lter (curve 3),
reduces even further the residual bremsstrahlung below the AgK lines and provides
pseudomonochromatic radiation, which yields high P=B ratios for lines in the energy range
515 keV. The strongly ltered AgK line excitation provides excellent sensitivity and
background reduction and a clear, intense Compton-scatter peak, which is good for trace
analysis where a matrix correction based on Compton scatter is used. The same can be said
for anode and lter materials of Mo, Rh, and Pd, which also provide characteristic K lines
in this important region of the spectrum.
A specic and well-documented example of optimum selection of x-ray tube anode,
excitation kV, and primary beam lter can be seen in work by Potts et al. (1986). In that
work, a Co anode x-ray tube and an iron primary beam lter were used to remove the
Figure 5 Scattered excitation spectrum provided by a silver target x-ray tube operated at 15 kV.
The plots show the effect of two thicknesses of an Al primary beam filter: (1) unfiltered; (2) thin Al
filter; (3) thick Al filter.
CoKb line which would otherwise strongly excite the Fe that typically dominates this part
of the spectrum in geological analysis.
Most modern EDXRF systems provide the ability to use more than one set of
conditions per analysis. Depending on the analytical needs, the kV and lter are chosen to
optimize the important parts of the spectrum and the data from spectra at each of these
conditions are consolidated to provide the best P=B values. In order to establish the op-
timum conditions and make the best use of analysis time, the best strategy is to select a
typical sample and then to make measurements with the dierent conditions available. Use
criteria such as detection limits to decide upon the optimum conditions for the required
analysis problem. Often, the instrument manufacturers recommendations can con-
veniently be taken as the starting point for any investigation.
C. SecondaryTarget Excitation
The basic geometry of secondary target excitation is shown in Figure 2. Use of this mode
of excitation for EDXRF spectrometry was rst described by Jaklevic et al. (1972), who
incorporated the secondary target inside a small, low-power x-ray tube. The high P=B
ratios that they reported were encouraging and Porter (1973) subsequently described the
rst work in which the secondary target was external to the x-ray tube. The primary ra-
diation from the x-ray tube strikes the secondary target, which then emits characteristic
radiation and generates some scattered bremsstrahlung radiation. The emitted
radiation is pseudomonochromatic and the degree of monochromaticity is further
enhanced, as in the case of the RMF in direct excitation, with a lter between the
secondary target and the sample. Filters are of the same material as the target and are
Figure 6 Scattered excitation spectrum provided by a silver target x-ray tube operated at 35 kV.
The plots show the effect of two thicknesses of Ag primary beam filter: (1) unfiltered; (2) thin Ag
filter; (3) thick Ag filter.
typically only used with the higher-Z targets (e.g., Mo, Ag, and Gd). With increasing
distance below the exciting lines, the absence of bremsstrahlung lower in energy than the
exciting lines results in a very rapid reduction in sensitivity. The provision of a number of
secondary targets with associated lters, which can usually be selected automatically,
provides a range of discrete and narrow excitation bands. This arrangement can be con-
veniently thought of as providing the equivalent of a number of transmission target x-ray
tubes, each with dierent anode materials. In order to generate intense characteristic ra-
diation from the secondary target, the tube kV should be two to three times the K ab-
sorption-edge energy of the element from which the secondary target is made. The K lines
are used, as they oer the highest uorescence yield, which means that there are lower
losses than with other line series. Typical secondary targets are, in decreasing energy order
of K line emission: Gd, Sn, Ag, Mo, Ge, Cu, Fe, Ti, and Al. The optimization of x-ray tube
kV, secondary target, and lter was described by Spatz and Lieser (1979).
The uorescence yield decreases as the target atomic number decreases and the ef-
ciency of x-ray production falls o rapidly below Ti. The result of this is that the lighter
elements Si to K are not well excited by secondary targets and there are few suitable
elements available to provide targets with K lines in this important region. One approach
is to use a reduced kV and a scattering target which scatters the x-ray tube L lines and
bremsstrahlung, which, as was seen for direct excitation, is eective in this energy region.
A stable polymer block provides a suitable target for this arrangement, although the
overall eciency is much lower than with direct excitation. There are two other ar-
rangements that eliminate this limitation. The rst is to use a second x-ray tube whose
geometry provides for direct, and perhaps direct ltered excitation. Such an arrangement
adds considerable cost and complexity but does oer optimum performance. It is possible
for both tubes to be run from the same high-voltage power supply. The second approach is
to provide mechanical repositioning of the x-ray tube such that it can be operated either in
secondary target or in direct and direct ltered mode. The positional repeatability of the
mechanical arrangement needs to be excellent if this approach is adopted. The mechanical
complexity, which inevitably adds cost and some possibility for unreliability, has not
stopped this approach from being used in the past with some success in one commercially
available instrument. One disadvantage of this approach is the time that is needed for the
mechanical switching, which can be a severe penalty if a number of acquisitions are re-
quired for a complete analysiswhich is usually the case. Very recently, a so-called Wide
Angle Geometry was described by Yokhin (2000), in which a single, xed x-ray tube was
used to deliver direct unltered or ltered and secondary target excitation. This ar-
rangement was made possible using the wide cone x-ray beam from the special x-ray tube
and a proprietary x-ray beam distributor.
The reduction in overall excitation eciency when using secondary targets is usually
oset by increasing the x-ray tube power available. A tube providing close geometric
coupling and power in the range 100400 W is typically used to oset the low overall
eciency of excitation. In order to eciently excite the GdK lines, it is preferable to use an
x-ray tube capable of being operated at 60 kV. A high-Z anode such as tungsten or gold
provides the highest bremsstrahlung intensity and, therefore, the best excitation eciency
for the higher-Z secondary targets.
The high degree of monochromatization in ltered secondary target systems pro-
vides for very high P=B ratios for elements with absorption edges immediately below the
target x-ray emission lines. The background in secondary target geometry can be further
reduced using 3-axis or Cartesian geometry as described by Standzenieks and Selin (1979),
Christensen et al. (1980), and Bisgard et al. (1981).
Despite secondary target excitation gaining wide acceptance through the early 1980s,
the use of direct and direct ltered excitation has remained as the most common excitation
arrangement. This is, perhaps, partly due to the restricted energy range oered by each
secondary target+lter combination and the general need for unltered direct excitation
to obtain the highest sensitivity for the light elements. In the 1990s, the use of polarized
EDXRF (see Chapter 10) tends to have supplanted secondary target EDXRF for the
provision of high P=B ratios in some applications. In addition, improved detection systems
have continued to improve the performance of instruments using direct ltered excitation.
An application in which secondary target systems have a valuable advantage is when the
secondary target lines are selected to be just below the absorption edge of a major element,
but just above the absorption edges of trace elements. One example of this is the use of a
copper secondary target for the determination of low levels of Mn and Fe in Cu alloys. In
this example, the CuK lines from the target do not excite the Cu but are highly eective for
exciting Fe. The detection and counting system is not dominated by CuK lines, neither is
the FeKa peak interfered with by the Si escape peak from CuKa. Such applications are
few in number and, in the case of the metals industry, analysts may often prefer to use
WDXRF spectrometers.
D. X-rayTubes
X-rays were rst discovered over a century ago (see Michette and Pfauntsch, 1996) by
Ro ntgen (1896a, 1896b), and since that time, they have become used in a great variety of
applications. These applications encompass medical and dental x-ray radiology and
imaging, industrial and baggage inspection, industrial nondestructive testing (NDT),
industrial thickness gauging, and x-ray spectrometry in all its guises. In most, if not all,
of these elds, the convenience of the high-voltage x-ray tube has substantial benets in
terms of convenience, safety, and availability of appropriate spectral and intensity output.
The modern x-ray tube used for EDXRF analysis is based on a design introduced by
Coolidge as long ago as 1913 (Coolidge, 1913). The basic design of x-ray tubes typically
used in EDXRF instrumentation consists of the following:
A radiation-shielded glass envelope
An independent tungsten lament with current control unit
A high-melting-point metallic anode
A high-voltage connection to the anode
A beryllium foil exit window
Some means of dissipating the heat generated
In order to operate, the x-ray tube requires a controllable, stable high-voltage power
supply capable of providing typically 560 kV. In addition, there is a low-voltage power
supply for providing current to heat the lament, thereby controlling the electron beam
current and output intensity. X-ray tubes used for EDXRF analysis are typically operated
with a power in the range of 1400 W. For direct excitation, the power output is typically,
no greater than 50 W. Reproducibility of analytical results is achieved for x-ray tube ex-
citation by operating for a measured amount of time at a xed emission current (dc op-
eration). This approach depends on the reasonable assumption that the total output x-ray
ux is proportional to the number of electrons striking the anode.
In some types of x-ray tube, a control grid can be used to modulate or pulse the
emission current. This can be used to modulate the electron beam current to ensure
constant output of radiation from the tube in dc operation or it can be used to rapidly
switch the electron beam on and o for pulsed operation. If the pulsing is synchronized
with x-ray detection, increased output countrate can be achieved by reducing pulse pileup
(see Sec. IV.C).
The key features of the x-ray tube used in EDXRF instruments are as follows:
Easily shielded and safe to operate
Compact and able to be placed close to the sample
Stable output over an extended period, typically months
Well-dened spectral output
High-voltage controllable in small increments, typically 1 kV, throughout the
operating range (typically 550 kV)
Beam current controllable in small increments, typically 10 mA, throughout the
operating range (typically 101000 mA).
The geometry and designs typically used and the characteristics of each are described in
the following sections. Further reading on the subject can be found in Skillicorn (1982,
1983).
1. Side-WindowGeometry
Side-window geometry is the oldest and, perhaps, the most common x-ray tube geometry
used in EDXRF instruments and it is suitable for both high-kV and high-power operation.
Figure 7 shows the essential details of this design.
The geometric coupling of tube anode spot to sample is limited rst by the distance
of the spot itself from the exit window and then, potentially, by the tube encapsulation
itself. Typically, these tubes are operated in the range 550 kV. They can dissipate 50 W
with the need only for forced-air cooling in order to keep the tube external body below a
temperature of, say, 55
C. It is important not to exceed the maximum temperature stated

by the x-ray tube manufacturer. Higher powers (up to 100 W or 120 W) normally need
some form of liquid cooling, which is typically achieved through the use of a closed-cycle
liquid heat exchanger.
The energy spectrum that is output from a side-window x-ray tube is governed by the
tube anode material, the angle of the anode, the kV applied to it, and the exit windows
material and thickness. Tube anode materials are usually Rh, Ag, or W, although Ti, Cr,
Co, Cu, Mo, Pd, or Au is also available. The selection of anode material depends on the
intended application, but Rh, Ag, and Pd are generally the most popular, as they are
highly compatible with tube manufacture and operation. In addition, their K and L
characteristic emission lines are in regions of the energy spectrum where they oer high
sensitivity with minimum spectral interference. Dual-target x-ray tubes have been used in
attempts to maximize exibility and performance. These eorts have met with limited
success in EDXRF, in part due to the spectral cross-contamination that is typically
experienced in the designs used to date. There has been, however, considerable success in
the use of dual-target x-ray tubes for WDXRF, where the problems of spectral con-
tamination have much less impact. Typically, the anode is cut at an angle of 20
35
from
normal to the incident electron beam and the exit window is usually made from beryllium
foil of thickness in the range 50250 mm.
The tube output spectrum can be measured or estimated and such information is
important in analytical correction procedures, particularly those using fundamental
parameter calculations for which accurate and computationally convenient tube output
spectrum models are required (see Chapter 2, Sec. I.B for further details.)
Figure 7 Side-window x-ray tube.
It should be remembered that the tube output spectrum, especially with higher-
power tubes, may change with time. One way in which this can occur is through deposition
of a thin tungsten lm on the inside of the tube output window through evaporation of
tungsten from the hot lament. Such deposition is unlikely to aect the low-power tubes
typically used in EDXRF systems and, in any event, is usually taken care of through the
normal restandardization process.
2. End-WindowGeometry
The design features of such an x-ray tube are shown in Figure 8. The same factors of
operation and tube spectrum apply to this type of tube as was applied to side-window
tubes. The tube spectrum is altered by the fact that the takeo angle is normal to the anode
surface and so there is minimal self-absorption by the target material. This high takeo
angle makes such a design particularly good for low-energy excitation. One of the im-
portant benets of the end-window design is the very tight coupling of anode spot to
sample that can be achieved with a sharp-nose design. The spot-to window coupling can
be close with suitable electron optics (e.g., 12 mm in the Varian EG50 design). The use of a
high positive voltage on the target minimizes the eect which repelled electrons would
have of causing an unacceptable amount of exit-window heating. This reduced heating
allows thinner beryllium windows to be used, which further improves the low-energy
x-ray output.
3. TransmissionTarget Geometry
The design features of such an x-ray tube are shown in Figure 9. In this type of x-ray tube,
the geometry is basically end window, but in this embodiment, there is a metal foil target
parallel to and inside the beryllium exit window. The incident high-voltage electron beam
Figure 8 End-window x-ray tube.
strikes and enters one side of the thin-lm target and the resulting radiation is heavily
ltered as it passes through the foil and exits the far side of the target. This novel design
was initially developed (Jaklevic et al., 1972) in order to reduce the bremsstrahlung from
the x-ray tube, which would then reduce the scattered background in the spectrum and
thereby improve detection limits. The initial design used a molybdenum transmission
target of 0.12 mm thickness and, when operated at 42 kV and up to 25 W, was shown to
give an output spectrum consisting principally of characteristic MoK radiation. The
output spectrum was comparable to an
125
I radioisotope source coupled to a molyb-
denum-foil secondary target.
This type of x-ray tube was made commercially available by WatkinsJohnson
(Hershyn, 1975a, 1975b). The spectrum output from this type of tube was investigated by
Zulliger and Stewart (1975), who calculated and measured spectra from Cr, Mo, and W
transmission target x-ray tubes. The targets were either thin (50 mm) metal foils or thin
lms (510 mm) on a beryllium substrate of 0.250.5 mm thickness. The thin targets mean
that only low-power tubes (<100 W typically) can be made successfully. These authors
found, as predicted, a substantial reduction in bremsstrahlung compared to the char-
acteristic lines and quoted detection limits for a number of applications. The Cr target was
found, not unsurprisingly, to be best for the light elements S and Ca. Although the energy
range covered was claimed to be wide, the intrinsic xed ltration of this design makes it a
less valuable general excitation source compared to a side- or end-window tube with an
external, selectable lter. A novel, multiple-target transmission tube has even been de-
scribed (Kis-Varga, 1988) in which the ve anode materials (Fe, Cu, Ge, Mo, and Ag) were
changed by a magnetic mechanism.
The intrinsic ltration of the low-energy bremsstrahlung makes this type of tube
much less suitable for excitation of low energy (i.e., <2-keV) x-ray lines. Consequently,
their usage is limited to specic applications where the intrinsic ltration and potential for
close geometric coupling of the tube anode spot to the sample are major benets. In fact,
in one design, the WatkinsJohnson tubes did not have a target closely coupled to the
exit window, which, when combined with the intrinsic lossess in the target, led to low
output ux from the tubes and, consequently, reduced sensitivity. Finally, these tubes are
not useful when operated at low voltages (Skillicorn, 1982) due to strong absorption in the
target. This makes them much less sensitive than solid-target, side- or end-window tubes
for selectively exciting the light elements in the presence of large amounts of heavier
elements.
Figure 9 Schematic of a transmission target x-ray tube.
III. SEMICONDUCTOR DETECTORS
In this type of detector, the total ionization produced by each x-ray photon striking the
detector is converted to a voltage signal with amplitude proportional to the incident en-
ergy. Specially designed preamplication and processing electronics are employed to
maintain the linearity of the voltage signal with respect to the original charge pulse.
A multichannel analyzer accumulates an energy spectrum of the sequential events in a
histogram memory. Because the energy analysis does not depend in any way on the dif-
fraction or focusing of the x-rays by the detector, the geometry of the system is relatively
insensitive to the placement of the detector with respect to the sample. An exception to this
is in polarized excitation XRF (Chapter 10), where the orientation angle can be used to
suppress scattered background. This insensitivity to geometry and ability to place the
detector element close to the sample provides for a large solid angle and high geometric
eciency. In addition, the mechanism by which the ionization signal is measured is not
restricted to a narrow energy region, thus allowing the simultaneous detection of x-rays
over a wide dynamic range of the emission spectrum. The principal advantages of EDXRF
derive from its capability for simultaneous detection, with high geometric eciency, of
characteristic x-rays from multiple elements.
A. Fabrication and Operating Principle
The energy-dispersive detecting element is based on the simple, semiconductor diode
structure shown in Figure 10. The example shown is a structure typical for lithium-drifted
silicon, Si(Li), detectors, although the basic elements are similar for high-purity
germanium (HPGe) and other semiconductor detectors. The device is fabricated on a
cylindrical wafer of high-quality semiconductor material with rectifying p or n contacts on
opposing end surfaces. The bulk of the material is characterized by a very low con-
centration of free-charge carriers. This reduced free-carrier concentration is achieved
either with the use of extremely pure material, in the case of HPGe detectors, or through
the charge compensation of p-type silicon with lithium donor atoms in the case of Si(Li)
detectors. A typical dimension for such a detector crystal is 1080 mm
2
active area with a
thickness of 35 mm.
In the geometry shown in Figure 10, the lithium-diused region acts as an n contact
and the metal surface barrier (typically an evaporated Au layer) serves as the p rectifying
contact. When the diode is reverse-biased, any remaining free carriers are swept out of the
bulk by the applied eld and an active depletion region is created. In this condition,
the only current that ows between electrodes on the respective contacts at each end of the
diode cylinder is due to thermally generated charge carriers, which are excited above the
narrow band gap of the semiconducting material. In order to minimize the noise from
these thermally generated charges, the detector crystal is operated at reduced temperature,
which is typically achieved using cryogenic cooling by means of a Dewar vacuum ask
lled with liquid nitrogen. Other cooling strategies can be adopted (see Sec. III.C).
When an x-ray photon is incident upon the active volume (i.e., depletion region) of
the diode, it normally interacts by photoelectric absorption to create an inner-shell va-
cancy in the semiconductor material together with an energetic photoelectron.
This photoelectron interacts with the atoms in the semiconductor crystal lattice to produce
multiple low-energy ionization events. This process continues until the electron comes to
rest at the end of a total range, which is short compared with the dimensions of the crystal.
The energy associated with the inner-shell vacancy is also absorbed in the crystal, in most
cases following the emission of Auger electrons or multiple low-energy x-rays and sub-
sequent re-absorption. The result of these multiple ionization process is the essentially
instantaneous production of a large number of free electronhole pairs in the sensitive
volume of the detector structure. These free-charge carriers form as a cloud from which
they are separated by the eld gradient. The front detector electrical contact, being biased
at 500 V, for example, attracts the hole and repels the electrons, the latter negative
charge cloud is swept to the rear contact and converted, by means of the FET, to an
amplied voltage pulse. The number of charge carriers produced is directly proportional
to the energy of the x-ray photon incident on the detector. Thus, the number of charges
collected results in a voltage pulse whose magnitude is, in turn, directly proportional to the
energy of the detected photon.
B. Crystal Materials
The characteristics of energy-dispersive semiconductor x-ray spectrometers derive pri-
marily from the properties of the materials used to make the device itself. Although the
most common material for semiconductor detectors in EDXRF is silicon, devices based on
the use of germanium or compound semiconductors such as mercury(II) iodide (HgI
2
),
CdTe, CdZnTe, or GaAs have also been used to varying degrees. In particular, mercury
(II) iodide detectors (Swierkowski et al., 1974; Slapa et al., 1976; Ponpon and Sieskind,
1996) have been used successfully in both research and commercial products for many
years. Early devices with adequate performance at room temperature were own on space
missions. More recently, devices have been used in hand-held EDXRF spectrometers
where the benet of ambient temperature operation, with or without thermoelectric
(Peltier) cooling of the eld-eect transistor (FET), have been successfully exploited.
Iwanczyk et al. (1996) compared the performance of HgI
2
, Si PIN photoiodide, and CdTe
detectors for this latter, important application. Large arrays of up to 100 HgI
2
detectors
Figure10 Cross section of a typical Si(Li) detector showing electrode contacts and active volume.
have also been fabricated (Iwanczyk et al., 1995; Patt et al., 1995). Dabrowski et al. (1981)
have been particularly successful in designing, fabricating, and characterizing HgI
2
de-
tectors throughout the past two decades and their work should be consulted for further
details of this important type of EDXRF detector. Although high-purity germanium
(HPGe) is widely used for detectors in electron microscopes as a result of its slightly better
resolution than Si(Li) detectors, the use of HPGe detectors is less popular in photon-
excited EDXRF spectrometry. One reason for this lack of acceptance may lie in the high
escape peak intensities (see Sec. III.E.1) which can strongly interfere in trace analysis.
Table 2 lists properties relevant to x-ray detection for Si, Ge, and HgI
2
, which are the
materials most commonly employed in commercial EDXRF spectrometers. A variety of
other compound semiconductor materials, such as GaAs, CdTe, and CdZnTe, have been
used for applications in which specic properties are particularly benecial. These prop-
erties include the following:
Higher atomic number for increased photoelectric cross section
Larger band gap for lower thermal leakage at room temperature
A lower band gap corresponding to a smaller average energy for creation of
holeelectron pairs (Knoll, 1979), which oers improved energy resolution.
Recalling the direct relationship described earlier between photon energy and number of
charge carriers and, therefore, the detectors signal resulting from detection of a particular
x-ray photon, one can use the data from Table 2 in the following example for detection of
CaKa
1
(KL3), which has an energy of 3.691 keV:
No. electronhole pairs produced 3691=3.86 956
Charge on electron 1.6610
19
C
Therefore,
Charge from CaKa
1
interaction 1.53610
16
C
Assuming a feedback capacitance in the rst stage amplication of 0.1 pF, the
resulting output voltage pulse is 1.53 mV.
From this, we can see the very small magnitude of the signals involved. This has led to very
great eorts having been made in the design of detector and signal processing systems to
minimize all sources of electronic noise which would otherwise interfere very strongly with
the signal being sought.
In addition to the conventional Si(Li) detector, Si PIN (Haselberger et al., 1996;
Cesareo et al., 1996) and Si drift detectors (Lechner et al., 1996; Bertuccio et al., 1996)
have also become available in recent years. The active area of these devices is generally
Table 2 Semiconductor Detector Material Properties
Detector properties Si Ge HgI
2
Atomic number 14 32 80.53
Atomic=molecular weight 28.09 72.60 454.45
Density (300 K) g=cm
3
2.33 5.33 6.3
Band gap (300 K) (eV) 1.115 0.665 2.13
Average energy E per electronhole pair (77 kV)
(eV)
3.86 2.96 4.15
a
Fano factor (77 K) 0.12 0.08
a
At 300 K.
310 mm
2
and the depletion thickness is of the order of 300 mm, which reduces detection
eciency (see Sec. III.F) compared to Si(Li) detectors.
In the following section, the details of detector operation are discussed, with parti-
cular emphasis on those aspects that impact EDXRF spectrometry most directly. These
include the detector energy resolution, detection eciency, spectral response, and counting
system throughput.
C. Cooling Systems
The need to minimize the electronic noise of the detection system is paramount for ob-
taining the best energy resolution. The main source of noise in the detector itself is leakage
current, which derives from the generation of charge carriers in the absence of x-rays
through, for example, thermal vibrations of the detector crystal lattice. Whatever the
cooling system used, the intention of it is to minimize leakage, and the lower the tem-
perature, the less leakage will occur. The boiling point of liquid nitrogen (77 K) is a typical
temperature used for the detector crystal, although the FET may require a dierent and
often higher temperature to minimize its noise contribution and, therefore, obtain opti-
mum detector resolution.
The need for reduced operating temperature results in the need for careful design in
the insulation from ambient temperatures of the detector crystal. Eective insulation is
typically achieved by enclosing the detector head (crystal and FET) assembly in a evac-
uated cryostat. In order for the low-energy x-rays (<2 keV) to reach the detector crystal,
the vacuum is usually retained by a thin (typically 550 mm) beryllium entrance window
(Fig. 11). In recent years, the thinnest windows (5, 8, and 12 mm) have become available
with coatings which ensure that there is no leakage of He through the Be window. Any
helium getting through the window would degrade the high vacuum within the cryostat
and lead to increased temperature, leakage current, and deteriorating performance.
The original and perhaps simplest way of cooling a detector unit is to attach the
measurement head via a cold-nger assembly to a dewar vessel containing liquid nitrogen
(LN). The dewar itself is typically a complex technological component if it is to provide
high performance and long operational lifetime. The modern LN cryostat delivers opti-
mum resolution and the ability to be cycled through multiple warm-up=cooldown cycles
without degradation in performance. The inevitable and natural boiling-o from the
dewar of LN over a period (1 L per day is typical) means that the dewar needs regular
replenishment. In order to minimize the frequency of replenishing LN, a large dewar is
preferable, although this desire for a long LN holding time may lead to a rather bulky
system. LN volumes of 715 L are typical, although some large systems may use volumes
up to 25 L and some small, hand-held units may use 1 L or less. In any event, the fol-
lowing are important:
Use only liquid nitrogen: Liquid air, although delivering the required temperature
range, will fractionate, yielding O
2
, which is an explosion hazard in the chemical
laboratory.
Ensure that there is no ice or dirt in the LN used. The presence of ice or dirt in the
dewar can cause microphony, which can degrade energy resolution. Ice and dirt
can be eliminated by pouring the LN through a funnel equipped with a wire
screen (e.g., a motor fuel metal lter funnel).
Observe safe LN handling procedures. Avoid overlling and spillages as liquid
nitrogen can cause embrittlement of polymers and cable insulation or result in
condensation from the atmosphere being deposited on components that are
sensitive to moisture.
It is essential that a Si(Li) detector be kept cold throughout the time that the bias is
applied. If this is not done, then there is the possibility of damage to the detector as-
sembly by, for example, migration of the drifted Li ions from the compensated region
of the crystal. Should this happen, the detector will fail and, for this reason, it is usual
for an automatic bias shuto system to be implemented. Such systems typically use a
temperature sensor or a LN level sensor to switch o the detector bias in case of the
dewar warming up. Other detectors, such as HPGe or high-purity Si, for which drifting
is not required, do not exhibit this particular problem but may still suer some pro-
blems if thermally cycled repeatedly, unless the cryostat assembly is specically designed
to do this.
The simplicity of the LN-lled dewar has led to its widespread use in EDXRFsystems.
However, the diculty in obtaining LN in remote areas, or the need for a no-LN solution,
has led to the introduction in the past decade or so of thermoelectric (Peltier eect) coolers or
mechanical refrigerating units. The mechanical units may employ the JouleThompson
(JT) eect or some other cycle such as the Stirling cycle to obtain essentially LN temper-
atures at the detector head. The major benet of this approach is that there is no dierence in
performance in terms of detector energy resolution from the conventional dewar LN sys-
tems, but the coolers come with penalties of increased complexity, cost, and bulk. HPGe
detectors, which typically need liquid-nitrogen temperature to operate, may use these me-
chanical coolers, but other detectors which will function at higher temperatures, albeit with
degraded energy resolution, are suitable for use with thermoelectric (Peltier eect) coolers.
Figure11 Cross section of a groove-type Si(Li) detector mounted in its cryostat end cap.
Peltier coolers can oer a very compact cryostat=detector assembly that requires
only electrical power to provide its cooling. Multistage (three to six) coolers may be used
to provide a DT cooling, from ambient, of 50
C to a maximum of perhaps 120
C. In an
ambient room temperature of 20
C, such coolers deliver working detector temperatures

typically in the range 30
C to 90
C, which are suitable for Si PIN, HgI

2
, and extremely
low-leakage Si(Li) detectors. Energy resolution in the range 200350 eV (see Sec. III.D) is
typically available with these systems and both Si PIN and HgI
2
detectors are commer-
cially available with Peltier cooling. More recently, Peltier-cooled Si drift detectors, which
oer energy resolution better than 150 eV, have been developed (Lechner et al., 1996;
Bertuccio et al., 1996) and are now commercially available.
D. Energy Resolution
The energy resolution of the semiconductor spectrometer system determines the ability of
a given system to resolve characteristic x-rays from multielement samples. It is normally
dened as the full width at half-maximum (FWHM) of the pulseheight distribution
measured for a monoenergetic x-ray at a specied energy. A convenient choice of x-ray
energy at which resolution is quoted is the weighted mean MnKa line at 5.895 keV, as this
emission line is readily available from
55
Fe radioisotope sources. The MnK x-rays are of
suciently low energy that the contribution to the FWHM of the unresolved Ka
1
Ka
2
doublet (5.898 and 5.887 keV, respectively) and the intrinsic width of the emission lines
can be neglected. This is not true for higher-energy characteristic x-rays (e.g., MoK lines)
for which the separation of the Ka
1
Ka
2
doublet and the intrinsic width of the emission
line must be considered. Figure 12 shows a typical pulseheight spectrum of MnK x-rays
taken from an
55
Fe source.
Typical state-of-the-art 30-mm
2
Si(Li) detectors achieve a FWHM better than
140 eV at 5.9 keV, although values as low as 130 eV are achievable. However, this number
is but one indicator of the quality of an EDXRF detector system, and other factors such as
maximum count rate or the presence of background and artifacts may be more important
in many analytical applications. Peltier-cooled Si PIN detectors oer FWHM values
typically in the range 165220 eV, whereas Si drift detectors claim <150 eV. The inter-
dependence of energy resolution and count rate is discussed below, although it is worth
noting at this point that the user can exert a large degree of control over this by making an
appropriate selection of pulse processor settings.
If one neglects the natural linewidth of the x-ray lines, the instrumental energy re-
solution of a semiconductor detector x-ray spectrometer is a function of two independent
factors. One of these is determined by the properties of the detector itself; the other is
dependent on the nature of the electronic pulse processing employed. In some systems,
a pulser or strobe signal may be injected into the measurement system in order to monitor
the resolution of the electronic system independent of any peak broadening due to the
detector itself.
The measured FWHM of the x-ray line (DE
Total
) is the sum, in quadrature, of the
contribution due solely to detector processes (DE
Det
) and that associated with the elec-
tronic pulse processing system (DE
Elec
):
DE
Total

DE
2
Det
DE
2
Elec
q
1
The DE
Det
component is determined by the statistics of the free-charge production process
occurring in the depleted volume of the diode. The average number of electronhole pairs
produced by an incident photon can be calculated as the total photon energy divided by the
mean energy required to produce a single electronhole pair (see Sec. III.B). If the uc-
tuation in this average were governed by Poisson statistics, the standard deviation would be
s
n
p

E
e
r
2
In semiconductor devices, the details of the energy-loss process are such that the individual
events are not strictly independent and a departure from Poisson behavior is observed.
This departure is taken into account by the inclusion of the Fano factor in the expression
for the detector contribution to the FWHM:
s
Fn
p

FE
e
r
3
Taking
sE
E

Fn
p
4
and, rearranging,
DE
Det
2:35
FeE
p
5
where e is the average energy required to produce a free electronhole pair, E is the energy
of the photon, F is the Fano factor (see Table 2), and the factor 2.35 converts the standard
deviation to FWHM for a Poisson distribution.
A typical value for the detector contribution to resolution, also known as the disper-
sion, is $120. Examination of the values of e and F listed in Table 2 shows that for an
Figure12 Pulseheight spectrum of MnK x-rays taken with a 30-mm
2
Si(Li) detector.
equivalent energy, the detector contribution to the resolution is 28% less for the case of Ge
compared to Si. This results in better energy resolution being obtained for HPGe detectors
and could be an important consideration in the choice of detector for certain applications.
However, this theoretical advantage in energy resolution of Ge over Si(Li) is mitigated
in many systems because of the dominance of electronic noise (e.g., from the FET). In ad-
dition, the very high GeK escape peak probability (see Sec. III.E.1) is likely to be a serious
limitation to the use of HPGe detectors in most EDXRF work. HPGe detectors are widely
used in electron microscopes, where energies <10 keV are likely to be of most interest.
E. SpectrumArtifacts
The simplicity of the element line spectra encountered in XRF spectrometry is one of its
major benets when compared with other atomic spectroscopy methods. However, a few
peaks can arise in the EDXRF spectrum from sources other than the elements in the
sample and it is wise to be aware of their nature. Unlike basic detector eciency and
spectrum background, which are dened by the selection of detector window and the
detector manufacturing process, the end user can exert some control over the eects of
spectrum artifacts. From the spectra presented so far, it is clear that the bremsstrahlung
continuum and the Compton (and Rayleigh)-scatter peaks arise from the interaction of the
exciting radiation with the sample. These features are not regarded as artifacts.
1. Escape Peaks
For an incident x-ray with energy higher than the SiK absorption edge, the detection
process will involve the generation, through x-ray uorescence of the detector material, of
SiK x-rays. The vast majority of these will themselves immediately be absorbed in the
detector volume and contribute to the overall charge collected for the original incident
x-ray photon. This is the normal mechanism of x-ray detection, which was described
earlier. There is, however, a nite probability that the SiKa x-rays produced will escape
from the detector volume and not contribute to the charge collected for the original
photon that was detected. The resulting energy detected will be reduced by 1.740 keV,
which is the energy of the SiKa x-ray that escaped. The greatest probability of escape arises
close to the front of the detector crystal from which SiK x-rays can more easily escape.
X-rays detected far within the volume will still generate SiK x-rays, but they will all be
absorbed before they can reach the outer surface of the crystal and escape. The probability
of generating the SiKb x-ray and of it escaping is extremely low and this eect can safely be
ignored. The result of the SiK escape process is a peak in the collected spectrum, which is
1.74 keV lower in energy than the parent peak. The Si escape peaks for TiKa and TiKb are
clearly seen, 1.74 keV below the TiK lines, in Figure 13 (indicated by 1 and 2, respectively)
(see also Table 3). In many detectors, the incomplete charge-collection tail on the low-
energy side of the parent peak will obscure the Si escape peak from TiKb.
The escape probability is highest for lines closest to the SiK absorption edge at
1.838 keV and may be calculated as described by Statham (1976) and Dyson (1974). The
intensity falls rapidly from around 3% of the parent peak at 23 keV to around 0.1% of
the parent peak at 10 keV. At energies above 10 keV, the eect is negligible, but below this
energy, it is important that spectrum-processing software takes account of the peak.
Typically, the processing software will make a correction in which the Si escape peak
is removed and the most comprehensive packages will reinstate the lost intensity to the
parent peak. If such packages are available, then make use of them before carrying out
qualitative analysis in order to avoid classic errors such as the Si escape peaks from ZnK
being identied as Co!
In the case of HPGe, the escape probability for GeL lines is negligible in XRF and
can be ignored. The escape of the GeK lines has, however, a very high probability, and for
Se, the escape peak intensity is around 16% of the parent peak. This is due to the com-
bination of the high detector eciency for GeK x-rays and the much greater depth within
the crystal from which the GeK lines can escape. There is further complication in that
there are many GeK lines and each of these lines will result in an escape peak. The
complexity and intensity of Ge escape peaks can easily be seen in the spectrum from a
molybdenum oxide sample, shown in Figure 14.
The principal GeK lines and their characteristic energies are as follows:
GeKa: 9.876 keV
GeKb
1
: 10.981 keV
GeKb
2
: 11.100 keV
The assignments of the numbered GeK escape peaks arising from the detection of the
MoK lines are listed in Table 4.
Figure13 Peak artifacts from a Ti spectrum collected by a Si(Li) detector (see Table 3 for details).
Table 3 Artifact Peak Energy and Assignments for Figure 13
Peak No. Energy (keV) Assignment
1 2.8 TiKaSiK escape
2 3.2 TiKbSiK escape
3 9.0 TiKa TiKa sum peak
4 9.4 TiKa TiKb sum peak
5 9.9 TiKbTiKb sum peak
The energy and intensity of these GeK escape peaks interferes very strongly over a
wide and important region of the spectrum. The interference is considerable from the GeK
escape peaks of Nb and Mo in stainless steels and corrections for these intense escape
peaks are not suciently accurate to retain the intrinsic performance of EDXRF for what
would be a reliable and straightforward analysis using a Si(Li) detector. The severe lim-
itation posed by the Ge escape peaks in EDXRF is also demonstrated in Figure 15 (see
also Table 5) for a typical determination of minor and trace heavy metals in a low-Z
matrix. In this case, the complex GeK escape peaks from the Rh backscatter peaks
completely dominate the important part of the spectrum for trace analysis.
In conclusion, the Si escape peak is small and easily corrected, but the number and
high intensity of the GeK escape peaks severely limit the value of the HPGe detector for
tube-excited EDXRF. In the case of energy-dispersive (ED) microanalysis, however,
Figure 14 GeK escape peaks from Mo spectrum collected by HPGe detector (see Table 4 for
details).
Table 4 GeK Escape Peak Assignments and Relative Intensity for Figure 14
Peak No. Energy (keV) Assignment % of parent
1 6.4 MoKaGeKb
1
1.5
2 7.57 MoKaGeKa 9.6
3 8.6 MoKbGeKb 1.0
4 9.74 MoKb
1
GeKa 8.8
5 10.12 MoKb
2
GeKa 2.5
the HPGe detector has benets in that the intensity of the GeL escape peaks is negligible
and the energy resolution is better than that of Si(Li) detectors.
2. SumPeaks
Sum peaks arise from a specic form of peak pileup (see Sec. IV.C) where two events from
high-intensity peaks arrive in the pulse processing electronics so close together in time that
the pileup inspector cannot recognize themas twoevents. The eect of this is for the signals to
be seen as one and for themto be registered at the energy that is the sumof the two. The sum
peaks of Ti are seen in Figure 13, in which the most intense peak (3) is from the sum of two
TiKa events. The smallest peak (5), fromthe sumof two TiKb events is only visible when the
parent peak is very intense. At rst glance, peaks 3 and 4 may appear like a typical Ka, Kb
Figure 15 Comparison of Si(Li) and HPGe detectors for tube-excited EDXRF trace analysis of
low-Z sample matrix (see Table 5 for details).
Table 5 GeK Escape Peak Assignments for Figure 15
Peak Assignment
1 RhKa ComptonGeKa
2 RhKa RayleighGeKa
3 RhKb ComptonGeKa
4 RhKb RayleighGeKa
doublet, but the peak separation is too small for Klines in the region of the spectrumin which
they occur. In addition, the relative line ratio is not the same as for a characteristic K line
series at this energy. Consequently, sum peaks are unlikely to be incorrectly identied as
elements, but they may interfere with important lines in a particular analysis. This is parti-
cularly the case in some environmental analyses, (e.g., where high concentrations of Fe lead
tointense FeKlines). This will result inFeKsumpeaks inthe regionof the Klines of Se andBr
and the L lines of toxic heavy elements such as Hg, Tl, and Pb.
Some spectrum-processing software packages are able to correct for sum peaks and
should be used to minimize potential errors in analysis (See Chapter 4). If it is found that
such features are not available, then reducing the count rate will substantially reduce the
eect of the sum peaks. In order not to lose analytical performance, however, selection of
alternate excitation conditions (e.g., using a more absorbing beam lter) will rebalance
the spectrum in favor of the peaks at higher energy and minimize the interference.
3. Diffraction Peaks
Whenever a crystalline sample is measured in an EDXRF spectrometer, there is the
possibility that the conditions for Bragg diraction will be met. This is exacerbated by the
divergent geometry of the incident and detected beam and the variety of excitation con-
ditions available. The worst cases are where unltered primary radiation is used, as there
are then many energies and angles which increase the probability of meeting the Bragg
condition for a crystalline component in the sample. The more monochromatic the ex-
citing beam is, the less likely it is that the Bragg condition will be met. Figure 16 shows the
diraction peak obtained from a boric acid pellet which was excited with a silver anode
x-ray tube operated at 5 kV with no primary beam lter and in an approximately 90
geometry.
The spectrum is overlaid with one from a sulfur pellet measured under exactly the
same conditions. It can be seen that the diraction peak is broader than a K series line at
that energy and the low-energy tailing is more pronounced. There is some possibility for
misidentication, but the most likely problem arises in any spectrum processing not setup
to take account of this peak. In cases such as silicon wafers, where the crystal planes are
highly oriented, the sample can be tilted or rotated to minimize the often sharp diraction
peaks that can be observed. Alternatively, eective use can be made of additional colli-
mation to constrain more closely the angles that can satisfy the Bragg condition or of
alternate excitation conditions, which change or reduce the incident energies available for
diraction. Figure 17 shows a comparison of the spectra taken from the same two samples
under dierent excitation conditions.
The increased kV and use of an absorption lter completely change the energy
distribution of the excitation spectrum and eliminate the diraction peak. This second set
of conditions is particularly eective for lines in this part of the spectrum and eectively
removes problems from diraction peaks. Once a diraction peak is identied as causing a
problem, a change of excitation conditions is often the best measure to adopt. The use of
monochromatic or polarized excitation or of secondary targets in Cartesian geometry will
also eliminate diraction peaks.
4. SystemContamination Peaks
Careful screening of all the components in an EDXRF spectrometer is required in order to
eliminate spurious element peaks in measured spectra. Each spectrometer designer will
adopt dierent approaches and materials for this purpose and, thus, there is a variety of
Figure 16 Spectrum from boric acid, overlaid with one from a sulfur pellet, showing the
diffraction peak. Conditions: Ag target x-ray tube, 5 kV, no primary beam filter.
Figure 17 Spectrum from boric acid, overlaid with one from a sulfur pellet, showing removal
of the diffraction peak seen in Figure 16. Conditions: Ag target x-ray tube, 15 kV, thin Al primary
beam filter.
potential spectrum contaminant peaks. Careful design will eliminate them, although, in
some cases, the use of a simple blank correction may be required in some trace analysis.
Detector components can be a cause of some system peaks. Beryllium entrance
windows usually contain some trace elements that, in extreme cases such as TXRF, can be
seen in blank spectra. The use of thick beryllium windows exacerbates this potential
problem, but window thicknesses commonly used (850 mm) should pose no practical
problem. The Si internal uorescence peak and absorption edge caused by the dead layer
are eects not seen in practice and need very careful characterization with specialized
conditions if they are to be seen at all.
The most likely source of spurious spectrum peaks is sample handling and pre-
sentation, both of which are largely in the control of the user.
F. Detection Efficiency and EntranceWindows
One of the more important advantages of semiconductor spectrometers is the absolute
eciency with which uorescence x-rays are detected and their energies measured. This is
the result of the intrinsically high photoelectric absorption eciencies for semiconductor
materials in the x-ray energy range and from the large solid angles achieved in typical
EDXRF geometries. The solid angle is determined by the area of the detector and the
sampledetector distance and varies with the design of the system. Typical areas are
1080 mm
2
for Si(Li) detectors. Although the additional solid angle is advantageous for
many applications, one must realize that the added capacitance associated with increased
active area results in an increased contribution in the electronic noise of the system. This,
in turn, results in an increased energy resolution of the detection system.
The intrinsic eciency of the semiconductor device can be approximated by a simple
model in which the probability of detecting an x-ray incident on the detector is assumed to
be the probability of photoelectric absorption within the sensitive volume. This can be
expressed as
eE e
mt
1 e
sd
where e(E) is the energy-dependent intrinsic eciency of the detector, t is the thickness of
any absorptive layer between the sample and the detector, mm(E) is the mass absorption
coecient of the absorptive layer, d is the detector thickness, and ss(E) is the photo-
electric mass-absorption coecient for the detector material. Figure 18 shows plots of the
above equation for the case of a 3-mm-thick Si(Li) and a 5-mm-thick HPGe detector.
The poor eciency at low energies is assumed to be determined by the combined
absorption of the 25-mm beryllium entrance window and a nominal 2-cm air pair between
sample and detector. The energies of the characteristic K emission lines for several
elements are also shown. The plots show the near-unity intrinsic eciencies for both
detectors over a wide range of useful x-ray energies. The Ge detector is ecient at much
higher energies than Si because of the higher atomic number and subsequent larger
photoelectric cross section.
The simple model gives a semi-quantitative picture of the eciency behavior of
semiconductor spectrometers. However, several other factors must be considered for
quantitative calibration of a uorescence spectrometer. The concept of a thin entrance
window that either absorbs or transmits an incident x-ray does not describe cases in which
the secondary electrons, either photoelectric or Auger, are emitted into the active volume
from the window layer. Similarly, detailed studies of the low-energy eciency have in-
dicated the presence of an absorbing layer on the surface of both Si and Ge devices
associated with the surface layer of the semiconductor material itself. This layer is com-
prised of an evaporated metal contact used to form the rectifying Schottky barrier and a
thin surface layer (the dead layer) of inactive semiconductor material from which charge
cannot be collected. The thickness of evaporated metal, normally Au, can be determined by
direct measurement during the manufacturing process and is typically in the range of 10 nm.
The eective dead layer of semiconductor material is a more complicated parameter to
determine. Empirical studies have attempted to measure the absorption inherent in the
semiconductor surface layer. Such studies established that the eective thickness is de-
termined largely by the absorption length of the low-energy photons and the charge-
transport characteristics of the associated ionization products. In the simplest model, there
is competition from the rate of diusion of the electronhole distribution, against the
gradient of the applied eld. For distances near the entry contact, a part of the charge can
diuse into the contact and be lost to the signal before the electrical eld can sweep it to the
opposing electrode. This loss of charge can be interpreted in terms of an eective window
thickness of typically 0.2 mm silicon equivalent. In addition, thin evaporated contacts are
deposited on the entry surface that can absorb incident low-energy photons.
Detailed experiments have indicated that the charge-collection eciency for events
near the surface depends in a complex way on low-energy x-ray and charge-transport
properties (Llacer et al., 1977; Goulding, 1977). As a consequence of these entry-window-
related eects, the eciency for low-energy photons can be reduced. The events lost from
the photopeak can then appear in a continuum background below the full-energy peak,
where they reduce detectability and interfere with spectral analysis. Similarly, secondary
electrons or photons originating from the photoelectric absorption events that occur in-
itially in the active volume can escape. This results in a collected charge pulse of reduced
Figure 18 Calculated intrinsic photopeak efficiency for Si and Ge detectors as a function of
incident photon energy. The high-energy limits are established by the photoelectric cross section of
the detector material and the diode thickness. The low-energy cutoff is determined either by
absorption in the thin Be window or in a nominal 2-cm air path from sample to detector or
fluorescence source.
amplitude. An easily observed manifestation involves the observation of discrete peaks in
the spectrum. Continuous-loss processes involving electron escape can also occur, al-
though the probability is small. These and related mechanisms that reduce the amplitude
for a given event can lower the photopeak eciency relative to the simple model described.
There have been studies in which the eciencies of Si(Li) and Ge have been carefully
measured using calibrated sources of x-rays spanning the energy region of interest (Cohen,
1980; Szoghy et al., 1981; Campbell and McGhee, 1986). These indicate that the maximum
intrinsic photopeak eciency is reduced by a few percent relative to the curves shown in
Figure 18 and is slightly higher at the upper energy cut o than calculated. These results
substantiate the overall validity of the simple photoelectric absorption model but de-
monstrate the limitations if precise results are required. For laboratory applications of
EDXRF, it is not necessary to explicitly determine the photoelectric eciency function
because it is included in the overall calibration factor of the instrument. In any event, the
internal eciency of the detector itself is dened by the design and manufacture of the
detector and this is out of the control of most users.
The eciency curve shown in Figure 18 illustrates that for conventional EDXRF
measurements, the absorption of uorescence x-rays in air and in the Be entry window
limits the accessible energy range to photons greater than approximately 2 keV. The ab-
sorption losses in the air path can be signicantly reduced by the common practice of
employing a vacuum or He atmosphere. A vacuum path is preferable due to higher x-ray
transmission, and if helium is used, the beryllium entrance window must be able to
eliminate leakage into the cryostat with subsequent loss of its vacuum. Coated beryllium
windows are commonly used nowadays to minimize helium leakage into the cryostat.
The necessity of a beryllium window to maintain vacuum integrity between the
cryostat enclosure and atmospheric pressure does not constitute a serious limitation for
most analyses. However, there are applications in which the detection of x-rays with en-
ergies below 1 keV (e.g., for F) becomes necessary. The relatively high detection limits
achieved by EDXRF systems because of the poor energy resolution (compared with
WDXRF) combined with absorption by the beryllium window generally make EDXRF
the second choice for these very low-energy x-ray lines. A beryllium window thickness of
8 mm is typically used for very light-element analysis, although windows as thin as 5 mm
have been used. The use of extremely thin windows may lead to increasing concerns for
helium integrity and equipment cost.
High-strength thin windows made from low-atomic-number elements that are cap-
able of withstanding a full 1-atm-pressure dierential have become commercially available
in the last decade. These include self-supporting 0.5-mm diamond polycrystalline lms
and 0.25-mm windows composed of a vapor-deposited amorphous material consisting of
90% boron by weight with nitrogen and oxygen for the remainder. These windows
exhibit signicant x-ray transmission for photons well below 1 keV and have found
widespread use in x-ray microanalysis.
G. Detector Background
Eects associated with the partial collection of the photoelectric signal by the detector
have a small eect on its eciency. However, these incomplete charge-collection processes
can have consequences that are far more serious for analytical performance through their
eect on spectral background. The eect of incomplete charge collection of these events is
to produce tailing on the low-energy side of a peak. In addition, it produces a continuum
of events that appear as a shelf on the low-energy side of major peaks in the spectrum. This
background tailing and shelf interfere with the measurement of lower-energy uorescence
x-rays and is a signicant factor in obtaining the lowest detection limits for the determi-
nation of trace quantities on the low-energy side of major peaks.
Studies designed to reduce this background have indicated that in addition to
fundamental x-ray and electron-energy-loss processes, a more signicant background
resulting from incomplete charge collection from the detector active volume is normally
the dominant contribution (Goulding et al., 1972; Jaklevic and Goulding, 1972). This
process is an artifact of the detector operation in which the collection of the free charge
from the depleted volume is inhibited as a result of nonuniformities in the applied
electrical eld. These nonuniformities are typically associated with edge eects at the
periphery of the cylindrical detector. The incomplete charge-collection background can
be reduced either by external collimators that prevent the incident radiation from in-
teracting in the periphery of the detector or by internal electronic collimation brought
about by the use of a guard-ring structure (Goulding et al., 1972). The tailing can
sometimes be improved by increasing the detector bias, but this is not an option
available to the majority of users. There has been much work on characterizing the
detector line shape and the eects on background and tailing of incomplete charge
collection (Campbell and Wang, 1991; Campbell et al., 1997; Heckel and Scholz, 1987;
Lepy et al., 1997). Such studies have led to a greater understanding of the processes
involved and to peak-tting procedures that can take account of them. However, im-
provements in this form of background can only be achieved through improvements in
detector design and manufacturing processes.
The P=B ratio of a detector is a standard measurement of detector quality. The
measurement is made using a
55
Fe radioisotope source to ensure that there is no other
contribution to background. The measurement cannot be made using x-ray tube excita-
tion, as it is extremely dicult to eliminate the residual bremsstrahlung continuum. The
peak is taken from the most intense channel in the MnKa peak and the background is
taken as the average intensity in the channels from 0.9 to 1.1 keV. A high-quality Si(Li)
detector will deliver a P=B ratio in excess of 10,000:1 and have minimal low-energy tailing.
IV. SEMICONDUCTOR DETECTOR ELECTRONICS
A. Sources of Electronic Noise
The contribution to resolution associated with electronic noise (DE
Elec
) is the result of
random uctuations in thermally generated leakage currents within the detector itself and
in the early stages of the amplier components. Although these processes are intrinsic to
the overall measurement process, there are methods for limiting the impact on the nal
system resolution. Figure 19 is a schematic diagram of a typical pulse processing system
employed in a semiconductor detector x-ray spectrometer. The pulse processing can be
divided between the charge integration, which takes place in the preamplier, and the
voltage amplication and pulse shaping, which occur in the main amplier (pulse
processor).
The function of the charge-sensitive preamplier and subsequent amplication stages
is to convert the integrated charge pulse, produced by collection of the photoelectrically
induced ionization, to a voltage pulse that can be measured and stored in the multichannel
pulseheight analyzer (MCA). The rst stage of the process occurs in the FET, which is
attached to the rear of the detector crystal. The method of charge restoration used for the
FET has a fundamental eect on the electronic noise of the overall detection system and is
particularly important. Early detectors used pulsed optical charge restoration, but newer
systems make use of integrated solid-state devices incorporating low-noise-junction FETs
to minimize electronic noise (Statham and Nashashibi, 1988; Lund et al., 1995, Lund et al.,
1996). However, the pulse processing must also achieve a very important goal of ampli-
fying the weak charge signal to a measurable level while suppressing random uctuations
in the signal amplitude produced by thermal noise. This is achieved by generating a
carefully dened pulse shape in the main amplier, which restricts the Fourier frequency
components in the nal signal in such a way that the signal contributions are emphasized
relative to the noise uctuations.
The most common pulse shapers employed in modern semiconductor spectro-
meters generate output pulses that are Gaussian, triangular, or cusp shaped (Fairstein
and Hahn, 1965; Kandiah et al., 1972; Landis et al., 1982). Each is capable of achieving
adequate energy resolution for EDXRF analysis; the dierences are due mainly to the
eective time interval required for processing a pulse. Because the relative amplitude of
the noise contribution is a strong function of the characteristic time constant associated
with the pulse shaper, the dierence between pulse shapes becomes important for ap-
plications in which high counting rates are important. A detailed analysis of the eects
of various pulse-shaping options on spectrometer performance is presented by Goulding
and Landis (1982). More recently, suciently fast, sampling analog-to-digital converters
(ADCs) have become available and these have resulted in the availability of digital pulse
processors (Warburton et al., 1988). These devices can implement the optimum noise-
reduction lters in conjunction with much higher count rates than conventional analog
pulse processors.
As pointed out below in the following subsection, however, it is not always desirable
to operate at the minimum-noise shaping time because an unacceptably large dead time
may result. Although EDXRF instruments are designed with a suitable compromise be-
tween energy resolution and count rate capabilities, an understanding of these trade-os
on the part of the user is important for optimum usage of the instrument.
Figure19 Typical pulse processing system used for energy-dispersive detectors.
B. Resolution and Count Rate
There exists a great deal of literature on the nature of the detection and pulse processing
systems and the great strides which have been made over the past 20 years to improve
resolution and increase count rate. For many years, the complete integration of the de-
tection and electronics systems within the instrumentation has meant that the individual
choice of and matching by the EDXRF user of detector, main amplier, ADC unit, and
MCA is no longer required. Once the application is determined, the choice of system will
typically revolve around achievable analytical performance.
The user will typically be left with a relatively straightforward selection of the single
signal processing setting providing the required resolution and count rate
(see Fig. 20). There is only a single setting and, unfortunately, resolution and rate go in
opposite directions when this setting is changed. In one direction, the amplier time
constant will increase, which gives better resolution (lower FWHM) at the expense of a
lower count rate into the MCA memory. In the opposite direction, resolution degrades but
count rate increases. Once the EDXRF system is chosen, this control is really the only way
in which the user can inuence resolution and count rate.
It is a little like choosing a car where you select the type of vehicle most suited to
your use. That vehicle then has a gearing selection system that allows you some degree of
trade-o in control. Low gears give highest accuracy in maneuverability (i.e., resolution)
but lowest speed (i.e., count rate). Conversely, the highest gears give a high speed (rate)
at the expense of accurate maneuverability!
At one end of the range, best resolution is obtained with lowest total count rate,
whereas at the other, highest count rate is delivered with the worst energy resolution.
When severe peak overlap is the dominant limitation to analytical performance, the best
resolution should be selected. In this case, which is typical for the light elements, the
Figure 20 Plots of energy resolution (at 5.9 keV) and count rate for a Si(Li) detector.
excitation conditions will need adjusting to make best use of the limited count rate
available. Where peak separation is good, such as above 15 keV, or where there are no
severe overlaps, select the fastest count rate. In both cases, the current is used to adjust for
optimum dead time (50% typically) and the measurement time is used to control the
precision.
C. Pulse Pileup
The count-rate limitations associated with a semiconductor spectrometer are an inherent
property associated with the nite pulse processing time required by the electronic shaping
network. When a random sequence of pulses is incident on the detection system, some of
the events cannot be processed without ambiguity. To appreciate the fundamental nature
of this limitation and its relationship to system performance, some elementary concepts of
electronic pulse processing must be considered.
Figure 21 illustrates the time sequence of pulses that occur at various stages in the
pulse processing chain. Trace A shows the output of the charge-integrating preamplier.
The steps at times 1, 2, and 3 represent the charge integrals of discrete events. Traces B and
C are the outputs of the fast (short shaping time) amplier and an associated discriminator
that serves as a timing marker for the individual events. The main shaping amplier output
is shown as the Gaussian pulse shapes (in trace D). For each event, a total pulse processing
time (neglecting analog-to-digital conversion in the pulseheight analyzer) of t
d
is re-
quired after the arrival of the pulse and before the system is ready to accept the next event.
Although the average counting rate detected by the system can be well below the
frequency dened by the reciprocal of the pulse width t
d
, that the events are statistically
uncorrelated implies that the events are not uniformly distributed in time. There then
exists a probability that two pulses will occur within the same processing time interval.
This is illustrated by the overlap of pulses 2 and 3 in the trace.
At a low average counting rate, this pulse overlap is not a limiting factor. As the
average counting rate increases, however, a point is reached at which there is a signicant
probability that a second event will occur before the rst event has been fully analyzed.
If the two events occur within a time less than the shaping time of the amplier, the charge
signals are indistinguishable and an erroneous pileup energy signal results.
Modern spectrometers employ some form of rejection circuitry to eliminate these
pileup events from the pulseheight spectrum. Typical systems rely on the inspection of
the fast discriminator output to determine if two pulses have occurred in rapid succes-
sion. Appropriate logic is then employed to gate the output of the processor to eliminate
the resultant ambiguous energy signals. This is shown in traces E and F of Figure 21, in
which the logic signal causes the output to be inhibited when the pulses overlapped to
produce an ambiguous pileup energy output. Because the fast shaper that generates the
discriminator output has inherently poorer energy resolution relative to the slow channel,
the pileup rejection circuit is limited in the minimum energy of pulses it can detect.
However, in typical tube-excited EDXRF, the major fraction of pulses occur from
scattered high-energy radiation and a pileup rejector system is an important feature in
the system design.
The pileup probability is obviously a function of the characteristic shaping time t
p
,
which, in turn, establishes the eective dead time, t
d
, of the system. This probability is
independent of the details of the specic type of pileup rejection circuit used to eliminate
the ambiguous events. The number of events that experience pileup and are consequently
eliminated from the spectrum can be estimated for the case of a totally random arrival
distribution. For a series of events randomly distributed in time with an average frequency
N
0
, the probability P that no pileup events occur within a characteristic time t
d
after a
given event can be expressed as
P N
0
e
N
0
t
d
From this expression, we can calculate the fraction of events transmitted through the
system. Figure 22 is a plot of nonpileup output rate versus input rate expressed in terms of
a characteristic pulse processing time.
The input rate for which the output rate is a maximum is seen to be the reciprocal of
the shaping time. The output rate at this point is reduced by a factor of 1=e. It should be
emphasized that this behavior is a fundamental consequence of random arrival statistics
and a nite measurement time. However, one should be aware that it is always possible to
reduce the characteristic processing time to achieve an increase in counting rate at some
sacrice in energy resolution. It is also worth noting that, by working at too high a dead
Figure21 Time sequence of pulses during the processing of a series of x-ray events; (A) the output
of the preamplifier is represented as a series of voltage steps reflecting the integrated charge from the
individual events; (B) the output from a fast shaping amplifier that operates with a shorter time
constant than the main shaping system; (C) a fast discriminator timing pulse derived from B; (D) the
output of the main shaper, with the pileup of pulses 2 and 3 indicated; (E) the dead-time gates; and
(F) the final output with the ambiguous 2 and 3 pileup pulses rejected.
time, the throughput curve inverts and the output rate begins to fall. Further increase
of the dead time will eventually lead to paralysis of the system and negligible output
countrate.
Although dierent algorithms can be used to correct for events lost to pileup, there
is no way to eliminate the eect through passive pulse processing (Gedcke, 1972; Hayes
et al., 1978; Statham, 1977). Because dierent manufacturers of x-ray equipment vary in
their approaches to pileup rejection, the only way to evaluate the throughput of the system
is using a variable intensity source of radiation. The input rate can be determined by
scaling the fast discriminator output, which is sometimes available from the instrument
data system. The output rate can be simultaneously measured in the pulseheight ana-
lyser. A plot of nonpileup output rate versus input rate can then be generated and com-
pared to the ideal case shown in Figure 22.
When the excitation source can be switched o in a time interval that is short com-
pared to the characteristic pulse processing time, it is possible to increase the average output
counting rate by eliminating the eects of pileup. Such pulsed excitation systems rely on the
ability to detect an event in the fast channel and to shut o the excitation before a second
pileup event can occur. In this mode of operation, the output rate can equal the input rate
up to the point at which the system is continuously busy. This method of pileup control has
been implemented using pulsed x-ray tubes (Jaklevic et al., 1976; Stewart et al., 1976),
although the increased complexity of the electron optics tends to lead to increased cost.
D. Dead-Time Correction
The presence of pulse pileup must be considered in any system designed for quantitative
measurements because it causes the eciency with which pulses are processed to be rate
dependent. EDXRF analytical systems are designed to correct for this discrepancy
through a variety of approaches. The most straightforward involve the use of a live-time
Figure 22 Nonpileup output rate (N
0
) as a function of input rate (N
1
) scaled as a function of
a characteristic shaping time. Maximum output is 0.37 of the input rate that is equal to the reciprocal
of the time constant.
clock consisting of a gated oscillator and scaler. The oscillator clock is turned o when the
system is busy processing pulses. In this way, the duration of the measurement in terms of
a live-time interval is extended to correct for those periods when the system is incapable of
processing a pulse. Alternative methods rely on the direct measurement of the fast dis-
criminator pulses to keep track of those events that were missed. An additional correction
is added to compensate for those intervals in which pileup occurs (Bloomeld et al., 1983;
Hayes et al., 1978).
A simple empirical method used to correct for dead-time losses is a measurement of
the ratio of input to output counts as a function of input rate over the range of values
normally encountered. Subsequent analyses require that the input rate be measured for
each experiment. The live-time correction can then be applied using the previously de-
termined response function.
Because all live-time correction methods have some limitation on the range of
counting rates over which they can be used, it is important that methods be devised to
evaluate the precision with which such corrections are generated. A carefully prepared
series of standards of varying concentrations represents a direct approach. A potentially
more precise method involves the use of a single thin-lm standard. Variable-mass targets
are placed behind the standard to vary the total counting rate over the range of interest.
If the variable mass target is chosen so that the variable intensity of scattered or uor-
escence radiation does not induce uorescence in the thin-lm standard, the measured
intensity of uorescence from the standard should be independent of total counting rate.
The ability of the dead-time correction system to compensate for pileup can then be
empirically evaluated. All modern EDXRF systems incorporate eective dead-time cor-
rection circuitry, which is likely to be at least as accurate as experiments designed to test
this standard feature.
V. SUMMARY
The technology that makes chemical analysis with EDXRF practical is based on the use of
semiconductor x-ray detectors and associated pulse processing and data acquisition sys-
tems. The present chapter attempted to explain to the analyst the basic concepts behind
the operation of these components and the manner in which they inuence overall system
performance. The trade-os one must make between such parameters as excitation con-
ditions, detector resolution, count rate, and other design variables determine how eec-
tively one can tailor a given instrument or experimental apparatus to a specic application.
Furthermore, a thorough understanding of the factors that limit performance should
enable one to implement experimental tests to determine the eectiveness of a particular
approach and evaluate various commercial options.
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4
Spectrum Evaluation
Piet Van Espen
University of Antwerp, Antwerp, Belgium
I. INTRODUCTION
This chapter deals with (mathematical) procedures to extract relevant information from
acquired x-ray spectra. Smoothing of the spectrum results in a graph that can be easier
interpreted by the human observer. To determine which elements are present in a speci-
men, peak search methods are used. To obtain the analytically important net peak areas of
the uorescence lines, a variety of methods, ranging from simple summation to sophisti-
cated least-squares-tting procedures, are to the disposal of the spectroscopist.
Spectrum evaluation is a crucial step in x-ray spectrometry, as much as sample pre-
paration and quantication. As with any analytical technique, the performance of x-ray
uorescence analysis is determined by the weakest step in the process. Spectrum evaluation
in energy-dispersive x-ray uorescence analysis (EDXRF) is certainly more critical than in
wavelength-dispersive spectrometry (WDXRF) because of the relatively low resolution of
the solid-state detectors employed. The often-quoted inferior accuracy of EDXRF can, to a
large part, be attributed to errors associated with the evaluation of these spectra. As a
consequence of this, most of the published work in this eld deals with ED spectrometry.
Although rate meters and=or strip-chart recorders have been employed in WD
spectrometry for a long time, the processing of ED spectra by means of computers has
always been more evident because of their inherent digital nature. Some of the techniques
to be discussed have their roots in g-ray spectrometry developed mainly in the sixties; for
others (notably the spectrum-tting procedures), EDXRF has developed its own specia-
lized data processing methodology. The availability of inexpensive and fast personal
computers together with the implementation of mature spectrum evaluation packages on
these machines has brought sophisticated spectrum evaluation within the reach of each
x-ray spectrometry laboratory.
In this chapter, various methods for spectrumevaluation are discussed, with emphasis
on energy-dispersive x-ray spectra. Most of the methods are relevant for x-ray uorescence,
particle-induced x-ray emission (PIXE), and electron beamx-ray analysis [electron probe x-
ray microanalysis (EPXMA), scanning electron microscopy energy dispersive x-ray
analysis (SEMEDX), and analytical electron microscopy (AEM)]. The principles of the
methods and their practical use are discussed. Least-squares tting, which is of importance
not only for spectrum evaluation but also for qualication procedures, is discussed in detail
in Sec. IX. Section X presents computer implementations of the main algorithms.
II. FUNDAMENTAL ASPECTS
The aims of spectrum evaluation is to extract analytically relevant information from ex-
perimental spectra. Obtaining this information is not straightforward because the spectral
data are always corrupted with measurement noise.
A. Amplitude and Energy Noise
In x-ray spectra, we can distinguish between amplitude and energy noise. Amplitude noise
is due to the statistical nature of the counting process, in which random events (the arrival
of x-ray photons at the detector) are observed during a nite time interval. For such a
process, the probability of observing N counts when the true number of counts is N
0
is
given by the Poisson distribution (Bevington and Robinson, 1992):
P(N; N
0
) =
N
N
0
N!
e
N
0
(1)
The number of counts in each channel of an x-ray spectrum as well as the sum over a
number of channels obey this Poisson distribution. For a Poisson random variable, the
population standard deviation is equal to the square root of the true number of counts:
s
N
0
=
N
0
_
(2)
The sample standard deviation, which is an estimate of the true standard deviation,
therefore can be calculated as the square root of the observed number of counts:
s
N
=
N
_
- s
N
0
(3)
The statistical nature of the counting process (Poisson statistics or counting statistics)
causes the typical channel to channel uctuations observed in x-ray spectra. That the
uncertainty of the data can be calculated from the data itself [Eq. (3)] is of great im-
portance for the spectrum evaluation methods.
Energy noise, on the other hand, causes the characteristic x-ray lines of ED spectra
to appear much wider than their natural linewidth of about 510 eV. Part of this line
broadening is due to the nature of photon-to-charge conversion process in the detector,
and part of it is associated with the electronic noise in the pulse amplication and pro-
cessing circuit, as discussed in Chapter 3. As a result, x-ray photons with energy E, which
on average correspond to a pulse height stored in channel i, from time to time gives rise to
slightly higher or lower pulses, causing the x-ray events to be stored in channels above and
below i, respectively. Accordingly, characteristic x-ray lines appear as relatively broad
(140250 eV), nearly Gaussian-shaped peaks in the spectrum. The peaks observed in
wavelength-dispersive spectra are also wider than the natural linewidth because of im-
perfections in the diraction crystal and the nite size of the collimators.
B. Information Content of a Spectrum
In the absence of these two noise contributions, spectrum evaluation would be trivial. A
spectrum would consist of a well-dened continuum on which sharp characteristic lines
were superimposed. The intensity of the continuum and the net x-ray line intensities could
be determined without error. Any remaining peak overlap (e.g., between AsKa and PbLa,
where the separation of 8 eV is less than the natural width of the AsKa line) could be dealt
with in an exact manner.
Unfortunately, we cannot eliminate the noise in the measurements completely. It is
possible, however, to reduce the noise in various ways. Amplitude noise (i.e., counting
statistics) can be reduced by acquiring the spectrumfor a longer period of time or by using a
more intense primary beam. The eect of energy noise can be lowered by using a detector
and associated electronics of good quality and by shielding the systemfromexternal sources
of electronic noise. Although these suggestions may sound straightforward and not ap-
propriate in the context of spectrum evaluation, it is important to realize that once a
spectrum has been acquired, the information content remains constant. No spectrum pro-
cessing procedure, no matter howsophisticated, can produce more information than present
originally. It is therefore much more ecient to employ optimal experimental conditions
when acquiring the data rather than to rely on mathematical techniques in an attempt to
obtain information which is not present in the rst place (Statham and Nashashibi, 1988).
From this point of view, spectrum processing can be seen as any (mathematical)
procedure that transforms the information content of a measured spectruminto a formthat
is more useful for our purposes (i.e., more accessible). As is indicated in Figure 1, most of
the procedures that calculate this useful information require some form of additional
input. Sometimes, this extra information is intuitive and not clearly dened; in other cases,
additional information is used in the form of mathematical model. In this respect, not the
complexity of model but rather the ability to accurately describe the physical reality is of
relevance. When we use a procedure to estimate the net peak area of a characteristic line by
summing the appropriate channels and interpolating the continuum left and right of the
peak, explicitly some additional information is given to this spectrum processing
method in the form of peak and continuum boundaries. In addition (implicitly), a certain
mathematical model is assumed regarding the shape of the peak and the continuum.
Provided this model is correct, this relatively simple procedure returns a correct estimate of
the net peak area as good as one could obtain by a complicated tting procedure.
The important distinction between simple and more sophisticated spectrum eva-
luation procedures lies in the incorporated exibility and applicability. A simple area es-
timation based on the integration of peak and continuum regions is not generally
applicable in real-world situations in which peak overlap, curvature in the continuum, and
peak tailing occur. Procedures employing more complex models are adaptable to each
specic situation, yielding reliable peak estimates. Spectrum evaluation procedures should
Figure 1 Spectrum evaluation seen as an information process: spectrum processing requires
additional information to extract useful information from measured spectral data.
therefore be compared on the basis of the explicit and implicit assumptions that are made
in the model(s) they employ.
C. Components of an X-ray Spectrum
To evaluate an x-ray spectrum correctly, it is necessary to understand all the phenomena
that contribute to the nal appearance of the spectrum. This includes the two main fea-
tures, characteristic lines and continuum, and also a number of spectral artifacts, which
become important especially in trace analysis work (Van Espen et al., 1980).
1. Characteristic Lines
The characteristic radiation of a particular x-ray line has a Lorentz distribution. Peak
proles observed with a semiconductor detector are the convolution of this Lorentz dis-
tribution with nearly Gaussian detector response function, giving rise to what is known as
Voigt prole (Wilkinson, 1971). Because the Lorentz width is of the order of only 10 eV
for elements with atomic number below 50, whereas the width of the detector response
function is of the order of 160 eV, a Gauss function is an adequate approximation of the
line prole. Only for K lines of elements such as U and Th does the Lorentz contribution
become signicant and need to be taken into account (Gunnink, 1977).
A more close inspection of the peak shape reveals some distinct tailing at the low
energy side of the peak and a shelf extending to zero energy. This is mainly due to
incomplete charge collection caused by detector imperfections (dead layer and regions of
low electric eld) as discussed in Chapter 3. The eect is most pronounced for low
energy x-rays. For photons above 15 keV Compton scatter in the detector also con-
tributes to deviation from the Gaussian shape. The distortion caused by incomplete
charge collection has been described theoretically (Joy, 1985; Heckel and Scholz, 1987).
Various functions have been proposed to model the real peak shape more accurately
(Campbell et al., 1987).
The observed emission spectrum of an element is the result of many transitions, as
explained in Chapter 1. The resulting x-ray lines, including possible satellite lines, need to
be considered in the evaluation of an x-ray spectrum. A more detailed discussion on the
representation of the K and L spectra and the peak shape is given in Sec. VII.
2. Continuum
The continuum observed in x-ray spectra results from a variety of processes. The con-
tinuum in electron-induced x-ray spectra is almost completely due to the retardation of the
primary electrons (bremsstrahlung). The intensity distribution of the continuum radiation
emitted by the sample is in rst approximation given by Kramers formula (Chapter 1).
Absorption in the detector windows and in the sample causes this continuous decreasing
function to fall o at low energies, giving rise to the typical continuum shape observed.
The attenuation of this bremsstrahlung by major elements in the sample also causes ab-
sorption edges to appear in these spectra. Continuum modeling for electron-induced x-ray
spectra has been studied in detail by a number of authors (Statham, 1976a, 1976b,
Smith et al., 1975; Sherry and Vander Sande, 1977; Bloomeld and Love, 1985).
For particle-induced x-ray emission, a similar continuum is observed also mainly due
to secondary electron bremsstrahlung. Other (nuclear) processes contribute here, making
it virtually impossible to derive a real physical model for the continuum. Special absorbers
placed between the sample and detector further alter the shape of the continuum.
In x-ray uorescence, the main source of the continuumis the coherent and incoherent
scattering of the excitation radiation by the sample. The shape can therefore become very
complex and depends both on the initial shape of the excitation spectrumand on the sample
composition. When white radiation is used for the excitation, the continuum is mainly ra-
diative and absorption edges can also be observed. With quasimonoenergetic excitation
(secondary target, radioisotope), the incomplete charge collection of the intense coherently
and incoherently scattered peaks is responsible for most of the continuum (see Chapter 3).
Also here, realistic physical models for the description of the continuum are not used.
The incomplete charge collection of intense uorescence lines in the spectrum further
complicates the continuum. The cumulative eect of the incomplete charge collection of all
lines causes the apparent continuum at lower energies to be signicantly higher that ex-
pected on the basis of the primary continuum generating processes.
3. Escape Peaks
Escape peaks result from the escape of SiK or GeK photons from the detector after
photoelectric absorption of the impinging x-ray photon near the edge regions of the de-
tector. The energy deposited in the detector by the incoming x-ray is diminished with the
energy of the escaping SiK or GeK photon. Typical examples of the interference due to Si
escape peaks are the interference of TiKa (4.51 keV) by the FeKa escape at 4.65 keV and
the interference of FeKa by the CuKa escape.
For a Si(Li) detector, the escape peaks is expected 1.742 keV (SiKa) below the parent
peak. Experimentally, it is observed that the energy dierence is slightly but signicantly
higher, 1.750 keV (Van Espen et al., 1980). Ge escape peaks are observed 9.876 (GeKa)
and 10.984 keV (GeKb) below the parent peak. The width of the escape peaks is smaller
than the width of the parent peak and corresponds to the spectrometer resolution at the
energy of the escape peak.
The escape fraction f is dened as the number of counts in the escape peak N
e
di-
vided by the number of detected counts (escape parent). Assuming normal incidence to
the detector and escape only from the front surface, the following formula can be derived
for the escape fraction (Reed and Ware, 1972):
f =
N
e
N
p
N
e
=
1
2
o
K
1
1
r
_ _
1
m
K
m
I
ln 1
m
I
m
K
_ _ _ _
(4)
where m
I
and m
K
are the mass-attenuation coecient of silicon for the impinging and the
SiK radiation, respectively, o
K
is the K uorescence yield, and r is the K jump ratio of
silicon. Using 0.047 for the uorescence yield and 10.8 for the jump ratio, the calculated
escape fraction is in very good agreement with the experimentally determined values for
impinging photons up to 15 keV (Van Espen et al., 1980). Equation (4) is also applicable
for estimating the escape fraction in Ge detectors, provided that the parameters related to
Si are substituted with these of Ge. Knowing the energy, width, and intensity of the escape
peak, corrections for its presence can be made in a straightforward manner.
4. Pileupand SumPeaks
With modern pulse processing electronics, the pileup eects are suppressed to a large
extend. With a pulse-pair resolution time of a few 100 ns or less, only true sum peaks are
observed. These sum peaks are, within a few electron volts, located at their expected
position, and they are slightly wider (5%) than normal peaks located at the same energy
in the spectrum (Van Espen et al., 1980). The count rate of a sum peak is given by
_
N
11
= t
_
N
1
_
N
2
(5)
and
_
N
12
= 2t
_
N
1
_
N
1
(6)
with
_
N
11
the count rate (counts=s) in a sum peak due to the coincidence of two x-rays with
the same energy,
_
N
12
the count rate of a sum peak resulting from two x-rays with dierent
energy, and t the pulse-pair resolution time in seconds. Sum peaks are often found when a
few large peaks at lower energy dominate the spectrum. Typical examples are PIXE
spectra of biological and geological samples. The high count rate of the K and CaK lines
produces sum peaks that are easily observed in the high-energy region of the spectrum
where the continuum is low. It is important to note that the intensity of sum peaks is
count-rate dependent, they can be reduced and virtually eliminated by performing the
measurement with a lower primary beam intensity. A method for correcting for the
contribution of sum peaks in least-squares tting has been proposed by Johansson (1982)
and is discussed further in Sec. VII.
5. Discrete Character of a PulseHeight Spectrum
Another aspect of spectral data that should be mentioned is that a pulseheight spectrum
is a discrete histogram representing a continuous function. Digitization of this continuous
function, especially the Gaussian peaks, into too few channels causes considerable sys-
tematic errors. If the peak contains less than 2.5 channels at the FWHM, the peak area
estimate, for example, obtained by summing the channel contents is largely overestimated.
This lower limit of 2.5 channels at FWHM corresponds to a spectrometer gain of
60 eV=channel for a peak width of 150 eV. In practice, 40 eV=channel or lower is re-
commended, otherwise peak position and width determinations and the results of spec-
trum tting become unreliable.
6. Other Artifacts
A number of other features might appear in an x-ray spectrum and can cause problems
during the spectrum evaluation. In the K x-ray spectra of elements with atomic number
between 20 and 40, one can detect a peaklike structure with a rather poorly dened
maximum and a slowly declining tail (Van Espen et al., 1979a). This structure is due to the
KLL radiative Auger transition, which is an alternative decay mode of the K vacancy.
The maximum is observed at the energy of the KLL Auger electron transition energy.
The intensity of the radiative Auger structure varies from approximately 1% of the Ka line
for elements below Ca to 0.1% for elements above Zn. For chlorine and lower atomic
number elements, the radiative Auger band overlaps with the Ka peak. In most analytical
applications, this eect will not cause serious problems. The structure can be considered as
part of non-Gaussian peak tail.
The scattering of the excitation radiation in x-ray uorescence is responsible for most
of the continuum observed in the spectrum. When characteristic lines are present in the
excitation spectrum, two peaks might be observed. The Rayleigh (coherently)-scattered
peak has a position and width as expected for a normal uorescence line. The Compton
(incoherently scattered) peak is shifted to lower energies according to the well-known
Compton formula and is much broader than a normal characteristic line at that energy.
This broader structure, resulting from scattering over a range of angles and Doppler eect,
is dicult to model analytically (Van Dyck and Van Grieken, 1983). The structure is
further complicated by multiple scattering phenomena in the sample (Vincze et al., 1999).
Apart fromthese commonly encountered scattering processes, it is possible to detect x-
ray Raman scattering (Van Espen et al., 1979b). Again, a bandlike structure is observed with
an energy maximumgiven by the incident photon energy minus the electron-binding energy.
The Raman eect is most prominently present when exciting elements with atomic number
Z72 to Z7 with the Kradiation of element Z. In this case, Raman scattering occurs on L
electrons. For x-ray excitation energies between 15 and 25 keV, the Raman scattering on the
K electrons of Al to Cl can also be observed. Because of its high-energy edge, the eect may
appear as a peak in the spectrumwith possible erroneous identication as a uorescence line.
The intensity of the Raman band increases as the incident photon energy comes closer to the
binding energy of the electron. The observed intensity can amount to as much as 10%of the
L uorescence intensity for the elements Rh to Cs when excitation with MoKx-rays is used.
When the excitation source is highly collimated diraction peaks can be observed in
the x-ray uorescence spectrum of crystalline materials. It is often dicult to deal with
these diraction patterns. They can interfere with the uorescence lines or even be mis-
interpreted as being uorescence lines, giving rise to false identication of elements.
III. SPECTRUMPROCESSINGMETHODS
Spectrum processing refers to mathematical techniques that alter the outlook of the
spectral data. This is often done, using some digital lter, to reduce the noise, to locate
peaks, or to suppress the continuum. In this section, various methods of ltering are
discussed. Because of its relation to the frequency domain, the concept of Fourier trans-
formation is introduced rst.
A. Fourier Transformation, Convolution, and Deconvolution
One can think of an x-ray spectrum as consisting of a number of components with dif-
ferent frequencies. In the spectrum shown in Figure 2, one recognizes a nearly constant
component (the continuum) as well as a component that uctuates from channel to
channel ( =fast). The latter is obviously the noise due to counting statistics. Peaks, then,
must have frequency components intermediate between these two. The frequency char-
acteristics of a spectrum can be studied in the Fourier space.
For any discrete function f(x), x=0, . . . , n 71 (e.g., a pulseheight spectrum), the
discrete Fourier transform is dened as
F(u) =
1
n
n1
x=0
f(x) exp
j2pux
n
_ _
=
1
n
n1
x=0
f(x) cos 2p
ux
n
j sin 2p
ux
n
_ _
(7)
with j =
1
_
and u =0, . . . , n 71. F(u) is a complex number. The real part, R(u), and the
imaginary part, I(u), represent respectively the amplitude of the cosine and the sine
functions that are necessary to describe the original data. The square of F(u) is called the
power spectrum,
[F(u)[
2
= R
2
(u) I
2
(u) (8)
and gives an idea about the dominant frequencies in the spectrum. Because there are n
dierent nonzero real and imaginary coecients, no information is lost by the Fourier
transform and the inverse transformation is always possible:
f(x) =
n1
u=0
F(u) exp
j2pux
n
_ _
(9)
Figure 3 shows that power spectrum of the pulseheight distribution in Figure 2 (a single
Gaussian on a constant continuum). The frequency (inverse channel number) is dened as
u=n, with n =256 and u =0, . . . , n=2. The amplitude of the zero frequency [F(0)[
2
, which is
equal to the average of the spectrum, is not shown. The dominating low frequencies
originate from the continuum and from the Gaussian peak, whereas the higher frequencies
are caused mainly by the counting statistics. It is clear that if we eliminate those high
frequencies, we are reducing this noise. This can be done by multiplying the Fourier
transform with a suitable function:
G(u) = F(u)H(u) (10)
An example of such a function is a high-frequency cuto lter:
H(u) =
1; u _ u
crit
0; u > u
crit
_
(11)
which sets the real and imaginary coecients above a frequency u
crit
to zero. If we apply
this lter to the Fourier transform of Figure 3 using u
crit
=0.05 and then apply the inverse
Fourier transformation [Eq. (9)], the result as shown by the solid line in Figure 2 is ob-
tained. The peak shape is preserved, but most of the statistical uctuations are eliminated.
Figure 2 A 256-channel pulseheight spectrum (single Gaussian on a constant continuum) and
the Fourier-filtered spectrum.
If we would cut o at even lower frequencies, peak distortions at the top and at the base of
the peak would become more pronounced.
This Fourier ltering can also be done directly in the original data space. Indeed, the
convolution theorem says that multiplication in the Fourier space is equivalent to con-
volution in the original space:
G(u) = F(u)H(u) =f(x) h(x) = g(x) (12)
The convolute at data point x is dened as the sum of the products of the original data and
the lter centered around point x:
g(x) = f(x) h(x) =
x
/
f(x x
/
)h(x
/
) (13)
h(x) is called a digital lter and is the inverse Fourier transformation of H(u). In
general, this convolution or ltering of a spectrum y
i
with some weighing function is
expressed as
y
+
i
=
1
N
j=m
j=m
h
j
y
ij
(14)
where h
j
are the convolution integers and N is a suitable normalization factor. The lter
width is given by 2m1. Fourier ltering with the purpose to reduce or eliminate some
(high or low) frequency components in the spectrum can thus be implemented as a con-
volution of the original data with a digital lter. This convolution also alters the variance
of the original data. Applying the concept of error propagation, one nds that the variance
of the convoluted data is given by
Figure 3 Fourier power spectrum of the pulseheight distribution shown in Figure 2.
s
2
y
+
i
=
1
N
2
m
j=m
h
2
i
y
ij
(15)
when the original data follows a Poisson distribution (s
2
y
= y).
Because the measured spectrum y(x) is itself a convolution of the original (x-ray
emission) signal f(x), with the instrument (or detector) response function h(x), it is, in
principle, possible to restore the measured signal if this response function is know. This
can be accomplished by dividing the Fourier transform (FT) of the measured spectrum by
Fourier transform of the (nearly Gaussian) response function, followed by the inverse
Fourier transform (IFT) of the resulting quotient:
y(x)
FT
Y(u)
h(x)
FT
H(u)
_
Y(u)
H(u)
= F(u)
IFT
f(x) (16)
The fact that the detector response function changes with energy (becomes broader) and,
more importantly, the presence of noise prohibits the straightforward application of this
Fourier deconvolution technique. Indeed, in the presence of noise, the measured signal
must be presented by
y(x) = f(x) h(x) n(x) (17)
and its Fourier transform
Y(u) = F(u)H(u) N(u) (18)
or
Y(u)
H(u)
= F(u)
N(u)
H(u)
(19)
At high frequencies, the response, H(u), goes to zero while N(u) is still signicant, so that
the noise is emphasized in the inverse transformation. This clearly shows that the noise
(counting statistics) is the ultimate limitation for any spectrum processing and analysis
method.
A clear introduction to Fourier transformations related to signal processing can be
found in the work of Massart et al. (1998). Algorithms for Fourier transformation and
related topics are given in the work of Press et al. (1998). Detailed discussions on Fourier
deconvolution can be found in many textbooks (Jansson, 1984; Brook and Wynne, 1988).
Fourier deconvolution in x-ray spectrometry based on maximum a posteriori or maximum
entropy principles is discussed by several authors (Schwalbe and Trussell, 1981; Nunez
et al., 1988; Gertner et al., 1989). Gertner implemented this method for the analysis of real
x-ray spectra and compared the results with those obtained by simple peak tting. The
problem that the deconvolution algorithms are limited to systems exhibiting translational
invariance was overcome by a transformation of the spectrum, so that the resolution
becomes independent of the energy.
B. Smoothing
Because of the uncertainty

y
_
on each channel content y
i
, ctitious maxima can occur
both on the continuum and on the slope of the characteristic peaks. Removal or sup-
pression of these uctuations can be useful during the visual inspection of spectra (e.g., for
locating small peaks on a noisy continuum) and is used in most automatic peak search and
continuum estimation procedures. Although smoothing can be useful in qualitative ana-
lysis, its use is not recommended as part of any quantitative spectrum evaluation.
Smoothing, although reducing the uncertainty in the data locally, redistributes the original
channel content over the neighboring channel, thus introducing distortion in the spectrum.
Accordingly, smoothing can provide a (small) improvement in the statistical precision
obtainable with simple peak integration but is of no advantage when used with least-
squares-tting procedures in which assumptions about the peak shapes are made.
1. Moving Average
The most straightforward way of smoothing (any) uctuating signal is to employ the
box-car or moving-average technique. Starting from a measured spectrum y, a
smoothed spectrum y* is obtained by calculating the mean channel content around each
channel i:
y
+
i
= " y
i
=
1
2m1
m
j=m
y
ij
(20)
This can be seen as a convolution [Eq. (14)] with all coecients h
j
= 1. The smoothing
eect obviously depends on the width of the lter, 2m1. The operation being a simple
averaging, the standard deviation of the smoothed data is reduced by a factor
2m1
_
in
regions where y
i
is nearly constant. On the other hand, such a lter introduces a con-
siderable amount of peak distortion. This distortion depends on the lter width-to-peak
width ratio. Figure 4 shows the peak distortion eects when a moving-average lter of
widths 9, 17, and 25 is applied to a peak with full width at half-maximum (FWHM) equal
to nine channels. Being a unit area lter

h
j
=N = 1 with N=2m1, the total counts in
the peak is not aected in an appreciable way other than by rounding errors.
Figure 4 Distortion introduced by smoothing of a peak with a moving-average filter 9, 17, and 25
points wide. The FWHM of the original peak is nine channels.
Figure 5 shows the eect on the peak height and width when applying this type of
lter with dierent sizes. The peak distortion is caused by the fact that in the calculation of
y
+
i
, the content of all neighboring channels is used with equal weight. Consequently, by
employing a nonuniform lter h, which places more weight on the central channels and
less on the channels near the edge of the lter, smoothing can be achieved with less
broadening eects.
2. Savitskyand Golay Polynomial Filters
Another way of dealing with statistical uctuations in experimental data is by drawing a
best-tting curve through the data points. This idea resulted in the development by
Savitsky and Golay (1964) of a general type of smoothing lters with very interesting
features. The method is based on the fact that nearly all experimental data can be modeled
by a polynomial of order r, a
0
a
1
x a
2
x
2
a
r
x
r
, when the data are conned to a
suciently small interval. If we consider a number of data points around a central channel
i
o
, such as y
i
0
2
; y
i
0
1
; y
i
0
; y
i
0
1
; y
i
0
2
, a least-squares t with the function.
y(i) = a
0
a
1
(i i
0
) a
2
(i i
0
)
2
(21)
can be made. Once we have determined the coecients a
j
, the value of the polynomial at
the central channel i
0
can be used as the smoothed value:
y
+
i
= y(i
0
) = a
0
(22)
This concept is schematically illustrated in Figure 6. By moving the central channel to the
right (from i
0
to i
0 1
), the next smoothed channel content can be calculated by repeating
the entire procedure.
Figure 5 Percent change in peak height and width introduced by filtering with a moving-average
and a Savitsky and Golay polynomial filter as a function of the filter width-to-peak FWHM ratio,
(2m1)/FWHM.
At rst sight, this smoothing method would require a least-squares t for each
channel in the spectrum. However, the fact that the x values are equidistant allows us to
formulate the problem in such a way that the polynomial coecients can be expressed as
simple linear combinations involving only y
i
values:
a
k
=
1
N
k
j=m
j=m
C
k; j
y
ik
(23)
This means that it is possible to implement the least-squares-tting procedure more e-
ciently as a convolution of the spectrum with a lter having appropriate weights. For this
second-order polynomial, the coecients are given by
C
0; j
N
0
=
3(3m
2
3m1 5j
2
)
(2m1)(2m1)(2m3)
(24)
Smoothing with a ve-point second-degree polynomial (2m1 = 5) thus becomes
y
+
i
= a
0
=
1
35
(3y
i2
12y
i1
17y
i
12y
i1
3y
i2
) (25)
In general, for a polynomial of degree r tted to 2m1 points, this can be written as
y
+
i
=
1
N
rm
j=m
j=m
C
rm; j
y
ij
(26)
where the convolution integers C
rm;j
and the normalization factors N
rm
do not depend on
the data to be smoothed but are a function only of the polynomial degree r and on the lter
Figure 6 Concept of polynomial smoothing. A parabola is fitted trough the points i
0
3 to i
0
3.
The value of the parabola at i
0
is the smoothed value (
v
).
half-width m. Table 1 lists the coecients of polynomial smoothing lters with widths
between 5 and 25 points. The coecients for a second- and a third-degree polynomial are
identical. In comparison with the moving-average lter of the same width, polynomial
smoothing lters are less eective in removing noise but have the advantage of causing less
peak distortion. The distortion eect as a function of the lter width-to-peak width ratio is
given in Figure 5. When the lter becomes much wider than the peak, the smoothed
spectrum features oscillations near the peak boundaries, as illustrated in Figure 7.
An interesting feature of this type of lters is that they can produce not only a
smoothed spectrum but also a smoothed rst and second derivative of the spectrum. If we
dierentiate Eq. (21) and take the value at the center position,
y
+/
=
dy(i)
di
i=i
0
= a
1
(27)
y
+//
=
d
2
y(i)
di
2
i=i
0
= 2a
2
(28)
it follows from Eq. (23) that the smoothed rst and second derivative of the spectrum can
also be calculated by means of suitable convolution coecients. For instance, for the rst
derivative of a second-order polynomial, using ve data points this becomes
y
+/
i
=
1
10
(2y
i2
y
i1
y
i1
2y
i2
) (29)
The corresponding convolution integers for the calculation of the smoothed rst and
second derivative are listed in Tables 24. The use of the derivative spectra is illustrated in
next section dealing with peak search methods. The FORTRAN implementation of the
Savitsky and Golay lters is given in Sec. X.
Variations on these smoothing strategies, such as the use of variable-width lters are
reviewed by Yule (1967). The eect of repeated smoothing on the accuracy and precision
of peak area determination is discussed by Nielson (1978). A more comprehensive treat-
ment on polynomial smoothing can be found in Enke and Nieman (1976) and its
references.
Table 1 Savitsky and Golay Coefcients for Second- and Third-Degree (r =2 and r =3)
Polynomial Smoothing Filter; y
+
i
= (1=N
rm
)
j=m
j=m
C
rm; j
y
ij
, Filter Width =2m1
j (C
rm; j
= C
rm;j
)
m N
rm
0 1 2 3 4 5 6 7 8 9 10 11 12
2 35 17 12 3
3 21 7 6 3 2
4 231 59 54 39 14 21
5 429 89 84 69 44 9 36
6 143 25 24 21 16 9 0 11
7 1105 167 162 147 122 87 42 13 78
8 323 43 42 39 34 27 18 7 6 21
9 2261 269 264 249 224 189 144 89 24 51 136
10 3059 329 324 309 284 249 204 149 84 9 76 171
11 805 79 78 75 70 63 54 43 30 15 2 21 42
12 5175 467 462 447 422 387 342 287 222 147 62 33 138 253
3. LowStatistics Digital Filter
Most smoothing techniques originate from signal processing and were initially introduced
in the eld of g-ray spectroscopy. Also in the PIXE community, considerable attention has
been devoted to a number of aspects of spectrum processing and evaluation. Within the
framework of continuum estimation (see later), a smoothing algorithm was developed that
removes noise from a spectrum on a selective basis (Ryan et al., 1988). The method
provides an n-point means smoothing in regions of low statistics (few counts) while
avoiding spreading of the base of peaks and degradation of valleys between peaks.
Figure 7 Effect of the smoothing of a peak with a Savitsky and Golay polynomial filter. The
FWHM of the original peak is nine channels.
Table 2 Savitsky and Golay Coefcients for Second-Degree (r =2) Polynomial, First-Derivative
Filter; y
+
i
= (1=N
rm
)
j=m
j=m
C
rm; j
y
ij
, Filter Width =2m1
j (C
rm; j
= C
rm;j
)
m N
rm
0 1 2 3 4 5 6 7 8 9 10 11 12
2 10 0 1 2
3 28 0 1 2 3
4 60 0 1 2 3 4
5 110 0 1 2 3 4 5
6 182 0 1 2 3 4 5 6
7 280 0 1 2 3 4 5 6 7
8 408 0 1 2 3 4 5 6 7 8
9 570 0 1 2 3 4 5 6 7 8 9
10 770 0 1 2 3 4 5 6 7 8 9 10
11 1012 0 1 2 3 4 5 6 7 8 9 10 11
12 1300 0 1 2 3 4 5 6 7 8 9 10 11 12
Table 3 Savitsky and Golay Coefcients for Third-Degree (r =3) Polynomial, First-Derivative Filter; y
+
i
= (1=N
rm
)
j=m
j=m
C
rm; j
y
ij
, Filter
Width =2m1
j (C
rm; j
= C
rm;j
)
m N
rm
0 1 2 3 4 5 6 7 8 9 10 11 12
2 12 0 8 1
3 252 0 58 67 22
4 1,188 0 126 193 142 86
5 5,148 0 296 503 532 294 300
6 24,024 0 832 1,489 1,796 1,578 660 1,133
7 334,152 0 7,506 13,843 17,842 18,334 14,150 4,121 12,922
8 23,256 0 358 673 902 1,002 930 643 98 748
9 255,816 0 2816 5,363 7,372 8,574 8,700 7,481 4,648 68 6,936
10 3,634,092 0 29,592 56,881 79,564 95,338 101,900 96,947 78,176 43,284 10,032 84,075
11 197,340 0 1,222 2,365 3,350 4,098 4,530 4,567 4,130 3,140 1,518 815 3,938
12 1,776,060 0 8,558 16,649 23,806 29,562 33,450 35,003 33,754 29,236 20,982 8,525 8,602 30,866
The rather heuristic algorithm is discussed in Section X, together with the computer im-
plementation. The eect of the lter is illustrated in Figure 8, where it is compared with the
other smoothing methods discussed.
C. Peak Search Methods
Several methods have been developed for the automatic localization of peaks in a spec-
trum. Nearly all methods follow a strategy where the original spectrum is transformed into
a form that emphasizes the peaklike structures and reduces the continuum, followed by a
decision whether these peaklike structures are statistically signicant. The latter involves
some adjustable parameter(s) controlling the sensitivity of the peak search.
Although visual inspection of the spectrum still appears to be the best method, peak
search algorithms, which are heavily used in g-ray spectrometry, may have some value in
x-ray spectrometry. Their use in energy-dispersive x-ray analysis as part of an automated
qualitative analysis procedure is hampered by the extreme peak overlap in these spectra.
More elaborated procedures involving articial intelligence techniques have been con-
sidered for this (Janssens and Van Espen, 1986; Janssens et al., 1988).
Peak search procedures usually involve three steps: (1) transformation of the original
spectrum so that continuum contribution is eliminated, peaks are readily locatable, and
overlapping peaks are (partially) resolved; (2) signicance test and approximate location of
the peak maximum; and (3) more accurate peak position estimate in the original spectrum.
The various peak search algorithms mainly dier in the choice of the transformation.
Some methods use the rst and second smoothed derivative of the spectrum. This method is
illustrated in Figure 9. The sign change (crossing of the x axis) of the rst derivative and the
minimumof the secondderivative are quire suitable todetect the peaks inthe original spectrum.
Other methods employ some form of correlation technique, which is basically the
convolution of the original spectrum with a lter that approximates the shape of the peak
and, therefore, emphasizes the peak. If a zero-area correlator (lter) is used, the continuum
is at the same time eectively suppressed. The simplest and most eective correlators belong
to the group of zero-area rectangular lters. These lters have a central window with
Table 4 Savitsky and Golay Coefcients for Second- and Third-Degree (r =2 and r =3)
Polynomial Second-Derivative Filter; y
+
i
= (1=N
rm
)
j=m
j=m
C
rm; j
y
ij
, Filter Width =2m1
j (C
rm; j
= C
rm;j
)
m N
rm
0 1 2 3 4 5 6 7 8 9 10 11 12
2 7 2 1 2
3 42 4 3 0 5
4 462 20 17 8 7 28
5 429 10 9 6 1 6 15
6 1,001 14 13 10 5 2 11 22
7 6,188 56 53 44 29 8 19 52 91
8 3,876 24 23 20 15 8 1 12 25 40
9 6,783 30 29 26 21 14 5 6 19 34 51
10 33,649 110 107 98 83 62 35 2 37 82 133 190
11 17,710 44 43 40 35 28 19 8 5 20 37 56 77
12 26,910 52 51 48 43 36 27 16 3 12 29 48 69 92
constant and positive coecients and two side lobes with constant and negative coecients.
Convoluting an x-ray spectrumwith this kind of lter yields spectra in which the continuum
is removed and peaks are easily locatable. They are similar to inverted second-derivative
spectra. An important representative of this group of lters is the top-hat lter, which has
a central window with an odd number of channels w and two side windows each n channels
wide. The value of the lter coecients follows from the zero-area constraint:
h
k
=
1
2n
; n
w
2
_ k <
w
2
1
w
;
w
2
_ k _
w
2
1
2n
;
w
2
< k _
w
2
n
_
_
_
(30)
The ltered spectrumis obtained by the convolution of the original spectrumwith this lter:
y
+
i
=
k=nw=2
k=nw=2
h
k
y
ik
(31)
The eect of this lter on a typical spectrum is shown in Figure 10. The variance of the
ltered spectrum is obtained by simple error propagation:
s
2
y
+
i
=
k=nw=2
k=nw=2
h
2
k
y
ik
(32)
Figure 8 Effect of various smoothing methods applied to part of a x-ray spectrum: (A) original
spectrum, (B) nine-point Savitsky and Golay filter, (C) nine-point moving average, (D) low-noise
statistical filter.
If y
+
i
is signicantly dierent from zero, a peak structure is found and the top of the peak
can approximately be located by searching for the maximum. Thus, i corresponds to the
position of a peak maximum in the original spectrum if
y
+
i
> rs
y
i
(33)
Figure9 Peak search using first and second derivatives: (A) doublet, peak width (s) four channels,
separation eight channels, on a constant continuum. (B) First and (C) second smoothed derivative
using a five-point Savitsky and Golay filter.
and
y
+
i1
_ y
+
i
> y
+
i1
(34)
In Figure 11, the positive part of the ltered spectrum (w=9 and n = 5) and the decision
line (rs
+
y
) for r =1 and 4 are displayed.
If required, other peak features can be obtained from the ltered spectrum: The
distance between the two local minima is a measure of the width of the peak and the height
at the maximum is related to the net peak area.
Because the width and heights of the peaks in the ltered spectrum strongly depend
on the dimensions of the lter, it is important that its dimensions are matched to the width
of the peaks in the original spectrum. From considerations of peak detectability (signal-to-
noise ratio) and resolution (peak broadening), it follows that the optimum width of the
positive window w is equal to the FWHM of the peaks (Robertson et al., 1972). The width
of the negative side windows should be chosen as large as the curvature of the continuum
allows. A reasonable compromise between sensitivity to peak shapes and rejection of
continuum is reached when n equals FWHM=2 to FWHM=3. Typical values for the
sensitivity factor r are between 2 and 4. Higher values result in the loss of small peaks;
lower values will cause continuum uctuations to be interpreted as peaks.
Other zero-area rectangular lters, variations to the top-hat lter, are also in use,
such as the square-wave lter with typical coecient sequence 1, 1, 2, 2, 1, 1 (Philips
and Marlow 1976; McCullagh, 1982) and the symmetric square-wave lter with coe-
cients 1, 1, 1, 1 (Op De Beeck and Hoste 1975). A detailed account of the performance
of this lter is given by Op De Beeck and Hoste (1975). A method using a Gaussian
correlator function is discussed by Black (1969).
Figure 10 Result of applying a top-hat filter. Dotted line: typical X-ray spectrum; solid line:
filtered spectrum.
Once the peak top is approximately located in the ltered spectrum, a more precise
maximum can be found by tting a parabola over a few channels around the peak. For a
well-dened peak on a low continuum (or after continuum subtraction), the channel
content near the top of the peak can be approximated by a Gaussian:
y
i
- h exp
(x m)
2
2s
2
_ _
(35)
The logarithm of the data then is a simple polynomial
ln y
i
= ln h
m
2
2s
2
_ _
m
s
2
x
m
2
2s
2
x
2
(36)
If we t ln y
i
with a polynomial a
0
a
1
x a
2
x
2
, where x represents the channel number,
the position of the peak m is obtained from
m =
a
1
2a
2
(37)
Figure 11 Peak search using the positive part of the top-hat filtered spectrum and the decision
level for one and four times the standard deviation. The original spectrum is shown at the bottom.
with an accuracy of 0.1 channel or better if the continuum contribution is small and if the
peak is interference free [i.e., if Eq. (35) accurately describes the data]. An estimate of the
peaks width and height is obtained at the same time:
FWHM = 2
2 ln 2
_
s = 2:3548
1
2a
2
_
(38)
h = exp a
0
a
2
1
4a
2
_ _
(39)
To obtain a reliable estimate of the parameters, only the channels in the FWHM or, at
most, within the FWTM region of the peak must be included in the t.
As a somewhat simpler and faster alternative, one can nd an estimate of the peak
maximum by tting the parabola over the three top channels of the peak. If i is the peak
maximum found in the ltered spectrum, a better estimate of the maximum in the original
spectrum is found by
m = i
1
2
y
i1
y
i1
y
i1
y
i1
2y
i
(40)
This method might be preferred for small peaks when the continuum cannot be
disregarded.
A FORTRAN implementation of a peak search algorithm is given in Section X.
IV. CONTINUUMESTIMATIONMETHODS
Except for some special quantication procedures (e.g., the peak-to-background method
in electron microscopy), the relevant analytical information is found in the net peak areas
and continuum is considered a nuisance. There are, in principle, three ways to deal with
the continuum: (1) the continuum can be suppressed or eliminated by a suitable lter;
(2) the continuum can be estimated and subtracted from the spectrum prior to the esti-
mation of the net peak areas; and (3) the continuum can be estimated simultaneously with
the other features in the spectrum. The rst approach is discussed in Section VI, where the
continuum is removed from spectra by applying a top-hat lter followed by linear least-
squares t of the spectrum with a number of (also ltered) reference spectra. Least-squares
t (linear or nonlinear) with analytical functions (Sec. VII) allows the simultaneous esti-
mation of continuum and peaks, providing a suitable mathematical function can be found
for the continuum. In this section, we discuss a number of procedures that aim to estimate
the continuum independently of the other features in the spectrum. Once estimated, this
continuum can be subtracted from the original spectrum and all methods for further
processing, ranging from simple peak integration to least-squares tting can be applied.
Any continuum estimation procedure must fulll two important requirements. First,
the method must be able to reliably estimate the continuum in all kinds of situations (e.g.,
small isolated peaks on a high continuum as well as in the proximity of a matrix line).
Second, to permit processing of a large number of spectra, the method needs to be nearly
free of user-adjustable parameters.
Although a number of useful continuum estimation procedures has been developed,
it must be realized that their accuracy in estimating the continuum is not optimal. In one
way or another, they rely on the dierence in frequency response of the continuum
compared to other structures such as peaks, the former mainly consisting of low
frequencies (slowly varying). Because the peaks also exhibit low frequencies at the peak
boundaries, it is dicult to control the method in such a way that it correctly discriminates
between peaks and continuum. This results in either a small underestimation or over-
estimation of the continuum, introducing potentially large relative errors for small peaks.
In this respect, the tting of the continuum with analytical functions may provide more
optimal results (Vekemans et al., 1994). A considerable advantage of the methods dis-
cussed here is that they do not assume an explicit mathematical model of the continuum.
Constructing a detailed and accurate analytical model for the continuum based in physical
theory is nearly impossible except for some simple geometry and particular excitation
conditions. Most often, some polynomial type of function must be chosen when tting a
portion of the spectrum with analytical functions.
A. Peak Stripping
These methods are based on the removal of rapidly varying structures in a spectrum by
comparing the channel content y
i
with the channel content of its neighbors. Clayton et al.
(1987) proposed a method which compares the content of channel i with the mean of its
two direct neighbors:
m
i
=
y
i1
y
i1
2
(41)
If y
i
is smaller than m
i
, the content of channel i is replaced by the mean m
i
. If this trans-
formation is executed once of all channels, one can observe a slight reduction in the height
of the peaks while the rest of the spectrum remains virtually unchanged. By repeating this
procedure, the peaks are gradually stripped from the spectrum. Because the method
tends to connect local minima, it is very sensitive to local uctuations in the continuum due
to counting statistics. This makes smoothing of the spectrum, as discussed in the previous
section, prior to the stripping process mandatory. Depending on the width of the peaks
after typically 1000 cycles, the stripping converges and a more or less smooth continuum
remains. To reduce the number of iterations, it might be advantageous to perform a log or
square root transformation to the data prior to the stripping: y
/
i
= log(y
i
1) or y
/
i
=

y
i
_
.
After the stripping, the continuum shape is obtained by applying the inverse transforma-
tion. A major disadvantage of this method is that after a number of cycles, the bases of
partially overlapping peaks are transformed into broad humps, which take much longer
to remove than isolated peaks. The method was originally applied to PIXE spectra but
proves to be generally applicable for pulseheight spectra.
In Figure 12, this method is applied to estimate the continuum of an x-ray spectrum
in the region between 1.6 and 13.0 keV. The spectrum results from a 200-mg=cm
2
pellet of
NIST SRM Bovine Liver sample excited with the white spectrum of an Rh-anode x-ray
tube ltered through a thin Rh lter (Tracor Spectrace 5000). Because of the white tube
spectrum, a considerable continuum intensity was observed, increasing quite steeply in the
region above 10 keV. To calculate the continuum, the following algorithm was used:
(1) the square root of the original spectrum was taken; (2) these data were smoothed with a
10-point Savitsky and Golay lter; (3) a number of iterations were performed applying
Eq. (41) over the region of interest; (4) the square of each data point was taken (back
transformation) to obtain the nal continuum shape. In Figure 12, the continuum after
10, 100, and, nally, 500 iterations is shown.
As a generalization of the above-discussed method, the average of two channels a
distance w away from i can be used:
m
i
=
y
iw
y
iw
2
(42)
Ryan et al. (1988) proposed using twice the FWHM of the spectrometer at channel i as the
value for w. They reported that only 24 passes were required to produce acceptable
continuum shapes in PIXE spectra. During the last eight cycles, w is progressively reduced
by the factor
2
_
to obtain a smooth continuum. To compress the dynamic range of the
spectrum, a double-log transformation of the spectrum, log[log( y
i
+1)+1], before the
actual stripping was proposed. In combination with the low statistics digital lter, this
procedure is called the SNIP algorithm (Statistical Nonlinear Iterative Peak clipping).
Avariant of this procedure is implemented in the procedure SNIPBG given in Sec. X.
Instead of the double logarithmic, we employed a square root transformation, and a Sa-
vitsky and Golay smoothing is performed on the square root data. The width w is kept
constant over the entire spectrum. The value of w is also used as the width of the smoothing
lter. Using this implementation, the continuum of the above-discussed spectrum is cal-
culated and represented in Figure 13. The width was set 11 to channels approximately
corresponding to the FWHM of the peaks in the center of the spectrum and 24 iterations
were done. Apart from delivering a smoother continuum with smaller humps, this
method executes much faster than the original method proposed by Clayton.
B. ContinuumEstimation Using Orthogonal Polynomials
Another interesting continuum estimation procedure was introduced by Steenstrup (1981),
who applied the method to energy-dispersive x-ray diraction spectra. The spectrum is
tted using orthogonal polynomials, and the weights of the least-squares t are iteratively
adjusted so that only channels belonging to the continuum are included in the t.
Figure 12 Continuum estimate after 10, 100, and 500 iterations obtained with simple iterative
peak stripping.
The method is generally applicable to pulseheight spectra and can be implemented as an
algorithm that needs little or no control parameters.
The continuum is described by a set of polynomials up to degree m:
y(i) =
m
j=0
c
j
P
j
(x
i
) (43)
where P
j
(x
i
) is an orthogonal polynomial of degree j. As an example of m=3, the function
becomes
y(i) = c
0
c
1
(x
i
a
0
) c
2
((x
1
a
1
)(x
i
a
0
) b
1
) (44)
The least-squares estimates of the parameters c
j
are given by
c
j
=
n
i=1
w
i
y
i
P
j
(x
i
)
g
j
(45)
where w
i
are the weights of the t. A detailed discussion on orthogonal polynomial tting
can be found in Sec. IX. Because the polynomial terms P
j
(x
i
) are orthogonal, no matrix
inversion is required to obtain the results. Orthogonal polynomials of a much higher
degree can be tted to the experimental data without running into problems with ill-
conditioned normal equations and oscillating terms.
The goal of this continuum estimation method is to t the continuum with the
above-described orthogonal polynomial of degree m and to interpolate under the peaks.
This can be achieved by careful manual selection of only those data pairs (x
i
; y
i
) that
belong to the continuum. The more elegant approach proposed by Steenstrup consisted of
using all channels and automatically adjusting the weights in such a way that the con-
tinuum contributions are emphasized. If y(i) is a polynomial approximation of the
continuum of degree m, then y
i
- y(i) if i is a continuum channel, otherwise y
i
> y(i).
Figure13 Continuum estimate using statistical nonlinear iterative peak clipping (SNIP algorithm)
with 24 iterations.
A better approximation to the continuum can then be found by choosing small weights for
the data points where y
i
> y(i) and repeating the t. The following weighting scheme is
proposed by Steenstrup:
w
i
=
1
y(i)
if y
i
_ y(i) r
y(i)
_
(46)
w
i
=
1
[ y(i) y
i
[
2
if y
i
> y(i) r
y(i)
_
(47)
where r is an adjustable parameter. Typically, r = 2 is used. If y
i
is normally distributed
(which is approximately the case for y
i
> 30 counts), y
i
_ y(i) 2
y(i)
_
holds for 97.7%
of the channels containing only continuum. A too high value of r will cause the inclusion
of the tails of the peaks into the t. With the new weights, a new polynomial t of degree m
is performed. The process is stopped when the new polynomial coecients c
j
are within
one standard deviation from the previous ones. We have also obtained good results by
setting the weights eectively to zero when the channel content is statistically above the
tted continuum [Eq. (47)].
The method can be made even more unsupervised by including a procedure to au-
tomatically select the best degree of the polynomial. This can be done by tting (as de-
scribed earlier) successive polynomials with higher degrees and testing the signicance of
each additional polynomial coecient. If the coecient C
m1
is statistically not signicant
dierent from zero,
[C
m1
[ < 2s
C
m1
(48)
a polynomial of degree m is retained.
Figure 14 shows the spectrum of bovine liver sample (same as Fig. 12) and the tted
continuum using a fourth-, fth-, and sixth-degree orthogonal polynomial. A value of 1.5
was chosen for r [Eqs. (46) and (47)] and the weights were set to zero for the channels not
belonging to the continuum; w
i
= 0 in Eq. (47). Table 5 gives the data on the ts. The nal
number of continuum channels retained, the number of weight adjustments performed,
and the value and standard deviation of the highest polynomial coecient are shown. The
total number of channels in the tting region was 571. Because the value of the seventh
degree polynomial coecient is insignicant [Eq. (48)], it is concluded that a sixth-degree
orthogonal polynomial is needed to model the continuum.
Section X lists the FORTRAN code that implements the complete procedure to esti-
mate the continuum of a given spectrum by an mth-degree orthogonal polynomial.
V. SIMPLE NET PEAK AREADETERMINATION
In both in WDXRF and EDXRF, the concentration of the analyte is proportional to the
number of counts under the characteristic x-ray peak corrected for the continuum. At
constant resolution, this proportionality also exits for the net peak height. In EDXRF,
preference is given to the peak area. In WDXRF, the acquisition of the entire peak prole
is very time-consuming and the count rate is usually measured only at the peak maximum.
A. Peak-Area Determination in EDXRF
The most straightforward method to obtain the net area of an isolated peak in a spectrum
consists of interpolating the continuum under the peak and summing the continuum-
corrected channel contents in a window over the peak, as shown in Figure 15.
The net peak area, N
p
, of an isolated peak on a continuum is given by
N
P
=
i
P1
i
P2
[ y
i
y
B
(i)[ =
i
y
i
i
y
B
(i) = N
T
N
B
(49)
where N
T
and N
B
are the total number of counts of the spectrum and the continuum in the
integration window i
P1
i
P2
. The uncertainty of the estimated net peak area due to
counting statistics is
s
N
P
=
N
T
N
B
_
(50)
The continuum y
B
(i) is calculated by interpolation, assuming a straight line (see Fig. 15):
y
B
(i) = Y
BL
(Y
BR
Y
BL
)
i i
BL
i
BR
i
BL
(51)
Figure 14 Continuum estimate obtained by fitting a fourth-, fifth-, and sixth-degree orthogonal
polynomial.
Table5 Data on the Fit of the Continuum of the Spectrum Shown in Figure 14 Using Orthogonal
Polynomials
Degree of
polynomial
No. of channels
used
No. of weight
adjustments
Highest degree coecient
and standard deviation
4 126 7 (3.980.20)10
6
5 199 16 (1.880.09)10
7
6 267 6 (7.660.28)10
10
7 266 6 (3.662.03)10
13
Y
BL
and Y
BR
are the values of the continuum at the channels i
BL
and i
BR
, left and right
from the peaks, respectively. These values are best estimated by averaging over a number
of channels:
Y
BL
=
1
n
BL
i
BL1
i=i
BL2
y
i
=
N
BL
n
BL
(52)
Y
BR
=
1
n
BR
i
BR1
i=i
BR2
y
i
=
N
BR
n
BR
(53)
The number of channels in the continuum windows are n
BL
= i
BL2
i
BL1
1 and
n
BR
= i
BR2
i
BR1
1. The center position of the continuum windows (not necessarily an
integer number!) used in Eq. (51) are i
BL
= (i
BL1
i
BL2
)=2 and i
BR
= (i
BR1
i
BR2
)=2.
If both continuum windows have equal width, n
BL
= n
BR
= n
B
=2, and are positioned
symmetrically with respect to the peak window (i
P
i
BL
= i
BR
i
P
) a much simpler ex-
pression is obtained for the net peak area:
N
P
= N
T
n
P
n
B
(N
BL
N
BR
) (54)
where N
BL
and N
BR
are the total counts in the left and right continuum windows, re-
spectively, each n
B
=2 channels wide, and n
P
equals the number of channels in the peak
window. Applying the principle of error propagation, the uncertainty in the net peak area
is then given by
s
N
P
=
N
T
n
P
n
B
_ _
2
(N
BL
N
BR
)
(55)
Figure15 Determination of the net peak area by interpolating the continuum.
From this equation, it can be seen that, in principle, the continuum should be estimated
using as many channels as possible (n
B
) to minimize random errors due to counting
statistics. In practice, the width will be limited by curvature of the continuum and by the
presence of other peaks. Most often, the total width of the continuum (n
B
= n
BL
n
BR
) is
taken equal to or slightly larger than the width of the peak window.
The optimum width of the peak window to minimize counting statistics depends on
the peak-to-continuum ratio (Jenkins et al., 1981). For low peak-to-continuum ratios, the
peak height being only a fraction of the continuum height, the optimum width of the
integration window is 1.17 times the FWHM of the peak. If the ratio of the peak height to
the continuum height is larger than 1, a slightly wider window is optimal, although, in
practice, the improvement in precision is negligible.
The method does not deliver the total net peak area, only a fraction of it. Integrating
over 1.176FWHM (from 1:378s to 1:378s) covers only 83% of the peak. To cover
99% of the peak, the window should be 2.196FWHM (2.579s). If position or width
changes are observed from one spectrum to the other, care should be taken to dene the
windows in such a way that cover the same part of the spectrum. The wider the peak
window, the less sensitive the method for peak shift.
Although such a peak-area-determination method seems naively simple, if correctly
used it provides results that are as accurate and precise as the most sophisticated proce-
dures. The premises for use are that the peak window should be known to be free from
interferences, that there should be no peaks in the continuum windows, and that the con-
tinuum should be linear over the extent of the windows. A peak search procedure can, in
principle, be used to setup the windows automatically. However, its practical use is limited
by complexity of the EDXRF spectra. Moreover, the use of such automated procedures is
hazardous because no measure can be given for the presence or absence of systematic errors.
Because of this restrictions, a simple peak integration method cannot be used as a
general tool for spectrum processing. In a limited number of applications, good results can
be obtained. An evaluation of various peak integration methods is given by Hertogen et al.
(1973).
B. Net Count Rate Determination inWDXRF
In WDXRF, the count rate at the 2Y angle of the peak maximum corrected for the
continuum is used as analytical signal. The continuum is estimated at a 2Y position on the
left or right side of the peak. Continuum interpolation as described in the previous section
is also possible.
If N
P
is the number of counts accumulated during a time interval t
P
at the top of the
peak and N
B
is the number of the continuum counts accumulated during time t
B
, then the
net count rate, I, is given by
I = I
P
I
B
=
N
P
t
P
N
B
t
B
(56)
and the uncertainty in the net count rate due to counting statistics is given by
s
I
=
N
P
t
2
P
N
B
t
2
B
(57)
Various counting strategies can be considered and the eect on the precision can be esti-
mated using Eq. (57) (Bertin, 1970). In a optimum xed time strategy, the minimum
uncertainty is obtained when, for a total measurement time t = t
P
t
B
; t
P
and t
B
are chosen
in such a way that their ratio is equal to the square root of the peak-to-continuum ratio:
t
P
t
B
=
I
P
I
B
_
(58)
Under, these conditions, the uncertainty in the net intensity is given by
s
I
=
I
P
_

I
B
_
t
P
t
B
_ (59)
VI. LEAST-SQUARES FITTINGUSINGREFERENCE SPECTRA
In this section, two techniques based on linear least squares are discussed. The lter-t
methods makes use of library spetra, measured or calculated spectra of pure compounds,
that are used to describe the spectra of complex samples. The other method is based on
partial least-squares (PLS) regression, a multivariate calibration technique. In this case, no
spectrum evaluation in the strict sense is performed, but, rather, relations between the
concentrations of the compounds in the samples and the entire spectrum are established.
In this way, quantitative analysis is possible without obtaining net peak areas of the
characteristic lines.
A. Filter-Fit Method
1. Theory
If a measured spectrum of an unknown sample can be described as a linear combination of
spectra of pure elements constituting the sample, then the following mathematical model
can be written:
y
mod
i
=
m
j=1
a
j
x
ji
(60)
with y
mod
i
the content of channel i in the model spectrum and x
ji
the content of channel i in
the jth reference spectrum. The coecients a
j
are a measure of the contribution of pure
reference spectra to the unknown spectrum and can be used for quantitative analysis. The
values of the coecients a
j
are obtained via multiple linear least-squares tting, mini-
mizing the sum of the weighted squared dierences between the measured spectrum and
the model:
w
2
=
n
2
i=n
1
1
s
2
i
[ y
i
y(i)[
2
=
n
2
i=n
1
1
s
2
i
y
i
m
j=1
a
j
x
ji
_ _
2
(61)
where y
i
and s
i
are the channel content and the uncertainty of the measured spectrum,
respectively, and n
1
and n
2
are the limits of the tting region. A detailed discussion of the
least-squares-tting method is given in Sec. IX.
The assumption of linear additivity [Eq. (60)] holds normally reasonable well for the
characteristic lines in the spectrum, but not for the continuum. To apply this technique,
the continuum can be removed from the unknown spectrum and from the reference
spectra using one of the procedures described in Sec. IV before the actual least-squares t.
Another, frequently used approach is to apply a digital lter to both unknown and
reference spectra. This variant is known as the lter-t method (Schamber, 1977; Statham,
1978; McCarthy and Schamber, 1981) and is discussed in some detail below.
By the discrete convolution of a spectrum with top-hat lter [Eqs. (30) and (31)], the
low-frequency component (i.e. the slowly varying continuum) is eectively suppressed as
discussed in Sec. III. Apart from removing the slowly varying continuum, a rather severe
distortion of the peaks is also introduced. If we apply this lter to both the unknown
spectrum and the reference spectra, the nonadditive continuum is removed and the same
type of peak distortion will be introduced in all spectra, allowing us to apply the method of
multiple linear least-squares tting to the ltered spectra. Equation (61) then becomes
w
2
=
n
2
i=n
1
1
s
/ 2
i
y
/
i
m
j=1
a
j
x
/
ji
_ _
2
(62)
Where y
/
i
and x
/
ji
are the ltered unknown and reference spectra, respectively, s
/ 2
i
is the
variance of y
/
i
given by
s
/2
i
=
k
h
2
k
y
ik
(63)
The least-squares estimates of the contribution of each reference spectrum is then given by
(see Sec. IX)
a
j
=
m
k=1
a
1
jk
b
k
; j = 1; . . . ; m (64)
with
b
j
=
n
2
i=n
1
1
s
/2
i
y
/
i
x
/
ji
(65)
a
jk
=
n
2
i=n
1
1
s
/ 2
i
x
/
ki
x
/
ji
(66)
The uncertainty in each coecient a
j
is directly estimated from the error matrix:
s
2
aj
= a
1
jj
(67)
Schamber (1977) suggested the following equation for the uncertainties, taking into ac-
count the eect of the lter:
s
2
aj
=
nw
n w
a
1
jj
(68)
Where w is the width of the central positive part of the lter and n is the width of the
negative wings. A measure of the goodness of t is available through the reduced w
2
value:
w
2
n
=
1
(n
2
n
1
1) m
w
2
(69)
which is the w
2
value of Eq. (62) divided by the number of points in the t minus the
number of reference spectra. A value close to 1 means a good t, indicating that the
reference spectra are capable of adequately describing the unknown spectrum.
Most of the merits and the disadvantages of the lter-t method can be deduced
directly from the mathematical derivation given in the preceding paragraphs. The most
interesting aspect of the lter-t method is that it does not require any mathematical
model for the continuum and that, at least in principle, the shape of the peaks in the
unknown spectrum are exactly represented by the reference spectra. Reference spectra
should be acquired with good counting statistics, at least better than the unknown spec-
trum, because the least-squares method assumes that there is no error in the independent
variables x
/
ji
. Reference spectra can be obtained from single-element standards. Only the
portion of the spectrum that contains peaks needs to be retained as reference in the t.
Multielement standards can be used if the peaks of each element are well separated.
The reference spectra must provide an accurate model of the peak structure present
in the unknown spectrum. This requires that reference and unknown spectra are acquired
under strictly identical spectrometer conditions. Changes in resolution and, especially,
energy shifts can cause large systematic errors. The magnitude of this error depends on the
degree of peak overlap. Peak shifts of more than a few electron volts should be avoided,
which is readily possible with modern detector electronics. If shifts are observed over long
periods of operations of the spectrometer, careful recalibration of the spectrometer is
required or, better, the reference spectra should be acquired again. Also, peak shift and
peak broadening due to dierences in count rate between standards and unknown must be
avoided. Dierential absorption is another problem that might inuence the accuracy of
the model. Because of the dierence in x-ray attenuation in the reference and the un-
known, the Kb to Ka ratios might be dierent in the two spectra. This becomes especially
problematic if the Kb line is above and the Ka line below an absorption edge of a major
element of the unknown sample. The magnitude of the error depends on the peak overlap.
Careful selection of the samples to produce the reference spectra is therefore required.
The procedure requires that a reference spectrum be included for each element
present in the unknown. The method allows no mechanism to deal with sum peaks. Apart
from removing the continuum, the lter also has some smoothing eect on the spectrum
and causes the peak structure to be spread out over more channels. This is equivalent to
tting a spectrum with a somewhat lower resolution than originally acquired. Therefore,
the precision and detection limits attainable with the lter-t method are slightly worse
than optimal. The width of the lter is important in this respect. Schamber (1977) suggests
taking the width of the top of the lter equal to the FWHM resolution of the spectrometer,
u =FWHM. The width of the wings can be taken as v = u=2.
2. Application
The calculation procedure is quite simple and requires the following steps. The top-hat lter
is applied to the unknown spectrumand the mreference spectra [Eqs. (30) and (31)], and the
modied uncertainties are calculated using Eq. (63). Next, the vector b of length m and the
mm square matrix a are formed using Eqs. (65) and (66), summing over the part of the
spectrum one wants to analyze (n
1
n
2
). Only the relevant part, such as the Ka or the Ka
plus the Kb, of the reference spectra needs to be retained; the rest of the ltered spectrum
can be set to zero. After calculating the inverse matrix a
1
, the contribution of each re-
ference to the unknown and its uncertainty are calculated using Eqs. (64) and (67) or (68).
A computer implementation of the lter-t method is given in Sec. X. The method
was used to analyze part of an x-ray spectrum of a polished NIST SRM 1103 brass sample
(Fig. 16A). The measurements were carried out using a Mo x-ray tube and a Zr secondary
target and lter assembly. Spectra of pure metals (Fe, Ni, Cu, Zn, and Pb) were acquired
under identical experimental conditions. A top-hat lter of width w = 5 was used. Table 6
shows how the spectra were divided in regions of interest to produce the reference spectra.
Because considerable x-ray attenuation is present in brass, separate references were created
for the Ka and Kb of Cu and Zn. This was not done for Fe, Ni, and Pb because these
elements are only present as minor constituents in the brass sample. Figure 16B shows the
ltered brass spectrum and the resulting t using the seven (ltered) reference spectra. The
region below CuKa is expanded 100 times, and the region above ZnKa is expanded 10
times. As can be seen, the agreement between the ltered brass spectrum and the t is very
good. The reduced w
2
value is 8.5. This high value is probably due to small peaks shifts in
the reference spectra compared to brass spectrum.
Table 7 compares the results of the lter t with the results obtained by nonlinear
least-squares tting using analytical functions (see Sec. VII). Although the w
2
value of the
nonlinear t is slightly better (2.7), one observes an excellent agreement between the two
methods for the analytical important data (i.e., intensity ratios). The uncertainties for
small peaks are slightly higher with lter-t method, as explained previously.
The lter-t method is fast and relatively easy to implement. It can produce reliable
results when the spectrometer calibration can be kept constant within a few electronvolts
and suitable standards for each element present in the sample are available. The method
Figure16 (A) Part of the x-ray spectrum of NIST SRM 1103 brass sample. (B) Top-hat-filtered
spectrum and result of fit using reference spectra.
performs well when one has to deal with a dicult to model continuum. If information on
trace elements and major elements is required (very large peaks next to very small ones),
the method might not be optimal. This lter-t method is frequently used to process x-ray
spectra obtained with electron microscopes (SEM-EDX), often in combination with a
ZAF or Phi-Rho-Z correction procedure.
B. Partial Least-Squares Regression
Spectrum evaluation as discussed in most of this chapter aims to obtain the net intensity of
the uorescence lines. These net peak intensities are then used to determine analyte con-
centrations using one of the many empirical, semiempirical, or fundamental approaches
detailed in various other chapters. In this, sub-section, we discuss an approach that is
relatively new for the XRF community and is based on multivariate calibration. We will
concentrate our discussion on partial least squares (PLS), a chemometrical technique that
is extensively used in infrared and relates spectrometric methods. The basic idea of the
method is to nd a (multivariate linear) model that directly relates the spectral data to the
analyte concentrations, thus avoiding the explicit evaluation of the spectrum in terms of
the net peak areas. The method involves a calibration step where a large number of
standards are used to build and validate the model and the actual analysis step where the
model is applied to spectra of unknown samples.
Table6 Data on the Reference Spectra and the Unknown Spectrum Used
in the Filter-Fit Procedure (Fig. 16)
Spectrum Region of interest (keV) Used as
Pure Fe 4.258.12 FeKa Kb reference
Pure Ni 4.739.57 NiKaKb reference
Pure Cu 5.708.46 CuKa reference
8.469.81 CuKb reference
Pure Zn 6.599.09 ZnKa reference
9.0910.30 ZnKb reference
Pure Pb 8.3613.68 PbLa reference
SRM 1103 5.2211.26 Unknown
Table 7 Comparison of Spectrum Evaluation Results Using Filter-Fit Method and
Nonlinear Least-Squares Fitting; Ratios of the Intensity from the SRM 1130 Standard to
the Pure Element Given
Ratio of intensity in SRM 1104 to pure element
Element Filter t Nonlinear t % Di
Fe 0.00530.0002 0.00470.0001 11
Ni 0.00190.0002 0.002010.00008 6
Cu 0.5460.001 0.5510.001 0.9
Zn 0.3900.001 0.39120.0008 0.31
Pb 0.03100.0006 0.03080.0003 0.65
1. Theory
Multivariate spectroscopic calibration attempts to predicts properties of samples (con-
centration of analytes) based on measured spectral data via the following relation:
Y = XB F (70)
The Y
nm
matrix holds concentration of m analytes in the n samples. The X
np
matrix
represents the spectral data, with n measured spectral data each having p x-ray intensities
(channels) and F
nm
is the matrix the residuals, part of the Y matrix not explained by the
model. The regression coecients B can be calculated in several ways. The most
straightforward approach is the use of multiple linear regression (see Sec. IX). The least-
squares solution is given then given by
B = (X
/
X)
1
X
/
Y (71)
When the number of x variables exceeds the number of samples ( p > n) and=or when there is
a high degree of correlation between the x variables, the least-squares solution becomes
unstable or cannot be obtained due to the fact that the covariance matrix X
/
X cannot be
inverted. This is exactly the fact when we attempt to apply multivariate calibration in XRF.
The number of channels in the spectrum (1024 or more) largely exceeds the number of
samples andthe intensities of neighboring channels in each peak are very strongly correlated.
Toovercome this problem, the methodof singular value decompositioncanbe used. The
X matrix is decomposed in a number of linearly independent variables, know as principal
components. In principle, there are as many principal components as there are original vari-
ables (channels), but only the most signicant [i.e., having the highest variance (or eigenvalue)]
are retained. Using the matrix of this smaller number of principal components scores, rather
than the entire Xmatrix in Eq. (70), is known as principal components regression (PCR). The
disadvantage of PCR is that the selection of the principal components is based on how much
variance they explain of the X matrix. The rst few principal components may have little re-
lation with the concentrations that need to be predicted by the model.
Partial least-squares regression (PLSR) is a variant of PCR that largely overcomes
this problem. The methods uses two outer relations and one inner relation. The outer
relations describe the decomposition of the X and Y matrices:
X = TP
/
E =
A
a=1
t
a
p
/
a
E (72)
Y = UQ
/
F =
A
a=1
u
a
q
/
a
F (73)
T
nA
and U
nA
are the score matrices, the values of the A(A p) latent variables. P
/
Ap
and Q
/
Am
are the loading matrices describing the relation between the latent variables
(T and U) and the original variables (X and Y). The number of latent variables A in the
model is of crucial importance and its optimum value must be found by cross-validation.
The matrices E and F contain the residuals, part of the original spectral data and the
concentration data, respectively, not accounted for when using A latent variables. The
inner relation is written as:
u
a
= b
a
t
a
; a = 1; . . . ; A (74)
fromwhich the regression coecients Bcan be obtained. This operation can be seen as a least-
squares t between the Xblock and Yblock scores. The nal PLS model can thus be written as
Y = TBQ
/
F
+
(75)
A graphical representation of the PLS model is given in Figure 17. In the normal PLS
algorithm Y is a vector of concentrations for one element and a separate model is build
for each element. If all Y-variables are predicted simultaneously, as in the case of
Equation (70), the PLS2 algorithm is used. This method performs better when the con-
centrations in the samples are highly correlated.
The quality of the calibration model can be judged by the root mean square error of
prediction (RMSEP):
RMSEP =
1
n
n
i=1
(^ y
i
y
i
)
2
_ _
1=2
(76)
where ^ y
i
is the concentration in sample i predicted by the model y
i
is the true concentration
in the standard. To determine the optimum number of latent variables, the RMSEP is
calculated using PLS models with dierent numbers of latent variables A. The RMSEP
values are plotted against A and the value where a minimum or a plateau is reached is
taken. For small datasets, the calculation of the RMSEP is done using cross-validation.
When a large number of standards are available, they are split in a training set (ap-
proximately two-thirds of the samples) and a prediction set (approximately one-third of
the samples). The training set is used to build the PLS model and the RMSEP is calculated
based on the concentrations of the prediction set. Alternatively, for smaller calibration
sets, leave-one-out cross-validation can be used. Each sample is excluded once from the
dataset and predicted by the model built with the remaining samples. This is repeated until
all samples have been excluded once.
Geladi and Kowalski (1986) published a tutorial on PLS and its relation to other
regression techniques. A standard work on the PLS method is the book by Martens and
Figure17 Graphical representation of the PLS algorithm.
Naes (Martens and Naes, 1989). Theoretical and statistical aspects of the method can be
found in chemometrics literature (Manne, 1987; Lorber et al., 1987; Pratar and De Jong,
1997; Hoskuldsson, 1988).
2. Application
The PLS method is illustrated with the analysis of aqueous solution containing Ni, Cu,
and As with concentration in the ranges 1850, 0.545, and 520 g=L, respectively,
whereas Zn, Fe, and Sb were present in more or less constant amounts. Spectra were
acquired for 1000 s from 5-mL solution using an EDXRF spectrometer equipped with a
Rh x-ray tube operating at 30 kV and a Si(Li) detector having 160 eV resolution at MnKa.
From the 22 samples, 10 were used to build the PLS mode and the remaining were
used as the prediction set. Table 8 gives the composition of the samples in the calibration
set. Figure 18 shows part of the spectrum between 5 and 14 keV of sample number 9. The
CuKa line is considerably interfered by the NiKb line. Absorption eects can be expected
because the NiK absorption edge (8.33 keV) is just above the CuKa line (8.04 keV) and the
AsK lines can cause secondary uorescence of Cu and Ni.
A PLS 1 model is build for Cu. The X matrix consists of 451 x-ray intensities
(variables) between 5 and 14 keV (channels 250 to 700) of the 10 samples. The Y matrix
contains the Cu concentration of those samples.
In Figure 19, the RMSEP based on leave-one-out cross-validation is plotted as
function of the number of latent variables. A minimum error of 0.57 g=L is obtained for
three latent variables so that the PLS model with three latent variable is retained.
Figure 20 compares the true Cu concentration with the predicted concentration for the
calibration set. The PLS model predicts very accurately the Cu concentrations in the
range from 1 to 40 g=L. The so-called regression coecients of the PLS model show
which variables (channels) are used in the model. They are plotted in Figure 21. As could
be expected, the Cu concentrations are predicted from the channel content corresponding
to the CuK lines. The inuence of absorption and enhancement results in a small negative
contribution from the Ni peak and a small positive contribution from the As peaks, re-
spectively. The PLS model thus handles both the problem of spectral interference and
matrix eects. The Cu concentration predicted by the PLS model for the test set is given in
Table 9. Except for the two samples with the highest concentrations, the Cu concentration
Table 8 Composition of Samples Used to Build the PLS Model
Concentration (g=L)
Sample No. Ni Cu Zn
1 18.0 6.7 6.1
2 18.1 5.0 6.0
3 18.5 3.5 6.1
4 18.1 8.4 5.7
5 53.6 1.8 20.1
6 53.8 0.8 19.8
7 57.3 1.1 19.3
8 56.9 1.5 20.0
9 51.4 17.7 20.9
10 17.9 41.5 5.3
in the unknown samples is very well estimated. The predicted of the test set is generally
somewhat worse that the prediction of the calibration set. To build an accurate model, a
large number of standards spanning the concentration range of interest for each element is
required. This is certainly the major drawback of PLS for its application in XRF,
Figure18 X-ray spectrum of sample number 9 in the calibration set used to build the PLS model.
Figure 19 RMSEP values versus the number of latent variables for the prediction of the Cu
concentration.
Figure 20 Comparison of true and predicted Cu concentrations for the samples in the PLS
calibration set.
Figure 21 Regression coefficients of the PLS model for Cu, showing which variables (channels in
the x-ray spectrum) are used to predict Cu.
especially when solid samples are considered. This problem can to some extend be
overcome by building a calibration set via Monte Carlo simulation. Just as with the lter-
t method, standards and unknowns need to be measured under strictly identical spec-
trometer conditions. Changes in gain or resolution will cause systematic errors in the
calculated concentrations.
Swerts and Van Espen (1993) demonstrated the use of PLS for the determination of
S in graphite using a Rh x-ray tube excitation XRF equipped with a Si(Li)detector. Be-
cause of diraction eects, least-squares tting of the spectra was nearly impossible. Using
PLS, the sulfur content could be determined in a concentration range 260%, with an
accuracy of better than 5% relative standard deviation. Urba nski and Kowalska applied
the PLS method to the determination of Sr and Fe in powdered rock samples and to the
determination of the S and ash content in coal using a radioisotope XRF system equipped
with a low-resolution gas proportional counter. They also demonstrated the usefulness of
this method for the determination of the thickness and composition of Sn-Pb and Ni-Fe
layered structures (Urba nski and Kowalska, 1995). Molt and Schramm (1987) compared
principal components regression (PCR), PLS for the determination of S, exhibiting strong
interference from Mo, in aqueous and solid samples. The results were also compared with
quantitative analysis using the method developed by Lucas-Tooth and Price (1961).
Equally good results were obtained with all three methods. Similar results were obtained
by Lemberge and Van Espen for the determination of Ni, Cu, and As in liquid samples.
They demonstrated that taking the square root of the data improves the PLS model and
that the PLS method extracts information from the scattered excitation radiation to de-
scribe the matrix eects (Lemberge and Van Espen, 1999).
VII. LEAST-SQUARES FITTINGUSINGANALYTICAL FUNCTIONS
A widely used and certainly the most exible procedure for evaluating complex x-ray
spectra is based on least-squares tting of the spectral data with an analytical function.
The method is conceptually simple, but not trivial to implement and use.
Table 9 Comparison of True and Predicted Cu Concentration Using the PLS Model
Cu concentration (g=L)
Sample No. True Predicted Dierence
11 6.30 6.38 0.08
12 7.20 7.34 0.14
13 6.30 6.32 0.02
14 7.50 7.40 0.10
15 6.30 6.09 0.21
16 0.90 1.27 0.37
17 1.00 0.75 0.25
18 1.20 1.55 0.35
19 1.80 2.11 0.31
20 2.50 2.86 0.36
21 17.60 16.51 1.09
22 44.70 40.59 4.11
A. Concept
In this method, an algebraic function, including analytical importantly parameters such as
the net areas of the uorescence lines, is used as a model for the measured spectrum. The
object function (w
2
) is dened as the weighted sum of squares of the dierences between
this model y(i) and the measured spectrum y
i
over a region of the spectrum:
w
2
=
n
2
i=n
1
1
s
2
i
y
i
y(i; a
1
; . . . ; a
m
) [ [
2
(77)
where s
2
i
is the variance of data point i, normally taken as s
2
i
= y
i
, and a
j
are the para-
meters of the model. The optimum values of the parameters are those for which w
2
is
minimal. They can be found by setting the partial derivatives of w
2
with respect to the
parameters to zero:
@w
2
@a
j
= 0; j = 1; . . . ; m (78)
If the model is linear in all the parameters a
j
, these equations result in set of m linear
equations in the m unknowns a
j
, which can be solved algebraically. This is known as linear
least-squares tting. If the model is nonlinear in one or more of its parameters, a direct
solution is not possible and the optimum value of the parameters must be found itera-
tively. An initial value is given to the parameters and they are varied in some way until a
minimum for w
2
is obtained. The latter is equivalent to searching for a minimum in the
m1-dimensional w
2
hypersurface. This is known as nonlinear least-squares tting. The
selection of a suitable minimization algorithm is very important because it determines to a
large extent the performance of the method. A detailed discussion of linear and nonlinear
least-squares tting is given in Sec. IX.
The most dicult problem to solve when applying this least-squares procedure is the
construction an analytical function that accurately describes the observed spectrum. The
model must be capable of describing accurately the spectral data in the tting region. This
requires an appropriate model for the continuum, the characteristic lines of the elements
and for all other features present in the spectrum such as absorption edges, escape, and
sum peaks. Although the response function of the energy-dispersive detector is, to a very
good approximation, Gaussian, deviation from the Gaussian shape needs to be taken into
account. Failure to construct an accurate model will result in systematic errors, which
under certain conditions may lead to gross positive or negative errors in the estimated
peak areas. On the other hand, the tting function should remain simple, with as few
parameters as possible. Especially for the nonlinear tting, the location of the w
2
minimum
becomes problematic when a large number of parameters is involved.
In general, the tting model consists of two parts:
y(i) = y
B
(i)
P
y
P
(i) (79)
where y(i) is calculated content of channel i and the rst part describes the continuum and
the second part the contributions of all peaklike structures.
Because the tting functions for both linear and nonlinear least-squares tting have
many features in common, we treat the detailed description of the tting function for the
most general case of nonlinear least squares. Moreover, if the least-squares t is done
using the Marquardt algorithm, the linear least-squares t is computationally a particular
case of the nonlinear least-squares t. Programs based on this algorithm can perform
linear and nonlinear tting using the same computer code. A large part of the discussion
given here is based on the computer code AXIL, developed by the author for spectrum
tting of photon-, electron-, and particle-induced x-ray spectra (Van Espen et al., 1977a,
1977b, 1979b, 1986).
B. Description of the Continuum
To model the continuum, various analytical expressions are in use, depending on the
excitation conditions and on the width of the tting region. Except for electron micro-
scopy, it is virtually impossible to construct an acceptable physical model that describes
the continuum, mainly because of the large number of processes that contribute to it. For
this reason, very often some type of polynomial expression is used.
1. Linear Polynomial
A linear polynomial of the type
y
B
(i) = a
0
a
1
(E
i
E
0
) a
2
(E
i
E
0
)
2
a
k
(E
i
E
0
)
k
(80)
is useful to describe the continuum over a region 23 keV wide. Wider regions often
exhibit too much curvature to be described by this type of polynominal. In Eq. (80), E
i
is
the energy (in keV) of channel i [see Eq. (84)] and E
0
is a suitable reference energy, often
the middle of the tting region. Expressing the polynomial as a functin of (E
i
7E
0
) rather
than as a function of the channel number is done for computational reasons; (E
i
7E
0
)
3
is,
at most, of the order of 10
3
, whereas i
3
can be as high as 10
9
. Most computer programs
that implement a polynomial model for the continuum allow the user to specify the degree
of the polynomial; k =0, 1, and 2 produce respectively a constant, a straight line, and a
parabolic continuum. Values of k larger than 4 are rarely useful because such high-degree
polynomials tend to have physical nonrealistic oscillations. Equation (80) is linear in the
tting parameters a
0
, . . . , a
k
, so that this function can be used in linear as well as in
nonlinear least-squares tting.
2. Exponential Polynomial
A linear polynomial cannot be used to t the continuum over the entire spectrum or to t
regions of high positive or negative curvature. Higher curvature can be modeled by
functions of the type
y
B
(i) = a
0
exp[a
1
(E
i
E
0
) a
1
(E
i
E
0
)
2
a
k
(E
i
E
0
)
k
[ (81)
where k is the degree of the exponential polynomial. A value of k as high as 6 might be
required for an accurate description of a continuum from 2 to 16 keV. This function is
nonlinear in the tting parameters a
1
, . . . , a
k
and requires a nonlinear least-squares pro-
cedure and some initial guess of these parameters. Initial values for these nonlinear
parameters can be determined by rst estimating the shape of the continuum using one of
the procedures described in Sec. IV followed by a linear t of the logarithm of this con-
tinuum. These initial guesses are then further rened in the nonlinear tting procedure.
3. Bremsstrahlung Continuum
The exponential polynomial is not suitable for describing the shape of the continuum
observed in electron- and particle-induced x-ray spectra, mainly because of the high
curvature at the low-energy region of the spectrum. The continuum results from photons
emitted from the sample by the retardation of fast electrons. The slope of the emitted
continuum is essentially an exponentially decreasing function according to Kramers for-
mula. At low energies, the emitted photons are strongly absorbed by the detector windows
and by the sample. A suitable function to describe such a radiative continuum is an
exponential polynominal multiplied by the absorption characteristics of the spectrometer:
y
B
(i) = a
0
exp[a
1
(E
i
E
0
) a
k
(E
i
E
0
)
k
[T
a
(E
i
) (82)
A detailed discussion of the function T
a
(E) is given on page 288. To be physically correct,
the absorption term must be convoluted with the detector response function, because
the sharp edges due to absorption by detector windows (Si or Au) or elements present in
the sample are smeared out by the nite resolution of the detector.
4. ContinuumRemoval
An alternative to an algebraic description of the continuum is to estimate the continuum
rst using one of the procedures outlined in Sec. IV and to substract this continuum from
the measured spectrum before the actual least-squares tting. To correctly implement the
least-squares t after subtraction of the continuum, the weights 1=s
2
i
[Eq. (77)] must be
adjusted. If y
/
i
represents the spectral data after subtraction of the continuum,
y
/
i
= y
i
y
B
(i), the variance of y
/
i
is given by s
/ 2
i
= s
2
i
s
2
y
B
(i)
. A reasonable approximation
for s
2
y
B
(i)
is y
B
(i) itself, so that the total variance becomes s
/ 2
i
= y
i
y
B
(i). If this adjust-
ment of the weights is not made, the uncertainty in the net peak areas are understimated,
especially for small peaks on a high continuum.
It is rather dicult for an inexperienced user to select the appropriate continuum
model for a given spectrum. The following might serve as a general guideline. For tting
regions 23 keV wide, a linear polynomial continuum is often adequate. To t large re-
gions of XRF spectra, the exponential polynomial provides the most accurate results, with
k typically, between 4 and 6. The same holds for the bremsstrahlung continuum of SEM-
EDX and PIXE spectra. The simplest method from the users point of view is the
continuum stripping, but this method does not provide optimum results. A slight under-
estimation or overestimation might occur, resulting in large relative errors in the area
determination of small peaks (Vekemans et al., 1995).
C. Description of Fluorescence Lines
Because the response function of most solid-state detectors is predominantly Gaussian, all
mathematical expressions used to describe the uorescence lines involve this function.
When dealing with the K lines of high-atomic-number elements, such as Pb or U, the in-
uence of the natural line shape becomes appreciable and the use of the more complicated
Voigt prole is required (Wilkinsin, 1971; Gunnink, 1977; Pessara and Debertin, 1981).
1. Single Gaussian
A Gaussian peak is characterized by three parameters: the position, width, and height or
area. It is desirable to describe the peak in terms of its area rather than its height because
the area is directly related to the number of x-ray photons detected, whereas the height
depends on the spectrometer resolution. The rst approximation to the prole of a single
peak is then given by
A
s
2p
_ exp
(x
i
m)
2
2s
2
_ _
(83)
where A is the peak area (counts), s is the width of the Gaussian expressed in channels,
and m is the location of the peak maximum. The often used FWHM is related to s by the
factor 2
2 ln 2
_
or FWHM=2.35s. In Eq. (83), the peak area is a linear parameter; the
width and position are nonlinear parameters. This implies that a nonlinear least-squares
procedure is required to nd optimum values for the latter two parameters. Using a linear
least-squares method assumes that the position and width of the peak are know with high
accuracy from calibration.
To describe part of a measured spectrum, the tting function must contain a number
of such functions, one for each peak. For 10 elements and 2 peaks (Ka and Kb) per element,
we would need to optimize 60 parameters. It is highly unlikely that such a nonlinear least-
squares t will terminate successfully at the global minimum. To overcome this problem,
the tting function can be written in a dierent way as shown in the next subsection.
2. Energyand Resolution Calibration Function
The rst obvious step is to drop the idea of optimizing the position and width of each peak
independently. In x-ray spectrometry, the energies of the uorescence lines are know with
an accuracy of 1 eV or better. The pattern of peaks observed in the spectrum is directly
related to elements present in the sample. Based on those elements, we can predict all x-ray
lines that constitute the spectrum and their energies. The peak function [Eq. (83)] is
therefore written in terms of energy rather than channel number. Dening ZERO as the
energy of channel 0 and expressing the spectrum GAIN in electronvolts=channel, the
energy of channel i is given by
E(i) = ZERO (GAIN)i (84)
and the Gaussian peak can be written as
G(i; E
j
) =
GAIN
s
2p
_ exp
[E
j
E(i)[
2
2s
2
_ _
(85)
with E
j
the energy (in eV) of the x-ray line and s the peak width given by
s
2
=
NOISE
2:3548
_ _
2
3:58(FANO)E
j
(86)
In this equation, NOISE is the electronic contribution to the peak width (typically
80100 eV FWHM) with the factor 2.3548 to convert to s units, FANO is the Fano factor
( ~0.114), and 3.85 is the energy required to produce an electronhole pair in silicon. The
term GAIN=s
2p
_
in Eq. (85) is required to normalize the Gaussian so that the sum over all
channels is unity.
For linear least-squares tting, ZERO, GAIN, NOISE, and FANO are physically
meaningful constants. In the case of nonlinear least squares, they are parameters to be
rened during the tting. The advantage of optimizing the energy and resolution calibra-
tion parameters rather than the position and width of each peak is a vast reduction of the
dimensionality of the problem. The nonlinear t of 10 peaks would now involve 14 para-
meters compared to 30. Even more importantly, all information available in the spectrumis
used to estimate ZERO, GAIN, NOISE, and FANO and thus the positions and the widths
of all peaks. Imagine a small, severely overlapping doublet with a well-dened peak on both
sides of this doublet. These two peaks will contribute most to the determination of the four
calibration parameters, virtually xing the position and the width of the two peaks in the
doublet. As a consequence, their areas can be determined much more accurately.
Referring to our discussion on information content in Sec. II, we did not obtain this
extra performance for nothing. We have supplied extra information: the energy of the
peaks and the two calibration relations [Eqs. (84) and (86)]. Fitting with Eq. (85) requires
that the extra information we supply is indeed correct.
With modern electronics, the linearity of the energy calibration [Eq. (84)] holds very
well in regions above 2 keV. Fitting the entire spectrum, including the low-energy region,
might require more complex energy calibration functions. To t PIXE spectra from 1 to
30 keV, Maenhaut and Vandenhaut (Maenhaut and Vandenhaut, 1986) suggested the
following function: i = C
1
C
2
E C
3
exp(C
4
E).
The relation between the square of the peak width and the energy [Eq. (86)] is based
on theoretical considerations. The relation holds very well if the doublet splitting of the
x-ray lines is taken into account. The Ka
1
Ka
2
separation increases from a negligible value
for Ca (3.5 eV) to nearly 100 eV for Mo. The observed peak shape of a K line is actually an
envelope of two peaks. This envelope can be represented rather well by a single Gaussian,
but failing to take this doublet splitting into account (i.e., tting with a single Gaussian
where doublets are required) will result in peak widths that do not obey Eq. (86). To
illustrate this, the observed width of a number of Ka lines as function of the x-ray energy is
presented in Figure 22. The dotted line represents the width of the Ka doublet tted as one
peak. The solid (straight) line shows the width of the individual lines in the doublet.
3. Response Function for an Element
A second modication to the tting function that will reduce the number of tting
parameters is modeling an entire element, rather than single peaks. A number of lines can
be considered as logically belonging together, such the Ka
1
and Ka
2
of the above-men-
tioned doublets or all K lines of an element. This group can be tted with one area
parameter A representing the total number of counts of all the lines in the group.
The spectrum of an element can then be represented by
y
P
(i) = A
N
P
j=1
R
j
G(i; E
j
) (87)
where G are the Gaussians for the various lines with energy E
j
and R
j
the relative in-
tensities of the lines. The summation runs over all lines in the group (N
P
) with
R
j
= 1.
The transition probabilities of all lines originating from a vacancy in the same (sub)
shell (K, L
I
, L
II
, . . .) are constants, independent of the excitation. However, the relative in-
tensities depend on the absorption in the sample and in the detector windows. To take this
into account, the x-ray attenuation must be included in Eq. (87). The relative intensity ratios
are obtained by multiplying the transition probabilities with an absorption correction term:
R
/
j
=
R
j
T
a
(En
j
)
j
R
j
T
a
(En
j
)
(88)
Contributions from various subgroups (i.e., between K and L, between L
I
and L
II
, etc.)
depend on the type of excitation (photons, electrons, protons) and on the excitation en-
ergy. General values cannot be given and must be determined for the particular excitation
if one wants to combine lines of dierent subgroups. Transition probabilities of lines in
various groups, determined experimentally and calculated from rst principles, can be
found in the literature (McCrary et al., 1971; Salem et al., 1970; Salem and Wimmer, 1970;
Scoeld 1970, 1974a, 1974b).
In Figure 23, the t of a tungsten L line spectrum using 24 transitions from the 3 L
subshells is shown. The relative intensities of the L lines within each subshell were taken
from the literature (Scoeld, 1974b). The t was thus done with one peak-area parameter
for the L
1
, the L
2
and the L
3
sublevels.
Fitting elements rather than individual peaks enhances the capability of the method
to resolve overlapping peaks. The area of the CrKa peak, interfered by a VKb peak, can be
obtained with higher precision (lower standard deviation) because the area of the VKb
peak is related to the area of the (interference free) VKa peak. Again, we have introduced
more a priori knowledge into our model. If this information (the relative intensity ratio) is
not correct, we will introduce systematic errors (e.g., the CrKa peak area, although having
a low standard deviation, will not be correct). In practice, there will be a trade-o between
the gain in accuracy and the gain in precision. Errors in the values of the transition
probabilities and in the value of the absorption correction term are suciently small so
that small to moderate high peaks (up to 10
5
counts peak area) can be tted as one group.
4. Modified Gaussians
When tting very large peaks with a Gaussian, the deviation from the pure Gaussian shape
becomes signicant. In Figure 24, a MnK spectrum with 10
7
counts in the MnKa peak is
shown. One observes a tailing on the low-energy side of the peaks and a continuum that is
Figure 22 FWHM of various Ka lines, tted as single peak and as a Ka
1
Ka
2
doublet.
Figure23 Fit of a complex L line spectrum of tungsten. In total, 24 transitions, divided over the 3
L subshells, are required for the description on the spectrum.
Figure 24 MnK line spectrum with very good counting statistics. The dierence from the
Gaussian response is obtained by subtracting all Gaussian peaks. From this, the peak-shape
correction is calculated.
higher at the low energy side of the Ka peak than at the high energy side of the Kb peak.
The observed peak shape is partially caused by nonideal behavior of the detector. For low-
energy lines ( <10 keV), incomplete charge collection and other detector artifacts play an
important role. For higher energetic lines, Compton scattering in the detector also con-
tributes. Another part of the deviation from the Gaussian shape is attributed to phe-
nomena taking place in the sample itself. X-ray satellite transitions such as KLM radiative
Auger transitions on the low-energy side of the Ka and peak and KMM transitions on the
low-energy side of the Kb contribute to the overall shape of the spectrum. In the literature,
considerable attention has been given to the explanation and to the accurate mathematical
description of the observed peak shape (McNelles and Compbell, 1975; Van Espen et al.,
1977b; Wielopolski and Gardner, 1979; Campbell et al., 1985, 1987, 1997, 1998, Gardner
et al., 1986; Yacout et al., 1986; Campbell, 1996).
Failure to account for the deviation from the Gaussian peak shape causes a number
of problems when tting x-ray spectra. Small peaks sitting on the tail of large ones (e.g.,
NiKa in front of CuKa) cannot be tted accurately, resulting in large systematic errors for
the small peak. Because the least-squares method seeks to minimize the dierence between
the observed spectrum and the tted function, the tail might become lled up with peaks of
elements that are not really present. Also, the continuum over the entire range of the
spectrum becomes dicult to describe. This is illustrated in Figure 25a, where a spectrum
Figure 25 Fit of the spectrum of a brass sample (NIST SRM 1106) (a) fitted with a simple
Gaussians and (b) fitted with Gaussians including tail and step functions.
of a brass sample (NIST SRM 1106) is tted with simple Gaussians and a linear con-
tinuum. An unrealistically high area for the NiKa peak is obtained in this way.
A number of analytical functions have been proposed to account for the true line
shape. Nearly all of them include a at shelf and an exponential tail, both convoluted with
the Gaussian response function. Similar functions are also used to describe the peak shape
of g-ray spectra (Phillips and Marlow, 1976).
To account for the deviation from the Gaussian peak shape, the Gauss function G(i,
E
j
) in Eq. (85) can be replaced by
P(i; E
jk
) = G(i; E
jk
) f
S
S(i; E
jk
) f
T
T(i; E
jk
) (89)
where G(i, E
j
) is the Gaussian part given by Eq. (85) and S and T are the step and tail
functions, respectively,
S(i; E
jk
) =
GAIN
2E
jk
erfc
E(i) E
jk
s
2
_
_ _
(90)
T(i; E
jk
) =
GAIN
2gs exp[1=(2g
2
)[
exp
E(i) E
jk
gs
_ _
erfc
E(i) E
jk
s
2
_
1
g
2
_
_ _
(91)
In these equations, s represents spectrometer resolution [Eq. (86)] and g is the broadening
of the exponential tail. The parameters f
S
and f
T
in Eq. (89) describe the fraction of the
photons that arrive in the step and the tail, respectively. The complement of the error
function used to convolute the step and the tail is dened as
erfc(u) = 1 erf(u) = 1
2
p
_
_
u
0
e
t
2
dt (92)
and can be calculated via series expansion (Press et al., 1988). Figure 25b shows a t of a
brass spectrum when these step and tail functions are included. In this case, a much more
realistic area for the NiKa is obtained and the continuum is described more correctly.
Campbell et al. (1987) used a Gaussian, a short-tail, and a long-tail exponential to t
the peak in energy-dispersive spectra obtained from Ka
1
and La
1
lines selected by Bragg
reection from a curved crystal. In this way, the inuence of the doublet structure and the
satellite lines is eliminated. Excellent ts with reduces chi-square values between 1.02 and
1.16 were obtained for peaks having 10
6
counts.
Fitting real x-ray spectra with modied Gaussians as given by Eq. (89) increases
dramatically the number of parameters that need to be optimized ( f
S
, f
T
, g) for each peak.
The phenomena contributing to the deviation from the Gaussian shape depend on the
energy of the detected x-ray line, so that these parameters can be expressed as smooth
functions of energy (Wielopolski and Gardner, 1979; Yacout et al., 1986). These relations
can be established using pure element spectra with very good counting statistics. An ad-
ditional problem is that the tailing of the Kb peaks tend to be larger due to the more
intense KMM radiative transition, thus requiring a separate relation for Ka and Kb tails.
A further modication of the tting function involves the use of a Voigt prole to
account for the natural line width of the x-ray lines. This becomes important when tting K
lines of higher-Z elements (Ba and above) where the natural linewidth becomes consider-
able ( >20 eV) compared to the detector resolution. The peak prole, G(i; E
j
) in Eq. (89)
must then be replaced by a Voigt prole (the convolution of a Lorenzian and a Gaussian):
GAIN
s
2p
_ K
E(i) E
jk
s
2
_ ;
a
L
2s
2
_
_ _
(93)
with Kthe real part of the complex error function and a
L
the natural width of the x-ray line:
K(x; y) = Ree
z
2
erfc(iz)|; z = x iy (94)
Voigt proles can be calculated using numerical approximations (Schreier, 1992). The
imaginary part of the complex error function can be used to calculate the derivatives
necessary in the least-squares-tting algorithm.
An alternative procedure to describe the peak shape is used in the AXIL program
(Van Espen et al., 1977b). The deviation from the Gaussian shape is stored as a table on
numerical values, representing the dierence of the observed shape and the pure Gaussian.
The table extends from zero energy up to the high-energy side of the Kb peak and is
normalized to the area of the Ka peak. The deviation is obtained from pure element
spectra having very good counting statistics. (Ka ~10
7
counts). Preferably, thin lms are
used to keep the continuum as low as possible and to avoid absorption eects. The area,
position, and width of all peaks in the spectrum are determined by tting Gaussians on a
constant continuum over the full width at tenth maximum (FWTM) of the peaks. The
Gaussian contributions are then stripped from the spectrum. The resulting non-Gaussian
part as shown in Figure 24 is further smoothed to reduce the channel to channel uc-
tuations and subsequently used as a numerical peak-shape correction. The tting function
for an element is then given by
y
P
(i) = A R
/
Ka
G(i; E
Ka
) C(i) [ [
N
P
j=2
R
/
j
G(i; E
j
)
_ _
(95)
where C(i) is the numerical peak-shape correction at channel i. Values in the table are
interpolated to account for the dierence between the energy scale of the correction and
the actual energy calibration of the spectrum. Similar to the parameters of the non-
Gaussian analytical functions, the shape of the numeric correction seems to vary slowly
from one element to another. This allows us to interpolate the peak-shape correction for
all elements from a limited set of experimentally determined corrections.
A major disadvantage of this method is that it is quite dicult and laborious to
obtain good experimental peak-shape corrections. Although they are, in principle, de-
tector dependent, experience has proven that the same set of corrections can be used for
dierent detectors with reasonable success, proving the fundamental nature of the ob-
served non-Gaussian shape. Another disadvantage is that the peak-shape correction for
the K becomes underestimated if strong dierential absorption takes place because the
peak-shape correction is only related to the area of the Ka peak. Also, it is nearly im-
possible to apply this method to the description of L-line spectra. A mayor advantage
however is the computational simplicity of the method and the fact that no extra para-
meters are required in the model.
5. Absorption Correction
The absorption correction term T
a
(E), used in the Eqs. (82) and (88), includes the x-ray
attenuation in all layers and windows between the sample surface and the active area of the
detector. For high energetic photons also, the transparency of the detector crystal needs to be
taken into account. In x-ray uorescence, the attenuation in the sample, causing additional
changes in the relative intensities, can also be considered, providing the sample composition
is known. The total correction term is thus composed of a number of contributions:
T
a
(E) = T
Det
T
Path
T
Sample
(96)
The detector contribution for a Si(Li) detector is given by
T
Det
(E) = e
m
Be
(rd)
Be
e
m
Au
(rd)
Au
e
m
Si
(rd)
Si
(1 e
m
Si
(rD)
Si
) (97)
where m, r, and d are the mass-attenuation coecient, the density, and the thickness of the
Be window, the gold contact layer, and the silicon dead layer. In the last term, D is the
thickness of the detector crystal.
Any absorption in the path between the sample and the detector can be modeled in a
similar way. For an air path, the absorption is given by
T
Path
(E) = e
m
air
(rd)
air
(98)
The mass-attenuation coecient of air can be calculated assuming a composition of 79.8%
N
2
, 19.9% O
2
, and 0.3% Ar. The density of air in standard conditions is 1.2610
73
g=cm
3
.
In PIXE setups, it is common practice to use additional absorbers between the sample and
the detector, with one absorber sometimes having a hole (funny lter). The absorption
behavior of such a structure can be modeled by
T
Path
(E) = e
m
f
(rd)
f
[h (1 h)e
m
ff
(rd)
ff
[ (99)
where the rst term accounts for the absorption in (all) solid lters and the second term
accounts for the absorption of the lter having a hole. The fraction of the detector solid
angle subtended by the hole is denoted by h.
The sample absorption correction in the case of x-ray uorescence, assuming ex-
citation with an (equivalent) energy E
0
, is given by
T
sample
(E) =
1 e
w
s
(rd)
s
w
s
(rd)
s
(100)
and the sample attenuation coecient is given by
w
s
=
m
s
(E)
sin y
1
m
s
(E
0
)
sin y
2
(101)
This sample attenuation coecient can only be calculated if the weight fractions of the
constituting elements are known, which is often not the case because the aim of the
spectrum evaluation is to obtain the net peak areas from which the concentrations are to
be calculated. Although x-ray attenuation in solid samples might become very large, it is
important to realize that not the absolute values of the absorption corrections but their
ratio is of importance in Eq. (88). This ratio changes less dramatically especially because
the energy dierence of the lines involved is small. For an innitely thin Fe sample, the
Kb=Ka intensity ratio is 0.134. In an innitely thick Fe matrix, the absorption correction
term T
a
(E
Kb
) and T
a
(E
Ka
) are respectively 161 and 134, assuming MoKa excitation,
causing the Kb=Ka ratio to change to 0.161. Therefore, a rough estimate of the sample
composition is often sucient. Van Dyck and Van Grieken (1983) demonstrated the
integration of spectrum analysis with quantitative analysis. The sample absorption term
is recalculated based on the estimated sample composition, and the spectrum tting is
repeated.
6. Sumand Escape Peaks
As indicated in Sec. II, Si escape peaks can be modeled by a Gaussian with an energy
1.750 keV below the parent peak. The area relative to the area of the parent peak can be
calculated from the escape fraction [Eq. (4)]:
Z =
N
e
N
p
=
f
1 f
(102)
Including the escape peaks, the description of the uorescence of an element becomes
y
P
(i) = A
N
P
J=1
R
/
j
[G(i; E
j
) ZG((i; E
j
1:750)[ (103)
Also, various polynomial type functions expressing the escape ratio as a function of the
energy of the parent peak are in use. The coecients of the function can be determined by
least-squares tting from experimental escape ratios. For spectra obtained with a Ge
detector, one needs to account in a similar way for both the GeKa and GeKb escape peak
for elements above arsenic.
The incorporation of the sum peaks in the tting model is more complex. The
method discussed below was rst implemented by Johansson in the HEX program
(Johansson, 1982). Initially, the spectrum is tted without considering pileup peaks. The
peaks are then sorted according to their height and the n largest peaks are retained. Peaks
that diers less than 50 eV are combined to one peak. Using Eqs. (5) and (6), the relative
intensities of all possible n(n 1)=2 pileup peaks and their energies are calculated and the
m most intense are retained. Knowing the relative intensities and the energies of these m
pileup peaks, they can be included in the tting model as one pileup element. In the next
iteration, the total peak area A of this pileup element is obtained. The construction of the
pileup element can be repeated during the next iterations as more reliable peak areas
become available. In Figure 26, part of an PIXE spectrum is shown tted with and without
sum peaks included.
D. Special Aspects of Least-Squares Fitting
1. Constraints
When using nonlinear least-squares tting, it can be advantages to impose limits on the
tting parameters to eliminate physically meaningless results. Some illustration of what
can happen if too much freedom is given to the tting parameters is provided by Statham
(1978).
The incorporation of the energy and resolution calibration functions [Eqs. (84) and
(86)] in the tting model already places a severe constraint on the t, avoiding the situation
in which two peaks that are very close together swapping their positions or becoming one
broader peak.
The tting parameter can be eectively constrained by dening the real physically
meaningful parameter P
j
[e.g., the GAIN in Eq. (84)] as an arctangent function of the
tting parameter a
j
(McCarthy and Schamber, 1981; Nullens et al., 1979):
P
j
= P
0
j

2L
j
p
arctan a
j
(104)
where P
0
j
is the expected value (initial guess) of the parameter P
j
, and L
j
denes the range.
As a result of this transformation, the parameter P
j
will always be in the range P
0
j
L
j
.
Apart from signicantly adding to the mathematical complexity, such transformation has
the disadvantage that the w
2
minimum, although lying within the selected interval, cannot
be reached because the path toward the minimum passes a forbidden region. Also, this
constraint makes no distinction between the more probable values of the parameter lying
near the center of the interval and the unlikely values at the limits.
An alternative approach, proposed by Nullens et al. (1979), relies on the modica-
tion of the curvature of the w
2
surface. The tting parameters, such as ZERO, GAIN,
NOISE, and FANO, are considered as random variables with an expected value equal to
the initial guess a
0
j
and having an uncertainty Da
j
. They can be included in the expression
of w
2
, just as the observed data points y
i
s
i
:
w
2
=
i
1
s
2
i
y
i
y(i) [ [
2
j
1
(Da
j
)
2
[a
0
j
a
j
[
2
(105)
Using this expression in the Marquardt nonlinear least-squares-tting algorithm results in
modied equations for the diagonal terms of the a matrix and for the b vector (see Sec. IX):
a
jj
=
i
1
s
2
i
@y
0
(i)
@a
j
_ _
2
1
(Da
j
)
2
(106)
and
b
j
=
i
1
s
2
i
[ y
i
y
0
(i)[
@y
0
(i)
@a
j
a
0
j
a
j
(Da
j
)
2
(107)
If no signicant peaks are present in the tting interval, the derivatives of the tting
function with respect to the position and width of the peaks are zero. Therefore, the
Figure 26 Fit of part of a PIXE spectrum having very high count rates for Fe and Zn. (Top:
without considering sum peaks; bottom: sum peaks included in the fitting model.)
second term in b
j
will dominate, causing the parameter estimate in the next iteration to be
such that a
j
tends toward a
0
j
(the initial value). If well-dened peaks are present, however,
the second term in b will be negligibly small compared to the rst term and the method
acts as if no constraints were present.
Another way to look at this is by considering the curvature of the w
2
surface near the
minimum. Figure 27 shows a cross section through the w
2
surface along the peak position
parameter. The variation of the w
2
values, with and without constraints, are shown for a
large (10,000 counts) and a small (100 counts) peak. The true peak position is at channel
100 and the FWHM of the peak is eight channels. The constraint, Da, on the peak position
is one channel. From Figure 27, it is evident that the w
2
minimum is much better dened
for a small peak when the constraint is applied, whereas this has no inuence for a large
peak. This method has been implemented in the AXIL program to constraint the energy
and resolution calibration parameters.
2. Weightingthe Fit
The weights w
i
used in the least-square methods [Eq. (77)] are dened in terms of the
true (population) standard deviation of the data y
i
, which can be obtained directly from
the data itself:
w
i
=
1
s
2
i
-
1
y
i
(108)
This approximation is valid for moderate to good statistics. When regions of the spectrum
with very bad statistics (low channel contents) are tted, estimating the weight from the
measured channel content causes a systematic bias leading to an underestimate of the peak
areas. To overcome this problem, Phillips suggested estimating the weights from the
Figure27 Effect of the use of a constraint on the shape of the w
2
response surface. (Left: marginal
effect for a large peak; right: important contribution for a small peak.)
average of three channels (Phillips, 1978). In the AXIL program, the weights are initially
based on the measured channel content, but when the overall w
2
value of the t falls
below 3, the weights are calculated from the tted channel content. This is based on the
idea that when the calculated spectrum approached the measured spectrum, the calculated
channel contents are a better estimate of the true channel content than the measured
values. The eect of the weighting on the t is considerable, as can be seen in Figure 28.
E. Examples
To illustrate the working of the nonlinear least-squares-tting method, an articial spec-
trum with CuK and ZnK lines is tted with four Gaussian peaks on a constant continuum.
Using the Marquardt algorithm, the position, width, and area of each peak are de-
termined. The tting function thus is
y(i) = a
0
i
4
j=1
a
j
exp
(i a
j1
)
2
2a
2
j2
_ _
(109)
with i the channel number (independent variable) and a
j
the parameters to be determined,
13 in total. In Table 10, the values of the parameters to generate the spectrum (true va-
lues), the initial guesses for the nonlinear parameters, and the nal tted values are given.
The initial guesses were deliberately taken rather far away from the true values. Figure 29
(top) shows the tted spectrum after the rst and second iterations. During the second
iteration, the Marquardt algorithm evolved into a gradient search, drastically changing the
position and width of the peaks. Even after ve iterations, the calculated spectrum deviates
considerably from the measured spectrum, as can be seen from Figure 29 (bottom).
Figure 28 The effect of weighing the least-squares fit is shown on part of an PIXE spectrum with
a very small number of counts per channel.
Finally, after 10 iterations, a perfect match between them is obtained, with a reduced w
2
value of 0.96.
From Table 10, it is evident that the t was quite successful, with all peak areas,
positions, and widths estimated correctly within the calculated standard deviation. One
observes that the uncertainties in the peak areas are approximately equal to the square
root of the peak area and that the position and the width of the peaks are estimated very
precisely (within 0.01 channel or 0.2 eV), especially for the larger peaks.
By observing how the iteration procedure changes the peak width and position
parameters, one can imagine that something might go wrong. Especially if the spectrum is
more complex, chances are high that the iteration stops in a false minimum or even drifts
away completely. In both cases, physically incorrect parameter estimates will be obtained.
In practice, it is course possible to give much better initial estimates for the peak position
and width parameters than used in this example.
In a next example, a complex spectrum (geological reference material JG1, excited
with MoK x-rays from a secondary target system) is evaluated using nonlinear least-
squares tting. In Figure 30, the spectrum and the t are shown together with the residuals
of the t (see p. 298). Due to the large number of overlapping lines, the method used in the
rst example (tting the position and width of each peak independently) is not applicable
in this case. For the description of the spectrum from 1 to 18 keV, the uorescence lines of
21 elements were used. Au, Hg, Pb, and Th were treated each as one L group
(L
1
L
2
L
3
) and Al, Si, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Al, Br, Sr, Rb, Y as one K group
(Ka Kb); K, Ca, and Fe were tted with individual Ka and Kb peaks. The coherently
scattered MoKa radiation was tted with a Gaussian and the incoherent scattered MoKa
radiation is tted with a Voigt prole. Including escape and sum peaks, this amounts to
well over 100 peak proles. Step and tail functions [Eq. (89)] were included for all peaks,
using expressions to relate the step and tail heights and the tail width to the energy of the
peak. The continuum is described by an exponential function [Eq. (81)] with six para-
meters. The least-squares t thus performed required the renement of 37 parameters
Table 10 True Value of Spectrum Parameters Used to Generate the Articial Spectrum in
Figure 29, Initial Guesses and Fitted Values of the Peak Area, Position, and Width Obtained by
Nonlinear Least-Squares Fitting
Parameter True value Initial guess Fitted value
Area (counts)
CuKa 100,000 0 100,134321
CuKb 13,400 0 13,163169
ZnKa 30,000 0 30,092213
ZnKb 4,106 0 413883
Position (channel number)
CuKa 402.05 395 402.030.01
CuKb 445.25 450 445.350.06
ZnKa 431.55 435 431.590.04
ZnKb 478.60 485 478.680.09
Width (channels)
CuKa 3.913 3 3.910.01
CuKb 4.033 3 3.990.05
ZnKa 3.995 3 4.020.03
ZnKb 4.123 3 4.060.08
(4 calibration parameters, 27 peak areas, 6 continuum parameters, 3 step and tail para-
meters, and 1 Voigt parameter). The minimum w
2
value of 1.47 is obtained after 16
iterations. The residuals indicate an overall good t with most of the residuals in the 73
to 3 interval, without any systematic patterns. Its interesting to note that the tted
continuum is well below the base of the peaks, especially in the region from channel 200 to
600. The continuum describes correctly the small scattered bremsstrahlung contribution
from the x-ray tube above 12 keV (channel 600) and the Compton scattering in the de-
tector at the low-energy side. Most of the apparent continuum in this secondary-target
EDXRF spectrum is due to incomplete charge collection and tailing phenomena of the
scattered Mo excitation radiation and the uorescence lines.
F. Evaluation of Fitting Results
In order to understand and appreciate the capabilities and limitations of least-squares
tting, either using library spectra, linear, or nonlinear analytical functions, it is useful to
study the eect of random and systematic errors in some detail. Random errors are as-
sociated with the uncertainty s
i
of the channel content y
i
. As will be seen, these un-
certainties inuence the precision of the net peak areas and determine the ultimate
resolving power of the least-squares method. Systematic errors, on the other hand,
Figure 29 Artificial CuK and ZnK line spectrum tted with a nonlinear least-squares procedures
to optimize peak area, position, and width. (Top: Fitted spectrum after rst and second iteration;
bottom: after fth and nal iterations.)
are caused by discrepancies between the tting model and the observed data and cause
inaccuracies in the net peak areas.
1. Error Estimate
Section IX explains how the least-squares-tting method (linear as well as nonlinear)
allows the estimation of the uncertainties in the tted parameters. These uncertainties
result from the propagation of the statistical uctuations in the spectral data into the
parameters. Intuitively, one could come to the conclusion that the standard deviation of
the peak area should be close to the square root of the peak area. This is indeed the case
for a large, interference-free peak on a low continuum, but if the peak is sitting on a high
continuum and=or is seriously overlapped by another peak, the uncertainty in the esti-
mated peak area will be much larger.
A properly implemented least-squares method not only correctly estimates the net
peak areas but also their uncertainty, taking into account the continuum and the degree of
peak overlap, providing, of course, that the tting model is capable to describe the
measured spectrum. The closer together the peaks are, the higher the uncertainties in the
two peak areas will become. (Theoretically, in the limit of complete overlap, the un-
certainty will be innite and the area of the two peaks will have complete erratic values,
but their sum will still represent correctly the total net peak area of the two peaks; in
practice, the curvature matrix a will be singular so that the matrix inversion fails.)
Figure 30 Example of the fit of a complex x-ray spectrum (thin film deposit of geological
reference material JG1 excited with a Mo secondary-target system). The residuals are plotted as an
indicator of the quality of the fit.
The uncertainties in the net peak areas can be used to decide if a peak is indeed
present in the spectrum and to calculate the detection limit. A peak area is statistically not
signicant dierent from zero if its value is in the range 3s. Any value above 3s gives
clear evidence that the peak is present; any value below 73s would indicate that there is
something wrong with the model because truly negative peak areas are physically mean-
ingless. Because the uncertainty in the net peak area includes the inuence of continuum
and peak overlap, it can be used to calculate the a posteriori detection limits of the ele-
ments (peaks) present in the spectrum. Three situations can occur:
1. Estimated peak area >36 standard deviation
? report: areastandard deviation
2. 736 standard deviation _estimated area _36 standard deviation
? report: detection limit equal to 36 standard deviation
3. Area <736 standard deviation
? revise the tting model
2. Criteria for Qualityof Fit
From the denition of the least-squares method, it follows that the w
2
value [Eq. (75)]
estimates how well the model describes the data. The reduced w
2
value, obtained by di-
viding w
2
by the number of degrees of freedom;
w
2
n
=
1
n
w
2
=
1
n m
w
2
(110)
has an expected value of 1 for a perfect t. The number of degrees of freedom equals the
number of data points (n) minus the number of parameters (m) estimated during the t.
Because w
2
is also a random variable, the observed value will often be slightly larger or
smaller than 1. Actually, w
2
follows (approximately) a chi-square distribution and the 90%
condence interval is given by
w
2
n;0:95
_ w
2
n
_ w
2
n;0:05
(111)
where w
2
n;0:95
and w
2
n;0:05
are the tabulated w
2
values at the 95% and 5% condence intervals,
respectively. For n =20, the condence interval is 0.5431.571, and for n =200, it is
0.8411.170. An observed value of w
2
n
in this interval indicates that the model describes the
experimental data within the statistical uncertainty of the data. In other words, all re-
maining dierences between the data and the t can be attributed to the noise uctuations
in the channel contents and are statistically not signicant. When tting complex spectra
with good statistics, much higher chi-square values will be obtained due to small im-
perfections in the continuum or peak model. This does not mean that the estimated peak
areas are not useful any more, but high reduced w
2
values ( >3) might indicate that the
tting model needs improvement.
The reduced chi-square value as dened in Eq. (110) gives an estimate of the overall
t quality over the entire tting region. Locally, in some part of the spectrum, the t might
actually be worse than indicated by this value. It is therefore useful to dene the chi-square
value for each peak separately:
w
2
P
=
1
n
1
n
2
m
i=n
2
1
s
2
i
[y
i
y(i)[
2
(112)
where n
1
and n
2
are the boundaries of the peak at FWTM and n
2
n
1
approximates the
number of degrees of freedom. High values of w
2
P
indicate that the peak is tted poorly and
the resulting peak area should be used with caution. In this case (w
2
P
> 1), it is advisable to
give a conservative estimate for the uncertainty in the net peak area, by multiplying the
calculated uncertainty with the square root of the w
2
value:
s
A
/ = s
A
w
2
P
_
(113)
Although the w
2
values gives an indication of the goodness of t, visual inspection of
the t is highly recommended. Because of the large dynamic range of the data, a plot of the
spectrum and the t on a linear scale nearly always give the impression of a perfect t. A
plot of the logarithm or the square root of the data is more appropriate. The best method
is to plot the residuals of the t as in done in Figure 30. The residuals are dened as
r
i
=
y
i
y(i)
s
i
(114)
It is the sum of the squares of these residuals that were minimized by the least-squares
method. Values in excess of 3 or 73 and especially the presence of a pattern in the
residuals then indicate poorly tted regions.
G. Available Computer Codes
In the literature, a number of computer programs for spectrum evaluation based on the
least-squares method are reported. Without attempting to be complete, the main char-
acteristics of a number of programs are summarized in the following paragraphs. Wa tjen
made a compilation of the characteristics of eight computer packages for PIXE analysis
(Wa tjen, 1987).
An intercomparison of ve computer program for the analysis of PIXE spectra re-
vealed a very good internal consistency among the ve programs (Campbell et al., 1987).
PIXE spectra of biological, environmental, and geological samples were used and their
complexity put high demands of the spectrum analysis procedures. The following pro-
grams were tested: AXIL, University of Gent, Belgium; HEX, University of Lund, Swe-
den; SESAM-X (Marburg, FRG), the Guelph program; PIXAN, Lucas Heights. It was
concluded that the most serious disagreement occurred for small peaks on the low-energy
tails of very large peaks, pointing to a need to a more accurate description of the tail
functions. Also, very good agreement between the linear (SESAM-X) and the nonlinear
least-squares approach was observed.
The Los Alamos PIXE Data Reduction software (Duy et al., 1987) contains three
components. The K and L relative x-ray intensities of the elements making up the sample
are computed taking into account the detector and sample absorption. Using Gaussian
peak shape, the energy and resolution calibrations of the spectrum are calculated. With the
relative peak areas and the calibration functions obtained is this way, the spectrum is tted
using a Gaussian peak shape and a polynomial continuum. Escape and pileup peaks can
be included. A linear least-squares t is done with the relative elemental concentrations
and the polynomial continuum coecient as unknowns. The continuum and the relative
concentrations are constrained to non-negative values and all elements having x-ray lines
in the spectrum interval considered are included.
The PIXASE computer package (Zolnai and Szabo , 1988) performs spectrum ana-
lysis using nonlinear least-squares tting. Elements are represented by groups of lines with
xed, absorption-corrected, relative intensities and including escape peaks. Each peak is
modeled by a Gaussian with the addition of a exponential tail and an error function as
step. The square of the peak width is a rst-order polynomial of the peak energy and the
position is a second-order polynomial of the peak energy. The continuum is described as
the sum of an exponential polynomial and two simple exponentials. Pileup eects are
treated as one pileup element. The nonlinear least-squares tting is done using a simple
grid search technique. The search space of each parameter is limited by user-supplied
minimum and maximum values. Fitting a large series of similar spectra linear least-squares
tting using a library of calculated spectrum components can be done.
Bombelka et al. (1987) described an PIXE analysis program based on linear least
squares. The peak shape includes a Gaussian low-energy tail function to account for the
incomplete charge collection and the escape peak. The position and the square of the
width of the peaks are given by rst-order linear function of the energy. The uorescence
lines of an element are modeled as a sum of those peak shapes with relative intensity ratios
corrected for absorption in the detector windows and absorbers. The continuum is com-
posed of a fourth-order exponential polynomial multiplied by the x-ray attenuation term
(bremsstrahlung continuum) and a second-order linear polynomial. Pileup is taken into
account as a pileup element. The energy and resolution calibration parameters are ob-
tained from selected peaks in the spectrum. The parameters of the exponential continuum
are calculated from continuum spectra. The parameters obtained by the linear least-
squares t are the amplitude parameters of each element and of one pileup element, the
amplitude parameter of the bremsstrahlung continuum, and the linear polynomial con-
tinuum parameters. The computer implementation for PIXE is called SESAMX and is
highly interactive with graphical representation of the spectral data. Other computer
program for tube-excited (Breschinsky et al., 1979) and synchrotron radiation- (Petersen
et al., 1986) excited XRF were developed based on this code.
SAMPO-X (Aarnio and Lauranto, 1989) is intended for the analysis of electron
induced x-ray spectra and is based on the well-known SAMPO code original developed for
g-ray spectroscopy (Routti and Prussin, 1969). A Gaussian with two exponential tails, as
in the original SAMPO program, is used to represent the peaks. The height and the po-
sition parameters are obtained by the nonlinear least-squares t. The peak width and the
tail parameters are obtained from shape-calibration tables by interpolation. The con-
tinuum is modeled by the semi-empirical electron bremsstrahlung intensity function
proposed by Pella et al. (1985). The thickness of the detector beryllium window and the
atomic number of the sample, which occur in this formula, are adjusted by the least-
squares t. The program also includes an element identication based on the energy and
intensity of the tted peaks and a standard ZAF matrix correction.
Jensen and Pind (1985) described a program for the analysis of energy-dispersive x-
ray spectra. The program uses a sum of Gaussians, one for each uorescence line. The
continuum is subtracted rst using a linear, parabolic, or exponential function tted from
peak-free regions in the spectrum. The peak width is obtained from a calibration function
which expressed the log of the peak width as a linear function of the peak position. The
width calibration is done using nonoverlapping peaks in a calibration spectrum or in the
spectrum to analyze. Peak positions are determined using a peak search method or entered
by the operator with the aid of a graphical display of the spectrum. The peak heights are
then determined using linear least-squares tting.
The computer code developed at the technical University of Graz (Marageter et al.,
1984a) is primary intended for the evaluation of x-ray uorescence spectra. A Gaussian
response function with an low-energy tail is used to describe the peaks. The square of the
peak width is a linear function of the peak energy. A straight-line equation relates the peak
position to the energy of the peaks. A parabola is used to describe the continuum, whereas
absorption edges are modeled by a complementary error function. The tting parameters
are the peak heights, the three continuum parameters, the height of the absorption edges,
and the two energy calibration parameters. Nonlinear least-squares tting is done with the
Marquardt algorithm using a tangent transformation to constrain the tting parameters to
physical meaningful values (Nullens et al., 1979). Provision for escape peaks and Auger
peaks is also made (Marageter et al., 1984b).
The AXIL program (Van Espen et al., 1977a) was originally developed for the ana-
lysis of x-ray uorescence spectra and later modied to allow the evaluation of electron-
and particle-induced x-ray spectra (Van Espen et al., 1979b, 1986). It uses the Marquardt
algorithm for nonlinear least-squares tting with a modied (constrained) chi-square
function. Linear, exponential, and bremsstrahlung polynomials can be used to model the
continuum as well as continuum stripping. X-ray lines are described by Gaussian functions
with an optional numerical peak-shape correction. Escape and sum peaks can be included
in the model. The peak position and the square of the peak width is related to the x-ray
energy by linear functions. Provision is made to correct for the absorption in detector
windows, lters, and the sample. In a later version, an orthogonal polynomial continuum
model was added, as well as step and tail functions to describe the deviation from the
Gaussian peak shape (Vekemans et al., 1994). The code was implemented as a Windows
application. An example of the screen output of this program is given in Figure 31.
VIII. METHODS BASED ONTHE MONTE CARLOTECHNIQUE
Monte Carlo techniques for the simulation of x-ray spectra are becoming more and more
popular, particularly because of the fast computers available today. These simulated
spectra are useful for studying the behavior and performance of various spectrum pro-
cessing methods. The Monte Carlo technique also can be used in quantitative analysis
procedures, as will be discussed in Sec. VIII. B.
A. Simulation of X-ray Spectra
During the development and test phase of a spectrum processing method, it is often ad-
vantageous to use computer-simulated spectra. For these spectra, such features as posi-
tion, width, and area of peaks are exactly known in advance. They can be generated to any
desired complexity. In order to make any real use of them, the simulated spectra must
possess the same channel-to-channel variation according to a Poisson distribution as ex-
perimental spectra.
A simple and adequate procedure consist of rst calculating, over the channel range
of interest, the ideal spectrum y
0
using, for example, a polynomial for the continuum and a
series of Gaussians as given by Eq. (109). More complex functions, including a more
physically realistic model for the continuum and tailed peaks, can be used if desired. The
next step is to add or subtract some number of counts from each channel content so as to
obtain data with the desired counting statistical noise. In other words, the true content
y
0
i
needs to be converted into a random variable, y
i
, so that is obeys a Poisson distribution
[Eq. (1)] with N
0
= y
0
.
Poisson-distributed random variables can be generated by various computer algo-
rithms. An example (Press, 1988) is given in Sec. X. For y
0
> 30 the Poisson-distributed
Figure 31 Screen capture of the spectrum analysis program WinAxil, showing the fitted spectrum and the results obtained.
random variable can be approximated by the much easier to calculate normal-distributed
random variable. The probability to observe y counts in a channel, assuming a normal
distribution, is given by
P(y) =
1
s
2p
_ e
(ym)
2
2s
2
(115)
with m = s
2
= y
0
. For large y
0
the normal distribution is a very good approximation of the
Poisson distribution. Even for small channel contents this approximation is quite sa-
tisfactory. The probability of observing 6 counts, assuming the true value is 4, is 0.10
according to a Poisson distribution, whereas it is 0.12 according to a normal distribution.
The problem of adding counting statistics to the calculated spectrum is thus reduced
to calculating a normal-distributed random variable y with mean value m = y
0
and var-
iance s
2
= y
0
. Starting from a uniformly distributed random variable U in the interval
(0, 1), which can be generated by a pseudo-random number generator, normal distri-
buted random variables with zero mean and unit variance can be obtained with the Box-
Muller method (Press, 1988).
n
1
= 2U
i
1
n
2
= 2U
i1
1
r = n
2
1
n
2
2
(116)
if r <1
z
1
= n
1
2 ln r=r
_
z
2
= n
2
2 ln r=r
_
n
1
and n
2
and r are calculated from two uniformly distributed random numbers U
i
and
U
i1
. If r is less than 1, two normally distributed random numbers z
1
and z
2
can be cal-
culated. If r _ 1; n
1
; n
2
; and r are recalculated using a new set of uniform random numbers.
The normally distributed random number y, with mean m = y
0
and variance s
2
= y
0
, is
then obtained by simple scaling:
y = m zs = y
0
z
y
0
_
(117)
Applying this to all channels will produce the desired counting statistics. Since z is nor-
mally distributed with mean 0 and unit variance, z can be negative as well as positive. The
count rate in each channel will thus be increased or decreased randomly and proportional
to
_
y
0
. The nal step in the computer simulation is to convert the real numbers that were
used during the calculation to integers.
Another interesting procedure is to generate articial spectra from parent spectra.
The parent spectrum is a spectrum acquired for a very long time so that it exhibits ex-
tremely good counting statistics (high channel content). A large number of child spectra
with lower and varying counting statistics can be generated by the procedure explained
below. This method is useful to study the eect of counting statistics on spectrum-
processing algorithms (Ryan, 1988).
From the parent spectrum y
i
, which might be rst smoothed to reduce the noise even
further providing not too much distortion is introduced, the normalized cumulative dis-
tribution function Y
j
is calculated
Y
j
=
j
i=0
y
i
n
i=0
y
i
(118)
n being the number of channels in the spectrum and Y
j
in the interval (01). To generate
the child spectrum we select N times a channel i according to the equation
i = Y
1
(U) (119)
where Y
1
is the inverse cumulative distribution and U is a uniformly distributed random
number. Each time channel i is selected, one count is added to that channel. Since N is the
total number of counts in the child spectrum, the counting statistics can be controlled by
varying N. However, Y
1
cannot be expressed as an analytical function, but for each
random number U we select the channel i for which Y
i
_ U < Y
i1
. Figure 32 shows an
EDXRF spectrum from a 0.187 mg=cm
2
pellet of IAEA Animal Blood reference material
acquired for 1000 s with a Tracor Spectrace 5000 instrument, which is used as a parent
spectrum. The cumulative distribution function and a child spectrum simulated with
N=3610
4
are also shown. The total number of counts in the original spectrum is 3610
6
.
The child spectrum is equivalent to a spectrum that would have been acquired for 10 s.
Some computer routines useful for simulation experiments are given in Sec. X.
Figure 32 Simulation of a child spectrum from a parent. (Top: original spectrum; middle:
the cumulative distribution; bottom: generated child.)
B. SpectrumEvaluation Using Monte CarloTechniques
Another interesting application of the Monte Carlo technique is the simulation of the
complete response of an x-ray uorescence setup. Given an excitation spectrum and the
excitation-detection geometry the interactions of the primary photons with the sample are
simulated and the events giving rise to detectable phenomena are registered. With such a
Monte Carlo simulation, the intensity of the characteristic lines and the scattered excitation
spectrum are estimated, taking primary and secondary eects (absorption, enhancement,
and single and multiple scattering) into account. The obtained spectrumis one as seen by an
ideal detector with innite resolution. This spectrum can then be convolution with the
response function of a real detector to mimic a typical observed pulse-height spectrum.
Apart from a detailed Monte Carlo simulation code, this technique requires detailed
knowledge of the excitation spectrum and a very accurate detector response function.
Doster and Gardner were among the rst to apply this technique to simulate the
complete spectral response of an EDXRF system (Doster and Gardner, 1982a; Doster and
Gardner, 1982b; Yacout and Dunn, 1987). More recently, Janssens and coworkers de-
veloped highly ecient computer codes for the simulation of conventional and synchro-
tron energy-dispersive x-ray uorescence systems, allowing such conditions as polarized
radiation and heterogeneous samples to be taken into consideration (Janssens et al., 1993;
Vincze et al., 1993; Vincze et al., 1995a, 1995b; Vincze et al., 1999). Figure 33 shows the
results of the application of this Monte Carlo simulation for a NIST SRM 1155 steel
sample excited with a ltered Rh-anode x-ray tube. At the top the simulated spectrum as
seen by a perfect detector is shown, at the bottom the spectrum after convolution with a
suitable detector response function is compared with a real measured spectrum of this
sample. Except for some sum peaks that occur in the measured spectrum, an excellent
agreement between the simulated and measured uorescence lines, scattered peaks, and
continuum is obtained.
These simulated x-ray spectra can be used in various ways in quantitative analysis.
Using the complete spectral response of spectrometer, one can try to nd a sample
composition that minimizes (in the least-squares sense) the dierence between the simu-
lated and the measured spectrum. The analysis involves the following steps: (1) simulation
of the X-ray intensities over the expected composition range of the unknowns; (2) con-
volution with the detector response function to obtain spectra; (3) construction of a w
2
map (weighted sum of squares of dierences between simulated spectra and experimental
spectrum) as a function of the sample composition; (4) interpolation of w
2
for the com-
position corresponding to the minimum. An interesting aspect of this method is that all the
information present in the spectrum (characteristic lines, scattered radiation, continuum)
is considered. Doster and Garnder demonstrated an analytical accuracy of the order of
2% absolute for the analysis of Cr-Fe-Ni alloys with a
109
Cd radioisotope system (Doster
and Gardner, 1982a). Based on this work, Yacout and Dunn (Yacout and Dunn, 1987)
demonstrated the use of the inverse Monte Carlo method, which requires in principle only
one simulation to analyze a set of similar samples.
Another method is called Monte Carlolibrary least-squares analysis (Verghese
et al., 1988). Starting from an initial guess of the composition of an unknown sample, a
spectrum is simulated taking into account all the interactions in the sample. During the
simulation one keeps track of the response of each element to construct library spectra.
After the simulation these library spectra are used to obtain the elemental concentrations
by linear least-squares tting (see Sec. VI). In the concentration in the unknown samples
dier too much from the initial assumed concentration, the simulation is repeated.
In contrast to the normal library least-squares method, this method has the advantage that
the library spectra are simulated for a composition close to the composition of the spec-
trum to analyzed, rather than measured from standards. This eliminates the necessity of
applying the top-hat lter and problems related to changes in Kb=Ka ratios, and again the
method combines spectrum evaluation with quantitative analysis.
Finally the ability to simulate x-ray spectra that agree very well with real measured
spectra opens the possibility to used them as standards for the quantitative analysis
based on partial least-squares regression (see Sec. VI.B). Indeed, as this method only
functions correctly if the PLS model is built using a large number of standards covering
the entire concentration domain, it seems advantageous to use simulated spectra for this.
All the inter-element interactions can be accounted for by the simulation and only a few
real standards are required to scale the simulated spectra.
Figure 33 Monte Carlo simulation of the spectral data from an NIST SRM 1155 sample excited
with a Rh-anode x-ray tube. (Top: simulated spectrum as seen by an ideal detector; bottom:
simulated spectrum after convolution with the detector response function and comparison with
measured spectrum.)
IX. THE LEAST-SQUARES-FITTINGMETHOD
The aim of the least-squares method is to obtain optimal values for the parameters of a
function that models the dependence of experimental data. The method has its roots in
statistics but is also considered part of numerical analysis. The least-squares parameter
estimate, also known as curve tting, plays an important role in experimental science. In
x-ray uorescence, it is used in many calibration procedures and it forms the basis of a
series of spectrum analysis techniques. In this section, an overview of the least-squares
method with emphasis on spectrum analysis is given.
Based on the type of tting function, one makes a distinction between linear and
nonlinear least-squares tting because one requires numerical techniques of dierent
complexity to solve the problem in the two cases. The linear least-squares method deals
with the tting of functions that are linear in the parameters to be estimated. For this
problem, a direct algebra solution exists. If the tting function is not linear in one or more
of the parameters, one uses nonlinear least-squares tting and the solution can only be
found iteratively. A group of linear functions of general interest are the polynomials, the
straight line being the simplest case. The special case of orthogonal polynomials will also
be considered. If more than one independent variable (x
1i
; x
2i
; . . . ; x
mi
) is associated with
each measurement of the dependent variable y
i
, one speaks of multivariate regression.
Spectrum analysis using the library function (e.g., lter-t method) belongs to this cate-
gory. If analytical function (e.g., Gaussians) are tted to a spectrum, the method of linear
or nonlinear least square is used, depending on whether nonlinear parameters, such as the
peak position and width, are determined.
A. Linear-Least Squares
Considered the problem of tting experimental data with the following linear function:
y = a
1
X
1
a
2
X
2
a
m
X
m
(120)
This function covers all linear least-squares problems. If m = 2; X
1
= 1, and X
2
= x, the
straight-line equation y = a
1
a
2
x is obtained. For m > 2 and X
k
= x
k1
, Eq. (120) is a
polynomial y = a
1
a
2
x a
3
x
2
a
m
x
m1
to be tted to the experimental data
points x
i
; y
i
; s
i
i = 1; . . . ; n. If X
1
; . . . ; X
m
represents dierent independent variables, the
case of multiple linear regression is dealt with. Because of this generality, we will discuss
the linear least-squares method based on Eq. (120) in detail.
Assume a set of n experimental data points:
x
1i
; x
2i
; . . . ; x
mi
; y
i
; s
i
; i = 1; . . . ; n (121)
with x
ki
the value of the kth independent variables X
k
in measurement i, assumed to be
known without error, and y
i
the value of the dependent variable measured with un-
certainly s
i
. The optimum set of parameters a
1
; . . . ; a
m
that gives a least-squares t of
Eq. (120) to these experimental data are those values of a
1
; . . . ; a
m
that minimize the chi-
square function:
w
2
=
n
i=1
1
s
2
i
(y
i
a
1
X
1
a
2
X
2
a
m
X
m
)
2
(122)
The minimum is found by setting the partial derivatives of w
2
with respect to the para-
meters to zero:
@w
2
@a
k
= 2
n
i=1
1
s
2
i
(y
i
a
1
X
1
a
2
X
2
a
m
X
m
)X
k
= 0; k = 1; . . . ; m (123)
Dropping the weights 1=s
2
i
temporarily for clarity, we obtain a set of m simultaneous
equations in the m unknown a
k
:
y
i
X
1
= a
1
X
1
X
1
a
2
X
2
X
1
a
m
X
m
X
1
y
i
X
2
= a
1
X
1
X
2
a
2
X
2
X
2
a
m
X
m
X
2
.
.
.
y
i
X
m
= a
1
X
1
X
m
a
2
X
2
X
m
a
m
X
m
X
m
(124)
where the summations run over all experimental data points i. These equations are known
as the normal equations. The solutionthe values of a
k
can easily be found using matrix
algebra. Because two (column) matrices are equal if their corresponding elements are
equal, the set of equations can be in matrix form as
y
i
X
1
y
i
X
2
.
.
.
y
i
X
m
_
_
_
_
=
a
1
X
1
X
1
a
2
X
2
X
1
a
m
X
m
X
1
a
1
X
1
X
2
a
2
X
2
X
2
a
m
X
m
X
2
.
.
.
a
1
X
1
X
m
a
2
X
2
X
m
a
m
X
m
X
m
_
_
_
_
(125)
The right-hand column matrix can be written as the product of a square matrix a and a
column matrix a:
y
i
X
1
y
i
X
2
.
.
.
y
i
X
m
_
_
_
_
=
X
1
X
1
X
2
X
1

X
m
X
1
X
1
X
2
X
2
X
2

X
m
X
2
.
.
.
X
1
X
m
X
2
X
m

X
m
X
m
_
_
_
_
a
1
a
2
.
.
.
a
2
_
_
_
_
(126)
or
b = aa (127)
This equation can be solved for a by premultiplying both sides of the equation with
the inverse matrix a
1
,
a
1
b = a
1
aa = Ia (128)
or, I being the identity matrix,
a = a
1
b (129)
Introducing the weights again, the elements of the matrices are given by
b
j
=
n
i=1
1
s
2
i
y
i
X
j
; j = 1; . . . ; m (130)
a
jk
=
n
i=1
1
s
2
i
X
k
X
j
; j = 1; . . . ; m; k = 1; . . . ; m (131)
and
a
j
=
m
k=1
a
1
jk
b
k
; j = 1; . . . ; m (132)
where a
1
jk
are the elements of the inverse of the matrix a
1
.
The uncertainty in the estimate of a
j
is due to the uncertainty of each measurement
multiplied by the eect that measurement has on a
j
:
s
2
a
j
=
n
i=1
s
2
i
@a
j
@y
i
_ _
2
(133)
Because a
1
jk
is independent of y
i
, the partial derive is simply
@a
j
@y
i
=
1
s
2
i
m
k=1
a
1
jk
X
k
(i) (134)
After some rearrangements, it can be shown that
s
2
aj
=
m
k=1
m
l=1
a
1
jk
a
1
jl
n
i=1
1
s
2
i
X
k
X
l
_ _
(135)
the term in the brackets being a
kl
and
s
2
aj
=
l
a
1
jk
a
1
jl
a
kl
= a
1
jj
(136)
This results in the simple statement that the variance (square of uncertainty) of a tted
parameter a
j
is given by the diagonal element j of the inverse matrix a
1
. The o-diagonal
elements are the covariances. For this reason, a
1
is often called the error matrix. Simi-
larly, a is called the curvature matrix because the elements are a measure of the curvature
of the w
2
hypersurface in the m-dimensional parameter space. It can easily be shown that
1
2
@
2
w
2
@a
j
@a
k
=
i
1
s
2
i
X
k
X
j
= a
jk
(137)
If the uncertainties in the data points s
i
are unknown and are the same for all data
points (s
i
= s), these equations can still be used by setting the weights w
i
= 1=s
2
i
to 1.
Assuming the tting model is correct, s can be estimated from the data:
s
2
i
= s
2
- s
2
=
1
n m
i
(y
i
a
1
X
1
a
2
X
2
a
m
X
m
)
2
(138)
The uncertainties in the parameters are then given by
s
2
a
j
= s
2
a
1
jj
(139)
If the uncertainties in the data points are known, the reduced w
2
value can be calculated as
a measure of the goodness of t:
w
2
n
=
1
n m
i
1
s
2
i
(y
i
a
1
X
1
a
2
X
2
a
m
X
m
)
2
=
1
n m
w
2
(140)
The expected value of w
2
n
is 1.0, but due to the random nature of the experimental data values
slightly smaller or greater than 1 will be observed even for a perfect t. w
2
n
follows a chi-
square distribution with n mdegrees of freedom, and a 90%condence interval is dened by
w
2
(n; P = 0:95) _ w
2
n
_ w
2
(n; P = 0:05) (141)
where w
2
(n; P) is the (tabulated) critical value of the w
2
distribution for n degrees of freedom
at a condence level P. Observed w
2
n
values outside this interval indicate a deviation
between the t and the data that cannot be attribute to random statistical uctuations.
B. Least-Squares Fitting Using Orthogonal Polynomials
A special group of linear functions are orthogonal polynomials. Orthogonality means that
the polynomial terms are uncorrelated, and this has some distinct advantages. Let P
j
(x
i
)
be an orthogonal polynomial of degrees j; a function can then be constructed as a sum of
these orthogonal polynomials of successive higher degree:
y(i) =
m
j=0
C
j
P
j
(x
i
) (142)
The least-squares estimates of the coecient C
j
are determined by minimizing the weighted
sum of squares:
w
2
=
n
i=1
w
i
(y
i
y(i))
2
(143)
which results in a set of m1 normal equations in the m1 unknown. Because the P
j
(x
i
)
are a set of orthogonal polynomials, they have the property that
n
i=1
w
i
P
j
(x
i
)P
k
(x
i
) = g
k
d
jk
(144)
with g
k
a normalization constant and d
jk
= 0 for j ,= k.
Because of this property, the matrix of the normal equations is diagonal and the
polynomial coecients are directly obtained from
C
j
=
n
i=1
w
i
y
i
P
j
(x
i
)
g
j
(145)
and the variance of the coecient is given by
s
2
cj
=
1
g
j
(146)
Another advantage of the use of orthogonal polynomials is that the addition of one
extra term C
m1
P
m1
does not change the values of the already determined coecients
C
0
; . . . ; C
m
. Further, if the y
i
are independent, then also the C
j
are independent; that is, the
variancecovariance matrix is also diagonal. As a result, much higher-degree orthogonal
polynomials can be tted compared to ordinary polynomials without running into pro-
blems with ill-conditioned normal equations and oscillating terms.
Orthogonal polynomials can constructed by following recurrence relation:
P
j1
(x
i
) = (x
i
a
j
)P
j
(x
i
) b
j
P
j1
(x
i
) j = 0; . . . ; m1 (147)
a
j
and b
j
are constants independent of y
i
given by
a
j
=
n
i=1
w
i
x
i
[P
j
(x
i
)[
2
g
j
; j = 0; . . . ; m (148)
b
j
=
n
i=1
w
i
x
i
P
j
(x
i
)P
j1
(x
i
)
g
j1
; j = 0; . . . ; m (149)
Further, the normalization factor is given by
g
j
=
n
i=1
w
i
[P
j
(x
i
)[
2
(150)
and
b
0
= 0 and P
0
(x
i
) = 1 (151)
Thus, an example of a rst-order orthogonal polynomial is
C
0
P
0
C
1
P
1
= C
0
C
1
(x
i
a
0
) (152)
with
a
0
=
n
i=1
w
i
x
i
_
w
i
(153)
C. Nonlinear Least Squares
In this part, we consider the tting of a function that is nonlinear in one or more tting
parameters. Examples of such functions are a decay curve,
y(x) = a
1
exp(a
2
x) (154)
or a Gaussian on a linear background,
y(x) = a
1
a
2
x a
3
exp
(x a
4
)
2
2a
2
5
_ _
(155)
Equation (154) is nonlinear in a
2
; Eq. (155) is nonlinear in the parameters a
4
and a
5
.
Equation (154) is representative for a group of functions for which linear least-squares tting
can be applied after suitable transformation. Fitting with Eq. (155) implies the application of
truly nonlinear least-squares tting with iterative optimization of the tting parameters.
1. Transformationto Linear Functions
Taking the logarithm of Eq. (154),
ln y = ln a
1
a
2
x (156)
and dening y
/
= ln y; and a
/
1
= ln a
1
, a linear (straight line) tting function is obtained,
y
/
= a
/
1
a
2
x (157)
and the method discussed earlier can be applied, but not without making the following
important remark. We have transformed our original data y
i
to y
/
i
= ln y
i
. Consequently,
also the variance s
/2
i
has been changed according to the general error propagation formula:
s
/ 2
i
= s
2
i
@y
/
@y
_ _
2
(158)
or in this particular case,
s
/ 2
i
=
s
2
i
y
i
(159)
Thus, even if all original data points had the same uncertainty (s
i
= s) and unweighed
linear least-squares tting could have been used, after the transformation a weighted linear
least-squares t is required. The results of the t are the parameters and the associated
uncertainties of the transformed equation, and to obtain the original parameter, we must
perform a back transformation with the appropriate error propagation,
a
1
= e
a
/
1
(160)
s
2
a
1
= s
2
a
/
1
@a
1
@a
/
1
_ _
2
= a
1
s
2
a
/
1
(161)
2. General Nonlinear Least Squares
For the general case of least-squares tting with a function that is nonlinear in one or more
of its tting parameters, no direct solution exists. Still, we can dene the object function w
2
:
w
2
=
i
1
s
2
i
[y
i
y(x
i
; a)[
2
(162)
whose minimumwill be reached when the partial derivative with respect to the parameters are
zero; however, this will result in a set of m equations for which no general solution exists. The
other approachtothe problemis thentoconsider w
2
as acontinuous functionof the parameters
a
j
(i.e., w
2
will take a certain value for each set of values of the parameters a
j
for a given dataset
x
i
; y
i
; s
2
i
). w
2
thus forms a hypersurface in the m-dimensional space, formed by the tting
parameter a
j
. This surface must be searched to locate the minimum of w
2
. Once found, the
corresponding coordinate values of the axes are the optimumvalues of the tting parameters.
The problem of nonlinear least-squares tting is thus reduced to the problem of
nding the minimum of a function in an m-dimensional space. Any algorithm that per-
forms this task should operate according to the following:
1. Given some initial set of values for the parameters a
ini
evaluate w
2
:
w
2
old
= w
2
(a
ini
)
2. Find a new set of values a
new
such that w
2
new
< w
2
old
.
3. Test the minimum of w
2
value:
if w
2
new
is the (true) minimum accept a
new
as the optimum values of the t
else w
2
old
= w
2
new
and repeat Step 2.
From the scheme, the iterative nature of the nonlinear least-squares tting methods be-
comes evident. Moreover, it shows some other important aspects of the method: Initial
values are required to start the search, we need a procedure to obtain a new set of
parameters which preferably are such that w
2
is decreasing, and we need to be sure that the
true minimum, not some local minimum, is nally reached.
A variety of algorithms has been proposed, ranging from brute-force mapping
procedures dividing the m-dimensional parameter space in small cells and evaluating w
2
in
each point, to more subtle simplex search procedures (Fiori et al., 1981). The most
important group of algorithms is nevertheless based on the evaluation of the curvature
matrix. The gradient method and the rst-order expansion will be discussed briey, as they
form the basis of the most widely used LeverbergMarquardt algorithm (Marquardt,
1963; Bevington and Robinson, 1992; Press et al., 1988).
a. The Gradient Method
Having a tting function y = y(x; a) and w
2
dened as a function of the m parameters a
j
,
w
2
= w
2
(a) =
n
i=1
1
s
2
i
[y
i
y(x
i
; a)[
2
(163)
the gradient of w
2
in the m-dimensional parameter space is given by
Hw
2
=
j
@w
2
@a
j
j (164)
where j is the unit vector along the axis j and the components of the gradient are given by
@w
2
@a
j
= 2
i
1
s
2
i
[y
i
y(x
i
; a)[
@y
@a
j
(165)
It is convenient to dene
b
j
=
1
2
@w
2
@a
j
(166)
The gradient gives the direction in which w
2
increases most rapidly. A method to locate the
minimum can thus be developed on this basis. Given the current set of parameters a
j
, a
new set of parameters a
/
j
is calculated (for all j simultaneously):
a
/
j
= a
j
Da
j
b
j
(167)
which follows the direction of steepest descent and guarantees a decrease of w
2
(at least if
the appropriate step sizes Da
j
are taken).
The gradient method works quite well away from the minimum, but near the
minimum, the gradient becomes very small (at the minimum, even zero). Fortunately, the
method discussed next behaves in the opposite way.
b. First-Order Expansion
If we write the tting function y(x
i
; a) as a rst-order Taylor expansion of the parameters
a
j
around y
0
,
y(x; a) = y
0
(x; a)
j
@y
0
(x; a)
@a
j
da
j
(168)
we obtain an (approximation) to the tting function which is linear in the parameter in-
crements da
j
. y
0
(x; a) is the value of the tting function for some initial set of parameter a.
Using this function, we can now express w
2
as
w
2
=
i
1
s
2
i
y
i
y
0
(x
i
; a)
j
@y
0
(x
i
; a)
@a
j
da
j
_ _
2
(169)
and we can use the method of linear least squares to nd the parameters da
j
so that w
2
will
be minimal. We are thus tting the dierence y
/
i
= y
i
y
0
(x
i
; a) with the derivatives as
variables and the increments da
j
as unknowns. With reference to the section on linear
least-squares tting [Eq. (122)],
X
j
=
@y
0
(x
i
)
@a
j
(170)
and [Eq. (130) and (131)]
b
j
=
n
i=1
1
s
2
i
[y
i
y
0
(x
i
)[
@y
0
(x
i
)
@a
j
(171)
a
jk
=
n
i=1
1
s
2
i
@y
0
(x
i
)
@a
j
@y
0
(x
i
)
@a
k
(172)
dening a set of m normal equations in the unknowns da
j
,
b = ada (173)
with solution
da
j
=
m
k=1
a
1
jk
b
k
(174)
It is not very dicult to prove that
b
j
=
1
2
@w
2
0
@a
k
(175)
(i.e., the component of the gradient of w
2
at the point of expansion) and
a
jk
-
1
2
@
2
w
2
0
@a
j
da
k
(176)
Thus, a
jk
in Eq. (172) is the rst-order approximation to the curvature matrix whose
inverse is the error matrix.
The rst-order expansion of the tting function is closely related to the rst-order
Taylor expansion of the w
2
hypersurface itself:
w
2
= w
2
0
j
@w
2
0
@a
j
da
j
(177)
where w
2
0
is the w
2
function at the point of expansion:
w
2
0
=
n
i=1
1
s
2
i
[y
i
y
0
(x
i
; a)[
2
(178)
At the minimum, the partial derivation of w
2
with respect to the parameter a
k
will be zero:
@w
2
@a
k
=
@w
2
0
@a
k
j
@
2
w
2
0
@a
j
@a
k
da
k
= 0 (179)
This results in a set of equations in the parameters da
k
:
@w
2
0
@a
k
=
m
j=1
@w
2
0
@a
j
@a
k
da
k
(180)
b
k
=
a
jk
da
k
(181)
which is the same set of equations, except that in the expansion of the tting function, only
a rst-order approximation of the curvature matrix is used.
Because near the minimum the rst-order expansion of the w
2
surface is a good ap-
proximation, we canconclude that alsothe rst-order expansionof the tting function(whichis
computationally more elegant because only derivatives of functions and not of w
2
are required)
will yield parameter increments da
j
which will direct us toward the minimum. For each linear
parameter in the tting function, the rst-order expansion of the function in this parameter is
exact and the calculated increment da
j
will be such that the newvalue a
j
da
j
is optimum(for
the given set of nonlinear parameters which might not be at their optimum value yet).
c. The Marquardt Algorithm
Based on the observation that away from the minimum the gradient method is eective
and near the minimum the rst-order expansion is useful, Marquardt developed an al-
gorithm that combines both methods using a scaling factor l that moves the algorithm
either in the direction of the gradient search or into the direction of rst-order expansion
(Marquardt, 1963).
The diagonal terms of the curvature matrix are modied as follows:
a
/
jk
=
a
jk
(1 l); j = k
a
jk
; j ,= k
_
(182)
where a
jk
is given by Eq. (172) and the matrix equation to be solved for the increments da
j
is
b
j
=
k
a
/
jk
da
k
(183)
When l is very large (l 1), the diagonal elements of a dominate and Eq. (183) reduces to
b
j
- a
/
jj
da
k
(184)
or
da
k
-
1
a
/
jj
b
j
-
1
a
/
jj
@w
2
@a
k
(185)
which is the gradient, scaled by a factor a
/
jj
. On the other hand, for small values of
l (l 1), the solution is very close to rst-order expansion.
The algorithm proceeds as follows:
1. Given some initial values of the parameters a
j
, evaluate w
2
= w
2
(a) and initialize
l =0.0001.
2. Compute b and a matrices using Eqs. (171) and (172).
3. Modify the diagonal elements a
/
jj
= a
jj
l and compute da.
4. If w
2
(a da) _ w
2
(a)
increase l by a factor of 10 and repeat Step 3;
If w
2
(a da) < w
2
(a)
decrease l by a factor of 10
accept new parameters estimates a a da and repeat Step 2.
The algorithm thus performs two loops: the inner loop incrementing l until w
2
starts to
decrease and the outer loop calculating successively better approximations to the optimum
values of the parameters. The outer loop can be stopped when w
2
decreases by a negligible
absolute or relative amount.
Once the minimum is reached, the diagonal elements are an estimate of the un-
certainty in the tting parameters just as in the case of linear least squares:
s
2
aj
= a
1
jj
(186)
which is equal to (a
/
jj
)
1
providing the scaling factor l is much smaller than 1.
In Sec. X, a number of computer programs for linear and nonlinear least-squares
tting are given. Further information can be found in many textbook (Press et al., 1988).
The book by Bevington and Robinson (1992) contains a very clear and practical discus-
sion of the least-squares method.
X. COMPUTER IMPLEMENTATIONOF VARIOUS ALGORITHMS
In this section, a number of computer routines related to spectrum evaluation are listed.
The calculation routines are written in FORTRAN. Some example programs, calling this
FORTRAN routines, are written in C. The programs were tested using Microsoft FORTRAN
version 4.0A and C version 5.1. Most of the routines are written for clarity rather than
optimized for speed or minimum space requirement.
A. Smoothing
1. Savitskyand Golay Polynomial Smoothing
The subroutine SGSMTH calculates a smoothed spectrum using a second-degree poly-
nomial lter (see Sec. III.B.2).
SUBROUTINE SGSMTH (Y, S, NCHAN, ICH1, ICH2, IWID)
INTEGER*2 NCHAN, ICH1, ICH2, IWID
REAL*4 Y(0:NCHAN1), S(0:NCHAN1)
REAL C(20:20)
C -- Calculate filter coefficients
IW =MIN(IWID, 41)
M =IW=2
SUM =FLOAT( (2*M 71)*(2*M 1)*(2*M 3) )
DO 10 J =M, M
C(J) =FLOAT( 3*(3*M*M 3*M 71 75*J*J) )
10 CONTINUE
C -- Convolute spectrum with filter
JCH1 =MAX( ICH1, M )
JCH2 =MIN( ICH2, NCHAN 71 7M )
DO 30 I =JCH1, JCH2
S(I) =0.
Input: Y Original spectrum
NCHAN Number of channels in the spectrum
ICH1, ICH2 First and last channel number to be smoothed
IWID Width of the filter (2m1), IWID<42
Output S Smoothed spectrum, only defined between ICH1 and ICH2
DO 20 J = 7M, M
S(I) =S(I) C(J)*Y(I J)
20 CONTINUE
S(I) =S(I)=SUM
30 CONTINUE
RETURN
END
2. LowStatistics Digital Filter
The subroutine LOWSFIL smooths a spectrum using the low statistics digital lter algo-
rithm (see Sec. III.B.3).
SUBROUTINE LOWSFIL (Y, S, NCHAN, ICH1, ICH2, IFWHM)
INTEGER*2 NCHAN, ICH1, ICH2, IFWHM
REAL Y(0:NCHAN 71), S(0:NCHAN 71)
LOGICAL NOKSLOPE, STOOHIGH
REAL AFACT, FFACT, MFACT, RFACT
PARAMETER (AFACT =75., FFACT =1.5, MFACT =10., RFACT =1.3)
C -- Adjust smoothing region
IW =NINT( FFACT*IFWHM )
JCH1 =MAX(ICH1 7IW, IW)
JCH2 =MIN(ICH2 IW, NCHAN 71 7IW)
DO 100 I =JCH1, JCH2
IW =NINT( FFACT*IFWHM )
SUML =0.
SUMR =0.
DO 20 J =I 7IW, I 71
SUML =SUML Y(J)
20 CONTINUE
DO 30 J =I 1, I IW
SUMR =SUMR Y(J)
30 CONTINUE
C -- Adjust window
50 CONTINUE
SUMT =SUML Y(I) SUMR
IF( SUMT .GT. MFACT ) THEN
SLOPE =(SUMR 1.)=(SUML 1.)
NOKSLOPE =SLOPE.GT.RFACT .OR. SLOPE .LT. 1.=RFACT
STOOHIGH =SUMT .GT. AFACT*SQRT(Y(I))
IF( NOKSLOPE .OR. STOOHIGH .AND. IW .GT. 1 ) THEN
SUML =SUML 7Y(I 7IW)
SUMR =SUMR 7Y(I 7IW)
IW =IW 71
GOTO 50
Input: Y Original spectrum
NCHAN Number of channels
ICH1, ICH2 First and last channel to be smoothed
IFWHM FWHM in channels of a peak in the middle of the smoothing region
Output: S Smoothed spectrum, only defined between ICH1 and ICH2
ENDIF
ENDIF
C -- Smoothed value
S(I) =SUMT=FLOAT (2*IW 1)
100 CONTINUE
C -- Copy data points that could not be smoothed
DO 110 I =ICH1, JCH1 71
S(I) =Y(I)
110 CONTINUE
DO 120 I =JCH2 1, ICH2
S(I) =Y(I)
120 CONTINUE
RETURN
END
For each channel i in the spectrum, two windows, one on each side of the channel of width
f6FWHM(E
i
) channels are considered. In both windows, the channel contents are
summed, yielding a left sum L and a right sum R. Both windows are subsequently reduced
in width until either the total sum S = L y
i
R falls below some constant minimum M
or until two conditions are met:
1. S is less than a cuto value N = A

y
i
_
, with A a constant.
2. The slope (R 1)=(L 1) lies between 1=r and r, with r a constant.
The minimum constant M sets the base degree of smoothing in a region of vanishing
counts. The rst condition ensures that smoothing is conned to the low statistics region
of the spectrum; the second condition avoids the incorporation of the edges of the peaks in
the averaging.
When the above conditions are satised, the average S=(2f6FWHM1) is adopted
as a smoothed channel count. The following parameters were found to yield good results
when treating PIXE spectra: f =1.5, A=75, M=10, and r =1.3.
B. Peak Search
The subroutine LOCPEAKS locates peaks in a spectrum using positive part of tophyhat
lter (see Sec III.C).
SUBROUTINE LOCPEAKS (Y, NCHAN, IWID, R, IPOS, NPEAKS, MAXP)
INTEGER*2 NCHAN, IWID, NPEAKS, MAXP
INTEGER*2 IPOS (MAXP)
REAL Y (NCHAN), R
C - - Width of filter (number of channels in the top)
Input: Y Spectrum
R Peak search sensitivity factor, typical 2 to 4
IWID Width of the filter, approx. equal to the FWHM of the peaks
MAXP Maximum number of peaks to locate (size of array IPOS)
Output: NPEAK Number of peaks found
IPOS Peak positions (channel number)
C must be odd, and at least 3
NP =MAX (IWID=2)*2 1, 3)
NPEAKS =0
C -- Calculate half width and start and stop channel
N =NP=2
I1 =NP
I2 =NCHAN-NP
C -- Initialize running sums
I =I1
TOTAL =0.
TOP =0.
DO 20 K = 7N*2, NP
TOTAL =TOTAL Y(I1 K)
20 CONTINUE
DO 22 K = 7N, N
TOP =TOP Y(I1 K)
22 CONTINUE
C - - Loop over all channels
LASTPOS =0
SENS =R*R
FI =0.
FNEXT =0.
SNEXT =0.
DO 100 I =I1 1, I2
TOP =TOP 7 Y(I-N-1) Y(I N)
TOTAL =TOTAL 7Y(I-NP) Y(I NP)
FPREV =FI
FI =FNEXT
SI =SNEXT
FNEXT =TOP TOP 7TOTAL
SNEXT =TOTAL
C Significant?
IF( FI.GT.0. .AND. (FI*FI.GT.SENS*SI) ) THEN
C Find maximum
IF( FI .GT. FPREV .AND. FI .GT. FNEXT ) THEN
IF( FPREV.GT.0. .AND. FNEXT.GT.0. ) THEN
C and store (ch# is array index 1 and FI refers to I1)
NEWPOS =I2
IF( NEWPOS.GT.LASTPOS 2 ) THEN
NPEAKS =NPEAKS 1
IPOS(NPEAKS) =NEWPOS
LASTPOS =NEWPOS
IF( NPEAKS .EQ. MAXP ) RETURN
ENDIF
ENDIF
ENDIF
ENDIF
100 CONTINUE
RETURN
END
The routine is optimized for speed and requires no other arrays than the spectrum and a
table to store the peak maxima found. This is achieved by using a variant of the top-hat
lter; that is, for a lter width of 5, the coecients are 71, 71, 1, 1, 1, 1, 1,
71, 71, 71. The next point in the ltered spectrum can be calculated from the current
by subtracting and adding and only the value of the previous, the current, and the next
points in the ltered spectrum are retained. This makes the routine quite cryptic, but it
works very fast and is reliable.
C. ContinuumEstimation
1. Peak Stripping
The subroutine SNIPBG, a variant of the SNIP algorithm, calculates the continuum via peak
stripping (see Sec. IV.A).
SUBROUTINE SNIPBG (Y, YBACK, NCHAN, ICH1, ICH2, FWHM, NITER)
INTEGER*2 NCHAN, ICH1, ICH2, NITER
REAL*4 Y(0:NCHAN-1), YBACK(0:NCHAN-1), FWHM
PARAMETER (SQRT2 =1.4142, NREDUC =8)
C -- Smooth spectrum
IW =NINT (FWHM)
I1 =MAX (ICH1 7IW, 0)
I2 =MIN (ICH2 IW, NCHAN-1)
CALL SGSMTH (Y, YBACK, NCHAN, I1, I2, IW)
C -- Square root transformation over required spectrum region
DO 10 I =I1, I2
YBACK(I) =SQRT (MAX(YBACK(I), 0.))
10 CONTINUE
C -- Peak stripping
REDFAC =1.
DO 30 N =1, NITER
C.. Set width, reduce width for last NREDUC iterations
IF( N .GT. NITER-NREDUC ) REDFAC =REDFAC=SQRT2
IW =NINT (REDFAC*FWHM)
DO 20 I =ICH1, ICH2
I1 =MAX (I 7IW, 0)
I2 =MIN (I IW, NCHAN-1)
YBACK(I) =MIN(YBACK(I), 0.5* (YBACK(I1) YBACK(I2)))
20 CONTINUE
30 CONTINUE
C -- Back transformation
DO 40 I =ICH1, ICH2
YBACK(I) =YBACK(I)*YBACK(I)
INPUT: Y Spectrum
ICH1,ICH2 First and last channels of region to calculate the continuum
FWHM Width parameter for smoothing and stripping algorithm, set it
to average FWHM of peaks in the spectrum, typical value 8.0
NITER Number of iterations of SNIP algorithm, typical 24
Output: YBACK Calculated continuum in the region ICH1ICH2
Comment: Uses subroutine SGSMTH
40 CONTINUE
RETURN
END
2. Orthogonal Polynomial Continuum
The subroutine OPOLBAC ts the continuum of a pulse-height spectrum using an ortho-
gonal polynomial. Continuum channels are selected by adjusting the weight of the t (see
Sec. IV.C).
The routine calls ADJWEIG to adjust the weights. Further, the subroutine ORTPOL is
used to t the polynomial. The iteration (adjustment of weights) stops when all coefcients
c
j
change less than one standard deviation or when the maximum number of iterations is
reached.
SUBROUTINE OPOLBAC (NPTS, X, Y, W, YBACK, WORK1, WORK2,
> NDEGR, A, B, C, COLD, SC, FAILED, RCHISQ, R)
INTEGER NPTS, NDEGR
REAL*4 X(NPTS),Y(NPTS),W(NPTS),YBACK(NPTS)
REAL*4 WORK1 (NPTS), WORK2 (NPTS)
REAL*4 A (NDEGR), B(NDEGR), C(NDEGR), COLD(NDEGR), SC(NDEGR)
REAL*4 RCHISQ, R
LOGICAL*2 FAILED
PARAMETER (MAXADJ =20)
LOGICAL*2 NEXT
C -- Initialize
DO 10 J =1, NDEGR
COLD(J) =0.
10 CONTINUE
DO 20 I =1, NPTS
YBACK(I) =0.
20 CONTINUE
C -- Main iteration loop
DO 100 K =1, MAXADJ
C .. Calculate weights
CALL ADJWEIG (NPTS, Y, W, YBACK, R, NBPNTS)
Input: NPTS Number of data points (channels)
X Array of channel numbers
Y Array of spectrum
R Adjustable parameter [Eqs. (51) and (52)], typical value 2
Output: YBACK Array of fitted continuum
W Array of weights
A,B Coefficients of the orthogonal polynomial
C Fitted parameters of the orthogonal polynomial
SC Uncertainties of C
FAILED Logical variable TRUE if no convergence after MAXADJ weight
adjustments
RCHISQ Reduced chi-square value of the fitted continuum
Workspace: WORK1, WORK2 of size NPTS
C .. Fit orthogonal polynomial
CALL ORTPOL (NPTS, X, Y, W, YBACK, WORK1, WORK2,
> NDEGR, A, B, C, SC, SUMSQ)
RCHISQ =SUMSQ=FLOAT (NBPNTS 7NDEGR)
S =SQRT (RCHISQ)
C .. Test if further adjustments of weights is required
NEXT =.FALSE.
DO 30 J =1, NDEGR
SC(J) =S * SC(J)
IF( ABS(COLD(J)-C(J)) .GT. SC(J) ) NEXT =.TRUE.
COLD(J) =C(J)
30 CONTINUE
C .. convergence
IF( .NOT.NEXT ) THEN
FAILED =.FALSE.
RETURN
ENDIF
100 CONTINUE
C -- No convergence after MAXADJ iterations
FAILED =.TRUE.
RETURN
END
SUBROUTINE ADJWEIG (NPTS, Y, W, YFIT, R, NBPNTS)
C * * Adjust weights to emphasize the continuum
INTEGER NPTS, NBPNTS
REAL*4 Y(NPTS), W(NPTS), YFIT(NPTS), R
NBPNTS =0
C -- Loop over all data points
DO 10 I =1, NPTS
IF (YFIT(I) .GT. 0.) THEN
IF (Y(I).LE. YFIT(I) R*SQRT (YFIT(I))) THEN
C .. Point is considered as continuum
W(I) =1./YFIT(I)
NBPNTS =NBPNTS 1
ELSE
C .. Point is NOT considered as continuum.
W(I) =1./(Y(I) 7YFIT(I))**2
ENDIF
ELSE
C .. Continuum <=0, weight based original data
C (initial condition)
W(I) =1./MAX(Y(I),1.)
NBPNTS =NBPNTS 1
ENDIF
10 CONTINUE
RETURN
END
D. Filter-Fit method
The C program FILFIT is a test implementation of the lter-t method (see Sec. VI). This
program simply coordinates all input and output, allocates the required memory, and calls
two FORTRAN routines that do the actual work. The subroutine TOPHAT returns the
convolute of the spectrum with the top-hat lter or the weights (the inverse of the variance
of the ltered spectrum). The general-purpose subroutine LINREG is called to perform the
multiple linear least-squares t. The output includes the reduced w
2
value, the parameters
of the t a
j
(which is an estimate of the ratio of the intensity in the analyzed spectrum to
the intensity in the standard for the considered X-ray lines), and their standard deviation.
The routine GETSPEC reads the spectral data and must be supplied by the user.
#include <stdio.h>
#include <malloc.h>
#include <float.h>
#include <math.h>
void fortran TOPHAT( );
void fortran LINREG( );
float spec[2048];
main( )
{
int nchan, first_ch_fit, last_ch_fit, width, ierr;
int i, first_ch_ref, last_ch_ref, ref, num_ref, num_points;
int filter_mode =0, weight_mode =1, ioff;
float meas_time, ref_meas_time, *scale_fac;
float *x, *xp, *y, *w, *yfit, *a, *sa, chi;
double *beta, *alpha;
char filename [64];
// input width of tophat filter
scanf(%hd, &width);
// input spectrum to fit and fitting region
scanf(%s, filename);
scanf(%hd %hd, &first_ch_fit, &last_ch_fit);
nchan =Getspec(spec, filename, &meas_time);
num_points =last_ch_fit 7first_ch_fit 1;
// filter spectrum and store in y[ ]
y =(float *)calloc(num_points, sizeof(float));
TOPHAT(spec, y, &nchan, &first_ch_fit, &last_ch_fit, &width, &filter_mode);
//calculate weights of fit and save in w[ ]
w =(float *)calloc(num_points, sizeof(float));
TOPHAT(spec, w, &nchan, &first_ch_fit, &last_ch_fit, &width, &weight_mode);
//read reference spectra, filter and store in x[ ]
scanf(%hd, &num_ref);
scale_fac =(float *)calloc(num_ref, sizeof(float));
x =(float *)calloc(num_points*num_ref, sizeof(float));
for(ref =0; ref <num_ref; ref) {
scanf(%s, filename);
nchan =Getspec(spec, filename, &ref_meas_time);
scale_fac[ref] =ref_meas_time/meas_time;
scanf(%hd %hd, &first_ch_ref, &last_ch_ref);
if (first_ch_ref <first_ch_fit) first_ch_ref =first_ch_fit;
if(last_ch_ref >last_ch_fit) last_ch_ref =last_ch-fit;
ioff =ref*num_points first_ch_ref 7first_ch_fit;
xp =x ioff;
TOPHAT(spec, xp, &nchan, &first_ch_ref, &last_ch_ref, &width, &filter_mode);
}
// perform least squares fit
yfit =(float *)calloc(num_points, sizeof(float));
a =(float *)calloc(num_ref, sizeof(float));
sa =(float *)calloc(num_ref, sizeof(float));
beta =(double *)calloc(num_ref, sizeof(double));
alpha =(double *)calloc(num_ref* (num_ref 1)/2, sizeof(double));
LINREG (y,w,x &num_points, &num_ref, &num_points, &num_ref, yfit, a, sa, &chi,
&ierr, beta, alpha);
if( ierr = =0 ) {
printf(Filter fit: Chi-square =%f\n, chi);
printf(Standard Int. in analyse spectrum/Int. in standard\n);
for(i =0; i <num_ref; i )
printf( %hd %f n%f\n, i 1, a[i]*scale_fac[i], sa[i]*sacle_fac[i]);
for(i =0; i <num_points; i ){
printf(%4hd %7.0f %9.2f, first_ch_fit i, y[i],yfit[i]);
for (ref =0;ref <num_ref; ref )
printf(%7.0f, x[ref * num_points i]);
printf(\n);
}
}
}
SUBROUTINE TOPHAT (IN, OUT, NCHAN, IFRST, ILAST, IWIDTH, MODE)
INTEGER*2 NCHAN, IFRST, ILAST, IWIDTH, MODE
REAL*4 IN (NCHAN), OUT(1)
C ** Tophat filter of width IWIDTH, MODE =0 calculate filtered specturm,
C MODE ! =0 calculate weights (1/variance of filtered spectrum)
C - - Calculate filter constants.
IW =IWIDTH
IF(MOD(IW,2).EQ.0)IW =IW 1
FPOS =1./FLOAT(IW)
KPOS =IW/2
IV =IW/2
FNEG = 71./FLOAT(2*IV)
KNEG1 =IW/2 1
KNEG2 =IW/2 IV
N =0
C - - Loop over all requested channels.
DO 30 I =IFRST 1, ILAST 1
C . . Central positive part,
YPOS =0.
DO 10 K = 7KPOS, KPOS
IK =MIN(MAX(I K,1),NCHAN)
YPOS =YPOS IN(IK)
10 CONTINUE
C . . Left and right negative part,
YNEG =0.
DO 20 K =KNEG1, KNEG2
IK =MIN(MAX(I 7K,1),NCHAN)
YNEG =YNEG IN(IK)
IK =MIN(MAX(I K,1),NCHAN)
YNEG =YNEG IN(IK)
20 CONTINUE
N =N 1
IF(MODE.EQ.0) THEN
OUT(N) =FPOS * YPOS FNEG * YNEG
ELSE
VAR =FPOS*FPOS*YPOS FNEG*FNEG*YNEG
OUT(N) =1./MAX(VAR,1.)
ENDIF
30 CONTINUE
RETURN
END
E. Fitting Using Analytical Functions
The C program NLRFIT is an example implementation of the nonlinear spectrum tting
using an analytical function (see Sec. VII). The program only coordinates input and
output. The actual tting is done using the Marquardt algorithm with the FORTRAN
subroutine MARQFIT. The tting function consists of a polynomial continuum width NB
terms and NP Gaussians. The continuum parameters and the area, position, and with of
each Gaussian are optimized during the t. The tting function is calculated using the
routine FITFUNC. The derivatives of the tting function with respect to the parameters are
calculated by the routine DERFUNC.
// Program NLRFIT
#include <stdio.h>
#include <malloc.h>
#include <float.h>
#include <math.h>
#define MAX_PERKS 10
#define MAX_CHAN 1024
void fortran MARQFIT();
float spec [MAX_CHAN];
// Fortran common block structure COMMON/FITFUN/NB, NP
struct common_block {short NB, NP;};
extern struct common_block fortran FITFUN;
main( )
{
char specfile[64];
int nchan, first_ch_fit, last_ch_fit, nb, np;
int i, j, n, num_points, num_param, ierr, max_iter;
float ini_pos[MAX_PEAKS], ini_wid[MAX_PEAKS];
float *x, *xp, *y, *w, *yfit, *a, *sa, chi, lamda, crit_dif;
float *b, *beta, *deriv, *alpha;
double *work;
// Input of parameters and spectral data
scanf(%s, specfile);
scanf(%hd %hd %hd %f, &first_ch_fit, &last_ch_fit, &max_iter, &crit_dif);
scanf(%hd %hd, &np, &nb);
for(i =0; i <np; i )
scanf(%f %f, &ini_pos[i], &ini_wid[i]);
nchan =GetSpec(spec, specfile);
num_points =last_ch_fit 7first_ch_fit 1;
num_param =nb 3*np;
//Allocate memory for y[ ], w[ ], x[ ]
y =(float *)calloc(num_points, sizeof(float));
w =(float *)calloc(num_points, sizeof(float));
x =(float *)calloc(num_points, sizeof(float));
// Store independent variable (spectrum), weights and dep. var (channel #)
for(i =first_ch_fit, n =0; i < =last_ch_fit; i , n ) {
y[n] =spec[i];
w[n] =(spec[i] >0.) ? 1./spec[i] : 1.;
x[n] =(float)i;
}
// allocate memory for other arrays required
yfit =(float *)calloc(num_points, sizeof(float));
a =(float *)calloc(num_param, sizeof(float));
sa =(float *)calloc(num_param, sizeof(float));
b =(float *)calloc(num_param, sizeof(float));
beta =(float *)calloc(num_param, sizeof(float));
deriv =(float *)calloc(num_param, sizeof(float));
alpha =(float *)calloc(num_param*(num_param 1)/2, sizeof(float));
work =(double *)calloc(num_param*(num_param 1)/2, sizeof(double));
// initialize, all linear parameters to zero, peak position and width
// to their initial guesses
lamda =0.001;
for(i =0; i <np; i ){
a[nb np i] =ini_pos[i];
a[nb 2*np i] =ini_wid[i];
}
// perform least squares fit
FITFUN.NP =np;
FITFUN.NB =nb;
MARQFIT(&ierr, &chi, &lamda, &crit_dit, &max_iter, x, y, w, yfit, &num_points, a,
sa, &num_param, b, beta, deriv, alpha, work);
if( ierr = =0 ) {
printf(\nNon-linear fit: Chi-square =%f\n, chi);
printf(Polynomial continuum parameters\n);
for(i =0; i <nb; i )
printf(%hd %f n %f\n, i 1, a[i], sa[i]);
printf(Peak parameters Area Position Width\n);
for(i =0; i <np; i ){
printf(%hd %10.0f n % 710.0f, i 1, a[nb i], sa[nb i]);
printf(%10.3f n % 710.3f, a[nb np i], sa[nb np i]);
printf(%10.3f n % 710.3f\n, a[nb 2*np i], sa[nb 2*np i]);
}
for (i =0; i <num_points; i )
printf(%4hd %7.0f %9.2f\n, first_ch_fit i, y[i], yfit[i]);
}
}
SUBROUTINE FITFUNC(X, YFIT, NPTS, A, NTERMS )
REAL*4 X(NPTS), YFIT(NPTS), A(NTERMS)
COMMON /FITFUN/ NB, NP
C ** Fitting function, polynomial continuum and NP gaussians
C with position, width and area as parameters
PARAMETER(SQR2PI =2.50663)
C - - Loop over all channels
DO 100 I =1, NPTS
C . . continuum
YFIT(I) =A(1)
DO 20 J =2, NB
YFIT(I) YFIT(I) A(J) * X(I)**(J 71)
20 CONTINUE
C . . Peaks
DO 30 K =1, NP
AREA =A(NB K)
POS =A(NB NP K)
SWID =A(NB 2*NP K)
Z =((POS 7X(I))/SWID)**2
IF( Z.LT.50.) THEN
G =EXP( 7Z/2.)/SWID/SQR2PI
YFIT(I) =YFIT(I) AREA*G
ENDIF
30 CONTINUE
100 CONTINUE
RETURN
END
SUBROUTINE DERFUNC(X, NPTS, A, NTERMS, DERIV, I)
REAL*4 X(NPTS), A(NTERMS), DERIV(NTERMS)
COMMON/FITFUN/NB, NP
C ** Derivatives of fitting function: polynomial continuum and NP Gaussians
C with postion, width and area as parameters
PARAMETER (SQR2PI =2.50663)
C -- Derivatives of function with respect to the continuum parameters
DERIV(1) =1.
DO 10 J =2, NB
DERIV(J) =X(I)**(J 71)
10 CONTINUE
C -- Derivatives of function with respect to the peak parameters
DO 30 K =1, NP
AREA =A(NB K)
POS =A(NB NP K)
SWID =A(NB 2*NP K)
Z =((POS 7X(I))/SWID)**2
IF(Z.LT.50.) THEN
G =EXP( 7Z/2.)/SWID/SQR2PI
C . . Peak area
DERIV(NB K) =G
C . . Peak position
DERIV(NB NP K) = 7AREA*G*(POS 7X(I))/SWID/SWID
C . . Peak width
DERIV(NB 2*NP K) =AREA*G*(Z 71.)/SWID
ELSE
DERIV(NB K) =0.
DERIV(NB NP K) =0.
DERIV(NB 2*NP K) =0.
ENDIF
30 CONTINUE
RETURN
END
F. Monte Carlo Methods
1. UniformRandom-Number Generator
The function URAND is a FORTRAN function returning uniform distributed random
numbers in the interval 0 _U<0. The random-number generator is based on Knuths
subtractive method (Press et al., 1988) (see Sec. VIII. A)
REAL*4 FUNCTION URAND (ISEED)
INTEGER*2 ISEED
REAL*4 UTABLE(56)
REAL*4 UBIT, USEED
PARAMETER (UBIG =4000000., USEED =1618033.)
SAVE I1, I2, UTABLE, INIT
C -- Initialize table
IF (ISEED.LT.0 .OR. INIT.EQ.0) THEN
U =USEED FLOAT(ISEED)
U =MOD(U,UBIG)
UTABLE(55) =U
UTMP =1.
DO 10 I =1, 54
II =MOD(I*21, 55)
UTABLE(II) =UTMP
UTMP =U 7UTMP
IF(UTMP.LT.0.) UTMP =UTMP UBIG
U =UTABLE(II)
10 CONTINUE
DO 30 K =1, 4
DO 20 I =1, 55
UTABLE(I) =UTABLE(I) 7UTABLE(1 MOD(I 30,55))
IF(UTABLE(I).LT.0) UTABLE(I) =UTABLE(I) UBIG
20 CONTINUE
30 CONTINUE
I1 =0
I2 =31
ISEED =1
INIT =1
ENDIF
C -- Get next random number
I1 =I1 1
IF(I1.EQ.56) I1 =1
Input: ISEED Set to any negative number to initialize the random generator
Output: URAND Uniform random number in the interval 0 _URAND<1
I2 =I2 1
IF(I2.EQ.56) I2 =1
U =UTABLE(I1) 7UTABLE(I2)
IF(U.LT.0.)U =U UBIG
UTABLE(I1) =U
URAND =U/UBIG
RETURN
END
2. Normal Distributed RandomDeviate
The function NRAND returns normal distributed random number with zero mean and unit
variance, using the BoxMuller method (see Sec. VIII. B).
REAL*4 FUNCTION NRAND (ISEED)
INTEGER*2 ISEED
SAVE NEXT, FAC, V1, V2
IF (NEXT.EQ.0 .OR. ISEED.LT.0) THEN
10 CONTINUE
V1 =2. * URAND(ISEED) 71.
V2 =2. * URAND(ISEED) 71.
R =V1*V1 V2*V2
IF(R.G.E.1. .OR. R. EQ. 0.) GOTO 10
FAC =SQRT( 72. * LOG(R)/R)
NRAND =V1*FAC
NEXT =1
ELSE
NRAND =V2*FAC
NEXT =0
ENDIF
RETURN
END
3. Poisson Distributed RandomDeviate
The function PRAND can be used to produce approximately Poisson distributed random
deviates. For small numbers ( <20), the direct method is used; for larger numbers, the
Poisson distribution is approximated by the Normal distribution.
Input: ISEED Set to any negative number to initialize the random sequence
Output: NRAND Normal distributed random deviate with zero mean and unit
variance.
Input: Y (population) mean of deviate
ISEED Set to any negative number to initialize the random sequence
Output: PRAND Poisson distributed random deviate with mean Y
REAL *4 FUNCTION PRAND(Y, ISEED)
INTEGER*2 ISEED
REAL*4 Y
REAL*4 NRAND, URAND
IF(Y.LT.20.) THEN
C -- Use direct method
G =EXP( 7Y)
PRAND = 71.
T =1.
10 CONTINUE
PRAND =PRAND 1.
T =T * URAND(ISEED)
IF(T.GT.G) GOTO 10
ELSE
C -- Approximate by normal distribution
PRAND =Y SQRT(Y) * NRAND(ISEED)
ENDIF
RETURN
END
G. Least-Squares Procedures
1. Linear Regression
Subroutine LINREGis a general-purpose (multiple) linear regression routine (see Sec. IX. A).
SUBROUTINE LINREG (Y, W, X, N, M, NMAX, MMAX,
> YFIT, A, SA, CHI, IERR, BETA, ALPHA)
INTEGER*2 N, M, NMAX, MMAX, IERR
REAL*4 Y(N), W(N), YFIT(N), A(M), SA(M), CHI
REAL*4 X(NMAX, MMAX)
REAL*8 BETA(M), ALPHA(1)
c Accumulate BETA and ALPHA matrices
JK =0
DO 10 J =1, M
BETA(J) =0.0D0
DO 2 I =1, N
Input: Y Array of dependent variable
W Array of weights 1/s
2
i
)
X Matrix of independent variables
N Number of data points
M Number of independent variables (columns of X)
NMAX,MMAX Size of X matrix
Output: YFIT Array of fitted Y values
A Estimated least-squares parameters
SA Standard deviation of A
CHI Chi-square value
IERR Error condition, 1 if fit failed (singular matrix)
Workspace: BETA of size M
BETA(J) =BETA(J) W(I)*Y(I)*X(I, J)
2 CONTINUE
DO 6 K =1, J
JK =JK 1
ALPHA(JK) =0.0D0
DO 4 I =1, N
ALPHA(JK) =ALPHA(JK) W(I)*X(I,K)*X(I,J)
4 CONTINUE
6 CONTINUE
10 CONTINUE
c Invert ALPHA matrix
CALL LMINV (ALPHA, M, IERR)
IF(IERR .EQ. 71) THEN
RETURN
ENDIF
c Calculate fitting parameters A
DO 20 J =1, M
A(J) =0.
JJ =J*(J 71)/2
DO 12 K =1, J
JK =K JJ
A(J) =A(J) ALPHA(JK)*BETA(K)
12 CONTINUE
DO 14 K =J+1, m
JK =J K* (K 71)/2
A(J) =A(J) ALPHA(JK)*BETA(K)
14 CONTINUE
20 CONTINUE
c Calculate uncertainties in the parameters
DO 30 J =1, M
JJ =J*(J 1)/2
SA(J) =DSQRT(ALPHA(JJ))
30 CONTINUE
c Calculate fitted values and Chi-square
CHI =0.
DO 40 I =1, N
YFIT(I) =0.
DO 32 J =1, M
YFIT(I) =YFIT(I) A(J)*(I, J)
32 CONTINUE
CHI =CHI W(I)*(YFIT(I) 7Y(I))**2
40 CONTINUE
CHI =CHI/FLOAT(N 7M)
RETURN
END
2. Orthogonal Polynomial Regression
Subroutine ORTPOL ts an orthogonal polynomial to a set of data points [x
i
, y
i
, w
i
] (see
Sec. IX.B).
SUBROUTINE ORTPOL (NPTS, X, Y, W, YFIT, PJ, PJMIN, NDEGR, A, B, C, SC,
> SUMSQ)
INTEGER NPTS, NDEGR
REAL*4 X(NPTS), Y(NPTS), W(NPTS), YFIT(NPTS)
REAL*4 PJ(NPTS), PJMIN(NPTS)
REAL*4 A(NDEGR), B(NDEGR), C(NDEGR), SC(NDEGR), SUMSQ
C -- Initialize
DO 10 I =1, NPTS
PJ(I) =1.
PJMIN(I) =0.
YFIT(I) =0.
10 CONTINUE
GAMJMIN =1.
C -- Loop over all polynomial terms
DO 100 J =1, NDEGR
C .. Accumulate normalization factor, A and B constants for term j
GAMJ =0.
A(J) =0.
B(J) =0.
DO 20 I =1, NPTS
GAMJ =GAMJ W(I)*PJ(I)*PJ(I)
A(J) =A(J) W(I)*X(I)*PJ(I)*PJ(I)
B(J) =A(J) W(I)*X(I)*PJ(I)*PJMIN(I)
20 CONTINUE
A(J) =A(J) / GAMJ
B(J) =B(J) / GAMJMIN
C .. Least squares estimate of coefficient C
C(J) =0.
DO 30 I =1, NPTS
C(J) =C(J) W(I)*Y(I)*PJ(I)
30 CONTINUE
C(J) =C(J)=GAMJ
SC(J) =SQRT(1.=GAMJ)
C .. Contribution of this term to the fit
DO 40 I =1, NPTS
YFIT(I) =YFIT(I) C(J)*PJ(I)
40 CONTINUE
C .. Next polynomial term
IF (J .LT. NDEGR) THEN
Input: NPTS Number of data points
X Array of independent variable
Y Array of dependent variable
W Array of weights (w
i
=1s
2
i
)
NDEGR Degree of orthogonal polynomial to be fitted
Output: A, B Parameters of the orthogonal polynomials
C Fitted orthogonal polynomial coefficients
SC Standard deviation of C
SUMSQ Chi-square value
Workspace: PJ, PJMIN of size NPTS
DO 50 I =1, NPTS
PJPLUS =(X(I) 7A(J))*PJ(I) 7B(J)*PJMIN(I)
PJMIN(I) =PJ(I)
PJ(I) =PJPLUS
50 CONTINUE
GAMJMIN =GAMJ
ENDIF
100 CONTINUE
C -- Weighted sum of squares value
SUMSQ =0.
DO 110 I =1, NPTS
SUMSQ =SUMSQ W(I)*(Y(I) 7YFIT(I))**2
110 CONTINUE
RETURN
END
3. Nonlinear Regression
The subroutine MARQFIT performs nonlinear least-squares-tting according to the Mar-
quardt algorithm (see Sec. IX.C).
The routine requires two user-supplied subroutines: FITFUNC to evaluate the tting
function y(i) with the current set of parameters a and the DERFUNC to calculate the de-
rivatives of the tting function with respect to the parameters.
SUBROUTINE MARQFIT (IERR, CHISQR, FLAMDA, CRIDIF, MAXITER,
> X, Y, W, YFIT, NPTS, A, SA, NTERMS,
> B, BETA, DERIV, ALFA, ARR)
INTEGER*2 IERR, NPTS, NTERMS
REAL*4 CHISQR, FLAMDA, CRIDIF
REAL*4 X(NPTS), Y(NPTS), W(NPTS), YFIT(NPTS)
REAL*4 A(NTERMS), SA(NTERMS)
REAL*4 B(1), BETA(1), DERIV(1), ALFA(1)
REAL*8 ARR(1)
PARAMETER (FLAMMAX =1E4, FLAMMIN =1E 76)
Input: MAXITER Maximum number of iterations
X Array of independent variable
Y Array of dependent variable
W Array of weights (w
i
= 1=s
2
i
)
NPTS Number of data points
NTERMS Number of parameters
A Array of initial values of the parameters
Output: IERR Error status, 71 indicates failure of fit
CHISQR Reduced chi-square value
FLAMDA Marquardt control parameter
YFIT Array of fitted data points
A Least-squares estimate of the fitting parameters
SA Standard deviation of A
CRIDIF Minimum percent difference in two chi-square values
to stop the iteration
Workspace: B, BETA, DERIV of size NTERMS
ALFA, ARR of size NTERMS + (NTERMS 1)=1
C -- Evaluate the fitting function YFIT for the current parameters
C and save the Chi-square value
NITER =0
CALL FITFUNC(X, YFIT, NPTS, A, NTERMS)
CHISQR =CHIFIT(Y, YFIT, W, NPTS, NTERMS)
FLAMDA =0.
C -- Set ALFA and BETA to zero, save the current value of the parameters A
100 CONTINUE
NITER =NITER 1
CHISAV =CHISQR
DO 110 J =1, NTERMS
B(J) =A(J)
BETA(J) =0.
110 CONTINUE
DO 112 J =1, NTERMS*(NTERMS 1)=2
ALFA(J) =0.
112 CONTINUE
C -- Accumulate Alpha and Beta matrices
DO 120 I =1, NPTS
D =Y(I) 7YFIT(I)
C .. Calculate derivatives at point i
CALL DERFUNC (X, NPTS, A, NTERMS, DERIV, I)
DO 120 J =1, NTERMS
BETA(J) =BETA(J) W(I)*D*DERIV(J)
JJ =J*(J 71)=2
DO 120 K =1, J
JK =JJ K
ALFA(JK) =ALFA(JK) W(I)*DERIV(J)*DERIV(K)
120 CONTINUE
C -- Test and scale ALFA matrix
DO 140 J =1, NTERMS
JJ =J*(J 71)=2
JJJ =JJ J
IF(ALFA(JJJ) .LT. 1.E 720) THEN
DO 130 K =1, J
JK =JJ K
ALFA(JK) =0.
130 CONTINUE
ALFA (JJJ) =1.
BETA(J) =0.
ENDIF
SA(J) =SQRT (ALFA(JJJ))
140 CONTINUE
DO 160 J =1, NTERMS
JJ =J*(J 71)=2
DO 150 K =1, J
JK =JJ K
ALFA(JK) =ALFA(JK)=SA(J)=SA(K)
150 CONTINUE
160 CONTINUE
C -- Store ALFA in ARR, modify the diagonal elements with FLAMDA
200 CONTINUE
DO 210 J =1, NTERMS
JJ =J*(J 71)=2
DO 205 K =1, J
JK =JJ K
ARR (JK) =DBLE(ALFA(JK))
205 CONTINUE
JJJ =JJ J
ARR(JJJ) =DBLE(1. FLAMDA)
210 CONTINUE
C -- Invert matrix ARR
CALL LMINV (ARR, NTERMS, IERR)
IF (IERR .NE. 0) RETURN
C -- Calculate new values of parameters A
DO 220 J =1, NTERMS
DO 220 K =1, NTERMS
IF(K .GT. J) THEN
JK =J K*(K 71)=2
ELSE
JK =K J*(J 71)=2
ENDIF
A(J) =A(J) ARR(JK) = SA(J)*BETA(K) = SA(K)
220 CONTINUE
C -- Evaluate the fitting function YFIT for the new parameters and Chi-square
CALL FITFUNC(X, YFIT, NPTS, A, NTERMS)
CHISQR =CHIFIT(Y, YFIT, W, NPTS, NTERMS)
IF (NITER .EQ. 1) FLAMDA =0.001
C -- Test new parameter set
IF (CHISQR .GT. CHISAV) THEN
C .. Iteration NOT succesful, increase flamda and try again
FLAMDA =MIN(FLAMDA * 10., FLAMMAX)
DO 300 J =1, NTERMS
A(J) =B(J)
300 CONTINUE
GOTO 200
ENDIF
C .. Iteration succesful, decrease LAMDA
FLAMDA =MAX(FLAMDA=10., FLAMMIN)
C .. Get next better estimate if required
PERDIF =100.*(CHISAV 7CHISQR)=CHISQR
IF (NITER .LT. MAXITER .AND. PERDIF .GT. CRIDIF) GOTO 100
C -- Calculate standard deviations and return
DO 320 J =1, NTERMS
JJ =J*(J 2)=2
SDEV =DSQRT(ARR(JJ)) = SA(J)
SA(J) =SDEV
320 CONTINUE
RETURN
END
FUNCTION CHIFIT(Y, YFIT, W, NPTS, NTERMS)
REAL*4 Y(NPTS), YFIT(NPTS), W(NPTS)
C ** Evaluate chi-square
CHI =0.
DO 300 I =1, NPTS
CHI =CHI W(I) * (Y(I) 7YFIT(I))**2
300 CONTINUE
CHI =CHI = FLOAT(NPTS 7NTERMS)
CHIFIT =CHI
RETURN
END
4. Matrix Inversion
Subroutine LMINV is a general-purpose routine to invert a symmetric matrix.
SUBROUTINE LMINV ( ARR, N, IERR )
INTEGER*2 N, IERR
REAL*8 ARR(1)
REAL*8 DIN, WORK, DSUM, DPIV
INTEGER*2 I, IND, IPIV, J, K, KEND, KPIV, L, LANF,
> LEND, LHOR, LVER, MIN
KPIV =0
DO 10 K =1, N
KPIV =KPIV K
IND =KPIV
LEND =K 71
DO 4 I =K, N
DSUM =0.DO
IF (LEND .GT. 0) THEN
DO 2 L =1, LEND
DSUM =DSUM ARR(KPIV 7L) * ARR(IND 7L)
2 CONTINUE
ENDIF
DSUM =ARR(IND) 7DSUM
IF (I .EQ. K) THEN
IF (DSUM .LE. 0.D0) THEN
IERR = 71
RETURN
ENDIF
DPIV =DSQRT(DSUM)
ARR(KPIV) =DPIV
DPIV =1.D0 = DPIV
ELSE
ARR(IND) =DSUM * DPIV
ENDIF
IND =IND I
4 CONTINUE
10 CONTINUE
IERR =0
IPIV =N*(N 1)=2
Input: ARR Upper triangle and diagonal of real symmetric matrix stored in
linear array, size =N+(N1)=2.
N Order of matrix (number of columns)
Output: IERR Error status, IERR=0 inverse obtained, IERR=1 singular
matrix
IND =IPIV
DO 20 I =1, N
DIN =1.DO = ARR(IPIV)
ARR(IPIV) =DIN
MIN =N
KEND =I 71
LANF =N 7KEND
IF (KEND .GT. 0) THEN
J =IND
DO 14 K =1, KEND
WORK =0.D0
MIN =MIN 71
LHOR =IPIV
LVER =J
DO 12 L =LANF, MIN
LVER =LVER 1
LHOR =LHOR L
WORK =WORK ARR(LVER) * ARR(LHOR)
12 CONTINUE
ARR(J) = 7WORK * DIN
J =J 7MIN
14 CONTINUE
ENDIF
IPIV =IPIV 7MIN
IND =IND 71
20 CONTINUE
DO 30 I =1, N
IPIV =IPIV I
J =IPIV
DO 24 K =I, N
WORK =0.D0
LHOR =J
DO 22 L =K, N
LVER =LHOR K 7I
WORK =WORK ARR(LVER) * ARR(LHOR)
LHOR =LHOR L
22 CONTINUE
ARR(J) =WORK
J =J K
24 CONTINUE
30 CONTINUE
IERR =0
RETURN
END
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5
Quantication of Innitely Thick Specimens
by XRF Analysis
Johan L. de Vries*
Eindhoven, The Netherlands
Bruno A. R. Vrebos
Philips Analytical, Almelo, The Netherlands
I. INTRODUCTION
Quantitative x-ray uorescence (XRF) analysis involves the conversion of measured
uorescent intensities to the concentration of the analytes. In most of the literature on this
subject, the measured intensities at this stage of the analytical procedure are assumed to be
corrected for background and line overlap. The same assumptions will be made here,
although some comments will be made on these topics throughout this chapter. Fur-
thermore, energy-dispersive and wavelength-dispersive x-ray spectrometers dier sig-
nicantly with respect to the counting channel and the resolution or resolving power that
can be achieved. This has a direct inuence on, for example, the line overlap correction
procedures that need to be applied (if any) to obtain net intensities. Wavelength-dispersive
x-ray uorescence spectrometry has been discussed in Chapter 2; energy-dispersive systems
are the subject of Chapters 3 (for x-ray tube excitation) and 7 (for radioisotope excitation).
The software provided by the vendors of x-ray spectrometry systems for their customers
compensates to some extent for the peculiarities of each design and considerable dier-
ences in the software packages oered with the instruments are to be expected. It is
therefore dicult to give guidelines that are generally applicable.
In some cases, most notably those where the intensity of the background is essen-
tially constant (between specimens), the correction for background can be neglected. This
is usually the case when the dierence in terms of composition of the standard specimens
and the unknowns is rather small [i.e., the concentration ranges (not necessarily the
concentration levels) of all components are rather small]. This condition of similarity
between specimens is sucient to ensure constant background, but it is not a requirement,
as, in certain cases, the intensity of the background is (nearly) constant even when the
concentration range of one or more analytes is quite large. Note that the only requirement
*Retired.
here is for the background to be constant; at this point, no restrictions on the magnitude of
the background have been imposed. Under these circumstances, correction for back-
ground is not required and the gross count rate (or intensity) can be used with equal
success as the net intensity for the determination of the specimens composition.
The situation with line overlap is somewhat more complicated, as it is almost never
constant. This is due to the intensity of the overlapping line(s): It is very rarely a constant
for dierent specimens. There are several methods to correct for line overlap, and the
preference of the individual analyst as well as the type of spectrometer and its associated
software (if any) are some of the factors inuencing the nal choice.
The basic principles of quantitative analysis have not changed much since the early
years of x-ray uorescence analysis, especially for the wavelength-dispersive systems.
Energy-dispersive systems have seen more changes due to, for example, development of
dierent solid-state detectors and primary optics, such as capillaries (see Chapter 11), and
the increasingly more easily available computing power which allowed for more com-
prehensive spectral treatment programs at the ngertips of the analysts (see also
Chapter 4). In general, the method has always involved some calibration step, during
which the intensities of selected elements in a suite of standard specimens are measured
according to a scheme or a recipe that has been optimized earlier. These intensities are
combined with the composition of the standard specimens, and the calibration curves for
the elements of interest are then constructed. These calibration curves might include a
correction for matrix eects of some sort. The resulting calibrations could then be used for
the analysis of unknown specimens with compositions similar to the standards. This
method is rather time-consuming, but it yields, in general, the highest possible analytical
accuracy. Also, approximate knowledge of the composition of the specimens prior to the
analysis is assumed. Such assumptions can be made very implicitly (e.g., when selecting the
calibration curve to be used for analysis). If the method is routinely used and the number
of unknown specimens to be analyzed is rather large, the benets of this instrumental
technique become very clear, when compared to classical wet chemistry methods, which
tend to be much more time-consuming.
Since the second half of the 1980s, interest has been growing for a dierent kind of
quantitative analysis on wavelength-dispersive spectrometers, in which the elements pre-
sent in the specimens and their approximate concentration levels are not known prior to
the analysis. Semiquantitative analysis consists of an intimate combination of qualitative
and quantitative analyses. During the qualitative analysis, the presence of the elements
present in the specimen is established. This can be done in a variety of ways. Qualitative
analysis is based on the collection of a spectrum of the specimen, followed by peak search
and peak identication. Alternatively, the intensities of a rather large and xed set of
characteristic lines are collected. The lines are selected by the manufacturer and allow for
the determination of most of the commonly occurring elements. In both cases, the net
intensities are then determined and a quantication is made, involving matrix correction
and general calibration lines for each of the elements. These calibration lines have been
determined earlier from a set of standard specimens, although some manufacturers insist
on calling their method standardless. The packages that are available commercially
dier on the basis of the qualitative analysis (accumulating a spectrum or measurement on
xed wavelength positions), the number of standard specimens used, the exibility of the
spectrometer conguration that they can cope with, and the method used to correct for
matrix eect.
The focus of energy-dispersive systems has always been somewhat more qualitative
and more oriented toward research, exibility, and the analysis of small batches of
unknown specimens. The software allowed for quantitative analysis without the need to
have standards similar to the unknowns. These systems are thus more exible in their use
in that respect. This does not mean that such systems are unsuitable for routine analysis in
industry; many of them actually are used for that purpose.
In this chapter, several methods for the quantication of innitely thick specimens
are discussed. For all methods described here, it is assumed that the specimens are
innitely thick: The intensity of the radiation from the specimen is constant and is not
aected by increasing the thickness of the specimen. The analysis of specimens with less-
than-innite thickness is discussed in Chapter 6. Also, the specimens are assumed to be
homogeneous: Their composition is the same throughout the specimen. This assumption is
valid for a large range of material types found in many applications. The most important
exception are specimens with one or more thin coatings.
II. CORRELATIONBETWEENCOUNT RATE ANDSPECIMENCOMPOSITION
A. Introduction
In quantitative analysis, the measured x-ray uorescent intensity of a given element is
converted into its weight concentration in the specimen. As a rst approximation, one
would expect a linear relationship. Each atom of the analyte element i has the same
probability of being excited by the primary photons and emitting its characteristic photons
with wavelength l
i
. Indeed, if separate atoms or ions (e.g., in a gas or in a very diluted
solution) are considered, the following relation holds:
I
i
K
i
W
i
1
where I
i
is the measured intensity of the uorescent radiation of the analyte i and W
i
is the
weight fraction of the analyte i in the specimen.
The proportionality constant K
i
consists of many physical and instrumental factors
such as the following:
The intensity and the distribution of wavelengths of the photons in the primary beam
The probability that an atom i emits its characteristic radiation l
i
The probability that these photons l
i
pass through the measuring channel:
collimators, diracting crystal, pulse-height window
The probability that these photons are being detected and registered.
For a given instrument, the voltage and power on the x-ray tube remain constant for the
analyte i and they can be determined by measuring the uorescent intensity of the pure
element i. However, we are generally dealing with compact specimens where the atoms are
arranged into chemical compounds. Both the primary x-rays and the uorescent x-rays
will be absorbed by the dierent atoms in the specimen.
B. General Relationship Between Intensity and Concentration
1. Primary Fluorescenceby Monochromatic Radiation
First, excitation by monochromatic radiation will be considered. Let the intensity of the
incident beam with wavelength l
0
at the surface of the specimen be given by I
0
(l
0
). This
beam strikes the surface of the specimen at an angle c
0
(see also Fig. 1). A parallel beam is
assumed here and the specimen is considered to be extending to innity in all three
dimensions. The incident radiation is gradually absorbed by the specimen, and at a layer at
depth t below the surface, the remaining fraction of the intensity I
t
(l
0
) is given by the
LambertBeer law:
I
t
l
0
I
0
l
0
expm
s
l
0
r
s
t csc c
0
2
m
s
(l
0
) is the mass-attenuation coecient of the specimen for photons with wavelength l
0
(the subscript s refers to the specimen) and r
s
is the density of the specimen. Note that due
to the angle of incidence, the path length traveled is given by t csc c
0
. The mass-attenuation
coecient m
s
(l
0
) in this equation is thus calculated for the specimen; this is done by adding
the mass-attenuation coecients for all elements j present in the specimen, each multiplied
with its mass fraction W
j
:
m
s
l
0

X
n
j1
m
j
l
0
W
j
3
where n is the total number of elements present in the specimen. The fraction of the in-
cident beam absorbed by the analyte i in the layer between t and (t dt) is given by
W
i
m
i
l
0
r
s
csc c
0
dt 4
It is assumed here that the composition of the specimen is uniform throughout. In other
words, W
i
and W
j
are independent of the position of the layer (t, t dt) within the
specimen.
Only a fraction of the photons absorbed creates vacancies in the K shell; this fraction
is given by (r
iK
1),r
iK
, where r
iK
is the absorption jump ratio of the K shell of element i.
The fraction of K vacancies emitting x-rays is given by the uorescence yield o
iK
. The
fraction of Ka photons in the total of x-rays emitted for the analyte is given by the
transition probability f
iKa
. These factors can be combined in a factor designated Q
i
(l
0
, l
i
):
Q
i
l
0
. l
i
o
i
r
iK
1
r
iK
f
iKa
5
In the above derivation, it is assumed that the characteristic line of interest is a Ka. If
another line is considered, the relevant changes need to be made.
The characteristic photons thus generated are isotropically emitted in all directions,
without a preferential direction. Only a fraction is emitted toward the detector. If O is the
solid angle as viewed by the collimator detector system, expressed in steradians, then the
fraction is given by O,4p. The angle O should be small enough so that the beam can be
considered to be a parallel beam leaving the specimen at a single well-dened angle c
00
with the surface. The fraction of characteristic photons with wavelength l
i
not absorbed
between the layer (t, t dt) and the surface is given by
Figure 1 Schematic representation of the geometry involved in the calculation of primary
fluorescence emission.
expm
s
l
i
r
s
t csc c
00
6
All photons reaching the surface and propagating in the direction indicated by the
angle c
00
are assumed to be detected. If the detector has absorbing elements (such as
windows) or detection eciencies dierent from unity, then these can also be taken into
account. Also, the attenuation by the medium (e.g., air) between specimen and detector
can be calculated using similar expressions.
The intensity of element i, as excited by the incident beam with wavelength l
0
, is
labeled P
i
(l
0
) (explicitly denoting the primary uorescence eect) and is given by
P
i
l
0
I
0
l
0
expm
s
l
0
r
s
t csc c
0
m
i
l
0
W
i
Q
i
l
0
. l
i
r
s
cscc
0
dt
O
4p
expm
s
l
i
r
s
t csc c
00
7
Combining factors leads to
P
i
l
0
I
0
l
0
m
i
l
0
W
i
Q
i
l
0
. l
i
csc c
0
O
4p
expm
s
l
0
csc c
0
m
s
l
i
csc c
00
r
s
tr
s
dt 8
The contribution of all layers between the surface and the bottom of the specimen have to
be summed. This canbe done by integratingthe above expressionover dt, from0 (the surface)
to the bottom. In practice, for x-rays, the thickness of bulk specimens can be considered to
be innite, so the upper limit is 1. Note that t is always used in combination with r
s
, so the
integration will be done over r
s
t. Taking all constant factors outside the integral, one obtains
P
i
l
0
I
0
l
0
m
i
l
0
W
i
csc c
0
Q
i
l
0
. l
i
O
4p
Z
1
0
expm
s
l
0
csc c
0
m
s
l
i
csc c
00
r
s
tr
s
dt 9
From a textbook on calculus,
Z
1
0
expax dx
1
a
10
Taking a (m
s
(l
0
) csc c
0
m
s
(l
i
) csc c
00
) and noting that r
s
dt d(r
s
t), the following
expression is obtained for the primary uorescence of the analyte i in the specimen s:
P
i
l
0

I
0
l
0
m
i
l
0
W
i
csc c
0
Q
i
l
0
. l
i
O,4p
m
s
l
0
csc c
0
m
s
l
i
csc c
00
11
Often, the element specic factors, given by Eq. (5), are combined with the instrument
specic factor O,4p. This leads to a simpler expression for the primary uorescence:
P
i
l
0
K
i
I
0
l
0
m
i
l
0
m
s
l
0
Gm
s
l
i
W
i
12
where K
i
O,4pQ
i
l
0
. l
i
and G csc c
00
,csc c
0
sin c
0
, sin c
00
.
In the above derivation, the following assumptions have been made:
(a) The specimen is completely homogeneous.
(b) The specimen extends to innity in three dimensions.
(c) The primary rays are not scattered on their way to the layer dt.
(d) No enhancement eects occur.
(e) The characteristic radiation is not scattered on its way to the specimen surface.
The simplest case is excitation of Ka (or Kb) photons. For the characteristic photons
associated with the L lines, other eects, such as CosterKronig transitions and so forth
have to be taken into account when describing the fraction of absorbed primary photons
that give rise to characteristic photons. For a more detailed discussion on these eects,
refer to Chapter 1.
2. Secondary Fluorescence Excitedby Monochromatic Radiation
Under certain conditions, the characteristic photons of an element j can excite atoms of
the analyte i. This will lead to additional characteristic photons of element i. The term
additional is used here in the sense that these photons are not considered in the above
derivation for the primary uorescence and, consequently, are not predicted by Eq. (12). It
is beyond the scope of this chapter to derive the mathematical expressions following a
rigorous approach, but certain aspects of secondary uorescence emission are readily seen
from the above derivation and from Figure 2. In Figure 2, two layers are now considered.
The layer on the left, indicated by j, at a depth of t
1
with a thickness of dt
1
, is where the
primary uorescence of element j is excited. This is described by Eqs. (2)(5). Obviously,
the element considered at this stage is the enhancing element j, so the fundamental
parameters for j need to be used instead of these for i in Eqs. (2)(5). Once the uorescent
radiation is created, it will be absorbed on its way through the specimen. The precise
direction is of no concern, as we are now no longer considering the fraction that travels
toward the detector. The attenuation along its path is described by equations such as
Eq. (2) or Eq. (6). Keep in mind that the angles and the distances involved are now dif-
ferent and that the wavelength l for which the mass attenuation needs to be calculated
[Eq. (3)] is now l
j
instead of l
0
. At the second layer, indicated by i, at a depth of t
2
with a
thickness of dt
2
, part of this (primary uorescence) radiation will be absorbed. Again, this
eect is described by an equation such as Eq. (4), with the angle c
0
replaced by the angle of
this path. The factors to be applied in order to lead to characteristic radiation of the
analyte i are given by Q
i
(l
j
, l
i
); Eq. (6) describes the attenuation (wavelength is now l
i
) on
the way toward the detector. These factors can easily be recalculated. The complication is
in the description of the geometry, especially in the description of the distance betwee
n
the
two layers: The position of the two layers relative to one another is not restricted, the path
of the photon l
j
does not have to be in the plane of the gure, nor is the second layer
Figure 2 Schematic representation of the geometry involved in the calculation of secondary
fluorescence emission.
always at a larger depth than the rst layer. The angle X
0
in Figure 2 can take any value
between 0 and 2p, and the three paths shown are not necessarily in one plane. This aspect
has been discussed by Li-Xing (1984).
Anyway, after integration, the nal result S
ij
l
0
. l
j
is given by
S
ij
l
0
. l
j

I
0
l
0
csc c
0
m
j
l
0
W
j
Q
j
l
0
. l
j
m
i
l
j
W
i
Q
i
l
j
. l
i
O,4p
2m
s
l
0
csc c
0
m
s
l
i
csc c
00
sin c
0
m
s
l
0
ln 1
m
s
l
0
m
s
l
j
sin c
0
!
sin c
00
m
s
l
j
ln 1
m
s
l
j
m
s
l
j
sin c
00
!
13
where S
ij
l
0
. l
j
describes the secondary uorescence (enhancement) of the analyte i by
characteristic photons with wavelength l
j
; these photons have been excited by primary
photons with wavelength l
0
.
The photons to be considered for the enhancement of the analyte are not limited to
Ka only, as the Kb lines and other characteristic lines that have sucient energy to excite
the shell of interest of the analyte i must also be taken into account. For this reason, all
individual contributions need to be added in order to calculate the total enhancement of
the analyte i by element j:
S
ij
l
0

X
i
S
ij
l
0
. l
j
14
There are two criteria to be satised for a characteristic photon l
j
to be able to cause
secondary uorescence:
1. It must be excited by the incident photon l
0
(this means that the energy of the
incident photon must be higher than the energy of the absorption edge
associated with l
j
).
2. The energy of the photon l
j
must be higher than the energy of the absorption
edge for the analyte.
The derivation of the intensities of characteristic x-rays as a function of specimen
composition has rst been done by Sherman (1955). The resulting equations, however,
were rather unwieldy. Equations (9) and (13) have been published later by Shiraiwa and
Fujino (1966) and Sparks (1976).
In practice, many computer programs only consider a few lines for enhancement,
and lines that have a low transition probability f are usually neglected. Data regarding
these transition probabilities for a line within a series can be found, for example, in
Appendix II of Chapter 1. The enhancement phenomenon will be more pronounced if the
x-rays of the enhancing elements are only slightly more energetic than the energy of the
absorption edge of the element i. The enhancement may contribute up to 4050% of
the total uorescent radiation I
i
, especially where the concentration of the enhancing
elements is much greater than the concentration of the analyte. This applies even more for
the light elements, where the primary spectrum may not be very eective as the most
intense wavelengths are far away from the absorption edges of these light elements.
The eect of scattered radiation is generally ignored, although its contribution can
also be calculated (Pollai et al., 1971).
If the characteristic line of the analyte considered is one of its L lines, then it is
possible that other lines of the analyte itself enhance the characteristic line considered. The
energy of the K edge of La (atomic number Z57) is 38.9 keV (see Chapter 1), so the K
lines of all elements with Z<57 are excited if, for example, an x-ray tube is used at
voltages above 40 keV, as is commonly the case with wavelength-dispersive spectrometers.
Under these conditions, the L lines of these elements are enhanced by the K lines. The
situation for elements with high atomic numbers is more complex. Let us consider Pb
(Z82). Lead is very often determined through its La
1
or Lb
1
line because the K lines of
Pb are too energetic to be measured with reasonable eciency by scintillation or Si(Li)
detectors. Also, excitation voltages higher than 88 keV are required in order to excite the K
lines. Thus, one would not readily expect enhancement by Pb on its own L lines. From the
data in Table 1, however, it follows that the PbLa
1
line (L
3
M
5
) is enhanced by PbLg
1
(L
2
N
4
) because its energy (14.76 keV) is higher than the energy of the L
3
edge (13.04 keV).
The total excited characteristic intensity is then given by adding the primary and the
secondary uorescence contributions:
I
i
l
0
P
i
l
0

X
j
S
ij
l
0
. l
j
15
Also, tertiary uorescence is possible, where the incident photon excites element k (pri-
mary uorescence), whose radiation excites element j (secondary uorescence), whose
radiation, in turn, excites element i, causing tertiary uorescence. This contribution is
generally lower than 3% of the total uorescence and is commonly ignored, as shown by
Shiraiwa and Fujino (1967, 1974).
3. Excitationby Continuous Spectra
If the incident beam is polychromatic rather than monochromatic, Eq. (15) needs to be
calculated for each wavelength. Wavelengths longer than the wavelength of the absorption
edge l
edge,i
of the analyte cannot excite uorescence, so these need not to be considered. If
Jl is the function representing the tube spectrum, then Eqs. (11) and (13) can still be
used, provided that I
0
l
0
is replaced by Jl, representing the intensity of the incident
spectrum at wavelength l:
I
i

Z
l
edge. i
l
min
I
i
Jl dl
Z
l
edge. i
l
min
P
i
l
X
j
S
ij
l. l
j
" #
dl 16
This equation allows the calculation of the intensity of characteristic radiation of a given
analyte in an innitely thick specimen. Equations such as Eqs. (11), (14), and (16) are often
referred to as fundamental parameter equations because they allow the calculation of the
intensity of uorescent radiation as a function of the composition of the specimen (weight
fractions W
i
), the incident spectrum [Jl], and the conguration of the spectrometer used
(c
0
. c
00
, and O). All other variables used are fundamental constants, such as the mass-at-
tenuation coecients for a given element at a given wavelength or its uorescence yield
and so forth.
Table1 Data for Selected Absorption Edges and Characteristic Line of Pb
Absorption edge Energy (keV) Characteristic line Energy (keV)
K 88.04
L
1
15.86 La
1
(L
3
M
5
) 10.55
L
2
15.20 Lb
1
(L
2
M
4
) 12.61
L
3
13.04 Lg
1
(L
2
N
4
) 14.76
Source: Appendix I and Appendix II of Chapter 1 (this volume).
C. Some Observations
The integration over t in Eq. (9) is taken from zero to innity. It is obvious that the rst
layers contribute more to the intensity of l
i
than the more inward layers. Theoretically,
even at large values of t, a very minor contribution to the intensity is still to be expected.
Often, the (minimum) innite depth is dened arbitrarily as that thickness t where the
contribution of the layer t. t dt is 0.01% of that of the surface layer. In this case, it is
dened relative to the surface layer. Alternatively, it is dened as the thickness where the
contribution to the total intensity is less than 1%. In this case, it is relative to the total
intensity from a truly innitely thick specimen. The value of the innite thickness de-
pends on the value of the absorption coecients and the density of the specimen. In
practice, it may vary from a few micrometers for heavy matrices and long wavelengths to
centimeters for short wavelengths and light matrices, as in solutions.
For a given element and a xed geometry, an eciency factor Cl
0
. l
i
can be in-
troduced:
Cl
0
. l
i

m
i
l
0
P
n
j1
W
j
m
j
l
0
G
P
n
j1
W
j
m
j
l
i
17
It is obvious that the terms
P
W
j
m
j
are the origin of nonlinear calibration lines, as
variations in W
j
inuence the value of the denominator. For a pure metal, this reduces to
Cl
0
. l
i

m
i
l
0
m
i
l
0
Gm
i
l
i
18
In the general case, the wavelengths in the primary spectrum close to the absorption
edge are the most eective in exciting the analyte i. The eciency factor Cl
0
. l
i
is thus a
combination of the absorption curve of analyte i as a function of l and the spectral dis-
tribution. In a rst approximation, an eective wavelength l
e
can be introduced, which
has the same eect of excitation of element i as the total primary spectrum. The exact value
of this l
e
will be inuenced by the characteristic tube lines if they are active in exciting i.
Otherwise, l
e
can, in general, be assumed to have a value of approximately two-thirds of
the absorption edge l
edge
. Its actual value is, however, dependent on the chemical com-
position of the specimen. For instance, for Fe, the wavelength of the K edge l
edge
is
0.174 nm (7.11 keV) and an eective wavelength l
e
of 0.116 nm is obtained using this rule
of thumb. In the ZnOFe
2
O
3
system, l
e
was found to vary from 0.130 nm for 100% Fe
2
O
3
to 0.119 nm for 10% Fe
2
O
3
in ZnO. The estimated value of 0.116 nm is in good agreement
with the experimental one for Fe
2
O
3
.
Another interesting case is the analysis of a heavy element i in a light matrix. In
the summation in the denominator of Eq. (12), the terms W
i
m
i
l
0
and W
i
m
i
l
i
are
then the most important. The other terms can, in rst approximation, be neglected if
W
i
is not small. However, that means that the terms W
i
in the numerator and the
denominator cancel and the measured intensity becomes independent of W
i
; thus, the
analysis becomes impossible in this extreme case. A solution to this problem is found
by making the inuence of the terms W
i
m
i
l in the denominator less dominating by
adding a large term W
a
m
a
l. This can be done be making W
a
large (e.g., diluting) or
m
a
l large, by adding heavy absorber. Equation (17) enables one to calculate before-
hand how large this term should be to eliminate uctuations in the concentration of the
other elements.
In the derivation of the uorescence of the analyte i in the preceding paragraphs, the
following simplications were made:
1. First, it was assumed that the primary rays follow a linear path to the layer dt at
depth t. However, the primary rays may also be scattered. In general, the loss in
intensity of the primary beam of photons due to scattering may be neglected.
These scattering eects become more important when the primary x-rays are
more energetic and the average atomic number of the matrix decreases. This
scatter may give a higher background in the secondary spectrum, thus leading to
a poorer precision of the analysis. On the other hand, the excitation eciency
may be enhanced, as the primary rays dwell longer in the active layers, thus
having a higher probability to encounter atoms of element i. This eect may
overrule the increase in intensity of the background radiation. A case in hand is
the determination of Sn in oils which gives better results using the SnK lines at a
high x-ray tube voltage, than using the SnL lines at moderate voltages.
Incidentally, this scattering of the primary radiation makes it possible to check
the voltage over the x-ray tube. According to Braggs law, the intensity of the
primary spectrum is zero at an angle y
0
, given by
y
0
sin
1
nl
min
2d
crystal

19
where 2d
crystal
is the 2d spacing of the crystal used and n is an integer number.
l
min
(in nm) is given by
l
min

1.24
V
20
where V is the voltage on the x-ray tube, expressed in kilovolts. In practice, a
lower value for V will be found when Compton scattering dominates over
Rayleigh scattering and thus l
min
found has a value too low by the Compton
shift, which is about 0.024 nm for most spectrometers; the actual value depends
on the incidence and exit angle (see also Sec. V.C.1.)
2. The integral in Eq. (9) was taken from zero to innity; further, it was assumed
that the specimen is completely homogeneous. This, of course, is never realized
in practice, as we are dealing with discrete atoms in chemical compounds. In
powders, the dierent compounds may have a tendency to cluster. The particles
will, in general, have dierent sizes and shapes. Putting the sample into solution,
either aqueous or solid (melt) may overcome this problem.
It was stated formerly that innite thickness may vary from 20 mm to a few cen-
timeters. However, the most eective layers are much thinner. Thus, the number of dis-
crete particles actually contributing to the uorescent radiation may be rather small.
III. FACTORS INFLUENCINGTHE ACCURACYOF THE INTENSITY
MEASUREMENT
A. Introduction
The total uncertainty of the analysis consist of many errors whose source may be the
following:
The measurement of the intensity
The reproducibility of the specimen preparation
The conversion of intensity into concentration
The uncertainty of a single determination may be found from n determinations of the same
analysis, given a mean result x
mean
, of the all individual results x
i
. If n is suciently large,
the standard deviation s may be found from
s
P
n
i1
x
i
x
mean
2
n 1
s
21
In this total standard deviation s, random and systematic uncertainties are combined.
Random uncertainties give an indication of the precision of an analysis (the scatter of
results around the mean value), whereas systematic errors are the reason for deviations of
the mean value from the true value. An analysis may thus be precise, but not very
accurate, if systematic errors are present, whereas accurate values could be found from the
mean of widely scattered measurements if only large random uncertainties were present.
The total error of a measurement is composed of all the separate errors. If only random
errors s
1
, s
2
, and so forth are considered, the resulting standard deviation is given by
s
2
s
2
1
s
2
2
s
2
3
s
2
n
22
where s
1
, s
2
, and so on are the errors associated with, for example, intensity measurements,
specimen preparation, instrumental settings, and so on. In practice, it is often found that s
is dependent on the concentration of the analyte W
i
(Johnson, 1967; Hughes and Hurley,
1987):
s K
W
i
W
b
p
23
where W
b
is a small concentration oset (typically 0.001 in weight fraction). Thus, K,
rather than s, becomes an indication of the accuracy of the determination.
B. RandomErrors
1. Counting Statistics
If an x-ray measurement consisting of the determination of a number of counts N is re-
peated n times the results N
1
,N
2
, N
3
, . . . ,N
n
would spread about the true value N
0
. If n is
large, the distribution of the measurements would follow a Gaussian distribution,
WN
1
2pN
p exp
NN
0
2
2N
" #
24
provided N is also large. The standard deviation s of the distribution is equal to
N
mean
p
,
again if n and N are large, where N
mean
is the mean of n determinations. From the
properties of the Gaussian distribution, the following hold:
68.3% of all values N will be between N
0
s and N
0
s.
0
2s and N
0
2s.
0
3s and N
0
3s.
Similarly, there is a certain probability that the true result N
0
will lie between N
N
p
and N
N
p
, assuming the same distribution for N and N
0
. Measurement results are
commonly expressed as a count rate (intensity per unit time) instead of an intensity,
which gives the number of counts collected in the counting interval. This allows an easier
comparison of measurements made with dierent counting times, but the measuring
time needs to be specied in order to be able to assess the counting statistical error.
The determined concentration is dependent on the net count rate, which is the peak
count rate R
p
minus the background count rate R
b
. The total measuring time T equals
t
p
t
b
, where t
p
and t
b
are the measurement times for peak and background, respec-
tively. In modern equipment, there is no signicant statistical error in the measurement
of t. We can thus assume that R follows the same Gaussian distribution as N with the
same relative standard deviation e
N
. e
N
is dened as
e
N

s
N
N
25
Hence,
e
N

N
p
N

1
N
p
1
R
p
t
p e
R
26
and
s
R
e
R
R
R
p
t
p 27
It is obvious that the relative counting error decreases as t increases.
When a net count rate has to be determined the peak, R
p
and the background, R
b
,
have to be measured; there are thus two independent variables. The standard deviation of
the net intensity, s
d
, is given by
s
d

s
2
p
s
2
b
q

R
p
t
p
R
b
t
b
s
28
and the relative standard deviation e
d
by
e
d

R
p
,t
p
R
b
,t
b
p
R
p
R
b
29
When using a sequential wavelength-dispersive x-ray uorescence spectrometer and when
the count rates are rather low and time is limited, it is of interest to divide the total
counting time available over t
p
and t
b
in the best possible way. In principle, there are three
methods to split up the total counting time T:
1. Fixed time. Peak and background are measured for the same time;
t
p
t
b
T,2. The resulting standard deviation in the dierence between the
peak and the background count rate is then given by
s
d

2
T
r

R
p
R
b
q
30
2. Fixed count. The same number of counts, N, is collected on the peak and on the
background: N
p
N
b
or
t
p
t
b
R
b
R
p
31
The resulting standard deviation for the dierence is given by
s
d

1
T
r

R
p
R
b
R
p
R
b
R
b
R
p
s
32
3. Fixed time optimal. The optimum division of the total measurement time T over
t
p
and t
b
can be found by dierentiating Eq. (29) with respect to t
p
, where t
b
Tt
p
. It is found that for optimal results, the ratio of the measuring times is
t
p
t
b
R
b
R
p
s
33
The resulting standard deviation is given by
s
d

1
T
r

R
p
p

R
b
p
34
and the relative standard deviation by
e
d

1
T
p
1
R
p
p

R
b
p 35
It can easily be demonstrated that
s
FTO
s
FT
s
FC
36
where s
FTO
refers to the method of xed time optimized, s
FT
is for xed time, and s
FC
is
for xed counts. When R
p
is very large compared with R
b
, s
FTO
is close to s
FT
. Thus, the
xed time method is often used in practice because R
p
and R
b
are not known beforehand.
If there is a great dierence between peak and background count rate, then usually all the
available time is spend counting the peak. Thus, the background is not measured. A
constant value for the background can be assumed or it can be ignored altogether.
Compared with method of xed time, the following observation can be made: If, R
b
is not
measured, the standard deviation in the net count rate (calculated as the dierence
between R
p
and R
b
) is given by
s
d

R
p
T
s
2
b
r
37
This approximation is allowed if this value is smaller than
2,T
p
R
p
R
b
p
. This is the
case if s
b
5
R
b
,T
p
. This applies if the background is more or less constant between
specimens and a xed value for the background can be deducted. If the background is
altogether ignored, s
b
R
b
. This is only allowed when R
b
is much smaller than
R
p
,T
p
.
It follows that when one aims for optimum instrumental conditions, the expression
R
p
p

R
b
p
is a good quality function. This parameter is often used as a gure of merit
(FOM). Obviously, the highest value of
R
p
p

R
b
p
gives the best result. When it can be
assumed that
R
p
p

R
b
p
approximates R
p
, for low intensities and high background,
optimizing this term, equals optimizing
M
R
b
p 38
where M (the slope of the calibration line in counts per second per percent) is proportional
to R
p
R
b
.
If the ratio of two count rates R
1
and R
2
has to be determined, the methods of xed
time and xed count give the same result, whereas the method of optimum division, where
t
1
t
2
R
2
R
1
r
39
always gives the best result.
The total counting uncertainty is the combination of instrumental error and
counting statistics. When the count rate is very high, the counting uncertainty is small and
it may be worthwhile to apply a ratio method to reduce possible instrumental un-
certainties. However, if the count rate is low, it is better to spend all the available time in
analyzing the specimen to reduce the counting error.
2. Instrumental Errors
If the instrumental and counting uncertainties are random and independent variables, then
e
tot

e
2
instr
e
2
count
q
40
e
instr

e
2
tot
e
2
count
q
41
Although the counting error is inuenced by the instrumental error, Eq. (41) is still a good
approximation. s
tot
can be found from a series of repeated results of one measurement;
thus, s
count
is known. To check the instrumental instability, all the functions should be
measured separately. A radioactive source
55
Fe, for example, can be used to check the
detector and electronic circuitry. The x-ray tube can be checked by repeating the mea-
surements with specimen and goniometer in a xed position, eliminating errors stemming
from the mechanics of the spectrometer.
In another series of experiments, recycling between dierent angles checks the re-
producibility of the goniometer, whereas repositioning the specimen between measure-
ments checks the specimen holder, the reproducibility of the specimen loading mechanics,
and so forth. A comprehensive series of tests for wavelength-dispersive x-ray uorescence
spectrometers is described in the Australian Standard 2563-1982 (1982). Sometimes the
error s
tot
found is smaller than expected, or even smaller than s
count
. This may indicate that
an unexpected systematic error is involved, or there may be an uncorrected deadtime in the
equipments, (i.e., the true counting rate is higher than measured, which means that the
relative error is smaller).
3. Detection Limit
A characteristic line intensity decreases with decreasing concentration of the analyte and
nally disappears in the background noise. The true background intensity may be con-
stant, but the results of the measurements uctuate around a mean value R
bmean
. To be
signicantly dierent from the background, a signal R
p
must, although it is larger than
R
bmean
, be distinguished from the spread in R
b
. In other words, if we measure a signal R
p
larger than R
b
and we assume the analyte is present, what is the probability that our
assumption is correct? If the results of the measurements are random and follow a
Gaussian distribution, then this probability is determined by s
Rb
. If the measurement R
p
is
higher than R
b
2s
Rb
, then the probability that our assumption is correct is approxi-
mately 95% if a higher certainty is required (e.g., 99.7%), then R
p
should be larger than
R
b
3s
Rb
. Thus, the net intensity is 3s
Rb
and the detection limit, DL, would be
DL
3s
Rb
M
42
where M is the sensitivity in counts per second per percent. So, the detection limit in the
above equation is the concentration corresponding to a net peak intensity of 3s
Rb
.
However, in x-ray spectrometry, the background signal is specimen dependent and cannot
be measured independently, as in radioactivity measurements. Hence, R
b
has to be mea-
sured in an o-peak location in the spectrum. The result R
b
found in measuring time t s is
assumed to be R
bmean
and s
Rb
is assumed to be
R
b
,t
p
. Thus, two measurements have to
be made: R
p
and R
b
, each in time t s. The detection limit thus becomes
DL
3
2
p
M
R
b
T
r
43
where T 2t. If we are satised with a 95% probability that our assumption is correct,
then
DL
2
2
p
M
R
b
T
r
44
which is roughly equal to
DL
3
M
R
b
T
r
45
It is obvious that the detection limit decreases if the counting time increases. However, the
total error in R
b
contains the instrumental error as well. Thus, there is no sense to increase
the counting time when the instrumental error dominates.
Ingham and Vrebos (1994) have shown that the detection limit can be improved by
carefully selecting a primary lter. If the application of such a primary beam lter re-
duces the intensity of the (scattered) continuum from the tube more than it aects the
sensitivity, the detection limit is improved. The loss in sensitivity M needs to be more
than compensated for by the reduction in background intensity; as from Eq. (45), the
detection limit is proportional to the square root of R
b
and inversely proportional to the
sensitivity M.
4. Variationin X-ray Spectrum
The uorescent intensity of the analyte I
i
is, in rst approximation, dependent on the
primary spectrum according to
I
i
KiV
0
V
c
p
46
where K is a constant, i is the current of the x-ray tube, V
0
is the working voltage, V
c
the
excitation voltage, and p varies between 1 and 2, depending on the ratio of excitation by
characteristic tube rays and white continuum. In modern instruments, the tube voltage is
not dependent on the mains cycle, but they run on constant potential, which still may
uctuate. If the working voltage V
0
, or the region or line of highest excitation probability
is rather close to V
c
, then small uctuations in V
0
will introduce a considerable error in I
i
.
For instance, if V
0
1.5 V
c
, then a 1% error in V
0
gives an error in I
i
of 6% when p 2.
It is therefore better to run the tube at three to ve times the excitation voltage of
the analyte. A too high voltage, however, might introduce an unproportionally high
background.
5. Other Instrument Errors
Other possible random instrumental errors include positioning the specimen and setting
the goniometer in wavelength-dispersive x-ray spectrometers. These errors have to be
checked by repeated measurements of one specimen in a systematic way:
Repeated counting with stationary specimen and goniometer
Repeated counting with stationary specimen and repositioning goniometer
Repeated counting with stationary goniometer and repositioning specimen
Repeated counting with stationary goniometer and reloading specimen holder.
Some diracting crystals have a rather high coecient of thermal expansion;
therefore, their d value may uctuate with uctuations in temperature. This results in a
setting of the goniometer, slightly o-peak, which introduces a change in measured in-
tensity. Therefore, most modern equipment are operating at a stabilized temperature.
6. Particle Statistics
Only a limited volume of the specimen can actually contribute to the uorescent radiation.
As long as this active volume is the same in standards and actual specimens and the atomic
distribution is completely homogeneous, this poses no problem. However, the atoms are
bound into chemical compounds, forming nite particles with dierent chemical compo-
sitions. The analyte may only occur in particles with a certain chemical composition and
not in other particles. Then, only these specic particles can contribute to the uorescent
radiation of the analyte i. Therefore, the count rate R
i
measured depends on the number of
those particles present in the active volume, where, evidently, the rst layers contribute
most of the uorescent radiation.
Table 2 gives an indication of the penetration depth of radiation of various wa-
velengths into matrices with varying absorption power. It is evident that for most solid
specimens, the uorescent radiation originates within 20 mm or less from the surface. To
get an idea of how many particles can actually contribute to the uorescent intensity of
analyte i, let us assume that the irradiated area of 10 cm
2
is covered with cubic particles
of 100 mm dimension in a random fashion. Assuming a lling factor of 0.8 and assuming
that the analyte i is only present in 10% of the particles, then 10 10
8
10
4
10
1
0.8 8000 particles could be actually contributing. Assuming a Gaussian distribution,

then this number would have a standard deviation of
8000
p
90 particles, or a relative
standard deviation of approximately 1.1%. If the concentration of analyte is only 1%,
then this relative standard deviation would be roughly 3.3%. In practice, these errors
might even be larger, as the radiation of the specimen is not homogeneous because the
primary spectrum originates in a rather small anode and passes through a large window
and is, thus, conically shaped. Spinning the specimen in its own plane during the ana-
lysis will reduce this error. Furthermore, the rst layers are the most eective, having
Table 2 Innite Thickness (in mm for Certain Analytical Lines as a Function of the Matrix)
Analytical line Fe base Mg base H
2
O solution Borate Borate La
2
O
3
10%
SnKa 300 10,000 100,000 70,000 10,000
MoKa 100 3,700 30,000 30,000 2,600
NiKa 12 340 2,400 2,000 300
CrKa 33 120 900 800 250
AlKa 1.5 4 10 15 5
NaKa 0.7 20 9 6 5
CKa 0.3 0.3 4 1 0.4
Note: Both the incidence and exit angles are 45
and excitation is by a Rh tube at 60 kV. The inuence of element-

specic absorption can be seen from, for example, the values for NiKa and CrKa in the Fe-base matrix.
only a small number of particles containing the analyte with corresponding larger re-
lative errors.
In extreme cases, it is evident that the eective layer is very thin, less than 1 mm. Care
should thus be taken that the specimen surface is as smooth as possible; as surface irre-
gularities (e.g., grooves, ridges) will introduce a considerable error. Spinning the specimen
will, again, reduce this error.
It is therefore vital that the specimen be completely homogeneous. If this is not
possible and powders have to be analyzed, care should be taken that the particles are very
small, less than a few micrometers in diameter. Specimen preparation will be discussed
in full detail in Chapter 14.
C. Systematic Errors
1. Dead T|me
After an x-ray photon is detected in the counter and accompanying electronics, it takes a
certain time before the counting circuit is ready to accept the next photon. Any photon
entering the counter within this period, called the dead time of the counter circuit, is
simply not registered and is thus lost. This dead time is of the order of a few microseconds.
The counting losses are thus dependent on the actual count rate. The measured count rate
R
m
is always lower than the true count rate R
T
. Their relation can be approximated by the
expression
R
T

R
m
1 t
d
R
m
47
where t
d
is the dead time. For instance, if t
d
1 ms and R
m
10
5
counts per second, the
dead-time loss is approximately 10%. With modern equipment, very high count rates can
be handled, to reach sucient precision in a short time. It is therefore necessary to reduce
these losses. In most wavelength-dispersive instruments, an automatic dead-time correc-
tion circuit is included. Energy-dispersive instruments, on the other hand, tend to collect
counts for the specied time; thus, the measurement takes longer because the total time
required in this case consists of the specied measuring time (lifetime) and the dead time.
2. Matrix Effects
The uorescent intensity of the analyte i is, as discussed earlier, not only dependent on its
concentration but can also be strongly dependent on the composition of the specimen
itself. The primary rays will be absorbed and scattered and secondary uorescence may
occur. All of these eects depend on the chemical composition of the specimen. The
importance of these eects depends on the concentration of these matrix elements and
their inuence (e.g., their absorption of primary and secondary x-rays). These matrix ef-
fects may introduce large systematic errors when they are not properly accounted for, as
discussed in Sec. V.
D. Choice of Optimal Conditions
1. Selectingthe Analytical Line
Some considerations in choosing the analytical line are the following:
1. High sensitivity, thus preferably the strongest line in the emission spectrum is
used; this is commonly the Ka
2. Low intensity of background radiation
3. Constant angle of Bragg diraction (wavelength-dispersive instruments)
4. No coincidence (line overlap) with lines of other elements
Each of these items will be discussed in more detail below.
1. For the light- and medium-Z elements, the Ka line is by far the strongest line in
their spectrum and is therefore often chosen as the analytical line. For the
elements with K-edge energies exceeding 40 keV, the L lines are preferred
because the K lines, in general, cannot be used, the maximum voltage for most
spectrometers being limited to 100 kV or less. Typically, a voltage of three times
V
c
or more is needed to get a high characteristic intensity. Furthermore, the
resulting K lines are very energetic and are only detected with mediocre
eciency by the Si(Li) detectors or NaI scintillation detectors. Ge detectors
have a higher eciency for that energy range and these are the preferred
detectors.
2. Another reason the L lines are preferred for the heavier elements is that in direct
tube-excited XRF, the background due to scattering of the primary x-rays is
much lower in the L region of the spectrum.
3. The wavelength of some analytical lines may shift slightly with the valence state
of the elements, especially for the light elements and the L lines of the transition
metals (Wood and Urch, 1978); thus, the standard used in setting the goniometer
to the analytical line should correspond to the specimen in this respect. Another
reason for an apparent shift in angle may be the change in d value of analyzing
crystal with temperature.
4. The analytical line should ideally be completely free of any disturbing lines.
However, there are many sources of distributing inuences; some of these are described
next.
The following sections deal with line overlap in the case of wavelength dispersive
spectrometers. For energy dispersive spectrometers, please refer to Chapter 4.
2. Spectral Overlap
Two or more characteristic lines may not be completely separated from the analytical line.
This separation may be improved by using a crystal with better dispersion (e.g., a lower d
value). However, the choice must often be made between high intensity and high disper-
sion. If the disturbing line is due to a high-order crystal reection, its inuence may be
strongly reduced by the proper setting of the pulse-height selector. However, in some
cases, the escape peak of the interfering line may be within the pulse-height selector
window. For instance, the third-order reection using a penta erythritol (PE) crystal, of
the characteristic tube lines of a Sc anode, scattered by the specimen will slightly interfere
with the analysis for Al in a light matrix, as the energy of the ScKa escape peak in an Ar-
lled gas detector is very close to the energy of the AlKa line.
Often, the overlap is due to a diagram line of an element of which another diagram
line is free of overlap. As, in general, two diagram lines of one element have a constant
intensity ratio, the measured intensity of the nonoverlapped line of the disturbing element
multiplied by a constant factor (experimentally determined) may be subtracted from the
measured intensity of the analytical line to give the characteristic intensity. Absorption
eects can, however, strongly inuence the ratio. This is most clearly the case when there is
an absorption edge of a major element between the two diagram lines considered.
3. Primary Radiation Scattered by the Specimen
Photons of all wavelengths present in the white spectrum of the incident beam are scat-
tered by the specimen, including the characteristic lines of the tube anode, giving rise to a
continuous background. If, however, the specimen consists of rather coarse grains, it may
happen that a crystallite is in a favorable position for Bragg diraction for a wavelength of
the continuum; thus, a sharp peak will be found in the spectral analysis. The inuence of
primary tube lines, coherently or incoherently scattered, may be eliminated by the proper
choice of the anode.
4. Spurious Reflectionsby the Analyzing Crystal
LiF(110) is a common analyzing crystal. The second order of reection is used because the
rst order is crystallographically forbidden; therefore, the actual planes used for the dif-
fraction are the 220 planes. Hence, some manufacturers refer to it as the LiF(220) crystal;
the same applies to the LiF(100) and LiF(200) denominations. However, when a very, very
high intensity is observed, a rst-order reection will still be found, due to asymmetry of
the electronic cloud. Similarly, a second order may be observed using a Ge crystal.
5. Satellite Lines
The common wavelength tables give only characteristic K, L, and M lines of most ele-
ments. The M lines of heavy elements may interfere with the K lines of light elements.
Nondiagram satellite lines may also occur, often giving rise to an unexpected background
level. One of the tables that includes such lines is provided by NIH (Bethesda, MD)
(Garbauskas and Goehner, 1983).* The lines that are most obvious to observe are some of
the satellites lines of Al, Si, and P with a wavelength-dispersive spectrometer. In Figure 3,
a spectrum over aluminum is shown, on which some of these lines have been annotated.
IV. CALIBRATIONANDSTANDARDSPECIMENS
A. Introduction
As shown earlier, standard specimens must cover the concentration range of interest, be
stable over time, and have a certied composition. They are, however, not the only spe-
cimens required to set up a calibration for routine use and to maintain it over extended
periods of time. Quality control specimens (also called quality assurance specimens) are
used to assess the quality of the analysis obtained over time, whereas drift-correction
monitors are used to correct for long-term drift of the equipment. Finally, recalibration
standards can be used if the calibration graph must be reconstructed.
B. Quality Control Specimens
The use of at least one sample with known composition to assess the accuracy at the time
of the calibration is highly recommended. The sample(s) used for this purpose should be
typical for the unknowns and should not be used for calibration to avoid biases and overly
optimistic estimates or accuracy. Furthermore, it is a sound practice to select at least one
specimen, with a composition similar to the unknowns, as a quality control specimen to
verify the repeatability over extended periods of time. Should the results on the quality
*Database made available through C. Fiori, National Institutes of Health, Bethesda, Maryland.
control specimen fall outside a predetermined range, then adequate measures must be
taken. The rst step is usually to perform a correction for drift. DeGroot (1990) has de-
scribed how the use of statistical process control (SPC) can be benecial in this respect.
The SPC charts that can be maintained in this way allow one to check the performance of
the spectrometer system.
C. Drift-Correction Monitors
Correction for drift can be made by measuring selected specimens for each of the ana-
lytes and calculate the ratio between the observed intensities and those obtained when the
calibration was performed. The ratios can then be applied as a correction to the slope
of the calibration graphs or, as is done more often, the measured intensities of the
unknowns are corrected for drift, prior to the conversion to concentration. If drift
correction is performed regularly (e.g., once a day), the drift between subsequent
measurements is very small and, thus, measurements with high precision are required,
otherwise the counting statistical error of the measurement would become dominant.
Drift correction should not even be applied unless the correction is signicant. Because
the precision of an intensity measurement is determined by the number of counts col-
lected, drift-correction monitors are, ideally, specimens on which high count rates can be
obtained. Drift-correction monitors do not have to be specimens with a composition
similar to the unknowns.
As dierent components of the spectrometer (such as the x-ray tube) age, not only will
the sensitivity be aected (this is generally a downward trend), but in some cases, the
background will vary also. To correct for this change in background intensity, measure-
ments of the background must be performed. This poses a problem, inasmuch as the count
Figure 3 Spectrum of aluminum-containing specimen. The peaks are the following emission lines:
(1) AlKb1, Kb3 doublet; (2) AlSKb
0
; (3) AlSKa7; (4) AlSKa5; (5) AlSKa4; (6) AlSKa3; (7) AlKa1,
Ka2 doublet. The satellite lines are explicitly labeled with S. Note the logarithmic scale on the
intensity axis. Conditions: wavelength-dispersive spectrometer with PE crystal, Rh tube.
rate on the background is usually low and thus measurements are not vary precise or they
require a long measuring time. However, the considerations on the counting statistical error
made earlier (Sec. III.B.1) oer some suggestions. First, the intensity of the background is
irrelevant when the intensity of the analyte peak is much higher. Obviously, this has to
apply for all specimens to be measured. If that is the case, then variations in the background
intensity are also negligible. When the background matters, it should already be measured
anyway and then drift correction on the background intensity is not required, as the net
count rate is corrected for drift. The only case that is not covered here is the contribution of
spectral contamination from the x-ray tube (e.g., Cu, W, Ag, Fe, etc.). In that case, the
background, including the contamination, must be measured on peak. This implies that
measurements must be done for specimens with zero analyte concentration. Again, two
cases can be distinguished: If the background including the contamination is not important
compared to the count rate observed, then no corrections are required. On the other hand,
if one of the analytes is present at low concentration, then the contribution to the back-
ground due to the contaminant must be checked periodically and taken into account.
After the drift correction is performed, a quality control specimen should be mea-
sured to verify the procedure.
D. Recalibration Standards
Sometimes (e.g., after a major maintenance on a spectrometer), drift correction does not
bring the quality control specimens back in line with the expectations. In those cases, the
calibration curve must be reconstructed. This can be done by measuring all the standard
specimens again and repeating the complete calibration procedure. Because calibrations
often use many standards and validating each calibration is required, this can be a time-
consuming process, even if the validation is limited to a quick visual inspection of the
calibration graphs. In such cases, a recalibration can be performed based on only a few
standards. The idea of recalibration is to reconstruct the calibration graph, without having
to measure all the standards again. This is done by selecting a few standard specimens for
each analyte and measuring these (the top and bottom point in Fig. 4). Subsequently,
when determining the parameters (such as slope and intercept) of the regression, for the
concentrations of these specimens in the calibration the certied values are no longer used,
but the values as found on the calibration line at the time of the original calibration (the
x-ray values) are. These x-ray values have been found based on all standard specimens
used, and the idea is to x the calibration line again through these points. As a result,
the statistical data are now skewed, but the values for the slope and the intercept are very
close to the original ones; the small dierences between old and new values are due to the
counting statistical errors in the measurements and these are also present when unknowns
are measured. The specimens used for recalibration have also been used for the calibra-
tion. The only requirement is that the recalibration specimens have count rates that are
dierent enough so that the determination of the slope is accurate enough. For each of the
calibration lines, the number of selected specimens must be at least the same as the number
of parameters to be determined. If the slope and intercept are determined, at least two
recalibration standards are required. However, if in this case three or four standards are
used, it is possible to detect gross counting artifacts (e.g., caused by mislabeled standards,
incorrect loading, etc.). The root mean square error or the correlation coecient on the
calibration line (which can only be calculated if more specimens are used than parameters
determined) has no relationship with the accuracy of the analysis. In fact, a near-perfect
correlation should be obtained. As in the case of drift correction, it is recommended to
measure, after recalibration, the quality control specimen(s), as gross errors might thus be
identied before unknown specimen are analyzed.
E. Conclusion
Setting up a calibration to be used over extended periods of time requires considerable
amounts of work and preparation. It involves not only the selection and procurement
of standard specimens but also drift correction monitors and recalibration standards.
Also, the specimen preparation method is an essential part of the whole procedure.
The result, however, is the ability to produce quantitative results to a previously as-
sessed degree of accuracy and precision over extended periods of time with minimal
work, once the specimen preparation procedure is set up and the initial calibration is
performed.
V. CONVERTINGINTENSITIES TO CONCENTRATION
A. Introduction
The simplest equation relating intensity to concentration is
I
i
K
0
i
W
i
48
where K
0
i
is assumed to be a constant. The equation holds in general for cases where the
total eect of the matrix on the analyte i is constant (e.g., elements at minor and trace
concentration levels in low-alloy steels or thin-lm specimens). The intensity I
i
in Eq. (48)
is a net intensity: measured intensity corrected for background, line overlap, and so forth.
Figure 4 The original calibration line, based on seven data points (h) can be reconstructed using
only two data points (in this case, top and bottom), with concentrations (x-ray values) modified to
those obtained on the calibration (j).
In practice, the measured intensity is often used directly without the subtraction of
background, leading to a more general equation:
I
i
B
0
i
K
0
i
W
i
49
where B
0
i
is the measured intensity when W
i
0. If there is no uncorrected line overlap, B
0
i
is the background. This equation can be rearranged to
W
i
B
i
K
i
I
i
50
The constant K
i
is called the sensitivity and is expressed in counts per second per unit
concentration (e.g., percent, mg,L, etc.).
The most common method of determining the constants B
i
and K
i
(or B
0
i
and K
0
i
)
is linear regression on a number of standard specimens. Linear regression can be done
by minimizing the sum of squared residuals of W, or I; see Figure 5. In theory, the
method of least squares assumes that the errors of the dependent variable [W in Eq.
(50)] are normally distributed. The two lines obtained (one by minimizing DW, the other
by minimizing DI ) are not the same. Because, for the analysis, the intensity I
i
is mea-
sured, it is recommended to minimize for W
i
. Also, in general, the relative error of
the measured intensities is smaller than the relative error of the concentrations in the
standard specimens. This is especially true for the determination of trace elements. The
following formulas can be used for the determination of the values of the parameters
K
i
and B
i
:
W
i
B
i
K
i
I
i
50
K
i

P
n
j1
W
ij
I
ij

P
n
j1
W
ij
P
n
j1
I
ij
,n
P
n
j1
I
2
ij

P
n
j1
I
ij
P
n
j1
I
ij
,n
51
Figure5 Straight lines through the data points can be determined by minimizing either the sum of
the squares of the residuals DI or DW.
and
B
i

P
n
j1
W
ij
K
i
P
n
j1
I
ij
n
52
where the sums are over the standard specimens, j 1. 2. . . . . n, with n the number of
standard specimens used for analyte i. Equally important, however, are the variances on
the parameters determined. Formulas to calculate the variances can be found in the lit-
erature [Draper and Smith (1966)], and many commonly used computer programs such as
spread sheets and statistical packages include the relevant calculations as well. Some
important conclusions are as follows:
1. The concentrations of the standard specimens must cover the expected range of
concentrations.
2. The calculated concentration is more accurate at the center of the line than at the
extremities; the estimated variance for W
x
increases with (W
x
W
average
).
3. Because a calibration line is derived using data from several standards, the
analysis of the unknown can sometimes be more accurate than the accuracy of
the individual standard specimens; this is due to the eect of averaging.
When the background is properly subtracted from the gross count rate, the background B
i
is equal to zero and Eq. (50) reduces to
W
i
K
i
I
i
53
In this case, the value for the slope K
i
is found from
K
i

P
n
j1
W
ij
P
n
j1
I
ij
P
n
j1
I
2
ij
54
B. Matrix Effect
Applying Eq. (50) or (53) requires that all standards must be similar to the unknown in all
aspects considered: matrix eect, homogeneity, and so on. This would lead to the use of
standard specimens with a very limited concentration range. Such a requirement is in
disagreement with the observation that the variance on the slope factor is smaller with
increasing range: The use of standard specimens covering only a small concentration range
will lead to a calibration graph with large uncertainty on the slope and intercept. On the one
hand, this advocates the use of a set of standards with a wide range of concentrations; on
the other hand, the requirement of similarity in matrix eects tends to limit the range.
Obviously, a compromise must be made. Equation (50) is a simplication of the more
general equation describing the relationship among analyte concentration W
i
, specimen
homogeneity S
i
, measured intensity I
i
, and matrix eect M
i
:
W
i
K
i
I
i
M
i
S
i
55
The term specimen homogeneity also includes the grain size eect and the mineralogical
eect. These are notoriously dicult to treat mathematically; in fact, most methods de-
scribing the grain size eect rigorously assume, for example, the dispersed phase to be
perfect spheres of a given diameter or an arrangement of cubes (Bonetto and Riveros,
1985). Other methods allow more variability, but these also require a priori more in-
formation about the specimen, such as the composition of the individual granular phases,
the average shape and size of the phases, and so forth (Hunter and Rhodes, 1972; Lubecki
et al., 1968; Holynska and Markowicz, 1981). The fact that the specimen homogeneity is as
yet not described by a single successful method is one of the reasons that Eq. (55) is
commonly reduced to
W
i
K
i
I
i
M
i
56
Fortunately, by using adequate specimen preparation methods the eect of S
i
between
specimens (standards as well as unknowns) can be rendered constant. This constant factor
is then absorbed by the sensitivity K
i
.
As a rst approximation, the degree of variation in matrix eect between two spe-
cimens for a given analyte i can be estimated by calculating, for both compositions, the
following parameter:
I
i
P
i
m
i
m
s
l
0
Gm
s
l
i
57
where m
s
l
0
and m
s
l
i
are the mass-attenuation coecients of the specimen considered
for wavelengths l
0
and l
i
, respectively, and G is the geometrical factor for both compo-
sitions. The relative dierence between these expressions should not exceed a few percent,
otherwise the matrix eects become too important to ignore. If the specimens include ux
or a binding agent, then these must also be considered in Eq. (57).
With increasing range of concentrations, deviations from linearity will be observed
due to variations in matrix eects between specimens and standards. The analyst must
then resort to other methods to obtain accurate results.
Matrix eects are studied most easily by considering binary systems (i.e., specimens
with only two elements or compounds).
In the case of absorption (both primary and secondary absorption must be con-
sidered), three cases can be distinguished (see Fig. 6):
1. A simple, linear relationship between relative intensity R and weight fraction W
(Curve 1 in Fig. 6). In this case, there is no matrix eect: The analyte and the
matrix have very similar (in principle, the same) attenuation coecients for the
incident and the characteristic radiations.
2. Curve 2 in Figure 6 is obtained when the matrix has a higher attenuation
coecient for the analytes characteristic radiation than the analyte itself: The
characteristic radiation is primarily absorbed by the matrix element. This is
usually called positive absorption.
3. Curve 3 in Figure 6 is obtained when the matrix absorbs less than the analyte
itself: The matrix has a smaller value for the attenuation coecient for the
characteristic radiation than the analyte itself. This can be the case, for example,
if the matrix has a much lower atomic number than the analyte, such as Mo in
Al. This eect is called negative absorption.
Enhancement will generally lead to a calibration graph like curve 4 in Figure 6. The
eect of enhancement is usually smaller than that of positive or negative absorption, as
indicated by the position, relative to curve 1, of curves 2 and 3 and curve 4.
It can be shown that the behavior of the calibration curves can be explained in terms
of attenuation coecients only if absorption is the only matrix eect. Furthermore,
if monochromatic excitation is used, a single constant (calculated from attenuation
coecients) suces to express the eect of one element on the intensity of another. In the
following section, various methods to deal with matrix eects will be discussed.
C. Elimination or Evaluation of theTotal Matrix Effect: Compensation Methods
1. Scattered Radiation: Compton Scatter (in cooperationwith Mark N. Ingham,
British Geological Survey, Keyworth, UK)
If the variation in matrix eects is mainly due to absorption, scattered x-rays can be used
to obtain an estimate of the absorption coecient of the specimen at a certain wavelength
l
s
. The intensity of the scattered radiation can be shown to be inversely proportional to the
mass-attenuation coecient m
s
of the specimen:
I
s
l
s

1
m
s
l
s
58
where l
s
is the wavelength of the scattered radiation and m
s
l
s
is the mass-attenuation
coecient of the specimen for wavelength l
s
. This is illustrated in Figure 7. The intensity
of the uorescent radiation, I
i
. is also inversely proportional to the mass-attenuation
coecient [Eq. (57)], but at a dierent wavelength:
I
i

W
i
m
s
l
0
Gm
s
l
i

W
i
m
s
59
where
m
s
m
s
l
0
Gm
s
l
i
60
Figure 6 Calibration curves for binaries. Curve 1: no net matrix-effect; curve 2: net absorption of
the analytes radiation by the matrix (positive absorption); curve 3: net absorption of the analytes
radiation by the analyte (negative absorption); curve 4: enhancement of the analytes radiation by
the matrix.
Mass-attenuation coecients at two dierent wavelengths are virtually proportional,
independent of matrix composition, provided there are no signicant absorption edges
between the two wavelengths considered (Hower, 1959). Hence, the ratio I
i
,I
s
is pro-
portional to the concentration of the analyte.
Both coherently and incoherently scattered primary radiation, such as tube lines
for tube excited x-ray uorescence (XRF), as well as the scattered continuous radiation
can be used. The method corrects also, to some degree, for surface nish, grain size
eects, and variations in tube voltage and current, but it does not correct for en-
hancement, thus limiting its use to analytes that are inuences by absorption only.
Furthermore, no absorption edges of major elements may be situated between the two
wavelengths considered. If that is the case, the ratio between the mass-attenuation
coecients for the wavelengths considered depends to a large degree on the concen-
tration of the major element(s) and the ratio is no longer constant between specimens.
This reduces the range of analytes that can be covered using the scattered tube lines. The
use of scattered continuum radiation close to the analyte peak may be disadvantageous
due to limited intensity, leading to either long measurement times or poor counting
statistics.
The intensity of the scattered Compton radiation is higher for specimens mainly
consisting of low-atomic-number elements than for specimens with a higher average
atomic number. This is illustrated in Figure 8, where the scattered radiation is plotted
as a function of wavelength for two specimens: iron and magnesium. In this experi-
ment, the spectrometer was equipped with a Rh anode x-ray tube. The two sharp
peaks that can be observed are the RhKb (at 0.0546 nm) and the RhKa (at 0.0613 nm),
respectively. The other two, much broader peaks are the Compton-scattered RhKb and
the RhKa. The Compton-scattered peaks are much broader than Rayleigh-scattered
Figure 7 The intensity of Compton-scattered radiation is inversely proportional to the mass-
attenuation coefficient (mac) of the specimen. Conditions: Rh tube at 60 kV.
characteristic lines. They are also shifted toward longer wavelengths by an amount Dl,
which is given by
Dl 0.002431 cos c 61
where c is the angle through which the radiation is scattered: c c
0
c
00
and Dl is ex-
pressed in nanometers.
In the spectrometer used for the recording of the spectra in Figure 8, c is 100
.
The Compton shift, Dl, is thus 0.0029 nm for this conguration. The maxima of the
Compton peaks (at 0.0576 nm and 0.0644 nm) in Figure 8 are in good agreement with
the theoretical values: 0.0546 nm0.0029 nm0.0575 nm and 0.0613 nm0.0029 nm
0.0642 nm, respectively.
The intensity of the Compton-scattered radiation is higher for shorter wavelengths
and for specimens consisting of elements with low atomic numbers. For a given wave-
length (e.g., the characteristic radiation of a tube line), the intensity of Compton scatter
decreases as the specimen consists of more and more elements with higher atomic
numbers. For specimens made up of oxides, the scattered intensity is usually so intense
that it can be measured with sucient precision in a relatively short time. On the other
hand, for specimens made up predominantly of heavier elements, such as steel and even
more so for brasses and solders, the intensity of the scattered radiation is very low (see
Fig. 8) and counting the statistical error can preclude precise analysis in a reasonable
amount of time. The most common application where this approach (or a variant
thereof) is used is in the determination of trace elements in specimens of geological
origin. This is illustrated in Figure 9 for the determination of Sr in specimens of widely
Figure 8 Intensity of scattered radiation as a function of wavelength. Two different specimens
have been used: iron and magnesium. A Rh anode tube was used in this experiment. Note the large
difference in intensity between the specimens. For the specimen consisting of the element with the
higher atomic number (Fe), the intensity of the Compton (incoherent)-scattered radiation is lower
than the intensity of the Rayleigh (coherent)-scattered radiation, compared to the specimen with the
lower-atomic-number element (Mg).
varying geological origin. In Figure 9a, the net count rate for SrKa is plotted against the
concentration for a large number of specimens. There is a considerable spread around
the calibration line established. The scatter is greatly reduced when the net count rate of
Figure 9 (a) Net count rate of SrKa as a function of Sr concentration for a large number of
specimens of varying geological origin. There is considerable spread around the calibration line.
(b) The ratio of the count rates of the SrKa radiation and the Compton-scattered tube line is plotted
against the concentration of Sr. The spread of the data points around the calibration line is now
much reduced compared to (a); this is especially the case for the point labeled A.
SrKa is divided by the count rate of the RhKa Compton-scattered tube radiation, as
indicated in Figure 9b.
Feather and Willis (1976) have shown that the intensity of the Compton peak can
also be used as an estimate for the background under characteristic lines; this eliminates
measuring the intensity of the background near the peak. With this method, not only is the
measurement time per specimen reduced (using WDS) but the dicult task of nding
interference-free background positions is no longer required.
2. Internal Standard
In this method, an element is added to each specimen in a xed proportion to the original
sample. This addition has to be made to the standard samples as well as to the unknowns.
The characteristic radiation of the element added should be similar to the characteristic
radiation of the analyte in terms of absorption and enhancement properties in the matrix
considered. Such an element is called an added internal standard, or internal stan-
dard for short. In practice, the method works equally well if a pure element or a pure
compound is added, or if a solution with the internal standard element is used. If a so-
lution is used, care must be taken that the solution itself does not contain any elements
that are to be analyzed. The composition of the solution used as the additive must be
constant, otherwise it might aect the matrix eect. The intensity of the internal standard
is aected by matrix eects in much the same way as the intensity of the analyte, provided
there are no absorption edges (leading to dierence in absorption) or characteristic lines
including scattered tube lines (leading to dierence due to enhancement) between the two
wavelengths considered. Because
W
i
K
i
I
i
M
i
62
for the analyte i and
W
s
K
s
I
s
M
s
63
for the internal standard s, the following ratio can be obtained by dividing Equation (62)
by Equation (63):
I
i
I
s
K
is
W
i
64
where
K
is

K
s
M
s
K
i
M
i
W
s
65
Because the same amount of internal standard is added to all specimens, W
s
is essentially a
constant and can be included in the constant K
is
. It should be noted that M
i
(and M
s
) is
not a constant over the concentration range of interest (otherwise linear calibration would
suce) but depends on the matrix elements. However, if both M
i
and M
s
vary in a similar
manner with the matrix elements, the ratio M
i
,M
s
is less sensitive to variation in the
matrix eect and, in practice, can be considered a constant. In practice, the constant K
is
is
determined using linear regression. The main advantage of the internal standard method
over the scattered-radiation method is its ability to correct eectively for enhancement as
well as for absorption. It also correctsat least partiallyfor variations in density of
pressed specimens. The requirement that the intensity of the characteristic radiation of
both the analyte and the internal standard element vary in the same manner with the
matrix eects imposes that there should be no absorption edges and no characteristic
radiation from other elements between the measured line of the analyte and that of the
internal standard. Furthermore, ideally, the analyte should not enhance the internal
standard or vice versa. If Ka radiation is measured and if the atomic number of the analyte
is Z (with Z23), then, very often, the elements with atomic number Z1 or Z1 are
very good candidates. This assures that there are no K absorption edges and no K emission
lines of other elements between the two elements considered. The element with atomic
number Z is not enhanced by Ka radiation from an element with Z1, but only by the
much weaker Kb radiation, whereas for elements with atomic number Z2 and higher,
both Ka and Kb contribute to enhancement. In practice, some enhancement between the
internal standard element and the analyte or vice versa is allowed, as the concentration of
the internal standard is constant and the ratio is based on intensities. The absence of major
elements in the specimens with L absorption edges and emission lines, however, must be
checked for. The situations that must be avoided are (1) the case where a major line of a
major matrix element is between the absorption edges of the analyte and the internal
standard and (2) the case where a major absorption edge of a major matrix element is
situated between the measured characteristic lines of the analyte and the internal standard.
In the rst case, the matrix element would enhance either the analyte or the internal
standard element, but not both; in the second case, the matrix element absorbs strongly
either the radiation from the analyte or the internal standard, but not both. In both of
these cases, varying concentrations of the matrix element will lead to variable and dierent
eects on the intensities of the analyte and of the internal standard, and the ratio used in
Eq. (64) will not compensate for such events.
The method, however, has some important limitations:
The specimen preparation is made more complicated and is more susceptible to
errors.
The addition of reagents and the requirement of homogeneity of the specimen tends
to limit the practical application of the method to the analysis of liquids and
fused specimens, although it sometimes nds application in the analysis of
pressed powders.
Although the rule Z1 or Z1 can serve as a rule of thumb, it is quite clear that for
samples where many elements are to be quantied, a suitable internal standard
cannot be found for every analyte element. Sometimes, more elements are used
in one internal standard solution to provide suitable internal standards for
more analytes.
Also, the fact that the internal standard method is easier to apply to liquids can
generate some problems. Heavier elements (e.g., Mo) are more dicult to
determine using this method, because liquid specimens are generally not of
innite thickness for the K wavelengths of these heavier elements. In such cases,
the L line can be used, with an appropriate internal standard. The method will,
however, also provide some compensation for the eects of noninnite
thickness, especially if the wavelength of the internal standard selected is very
similar to that of the analyte line.
Theoretically, L lines of a given element can be used as internal standards for K lines
of other elements and vice versa if these wavelengths are reasonably close to each other
and neither interfering lines nor edges occur between them. In principle, the method allows
the determination of one or two elements in a specimen without requiring analysis (or
knowledge) of the complete matrix.
The range of concentration over which this method is suitable can be quite large, up
to 1020 % in favorable situations, but the internal standard technique is most eective at
low concentrations (or high dilutions). The method nds, for instance, application in the
determination of Ni and V in petroleum products, where MnKa is used as an internal
standard (ISO, 1995). The internal standard method allows an accurate determination of
these elements in a much wider variety of petroleum products than the method based on
linear calibration.
3. Standard Addition Methods
Another method of analysis involves the addition of known quantities of the analyte to the
specimen and is referred to as the standard addition method.
If the analyte element is present at low levels, and no suitable standards are available
(e.g., the matrix is unknown), standard addition and,or dilution may prove to be an al-
ternative, especially if the analyst is interested in only one analyte element. The principle is
the following: Adding a known amount of the analyte i DW
i
to the unknown specimen
will give an increased intensity I
i
DI
i
. Assuming a linear calibration, the following
equations apply:
W
i
K
i
I
i
62
for the original specimen and
W
i
DW
i
K
i
I
i
DI
i
66
for the specimen with the addition. Thus, the method assumes that linear calibration is
adequate throughout the range of addition, because it assumes that an increase in the
concentration of the analyte by an amount DW
i
will increase the intensity by K
i
DI
i
.
Figure 10 Standard addition method. The net intensity is plotted versus weight fraction of the
element added to the sample and a best-fit line is determined. The intercept of that line with the
concentration axis is W
i
.
These equations can be solved for W
i
. To check the linearity of the calibration, the process
can be repeated by adding dierent amounts of the analyte to the specimen and plotting
the intensity measured versus the concentrations added (Fig. 10). The intercept of the line
on the concentration axis equals W
i
. Note that the concentration in the unknown is
actually found through extrapolation of the linear calibration toward zero intensity. The
intensities used for calibration must be corrected for background and line overlap. If this
correction is not performed (or not performed accurately), the value of the concentration
determined will be overestimated by an amount proportional to the intensity of the
background (or line overlap) and inversely proportional to the sensitivity.
The method is suitable mainly for determination of trace and minor concentration
levels, as the amount DW
i
added to the sample must be in proportion to the amount W
i
in
the sample itself. The extrapolation error can be quite large if the slope of the line is not
known accurately. Adding signicant amounts of additives to the sample might, however,
lead to nonlinearity, as it will alter the matrix eect.
Compounds and solutions can be used for the standard addition. If the analyte i in
the original sample is in a dierent phase than in the additive, care must be taken in the
calculation of the concentration sought. The relevant stoichiometric or gravimetric factors
must be included. This also applies if the analyte is present under elemental or ionic form
in, for example, the original sample and in a compound phase in the additive, or vice versa.
Another way to alter the concentration of the analyte is by diluting the liquid or solid
solution of the sample. By diluting several times by known amounts, a line can be es-
tablished. By repeating this procedure with a standard solution containing a known
amount of i, the unknown concentration can be found.
4. Dilution Methods
Dilution methods can also eliminate or reduce the variation of the matrix eect, rather than
compensating for such variation. The dilution method can be explained using Eq. (17):
C l
0
. l
i

m
i
l
0
P
n
j1
W
j
m
j
l
0
G
P
n
j1
W
j
m
j
l
i
17
which can be rewritten as
C l
0
. l
i

m
i
l
0
m
s
l
0
Gm
s
l
i
67
where m
s
l
0
and m
s
l
i
are the mass-attenuation coecients of the specimen for the pri-
mary wavelength l
0
and analyte wavelength l
i
, respectively. Apparently, deviations from
linearity are due to variations in m
s
l
0
and,or m
s
l
i
. Enhancement is ignored at this
stage. If one adds, to the sample, D grams of a diluent (d ) for each gram of sample, the
denominator or Eq. (67) becomes
1
1 D
m
s
l
0
Gm
s
l
i

D
1 D
m
d
l
0
Gm
d
l
i
68
If the term D,1 Dm
d
l
0
Gm
d
l
i
is much larger than 1,1 Dm
s
l
0
Gm
s
l
i
,
the factor Cl
0
. l
i
becomes essentially a constant and variations due to varying matrix
eects between samples become negligible. This can be done in two ways.
(a) Making D,1 D large by diluting each sample by adding a large, known
amount of a diluent.
(b) Adding a smaller quantity of diluent than in the previous case, but with a much
larger value for m
d
l
0
Gm
d
l
i
. This is called the technique of the heavy
absorber.
Both of these procedures, however, require the addition of reagents to the sample. This
can easily be done for dissolved samples, either in liquids or fused samples, but it is more
dicult for powdered samples (homogeneity!).
These methods do not eliminate the matrix eects completely, but reduce their
inuence. On the other hand, they also reduce the line intensity of the analyte; thus, a
compromise must be sought.
Dilution methods also have the advantage of reducing the enhancement eect if one
uses a nonuorescing diluent (e.g., H
2
O or Li
2
B
4
O
7
). In this case, the eect is reduced by
the fact that the concentrations of both the enhancing element and the analyte are reduced.
If the diluent contains elements whose characteristic x-rays can excite the analyte, as well
as some other matrix elements, then the contribution of those unknown quantities of
matrix elements to the total enhancement is reduced: The enhancement of the analyte by
the diluent would then be determining and can be considered to be constant.
This method allows the determination of all measurable elements in the sample, as
opposed to the standard addition method, where an addition must be made for each
element of interest.
D. Mathematical Methods
1. General
The term mathematical methods refers to those methods that calculate rather than
eliminate or measure the matrix eect.
Mathematical methods are independent of the specimen preparation in the sense that
specimen preparation is taken into account if the composition of the specimen presented to
the spectrometer has been changed (e.g., by fusion), but mathematical methods do not
prescribe the specimen preparation method as is done, for example, by the standard ad-
dition method. The actual calculation method used to convert intensities to concentrations
does not aect the choice of the specimen preparation method. The aim of the specimen
preparation is limited to the presentation to the spectrometer of a specimen that is
homogeneous (with respect to the XRF technique) and that has a well-dened, at surface
representative for the bulk of the specimen. Mathematical methods usually require
knowledge of all elements in the standard specimens and allow determination of all mea-
surable elements in the unknowns. In practice, trace elements can be neglected in the cal-
culations for the analytes present at higher concentrations, as these trace compounds are
neither subject to an important (and variable) matrix eect nor do they contribute sig-
nicantly to the matrix eect of other elements. Their concentrations are often found by
straightforward linear regression. The mathematical methods are divided in two main ca-
tegories: the fundamental parameter method and the methods using inuence coecients.
2. The Fundamental Parameter Method
a. Introduction
The fundamental parameter method is based on the theory that enables one to calculate the
intensity of uorescent radiation, originating from a specimen of known composition. The
equations used usually consider both primary and secondary ourescence (enhancement).
Higher-order eects and eects due to scattered radiation are usually neglected. Formulas to
calculate intensities of uorescent radiation were proposed very shortly after the introduc-
tion of the commercial XRF spectrometers, in the early 1950s (Gillam and Heal, 1952). The
equation describing the intensity of the uorescent radiation as a function of specimen
composition, spectrometer conguration, and incident spectrumwas derivedearlier (see Sec.
II.B) and is repeated here:
I
i
Jl
Z
l
edge.i
l
min
P
i
l
X
j
S
ij
l. l
j
" #
dl 69
where P
i
l is the contribution of the primary uorescence caused by incident photons
with wavelength l, and S
ij
l. l
j
is the contribution of the secondary uorescence (en-
hancement) by characteristics photons l
j
which have been excited by primary photons l.
The summation in Eq. (16) or (69) is over all elements j that have characteristic lines that
can excite the analyte i. For each of these elements j, all characteristic lines must be
considered. This is quite simple if none of the L lines or M lines of element j can excite the
analyte. In that case, only the Ka and Kb lines are to be considered. If the L lines of an
element j are energetic enough for enhancement of the analyte, the sheer number of L lines
(e.g., W has more than 20 characteristic L lines that can be considered) would make the
calculation very time-consuming. Therefore, most programs consider only three to ve L
lines for each element. A similar reasoning holds for the M lines.
Application of these formulas was originally limited to the prediction of intensities
for specimens with given composition. The application of those formulas for analysis was
not pursued until the 1960s. The method of analyzing specimens by fundamental para-
meter equations has been developed independently around the same time by Criss and
Birks (1968) and by Shiraiwa and Fujino (1966). Due to the large amount of calculations
involved (especially the integration of the incident spectrum and the calculation of the
contribution of enhancement), these programs initially ran on mainframes and mini
computers. A PC version of the same program was proposed by Criss in 1980 (Criss,
1980a).
The application of a fundamental parameter method for analyzing specimens con-
sists of two steps: calibration and analysis. Both steps will be discussed in more detail in
the following subsections.
b. Calibration
The fundamental parameter equation is used to predict the intensity of characteristic lines
for a composition identical to that of the standard used. If more than one standard spe-
cimen is used, the calculations are repeated for each of the standards. The calculations are
performed using the appropriate geometry (i.e., incidence and take-o angles are taken in
agreement with those of the spectrometer used) and the parameters determining the tube
spectrum (such as the anode material, voltage, thickness of beryllium window, and so on)
correspond to the ones used in the spectrometer for the measurements. The intensities
predicted are (almost always) net intensities, void of background, line overlap, crystal
uorescence, and so on. Hence, the measured intensities must be corrected for such
spectral artifacts. These theoretically predicted intensities are then linked to the actually
measured ones. If only one standard specimen is used, the ratio between the measured
intensity and the calculated intensity is calculated. If more than one standard is used, the
net intensities obtained from the measurements are plotted versus the calculated intensities
and a straight line can be determined for each characteristic line measured. The slope of
such a line is the proportionality factor between predicted (calculated) and measured in-
tensities. In general, this relationship will be determined more accurately if more standards
are used.
A special case of calibration ensues when one uses pure elements as standards. Di-
viding each of the measured (net) intensities of the corresponding pure element gives the
relative intensity. This relative intensity can be calculated directly by some fundamental
parameter programs. In fact, some programs use equations that express the intensity of
characteristic radiation directly in terms of relative intensity. The relative intensity in this
respect is thus dened as the intensity of the sample, divided by the intensity of the cor-
responding pure element (or compound, if the concentration of the analyte is dened in
compound concentration), under identical conditions for excitation and detection.
Basically, the calibration function, which is determined using the measured in-
tensities of the standards and the calculated intensities, accounts for instrument-related
factors only; matrix eects are accounted for by using the physical theory as described in
the fundamental parameter equation.
The instrument-related parameters for a wavelength-dispersive spectrometer are as
follows:
Collimation
Crystal reectivity
Eciency of detector(s)
Fraction of emergent beam, allowed into the detectors, after Bragg reection (is also
dependent on Bragg angle)
For energy-dispersive spectrometers, the instrument-related parameters are collimation
and detector eciency. The eect of the windows of the detector, the dead layer, and so
forth can also be taken into account.
c. Analysis
Step 1. For every unknown specimen, a rst estimate of the composition is made.
There are several ways to obtain such a rst estimate. They vary from using a simple, xed
composition (e.g., equal to 100%, divided by the number of elements considered; in the
rst estimate, all the concentrations of each of the elements are thus taken equal to one
another) to the composition derived from the measured intensities in combination with the
calibration curves. Using the calibration data, it is possible to estimate for each element
the intensity that would be obtained if the pure elements were measured. These numbers
are then used to divide the intensity of the corresponding element, measured in the un-
known specimen. The resulting fractions are scaled to 100% and used as the rst estimate.
Step 2. For this estimate of composition, the theoretical intensities are calculated.
These are converted to measured intensities, using the calibration data, so that these two
sets of intensities for the same specimen can be compared.
Step 3. The next estimate of composition is obtained based on the dierence between
the measured and calculated intensities. Again, there are dierent methods available:
1. The simplest method is based on linear interpolation. If, for a given element, the
measured intensity is 10% higher than the calculated intensity, the concentration
of that element is increased by 10%.
2. Rather than a linear relationship, some authors (Criss and Birks, 1968) use an
interpolation based on three points. This is done because the relationship
between concentration and intensity is usually non linear over a wider range.
If the specimen is a pseudobinary, hyperbolic relationships have proven to be
better approximations. For more complex specimens, it still works out quite
well, because the concentrations of the other elements are considered xed at this
stage. The hyperbolic equation requires a minimum of three points for its
parameters to be determined. The points requiring the least additional
calculation time are the following:
The origin (net intensity zero, at concentration zero).
The pure element, W100%; the corresponding intensity has already been
calculated.
The point Wcurrent estimate, the intensity has already been calculated.
These three points allow an hyperbolic relation to be established around the
current estimated composition. From this curve and the measured
intensity, the new concentration estimate is derived. This approach is
repeated for every analyte element. This method usually provides a faster
convergence than using the simple straight line.
3. It is also possible to use gradient methods to determine the next composition
estimate. The formula for the rst derivative, with respect to concentration, of
the fundamental parameter equation have been published (Shiraiwa and Fujino,
1968), but the calculation is cumbersome and time-consuming. Also, the
derivatives can be obtained by a nite-dierence method, where the eect of a
small change in composition on the intensity is observed.
Step 4. The process, starting at Step 2, is now repeated until convergence is obtained.
Dierent convergence criteria exist. The calculation can be terminated if one of the fol-
lowing criteria is satised for all the elements (compounds) concerned:
1. The intensities, calculated in Step 2, do not change from one step to another, by
more than a present level.
2. The intensities, calculated in Step 2 agree, to within a preset level, with the
measured intensities
3. The compositions, calculated in Step 3, do not change from one step to another
by more than a present level (e.g., 0.0005 or 0.0001 by weight fraction).
One or more of these criteria might be incorporated in the program. These criteria,
however, are no guarantee that the nal result is accurate to within the level, specied in
the convergence criteria. Furthermore, especially with convergence criteria based on
concentrations (such as criteria 3), it must be realized that a convergence criterion of
0.0005 is unacceptable when determining elements at levels below 0.0005.
d. Extensions to the Method
More complex scenarios are possible. The most common one includes the calculation
of a set of inuence coecients (based on theoretical calculations) to obtain a com-
position quickly, close to the nal result. Next, the fundamental parameter method is
applied (Rousseau, 1984a). This should yield faster convergence in terms of compu-
tation time, because the calculation by inuence factors of the preliminary composition
is very fast. This method reduces the number of evaluations of the fundamental param-
eter equation.
Also, the dierent programs available dier quite markedly in their treatment of
the intensities of the standards measured. Some programs use a weighting of the stan-
dards, stressing the standard(s) closest (in terms of intensity) to the unknown (Criss,
1980a). Such programs use a dierent calibration for each unknown specimen. The
unknown specimen dictates which standards will be given a high weighting factor and
which standards will be used with less weighting. Other programs use all standards with
equal weighting.
e. Typical Results
Early results of the fundamental parameter method on stainless steels are given by Criss
and Birks (1968). The average relative dierences between x-ray results and certied values
were about 34%. Later, Criss et al. (1978) reported accuracies of about 1.5% relative for
stainless steels, using a more accurate fundamental parameter program. Typical results for
tool steel alloys are given in Table 3. Often, the fundamental parameter method is con-
sidered to be less accurate than an inuence coecient algorithm. This is caused primarily
by the fact that the fundamental parameter method has extensively been used and
described as a method that allows quantitative analysis with only a few standards. This
is obviously an advantage, but it does not imply that fundamental parameter methods
cannot be used in combination with many standards similar to the unknown. As a matter
of fact, on several occasions and with a variety of matrices, the authors have obtained
results of analysis with an accuracy similar to that of inuence coecient algorithms when
using the same standards in both cases.
f. Factors Aecting Accuracy
The accuracy of the nal results is determined by the following:
The measurement
The specimen preparation
The physical constants used in the fundamental parameter equation
The limited description of the physical processes that are considered in the
fundamental parameter equations
The standard and the calibration
In the following discussion, the eect of measurements and specimen preparation
will not be considered.
Table 3 Analysis of Seven Tool Steels with a Fundamental Parameter Program [XRF11, from
CRISS SOFTWARE, Largo, MD (Criss, 1980)]
Element Minimum conc. (%) Maximum conc. (%) Standard deviation (%)
W 1.8 20.4 0.52
Co 0.0 10.0 0.20
Mn 0.21 0.41 0.01
Cr 2.9 5.0 0.013
Mo 0.2 9.4 0.04
S 0.015 0.029 0.003
P 0.022 0.029 0.003
Si 0.14 0.27 0.03
C 0.65 1.02 0.16
Note: One standard has been used. The minimum and maximum concentrations refer to the minimum and
maximum concentrations in the set of analyzed specimens, respectively. The standard deviation is calculated from
the difference between concentration values found and certied.
Source: Data courtesy of Philips Analytical, Almelo, The Netherlands.
g. Physical Constants
The physical constants used in the fundamental parameter equations are as follows:
Incidence and exit angles
Spectrum of incident beam
Mass-attenuation coecients
Flourescence yields
Absorption jump ratios
Ratios of intensity of dierent lines within a given series (e.g., Ka,Kb ratio)
Wavelengths (or energies) of absorption edges and emission lines
Incidence and exit angles. The incidence angle in most wavelength-dispersive (WD) and
energy-dispersive (ED) spectrometers is, infact, denedbyarelativelywide cone withadierent
intensity at the boundaries compared to the center. This incident cone is neglected and the
incident radiation is considered parallel, along a single, xed direction. A similar observation
holds for the exit angle. The eect is far less pronounced if diraction from a plane crystal
surface is used for dispersion, as is done, for example, in most sequential WD spectrometers.
This has been studied to some extent by Mu ller (1972). To our knowledge, none of the fun-
damental parameter programs available takes this eect intoaccount. Its inuence, however, is,
to some extent, compensated for by calibration with standard specimens.
Spectrum of incident beam. The spectrum of the incident beam from an x-ray tube
spectrum requires more attention. Parts of the primary spectrum might excite an element B
that, in turn, excites element A very eciently. In such cases, this enhancement may make
the intensity of element A sensitive to small errors in the tube spectrum representation,
which would not be compensated for if the pure A was used for calibration. This can arise,
for example, in the analysis of silicazirconia specimens with a Rh tube (Criss, 1980b).
Pure silica is relatively insensitive to the intensity of the characteristic K lines of Rh. In
combination with Zr, however, the situation is dierent. Indeed, the RhK lines are strongly
absorbed by Zr. Zr then emits K and L lines that enhance Si. As a result, the Si intensity is
more sensitive to the RhK lines in SiO
2
ZrO
2
mixtures than it is in pure SiO
2
. Tube spectra
have been calculated using, for example, the algorithm of Pella et al. (1985).
Mass-attenuation coecients. There are several compilation of mass-attenuation
coecients, published in the literature. A continuing eort to compile the most compre-
hensive table has been undertaken by the National Institute of Standards and Technology
(formerly National Bureau of Standards), Gaitherburg, MD.
When selecting a table of mass-attenuation coecients for use in a fundamental
parameter program, the following question must be addressed: Does the table cover all the
analytical needs? (In practice, does it cover the complete range of interest from the longest
wavelength considered, down to the excitation potential of the tube?)
The analyst should be aware that the use of formulas to generate mass-attenuation
coecients can lead to values that can be signicantly dierent from the corresponding
table values.
Presently, for applications in XRF, the complications of McMaster et al. (1969),
Heinrich (1966), Leroux and Thinh (1977), or Veigele (1974) are most often used. A short
discussion on the agreement between some of these compilations has been presented by
Vrebos and Pella (1988). A more recent compilation has been published by de Boer (1989).
Fluorescence yields. A comprehensive reference to uorescence yields, including
CosterKronig transitions, can be found in the work of Bambynek et al. (1972). (see
also Chapter 1, and Appendix VI).
Absorption jump ratios. These can be derived from the tables of attenuation coef-
cients.
Ratios of dierent uorescent lines within a family. Data for the K spectra can be
found in the work by Venugopalo Rao et al. (1972) (see also Chapter 1).
Wavelengths of absorption edges and emission lines. A comprehensive table was
published by Bearden (1967) and is also presented in the appendices to Chapter 1. Because
attenuation coecients are wavelength dependent, an error in a wavelength of any char-
acteristic line will automatically lead to a bias in the corresponding attenuation coecients.
h. Limited Physical Processes Considered
The fundamental parameter equation [Eq. (16)] does not consider all physical processes in
the specimens. Three of the most obvious that are missing are described here.
Tertiary uorescence. Although the formula for tertiary uorescence has been de-
rived by, for example, Shiraiwa and Fujino (1966) and Pollai and Ebel (1971), it is not
included in most fundamental parameter programs. Usually, the tertiary uorescence eect
is considered small enough to be negligible. Shiraiwa and Fujino (1967, 1974) have pre-
sented data showing a maximum contribution of tertiary uorescence of about 3% relative
to the total intensity of Cr in FeCrNi specimens. Therefore, even in FeCrNi specimens
whose characteristic lines and absorption edges are ideally positioned relative to one an-
other to favor enhancement, the eect of tertiary uorescence is quite limited. Higher-order
enhancement is also possible, but it is even less pronounced than tertiary uorescence.
Scatter. Other processes not considered in most of the fundamental parameter
methods are coherent and incoherent scatter of both the primary spectrum and the
uorescent lines. This is usually justied by pointing out that the photoelectric eect is, by
far, the major contribution to the total absorption. It is believed that the contribution by
scattered photons to the excitation of characteristic photons is negligible. However, in
some cases the scattered primary spectrum may have a considerable inuence, as illu-
strated earlier in this chapter. The equations describing the contribution of scatter to
uorescent intensity have been derived by Pollai et al. (1971). These equations have ob-
viously many similarities to those for secondary uorescence.
Photoelectrons. The processes that are probably the must unknown in the funda-
mental parameter method are related to the contributions of the photoelectrons and of the
Auger electrons that are produced as a result of absorption of the primary and uorescent
x-ray photons. These electrons have sucient energy to excite other atoms and thus create
additional uorescence. This is especially important in the case of low-atomic-number
elements, as has been described by Mantler (1993) and has been illustrated, for example,
by Kaufmann et al. (1994).
i. Standards and Calibration
The use of good standards (similar to the unknown) will almost always lead to more
accurate results, compared to a situation where the standards used have a widely dierent
composition from that of the unknown. This is because most of the uncertainties, caused
by inaccuracies in the physical constants, cancel. The degree of similarity between stan-
dards and unknown has an important eect on the accuracy of the analysis.
3. Influence Coefficient Algorithms
Another class of mathematical methods calculates the matrix eect by means of coe-
cients, rather than by evaluating the fundamental parameter equation for each unknown.
It will be shown that these coecients can also be calculated from theory, using funda-
mental parameters. Many of such inuence coecient algorithms have been proposed and
they have been divided and subdivided in dierent ways (Lachance, 1979). It is not the
intention to discuss all of the algorithms here; only a few selected ones will be discussed.
This selection is based on the popularity of the methods and,or on some interesting
characteristics of their underlying theory. Some of these algorithms use only one single
coecient per interfering element; others use more than one. The distinction used here,
however, depends on whether the inuence coecients is considered to be a constant for a
given application or whether the value of the coecient varies with composition. The
latter methods will be discussed in Sec. V.5. Only two algorithms that use constant in-
uence coecients will be discussed here: the LachanceTraill and the de Jongh algo-
rithms. The practical application of the resulting equations (i.e., calibration and analysis)
will be treated separately in Sec. V.7. One has to emphasize that the approach based on
constant inuence coecients has many common aspects with all the inuence coecient
algorithms discussed in Secs. V.4 and V.5.
All of the inuence coecient models express the total matrix eect M
i
for a binary
mixture ij as follows:
M
i
1 m
ij
W
j
70
where m
ij
indicates the true binary inuence coecient describing the matrix eect of j on
the analyte i in binaries ij. More generally,
M
i
1
X
n
j1
j6e
m
ij
W
j
2
6
6
4
3
7
7
5
71
for a multielement specimen, with n being the total number of elements or compounds. In
most of the inuence coecient algorithms, one element is eliminated from the summation
{i.e., one inuence coecient is used when dealing with binaries, as in Eq. (70), and n1
coecients deal with a specimen consisting of n compounds [Eq. (71)]}. In Eq. (71) this is
explicitly indicated by the j 6 e under the summation sign. The eliminated compound e can
be any of the ones present in the specimens; however, most authors eliminate the analyte.
The expression for M
i
is then used as follows:
W
i
R
i
1
X
n
j1
j6e
m
ij
W
j
2
6
6
4
3
7
7
5
72
which links the relative intensity and the inuence coecients to the composition of the
specimen. The relative intensity R
i
for a given analyte is dened as the ratio of the net
measured intensity I
i
in the specimen and the intensity that would have been measured on
the pure analyte I
i
under identical conditions:
R
i

I
i
I
i
73
In practice, the relative intensity is often derived indirectly from measurements on stan-
dards, and the pure element (or compound) is not required. Equation (56) can be rewritten
in terms of R
i
:
W
i
R
i
M
i
74
By denition,
M
i

W
i
R
i
75
The ratio of the weight fraction of the analyte W
i
and its relative intensity R
i
is the
matrix eect M
i
. When the analyte radiation is absorbed (or when the absorption eects
are dominating over enhancement), M
i
is larger than 1. On the other hand, when en-
hancement is dominant, M
i
is smaller than 1. Also, M
i
is smaller than 1 in the absence
of enhancement, but when the absorption by the analyte is signicantly higher than that
of the matrix elements, as indicated by curve 3 in Figure 6. One of the consequences of
Eq. (74) is that for the pure analyte W
i
1, R
i
1 and, thus, M
i
is also equal to 1. This
implies that the matrix eect as introduced here should be viewed as relative to the pure
element and not in absolute terms. Even in the pure element specimen, x-ray photons are
subject to matrix eect. It is possible, even in the pure analyte, to be subjected to en-
hancement eects. This is, for example, the case when L lines are analyzed if the K lines
of the same analyte are also excited. Furthermore, the L lines of elements with large
atomic numbers can be uoresced by other L lines, as indicated in Table 1. However, it
is customary to refer to the situation as a situation without matrix eect. Also, if
M
i
1, Eq. (74) reduces to
W
i
R
i
76
In other words, in the absence of matrix eect, the concentration of the analyte is equal to
the relative intensity. For a specimen containing, for example, 25% (by weight) of the
analyte, an intensity will then be measured that is 25% of that of the pure analyte.
Comparing Eqs. (56) and (74) and considering the denition of the relative intensity
given by Eq. (73) yields
K
i

1
I
i
in other words, the sensitivity is the reciprocal of the intensity of the pure analyte. So, the
intensity of the pure analyte can also be obtained without making measurements for a
specimen of the pure element. It can be obtained from the slope of the calibration line or
even from the measurement on a single specimen:
I
i

I
i
M
i
W
i
77
where M
i
is calculated and I
i
is measured. M
i
can be calculated using Eq. (75), where R
i
is
calculated from theory for the standard specimen of known composition. Therefore, al-
though many inuence coecient algorithms are presented using the format of Eq. (72),
involving the relative intensity, there is no real need to perform measurements of the pure
analyte, as Eq. (72) can be written as
W
i
K
i
I
i
1
X
n
j1
j6e
m
ij
W
ij
2
6
6
4
3
7
7
5
78
where K
i
is then determined during the calibration phase. Furthermore, if the background
is not subtracted, Eq. (78) can be written as
W
i
B
i
K
i
I
i
1
X
n
j1
j6e
m
ij
W
ij
2
6
6
4
3
7
7
5
79
where B
i
is the background expressed as a concentration equivalent. The constants K
i
and
B
i
are then determined during regression analysis.
4. Algorithmswith Constant Coefficients
a. The LachanceTraill Algorithm
Formulation. In 1966, Lachance and Traill proposed a correction algorithm based
on inuence coecients (Lachance and Traill, 1966). The equations are, for a ternary
consisting of the elements (or compounds) A, B, and C:
W
A
R
A
1 a
AB
W
B
a
AC
W
C
80a
W
B
R
B
1 a
BA
W
A
a
BC
W
C
80b
W
C
R
C
1 a
CA
W
A
a
CB
W
B
80c
R
A
, R
B
, R
C
are the relative intensities of A, B, and C, respectively. The coecients a
AB
,
a
AC
, a
CA
, and so forth are called inuence coecients. A more general notation of the
LachanceTraill algorithm is, for analyte i,
W
i
R
i
1
X
n
j1
j6i
a
ij
W
j
2
6
6
4
3
7
7
5
81
where the summation covers all n elements (or compounds) in the specimen, except the
analyte itself. Hence, there are n1 terms in the summation. This is common to all cur-
rently used algorithms. Most of the algorithms, developed earlier [such as Shermans
(1953) and Beattie and Brisseys (1954)], used to have n terms, rather than n1, for spe-
cimens with n elements.
Equations (80a), (80b), and (80c) are linear equations in the concentrations of the
elements W
A
, W
B
, and W
C
, respectively. Note that there are only two coecients for each
analyte element. Consider, for example, the rst equation of the set 80, namely Eq. (80a):
Element A is the analyte and its concentration is equal to the relative intensity R
A
, mul-
tiplied by the matrix correction factor (1 a
AB
W
B
a
AC
W
C
). This matrix correction
factor has only two coecients: one (a
AB
) to describe the eect of element B on the in-
tensity of A and, similarly, one to describe the eect of element C on the intensity of A.
The value of the coecient a
AA
, which would correct for the eect of A on its own in-
tensity (sometimesbut incorrectlyreferred to as self-absorption) is zero. Similarly, a
BB
and a
CC
are also zero. The eect of A on A, however, is taken into account, as will be
shown in the next subsection.
Calculation of the coecients. Lachance and Traill also showed that the inuence
coecients, c
i,
can be calculated for monochromatic excitation by photons with wave-
length `
0
(assuming absorption only) from the expression
a
ij

m
j
l
0
cscc
0
m
j
l
i
cscc
00
m
i
l
0
cscc
0
m
i
l
i
cscc
00
1 82
When secondary uorescence (enhancement) is involved, the coecients are calculated in
the same way. Thus, enhancement is being treated as negative absorption. This assump-
tion is not valid when enhancement is quite severe. Dierences in primary absorption may
easily be confused with enhancement (see Fig. 6). From Eq. (82), it follows clearly that a
ii
is always zero. Therefore, it is not included in the summation of Eq. (81). Also, from
Eq. (82), it follows that the value of the coecients for the LachanceTraill algorithm
cannot be less than 1. It must be stressed that Eq. (82) is only valid strictly for mono-
chromatic excitation and for those analytes that are only subject to absorption (no en-
hancement). In this case, the inuence coecient is concentration independent: It is a
constant, even for the complete concentration range from 0% to 100%. It does, however,
depend on parameters, such as the wavelength of the primary photons and the incidence
and exit angles. In all other cases (polychromatic excitation and,or enhancement),
Eq. (82), strictu sensu, cannot be used. A polychromatic beam (from, e.g., an x-ray tube)
can be replaced by a monochromatic one, by resorting to the eective wavelength. The
eective wavelength, however, is composition dependent (see Sec. II.C). The value of the
coecients, calculated using Eq. (82), is also dependent on composition, although W
i
nor
W
j
gure explicitly in Eq. (82). If enhancement is dominant, another method must be
applied to calculate the coecients.
Inuence coecients for the algorithm of, for example, LachanceTraill can also be
calculated based on actual measurements. Rewriting
W
i
R
i
1 a
ij
W
j
83
to
a
ij

W
i
,R
i
1
W
j
84
yields an expression that can be used to obtain a
ij
, based on the composition of the
binary and the relative intensity R
i
. The drawbacks associated with this method are as
follows:
1. The calculation of R
i
requires the measurements of the intensity on the pure i
(element or compound). This could lead to large errors if the intensity of i in the
binary is much lower than that of the pure, due to, for example, nonlinearity of
the detectors.
2. The pure elements (or compounds) are not always easily available or could be
unsuitable to present to the spectrometer (e.g., pure Na or Tl).
3. Equation (84) is very prone to error propagation when W
i
is close to 1. The
numerator is then a dierence between two quantities of similar magnitude, and
the denominator is then close to zero, magnifying the errors.
4. Also, the availability of suitable binary specimens can present problems: Some
alloys tend to segregate and homogeneous specimens are then dicult to
obtain.
The coecients a
ij
can also be calculated from theory: Calculate R
i
for the binary
with composition W
i
. W
j
rather than obtain it from measurements and substitute in Eq.
(84). This method eliminates drawbacks 1, 2, and 4. However a better methodwithout
the problem associated to error propagationis to use Eq. (75) directly with the values for
R
i
and W
i
. Lachance (1988) has also presented methods to calculate the values of the
coecients from theory.
The LachanceTraill algorithm assumes the following:
1. The inuence coecients can be treated as constants, independent of
concentration; this limits the concentration range in cases where the matrix
eects change considerably with composition.
2. The inuence coecients are invariant to the presence and nature of other
matrix elements. So a
FeCr
, determined for use in FeCrNi ternary specimens, is
the same as a
FeCr
in FeCrMoWTa or FeCr specimens.
b. The de Jongh Algorithm
Formulation. In 1973, de Jongh proposed an inuence coecient algorithm (de
Jongh, 1973), based on fundamental parameter calculations. The general formulation of
his equation is
W
i
E
i
R
i
"
1
X
n
j1
j6e
a
ij
W
j
#
85
where E
i
is a proportionality constant (and is usually determined during the calibration).
The summation covers n1 elements (as is the case with the algorithm of Lachance and
Traill), but the eliminated element, e, is the same for all equations. If, for a ternary spe-
cimen, element C is eliminated, the following equations are obtained:
W
A
E
A
R
A
1 a
AA
W
A
a
AB
W
B
86a
W
B
E
B
R
B
1 a
BA
W
A
a
BB
W
B
86b
W
C
E
C
R
C
1 a
CA
W
A
a
CB
W
B
86c
Note that in order to obtain the concentration of elements A and B, the concentration of
C, W
C
, is not required. This is dierent from Lachance and Traills algorithm: In order to
calculate the concentration of A, using Eq. (80a), the concentrations of both B and C are
required. If the user is not really interested in element C (e.g., element C is iron in stainless
steels), Eq. (86c) need not be considered and the analysis of the ternary specimen can be
done by measuring R
A
and R
B
and solving Eqs. (86a) and (86b).
Calculation of the coecients. de Jongh also presented a method to calculate the
coecients from theory. The basis is an approximation of \
i
,1
i
by a Taylor series
around an average composition:
W
i
R
i
E
i
d
i1
DW
1
d
i2
DW
2
d
in
DW
n
87
where E
i
is a constant given by
E
i

W
i
R
i

average
88
and
DW
i
W
i
W
i.average
89
d
ij
are the partial derivatives of W
i
,R
i
with respect to concentration:
d
ij

0W
i
,R
i
0W
j
90
In practice, these derivatives are calculated as nite dierences. W
i
,R
i
is calculated
for a specimen with the average composition W
1.average
,W
2.average
, . . . ,W
n.average
(symbol
W
i
,R
i
average
. Then, the concentration of each element j in turn is increased by a small
amount [e.g., 0.1% (0.001 in weight fraction)] and W
i
,R
i
is calculated for that composi-
tion (symbol [W
i
,R
i
W
j
0.001
). Substituting in Eq. (90) yields
d
ij

0W
i
,R
i
0W
j
W
i
,R
i
W
j
0.001
W
i
,R
i
average
0.001
91
This process is repeated for each of the elements j to calculate all the coecients for
analyte i. This is also repeated for the other analyte elements. The coecients, calculated
from Eq. (91), can be used in Eq. (87) for analysis. Equation (87), however, has n factors
rather than n1 and uses DW
j
rather than W
j
. Using the fact that
X
n
j1
DW
j
0 92
or
DW
e
DW
1
DW
2
DW
n
93
one element e can be eliminated. The resulting equation is similar to Eq. (87), but has only
n1 terms:
W
i
R
i
E
i
b
i1
DW
1
b
i2
DW
2
b
in
DW
n
94
with
b
i1
d
i1
d
ie
95
for all b
ij
except b
ie
, which is equal to zero. Equation (94) has n1 terms, but they are still
in DW, rather than W. Transformation of DW to W is done by substituting Eq. (89) in
Eq. (94):
W
i
R
i
E
i

X
n
j6e
b
ij
W
j.average

X
n
j6e
b
ij
W
j
96
which can be rearranged to Eq. (85) with
a
ij

b
ij
E
i

P
n
j6e
b
ij
W
j.average
97
Combining Eq. (85) with Eqs. (75) and (88) yields
W
i
M
i.average
R
i
1
X
n
j1
j6e
a
ij
W
j
2
6
6
4
3
7
7
5
98
indicating that the weight fraction of the analyte is calculated from its relative intensity, a
matrix correction term, and the matrix correction term for the average composition (which
for a given composition is a constant). The value for M
i,average
can be calculated using the
inuence coecients calculated and taking the composition (W
i
, W
j
) equal to the average
composition. This equation is very similar at rst sight to the LachanceTraill equation
[Eq. (81)], except for the term M
i,average
.
Typical results. Tables with de Jonghs coecients have been used for a wide
variety of materials, including high-temperature alloys, brass, solders, cements, glasses,
and so forth. An example for stainless steels is given in Table 4. Results are shown for
Mn, Ni, and Cr only. For these analytes, the matrix eects are the most important.
Other elements, such as Si, P, S, and C, are also present at trace level. The coecients are
calculated at a given composition [see Eq. (91)]. The practical range of concentration over
which these coecients yield accurate results varies from 5% to 15% in alloys to the whole
range from 0% to 100% in fused oxide specimens.
Comparison between the algorithms of de Jongh and LachanceTraill. The following
points can be noted:
1. The basis of the de Jongh algorithm is a Taylor series expansion, around an
average (or reference) composition. The values of the coecients calculated
depend on this composition.
2. De Jongh can eliminate any element; Lachance and Traill eliminate the analyte
itself: a
ij
is zero. De Jongh eliminates (i.e., xes the coecient to zero) the same
element for all analytes. Eliminating the base material (e.g., iron in steels) or the
loss on ignition (for beads) generally leads to smaller numerical values for the
coecients and avoids the necessity to determine all elements.
3. De Jonghs coecients are calculated at a given reference composition. They are
composition dependent and take into account all elements present. A coecient
a
ij
represents the eect of element j on the element i in the presence of all other
elements: They are multielement coecients rather than binary coecients. This
is seen in Table 5, where the values of the coecients a
CrCr
and a
CrNi
are shown
for several dierent specimens, but with identical concentrations for the analyte
Table4 Analysis of Stainless Steels with Theoretical Inuence Coefcients (de Jongh)
Element Min.
a
(%) Max.
a
(%) Std. dev.
b
(%)
Mn 0.64 1.47 0.015
Cr 12.40 25.83 0.06
Ni 6.16 20.70 0.06
a
Min., Max.: minimum and maximum concentration in the set of analyzed specimens, respectively.
b
Std. dev.: standard deviation, calculated from the difference between concentration values found
and certied.
Source: Data courtesy of Philips Analytical, Almelo, The Netherlands.
Table 5 Values for Inuence Coefcients a
CrCr
and a
CrNi
, Calculated According to the Algorithm
of de Jongh, for Selected Specimens
W
Cr
W
Fe
W
Ni
W
Ti
W
W
a
CrCr
a
CrNi
0.18 Bal. 0.08 0 0 2.06 0.750
0.18 Bal. 0.08 0 0.08 2.30 0.817
0.18 Bal. 0.08 0.08 0 2.49 0.868
Note the variation of the values of the coefcients, depending on the presence of Ti or W.
and the interferent. In all cases, Fe has been eliminated and W and Ti are either
present at 0.08 or not.
4. The calculation of the coecients is based on theory, treating both absorption
and enhancement eects. Hence, the coecients are susceptible to the errors,
described earlier (Sec. V.D.2). However, the calculation of the coecients
involves a division of the matrix correction terms for the slightly aected
composition by the corresponding term of the reference composition [Eq. (97)].
This compensates to a large degree for some of the biases introduced by the
fundamental parameters.
5. For a specimen, containing n elements, there are n equations (one for each of the
elements) if one uses the LachanceTraill algorithm. Each of these equations has
n1 inuence coecients; the coecient of the analyte in each of the equations
has been set to 0. For the same specimen, de Jongh only requires n1 equations,
using n1 coecients per equation. One element has been eliminated
throughout. This element (or compound) is usually one that is of no or little
interest to the analyst (e.g., iron in steels or the loss on ignition in fused beads)
(de Jongh, 1979). The nth equation (for the eliminated element) can also be
written: Its form is identical to the others, it has also n1 terms, and the
coecients can be calculated following exactly the same procedure as for the
other coecients.
6. The coecients in the LachanceTraill equation have been calculated
empirically, using measured data from many more standards than used in the
de Jonghs algorithm, which always used theoretical coecients. These
coecients could be obtained from Philips, eliminating the need for a large
computer at each users site. With increased computer capabilities at the
disposition of every analyst, the calculation of the coecients from theory has
now been feasible for some years. It is possible to calculate the coecients for
the LachanceTraill algorithm from theory as well (Lachance, 1988).
5. AlgorithmswithVariable Coefficients
a. Introduction
Both algorithms discussed so far use a single, constant coecient for each (except one)
interfering element: The expression from Lachance and Traill uses coecients, expressing
the eect of one element on the characteristic intensity of the analyte, relative to the
analyte, ignoring all other elements. Such coecients are therefore referred to as binary
coecients. The algorithm of de Jongh calculates multielement inuence coecients ef-
fectively. Such coecients predict the eect of one element on the intensity of another in a
given matrix.
This distinction between binary and multielement coecients can clearly be seen in,
for example, a ternary specimen. Algorithms based on binary coecients add interelement
eects from each of the constituent elements. They calculate the matrix eect using in-
uence coecients that have been calculated for binaries. Assume a NiFeCr specimen.
The total matrix eect of Cr is accounted for using a coecient expressing the inuence of
Ni on Cr (a
CrNi
) and a similar coecient for Fe on Cr (a
CrFe
). Both of these coecients are
calculated for the corresponding binaries (NiCr and FeCr, respectively). In a ternary
specimen (e.g., NiFeCr), however, the eect of, for example, Ni on Cr is aected by the
presence of Fe (and Ni similarly aects the eect of Fe on Cr). This eect is called the
crossed eect and will be discussed in a following section.
The original expression presented by Lachance and Traill (1966) to calculate the
inuence coecients required the use of monochromatic excitation. An equivalent
wavelength was used to calculate the coecients when the polychromatic excitation is
applied. The equivalent wavelength, however, has been shown to vary with composition,
as treated earlier in this chapter. The theoretical coecients, calculated according to
de Jongh, are also composition dependent, as the reference composition is used explicitly
in the calculations.
This variation is due to the fact that the composition of the matrix varies con-
siderably if analysis is required over a wider range of concentrations. This has been re-
cognized early in the development of inuence coecient algorithms, and many dierent
algorithms with variable coecients have been proposed. A variable inuence coecient
in this respect is an inuence coecient that varies explicitly with concentration of one or
more components in the specimen. Some of these will be discussed in the subsequent
subsections.
b. The ClaisseQuintin Algorithm
Formulation. Claisse and Quintin (1967) extended Lachance and Traills algorithm
by considering a polychromatic primary beam. The resulting equation for W
A
can be
expressed as
W
A
R
A
1
X
n
j6A
a
Aj
W
j

X
n
j6A
a
Ajj
W
2
j

X
n
j6A
X
n
k6A.kj
a
A
j
k
W
j
W
k
" #
99
where the summation over j has n1 terms (all n elements, except i), and the summation
over k has (n2),2 terms (all n elements, except the analyte i and element j; furthermore, if
a
A
j
k
is used, then a
Akj
is not). For a binary specimen, Eq. (99) reduces to
W
A
R
A
1 a
0
AB
W
B
100
with
a
0
AB
a
AB
a
ABB
W
B
101
clearly showing that the inuence coecient a
0
AB
varies linearly with composition (i.e.,
W
B
). For binaries, W
A
1 W
B
; hence, Eq. (101) can also be rearranged to
a
0
AB
a
AB
a
ABA
W
A
102
Equations (101) and (102) are, at least theoretically, identical. It has been shown, however,
that Eq. (102) is preferable to Eq. (101) if specimens with more than two elements (or
compounds) are analyzed (Lachance and Claisse, 1980). This will be discussed in more
detail in Sec. V.D.6. Note that the value of a
AB
in Eq. (101) is dierent from its value in
Eq. (102).
Cross-product coecients. For a ternary specimen, the ClaisseQuintin algorithm
can be written
W
A
R
A
1 a
AB
W
B
a
ABB
W
2
B
a
AC
W
C
a
ACC
W
2
C
a
ABC
W
B
W
C
103
The terms
a
AB
W
B
a
ABB
W
2
B
and
a
AC
W
C
a
ACC
W
2
C
are the matrix corrections, due to B and C, respectively. The term a
ABC
W
B
W
C
corrects for
the simultaneous presence of both B and C and is referred to as a cross-product coecient.
Calculation of the coecients. Claisse and Quintin (1967) also published methods to
calculate the coecients frommeasurements on binary and ternary mixtures or fromtheory.
These methods, however, are now generally superseded by theoretical calculations, such as
discussed in Sec. V.C.4.c and V.C.4.d. Rousseau (1984b) has presented a calculation method
for the coecients in the ClaisseQuintin algorithm, and Wadleigh (1987) has commented
upon this approach.
c. The RasberryHeinrich Algorithm
Following a systematic study of the FeCrNi ternary system, Rasberry and Heinrich
(1974) concluded that the two phenomenaabsorption and enhancementare to be de-
scribed by two dierent equations. They introduced the following algorithm:
W
i
R
i
1
X
n
j6i
A
ij
W
j

X
n
k6i
B
ik
1 W
i
W
k
" #
104
where only one coecient is used for each interfering element. The coecients A
ij
are used
for cases where absorption is the dominant eect. In this case, the coecient B
ik
is taken
equal to zero. If, for a given analyte, all B
ik
coecients are zero, Eq. (104) reduces to the
LachanceTraill expression. When enhancement by element k dominates, a B
ik
coecient
is used. The corresponding A
ij
coecient is then taken equal to zero. Hence, the total
number of terms in both summations is n 1.
The correction factor for enhancement by element k can be rewritten as
a
ik

B
ik
1 W
i
105
showing that a
ik
varies with concentration in a nonlinear fashion. The algorithm is very
popular when analyzing stainless steels and steels in general.
Among the disadvantages of the RasberryHeinrich algorithm are the following:
1. It is not always clear which interfering elements should be assigned a B
coecient and which one an A. In PbSn alloys, the SnLa line is uoresced
(enhanced) by both SnK and PbL lines. Yet, the calibration curve for SnLa
clearly shows that absorption is dominant (Fig. 11).
2. Furthermore, Eq. (105) suggests that the value of B
ik
at W
i
0 is twice the value
at the other end of the calibration range when W
i
1. This is not generally
valid. Mainardi and co-workers (1982) have therefore suggested replacing the 1
in the denominator by an additional coecient.
3. Rasberry and Heinrich did not publish a method for calculating the coecients
from theory.
Some of the disadvantages of calculating empirical coecients have been discussed
in Sec. V.D.4.a. For these reasons, the RasberryHeinrich algorithm is not generally
applicable. However, the concept of a hyperbolically varying inuence coecient has been
incorporated in the three-coecient algorithm of Lachance.
d. The Three-Coecient Algorithm of Lachance
Formulation. In 1981, Lachance (1981) proposed a new approximation to the
binary inuence coecient c
1
i,
given by
m
ij
a
B
ij
a
ij1

a
ij2
W
m
1 a
ij3
1 W
m
106
with
W
m
1 W
i
107
W
m
is the concentration of all matrix elements. It has been shown by Lachance and Claisse
(1980), as well as by Tertian (1976), that variable binary coecients must be expressed in
terms of W
m
(or 1W
i
). For binary specimens, Eq. (106) can be rewritten using W
j
for W
m
and W
i
for (1W
m
):
m
ij
a
B
ij
a
ij1

a
ij2
W
j
1 a
ij3
W
i
108
For specimens with more than two compounds, however, the dierence between Eqs. (106)
and (108) becomes clear. The value for the inuence coecient m
ij
is approximated over
the complete concentration range for the binary by the function in Eq. (106), which relies
on three coecients only. The excellent agreement between the true inuence coecient
m
ij
and the approximation of Eq. (106) is shown in Figure 12 for Fe in FeNi (severe
enhancement) and for Fe in FeCr (pronounced absorption).
For multielement specimens, cross-product coecients a
ijk
are used to correct for the
crossed eect, similar to Eq. (99). The general equation for a multielement specimen is
W
i
R
i
1
X
n
j6i
a
ij1

a
ij2
W
m
1 a
ij3
1 W
m

W
j

X
n
j6i
X
n
k6i.kj
a
ijk
W
j
W
k
" #
109
Figure11 Calibration curves for PbLa (solid line), SnKa (dashed line), and SnLa (dotted line) in
PbSn binaries. The SnLa is apparently dominated by absorption, rather than by enhancement of
SnK and PbL lines.
where the summation over j has n 1 terms (all n elements, except i) and the summation
over k has (n 2),2 terms (all n elements, except the analyte i and element j; furthermore if
a
ijk
is used, then a
ikj
is not).
Vrebos and Helsen (1986) have published some data on this algorithm, clearly
showing the accuracy of the algorithm, using theoretically calculated intensities. The use of
Figure 12 The binary influence coefficient m
FeNi
in FeNi binary systems (j, enhancement, top)
and m
FeCr
in FeCr (j, absorption, bottom) and the approximation by the hyperbolic three-
coefficient algorithm for Lachance (COLA). Note the excellent agreement in both cases. Conditions:
W tube at 45 kV, in a spectrometer with an incidence angle of 63
and 33
take-off angle.
theoretically calculated intensities has the advantage that it avoids errors due to specimen
preparation and measurement errors associated with actual measured data. Pella and co-
workers (1986) have presented a comparison of the algorithm with several others and with
a fundamental parameter method using experimental data.
Calculation of the coecients. The coecients a
ij1
, a
ij2
, and a
ij3
are calculated using
fundamental parameters at three binaries i j. The cross-product coecients are calculated
from a ternary. The compositions of the specimens concerned are listed in Table 6. The
specimens referred to in Table 6 are hypothetical specimens. The intensities are calcu-
lated from fundamental parameters and require no actual measurements on real specimens.
Step 1. Calculate the relative intensity R
i
for the rst composition in Table 6. If the
analysis of interest has more than three elements, then the system is divided in combi-
nations of three elements i, j, k at a time. The analyte is element i, and j and k are two
interfering elements. If the system considered is with compound phases, such as oxides,
then the compositions in Table 6 are assumed to be for the oxides.
Step 2. Using Eq. (84), the corresponding inuence coecient a
B
ij
can be calculated.
Step 3. For this composition, W
m
1 W
i
W
j
0.001, which is small enough to
be considered zero. Hence, Eq. (106) reduces to
a
B
ij
a
ij1
110
a
B
ij
has been calculated in Step 2, so a
ij1
can be computed.
Step 4. Calculate the intensity for the second composition of Table 6 and use Eq. (84)
to calculate a
B
ij
. In most cases, this value will be dierent from the one found in Step 2
because the compositions involved are dierent.
Step 5. 1 W
m
W
i
0.001 is small enough to be considered zero; hence, Eq. (106)
reduces to
a
B
ij
a
ij1
a
ij2
111
a
ij1
and a
B
ij
are known so a
ij2
can be calculated.
Step 6. Calculate the intensity for the third composition of Table 6 and use Eq. (84)
to calculate a
B
ij
. In most cases, this value will be dierent from the one found in Step 2 or 4
because the compositions involved are dierent.
Step 7. Using W
m
1 W
i
0.5 W
i
, Eq. (106) reduces to
a
B
ij
a
ij1

a
ij2
0.5
1 a
ij3
0.5
112
Table 6 Composition of the Specimens Used for the Calculations of the
Coefcients for Lachances Three-Coefcient Algorithm, in Weight Fraction
Specimen No. W
i
W
j
W
k
1 0.999 0.001 0.0
2 0.001 0.999 0.0
3 0.5 0.5 0.0
4 0.999 0.0 0.001
5 0.001 0.0 0.999
6 0.5 0.0 0.5
7 0.30 0.35 0.35
which can be rearranged to
a
ij3

a
ij2
a
B
ij
a
ij1
2 113
all coecients on the right-hand side are known, so a
ij3
can be calculated.
Step 8. Repeat Steps 17 for W
i
and W
k
, to compute the coecients a
ik1
, a
ik2
,
and a
ik3
.
Step 9. Calculate the intensity R
i
for the ternary (composition 7 in Table 6). Cal-
culate a
B
ij
and a
B
ik
, using Eq. (106) and the coecients determined earlier.
Step 10. Eq. (109) combined with Eq. (106) for a ternary specimen ijk reduces to
W
i
R
i
1 a
B
ij
W
j
a
B
ik
W
k
a
ijk
W
j
W
k
114
which can be rearranged to solve for a
ijk
:
a
ijk

W
i
,R
i
1 a
B
ij
W
j
a
B
ik
W
k
W
j
W
k
115
All variables on the right-hand side of Equation (115) are known, so a
ijk
can be calculated.
Step 11. Repeat for other interfering elements ( j and k) and repeat for other analytes i.
Tao et al. (1985) published a complete computer program illustrating the method
and allowing the calculation of the coecients and analysis of unknowns. This program
suers from an oversimplication in that only the measured analytical lines are considered
for enhancement. This would generate erroneous values for the coecients in cases such as
CuZn alloys, where the ZnKa line cannot uoresce the K shell of Cu, but the ZnKb can
do so. If the ZnKa line is used for analysis, the eect of the ZnKb line (enhancement of Cu)
is not taken into account by the program. In practice, however, the only lines that are
considered for enhancement are the characteristic lines used for the analysis of the other
elements. This can be seen, for example, by calculating the coecients twice for FeSi with
identical conditions; once indicating FeKa and SiKa lines are to be used and once in-
dicating that the FeLa be used (Table 7). The value of the coecients for Fe will change;
this is quite obvious because the magnitude and the sort of the matrix eects on the FeKa
and the FeLa characteristic lines are quite dierent. The value for Si, however, should not
change: in both cases, the same elements are present, and using the same excitation
conditions, there is no reason why the coecients should be dierent as the matrix eects
are the same.
e. The Algorithm of Rousseau
Formulation. Rousseau and Claisse (1974) used a linear relationship to approx-
imate the binary coecients and cross-product coecients:
W
i
R
i
1
X
n
j6i
a
ij1
a
ij2
W
m
W
j

X
n
j6i
X
n
k6i.kj
a
ijk
W
j
W
k
" #
116
The binary inuence coecients are thus approximated by
m
ij
a
B
ij
a
ij1
a
ij2
W
m
117
This model can be used as a stand-alone inuence coecient algorithm, but it has also
been proposed as the starting point for a fundamental parameter algorithm (Rousseau,
1984a). The degree of agreement between the inuence coecient m
ij
and the approxi-
mation is shown in Figure 13 for the FeNi and the FeCr binaries. The agreement for the
straight line is obviously not as good as with the COLA algorithm, especially in those cases
where the value of the true inuence coecient varies markedly, as is the case for Fe in
FeCr (absorption). Equation (117) has been compared to the three-coecient algorithm of
Lachance by Vrebos and Helsen (1986). They show that the accuracy is somewhat less
than for Lachances method, but for most practical purposes, the Rousseau algorithm
should give acceptable results.
Calculation of the coecients. Rousseau has shown that the fundamental para-
meter equation can be rearranged to
W
i
R
i
1
X
n
j61
a
ij
W
j
" #
118
and he also proposed a method to calculate the a coecients directly from fundamental
parameters, without calculating the intensity rst (Rousseau, 1984a). As a matter of fact,
Rousseau rst calculates the coecients for a given composition and then calculates the
intensity, using Eq. (118). The coecients in Eq. (116) are calculated in a way very similar
to the method described in Sec. V.D.5.d. The compositions involved are given in Table 8.
The specimens referred to in Table 8 are hypothetical specimens. The intensity is cal-
culated from fundamental parameters and requires no actual measurements on real spe-
cimens. For the rst two binaries of Table 8, the inuence coecient is calculated [symbol
a
ij
(0.20,0.80) and a
ij
(0.80,0.20), respectively]. Then the corresponding values are sub-
stituted in Eq. (117):
a
ij
0.20. 0.80 a
ij1
a
ij2
0.80 119a
a
ij
0.80. 0.20 a
ij1
a
ij2
0.20 119b
These equations can be solved for a
ij1
and a
ij2
. Similarly, using compositions 3 and 4 from
Table 8, the corresponding coecients for ik can be calculated. The cross-product
coecients a
ijk
are calculated using Eq. (115).
6. Specimenswith MorethanTwo Compounds
The methods described by Lachance [Eq. (106)] and Rousseau [Eq. (117)] explicitly de-
scribe algorithms to calculate the value of the binary inuence coecient by a rather
simple, hyperbolic or linear, relationship. Combining these binary coecients to describe
the matrix eect for specimens with more than two elements (or compounds) is described
in this subsection. The ternary system FeNiCr is taken here as an example. Figure 14 gives
Table7 Values for the Coefcients for Eq. (109) for Si in FeSi Binaries
SiKa(FeKa) SiKa(FeLa)
a
ij1
5.396 6.284
a
ij2
1.890 0.015
a
ij3
0.409 0.846
Note: In the second column, Fe is measured using the Ka line and in the last
column, the La line is used. Conditions: W tube at 45 kV, in a spectrometer with an
incidence angle of 63
and a 33
take-off angle.
the relative intensity of FeKa as a function of the weight fraction of Fe in FeNiCr spe-
cimens. There is considerable spread of the intensity of FeKa, even for a constant weight
fraction of Fe. For specimens with a weight fraction of 0.10 Fe, the relative intensity of
FeKa varies between 0.036 and 0.16 (points marked 1 and 2 in Fig. 14). This is due to the
Figure 13 The binary influence coefficient m
FeNi
in FeNi binary systems (j, enhancement, top)
and m
FeCr
in FeCr (j, absorption, bottom) and the approximation by the straight line as suggested
by Rousseau and Claisse. Note the rather large deviations, especially at the high concentration
ranges in FeCr. Conditions: W tube 45 kV, in a spectrometer with an incidence angle of 63
and 33
take-off angle.
rather dierent eect that Ni and Cr have on Fe:Cr is an absorber for FeKa radiation,
whereas the NiK radiation can enhance FeK radiation through the process of secondary
uorescence (enhancement). For these specimens, the matrix eect M
Fe
can be calculated
from Eq. (75). The total matrix eect on Fe, M
Fe
(FeNiCr), in these specimens, at a xed
Fe concentration of 0.1, for example, varies from 0.63 (for 0.1 Fe in FeNi, point 2) to 2.8
(for 0.1 Fe in FeCr, point 1).
Now, the problem is how to calculate the matrix eect in this case, based on in-
uence coecients. Assume a specimen with the following composition: W
Fe
0.1,
Table 8 Composition of the Specimens Used for the Calculations of the
Coefcients for the Linear Approximation According to Rousseaus Algorithm,
in Weight Fraction
Specimen No. W
i
W
j
W
k
1 0.20 0.80 0.0
2 0.80 0.20 0.0
3 0.20 0.0 0.80
4 0.80 0.0 0.20
5 0.30 0.35 0.35
Figure14 The relative intensity of FeKa as a function of the concentration of Fe, in the presence
of Ni and Cr. For every given weight fraction of Fe, the highest value of the intensity is obtained for
the binary system FeNi (enhancement), whereas the lowest intensity is for the binary FeCr
(absorption). The intermediate values are for ternary specimens, where the concentrations of Ni and
Cr vary in steps of 0.1 weight fraction. At a weight fraction of Fe 0.7, the four data points labeled
a, b, c, and d represent the following specimens (W
Fe
, W
Ni
, W
Cr
): a (0.7, 0.0, 0.3), b(0.7, 0.1,
0.2), c (0.7, 0.2, 0.1), and d (0.7, 0.3, 0.0). Points labeled 1 and 2: see text. Experimental
conditions: W tube at 45 kV, 1-mm Be window, incidence and take-off angles 63
and 33
,
respectively.
W
Cr
0.3, and W
Ni
0.6 (again, all concentrations are expressed as weight fractions). The
total matrix eect on Fe will be caused by both Ni and Cr and its magnitude will be
between M
Fe
(FeNi; W
Fe
0.1) 0.63 (for Fe in FeNi) and M
Fe
(FeCr; W
Fe
0.1) 2.8
(for Fe in FeCr). It is assumed that the total eect M
Fe
(FeNiCr; W
Fe
0.1) is proportional
to the concentrations of Ni (0.6) and Cr (0.3) in this example. Applying the law of
weighted averages, the total matrix eect is given by
M
Fe
FeNiCr; W
Fe
0.1 M
Fe
FeNi; W
Fe
0.1
W
Ni
W
Ni
W
Cr
M
Fe
FeCr; W
Fe
0.1
W
Cr
W
Ni
W
Cr
120
There is not a strict derivation indicating the validity of Eq. (120) in the general case.
For cases involving absorption only, the derivation is rather straightforward and based
on the additivity law for absorption. For now, let it suce to indicate that the matrix
eect will change gradually when adding an element or when changing the composition
of the specimen slightly; this is described by Eq. (120). By substituting the numerical
values,
M
Fe
FeNiCr; W
Fe
0.1 0.63
0.6
0.6 0.3
2.8
0.3
0.6 0.3
1.35 121
a value of 1.35 is obtained. This is in good agreement with the theoretical value of 1.31.
Equation (120) is based on the availability of binary inuence coecients calculated at
specimen compositions given by W
Fe
0.10; W
Ni
0.90 and W
Fe
0.10; W
Cr
0.90.
Using the more general expressions for matrix eects,
M
Fe
FeNi 1 m
FeNi.bin
W
Ni.bin
122a
and
M
Fe
FeCr 1 m
FeCr.bin
W
Cr.bin
122b
the following is obtained:
M
Fe
FeNiCr 1 m
FeNi.bin
W
Ni.bin
W
Ni
W
Ni
W
Cr
1 m
FeCr.bin
W
Cr.bin
W
Cr
W
Ni
W
Cr
123
where W
Ni,bin
is the concentration of Ni in the binary FeNi (for example, C
Ni,bin
0.90).
Because
W
Ni.bin
W
Cr.bin
1 W
Fe
W
Ni
W
Cr
124
Equation (123) can be rearranged to
M
Fe
FeNiCr 1 m
FeNi.bin
W
Ni
m
FeCr.bin
W
Cr
125
stressing the point again that the inuence coecients are to be calculated for binaries ij
with the composition W
i
. W
j
1 W
i
. This is the reason why Eqs. (106) and (117) use
W
m
instead of W
j
.
However, applying binary coecients to multielement specimens leads to an in-
complete matrix correction because we are trying to describe the eect of Cr and Ni on
Fe in FeNiCr based on the matrix eects in the corresponding binaries only. This eect
is referred as the crossed eect and has been described by Tertian (1987), who also
proposed a method to correct for this. The proposed method (Tertian, 1987) involves
the use of weighting factors based on the reciprocals of the relative intensities of the
binaries involved. It is a rather cumbersome method, but theoretically valid, and it does
not imply any approximation whatsoever; a discussion is outside the scope of this work.
An easier method is to use the cross-product coecients as used in Eq. (99). The
derivation from Tertian and Vie le Sage (1977) oers some insight in this matter.
Tertian and Vie le Sage (1977) assume that a multielement inuence coecient a
M
ij
can
be approximated as the sum of the binary coecient a
B
ij
and a linear variation with the
other elements:
a
M
ij
a
B
ij
t
ijk
W
k
126
where t
ijk
is a coecient expressing the eect of element k on the inuence coecient a
M
ij
.
Similarly,
a
M
ik
a
B
ik
t
ikj
W
j
127
Substituting Eqs. (126) and (127) in
1 a
M
ij
W
j
a
M
ik
W
k
128
(the superscript M is used to explicitly indicate the use of multi element inuence coe-
cients) yields
1 a
B
ij
W
j
a
B
ik
W
k
a
ijk
W
j
W
k
129
with
a
ijk
t
ijk
t
ikj
130
It is to be realized that crossed eect is introduced by the use of binary coecients; use of
multi element coecients would not lead to crossed eect. Thus, the equation expressing
the matrix eect using binary inuence coecients for specimens with more than two
compounds is
M
i

"
1
X
n
j1
j6i
m
ij.bin
W
j

X
n1
j1
j6i
X
n
kj1
k6i
a
ijk
W
j
W
k
#
131
and is based on cross-product coecients to correct for crossed eect introduced by the
use of binary inuence coecients. The use of the cross-product coecients is not
mandated by the concentration range to be covered (the binary coecients as calculated
by, for example, the algorithm of Lachance are more than adequate) but is a consequence
of the use of binary coecients.
7. Application
In Secs.V.D.4 and V.D.5, several inuence coecient algorithms have been discussed.
Application of the resulting equations for calibration and analysis will be discussed here
and is equally valid for any of the inuence coecient algorithms.
a. Calibration
Step 1. It is assumed that the coecients have been calculated from theory, for
example, using Eq. (84) or (97).
Step 2. Calculate the matrix correction term [the square brackets in Eq. (81), (85),
(99), (104), and (109)] for all standard specimens and for a given analyte. The coecients
are known (Step 1), and for standard specimens, all weight fractions W
i
and W
j
are
known.
Step 3. Plot the measured intensity of the analyte, multiplied by the corresponding
matrix correction term against analyte weight fraction. Then, determine the best line,
W
i
B
i
K
i
I
i
1 132
by minimizing DW
i
(see Sec. V.A). Note that Eq. (132) is more general than Eq. (50),
which does not correct for matrix eects. This process is repeated for all analytes. Other
methods are also feasible. The most common variant is the one where
W
1
B
i
K
i
I
i
133
is used. This is nearly equivalent to Eq. (132) but with brackets:
W
i
B
i
K
i
I
i
1 134
The term B
i
K
i
I
i
is related directly to the relative intensity R
i
. Corrections for line
overlap should only aect this term.
b. Analysis
For each of the analytes, a set of equations has to be solved for the unknown W
i
, W
j
and
so forth. If the matrix correction term used is the one according to Lachance and Trail
[Eq. (81)] or de Jongh [Eq. (85)], then the set of equations can be solved algebraically (n
linear equations with n unknowns for Lachance and Traill and n1 equations with n1
unknowns for de Jongh). Mostly, however, an iterative method is used. As a rst estimate,
one can simply take the matrix correction term equal to 1. This yields a rst estimate of the
composition W
i
, W
j
, and so on. This rst estimate is used to calculate the matrix cor-
rection terms for all analytes. Subsequently, a new composition estimate can be obtained.
This process is repeated until none of the concentrations changed between subsequent
iterations by more than a preset quantity.
If the matrix correction is done using algorithms which use more than one coecient
{e.g., Claisse and Quintin [Eq. (99)] or Rasberry and Heinrich [Eq. (104)]}, then the
equations are not linear in the unknown concentrations and an algebraic solution is not
possible. An iterative method, such as described earlier can be used.
8. Algorithmswith Empirical Coefficients
Empirical coecients are coecients that are not calculated from theory but from ac-
tually measured specimens using regression analysis (Anderson et al., 1974). They were
the basis of the earliest correction methods, but now they are largely superseded by more
theoretical ones. Such empirically determined coecients tend to mix the matrix correc-
tion with the sensitivity of the spectrometer. On the one hand, the matrix eect is de-
termined by the composition of the sample and physical parameters such as take-o
and incidence angles and tube anode and voltage. These are the same for spectrometers of
similar design. The sensitivity of the spectrometer, on the other hand, depends on the
reectivity of the crystals, the eciency of the detectors, and so on. These parameters are
unique for each spectrometer. Also, if one of the analyte lines is overlapped by another
x-ray line, some of this eect can also aect the value of the inuence coecients. The
coecients thus determined are instrument-specic and are not transferable to other
instruments.
Stephenson (1971) has noted that the regression equations involved in the determi-
nation of the coecients in such an empirical way become unstable as the degree of
correlation between the independent variables increases. This mandates careful planning
of the experiment, including the composition of the synthetic standards. Klimasara (1994,
1995) has illustrated the use of standard spreadsheet programs for the calculation of the
values of empirical inuence coecients and composition.
a. The Sherman Algorithm
Sherman (1953) was among the rst to propose an algorithm for correction of matrix
eects. For a ternary system, the algorithm can be represented by the following set of
equations:
a
AA
t
A
W
A
a
AB
W
B
a
AC
W
C
0
a
BA
W
A
a
BB
t
B
W
B
a
BC
W
C
0 135
a
CA
W
A
a
CB
W
B
a
CC
t
C
W
C
0
where a
ij
represents the inuence coecient of element j on the analyte i and t
i
is the time
(in s) required to accumulate a preset number of counts. The constants a
ij
are determined
from measurements on specimens with known composition. Determination of the com-
position of an unknown involves the solving of the above set of linear equations
[Eq. (135)]. This set, however, is homogeneous: Its constant terms are all equal to zero. So,
only ratios among the unknown W
i
can be obtained. In order to obtain the weight frac-
tions W
i
, an extra equation is required. Sherman proposed using the sum of all the weight
fractions of all the elements (or components) in the specimen, which ideally, should be
equal to unity. For a ternary specimen,
W
A
W
B
W
C
1 136
Using Eq. (136), one of the equations in the set of Eqs. (135) can be eliminated. The
solution obtained, however, is not unique: For a ternary, any one of the three equations
can be eliminated. This yields three dierent combinations. Furthermore, any of the
three elements can be eliminated in each of the combinations. Hence, a total of 363 9
dierent sets can be derived from Eqs. (135) and (136), and each of these sets will
generate dierent results. In general, the algorithm yields n
2
dierent results for a system
with n elements or compounds. This is clearly undesirable, because it is hard to de-
termine which set will give the most accurate results. Another disadvantage is the fact
that the sum of the elements determined always equals unity, even if the most abundant
element has been neglected. Furthermore, the numerical values of the coecients de-
pend, among other parameters such as geometry and excitation conditions, also on the
number of counts accumulated. Nonquantiable parameters, such as reectivity of the
diracting crystal used in wavelength-dispersive spectrometers, or tube contamination
will also aect the value of the coecients. The coecients determined on a given
spectrometer cannot be used with another instrument; they are not transferable.
The other algorithms discussed use some form of a ratio method: The Lachance and
Traill algorithm, for example, uses relative intensities. The measurements are then done,
relative to a monitor; this reduces, or eliminates, the eect of such nonquantiable
parameters.
b. The Algorithm of Lucas-Tooth and Price
Lucas-Tooth and Price (1961) developed a correction algorithm, where the matrix eect
was corrected for, using intensity (rather than concentration) of the interfering elements.
The equation can be written as
W
i
B
i
I
i
k
0

X
n
j6i
k
ij
I
j
" #
137
where B
i
is a background term and k
0
and k
ij
are the correction coecients. A total of
n 1 coecients have to be determined, requiring at least n 1 standards. Usually,
however, a much larger number of standards is used. The coecients are then determined
by, for example, a least-squares method. The corrections for the eect of the matrix on the
analyte are done via the intensities of the interfering elements; their concentrations are not
required. The method assumes that the calibration curves of the interfering elements
themselves are all linear; the correction is done using intensities rather than concentra-
tions. The algorithm will, therefore, have a limited range. Its use will be limited to ap-
plications where only one or two elements are to be analyzed (it still involves
measurements of all interfering element intensities) and where a computer of limited
capabilities is used (although calculation of the coecients involves much more compute
capabilities than the subsequent routine analysis of unknowns).
The advantages of the method are as follows:
The method is very fast, because the calculation of composition of the unknowns
requires no iteration.
Analysis of only one element is possible; this requires, however, the determination of
all relevant correction factors.
Very simple algorithm, requiring very little calculation.
c. Algorithms Based on Concentrations
Algorithms similar to Eq. (137) have been proposed, using corrections based on con-
centrations rather than intensities. The values of the coecients were then to be derived
from multiple-regression analysis on a large suite of standards. The main aim was to
obtain correction factors that could be determined on one spectrometer and used, without
alteration, on another instrument. In practice, the coecients still have to be adjusted
because of the intimate and inseparable entanglement of spectrometer-dependent factors
with matrix eects. Furthermore, compared to the algorithms based on intensities, some of
the advantages of the latter are not retained: A calibration for all elements present is now
required, calculation of the composition of unknowns requires iteration, and so forth.
In principle, methods based on theoretically calculated inuence coecients are re-
commended.
VI. CONCLUSION
Among the advantages of XRF analysis are the facts that the method is nondestructive
and allows direct analysis involving little or no specimen preparation. Analysis of major
and minor constituents requires correction for matrix eects of variable (from one spe-
cimen to another) magnitude. If the matrix varies appreciably from one specimen to the
next, then even the intensity of elements present at a trace level can be subject to matrix
eects and a correction is required. Several methods for matrix correction have been
described. Each of these methods have their own advantages and disadvantages. These, by
themselves, do not generally lead to the selection of best method. The choice of the
method to use is also determined by the particular application.
From the previous sections, it may appear that the mathematical methods are more
powerful than the compensation methods. Yet, if only one or two elements at a trace level
in liquids have to be determined, compensation methods (either standard addition or the
use of an internal standard) can turn out to be better suited than, for examples, rigorous
fundamental parameter calculations. Compensation methods will correct for the eect of
an unknown, but constant, matrix. Also, they do not require the analysis of all con-
stituents in the specimen. The mathematical methods (fundamental parameters as well as
methods based on theoretical inuence coecients), on the other hand can handle cases in
which the matrix eect is more variable from one specimen to another. In this respect, they
appear to be more exible than the compensation methods, but they do require more
knowledge of the complete matrix. All elements contributing signicantly to the matrix
eect must be quantied (either by x-ray measurement or by another technique) even if the
determination of their concentrations is not required by the person who submits the
sample to the analyst. Once a particular algorithm is selected, it is customary to use for all
analytes. However, it must be stressed that this is not a requirement. There is only one
requirement for adequate matrix correction: Each analyte should be corrected adequately,
by whatever method.
If complete analysis (covering all major elements) is required, the analyst has the
choice between the fundamental parameter method and algorithms, based on inuence
coecients. Commonly, fundamental parameter methods are (or were) used in research
environments rather than for routine analysis in industry. This choice is more often made
on considerations such as the availability of the programs and computers than on dif-
ferences in analytical capabilities. Inuence coecient algorithms tend to be used in
combination with more standards compared to fundamental parameter methods, because
their structure and simple mathematical representation facilitates interpretation of the
data (establishing a relationship between concentration and intensity, corrected for matrix
eect). The nal choice, however, has to be made by the analyst.
REFERENCES
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Australian Standard 2563-1982, Wavelength Dispersive X-ray Fluorescence Spectrometers
Methods of Test for Determination of Precision. North Sydney, NSW: Standards Association
of Australia, 1982.
Bambynek W, Crasemann B, Fink RW, Freund HU, Mark H, Swift CD, Price RE, Venugopala
Rao P. Rev Mod Phys 44:716, 1972.
Bearden JA. Rev Mod Phys 39:78, 1967.
Beattie HJ, Brissey RM. Anal Chem 26:980, 1954.
Bonetto RD, Riveros JA. X-Ray Spectrom 14:2, 1985.
Claisse F, Quintin M. Can Spectrosc 12:129, 1967.
Criss JW. Adv X-Ray Anal 23:93, 1980a.
Criss JW. Adv X-Ray Anal 23:111, 1980b.
Criss JW, Birks LS. Anal Chem 40:1080, 1968.
Criss JW, Birks LS, Gilfrich JV. Anal Chem 50:33, 1978.
de Boer DKG. Spectrochim Acta 44B:1171, 1989.
de Jongh WK. X-Ray Spectrom 2:151, 1973.
de Jongh WK. X-Ray Spectrom 8:52, 1979.
DeGroot PB. Adv X-Ray Anal 33:53, 1990.
Draper NR, Smith H. Applied Regression Analysis. New York: Wiley, 1966.
Feather CE, Willis JP. X-Ray Spectrom 5:41, 1976.
Garbauskas MF, Goehner RP. Adv X-Ray Anal 26:345, 1983.
Gillam E, Heal HT. Br J Appl Phys 3:353, 1952.
Heinrich KFJ. In: McKinley TD, Heinrich KFJ, Wittry DB, eds. The Electron Microprobe.
New York: Wiley, 1966, p 296.
Holynska B, Markowicz A. X-Ray Spectrom 10:61, 1981.
Hower J. Am Mineral 44:19, 1959.
Hughes H, Hurley P. Analyst 112:1445, 1987.
Hunter CB, Rhodes JR. X-Ray Spectrom 1:107, 1972.
Ingham MN, Vrebos BAR. Adv X-Ray Anal 37:717, 1994.
ISO, Determination of Nickel and Vanadium in Liquid FuelsWavelength-Dispersive X-Ray
Fluorescence Method, ISO 14597. Geneva: ISO, 1995.
Johnson W. International Report BISRA MG,D,Conf Proc,610,67, 1967.
Kaufmann M, Mantler M, Weber F. Adv X-Ray Anal 37:205, 1994.
Klimasara AJ. Adv X-Ray Anal 37:647, 1994.
Klimasara AJ. Workshop on the Use of Spread Sheets in XRF Analysis, 44th Annual Denver X-Ray
Conference, Colorado Springs, CO, 1995.
Lachance GR. X-Ray Spectrom 8:190, 1979.
Lachance GR. International Conference on Industrial Inorganic Elemental Analysis, Metz, France,
1981.
Lachance GR. Adv X-Ray Anal 31:471, 1988.
Lachance GR, Claisse F. Adv X-Ray Anal 23:87, 1980.
Lachance GR, Traill RJ. Can Spectrosc 11:43, 1966.
Leroux J, Thinh TP. Revised Tables of Mass Attenuation Coecients. Quebec: Corporation
Scientique Claisse, 1977.
Li-Xing Z. X-Ray Spectrom 13:52, 1984.
Lubecki A, Holynska B, Wasilewska M. Spectrochim Acta 23B:465, 1968.
Lucas-Tooth HJ, Price BJ. Metallurgia 64:149, 1961.
Mainardi RT, Fernandez JE, Nores M. X-Ray Spectrom 11:70, 1982.
Mantler M. Adv X-Ray Anal 36:27, 1993.
McMaster WH, Delgrande NK, Mallet JH, Hubbel JH. Compilation of X-Ray Cross Sections,
UCRL 50174, Sec II, Rev 1, 1969.
Mu ller RO. Spectrochemical Analysis by X-Ray Fluorescence. New York: Plenum Press, 1972,
chap 9.
Pella PA, Feng LY, Small JA. X-Ray Spectrom 14:125, 1985.
Pella PA, Tao GY, Lachance GR. X-Ray Spectrom 15:251, 1986.
Pollai G, Ebel H. Spectrochim Acta 26B:761, 1971.
Pollai G, Mantler M, Ebel H. Spectrochim Acta 26B:733, 1971.
Rasberry SD, Heinrich KFJ. Anal Chem 46:81, 1974.
Rousseau RM. X-Ray Spectrom 13:121, 1984a.
Rousseau RM. X-Ray Spectrom 13:3, 1984b.
Rousseau RM, Claisse F. X-Ray Spectrom 3:31, 1974.
Sherman J. The Correlation Between Fluorescent X-Ray Intensity and Chemical Composition.
ASTM Special Publication No 157. Philadelphia: ASTM, 1953, p 27.
Sherman J. Spectrochim Acta 7:283, 1955.
Shiraiwa T, Fujino N. Bull Chem Soc Japan 40:2289, 1967.
Shiraiwa T, Fujino N. Adv X-Ray Anal 11:63, 1968.
Shiraiwa T, Fujino N. X-Ray Spectrom 3:64, 1974.
Sparks CJ. Adv X-Ray Anal 19:19, 1976.
Stephenson DA. Anal Chem 43:310, 1971.
Tao GY, Pella PA, Rousseau RM. NBSGSC, a FORTRAN program for quantitative X-Ray
Fluorescence Analysis. NBS Technical Note 1213. Gaithersburg, MD: National Bureau of
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Tertian R. Adv X-Ray Anal 19:85, 1976.
Tertian R. X-Ray Spectrom 16:261, 1987.
Tertian R, Vie le Sage R. X-Ray Spectrom 6:123, 1977.
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Vrebos BAR, Pella PA. X-Ray Spectrom 17:3, 1988.
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Venugopala Rao P, Chen MH, Crasemann B. Phys Rev A 5:997, 1972.
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SUGGESTIONS FOR FURTHER READING
Bertin EP. Principles and Practice of X-Ray Spectrometric Analysis. 2nd ed. New York: Plenum
Press, 1975.
Jenkins R, Gould RW, Gedcke D. Quantitative X-Ray Spectrometry. 2nd ed. New York: Marcel
Dekker, 1995.
Tertian R, Claisse F. Principles of Quantitative X-Ray Fluorescence Analysis. New York: Wiley,
1982.
6
Quantication in XRF Analysis
of Intermediate-Thickness Samples
Vienna, Austria
Rene E. Van Grieken
I. INTRODUCTION
A number of approaches have been developed for quantitation in x-ray uorescence
(XRF) analysis of intermediate-thickness samples whose mass per unit area m fullls the
relation
m
thin
< m < m
thick
1
where m
thin
and m
thick
are the values of mass per unit area for thin and thick samples [for
a denition, see Chapter 1, Eqs. (93) and (95)]. Intermediate samples can be preferable
to thick specimens because remaining uncertainties about mass-attenuation coecients
have a smaller eect on the analysis results, less material is required, the sensitivity
is more favorable for low-Z elements, and secondary enhancement eects are less
important.
Historically, the oldest correction method applied in quantitative XRF analysis of
intermediate-thickness samples is the emissiontransmission (ET) method in which the
specic x-ray intensities from a sample are measured successively with and without a
target positioned adjacent to the back of the sample in a xed geometry. Recently, the
ET method has thoroughly been evaluated, and both the advantages and limitations of
the technique are well identied. A number of modications of the ET method, de-
veloped in recent years, allowed an essential extension of its applicability range. To
avoid additional measurements that are inevitable in the emissiontransmission method,
some alternative correction procedures based on the use of scattered primary radiation
were also developed. In recent years, however, only a few papers have been published in
this eld.
The underlying principles as well as the ranges of applicability and the limitations of
the correction procedures applied to XRF analysis of both homogeneous and hetero-
geneous intermediate-thickness samples are outlined here.
II. EMISSION---TRANSMISSIONMETHOD
In the absence of enhancement eects and assuming monochromatic excitation, the mass
per unit area of the element i. m
i
, for homogeneous intermediate-thickness samples, can be
calculated from [see Eq. (90) in Chapter 1]:
m
i

I
i
E
i
B
i
Ab
corr
2
where
B
i

GI
0
E
0
E
i
t
0
i
E
0
.
i
p
i
1 1,j
i
sin
1
3
and Ab
corr
is the absorption correction factor given by
Ab
corr

jE
0
csc
1
jE
i
csc
2
m
1 expfjE
0
csc
1
jE
i
csc
2
mg
4
[The symbols used in Eqs. (2)(4) are explained in Chapter 1, Eqs. (88) and (89).]
The value of the constant B
i
(sometimes called the sensitivity factor) can be de-
termined either experimentally as the slope of the straight calibration line for the ith
element obtained with thin homogeneous samples or semiempirically based on both the
experimentally determined GI
0
E
0
value and the relevant fundamental parameters (Yap
et al., 1987; Markowicz et al., 1992a).
The absorption correction factor Ab
corr
represents the combined attenuation of
the primary and uorescent radiations in the whole specimen and can be determined
individually for each sample by transmission experiments (Leroux and Mahmud, 1996;
Giauque et al., 1973). These are done by measuring the x-ray intensities with and without
the specimen from a thick multielement target located at a position adjacent to the back of
the specimen, as shown in Figure 1.
If I
i
S
. I
i
T
. and I
i
0
are the intensities after background correction from the
sample alone, from the sample plus target, and from the target alone, respectively, then the
combined fraction of the exciting and uorescent radiations transmitted through the total
sample thickness is expressed by
expfjE
0
csc
1
jE
i
csc
2
mg
I
i
T
I
i
S
I
i
0
H 5
After a simple transformation, Eq. (2) can be rewritten as
Figure1 Experimental procedure used in the emissiontransmission method for the correction of
matrix absorption effects.
m
i

I
i
E
i
B
i
ln H
1 H
6
The emissiontransmission method can only be applied in the quantitative XRF
analysis of homogeneous samples of which the mass per unit area is smaller than the
critical value, m
crit
. dened by
m
crit

ln H
crit
jE
0
csc
1
jE
i
csc
2
7
where H
crit
is the critical value of the transmission factor dened by Eq. (5); in practice,
H
crit
0.1 or 0.05.
To minimize possible absorption correction errors resulting from enhancement of
the specimen radiation by scattered target radiation, targets that yield a high ratio of
scattered to uorescent radiation should not be used.
Giauque et al. (1979) developed a modied version of the emissiontransmission
method. Using data from the attenuation measurements and Eq. (5), the values of
jE
0
csc
1
jE
i
csc
2
m j
T
m are calculated for the energies of characteristic
x-rays of all elements present in a thick multielement target. If these values are plotted
versus the uorescence x-ray energy on a loglog scale (Fig. 2), an approximate value for
Figure 2 Curves of [m(E
0
) csc
1
j(E
i
) csc
2
]m and mm(E
i
) csc
2
values versus fluorescence
x-ray energy for an NBS SRM 1632 coal specimen. (From Giauque et al., 1979. Reprinted with
permission from Analytical Chemistry. Copyright American Chemical Society.)
jE
0
csc
1
can be obtained by extrapolation of the curve to the energy of the excitation
radiation. In turn, values for mjE
i
csc
2
can be calculated, a curve for these values
drawn, and a new value for mjE
0
csc
1
established. This last step is iterated several
times. Using data from the latter curve, the absorption correction factors for all radiations
of interest can be calculated from Eq. (4). If some elements to be determined are major or
minor constituents, a few separate curves for mjE
i
csc
2
values should be plotted be-
tween the preselected x-ray energies corresponding to the relevant absorption edges. In the
emissiontransmission method of Giauque et al. (1979), the incoherent scattered radiation
corrected for matrix absorption is used as the internal standard to compensate for var-
iations in sample mass, x-ray tube output, and sample geometry.
In practical applications of the emissiontransmission method, the values of the
transmission factor H [Eq. (5)] determined for a few energies of the characteristic x-rays
of some elements present in a multielement target are used to construct a curve
ln lnH
1
lnj
T
m versus ln E. which enables one to calculate the absorption cor-
rection factor Ab
corr
for any energy. In some cases, however, the relationship of
ln lnH
1
versus ln E exhibits some discontinuities which correspond to the absorption
edges of minor (major) elements present in the unknown samples. In such cases the
approach proposed by Giauque et al. (1979), based on the construction of separate
curves for the predened energy regions, can only be used if at least two experimental
points are available for each energy region. When only one or no experimental point is
available, a modied version of the emissiontransmission method can be used (Mar-
kowicz and Haselberger, 1992). To explain the modied procedure, let us assume that a
multielement target consists of Ca, Ti, Fe, Zn, Sr, Zr, and Pb, and the material to be
analyzed contains some minor elements, such as Fe and Ca. From the ET measure-
ments, the values of A A H
1
are easily obtained for higher energies (e.g., for the
characteristics x-rays of Fe, Zn, Sr, Zr, and Pb in this case) (see Fig. 3). First, a straight
line is tted to the points corresponding to Zn, Pb, Sr, and Zr (region I). Second, a
straight line of the same slope and passing through a point for Fe is constructed (region
II). If no experimental point is available for Ca, the discontinuity for the K absorption
edge of Ca has to be taken into account by applying a computation routine. In the rst
step, the product
1
W
Ca
j
above
j
below
is calculated, where W
Ca
is the weight
fraction of Ca obtained by using a direct extrapolation of curve II and j
above
and j
below
are the mass absorption coecients just above and below the K absorption edge of Ca,
respectively. Next, the corrected value of the total mass absorption coecient
j
cor
T
ln A,m
1
csc
2
is calculated for the energy of the CaK
abs
edge, where A is
taken from curve II and
2
is the emerging angle for the characteristic x-rays. Based on
the j
cor
T
value, a straight line passing through point C and having the same slope as that
one in region II is constructed (the coordinates of the point C are x ln CaK
abs
and
y lnln A m
1
csc
2
). In the next step, the values of ln j
T
m and the absorption
correction factor Ab
corr
are calculated for the energy of Ca characteristic x-rays based
on the straight line for region III. Because the true value of the weight fraction for Ca is
unknown, all calculations for the absorption edge of Ca (region III) are iterated until the
following convergence is obtained:
W
Ca
n
W
Ca
n1
W
Ca
n
0.001 8
where W
Ca
n
and W
Ca
n1
are the values of the weight fractions for Ca obtained in the
subsequent iterations.
A calculation procedure applied for the Ca absorption edge can easily be repeated
for any other absorption discontinuity at a lower energy and, nally, a total absorption
curve ln ln A versus ln E is obtained.
The importance of the additional correction for the discontinuities in the absorption
properties of the samples to be analyzed was demonstrated, among others, for the analysis
of coal samples. Neglecting the absorption edges correction for Fe and Ca at the con-
centration level of around 1% resulted in considerable errors of the analysis, up to 60%
for the determination of Ca (Markowicz and Haselberger, 1992).
Van Dyck et al. (1980) developed a correction method that allows calculations of the
absorption coecients (and absorption correction factors as well) at any energy for in-
termediate-thickness samples, without additional measurements, by using the ratio of the
x-ray signals from a Zr wire positioned in front of the sample and from a Pd foil placed
behind the sample, both in a xed geometry, as shown in Figure 4. The Zr wire provides an
external reference signal ZrKc. which is applied for normalization of all measured
uorescent intensities to reduce considerably the eect of variations in exciting x-ray tube
intensity and of dead-time losses.
The coecients for higher energies are calculated with an iterative program from the
experimentally measured absorption coecient at the PdL energy (2.9 keV), jE
Pd
. In the
rst step, the total attenuation coecient at the PdL energy, caused exclusively by the low-
Z elements (e.g., Z < 17) in the sample that show no characteristic peak above 3.0 keV in
the spectrum, is calculated from the normalized measured intensities, I
Pd
T
and I
Pd
0
and
Figure3 Graphical explanation of the idea for the modified version of the ET method: see text for
details. (From Markowicz and Haselberger, 1992. Reprinted with permission of Pergamon Press Ltd.)
the dierent characteristic peaks recorded in the spectrum. This attenuation coecient due
to low-Z elements, j
low-Z
E
Pd
, is given by (Van Dyck et al., 1980)
j
low-Z
E
Pd
lnI
Pd
0
,I
Pd
T
,mcsc
2
jE
0
csc
1
,csc
2

P
n
0
j1
W
j
j
j
E
Pd
1
P
n
0
j1
W
j
9
where n
0
is the number of characteristic peak in the XRF spectrum and j
j
E
Pd
is the mass
attenuation coecient for the PdL energy in the element j (McMaster et al., 1969), giving
rise to a characteristic peak in the XRF spectrum.
The weight fraction of the element j in the sample, W
j
, is correlated with the recorded
characteristic peak through the sensitivity factor, routinely obtained by measuring thin
single or multielement standards. As a rst approximation, the characteristic peak in-
tensities are not corrected for absorption. In a second step, based on the j
low-Z
E
Pd
value,
the absorption coecients of the low-Z matrix for other energies, j
low-Z
E, are calculated
quantitatively by assuming nearly parallel properties of the logarithmic absorption curves
ln jE versus ln E.
The total mass attenuation coecient jE for the characteristic x-rays of an element
in the whole sample can now be calculated, taking into account the contributions j
j
E of
the high-Z elements:
jE 1
X
n
0
j1
W
j
!
j
low-Z
E
X
n
0
j1
W
j
j
j
E 10
The overall procedure is summarized and schematically represented in Figure 5.
Better jE values [Eq. (10)] are obtained in the second and following loops by
carrying out appropriate absorption corrections to the characteristic intensities from
which the W
j
values are derived using jE and jE
0
values from the previous loop and
by including in Eq. (9) the jE
0
values, taken as zero in the rst loop. The iteration is
stopped when the dierence in jE between two loops is negligible.
Subroutine ENHANC is applied to evaluate the enhancement eect of the PdL
x-rays caused by all elements in the sample of which the x-ray energy is higher than the
L
1
. L
2
and L
3
absorption edges of Pd. The intensity caused by this enhancement eect can
be considered to result in an apparent increase in I
Pd
0
. The enhancement contributions,
I
enhPd
, are added to the I
Pd
0
in Eq. (9). This total I
Pd
Oeff
value and the detected I
Pd
T
signal allow us to calculate the correct j values via Eqs. (9) and (10).
A comprehensive discussion of the inuence of secondary enhancement of the PdL
x-rays by the samples as well as of the inuence of two other complicating factors, grain
Figure 4 Measurement geometry applied in an automatic absorption correction method. (From
Van Dyck et al., 1980. Reprinted by permission of John Wiley & Sons, Ltd.)
size eects, and a heterogeneous sample load is presented in the work of Van Dyck et al.
(1980). The grain size and sample heterogeneity eects induce inaccuracies on the ab-
sorption coecient determinations that may well reach 20% for particulate samples, such
as intermediate-thickness deposits of geological materials. Thus, this approach has the
same limitations as all emissiontransmission methods applied to heterogeneous samples.
A. Accuracy and Limitations of the Emission--Transmission Method
The overall (total) absolute uncertainty of the mass per unit area of the ith element, m
i
, can
be calculated fromthe lawof error propagation applied to Eq. (2) (Markowicz et al., 1992b):
m
i

Ab
corr
B
i

2
I
i
E
i
I
i
E
i
B
i

2
Ab
corr
I
i
E
i
Ab
corr
B
2
i

2
B
i
2
" #
1,2
11
where I
i
E
i
is the absolute uncertainty of the characteristic x-ray intensity I
i
E
i
(usually
provided by a computer routine applied for spectrum evaluation), Ab
corr
is the absolute
uncertainty of the absorption correction factor, and B
i
is the absolute uncertainty of the
sensitivity (or calibration) factor B
i
(usually provided by a computer calibration routine,
as a mean percent dierence between the experimental and tted values for the calibration
factors). The total relative uncertainty of the mass per unit area m
i
,m
i
is calculated from
m
i
m
i
I
i
E
i
I
i
E
i
Ab
corr
Ab
corr

2
B
i
B
i

2
" #
1,2
12
Figure 5 The calculation steps. From the experimentally measured total absorption coefficient at
the PdL energy, m(E
Pd
), the calculated contribution from high-Z elements (giving a characteristic
peak in the spectrum) is substracted; through this low-Z matrix contribution at the PdL energy, the
total low-Z absorption curve (dashed line) is calculated; the contribution from high-Z elements (e.g.,
Ca and Fe) is then added, to yield the total absorption curve (thick line). (From Van Dyck et al.,
1980. Reprinted by permission of John Wiley & Sons, Ltd.)
In order to calculate Ab
corr
, one has to apply the law of error propagation to Eqs. (4)
and (5):
Ab
corr

A 1 ln A
A 1
2
A 12a
with A H
1
[Eq. (5)] and
A
I
i
2
I
i
T
I
i
2

I
i
2
I
i
2
I
i
T
I
i
4

I
i
2
I
i
2
I
i
T
I
i
4
" #
1,2
12b
where I
i
0
and I
i
T
are the absolute uncertainities of the characteristic x-ray
intensities obtained from the target alone and from the sample plus target, respectively.
After a simple transformation, m
i
,m
i
can be given by
m
i
m
i
I
i
E
i
I
i
E
i
A 1 ln A
2
A 1
2
A
2
ln A
2
A
2
B
i
B
i

2
" #
1,2
13
It is obvious that the total relative uncertainty of the weight fraction of the ith element
W
i
,W
i
is equal to m
i
,m
i
.
Equations (13) and (12b) can be used for calculating the total uncertainities of
the emissiontransmission method as well as the contribution from various sources of
the uncertainties I
i
E
i
. Ab
corr
. B
i
. It has been demonstrated that in the de-
termination of trace elements, the dominant contribution to the total uncertainty is
from the uncertainty of the peak-area calculation for the characteristic x-rays of the
element of interest. In this case, the contribution from the uncertainties of the ab-
sorption correction factor and sensitivity can practically be neglected. In the determi-
nation of major elements, the largest contribution to the total uncertainty is from the
uncertainty of the absorption correction factor and,or sensitivity; in this case, the
contribution of the uncertainty of the peak-area calculation can safely be neglected.
Such a detailed analysis of the contribution of various sources of uncertainties can
be useful when there is a need to identify the most critical point of the whole
analytical procedure and some reduction of the total uncertainty of the analysis is
required.
Another factor which inuences the accuracy of the emissiontransmission
method is the heterogeneity of the sample loading. Markowicz and Abdunnabi (1991)
derived general expressions describing the accuracy of the ET method for various
types of sample loading heterogeneities (including incompletely loaded samples) within
a wide range of sample thicknesses and characteristics x-ray energies. The results,
conrmed by experiments, clearly show that inhomogeneities of sample loading may
critically aect the accuracy of the ET method, in particular in the analysis of in-
termediate-thickness samples with strong inhomogeneities and large values for the
jE
0
csc
1
mand jE
i
csc
2
m factors. The most critical inuence of sample loading
heterogeneity on the accuracy of the analytical results is observed for incompletely
loaded samples of intermediate thickness. The method proposed in the work of
Markowicz and Abdunnabi (1991) gives a possibility for evaluating the errors arising
from some types of sample loading heterogeneities as well as for evaluating the range
of applicability of the simplest version of the ET method (Markowicz et al., 1992b) if
a certain value for the total uncertainty W
i
,W
i
is accepted.
III. ABSORPTIONCORRECTIONMETHODSVIASCATTEREDPRIMARY
RADIATION
The use of scattered primary radiation in XRF analysis provides an alternative to the
common problem of matching standards of similar composition to samples to be analyzed.
The backscatter peaks are sometimes treated as uorescent peaks from internal standards
because they suer matrix absorption similar to that of uorescent peaks and behave si-
milarly with instrumental variations. They also provide the only direct spectral measure of
the total or average matrix of geological, biological, or other materials containing large
quantities of light elements, such as carbon, nitrogen, and oxygen, usually not observed by
their characteristic x-ray peaks.
X-ray uorescence matrix correction methods based on the use of scattered radiation
have mostly been applied in quantitative analysis of innitely thick samples under a wide
variety of experimental conditions, including discrete and continuum primary radiation
sources and detection by both wavelength- and energy-dispersive systems (Andermann
and Kemp, 1958; Kalman and Heller, 1962; Taylor and Andermann, 1971, 1973; Leo-
nardo and Saitta, 1977; Livingstone, 1982; Kikkert, 1983; Markowicz, 1984). The scat-
tered-radiation methods utilize the incoherent (Compton) and,or coherent (Rayleigh)
scatter peaks from line excitation sources or the intense high-energy region from con-
tinuum sources.
A. Absorption Corrections Based on Incoherent Scattered Radiation
For specimens of less than innite thickness, the intensity I
Com
of Compton-scattered
radiation can be expressed by (Meier and Unger, 1976)
I
Com

k
0
I
0
o
Com
E
0
1 expfjE
0
csc
1
jE
Com
csc
2
mg
jE
0
csc
1
jE
Com
csc
2
14
where k
0
is a constant for a given measurement geometry and detection eciency, o
Com
E
0
is the Compton mass-scattering coecient of the sample material for the primary radiation
of energy E
0
cm
2
,g. jE
Com
is the total mass-attenuation coecient of the sample
material for Compton-scattered primary radiation of energy E
Com
cm
2
,g [see Eq. (52) in
Chapter 1]. Equation (14) is valid for monochromatic excitation.
Assuming that the relation of the atomic number to the mass number is constant for
every element to be found in the sample and that jE
0
jE
Com
, the following sim-
plied formula for the intensity of Compton-scattered radiation from a multielement
sample can be obtained:
I
Com

k
0
1
I
0
f1 exp jE
0
csc
1
1 csc
2
,csc
1
m g
jE
0
csc
1
1 csc
2
,csc
1
15
where k
0
1
is a constant for given geometry of measurement and the energy of the incident
radiation. The value of the product k
0
1
I
0
is determined experimentally from a reference
scatterer and is valid as long as the reference scatterer has a matrix that is not too dierent
from that of the specimens.
Kieser and Mulligan (1979) worked out a method based on the use of the incoherent
scatter radiation, which gives accurate mass absorption coecients for a limited average Z
range. The mass absorption coecient jE
0
for specimens of intermediate thickness is
found from Eq. (15) after a numerical solution. To obtain a value of the mass absorption
coecient jE at any energy E, Kieser and Mulligan (1979) assumed that the slope of the
curve log jE versus log E is constant for all elements (approximately 2.7) over a range
of x-ray energies. The proposed Compton-scattered method for the determination of an
intermediate specimens mass absorption coecient at any energy can be applied as long
as no absorption edge of a major or minor element intervenes. When the values of the jE
are determined, calculation of the absorption correction factor [Eq. (4)] is straightforward
if, of course, the mass of the sample to be analyzed is known.
A modied uorescent Compton correction method for quantitative XRF of in-
termediate specimens was developed by Holynska and Markowicz (1979). The method is
based on the use of the measured x-ray uorescent intensities of all determined elements
and the intensity of Compton-backscattered radiation. The authors derived the following
expression for the determination of the mass per unit area of the element i, m
i
:
m
i

a
i
I
i
1
P
n
0
l1
a
il
I
l
b
i
I
Com
,m
16
where a
i
. a
il
. and b
i
are constant coecients obtained experimentally on the basis of
standard samples and n
0
is the number of the elements to be determined, including the ith
element. As is seen from Eq. (16), the absorption matrix correction is carried out via the
intensities of characteristic x-rays of all elements determined and the intensity I
Com
, re-
ecting, for the most part, the variations in the composition of light matrix. To apply the
absorption matrix correction, Eq. (16), the total mass per unit area of the specimen must
be evaluated, for example, by sample weighing. This uorescentCompton correction
method can be used in the XRF analysis of homogeneous intermediate-thickness samples
in a limited range of mass per unit area (m<10m
thin
).
B. Absorption Corrections Based on Both Coherent and Incoherent
Scattered Radiations
Several absorption correction methods based on both coherent and incoherent scattered
radiations have been developed, mostly in the 1970s and 1980s, and applied in quantitative
XRF analysis of intermediate samples. This group of correction methods is represented
either by relatively simple approaches (Bazan and Bonner, 1976; Markowicz, 1979) or by
very sophisticated fundamental parameter procedures (Nielson, 1977; Van Dyck and Van
Grieken, 1980; Nielson et al., 1982; Nielson and Rogers, 1984) providing superior ana-
lytical exibility.
For specimens of less than innite thickness, the intensity I
coh
of coherent scattered
radiation can be calculated from
I
coh

k
00
I
0
o
coh
E
0
jE
0
csc
1
csc
2
1 exp jE
0
csc
1
csc
2
m f g 17
where k
00
is a constant for a given measurement geometry and detection eciency for the
primary x-rays of energy E
0
, and o
coh
E
0
is coherent mass-scattering coecient of the
sample material for the primary radiation (cm
2
,g) [see Eq. (73) in Chapter 1].
Bazan and Bonner (1976) showed, for the rst time, a linear relation between the
eective absorption coecient (dened as the sum of the sample absorption coecients for
exciting and characteristic x-rays) and the ratio of incoherent to coherent scattering.
However, the coecients of the calibration line varied somewhat with the matrix, and this
hampered practical applications of this simple approach.
Markowicz (1979) found that, theoretically the sensitivity of the absorption cor-
rection via the incoherent,coherent scattered x-ray intensities ratio is better than that of
the absorption procedure involving each of the scattered radiations individually. For in-
termediate-thickness samples, in a limited range of rather small values of mass per unit
area, the intensities of the Compton-scattered radiation I
Com
and the coherent scattered
radiation I
coh
are dierent functions of the total mass-attenuation coecient of the
incident radiation jE
0
; the intensity I
Com
is a linearly decreasing function and the
intensity I
coh
appears to be a linearly increasing function of the jE
0
. For a limited
range of jE
0
values, the following simple expression can be used to evaluate jE
0
(Markowicz, 1979):
jE
0
C
1
C
2
m C
3
r C
4
mr 18
where
r
I
Com
I
coh
and C
1
C
4
are constants calculated by the least-squares t on the basis of experimental
results for standard samples.
The values of the total mass-attenuation coecient of the uorescent radiation in a
whole sample, jE
i
, is obtained from the simple dependence of the jE
i
,jE
0
ratio on
the values jE
0
, calculated separately for each element to be determined. Finally, sample
weighing provides the value of mass per unit area, m, and the calculation of the absorption
corr
via Eq. (4) can be simply performed if, of course, the values of the
eective angles
1
and
2
are evaluated experimentally or theoretically. The applicability
of the proposed matrix correction method (Markowicz, 1979) involving both incoherent
and coherent scattered primary radiations is limited to XRF analysis of intermediate-
thickness samples of mass per unit area smaller than about 10m
thin
.
A backscattered fundamental parameters (BFP) method for quantitative XRF
analysis of intermediate samples of variable composition and thickness was developed by
Nielson (1977). The method utilizes thin-lm multielement calibration of the spectrometer
and mathematical matrix correction in which the samples are modeled as a composite of
heavy elements, which are quantied through their characteristic radiation, and light
elements, estimated through the coherent and incoherent x-ray scatter peaks. Figure 6
schematically illustrates the basis for analyzing the heavy elements (Z13) and the light
elements (H, C, N, O, Na, and others), which must be estimated by the dierence from the
scattered x-ray peaks. The BFP method utilizes coherently and incoherently scattered
x-rays to identify and estimate the quantities of two light elements representative of the
light-element portion of sample matrix. The quantities of the two light elements a and b
are estimated by solving for W
a
and W
b
in the simultaneous equations
gI
coh

X
n
0
j1
W
j
o
cohj
E
0
W
a
o
coha
E
0
W
b
o
cohb
E
0
19
and
hI
Com

X
n
0
j1
W
j
o
Comj
E
0
W
a
o
Coma
E
0
W
b
o
Comb
E
0
20
where g and h are the geometry-dependent calibration factors determined experimentally
by using any standard of known total composition. Because several light-element pairs
may satisfy Eqs. (19) and (20), the pair is chosen whose incoherent,coherent scattering
cross-sectional ratios lie immediately on either side of the ratio of the observed scatter
attributable to light elements (Nielson, 1977):
o
Coma
E
0
o
coha
E
0
<
hI
Com

P
n
0
j1
W
j
o
Comj
E
0
gI
coh

P
n
0
j1
W
j
o
cohj
E
0
<
o
Comb
E
0
o
cohb
E
0
21
The heavy- and light-element concentrations are used in computing the absorption
corr
[Eq. (4)] and the enhancement correction factor [Eq. (91) in
Chapter 1]. Because the concentrations and corrections are interdependent, all calculations
are carried out by iteration [for more details see (Nielson, 1977)].
To improve the sensitivity of the determination of low-Z elements, Sanders et al.
(1983) extended the previously described BFP method. The new method utilizes the co-
herent and incoherent backscatter intensities to compute matrix corrections (Nielson and
Sanders, 1982) from the combined results of two separate energy-dispersive XRF
(EDXRF) data from dierent (TiKc and ZrKc) excitation sources. The Ti-excited spec-
trum allows a more sensitive determination of elements in the AlCa range.
The coherent,incoherent scatter ratio is also applied in an absorption correction
procedure developed by Van Dyck and Van Grieken (1980) for monochromatic x-ray
excitation. In this method, coherent and incoherent scattered radiations are used to cal-
culate, rst, the eective mass of the sample and, second, the absorption coecients for
x-rays of interest and, hence, the absorption correction factors. The eective thickness is
the sample thickness weighted at every point for the excitation-detection eciency, in the
same way as the measured characteristic radiation is weighted.
Figure 6 Light-element contributions to x-ray scattering, from which absorption corrections are
computed. (From Nielson, 1977. Reprinted with permission from Analytical Chemistry. Copyright
American Chemical Society.)
Assuming that the major elements of the sample do not dier too greatly in atomic
number, the eective thickness m
e
can be calculated from (Van Espen et al., 1979)
m
eff

I
Com
b
0
Ab
corr
E
Com
b
0
I
coh
Ab
corr
E
Com
,a
0
I
Com
Ab
corr
E
coh
b
1
f ga
1
b
1
1
22
where a
0
. a
1
. b
0
. and b
1
are experimental constants obtained by tting the results of
measured standards; for mixtures or compounds, the coherent and incoherent scatter
factors S
coh
and S
Com
, (in fact, the relevant mass-scattering coecients), are given by
S
coh
a
0
X
n
j1
W
j
Z
a
1
j
and
S
Com
b
0
X
n
j1
W
j
Z
b
1
j
23
respectively. Ab
corr
(E
Com
) and Ab
corr
(E
coh
) are the absorption correction factors for the
incoherent and coherent scatter radiation, respectively, as dened in Eq. (4).
A reasonably accurate eective mass is obtained by modeling the sample as a
composite of high-Z elements, calculated from their characteristics peaks using Eq. (2),
and of a light matrix with mass per unit area, m
low-Z
, evaluated from the coherent and
incoherent scatter peaks after subtraction of the high-Z element contribution. The method
for the determination of the eective thickness allows the analysis of samples of hetero-
geneous thickness and irregular shape.
More recently, Arau jo et al. (1990) have developed a very similar procedure for
eective sample mass assessment of intermediate thickness samples via the coherently and
incoherently scattered radiation, as a rst step in the automated matrix eect evaluation,
for the case of ltered polychromatic continuum excitation with a Rh tube. Validation
with geological standards and deposited slurries on Mylar foils and Nuclepore lters gave
very satisfactory results.
In the method proposed by Van Dyck and Van Grieken (1980), calculation of the
mass-attenuation coecient for x-rays of interest is preceded by an evaluation of the
mass-attenuation coecient m (2.956 keV) at the ArKa energy (2.956 keV). This energy is
preferred because it is at the lower end of the energy range that can safely be used in
conventional EDXRF analysis and because, when working under vacuum, it is situated
in a peak-free part of an XRF spectrum. The value of m (2.956 keV) is derived from the
ratio coherent to incoherent scatter intensities R, based on the relationship (see Fig. 7)
of the calculated mass-attenuation coecient at 2.956 keV versus the measured R ratio:
j2.956 keV g
0
g
1
R g
2
R
2
24
where g
0
. g
1
. and g
2
are constant coecients derived by means of a least-squares t based
on the experimental results with standard samples. To improve the accuracy of the
method, the mass absorption coecient of the low-Z matrix at 2.956 keV, m
low-Z
(2.956 keV), must be calculated from the measured ratio of coherent to incoherent scatter
intensities, corrected for the high-Z elements contribution using their characteristic x-ray
intensities. Through this low-Z matrix contribution at 2.956 keV, the total low-Z ab-
sorption curve is calculated (in full analogy to the low-Z matrix contribution at the PdL
energy in Fig. 5). Finally, the mass absorption coecients for the dierent x-ray energies E
are calculated by adding the low-Z and high-Z absorption contributions [see the total
absorption cure, Eq. (10) and Fig. 5].
The proposed procedure for the automatic determination of the mass-attenuation
coecient, based on the coherent,incoherent scatter ratio, has several obvious merits
compared with the emissiontransmission absorption correction method. First, there is
no supplementary measurement or work needed [apart from experimentally obtaining
the semiempirical dependence of the j (2.956 keV) on the R ratio (Fig. 7) and sensi-
tivity factors B
i
, Eq. (2), on the basis of thin standard samples], because the additional
information on a sample composition is present in the spectrum itself. Second, because
the energies of coherently and incoherently scattered primary radiation, from which the
information is extracted, are higher than that of the incident radiation used in trans-
mission experiments, secondary eects (i.e., grain size eects, inhomogeneous thickness
of the sample, and irregular sample surface) are less important. A third positive point
Figure 7 Calculated mass absorption coefficient at 2.956 keV versus measured coherent,incoher-
ent scattered intensity ratios for pure elements and compounds (circles) and a graphitesulfur
mixture (crosses). (From Van Dyck and Van Grieken, 1980. Reprinted with permission from
Analytical Chemistry. Copyright American Chemical Society.)
of the described procedure (Van Dyck and Van Grieken, 1980) is the independence,
within certain limits, of the analytical results on the mass of the specimen. Also, it is
worth emphasizing the capability of determining reasonably accurate mass absorption
coecients when the mean atomic number of the sample varies drastically.
Most of the existing correction procedures in XRF analysis of intermediate-thickness
samples ignore the enhancement eect. It appears, however, that for some special cases,
the enhancement eect should be taken into account. Van Dyck et al. (1986) derived
theoretical formulas for secondary uorescent x-ray intensities in medium-thickness
samples based on the Sherman equations. Their computer routine for enhancement cor-
rections was incorporated into an overall program for evaluation of x-ray spectra and
calculation of x-ray absorption correction factors from scatter peaks.
The methods, based on coherent and incoherent scatter radiation, developed by
Van Dyck and Van Grieken (1980) for overall matrix eect corrections in the case of
monochromatic excitation and by Arau jo et al. (1990) for eective sample mass
determination in case of polychromatic radiation have later been expanded by He and
Van Espen (1991) into a general and versatile procedure for quantitative EDXRF with
polychromatic excitation. The comprehensive method uses the scattered radiation to es-
timate the composition and mass of the low-Z element matrix (with optimal use of the
fundamental parameter approach) and also uses the characteristic x-ray peaks to estimate
the concentrations of the higher-Z elements. An iterative process is then executed. Using
the initially estimated sample mass and composition, the weight fraction of each element is
calculated until the calculated composition converges. The absorption and enhancement
corrections are calculated from the latest iteration. Better sample mass, low-Z matrix
composition, and analyte concentrations are computed after this. This overall procedure is
repeated again until subsequent overall iterations do not yield signicant dierences. The
method is, in principle, applicable to samples of any thickness and composition and to
polychromatic excitation. The procedure has been implemented as part of the popular
software package AXIL-QXAS (Van Espen et al., 1997), which includes spectrum ac-
quisition and spectrum analysis and runs on a PC. Excellent quantitative results have been
obtained with it.
Wegrzynek et al. (1993) have recently developed a direct correction procedure for the
enhancement eect in intermediate thickness samples, which is based on the results of the
emissiontransmission measurements and does not require any iterative calculations. The
enhancement term ENH
i
is calculated for the intermediate-thickness samples from
(Wegrzynek et al., 1993)
ENH
i

1
2j
i
E
0
D 1SUM1 DSUM2 SUM3 25

with
D exp
jE
0
sin
1
jE
i
sin
2
!
m
& '
1

1
25a
SUM1
X
j.q
t
i
E
q
K
j
q
E
0
W
j
sin
1
jE
0
ln
jE
0
,jE
q
sin
1
1
&
sin
2
jE
i
ln
jE
i
,jE
q
sin
2
1
!'
25b
SUM2
X
j.q
t
i
E
q
K
j
q
E
0
W
j
sin
1
jE
0
ln
jE
0
,jE
q
sin
1
1
&
sin
2
jE
i
ln
jE
i
,jE
q
sin
2
1
!'
25c
SUM3
X
j.q
(
t
i
E
q
K
j
q
E
0
W
j
sin
1
jE
0
sin
2
jE
i
!
exp
jE
0
m
sin
1
! & (
exp
jE
i
m
sin
2
!'
Ei jE
q
m

exp
jE
0
sin
1
jE
i
sin
2
!
m
& '
sin
1
jE
0
Ei jE
q
jE
0
sin1
!
m
& '
sin
2
jE
i
Ei jE
q
jE
i
sin
2
!
m
& '
sin
1
jE
0
Ei jE
q
jE
0
sin1
!
m
& '
sin
2
jE
i
Ei jE
q
jE
i
sin
2
!
m
& ')'
25d
Eix
Z
x
1
expt dt
t
ln jxj
X
1
n1
x
n
n n!
Exponential integral
0.577215664 . . . Euler constant
where
t
i
E
q
is the photoelectric mass absorption coecient for the ith element at the
energy of the qth characteristic line of the jth enhancing element (E
q
),
jE
q
is the total mass absorption coecient for the sample at the energy E
q
,
K
j
q
E
0
t
j
E
0
1
1
J
j
q
!
.
j
p
j
q
J
j
q
and p
j
q
are the jump ratio for the relevant absorption edge and probability of the
emission of the qth characteristic x-ray of the jth element, respectively.
The calculation of the enhancement eect correction is included in a complete pro-
cedure based on the emissiontransmission measurements (Holynska et al., 1994). In the
rst step, the calibration of the XRFsystemis performed [to nd the values of GI
0
E
0
E
i
],
and sin
1
and sin
2
are determined from the x-ray measurements for single-element
standard samples of known mass per unit area. In the next step, the concentrations of the
elements not enhanced by any other element present in the sample are calculated (with the
absorption eect correction based on the emissiontransmission measurements). In the nal
step, the correction for the enhancement eect is made; the values of the fundamental
parameters are taken from the published tables, whereas the values of jE
0
. jE
i
, and
jE
q
are derived from the results of the emissiontransmission measurements.
The enhancement factor for the intermediate thickness samples, ENH
i
, can also be
assessed by using another simple formula (Markowicz et al., 1992b; Austrian Matrix
Correction Routine, 1990):
ENH
i

X
j
ENH
i
thick
W
j
1 expfjE
j
mg 26
with (ENH
i
)
thick
is the enhancement factor for the thick sample of the same composition as
the intermediate thickness sample to be analyzed:
ENH
i
thick

1
2
1
1
J
j

.
j
p
j
j
j
E
0
j
i
E
0
j
i
E
j
ln 1
jE
0
, sin
1
jE
j

sin
1
jE
0
ln 1
jE
i
, sin
2
jE
j

sin
2
jE
i
1
!
26a
where p
j
is the transition probability for a given spectral line in an x-ray series of the
enhancing jth element. Also in this case, the emissiontransmission measurements can be
used to support the enhancement eect correction. The enhancement factor is calculated
either for each spectral line of the enhancing element separately or for a weighted average
energy of the whole x-ray series. The dierences in the results obtained by using the two
approaches are practically negligible (Markowicz et al., 1992b). Equation (26), although
very simple, can also be applied in order to (1) dene the region of sample thickness where
the enhancement eect is negligible (or smaller than a certain predened level) and (2) to
determine the minimum sample thickness for which the bulk enhancement correction can
already be used.
IV. QUANTITATIONFORINTERMEDIATE-THICKNESS GRANULAR SPECIMENS
The fundamentals of the quantitative XRF analysis of granular specimens involve typical
problems of radiation physics (i.e., the interaction of photons with a specimen of nite
size).
A. Particle Size Effects in XRFAnalysis of Thin and Intermediate-Thickness
Specimens
The analysis of granular materials by XRF, when traditional methods of fusing or
grinding cannot be used, requires careful consideration of the so-called particle size eects.
These eects exist in XRF analysis of any granular materials, irrespective of the mass per
unit area of the specimen, and may constitute a major source of error in quantitative
analysis. The size of particles aects not only the intensity of characteristics x-rays but the
intensity of both backscattered and transmitted x-rays and low-energy g-radiation as well
(Van Dyck et al., 1980; Berry et al., 1969).
Dierent models have been proposed to account for the inuence of particle size on
the characteristic x-ray intensity leaving the sample (Berry et al., 1969; Claisse and
Samson, 1962; Lubecki et al., 1968; Hunter and Rhodes, 1972; Rhodes and Hunter, 1972;
Hawthorne and Gardner, 1978; Krasnopolskaya and Volkov, 1986). Many of these
models involve relatively complex calculations, particularly when the particle size eects
for thick granular samples must be evaluated. This section is limited to the particle size
eects in the quantitative XRF analysis of thin and intermediate-thickness (monolayer)
samples.
For granular intermediate-thickness samples, the mass per unit area of the element,
i. m
i
, is given by (Rhodes and Hunter, 1972)
m
i

I
i
E
i
B
i
F
i
27
where B
i
is the sensitivity factor as in Eq. (1) and F
i
is the heterogeneity factor which for a
certain discrete particle size is dened by
F
i

1 expj
f
E
0
csc
1
j
f
E
i
csc
2
a
r
f
E
0
csc
1
j
f
E
i
csc
2
a
r
28
where j
f
E
0
and j
f
E
i
are the linear attenuation coecients (cm
1
) for primary and
uorescent radiation in uorescent particles, respectively, and a
r
is the radiometric particle
diameter.
The radiometric diameter, introduced by Claisse and Samson (1962), represents the
mean geometrical path of x-rays through one particle. These and many other authors (Berry
et al., 1969; Lubecki et al., 1968; Hunter and Rhodes, 1972; Rhodes and Hunter, 1972) have
taken a
r
as simply equal to the volume of the grain divided by the particle area presented to
the radiation, averaged over all possible orientations of the grain. Hence, for spherical
particles, the radiometric diameter is equal to 0.67a (with a geometric diameter). One can
easily visualize, however, that such an approach assumes equal weighting of the con-
tribution from all possible radiative paths to the average. In view of the dierent absorption
eects themselves, this is untrue. Markowicz et al. (1980) introduced, instead of the com-
monly used radiometric diameter approach, the concept of an eective absorption-weighted
radiometric diameter for uorescent radiation, depending on both the geometry and ab-
sorption eects, and provided a comparison of these two approaches for single spherical
particles for two excitation-detection geometries ( and /2). This alternative approach
allows quantitative evaluation of the discrepancies resulting from the concept a
r
particle
volume,average area. It was concluded that for the geometry, both approaches give
practically the same results (maximum relative dierences amount only to 5%), but for /2
geometry, the radiometric diameter approach can safely be applied only for very small
particles and,or at relatively high energies of primary radiation (Markowicz et al., 1980).
For samples with a certain particle size distribution described by a function fa
r
, the
heterogeneity factor F
i
can be calculated according to the formula (Rhodes and Hunter,
1972)
F
i

Z
a
r max
a
r min
fa
r
1 expa
r
j
f
E
0
csc
1
j
f
E
i
csc
2
da
r
j
f
E
0
csc
1
j
f
E
i
csc
2
a
r
29
where a
r min
and a
r max
are the smallest and the largest radiometric particle diameters,
respectively, and
fa
r

dV
f
V
f
t
da
r
30
where dV
f
is the volume of uorescent particles having a size between a
r
and a
r
da
r
and
V
f
t
is the total volume of the uorescent particles.
The theoretical predictions given by Eqs. (28) and (29) have been compared with the
experimental results for the heterogeneity factors obtained for samples with some discrete
particle sizes and various particle size distributions (Holynska and Markowicz, 1981). For
granular samples of copper sulde, a satisfactory agreement has been obtained; for samples
of iron oxide, some discrepancies due to agglomeration of the particles have been observed.
An in-depth study of the inuence of sample thickness, excitation energy, and
excitation-detection geometry on the particle size eects in XRF analysis of intermediate-
thickness samples was carried out and the results are presented in the work of Van Dyck
et al. (1985).
B. Correction Methods for the Particle Size Effect in XRFAnalysis
of Intermediate-Thickness Specimens
As already mentioned, the heterogeneity factor F
i
describing the magnitude of the particle
size eect in XRF analysis of thin and monolayer samples can simply be calculated if the
particle size or the function of the particle size distribution is known. This occurs in XRF
analysis of air particulates (or aerosols), for example, when special sampling techniques,
involving a cascade impactor, are applied. At dierent stages of the cascade impactor, the
particles of denite sizes are collected (Katz, 1977) and calculation of the heterogeneity
factor F
i
may be straightforward if, of course, the kind of uorescent particles is known.
A simple empirical particle size correction factor 1 ba
2
was proposed by Criss
(1976), in which a is the particle diameter b is a coecient that depends on particle
composition and experimental conditions. The author has provided a table of the values
for b for the determination of 48 dierent elements in 200 compounds using either a Cr- or
W-target x-ray tube.
Another correction for the particle size eect based on the model of Berry et al.
(1969), also requiring evaluation of the particle size in a sample, is due to Nielson (1977).
All the particle size corrections mentioned are of limited applicability because eva-
luation of a particle size or particle size distribution function must be done before XRF
analysis. Moreover, in many cases it may be necessary to consider how the indirectly
determined particle sizes relate to true sizes. However, even when there is some uncertainty
in the sizes and compositions of the particles, which are input parameters in the particle
size correction, it is better to make an appropriate correction than no correction at all.
1. Empirical Particle Size Correction Method Using Dual Measurements
To overcome the problems encountered when calculated particle size correction factors are
applied in the quantitative XRF analysis of granular samples, a particle size correction
method based on dual measurements of characteristic x-rays excited by x- or g-radiation of
two dierent energies was developed (Holynska and Markowicz, 1982). The method utilizes
the dierence in the particle size eect for two excitation energies and oers the possibility
of experimental detection and correction of this eect. In general, these two excitation
energies should be chosen so that the eect of particle size is small for one of them and large
for the other. Thus, the measured intensities of the characteristic x-rays of the element to be
determined are dierent functions of the particle size. The ratio of these two intensities
is sensitive to the particle size and it can be used for obtaining the particle size correction
factor K
i
1,F
i
. First, a calibration curve giving the relationship between the correction
factor K
i2
and the ratio I
i1
,I
i2
rel
must be plotted. The ratio I
i1
,I
i2
rel
is given by
I
i1
I
i2

rel
I
i1
,I
i2
I
i1
,I
i2
hom
31
where I
i1
,I
i2
is the ratio of the intensities of the characteristic x-rays of the ith element
excited in a granular sample by primary x-rays of two dierent energies (indexes 1 and 2,
respectively) and I
i1
,I
i2
hom
is the same for a thin homogeneous sample. Taking into
account that in the thin-sample technique, interelement eects may be neglected, single-
element standard samples can be used to obtain the I
i1
,I
i2
hom
ratio. The calibration curve
mentioned earlier can be obtained either theoretically or experimentally with the use of
calibration samples of known discrete particle size fractions. It has been shown (Holynska
and Markowicz, 1982) that there is also a possibility of applying such a calibration curve
for granular samples with various particle size distribution functions. For a p geometry,
the calibration curves for the determination of the correction factor K
i2
are described by
the equation (Markowicz, 1983)
K
i2

I
i1
I
i2

rel
t
0
a
r
1 e
t
0
a
r
32
where
t
0

j
f
E
01
j
f
E
i
f
E
02
j
f
E
i
33
j
f
E
02
j
f
E
i
34
j
f
E
01
and j
f
E
02
are the linear absorption coecients for primary radiation of two
dierent energies (indexes 1 and 2, respectively) in uorescent particles (cm
1
). The par-
ticle size correction factor K
i2
is given by
K
i2

a
r
1 e
a
r
35
The proposed method of particle size correction was veried experimentally for the
determination of copper, applying
238
Pu and
241
Am radioisotopes as sources of primary
radiation, and a satisfactory agreement between theoretical predictions and experimental
results was reported (Holynska and Markowicz, 1982).
2. Applicabilityof the Particle Size Correction Method
Accurate determination of the correction factor K
i2
is mainly aected by uctuations
resulting from counting statistics in all measured intensities of the characteristic radiation.
The absolute error K
i2
in determining the correction factor K
i2
can be calculated from
the formula
K
i2

t
0
a
r
1 e
t
0
a
r
S
c
36
where S
c
is standard deviation resulting from counting statistics for the ratio I
i1
,I
i2
rel
.
The relative error in determining the particle size correction factor K
i2
is given by
K
i2
K
i2
S
c
I
i1
,I
i2
rel
S
r
37
where S
r
is relative standard deviation resulting from counting statistics for the ratio
I
i1
,I
i2
rel
.
Equations (32) and (37) enable us to estimate the applicability of the particle size
correction method. This can be done with the aid of Figure 8. From two families of curves
in Figure 8, one can estimate the maximum value of the particle size correction factor
K
i2
max
that can be determined with the particle size correction method for given values of
S
r
and t
0
. Figure 9 presents the theoretical relationship of the maximum value of the
correction factor K
i2
max
with the parameter t
0
for dierent values of the relative standard
deviation S
r
; Figure 10 shows the theoretical relationship of K
i2
max
with S
r
for dierent
values of t
0
. The families of curves shown in Figures 9 and 10 allow us to determine the
application limits of the particle size correction method [i.e., to determine K
i2
max
in
various congurations]. In practice, however, it is more interesting to know the maximum
value of the radiometric particle diameter for which the particle size eect can still be
corrected. This can be determined from Eq. (32).
3. Selectionof the OptimumMeasurement Conditions
When the ith element is present in a given chemical compound and the maximum values of
the radiometric diameter of the particle in a sample are known, it is possible to dene the
optimum value t
0
opt
of the parameter t
0
for a given energy of exciting radiation E
02
.
Figure 8 Theoretical relationship of the particle size correction factor K
i2
with the ratio of the
intensities I
i1
,I
i2
rel
for different values of the parameter t
0
(family curves) and with the error K
i2
for different values of the relative standard deviation S
r
(family of straight lines). (From Markowicz,
1983. Reprinted by permission of John Wiley & Sons, Ltd.)
The value of t
0
opt
can be determined from Figure 9 for a given value of the relative standard
deviation S
r
. Thus, one can obtain the following inequality, which should be fullled by
the parameter t
0
:
t
0
t
0
opt
38
This means that the value of the energy of the exciting radiation E
01
of the correction
source should fulll the inequality
E
01
! E
01
opt
39
where E
01
opt
is the energy of the exciting radiation E
01
for which t
0
t
0
opt
. Taking into
account that the eciency of photoexcitation depends on the energy of the primary
Figure 9 Theoretical relationship of the maximum value of the particle size correction factor
K
i2
max
with the parameter t
0
for different values of the relative standard deviation S
r
. t
0
opt
is the
optimum value parameter t
0
(see text for details). (From Markowicz, 1983. Reprinted by permission
of John Wiley & Sons, Ltd.)
radiation, the practical conclusion can be drawn that the values of both the parameter t
0
and the energy of the exciting radiation E
01
should be as close as possible to the values of
t
0
opt
and E
01
opt
, respectively.
On the other hand, for a given pair of sources of primary radiation (i.e., for a given
value of the parameter t
0
), it is possible to estimate, using Figure 10, the maximum ac-
ceptable value S
r
0
of the relative standard deviation of the ratio I
i1
,I
i2
rel
. In con-
sequence, the appropriate measurement times and,or activities of the sources of primary
radiation can be selected.
Although the correction method may look complicated, it is currently the only
real correction procedure dealing with the particle size eect in XRF analysis of granular
intermediate-thickness specimens. The idea of applying dierent excitation x-ray energies to
estimate particle size corrections was also exploited by Nielson and Rogers (1986).
Figure 10 Theoretical relationship of the maximum value of the particle size correction factor
K
i2
max
with the relative standard deviation S
r
for different values of the parameter t
0
. S
r
0
is the
maximum acceptable value of the relative standard deviation S
r
(see text for details). (From
Markowicz, 1983. Reprinted by permission of John Wiley & Sons, Ltd.)
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Claisse F, Samson C. Adv X-ray Anal 5:335, 1962.
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Giauque RD, Garrett RB, Goda LY. Anal Chem 51:511, 1979.
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7
Radioisotope-Excited X-ray Analysis
Stanislaw Piorek*
Niton Corporation, Billerica, Massachusetts
I. INTRODUCTION
Radioisotope x-ray uorescence (XRF) and x-ray preferential absorption (XRA) techni-
ques are used extensively for the analysis of materials, covering such diverse applications
as analysis of alloys, coal, environmental samples, paper, waste materials, and metalli-
ferous mineral ores and products (Rhodes, 1971; Rhodes and Rautala, 1983; Watt, 1978
and 1983; Watt and Stener, 1985; Piorek 1997). Many of these analyses are undertaken in
the harsh environment of industrial plants and in the eld. Some are continuous on-line
analyses of material being processed in industry, where instantaneous analysis information
is required for the control of rapidly changing processes.
Radioisotope x-ray analysis systems are often tailored to a specic but limited range
of applications. They are similar and often considerably less expensive than analysis
systems based on x-ray tubes, but these attributes are often gained at the expense of
exibility of use for a wide range of applications.
Operators making analyses in the eld or in industrial plants are usually less skilled
than those working in the laboratory with x-ray tube systems. Manufacturers of radio-
isotope x-ray analysis systems compensate for this by producing simple semiautomated or
fully automated systems whose output, calibrated for the specic application, is given
directly in terms of concentrations of elements required or in terms of a simple pass=fail-
type decision.
Radioisotope x-ray techniques are preferred to x-ray tube techniques when simpli-
city, ruggedness, reliability, and cost of equipment are important, when minimum size,
weight, and power consumption are necessary, when a very constant and predictable x-ray
output is required, when the use of high-energy x-rays is advantageous, and when short
x-ray path lengths are required to minimize the absorption of low-energy x-rays in air.
Also of signicant analytical importance is the fact that the radioisotope excitation is
usually monoenergetic (monochromatic) as opposed to polyenergetic (polychromatic)
excitation characteristic for x-ray tubes.
*Previous aliation: Metorex Inc., Princeton, New Jersey.
X-ray uorescence techniques based on the x-ray tubeBragg crystal spectrometer
are considerably more sensitive than those based on radioisotope sources. This high
sensitivity is due to the excellent x-ray resolving power of the crystal spectrometer, which is
superior to that of the gas-lled or solid-state detector typically used with radioisotopes.
Radioisotopes cannot be used with crystal spectrometers because of the low geometrical
eciency of this spectrometer coupled with the fact that the x-ray photon output of
radioisotope sources is relatively very low, about six orders of magnitude less than that of
x-ray tubes used with crystal spectrometers.
Presently, the bulk of use of XRF analysis is in portable and on-line equipment.
Portable systems outnumber on-line installation, and the gap increases from year to year.
A signicant number of radioisotope benchtop XRF systems have been installed for
quality control applications, as o-line auxiliary instruments. These, however, are very
quickly yielding the eld to XRF systems based on low-power x-ray tubes.
For some applications, x-ray preferential absorption (XRA) and x-ray scattering
(XRS) techniques are preferred to XRF techniques, particularly when coarse particulate
material is to be analyzed. Radioisotopes are the only practical source of x-rays for these
applications, because to penetrate deep into the material, high energy, usually above
100 keV, x-rays are required. The most important applications of XRA and XRS tech-
niques are the on-line analysis of particulate material on conveyors.
Some of the terminology used in this chapter is now briey dened. The element
whose concentration in the sample is to be determined is the analyte and the other ele-
ments of the sample are the matrix elements, or simply the matrix.
Sensitivity of an analytical method for a given analyte is dened as net change (in-
crease) of the measured signal of the analyte per unit concentration change (increase) of
that analyte. This term is notoriously, but wrongly, used in place of minimum detectable
level. A minimum detectable level (DL) for a given analyte is understood as that amount of
analyte in a sample that produces spectral signal equal to or greater than three standard
deviations of a signal obtained on a sample with no analyte present. The DL improves
when sensitivity of analysis improves.
The common link between all techniques and applications discussed here is the de-
pendence of the analysis primarily on the absorption of x- and g-rays. Compton and
coherent scattering are the other important interactions taking place in the sample. The
terms x-ray and g-ray can often be used interchangeably. The term x-ray is always used
when discussing uorescent x-rays. Radioisotope sources emit either g-rays directly from
the nucleus or uorescent x-rays emitted following the ejection of an atomic electron.
g-Rays emitted by radioisotopes usually have energies greater than 50 keV. X-ray uor-
escence analysis depends on both x-ray and g-ray excitation, but most XRA and XRS
analyses are based on the use of g-rays. The term high-energy g-ray is used when the
g-ray interaction in the sample is essentially entirely due to Compton scattering (typically
above 300 keV) which is being used to determine either the bulk density or mass per unit
area of the sample. The term low-energy g-ray is used when photoelectric interactions
are important to the analysis.
This chapter reviews radioisotope-excited x-ray uorescence, preferential absorp-
tion, and scattering techniques. The characteristics of radioisotope sources and x-ray
detectors are described, and then the x-ray analytical techniques are presented. The choice
of radioisotope technique for a specic application is discussed along with major factors
aecting the overall accuracy of analysis. This is followed by a summary of applications of
these techniques, with a more detailed account given of some of the most representative
applications, particularly those of considerable industrial importance.
II. BASICEQUATIONS
The basic equations for x-ray analysis are given in Chapter 1. Some additional equations
used for XRF, XRA, and XRS analyses are presented here. The typical geometries (Watt
and Stener, 1985; Jenkins et al., 1981 b) of the radioisotope source, sample, and detector
used are shown in Figures 1 and 2.
Figure 1 The three geometries for radioisotope-excited x-ray fluorescence analysis: (a) annular
source, (b) central source, and (c) side source. (From Jenkins et al., 1981b.)
A. Absorption of X-rays
The intensity, I, of a narrow beam of monoenergetic x- or g-rays transmitted through a
sample (already shown in Chapter 1) is given by
I I
0
e
mrt
1
where
m
X
n
i1
W
i
m
i
2
Figure 2 Arrangement of radioisotope g-ray source, collimators, and scintillation detector used in
x-ray preferential absorption analysis. (From Watt and Steffner, 1985.)
and
X
n
i1
W
i
1 3
I
0
is the intensity of x-rays detected without the sample. m and t are the mass absorption
coecient and path length of x-rays in the sample, respectively, r is the bulk density of the
sample, and m
i
and W
i
are the mass absorption coecient and weight fraction of the ith
element in the sample, respectively.
Equation (1) also holds for broad beams of x-rays when the cross section for pho-
toelectric absorption is much greater than that for Compton and coherent scattering [i.e.,
particularly for low-energy x-rays and high-atomic-number (Z) elements]. This assump-
tion can be veried by reference to Appendices VIVIII of Chapter 1.
B. Fluorescent X-ray Intensity
When a monoenergetic beam of x-rays excites the K shell x-rays of the analyte i in an
innite-thickness sample and both the incident and emitted x-rays are normal to the
sample surface, the detected intensity I
i
of the Ka x-rays of analyte i is given approximately
by Eqs. (94) and (90) in Chapter 1, namely
I
i

GeE
i
a
i
E
0
I
0
E
0
mE
0
mE
i
4
where
G Geometrical constant
eE
i
Intrinsic eciency of the detector to the x-rays of the analyte i
a
i
E
0
W
i
t
0
i
E
0
o
i
r
i
1 1=j
i
I
0
E
0
The source emission (photons=s)
mE
0
; mE
i
Mass absorption coecients for the exciting radiation with energy
E
0
and the characteristic radiation with energy E
i
, respectively, in
the sample (cm
2
/g)
t
0
i
E
0
Total photoelectric mass absorption coecient for the ith element
at energy E
0
(cm
2
/g)
o
i
The K shell uorescent yield for the analyte i
r
i
Relative transition probability for Ka lines of analyte i
j
i
Jump ratio
Enhancement eects (discussed in Chapter 5, Sec. II.B.2) have been assumed to be
negligible.
The intensities of L and M shell uorescent x-rays can be calculated from equations
similar to Eq. (4). For radioisotopes emitting x-rays of more than one energy, I
i
can be
separately calculated for each emitted energy and the total uorescent x-ray intensity
determined by summing the products of I
i
and the probability of emission of the given
x-ray energy from the radioisotope.
C. Scattered X-ray Intensities
X-rays are scattered from the sample and its surroundings to the detector by a mechanism
of coherent and Compton (or incoherent)-scattering interactions. There is no loss of
energy of incident radiation during coherent scattering. The energy E of the Compton-
scattered x-ray is given by [Eq. (52) of Chapter 1]
E
E
0
1 g1 cos y
5
where E
0
is the energy (in the units of keV) of the incident x- or g-ray, g E
0
=511, and y
is the scattering angle. The scattering angle y, measured from the direction of the incident
x-ray, in most radioisotope XRF systems (Fig. 1) is in the range 90
150
. The loss in
energy of the incident x-ray due to Compton scattering at 90
, 120
, and 150
is shown in
Figure 3 and can be seen to be relatively very small at energies below 20 keV. The de-
tected intensity I
s
of x-rays scattered from an innitely thick sample to the detector is
given by
I
s

GI
0
E
0
T
s
e
s
P
m
si
yW
i
P
m
i
m
si
W
i
6
where G; I
0
E
0
, and W
i
are the same as in Eq. (4), T
s
is the transmission of the scattered
x-rays through the lter and the detector window; e
s
is the eciency of the detector for the
scattered x-rays; m
si
y is the dierential scattering cross section for the x-rays scattered by
the ith element toward the detector, and m
si
is the mass absorption coecient of the
scattered x-rays for the ith element of the sample.
Equation (6) holds for both coherent and Compton scattering when the appropriate
scattering cross section [Eqs. (73) and (65) of Chapter 1] is used. It assumes that the
photoelectric absorption cross section of the x-rays in the sample is much greater than
that for scattering and that incident and emergent x-rays are normal to the sample
surface.
The dierential and total Compton-scattering cross sections per atom are propor-
tional to Z=A, where A is the atomic weight of the atom, and, except for hydrogen, are
almost independent of the atomic number of the atom. Hence, the scattered intensity is
approximately inversely proportional to the sum of the mass absorption coecients in the
sample of the incident and emerging x-rays.
Figure 3 Loss in energy of x-rays in Compton scattering at angles 90
, 120
, and 150
.
The cross section for coherent scattering is highest for small scattering angles, low-
energy x-rays, and high-atomic-number atoms. For angles greater than 90
, the cross
section is low and varies by only a factor of about 2.
D. X-ray Fluorescence Analysis
The concentration of the analyte in the sample is determined from measurement of the
intensity of its uorescent x-rays, often combined with measurements of the intensities of
the uorescent x-rays of matrix elements and=or the Compton-scattered x-rays. Often the
denominator of Eq. (4) is proportional to that of Eq. (6); that is,
mE
0
mE
i
/
X
m
i
m
si
W
i
7
Hence, Eqs. (4) and (6) can be combined to give
W
i
k
I
i
I
Com
8
where k is a constant. Note that the intensity of scattered radiation, I
s
, is replaced here by
I
Com
, because Eq. (6) holds for both coherent and Compton scattering when the appro-
priate scattering cross section is used. If a major matrix constituent, a, has an absorption
edge energy between the energy of the characteristic x-rays of the analyte and the energy of
the incoherently (Compton) scattered primary radiation, then
W
i
kI
i
1
I
Com
k
1
m
a
W
a

9
where k
1
is a constant and the subscript a refers to the major matrix constituent. Equa-
tions (8) and (9) can be checked for accuracy for any specic application by substituting
mass absorption coecients (see Appendices VIIIX of Chapter 1) and elemental con-
centrations into Eqs. (4) and (6).
Relation (8) has a great analytical signicance; in many applications, it linearizes the
calibration curve for a given analyte, thus making analysis more accurate and robust.
Analysis of Eqs. (4) and (3) reveals that the intensity of the characteristic x-rays of a
given analyte is a function not only of this analyte concentration but also of the con-
centrations of all the other elements in the sample. This poses diculty in solving this
equation directly for W
i
. However, by adopting, for example, a simple approximation
proposed by Lucas-Tooth and Price (L-TP) (1962), this problem can be solved. The L-TP
approximation states that because the x-ray intensities of elements are functions of their
respective concentrations, one can substitute their measured x-ray intensities for con-
centrations of matrix elements. In this way, Eq. (4), via Eq. (3), can be solved for W
i
,
which is now expressed, for each analyte, by all measured x-ray intensities of the elements
in the sample:
W
i
b
1
I
i
k
0
X
jn
j6n
k
ij
I
j
!
10
The I s are the x-ray intensities of the elements measured, k
ij
are correction coecients
determined by multivariable linear least-squares tting, and W
i
is concentration of the
analyte i. There are as many of this equations as there are analytes to be measured.
The L-TP model allows for the calibration of an x-ray analyzer with the suite of
calibration samples without the necessity of knowing assays for any element but the
desired analyte. Due to its simplicity and ruggedness, this approach is often used in the
calibration of benchtop and portable x-ray analyzers; the analyzer measures x-ray in-
tensities of the important interfering elements in calibration samples and then develops a
calibration equation for the analyte(s) by multivariable, linear least-squares tting.
E. X-ray Preferential Absorption Analysis
X-ray preferential absorption analysis is based on the measurement of the intensities of
two or more monoenergetic x-rays transmitted through the sample (Fig. 2). Sensitivity of
analysis depends on the selective absorption of the transmitted x-rays by the analyte
compared with absorption by the sample matrix. The greater the dierence (or contrast)
between the mass absorption coecients of the analyte and matrix for the transmitted
x-rays, the better the sensitivity of analysis for that analyte. From Eqs. (1)(3), the
concentration of the analyte is given by
W
i

lnI
0
=I=rt m
M
m
i
m
M
11
where m
i
is the mass absorption coecient of the x-rays in the analyte and m
M
is the ab-
sorption coecient of the matrix, given by
m
M

X
n
j6i
m
j
W
j
12
and the subscript j refers to the matrix elements and SW
j
1 W
i
. The concentration of
the analyte can thus be determined if the product of the bulk density and thickness of the
sample is known and the mass absorption coecients of the matrix elements are ap-
proximately equal or the composition of the matrix does not vary.
In practice, XRA analysis usually involves measurements of transmission of narrow
beams of x-ray, at two x-ray energies, through the sample (Watt and Stener, 1985). This
is called dual-energy (x- or g-ray) transmission (DUET) analysis. The beams are usually
coincident and thus not dierently aected by heterogeneity of the sample in the beam
path (Fig. 2).
From Eq. (11), the concentration W
i
of the desired analyte is
W
i

m
0
M
Rm
00
M
m
0
i
m
0
M
Rm
00
i
m
00
M
13
where
R
lnI
0
=I
0
lnI
0
=I
00
14
and
R
m
0
M
m
0
i
m
0
M
W
i
m
00
M
m
00
i
m
00
M
W
i
m
0
m
00
15
The prime and double prime refer to the rst and second x-ray energies, respectively. The
concentration is thus determined independently of the density and thickness of the sample
through which the coincident x-ray beams pass.
The sensitivity of analysis is high when m
0
i
)m
0
M
and when rt is large. The analysis is
accurate when the ratio m
0
M
=m
00
M
is constant, independently of variations in composition of
the sample matrix. This ratio is approximately constant when the x-ray energies of the
transmitted x-ray are just above and below the K shell absorption edge energy of the
analyte and at higher energies when, at each x-ray energy, the mass absorption coecients
of all matrix elements are about the same. In the latter case, the energy of the higher-
energy x-ray is usually chosen so that the mass absorption coecients of the analyte and
matrix elements are the same, the transmission measurement thus determining the mass
per unit area of sample in the x-ray beam.
The uncertainty in determination of R [Eq. (14)] caused by counting statistics is
dR
R
rt
dI=I
0
m
0
!
2
dI=I
00
m
00
!
2
s
16
where
dI
I

0
!
2
dI
0
0
I
0
0
!
2
dI
0
I
0
!
2
17
and
dI
I

00
!
2
dI
00
0
I
00
0
!
2
dI
00
I
00
!
2
18
and where dI=I is the relative counting statistical uncertainty and m is the mass absorption
coecient of the x-ray in the sample. The corresponding uncertainty in determining the
concentration of the analyte can be found by substituting RdR for R in Eq. (13).
The uncertainty in the determination of the concentration of the analyte, caused by
an increase in the concentration (dC) of one matrix element k replacing another matrix
element l, can be calculated by increasing the mass absorption coecient of the sample
matrix by
m
M
new m
M
old m
k
m
l
dC 19
and substituting the new mass absorption coecient into Eq. (13).
These equations accurately predict all aspects of XRA analysis (Watt and Stener,
1985) except when the sample is so highly heterogeneous that within the beam of x-rays,
there are signicant dierences in absorption of the x-rays.
F. X-ray Scattering Analysis
Of the two x-ray scattering methods of analysis, one relies on comparison of the detected
intensities of the Compton-scattered and coherent scattered x-ray (Schatzler, 1979),
whereas the other one is based on determination of the intensity of the Compton-scattered
x-rays (Fookes et al., 1975). The former method is essentially a measure of the ratio of the
dierential scattering cross sections of the two components, which is proportional to
between Z and Z
2
(Siegbahn, 1965). The latter methods depends on the absorption of
x-rays in the sample, which, in the photoelectric region, is proportional to between Z
4
=A
and Z
5
=A (Siegbahn, 1965). Thus, the method is very similar to XRA analysis and is
considerably more sensitive than the Compton-scattered to coherent scattered ratio x-ray
method. Both methods are accurate only when the changes in detected x-ray intensities
caused by changes in the concentration of the analyte are much greater than those caused
by changes in the concentration of the matrix elements.
The sensitivity of both techniques and uncertainties due to variations in con-
centrations of matrix constituents can be predicted using Eq. (6), where the photoelectric
absorption cross section in the sample is much greater than the scattering cross section.
Dual-energy scattering techniques (Outokumpu Mintec, 1986), analogous to dual-
energy preferential absorption techniques, are used to minimize the eects of sample
heterogeneity. The x-ray scattering techniques are used in applications in which only one
side of the sample is accessible and thickness of the sample is too great to allow sucient
penetration of x-rays. Compared with DUET analysis, the main disadvantage is that
narrow beams of x-rays cannot often be used because of the lower geometrical eciency of
the source, sample, and detector. Hence, multiple scattered x-rays are detected with a
consequent loss in accuracy of analysis.
III. RADIOISOTOPE X-RAYSOURCES ANDDETECTORS
The characteristics of radioisotope x-ray sources and detectors are described here. A full
understanding of the dierent characteristics of scintillation, proportional, and solid-state
detectors is essential because of the need to tailor their use to specic applications and to
environmental conditions in the eld and in industrial plants.
A. Radioisotope Sources
There are only a fewradioisotope sources that are usedfrequently for x-ray analysis; these are
listed with their most important characteristics in Table 1. Also included are two radio-
isotopes that emit high-energy x-rays and they are used most frequently with the x-ray
sources to correct for changes in sample mass per unit area, thickness, or bulk density.
The activity of radioisotopes is specied in terms of the rate of disintegration of the
radioactive atoms [i.e., decays per second, or becquerel (Bq)]. One becquerel (Bq), an SI
unit, is dened as one disintegration per second. The unit of becquerel replaces the non-SI
unit, the curie (Ci), which equals 3.7610
10
becquerel. Unfortunately, the unit of becquerel
is not very practical. For example, a typical, useful activity of 100 mCi has to be expressed
in gigabecquerels (GBq). A practical conversion relation between the two units is
100 mCi 3:7 GBq
The typical number of x- or g-rays emitted per disintegration by the given radioisotope is
listed in Table 1 so that the essential parameter of the radioisotope source, the number of
x-rays or g-rays emitted per second, can be calculated. The emission rate of radioisotope
decreases with time according to the law of natural decay, the number of radioisotope
atoms decaying from N
0
to N after an elapsed time t being given by
N N
0
e
0:693t=T
1=2
20
where T
1=2
is the so-called half-life of the radioisotope. The source decays to half of its
original emission rate during the time equal to its half-life. The radioisotope source is
usually replaced after one to two half-lives.
The physical size of radioisotope x-ray sources is small. Figure 4 shows the en-
capsulations of typical cylindrical and annular sources of
109
Cd (Amersham, 1986).
Cylindrical sources used in portable analyzers are usually 8-mm-diameter by 5-mm-thick
capsules and are often referred to as pellets. When economics justies it, a special source
may be designed for a particular type of the analyzer. A so-called lollipop source, de-
signed specically for light-element analysis probes made by Metorex Int. is such an ex-
ample (Amersham IEC.600 series). It is made in a form of a at copper ring, 1 mm thick,
15 mm in diameter, with a 8-mm opening. One side of this at copper annulus is elec-
troplated with a
55
Fe isotope, over which a few-micrometer-thick Ni ashing is applied.
Such source geometry allows for a very close coupling between sample and a proportional
detector window. Consequently, the quantitative analysis of light elements, down to A1, is
possible without the nuisance of helium purge or vacuum.
There are international codes for the safe use of radioisotopes, and a simple in-
troduction to radiation protection has been published (Martin and Harbison, 1986). Each
organization using radioactive substances is required to hold a license, issued in most
countries by a government health department or atomic energy authority. The Interna-
tional Commission on Radiological Protection (ICRP, 1985) recommends that, for
members of the public, it would be prudent to limit exposures to radiation on the basis of a
lifetime average annual dose of 1 millisievert (mSv). Table 1 lists the approximate, typical
dose rates at 1 m from each radioisotope source, assuming no absorption of the emitted
radiation within the source or by air. The x-ray dose is inversely proportional to the square
of the distance from the source. X-ray doses received during the operation of x- and g-ray
instrumentation and gauges are trivial compared with the maximum permitted doses be-
cause of the low x-ray output of radioisotope sources, careful design of operating tech-
niques, and x-ray shielding.
Table1 Properties of Radioisotope Sources Used for XRF, XRA, and XRS Analysis and
Determination of Bulk Density r, Mass per Unit Area (rt), and Thickness t in X-ray Analysis
Radio-
isotope
Half-life
(years)
X- or g-ray
energy (keV)
Photons per
disintegration
Dose at 1 m
from 1 GBq
(27 mCi) (mSv=h)
Analytical
technique
55
Fe 2.7 MnK x-rays (5.9, 6.5) 0.28
a
XRF
238
Pu 88 UL x-rays (1330) 0.13
a
XRF
244
Cm 17.8 PuL x-rays (1421) 0.08
a
XRF
109
Cd 1.3 AgK x-rays (22, 25) 1.02
a
XRF
g-rays at 88 0.04
125
I 0.16 g-rays at 35 0.07 2.7 XRF
TeK x-rays (2732) 1.38
241
Am 433 g-rays at 59.5 0.36 3.6 XRF, XRA, XRS
153
Gd 0.66 EuK x-rays (4148) 1.10 27 XRA
g-rays at 97 0.30
g-rays at 103 0.20
57
Co 0.74 g-rays at 122 0.86 24 XRF, XRA, XRS
g-rays at 136 0.11
133
Ba 10.8 g-rays at 81 0.34 65 XRA, XRS,
g-rays at 276 0.07 rt
g-rays at 303 0.18
g-rays at 356 0.62
0.09
137
Cs 30.2 g-rays at 662 0.85 83.7 rt
a
It is difcult to assign a radiological protection meaning to the dose of low-energy x-rays.
Figure 4 Encapsulation of disk and annular
109
Cd g-ray sources. Dimensions are in millimeters.
(From Amersham, 1986.)
The International Organization for Standardization (ISO, Geneva) has produced a
system for classifying sealed radioisotope sources based on safety requirements for typical
uses (Amersham, 1986). Prototype sealed radioisotope sources undergo temperature, ex-
ternal pressure, impact, vibration, and puncture tests (Table 2), which increase in severity
as the class designation increases from 1 to 6. The ISO classies the test requirements for
specic types of application of the sealed sources. The classication for low-energy g-ray
gauges and XRF analysis instruments used in industry is C33222 [i.e., from Table 2, the
rst classication 3 is temperature ( 740
C and 180
C), the second classication 3 is

25 kPa to 2 Mpa, and so on]. This classication, which meets the minimum requirements,
is marked in Table 2 by shaded areas. Most radioisotope sources are designed and
manufactured to have a greater integrity than required by this classication. For example,
the
109
Cd sources (Fig. 4) are coded C64344 and C33344 according to the ISO classi-
cation, compared with C33222 required.
The use of radioisotope-containing devices is regulated in each country by the ap-
propriate government agency, which may require the user to just register the device with it
or obtain special license to posses and use the device.
B. X-ray and g-ray Detectors
Scintillation, proportional, and solid-state detectors arein this ascending order of im-
portanceextensively used in radioisotope x-ray analysis. The important characteristics of
these detectors are x-ray energy resolution, eciency, the ratio of the full energy peak to
total detection eciency, the spectrum of x-rays not in the peak, the sensitive area and
thickness of the detector, the count rate capability of detector and associated electronics,
the complexity of the detector and associated electronics, the robustness of the overall
system, andlast but not leastits cost. An excellent source on all aspects of detectors of
nuclear radiation can be found in the work of Knoll (1999).
The complexity and associated cost of equipment is greatest for solid-state detectors
and least for scintillation detectors. The need to use liquid nitrogen (LN
2
) with solid-state
detector systems and their relative complexity and cost have proven to be a cost penalty
but not a limiting factor, even for applications of on-line analysis in industry. Successful
application of thermoelectric cooling (Peltier eect) for semiconductor detectors, speci-
cally those based on the structure of p-i-n junction (diode), allowed the abandonment of
LN
2
cooling without compromising analytical performance of those detectors (Amptek,
1977; EPA, 1997; Shefsky, 1997).
1. Energy Resolutionof the Detector
Energy resolution is the detector parameter by which dierent detectors are compared to
each other. For detectors of x-rays and low-energy g-rays, the energy resolution is dened
as the full width of the MnKa peak measured at half of its maximum (a so-called FWHM),
when the detector is irradiated directly by the collimated beam from the
55
Fe radioisotope,
at a total count rate in the whole spectrum not exceeding 1000 counts=s (see Fig. 5).
Usually, also a shaping time constant of the amplier is specied to be not less than 10 ms.
For semiconductor detectors, their energy resolution is expressed directly in units of en-
ergy (eV). For gas-lled proportional and scintillation detectors, their energy resolution is
customarily expressed as percent relative to the energy of the MnKa peak (5895 eV). For
example, the best gas-lled detectors may reach FWHM of about 700 eV, which, when
related to 5895 eV of the peak energy, equals about 12% relative. On the other hand,
semiconductor detectors such as Si(Li) crystals feature energy resolution better than 3%
Table 2 Classication of Performance Standards for Sealed Radioisotope Sources as per ISO.2919
a
Test for
resistance to
Class
1 2 3 4 5 6
Temperature No test 740
C (20 min.),
80
C (1 h)
740
C (20 min.)
180
C (1 h)
740
C(20 min.),
400
C (1 h) and
thermal shock
from 400
C to 20
C
740
C (20 min.),
600
C (1 h),
thermal shock from
600
C to 20
C
740
C (20 min.),
800
C (1 h)
thermal shock from
800
C to 20
C
External
pressure
b
No test 25 kPa absolute to
atmospheric pressure
25 kPa absolute to
2 MPa absolute
25 kPa absolute
to 7 MPa absolute
25 kPa absolute
to 70 MPa absolute
25 kPa absolute to
170 MPa absolute
Impact
c
No test 50 g from 1 m 200 g from 1 m 2 kg from 1 m 5 kg from 1 m 20 kg from 1 m
Vibrations No test 30 min, 25500 Hz at
5gn peak amplitude
30 min, 2550 Hz at
5gn peak amplitude;
5090 Hz at 0.635 mm
amplitude peak-to-peak;
90500 Hz at 10gn
90 min, 2580 Hz
at 1.5 mm amplitude
peak-to-peak;
802000 Hz at 20gn
Puncture
d
No test 1 g from 1 m 10 g from 1 m 50 g from 1 m 300 g from 1 m 1 kg from 1 m
a
Details of the testing procedures are given in ISO.2919 and BS.5288. A further class X can be used when a special test procedure has been adopted.
b
External pressure 100 kPa 1 atm (approximate).
c
The source, positioned on a steel anvil, is struck by a steel hammer of the required weight; the hammer has a at striking surface, 25 mm in diameter, with the edges
rounded.
d
The source, positioned on a hardened steel anvil, is struck by a hardened pin, 6 mm long and 3 mm diameter, with a hemispherical end, xed to a hammer of the required
weight.
Note: The shaded cells of the table when read from top to bottom will correspond to class C33222, which is the minimum requirement for low-energy g-ray and x-ray sources
used in XRF instrumentation and g-ray gauges.
relative, and its is therefore more convenient and accurate to express their FWHMs in
units of energy rather than percent. Energy resolution, expressed as the full width at
half(peak)-maximum (FWHM) and shown for each type of detector as continuous line in
Figure 6, was calculated from equations given by Jenkins et al. (1981d). It is important to
remember that practical energy resolution for any detector is always worse than that
quoted by 10% to sometimes 20% relative. This is because the spectra measured from real
samples usually contain large amounts of backscattered radiation, and, additionally, the
intensities of the analytes may be very high.
As mentioned earlier, the energy resolution of solid-state detectors is superior to that
for proportional and scintillation detectors (see Fig. 26 in Chapter 2). Figure 7 shows the
calculated energy spectrum for the detection of 8-keV x-rays in each detector and also the
energies of the Ka x-rays in the 69-keV energy range. Figure 8 shows the dierence in
energy of Ka x-rays between adjacent atomic number elements.
Table 3 compares the dierence in Ka x-ray energies with the energy resolution for
aluminum, iron, and tin based on data given in Figures 6 and 8. Solid-state detectors are the
only detectors that can fully resolve Ka x-rays of adjacent Z elements. The factors aecting
their resolution are discussed in detail in Chapter 3 (Sec. III.D). Proportional detectors have
an energy resolution less than twice the energy dierence in Ka x-rays of adjacent Zelements.
Hence, their energy-resolving power is useful even if there are adjacent Z elements in the
sample. Scintillation detectors (see Chapter 2, Sec. III.F.2) have suchlimited resolving power
that other techniques must be used to discriminate between adjacent Z elements, such as
balanced lters. This achieved, however, at the expense of some loss in sensitivity of analysis.
Figure 9 illustrates the resolving capabilities of detectors by showing calculated energy
spectra for identical concentrations of Fe and Ni in the same sample.
Figure 5 Definition of energy resolution, FWHM, of an x-ray detector, which is measured at the
half height of MnKa peak. Note the shaded area, which indicates the width of background window.
2. Energy Resolutionof Detector and MinimumDetectable Level
The energy resolution of the detector not only determines its ability to resolve the x-rays of
adjacent elements but also decides about the minimum quantity of the element that can be
detected by the detector, a so-called minimum detection limit, or the detection limit (DL).
The better the resolution (i.e., the narrower the x-ray peak), the better (i.e., smaller) the
minimum detectable quantity of element. The detection limit is frequently dened by
DL
3
S
I
bgd
t
r
21
where S is the sensitivity (in counts=s per unit concentration of analyte), I
bgd
is the
background intensity measured in the analytes integration window, and t is the mea-
surement time.
Figure 6 X-ray energy resolution (FWHM) of scintillation, proportional, and solid-state
detectors. The continuous lines are calculated (data from Jenkins et al., 1981d), the silicon detector
results being based on a small detector (10 mm
2
63 mm): The (diamonds) resolutions are for various
solid-state detectors (EG&G Ortec, 1986); () typical and (6) best for the high-resolution
proportional detectors (Metorex, 1986); and (open circles) typical and (solid circles) best resolutions
for specific NaI scintillation detectors (Harshaw).
The background intensity, I
bgd
, is measured in the same window as the intensity
of a given x-ray peak. The width of the window is usually set equal to the peak
FWHM. If a sample containing a certain percentage of the analyte is measured with a
detector of energy resolution E
1
(where E
1
FWHM), it will generate in its FWHM-
wide window a certain intensity, I
1
. If the detector resolution now degrades to, say, E
2
(i.e., the analytes x-ray peak is now wider), the intensity I
2
will still be equal to I
1
(as
long as the measurement window is FWHM-wide). This is because the energy de-
posited by the photon in the detector is represented by the area of the whole peak.
Therefore, if the peak is wider, it has to be smaller, and if it is narrower (better re-
solution), it has to be tallerfor the area of the peak to remain constant (see Fig. 5).
However, the background intensity will be larger in the case of a worse energy re-
solution, E
2
, than in the case of E
1
, because the integration window for the back-
ground intensity is wider in the case E
2
than in the case E
1
. Then, it follows from
Eq. (19) that the DL for the E
2
case will be larger (worse) than in the case of E
1
energy resolution. Therefore, for the best DLs, it is of paramount importance to use
the detector with the best energy resolution.
3. Detector Efficiency for X-raysand Detector-Sensitive Area
Figure 10 shows the calculated eciencies of scintillation and solid-state detectors over
the energy range 1150 keV (see also Chapter 3). At low energies, the decrease in ef-
ciency is due to the absorption of x-rays in the beryllium window at the front of the
detector.
Figure 7 The calculated energy spectra for the detection of 8 keV x-rays in scintillation,
proportional, and solid-state detectors. (From Watt, 1983.)
The eciency of the detector for registering the x-rays at high x-ray energies is
determined by the probability that the x-ray interacts with atoms in the sensitive volume of
the detector. The most ecient detectors are those with a high atomic number and a high
mass per unit area. For x-ray energies above about 40 keV, solid-state detectors made of
germanium are preferred to those made of silicon. Also, of the two detectors made of the
same material, the thicker one will have a better eciency for high-energy x-rays. This is
why even the smallest Si(Li) detector (usually at least 3 mm thick) is superior to the
siliconp-i-n diode detector, which is usually not thicker than 0.5 mm. The eciency of
Table 3 Difference in Energy of the Ka X-rays of Adjacent Atomic Number Elements,
and the Energy Resolution of Three Types of Detector
Atomic No.
of element
Energy of
Ka x-rays (eV)
Dierence in
Ka energies (eV)
Energy resolution of detector, FWHM (in eV)
Solid
state
Gas-lled
proportional Scintillation
13 (Al) 1,490 253 117 425 3,000
26 (Fe) 6,400 527 160 660 6,200
50 (Sn) 25,300 1087 275 1,750 12,200
Figure 8 The energy difference between the Ka x-rays of adjacent atomic number elements.
Figure 9 Comparison of energy resolution of Si(Li) (FWHM160 eV) and gas proportional
detector (FWHM660 eV). The solid line is spectrum of the 1-to-1 ratio of iron and nickel collected
with the Si(Li) detector. The dotted spectrum is generated with a gas proportional detector for the
same sample.
Figure 10 Calculated efficiencies of NaI scintillation detector and silicon and germanium solid-
state detectors used in XRF analysis.
proportional detectors depends on the type and pressure of the lling gas and the diameter
of the detector (Fig. 11).
The sensitive area for scintillation detectors is usually from 1000 to 2000 mm
2
; for
proportional detectors, it ranges from about 500 to 1000 mm
2
; for silicon solid-state de-
tectors, it is 10100 mm
2
; and for the commercially available silicon p-i-n diode detectors,
Figure11 X-ray detection efficiencies of Metorex International (formerly Outokumpu Electronics)
proportional detectors with different types of gas fillings. The number code below each graph is gas
pressure, bar (1), window thickness (in mm) (2), gas mixture (3), low background (4), high efficiency
(5) long lifetime (6), high count rate (7), and high resolution (8). The ratings shown are excellent
(xxx), good (xx), fair (x).
it is currently 313 mm
2
. Hence, in general, count rates are highest for the poor-
er-resolution detectors. The sensitive area of the detector determines the type of mea-
surement geometry that can be used with each detector type. Central source geometry
(Fig. 1b) is normally used with scintillation and proportional detectors, because the large
sensitive area compensates for the shadowing eect of the centrally located source. An
annular source geometry (Fig. 1a) is characteristic for Si(Li) solid-state detectors and
especially for their stationary installations. A side source geometry (Fig. 1c) is the only
choice for the small-area detectors, specically the most recent semiconductor detectors
such as HgI
2
, silicon p-i-n-diode, CdTe, CdZnTe, and so forth. The eciency of solid-state
detectors is discussed in some depth in Chapter 3 (Sec. III.F).
4. Ratio of Full-Energy Peak toTotal Spectrum
The ratio of the area of the full-energy peak to the total area of the x-ray spectrum is
critical to the sensitivity of XRF analysis. The spectrum outside the full-energy peak is
caused by many factors.
The rst and most important is the occurrence of the so-called escape peak
(Jenkins et al., 1981c), resulting from incomplete photoelectric absorption of the incident
x-ray in the detector material followed by escape of some of its uorescent x-rays from
the detector. For example, if an x-ray photon of iron energy 6.4 keV enters the active
volume of the detector, its energy is being absorbed by the detector material also by the
mechanism of excitation of characteristic x-rays of the detector material, such as Si, Ar,
and so forth. If, in turn, the excited x-ray photon of, say, silicon, of energy 1.74 keV, is
not absorbed in the detector but wanders outside of it, then the total energy deposited in
the detector by the original iron photon will be smaller by the energy of silicon x-ray
photon which escaped from the system. The energy left in the detector equals the
dierence in energy of the x-ray entering the detector and that of the escaping uor-
escent x-ray. This will give rise to the small peak always located left to the original x-ray
peak, at a distance equal to the energy of characteristic x-rays of the detector material.
Thus, for example, for silicon-based detectors, the escape peak may be observed
1.74 keV left to any original photopeak. The escape peak is greatest for the higher-Z
detectors. The ratio of x-rays in the escape and full-energy peaks is highest for pro-
portional detectors with gas llings of Xe (Ka x-ray of 29.7 keV), Kr (12.6 keV) and Nal
(iodine Ka of 28.5 keV) scintillation detectors. However, even silicon (1.74 keV) has
about 12% of the detected counts in the escape peak when excited by 2 keV or higher-
energy x-rays. The magnitude of the escape peak is also strongly dependent on the size,
shape, and geometry of the detector itself. The smaller the detector, the more likely the
escape of the characteristic x-ray of detector material is, because it is more likely for the
photon to be generated at the wall of the detector. Also, escape peaks are more intense
for more intense original photopeaks.
Other factors that lead to incomplete absorption of the energy of the x-ray in the
detector are Compton scattering of the incident x-ray in the detector, with the scattered
x-ray or Compton electron escaping from the sensitive volume; alternatively, the incident
x-ray may be photoelectrically absorbed in the detector, but the photoelectron escapes
from the sensitive volume of detector before losing all its energy. These phenomena, which
are dierent manifestations of the escape mechanism, result in the contribution to the
spectrum at energies dierent from the energy of the original x-ray photon. The full-energy
peak to total spectrum is highest for the high-Z detector materials and for low-energy
x-rays. It is lowest for the low-Z gases used in some proportional detectors.
Apart from the phenomena taking place within the detector itself, the total spectrum
is also a function of the instrument design. For example, typically most of the radiation
reaching the detector is not characteristic x-ray radiation from elements in the sample, but
primary radiation from the source scattered on sample and its environment. It is, there-
fore, very important that the design of the instrument be focused on minimizing and
optimizing of measurement geometry in order to reduce to absolute minimum any para-
sitic radiation reaching the detector.
5. Comments onthe Characteristics of Proportional Detectors
The characteristics of proportional detectors vary considerably with type of lling gas and
its pressure and are much more variable than the characteristics of scintillation and solid-
state detectors. The best energy resolution is obtained by using Penning mixtures as gas
llings of these detectors (Jarvinen and Sipila, 1984b). Although the improvement in en-
ergy resolution is relatively small (Fig. 6), it is critically important for applications in the
atomic number range 2630 (iron to zinc). The low average ionization energy of Penning
mixtures also leads to other important advantages (Jarvinen and Sipila, 1984b): the vol-
tage required is lower, hence the gas pressure can be higher. This leads to a higher e-
ciency of detection, fewer wall eects, and smaller escape peaks and, consequently, to a
higher ratio of peak to total spectrum. The life of the detector is also increased to more
than 10
13
counts because of the use of only noble gases.
The characteristics of proportional detectors supplied by Metorex International
(formerly Outokumpu Oy) are summarized in Figure 11. The recommended gas llings for
proportional detectors depend on the specic analysis application. The eciency of de-
tection of low-energy x-rays is limited by the absorption of the x-rays in the beryllium
window. Proportional detectors with lower gas pressures are used in the detection of low-
energy x-rays because the thinner windows do not withstand high pressures. For those
low-energy x-rays, the detectors lled with neon gas and tted with Be windows as thin as
13 mm are commercially available.
6. Developmentsin Solid-State Detectors
The solid-state detector (SSD) is the best type of x-ray detector for XRF analysis, but,
until recently, its potential has not been fully realized, particularly in industrial and eld
use, because of the need for liquid-nitrogen cooling. The only successful exceptions have
been pioneering and notable Kevex designs, known as Analyst
TM
Model 6700a factory
oor modeland X-SITE
TM
a very rst portable, solid-state detector alloy analyzer
(Spiegel and Horowitz, 1981; Kevex Corp.). Both of these models featured a traditional
Si(Li), liquid-nitrogen-cooled detector and either annular or capsule-type radioisotope
source(s). Perhaps the best testimonial to the success of these designs of the early eighties is
the fact that owners of quite a few still working systems spare no eort and ingenuity to
keep them alive, despite a total abandonment by the original manufacturer.
There has been much promising research into mercuric iodide, cadmium telluride
and gallium arsenide SSDs (Cuzin, 1987) which can operate at or near ambient tem-
peratures. The eld-eect transistor (FET) of the low-noise charge preamplier associated
with these detectors must be cooled to at least 720
C and stabilized at this lower tem-

perature in order to reduce electronic noise. This is achieved with the Peltier element; the
one-stage Peltier cryostat can reduce the temperature of cooled object by about 20
C. Over
the last decade, the Peltier-cooled mercuric iodide detector has been used in the com-
mercially available, portable x-ray analyzers (Berry and Voots, 1989; Piorek, 1997).
However, production yields for these detectors are still problematic, and the same applies
to other semiconductor detector materials such as CdZnTe. It is reasonable to say that
should the demand for those detectors be as high as for silicon in the electronics industry,
we would most likely had mastered the technology of these promising semiconductor
materials a long time ago. Developments have led to the production of silicon-lithium-
drifted detectors that can be operated at temperatures much higher than that of liquid
nitrogen (195
C). Madden et al. (1986) used these silicon detectors cooled in a Peltier
cryostat. The front-end assembly, mounted in the cryostat, contains a silicon detector and
a FET and is mounted on a four-stage Peltier cooling cell. With the assembly under high
vacuum, a temperature of 774
C is achieved with a cell power of 4.3 W. For a

16-mm
2
62-mm-thick detector, an energy resolution of 190 eV at 5.9 keV was achieved. As
the rst commercial manufacturer, Kevex Corp. announced the development of a Peltier-
cooled silicon detector system with x-ray energy resolutions of 155, 180, and 240 eV (at
6 keV) respectively for 10-, 30-, and 80-mm
2
detectors, which is as good as have been
achieved for liquid nitrogen cooling. Other organizations have developed silicon detectors
and Peltier cryostats that also give good energy resolutions for x-rays (Tractor X-Ray,
now Spectrace). Systems based on these detectors are available as either laboratory or
benchtop versions.
It should not come as surprise that the most recent room-temperature detector is
a silicon p-i-n diode, manufactured using well-known technologies of silicon wafer and
chip fabrication. Two U.S. companies manufacture these detectors commercially. These
truly silicon (no lithium doping) detectors are supplied in a TO-8 package, containing a
detector element, a FET, a feedback loop, and a Peltier element. Typically, the detector is
a tiny, 713-mm
2
area by 0.3-mm-thick silicon diode, with energy resolution currently
reaching below an impressive barrier of 190 eV (Amptek, 1997). These small detectors are
predominantly used in portable designs. Their main drawback is relatively high power
consumption (12 W on average) by Peltier cooler, which in the case of a portable,
battery-operated device is not desirable. The small thickness of these detectors (0.5 mm
appears to be maximum these days) makes them inecient for the detection of x-rays
above 25 keV. However, these Peltier-cooled systems did indeed replace liquid-nitrogen-
cooled systems and opened the way for the widespread use of silicon detectors in
industry.
A very good insight into the current status of research in solid-state detectors is
provided by Schlesinger and James (1995). From this reference, one may infer that the next
major development in detector technology may come from gallium arsenide. This semi-
conductor material is very important for semiconductor electronic and optoelectronic
industry and, therefore, is a subject of serious research. The windfall of this research may
be a new detector material for x-rays.
C. Electronics
The electronics used with the various detectors are discussed in Chapters 2 (Sec. III.F) and
in 3 (Sec. IV) and are also covered in detail by Jenkins et al. (1981a). The limits to accuracy
and sensitivity of XRF analysis are usually determined by the limitations of the detector in
energy resolution, eciency of detection, and maximum count rate, for example, rather
than of the electronics. With the excellent gain stabilization electronics now available and
the reliability of low-power, surface-mount components, it is rare that the electronics
system is a signicant limiting factor even in the harsh environmental conditions of
industrial plants.
IV. X-RAYAND g-RAY TECHNIQUES
The range of radioisotope x- and g-ray techniques used for analysis is far more extensive
than the range based on x-ray tube techniques. Almost all x-ray tube systems are based on
the high-energy resolution of wavelength-dispersive (the crystal spectrometer) or energy-
dispersive (the solid-state detector) devices. With this high resolving power, there is less
need to tailor a technique to the specic application. Radioisotope x-ray systems, espe-
cially those involving scintillation or proportional detectors, usually must be carefully
matched to the specic application. This disadvantage is more than compensated for by
such attributes as mechanical ruggedness, simplicity, and portability, which are so im-
portant in industrial and even more so in eld applications.
The selection of the radioisotope source to analyze dierent elements depends on
many factors, including whether the energy of the radioisotope x- or g-rays is sucient to
excite the element, the energies of the x-rays scattered by the sample, and the energy re-
solution of the detector. Figure 12 is an approximate guide and, although prepared for
proportional detectors (courtesy of Metorex Int., formerly Outokumpu Oy), can be used
for solid-state detectors and to a more limited extent for scintillation detectors. The iso-
topes of
238
Pu and
244
Cm, emitting x-rays similar in energy, can be used interchangeably
although curium is preferred for safety reasons. A
57
Co isotope can be used with scintil-
lation detectors or germanium solid-state detectors for the K shell XRF analysis for high-
Z elements, such as uranium, gold, and lead.
This section reviews the radioisotope XRF techniques used with solid-state, pro-
portional, and scintillation detectors, x-ray preferential absorption techniques that are
normally based on the use of scintillation detectors, and x-ray scattering techniques that
are often based on use of scintillation detectors. An example of the application of each
technique is also given.
A. XRF Techniques Based on Solid-State Detectors
The analysis of samples of copper ores taken from the process streams of three dierent
mineral concentrators is used to illustrate XRF analysis with a solid-state detector
(Gravitis et al., 1974). The ore samples were excited by x-rays from a 3.3-GBq (or about
90 mCi)
238
Pu source and the uorescent x-rays were detected by a 28-mm
2
63-mm-thick
silicon-lithium-drifted [Si(Li)] detector. The x-ray spectrum (Fig. 13) of one of the samples
shows well-resolved peaks of Ka x-rays from iron, copper and zinc, and La; Lb, and Lg
x-rays from lead and the complex spectra of the Compton-scattered and coherently
scattered x-rays. The count rates of the copperKa x-rays (Fig. 14a) lie within three bands,
separated from each other because of the large dierence in absorption of x-rays in the
sample matrix caused by the widely dierent iron concentrations (5, 20 and 50 wt%) of the
dierent ores. The use of the scattered x-ray component in the calibration equation for
copper corrects for matrix absorption and reduces the overall uncertainty to better than
0.15 wt% copper (Fig. 14b).
Solid-state detectors are the only type of detector for which the x-ray energy re-
solution (Fig. 6) is sucient to resolve the uorescent x-rays of adjacent Z elements
(Fig. 8). There are minor problems of overlap in some cases in which the energy of the Ka
x-ray of the analyzed, Z element, overlaps the energy of the Kb x-ray of another, usually
Z71, element in a sample. These overlaps can easily be identied from the energies of
uorescent x-rays as a function of Z (see Appendix II of Chapter 1). Fluorescent x-rays
can also overlap slightly if the concentration of an interfering, adjacent Z element is much
Figure12 Appropriate radioisotope x-ray source for use with proportional or solid-state detectors
to gain a high sensitivity of XRF analysis for elements in a specified atomic number range. The
principal energies of the x-rays emitted by each source are indicated above the x axis. The diagonal
lines are the K and L shell absorption-edge energies. K and L shell excitation is required to gain a
wider coverage of atomic number elements using the same radioisotope source and, in some cases,
for high-atomic-number elements.
Figure13 The spectrum of x-rays from a copper, lead, and zinc ore sample excited by
238
Pu x-rays
and detected by a Si(Li) solid-state detector.
Figure 14 XRF analysis of copper in flotation feed samples from three mineral concentrators,
based on the intensity of (a) copper Ka x-rays and (b) the ratio of the intensities of copper Ka and
scattered x-rays. The analysis was based on a
238
Pu source and silicon solid-state detector.
higher than that of the analyte. The extent of this overlap can be calculated using the
uorescent x-ray energies and x-ray energy resolution (FWHM) of the detector. The
overlaps of this type, which are known as spectral overlaps or spectral interferences,
can be easily corrected either mathematically or empirically.
The small sensitive area and, consequently, small solid angle are the main limitations
of solid-state detector compared with proportional and scintillation detectors. With solid-
state detectors, it takes longer to obtain the same counting statistics. It is not always
possible to use higher-activity sources to overcome this limitation because of self-ab-
sorption of x-rays in the source and, for some radioisotopes, the cost of the source. On the
other hand, the relatively small solid angle limits the amount of scattered x-rays reaching
the detector, which reduces the spectral background considerably and improves the de-
tector peak-to-background ratio.
Figure 15 shows the 3s minimum detection limits for low concentrations of various
elements in a low-Z matrix (Homann, 1986; Spatz and Lieser, 1977). The counting time
was 600 s. The measurements with
109
Cd (185 MBq or 5 mCi),
241
Am (370 MBq or
10 mCi), and
57
Co (370 MBq or 10 mCi) were made using a 30-mm
2
65-mm-thick silicon-
lithium-drifted, solid-state detector (FWHM of 250 eV at 6.4 keV), and the sample matrix
was silica gel. The measurements with
125
I isotope (185 GBq or 5 Ci) were made using a 50-
mm
2
63-mm silicon detector (FWHM 250 eV) and a matrix of average atomic number 10.
The measurements with
133
Ba isotope (370 GBq or 10 Ci) were made using an 800-
mm
2
613-mm germanium detector (FWHM 590 eV at 122 keV) and a water matrix. The
detection limits using one source vary greatly with atomic number; hence, to maintain low
detection limits over a wide atomic-number range, several radioisotope sources, emitting
x-rays of dierent energies, must be used. In this case, detection limits less than 10 mg=g are
achieved for many elements. Iron-55 can be used to extend the range of sensitive detection
down to Z15. Similar detection limits for elements in a soil matrix were reported using a
portable, Si(Li)-detector-based x-ray analyzer (Piorek, 1994).
B. XRF Techniques Based on Proportional Detectors
The main advantages of proportional detectors over classical, Si(Li) solid-state detectors
are the larger sensitive area, simpler equipment, and no need for cooling the detector to a
very low temperature. The higher count rates possible with these detectors lead to shorter
analysis times, except for those applications in which the energy resolution (Fig. 6) limits
the sensitivity of analysis. Many important XRF applications are not limited by the poorer
energy resolution, and many do not involve adjacent Z elements.
Selection of the appropriate type of proportional detector for the specic XRF
application is very important. The best type of detector is determined by optimizing the
various characteristics summarized in Figure 11 for a specic application. In practical
terms, it means proper matching of the detector gas ll, its pressure, and type and
thickness of detector window, with given analytical requirements. For example, in order to
analyze the fraction of percent of zinc and phosphorus in oil, one can select a single probe
with a detector, which will usually compromise eciency for both analytes. On the other
hand, a much higher eciency of detection and, hence, better analytical sensitivity for
these two analytes can be achieved by using two dierent probes, each with the detector
matched to the analyte; neon lling and thin window detector for phosphorus and a high-
pressure argon detector for zinc.
Figure 16 shows the spectra of x-rays, taken with 4-mm-thick samples of pure water
and water containing 100 mg=g of both iron and zinc, measured with a
244
Cm source and a
proportional counter lled with a neonargon Penning mixture gas to a pressure of 7 bar
(Jarvinen and Sipila, 1984b). The detection limits are comparable to those obtained with a
silicon solid-state detector with x-ray tube excitation (Jarvinen and Sipila, 1984b). If other
elements in the atomic number range 2630 had been present, however, there would have
been incomplete resolution of the K x-rays emitted and, hence, poorer sensitivity of
analysis.
Figure 17 shows detection limits for the elements in water (Jarvinen and Sipila,
1984a; other data courtesy of Asoma Instruments), normalized to a common counting
time of 100 s. The low detection limits were obtained by careful choice of lling gas and
pressure in relation to the exciting x-ray energy used. The issue of proper match of the
detector with the energy of exciting radiation is much more important for gas-lled pro-
portional detectors than for the solid-state ones. This is because of the much greater
uniform detection eciency of the solid-state detector for x-rays than that of the gas-lled
one. For most, except low-atomic-number elements, the detection limits were less than
10 mg=g, which is similar to the results for solid-state detectors (Fig. 15); however, they
were achieved in a time six times shorter than before. These low detection limits were
achieved using dierent proportional-counter gas llings, and, as a consequence, the
technique is less exible than that based on the solid-state detector. If adjacent Z elements
had been present, the detection limits for the proportional counter would have been
considerably worse, but for the solid-state detector, they would have been much less
changed.
Figure 15 Detection limits (3s) determined with various radioisotope x-ray sources and a solid-
state detector. [Data from Hoffman (1986) and Spatz an Lieser (1977).]
The relatively modest improvement in energy resolution of the high-resolution
gas-lled detector over standard proportional detectors leads to considerable im-
provement in the accuracy of analysis in some applications. Hietala and Viitanen
(1978) indicated that an improvement in resolution from 16% to 10% at 8 keV results
in the relative standard deviation for determination of zinc in copperzinc tailing,
containing 0.1 wt% of both copper and zinc, to be reduced from 0.40% to 0.05%
relative.
C. XRF Techniques Based on Scintillation Detectors
The energy resolution of scintillation detectors is so poor (Fig. 6) that the detector cannot
be used in most applications to resolve the K x-rays of the analyte and matrix elements.
Selectivity to the analyte is obtained with lters and radiators and by a proper choice of
the energy of the x-rays exciting the sample (Watt, 1983). Scintillation-detector XRF
systems have been used extensively in eld work and in industrial plants because of their
simplicity, high x-ray detection eciency, portability, ruggedness of the detector and
electronics, and low cost. These systems are simpler than those based on proportional
detectors and hence, if suciently sensitive and selective to the desired analyte, are the
preferred system. They are best used for applications requiring the determination of the
concentration of one or two elements only. Applications involving the determination of
Figure16 Spectrum of x-rays from a pure water sample and from water spiked with 100 mg/g of
iron and zinc as determined using a (Ne Ar)-filled proportional detector and excited by x-rays from
a
244
Cm source. (From Jarvinen and Sipila, 1984b.)
Figure 17 Minimum detectable levels (3s) for low concentrations of elements in water using
proportional detectors and 100 s counting time. The measurements with the argon detector (gas
pressure, 5 bar) were made with 9-mm-thick water samples and 111 MBq of
109
Cd, 2.2 GBq of
244
Cm, and 1.67 GBq of
241
Am, with the neon detector (1 bar pressure and a 0.05-mm-thick
beryllium window), with 20-mm-thick water samples and 3.7 GBq of
55
Fe, and with the xenon
detector (1 bar) with 110 MBq of
109
Cd. (Data from Jarvinen and Sipila, 1984a; Asoma
Instruments.)
more elements are best undertaken with proportional and solid-state detector systems. The
detection limits of scintillation techniques are at least a factor of 10 higher (i.e., worse)
than those for solid-state detectors.
Three types of head unit are used with scintillation detectors: direct excitation, g-
rayx-ray source excitation, and detectorradiator (Fig. 18). Filters can be used with all
three assemblies.
1. Filters
Filters placed between the sample and detector (Fig. 18) increase the sensitivity of analysis
by ltering out a higher proportion of uorescent x-rays of matrix elements than those of
the analyte. Zinc, for example, may be the analyte in samples also containing iron. Cal-
culations based on Eq. (1) and mass absorption coecients [see Eq. (76) in Chapter 1]
show that a 27-mg=cm
2
aluminum lter transmits 27% of the Ka x-rays of 8.6 keV but
only 4.5% of the iron Ka x-rays of 6.4 keV (Fig. 19); that is, it reduces the intensity of iron
K x-rays relative to the zinc K x-rays by a factor of 6. If the sample also contains lead,
however, about 55% of the lead La x-rays (10.5 keV) would be transmitted, twice that of
the zinc Ka x-rays. In this case (Fig. 19), an absorption-edge-type lter of copper (22.4 mg/
cm
2
) could be used to reduce the lead La x-ray transmission to only 1 % and also to reduce
the iron K x-ray peak. This selective enhancement of the zinc compared with the iron and
lead x-ray components partly compensates for the limitation of the poor resolution of the
scintillation detector. Although some iron and lead uorescent x-rays will still be detected
within the pulse-height channel set about zinc Ka x-ray peak, in many applications this
component will have been suciently reduced to make the analysis possible.
If the measurement with one absorption-edge lter does not give sucient selectivity
to the desired elements uorescent x-rays, balanced lters are used (Fig. 20). The in-
tensities of x-rays in the uorescent x-ray channel are measured separately, rst with one
lter and then with the other (with up and down lter). The atomic numbers of the
two lters are chosen so that their K shell absorption-edge energies are just above and
below the energy of the Ka x-rays of the analyte. The masses per unit area of the two lters
are chosen so that the product mrt [Eq. (1)] is practically identical for both lters, except
Figure18 Three types of radioisotope XRF assembly based on scintillation detectors.
Figure19 X-ray transmission through aluminum and copper filters.
Figure 20 X-ray transmission through balanced filters of copper (6) and nickel (solid circle).
Count-rate measurements made first with one and then with the other filter are subtracted to give a
count rate proportional to the intensity of zinc Ka x-rays from a sample.
within the energy window enclosing the Ka x-ray energy of the measured element. Hence,
the dierence in the count rates using the two lters is proportional to the intensity of
uorescent x-rays of the analyte. An excellent example of the balanced-lter application
has been Metallurgist
TM
, Model 9266, by TN Technologies (Spiegel and Horowitz,
1981). The portable analyzer used a series of balanced lters to quantitatively analyze
stainless steels, nickel, copper, and cobalt alloys.
It needs to be mentioned here that lters are also used with some low-energy-
resolution gas proportional detectors and also with x-ray tube excitation (Oxford In-
struments). A rather unique application of a single absorption-edge lter has been
reported for analysis of Mn in Hatled steels using a gas-lled proportional detector
(S. Piorek, personal communication, 1987). There, a MnKa peak is wedged between in-
tense CrKa and FeKa peaks. By placing a Cr lter over the detector window, the FeKa x-
ray intensity is reduced by a factor of 6 relative to MnKa x-ray, thus enabling quantitative
analysis of Mn. However, because manufacturing of the lters and necessary mechanics is
rather expensive, the practice of using lters becomes less and less common, in favor of
using systems with better energy resolution.
Figure 20 shows the transmission of x-rays by copper and nickel lters, which are
chosen when the analyte is zinc (Rhodes, 1966). Except in the energy window enclosing the
zinc Ka x-rays, the transmission is the same for the two lters. The balanced-lter tech-
nique is thus highly selective to the zinc Ka x-rays. The count rates, measured separately in
the uorescent x-ray channel with the two lters, are usually high and the dierence in
count rates can be quite small, often resulting in high relative uncertainties of measure-
ment. This is one of the main disadvantages of the balanced-lter technique.
There are two other disadvantages of lter techniques: The sensitivity of analysis is
poor when the uorescent x-rays of the main interfering matrix element have an energy
just below that of uorescent x-rays of the analyte (Fig. 19), and the sensitivity is
considerably less than the obtained with detectors that have the inherent resolving power
to isolate the uorescent x-rays of desired and matrix elements. These losses in sensitivity
result from the only partial absorption of interfering x-rays in the lter and, for absorp-
tion-edge lters, from the detection of lter K x-ray in the channel of the analyte. The
latter is a direct consequence of the use of the broad-beam geometries of radioisotope
XRF system. The lter K x-rays are mainly excited by the source radiation scattered from
the sample.
2. DirectExcitation Assemblies
The directexcitation technique (Fig. 18) is the most widely used of the three scintillation
detector assemblies. The energy of the radioisotope x-ray is usually chosen so that the
uorescent and backscattered x-rays are resolved by energy analysis (Fig. 21). The in-
tensity of the backscattered x-rays is used to correct for the absorption of the analytes
uorescent x-rays by the sample matrix [Eq. (8) or (9)]. The lter enhances the sensitivity
and selectivity of analysis.
Direct-excitation assemblies are used extensively in industry (e.g., in laboratory and
portable elemental analyzers (Rhodes, 1971) and in on-line (in-stream) analysis of mineral
slurries (Watt, 1983).
3. DetectorRadiator Assemblies
The detectorradiator assembly (Fig. 18) discriminated well against interfering x-rays of
energy just below that of the uorescent x-rays of the measured element (Watt, 1972). The
basis of this discrimination is that the atomic number of the radiator element can be
chosen so that, of the two x-ray components with nearly similar energies, only the higher
of the two has sucient energy to excite the K x-rays of the radiator element. The detector
is shielded from the sample and, hence, sees only the x-rays emitted by the radiator. Ba-
lanced-radiator techniques, analogous to balanced-lter techniques, can also be used to
improve selectivity to the analyte if there is another matrix element, in this case emitting
uorescent x-rays of energy higher than those of the analyte. The count rates obtained
with detectorradiator assemblies are about 5% of those obtained with direct-excitation
assemblies, using a source of the same activity, because of the additional excitation stage
of the radiator.
The intensity of higher-energy x-rays scattered by the sample can be measured si-
multaneously in the one assembly by use of a second radiator element of atomic number
considerably higher than that of the rst radiator. The x-ray energies of the two com-
ponents are well resolved and similar to that shown in Figure 21.
Detectorradiator systems are much less widely used than balanced-lter techni-
ques. They are less versatile than balanced-lter systems. Applications include the de-
termination of lead in zinc concentrates, in which the zinc Ka x-rays (8.6 keV) from the
high concentration of zinc (e.g., 50 wt%) swamp the lead L x-rays (10.514.8 keV) from
the low concentration of lead (e.g., 0.5 wt%). A radiator of zinc (absorption-edge energy
of 9.66 keV) is excited by the lead L but not by the zinc K x-rays. This radiator technique
Figure 21 Typical spectrum of x-rays from copper ore slurry excited by a
238
Pu source and
measured using a scintillation detector.
improves the sensitivity to lead to that of zinc by a factor of about 20. However, the
absolute signals from the analytes when using the radiator technique may be up to an
order of magnitude smaller than when excited directly.
4. -Ray-Excited X-ray Assemblies
A limited number of x- or g-ray energies are emitted by radioisotope sources (Table 1).
A secondary x-ray source, in which g-rays from a radioisotope source excite the uorescent
x-rays of a target material, can be used to obtain essentially monoenergetic x-rays of
energy determined by the atomic number of the target element (Fig. 18). Hence, the energy
of the x-rays incident on the sample can be chosen to suit the specic XRF application.
The g-ray-excited x-ray assembly (Watt, 1983) makes use of lters, including balanced
lters, similarly to the direct excitation assembly. The count rates using the secondary
excitation source assembly are only about 5% of the count rate of a direct excitation
assembly using the same activity source.
A balanced-energy technique, in which separate measurements are made with two tar-
gets (in the secondary source) whose uorescent x-rays straddle the K shell absorption-edge
energy of the wanted element, can be used to obtain more selectivity to the analyzed element.
The g-ray-excited x-ray assembly is used as an alternative to direct excitation when
no suitable energy x-ray is emitted by radioisotope source. One application is in the de-
termination of the coating mass of tin on steel by the detection of the tin K x-rays. If
60-keV g-rays from
241
Am isotope are used to excite the tin, K x-rays from both sides of
the steel are detected; by choosing the energy of the exciting radiation to be just above that
of the tin K shell absorption edge, tin K x-rays from only the one side are detected because
of the high absorption of the lower-energy excitation radiation in the steel.
D. X-ray Preferential AbsorptionTechniques
X-ray preferential absorption analysis is often based on the dual-energy g-ray transmission
technique (Fig. 2) because of important industrial applications involving the analysis of
coarse and heterogeneous materials, such as coal (Fookes et al., 1983; Gravitis et al., 1987)
and metalliferous mineral ores. Low-energy g-rays must be used in these applications to
obtain sucient transmission through the material, so that the only practical approach is
to use radioisotope sources. Scintillation detectors are used to ensure ecient detection of
the g-rays, with pulse-height analysis to separate the two energies.
Figure 22 illustrates the results using the DUET technique to determine the lead
content of zinc concentrate and residue (tailings) samples (Ellis et al., 1969). The radio-
isotopes
241
Am and
153
Gd were used. Their g-ray energies, 60 keV of
241
Am and 97 and
103 keV of
153
Gd, envelope the K shell absorption-edge energy of lead (88 keV). A com-
mon calibration curve is obtained despite the great dierence in absorption by the matrix
of the concentrates (with about 50 wt% zinc) and of the tailings, also called residues (with
about 0.6 wt% zinc).
This technique becomes more complicated when the g-ray transmission measure-
ments are made on material on fast-moving conveyors, as for the on-line determination of
the ash content of coal (Fookes et al., 1983; Gravitis et al., 1987). Equations (13) and (14)
hold only for time intervals during which there is little change in mass per unit area,
whereas there would be a linear summing of count rates in time although the correct re-
sponse is logarithmic [Eq. (14)]. This problem can be addressed by counting for shorter
intervals during which the mass per unit area changes little and summing the logarithms of
the counts during many of these intervals (Gravitis et al., 1987).
Figure 22 g-Ray preferential absorption analysis for lead, showing (left) the transmission of
153
Gd g-rays ( $100 keV),
and (right) the combination of the separate transmission measurements for
153
Gd and
241
Am (59.5 keV) g-rays.
E. X-ray ScatteringTechniques
The single most important applications of x-ray scattering techniques are in the on-line
systems, such as for the continuous analysis of particulate material on conveyors and
sample bylines in industrial plants. There is often no need to crush the material before
analysis because of the penetration of the g-rays in the material. Americium-241 g-ray has
been used to determine the ash content of coal both in a sample byline (Fauth et al.,
1986) and, when sucient thickness of coal is available, directly on a conveyor belt
(Cierpicz 1986). Dual-energy g-ray scattering has been used in ore-sorting applications
(Outokumpu Mintec Oy, 1986), in which the thickness of the ore lumps is too great for
XRA techniques.
F. Count Rates and Calibration
The count rates, or intensities, of uorescent and backscattered x-rays from the sample are
determined by many factors [Eqs. (4) and (6)]. Activities of the radioisotope sources used
range from 100 MBq to 10 GBq (or 3300 mCi), the higher activities being used mainly
with solid-state detectors, which have a smaller eective area than scintillation and pro-
portional detectors. For x-ray preferential absorption analysis, higher activities of
110 GBq (30300 mCi) are used for industrial on-line applications in which high count
rates are essential with the rapidly changing mass per unit area and where distances be-
tween analyzed medium and detector are relatively large. The source activities used for
x-ray scattering analysis are approximately the same as those for XRA analysis.
X-ray uorescence analysis is, as is the vast majority of other analytical methods, a
comparative analytical technique. Radioisotope x-ray systems are usually calibrated by
comparing the measured count rates with analyses of the same samples by more con-
ventional techniques. The coecients linking the count rates and chemical analysis are
determined by linear multiple regression. This empirical in nature method of calibration is
essential in most applications, especially when the materials to be analyzed have an un-
known particle size. For the calibration to be valid, it is essential to calibrate with ma-
terials covering the full range of variations in elemental composition and particle size. In
some industrial applications, these factors may change slowly with time and, hence, the
calibration must be regularly updated.
The widespread use of room-temperature solid-state detectors as well as availability
of microcomputers made so-called standardless methods of calibration a realistic alter-
native to the empirical ones. These standardless methods are variations of the funda-
mental parameters (FP)-based approaches, in which the concentrations of analytes are
deduced iteratively by combining spectral information from the sample with that of one
known standard and=or with fundamental equations of x-ray physics. It is to be noted,
however, that any empirical calibration based on a good set of standards will always be
more accurate than that derived with the FP algorithm.
V. FACTORS AFFECTINGTHE OVERALL ACCURACYOF XRFANALYSIS
The choice of a radioisotope x-ray analysis technique for a specic application depends on
several interacting factors: the overall accuracy of the sampling and analysis required, the
time available to achieve this accuracy, technique available to obtain a suciently
representative sample of the material being analyzed, and the sample preparation
requirements, such as grinding, pressing, and so forth. The inuence of each of these
factors on the accuracy of XRF analysis is discussed here.
A. Overall Accuracy and Time for Analysis
The overall accuracy of analysis depends on uncertainties in calibration, sampling, sample
preparation, and x-ray analysis. The requirements of a good accuracy of analysis stay in
striking contrast with the time allotted for analysis. The maximum acceptable time must
include not only the time for the x-ray analysis but also the time for sampling and sample
preparation. Uncertainties due to nonrepresentative sampling are too often under-
estimated in industrial and eld applications, resulting in the accuracy of the overall
analysis often being compromised.
The total uncertainty of analysis, s
tot
, can be expressed as the sum of all contributing
uncertainties:
s
tot

s
2
instr
s
2
stat
s
2
het
s
2
cal
s
2
samp:plac:
s
2
matrx
s
2
part:size
s
2
??
q
22
where
s
instr
Instrumental component such as thermal drift
s
stat
Uncertainty due to statistics of counting
s
het
Uncertainty reecting sample heterogeneity
s
cal
Reects uncertainties contributed by reference analysis and calibra-
tion t
s
samp:plac:
Uncertainty due to sample placement
s
matrx
Uncertainty associated with matrix eects
s
part:size
Uncertainty caused by varying particle size of analyzed material
s
??
Any other potential, unidentied uncertainty
This formula assumes that all uncertainties included are random and normally distributed
and that systematic uncertainty (bias) is negligible. Under these assumptions, the s
tot
can
be regarded as a good measure of the accuracy of analysis.
The rst two uncertainty components, s
instr
and s
stat
, are often treated together
as main constituents of instrument precision (repeatability), whereas all the other
uncertainties identied in Eq. (22) can be regarded as contributing to user or application
related uncertainty. Thus, Eq. (22) can be written as follows:
s
tot

s
2
instr:precis:
s
2
applic:
q
23
where
s
instr:precis:

s
2
instr
s
2
stat
q
24
and
s
applic:

s
2
het
s
2
cal
s
2
samp:plac:
s
2
matrx
s
2
part:size
s
2
??
q
25
Some of the uncertainties can be identied and easily controlled or minimized by the
analyst, such as uncertainty due to statistics of counting, or calibration uncertainty. For
example, the statistical uncertainty of counting, s
stat
, can be easily reduced by extending
the measurement time, whereas the uncertainty associated with calibration, s
cal
, can be
reduced by using more accurately analyzed calibration samples and by selection of a better
calibration equation.
Sample placement uncertainties, s
samp:plac:
, can be reduced by always following the
same procedure for preparing and loading the sample into the measuring chamber of the
analyzer, orpartiallyby spinning the sample during measurement.
Uncertainties due to matrix variability, s
matrx
, and particle size, s
part:size
, can be sig-
nicantly reduced by proper sample preparation techniques such as matrix dilution
(Jenkins et al., 1981a) and by grinding, pelletizing, or fusing the sample with spectrometric
ux, respectively.
Although all these uncertainty minimization techniques are valid and readily ap-
plicable in laboratory environments, they are an unattainable luxury in eld and industrial
applications where grinding, fusing or any type of sample preparation is simply out of the
question.
This is why the accuracy of analysis in eld and industrial environments tend to be
governed by the application-related uncertainties rather than by the usually much smaller
contribution from the instruments precision. It is also for this reason that the measure-
ment time may often be selected from the point of view of process throughput rather than
overall uncertainty of analysis; usually, good instrumental precision allows the analyst to
shorten the measurement time without sacricing the former. Nevertheless, the mea-
surement time is always a compromise between the throughput of the process and ana-
lytical requirements.
In the coating industry, the time for the determination of the coating mass of tin
and zinc on steel must be less than a few seconds if the result is to be useful; hence
continuous analysis directly on the main coating line is essential. In mineral con-
centrators, rapid changes in the grade of ore entering the plant and the time taken for
the ore to pass through the plant (about 15 min) make it essential for the process
slurries to be analyzed within 5 min. This can be achieved by continuous analysis either
directly in stream or on slurries in sampling loops (bylines). In scrap yards, alloys must
be sorted into dierent types in short periods: otherwise the sorting operation is not
economical. The lower the price per pound of scrap, the faster the sorting has to be. In
this case, it is essential to have analysis equipment that is both portable and capable of
producing rapid results.
It is important to realize that XRF analysis does require some nite time period
within which a meaningful measurement can take place. The consequence of this fact is
that XRF analysis results in process control applications are, most of the time, the average
rather than point estimates of the process parameters such as coating thickness, sulfur
concentration of diesel fuel, and so forth.
B. Uncertainties of Sampling and Sample Presentation
Uncertainties originated by sampling processes are probably one of the most signicant
contributors to the overall analytical uncertaintythe point we attempted to make in the
previous subsection. This is especially true for eld and industrial applications of XRF
methods, where sample preparation and conditioning is nonexistent, and which, as we
stated in the Introduction to this chapter, are mostly radioisotope based. That is also why
we devote so much space in this section to this issue.
All analyses involve sampling, some more than others. In the continuous on-line
measurement of material on conveyors or in process slurry streams, the analysis is
averaged over large quantities of material, but still has the potential for sampling un-
certainties because not all of the material on the belt or in the slurry stream is viewed. If
material is continuously sampled from the main stream and fed through a sampling loop
past the x-ray analyzer, the uncertainties in sampling the main stream and in viewing only
part of the sample loop must both be considered.
A mathematical approach to sampling of a particulate media has been detailed by
Gy (1982) and Pitard (1993). The most readily accessible information on sampling is given
in the various international standards for the sampling of process material from moving
conveyors and from slurry streams (ISO, Geneva). These describe preferred sampling
practices and estimate the accuracies of sampling, including the eects of dierent top sizes
and the number and mass of sample increments taken. These standards are regularly
amended.
Sampling uncertainties are of critical importance to the exploration for and assess-
ment of deposits and the mining of both metalliferous ores and coal. After all, it is possible
to analyze only a very small proportion of the ore. There are established practices for
choosing where to sample (e.g., on a regular spaced grid), the number of samples to be
taken, and the weight of each sample to be taken. This complex eld of sampling geo-
statistics is thoroughly covered in textbooks (David, 1971; Ingamells and Pitard, 1986;
Isaaks and Srivastava, 1989).
1. Uncertainty Dueto Sample Heterogeneity
Samping uncertainties, specically in analysis of particulate type of material, are mainly
caused by heterogeneity of the measured medium. Should the analyte be uniformly
distributed throughout the mass=volume of the measured material, any sample taken
for analysis would contain the same concentration of the analyte. However, even this
ideal condition would be compromised by the morphology of the sample. If the sample
is liquid, then the dissolved analyte can, indeed, be homogeneously dispersed in a
liquid matrix. However, if the analyzed medium is ore or soil, or any other powder, the
chances of nonuniform distribution of the analyte in matrix increase dramatically. Not
only might the grains of the analyte not mix well with grains of the matrix, but any
handling of the sample will promote tendencies for segregation of one type of grain
from the other. A very important contributing factor is the size of the sample taken for
XRF analysis. The smaller sample is likely to emphasize its heterogeneity as compared
to a larger sample. The main consequence of heterogeneity of the material analyzed is
the fact that the sample of this material taken for analysis may not be representative of
the material.
If the uncertainty cannot be minimized, the next best way of dealing with it is to
estimate its magnitude. It is rather easy to evaluate the contribution of material hetero-
geneity factor to the total uncertainty. The only requirement is the availability of a suf-
cient quantity of analyzed material. Two series of measurements are required. In the rst,
a sample of material to be analyzed is measured in x-ray analyzer for at least seven times,
without being disturbed in any way. This series of measurements will yield a standard
deviation, which will correspond to s
tot
, as per Eq. (20), except for the s
het
, that being
equal to zero because only one sample was measured. Next, at least seven dierent samples
of the same material are measured under the same conditions as before (i.e., the same
measuring cup, counting time, etc.). This second series of results will yield a standard
deviation, which will correspond to s
tot
, exactly as per Eq. (20), now including the het-
erogeneity factor, s
het
. By subtracting the squared standard deviation of the rst series
from that of the second and taking the square root of the dierence, a numerical value of
s
het
is readily obtained. For example, in soil analysis for lead, the two standard deviations
obtained were 25 and 65 mg=kg, respectively. Therefore, after subtraction, the s
het
was
60 mg=kg, a signicant contribution to the total uncertainty.
It is very important to realize the fact that in the majority of analyses of granular or
particulate material, its heterogeneity determines the overall accuracy of analysis. This is
true not only for XRF, which by its nature is a surface measurement method, but also for
other instrumental techniques such as atomic absorption or inductively coupled plasma,
as long as an aliquot analyzed is not representative of the material from which it was
taken. It is therefore of paramount importance that good homogenization is applied to
analyzed material and that the amount of sample taken is sucient to be representative of
it, especially if verication or validation of XRF results with other analytical techniques is
required.
2. Sample Heterogeneityand Detection Limits
A detection limit (DL) for a given analyte is understood to be that amount of analyte in a
sample that produces a spectral signal equal to or greater than three standard deviations of
a signal obtained on a sample with no analyte present.
The authors own data and values cited in literature indicate that a typical DL for lead
in soil is about 50 kg=kg when a
109
Cd isotope and semiconductor detector are used for
analysis. The
109
Cd isotope x-rays reach to a depth of about 1.3 cm into a silica-based soil.
However, if there is leadinthis sample, the excitedleadLseries x-rays canreachthe surface of
soil only if they are generated at a depth not greater than 0.20.3 cm, as measured from the
soil surface. A 50-mg=kg DL for lead means, in practice, about 650 mg of total lead as po-
tentially seen by the analyzer in a soil cylinder of 13 g mass (cylinder base area of 5 cm
2
by
1.3 cm high by 2 g=cm
3
of assumed specic density of silica soil). However, the lead x-rays
reach the detector from a depth of only 0.3 cm and, therefore, the eective mass of total lead
seen is only 150 mg. This mass of lead translates into a 0.030-cm (or 12 mils)-diameter
sphere of pure lead. Even in a form of an oxide, the size of the lead oxide grain would not be
much more. If this small, by all means, lead grain happens to be within the rst 3 mm of soil,
the XRFanalyzer will be able tomeasure it. However, if the leadgrainends upat deeper layer
of soil, it will never be noticed. Obviously, depending on its characteristic x-rays energy and
excitation source, any other element will be similarly aected by its location in the sample.
This perhaps extreme but simple example illustrates how illusionary and misleading the
concept of detection limit may be in case of granular material.
C. Choice of Radioisotope X-rayTechnique
The choice of the most appropriate radioisotope x-ray technique for a specic application
depends on the requirements of accuracy of sampling and x-ray analysis and the time
available for the analysis. The simplest radioisotope x-ray technique that satises these
requirements is usually chosen.
In the laboratory, where many dierent types of analyses can be performed, XRF
analysis with a solid-state detector is the most exible method. For industrial and eld
applications, there is often a more restricted range of analyses paired with a greater need
for simple and reliable equipment, the cost of which may also be an important con-
sideration. X-ray uorescence analysis based on scintillation or proportional detectors is
often, but not always, the best approach. These considerations lead to the use of a much
wider range of radioisotope x-ray techniques in industry than in the laboratory. The choice
of technique is more complicated. Should an ore sample be ground before analysis and L
shell XRF be used for a high-Z element, such as uranium, or can K shell XRF techniques
determine the concentration with sucient accuracy despite the heterogeneity of the
sample? Should the analysis technique be chosen to make a direct measurement on-line, in
a sampling loop of the process stream, or on a sample taken to a laboratory? Should XRF
techniques even be used in an on-line application, given the inaccuracies introduced by the
heterogeneity of the material to be analyzed? The practical alternative may be to use XRA
or XRS techniques or a nuclear technique, based on more penetrating radiation, such as
high-energy g-rays or neutrons. The applications discussed in the next section indicate the
preferred solutions to some important analysis applications, particularly in industry.
VI. APPLICATIONS
Table 4 lists some important applications of radioisotope x-ray techniques based on XRF
equipment, usually referred to as laboratory or portable elemental analyzers. The analysis
techniques involve the use of scintillation, proportional, and semiconductor detectors.
These analyzers are in widespread use in many application areas and in many industries
(Rhodes, 1971; Rhodes and Rautala, 1983). The total number used worldwide probably is
about 10,000. Some major suppliers of radioisotope based instruments are listed in Table 5.
A photograph of a portable model of an x-ray analyzer for alloys, build around a silicon
p-i-n diode detector is shown in Figure 23 and a laboratory model based on gas-lled
proportional detectors is shown in Figure 24. Many solid-state detector systems are also in
routine use in laboratories.
Table 6 lists types of on-line analysis systems in routine use. These include systems
for the on-line analysis of mineral slurries, owing powders, coal, coal slurries, paper,
determination of sulfur in oil and petroleum products, and analysis of coatings. Most of
the analysis systems tend to be based on scintillation and proportional detectors, but some
of the more recently developed systems also use solid-state detectors. Table 6 is also an
attempt to list some commercial suppliers of the on-line equipment. Example of the ap-
plication of these techniques are now discussed in details, with emphasis given to appli-
cations of industrial importance. Some examples illustrate the interaction of sampling and
sample presentation with the selection of the appropriate radioisotope technique.
A. Identification of Alloys
Historically, the rst applications of portable XRF analyzers were in mining and pro-
specting. It was only with the advent of the on-board memory and microprocessors that the
portable XRF analyzers found wider acceptance and use for analytically more demanding
alloy identication and analysis. Since then, several thousand of these analyzers have been
sold, making alloy sorting and analysis a agship application for portable XRF analy-
zers. These analyzers can assay the alloy and=or identify it by its grade or common name.
Rapid sorting of alloys is required in many areas of the metals industry, such as
smelting, fabrication, inventory and incoming material control, and the sorting of scrap
(Piorek and Rhodes, 1986; Berry, 1981; Piorek, 1989). Some common alloy groups include
nickel alloys, copper alloys, stainless and high-temperature steels, and carbon and chro-
miummolybdenum steels. Although 4050 elements are involved in the alloying process,
in any given alloy there are only 1020, and of these, only about 10 are required for the
identication of specic alloy.
The main requirements of analytical equipment for alloy identication are port-
ability, speed and reliability of identication, and an ability to be used by unskilled
operators. Balanced-lter techniques have two main disadvantages. Concentrations of at
least several elements must be determined; hence, separate measurements must be made
with several sets of balanced lters. The sensitivity of analysis is insucient for the lower
concentrations of some specic elements in the alloys.
Piorek and Rhodes (1986) showed that by using XRF analysis based on a 111-MBq
(3 mCi)
109
Cd source and a high-resolution proportional detector, many alloys can be
identied in one measurement. Measurement is rst made to identify the alloy by group.
The spectrum of the unknown alloy is then compared with the key features of spectra of
known alloys in the group, which are stored in a memory chip in the equipment. This so-
called grade-identication mode of analysis is particularly useful because it does not
require the operator to be procient in the specics of alloy composition. In the grade-
identication mode, the analyzer uses a pattern-recognition algorithm to compare the
x-ray intensities of the measured sample with those of the stored references of alloy
standards. This approach is very fast, taking about 35 s to identify a single alloy. In
Table 4 Some Typical Applications of Radioisotope Based Laboratory and Portable
Elemental Analyzers
Application Typical examples
Alloy sorting and
identification
Low-alloy steels; stainless steels; nickel alloys; high-temperature alloys;
titanium, aluminum alloys; specialty alloys; metal scrap
Mining and mineral Copper, lead, zinc, tin, arsenic, molybdenum, nickel, iron, chromium,
bismuth, and uranium in commercial-grade ores, concentrates,
and tailings; titanium and iron in silica sand; silicon, potassium,
titanium, and iron in clays; phosphate rock
Pulp and paper Thickness of silicone coatings on paper and polymer membranes; calcium,
titanium, filler in paper
Environmental Soil screening for metals (Cr, Cu, Ni, Pb, Zn, As, Cd, Hg, Sb); hazardous
materials (e.g., lead, arsenic, chromium, or cadmium in waste sludge);
trace elements in wastewater discharge; metals in air particulates on
filters; chlorine (halogens) in waste oil; sulfur in diesel fuel
Fibers, films and
coatings
Copper, zinc, tin, gold, silver and chromium plating thicknesses; metals
in plating solutions; silver in photographic film; manganese coating
thickness on magnetic tape; titanium on glass; ruthenium on electrodes
Chemicals and
process control
Lead, titanium, and zinc in paint; sulfur, iron, alumina, silica, and calcium
in cement; vanadium in catalysts; palladium and gold coatings on silica
spheres uses as catalysts; zinc, chromium, nickel in plating baths
Plastics Calcium, lead, tin, and chlorine in PVC; zinc and bromine in polystyrene;
chlorine in urethane rubbers; bromine and chlorine in butyl rubbers;
silicon in polythene; TiO
2
in nylon; bromine in Styrofoam
Agricultural Fertilizers (calcium, phosphates, potassium); copper, chromium, and arsenic
in wood preservatives and treated wood; bromine in almonds; ironzinc
ratio in meat for grading; minerals in cattle feed; titanium in fillers
Cosmetics Titanium, iron, lead in powders
Pharmaceutical Metals in vitamin pills; zinc in insulin
Petroleum products Lead, calcium, sulfur, vanadium, and chlorine in gasoline or oil;
sulfur in petroleum coke; sulfur and ash in coal; lubricating oils additives
Table 5 Manufacturers and Suppliers of Radioisotope-Based Laboratory and Portable
Elemental Analyzers
Manufacturer
a
Analyzer type Detector type
Amdel Laboratory Scintillation
ASOMA
b
Laboratory Gas proportional
BRGM Laboratory Solid-state Si(Li)
Metorex Int.
b
Portable, laboratory High-resolution gas
proportional; solid state:
Si(Li) or silicon p-i-n diode
Niton Corp. Portable Solid state: silicon
p-i-n diode, CdZnTe
Outokumpu Electronics, Oy Portable, laboratory High-resolution
gas proportional;
solid state: Si(Li)
Oxford Instruments
b
Laboratory Gas proportional
Radiation Monitoring Devices Portable Solid state: CdTe
TN Technologies Portable Solid state: mercuric
iodide, HgI
2
a
See the list of manufacturers and their addresses in the Appendix of this chapter.
b
These manufacturers reacted to the dynamics of the market and industry by switching from isotope-based
instrumentation to x-ray-tube-excited devices.
Figure 23 The Metorex Int. portable alloy analyzer based on high-resolution silicon p-i-n diode
detector, MetalMaster
TM
2000. (Courtesy Metorex Int.)
comparison, assaying the alloy may take up to 4 min in order to maintain low measure-
ment uncertainty. Table 7 shows the identication results for dierent alloys by group,
obtained with the analyzer pictured in Figure 23. The probability of correct identication
is satisfactory for all alloys except the carbon steels. The results in Table 7 were generated
by measuring each alloy sample for 5 s for at least 10 times and comparing its spectral
features against the library of about 145 dierent alloys. The number of correct identi-
cations ratioed to the total number of trials for a given alloy group was then recorded in
Table 7 as a measure of probability of correct identication. Some of the identication
failures are for alloys very close in composition, for which the main alloying elements
dier in concentrations by less than 1%. The most dicult identication is for carbon
steels in which the concentrations of alloying elements are very low in the presence of
almost 100% iron, and the dierence in concentrations of the same elements between two
grades approaches the sensitivity of the XRF technique. Therefore, the XRF is not a
method of choice for identication of carbon steels, for which better techniques, such as
optical emission spectrometry, exist (Piorek et al., 1997).
By using a silicon p-i-n diode detector in place of a gas proportional one, it has been
possible to extend positive identication to such specic alloys as B1900 and B1900Hf,
which dier from each other by less than about 1% Hf, in the presence of several percent
of W and Ta and a balance of nickel.
Overall, the portable alloy analyzers oer a much simpler approach to identication
of alloys, with a reliability of identication as good as that for more complex techniques.
Despite the signicant dierences in design, the portable alloy analyzers exhibit si-
milar performance in the assay mode; that is, they oer measurement precisions ranging
from 0.01% to 0.5% absolute depending on the element, its concentration range, and the
Figure 24 A laboratory, benchtop, elemental analyzer based on a high-resolution proportional
counter, X-MET
TM
820. (Courtesy of Outokumpu Electronics.)
matrix. Several references treat this subject in greater detail (Fookes et al., 1975; Jenkins
et al., 1981c, 1981d; Piorek and Rhodes, 1986; Piorek 1989; Spiegel and Horowitz, 1981;
Berry, 1981). Table 8 shows typical performance data for a contemporary portable XRF
alloy analyzer, such as illustrated in Figure 23.
Table 6 On-line Analysis Systems Based on Radioisotope X-ray Sources
a
Application Analytical technique, detector
b
Manufacturer
c
Metal content of
mineral slurries
XRF/XRA, s and ss, in-stream
XRF, p, sample line
Amdel
Asoma
XRF, ss, sample line Outokumpu Mintec, Oy
XRF, ss, in-stream Texas Nuclear
XRF, ss, sample line Ramsey
Metal content of clay
and mineral powders
XRF, p, sample line
XRF, ss, sample line
Asoma
Outokumpu Mintec, Oy
Iron and chromium in
ore on converyors
Dual-energy XRS, s, on-line Outokumpu Mintec, Oy
Ore sorting Dual-energy XRS, s, on-line Outokumpu Mintec, Oy
Ash in coal on conveyor Dual-energy XRS, s, on-line MCI; Harrison Cooper; SAI
XRS, s, on-line EMAG
XRS, s, sample line Humboldt-Wedag
XRS, p, sample-line Sortex
Solids weight fraction and
ash in coal in slurries
XRF, neutron, and g
transmission, s, on-line
Amdel
Tin content of galvanizing
solutions
XRS, p Rigaku
Calcium in cement raw mix XRF, s Rigaku; Outokumpy Mintec,
Oy
Sulfur in oil, diesel fuel,
gasoline
XRF, ion chamber,
sample line
Yokogawa
XRF, p, sample-line Mitsubishi; Metorex Int.
Lead in gasoline XRF, p, sample-line Metorex Int.
Metals in plating bath
solutions (Ni, Cu, Cr, Ta, etc.)
XRF, p, sample-line Asoma; Metorex Int.
Cement analysis for
Ca, Si, Mg, Al, S, Fe
XRF, p, sample-line Metorex Int.
Corrosion products (Cr, Fe) in
steam generator feedwater
of nuclear power plants
XRF, p, sample-line Detora Analytical
Ash content and/or mineral
filler material in paper
XRA, p, b-rays
transmission, on-line
Sentrol; Yokogawa;
Paul Lippke
XRF, p, on-line Sentrol
Coating mass of: Zn, Sn/Cr,
Sn/Ni, Zn/Fe, Sn/Pb on steel
and other substrates
XRF, p, on-line Data Measurement; FAG;
Gammametrics
a
X-ray tube techniques can be used in some of these applications.
b
Detectors: s scintillation, p gas proportional, ss solid state [usually Si(Li)].
c
See the list of manufactures and their addresses in the Appendix of this chapter.
B. Determination of Uraniumand Gold in Ore
During the exploration of mining of metalliferous ores, large numbers of ore samples must
be analyzed to compensate for the inherent variability of expression of the ore. The ore
may be analyzed in the laboratory or, for higher-Z elements, at the mine face or in situ in
boreholes.
K shell XRF techniques are often preferred for the analysis for uranium; because of
the penetration of the uranium K x-rays in the ore, little or no crushing of samples is
required and, additionally, the uranium concentration is averaged over much larger
samples. Uranium can be determined down to 20 mg=g or about 0.7 oz.=ton (1s) in 30 s
using a 222-MBq (6 mCi)
57
Co and a 28-mm
2
65-mm germanium detector (EG&G Or-
tec, 1986). This technique was used routinely to survey samples for uranium and other
Table 7 Performance of a Portable X-ray Analyzer in Alloy Identication
Alloy group Measured elements
Identication results
(% feasible)
Nickel and cobalt alloys Ti, Cr, Fe, Co, Ni, Cu, Nb, Mo, W, Hf, Ta 100
Copper alloys Mn, Fe, Ni, Cu, Zn, Pb, Sn 90100; 98100
Stainless steels and
high-temperature alloys
Ti, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo 90100; 100
Cr/Mo steels Cr, Fe, Ni, Mo 90100; 100
Low-alloy steels Cr, Mn, Fe, Ni, Cu, Nb, Mo 6580; 90100
Titanium alloys Ti, V, Mn, Cr, Zr, Mo, Sn 95100;
Aluminum alloys Mn, Fe, Cr, Cu, Zn 90100; 95100
Note: If two results are given, the rst refers to a gas-lled proportional detector, and the second to a solid state,
silicon p-i-n diode detector.
Source: From Piorex et al., 1997.
Table 8 Standard Performance Data for a Typical, Contemporary, Commercially
Available Portable XRF Alloy Analyzer
Alloy group Ti Cr Mn Fe Co Ni Cu Zn Nb/Mo Sn Pb
Low-alloy steels 0.01 0.04 0.1 0.25 0.25 0.10 0.05 0.10 0.006 0.15 0.15
0.02 0.1 0.2 0.50 0.25 0.15 0.01
Stainless, hi-temp steels 0.015 0.20 0.10 0.20 0.20 0.20 0.06 0.20 0.01 0.30 0.05
0.03 0.30 0.20 0.30 0.30 0.10 0.03 0.30
Ni/Co alloys 0.10 0.20 0.10 0.12 0.10 0.20 0.05 0.30 0.02 0.30 0.15
0.50 0.30 0.50 0.50 0.50 0.30 0.08
Cu alloys, brass/bronze 0.02 0.10 0.02 0.02 0.05 0.05 0.15 0.07 0.01 0.008 0.20
0.06 0.06 0.08 0.40 0.30 0.20 0.30
Aluminum alloys 0.02 0.05 0.10 0.05 0.05 0.04 0.05 0.06 0.003 0.005 0.01
0.20 0.10 0.005 0.20 0.02
Titanium alloys 0.40 0.10 0.10 0.06 0.05 0.05 0.02 0.02 0.008 0.005 0.01
Notes: The values listed are typical precision ranges in percent absolute for total assay time per sample not longer
than 60 s. The differences are due to the analyzer model and/or the radioisotope(s) used.
Precision data listed are obtained with a 185-MBq (5 mCi)
109
Cd and 1.48-GBq (40 mCi)
55
Fe sources.
Source: From Piorek et al., 1997.
high-Z elements (Z ! 40) in the laboratory by the Australian company Geopeko in the
extensive exploration programs that found the large Ranger uranium deposit at Jabiru in
the Northern Territory, Australia (G. Sherrington, personal communication, 1987). It is
also used for borehole logging, with detection limits of 0.04 wt% (1s) for uranium,
tungsten, and lead and 6 mg=g for gold in 120 s counting time using a 518-MBq (14 mCi)
57
Co source and a small silicon detector in a 32-mm-diameter borehole probe (Scitech
Corp. undated).
An analysis system has been developed for the in situ determination of gold in ore at
the mine face (Hill and Garber, 1978). The hand-held probe consists of a 4.4-GBq
(120 mCi)
109
Cd (88-keV g-rays) source, a 200-mm
2
67-mm-thick germanium detector,
and a small Dewar ask containing liquid nitrogen, which must be replenished after 6 h of
operation. The sensitivity to gold has been optimized by careful choice of the incident
g-ray energy and by measuring gold Kb x-rays whose energy is greater than the energies of
most of the Compton-scattered g-rays. The precision for a 30-s scan time is 20 mg=g (1s)
and 2 mg=g for 100630-s scans. The technique is suitable for use in high-grade gold mines
but has insucient sensitivity to be applied widely in gold mining, in which 0.3 mg=g or
0.01 oz.=ton (1s) is normally required.
C. On-Line Determination of Coating Mass
Tin on steel (tinplate), zinc on steel (galvanized iron), zinc and aluminum on steel (zin-
calum), iron oxide on plastic (magnetic tape), and silicon coating on paper are only a few
examples of coated products manufactured in large quantities. The coatings are applied at
high speed. Accurate control of the coating mass per unit area is essential to economize the
operation.
Two XRF techniques can be used to determine the mass of the coating. Fluorescent
x-rays of the coating element can be excited and their intensity measured. The intensity of
the coating element x-rays increases with coating thickness. Alternatively, uorescent
x-rays of element in the base material can be excited. Their intensity decreases with the
increase in coating mass because of the absorption of the incident and excited x-rays in the
coating. Both radioisotopes and x-ray tubes are used as the source of x-rays, with
radioisotope sources preferred, except for those applications requiring very fast response,
such as 0.1 s.
Radioisotope XRF techniques for the on-line determination of coating mass are
based on the use of proportional detectors. These are preferred to scintillation detectors
because of their better energy resolution and because they can be used at the relatively high
temperatures that occur above the hot tin and galvanized iron coating processes. In
commercially available systems (Table 6), the analysis head unit continuously scans across
the width of the strip so that coating mass can be controlled across the whole strip. These
commercial systems are used worldwide in most high-throughput coating operations. They
can also be used to determine the separate coating masses of multiple coatings.
Coated products are usually sold with a specied minimum coating mass. The ac-
curate coating mass determination has led to coatings being controlled much closer to the
minimum specication. The variations in coating mass obtained on the zinc galvanizing
line of John Lysaght Pty. Ltd., Port Kembia, Australia, corresponding to no gauge, gauge
with manual control, and gauge with automatic control are shown in Figure 25. In 1977,
improved control of zinc coating mass led to savings of A$300,000 per year per line; si-
milarly, at the nearby Australian Iron and Steel Pty. Ltd., savings of A$1 million per year
(Watt, 1978) were made for tinplate.
Another typical coating mass application for XRF instruments is measurement of
zinc phosphate coating on steel (Johnson et al., 1989), where phosphorus x-ray intensity is
used rather than zinc to increase the sensitivity of analysis. A precision of 2 mg=cm
2
was
achieved in a 30 s with gas-lled proportional detector and a 1.5 GBq (40 mCi)
55
Fe source,
for up to 450 mg=cm
2
coating mass.
D. On-StreamAnalysis of Metalliferous Mineral Slurries
Most metalliferous minerals are concentrated from their ores by froth otation. The grade
of ore fed to the concentrator can vary rapidly; hence, to control the otation process, the
concentrations of valuable minerals in the plant process slurries should be determined
continuously. The concentrations, in the slurry solids, of such base metal minerals as
nickel, copper, zinc, and lead are usually in the range of 0.315 wt% for feed streams, tens
of weight % in concentrate streams, and 0.030.3 wt% in tailings (residue) streams. The
Figure 25 The frequency distribution for product zinc coating mass before and after installation
of an on-line zinc coating mass gauge at John Lysaght Pty. Ltd. Product minimum specification is
300 g/m
2
. (From Watt, 1978).
solids weight fraction is in the range of 1550 wt%. The time for analysis (less than 5 min)
is too short for laboratory analysis of samples taken from the process streams.
A radioisotope x-ray based on the use of scintillation detectors was introduced
in 1973 (Watt, 1985). Cesium-137 g-ray transmission is used to determine the bulk density
of the slurry and, hence, the solid weight fraction. X-ray uorescence techniques based
on direct excitation and detectorradiator assemblies (Fig. 18) are used to determine the
concentration of all but some high-Z elements, such as lead, which are determined by
153
Gd g-ray (about 100 keV) transmission. In each case, the x- or g-ray measurements are
combined with the solids determination to obtain the concentration of elements in the
slurry solids. These techniques are suciently sensitive for all but a few tailing streams
containing very low concentrations of valuable mineral. This limitation was overcome
later by the introduction of a solid-state detector probe.
The radioisotope x-ray system (Fig. 26) is based on probes, each containing a
radioisotope source and a detector, which are immersed directly into the plant process
slurries (Watt, 1985). Electrical signals from the probes are fed to an analyzer unit and its
output to a central computer. Thus, not only is there no need for sampling from the plant
process streams, but all streams are analyzed continuously rather than sequentially.
This radioisotope x-ray system is very dierent from x-ray tube and crystal spec-
trometer systems for on-stream analysis. These systems were developed in the 1960s to
scan slurries sequentially in up to 14 simple sampling loops (Leppala et al., 1971). Analysis
of the slurries involved sampling from the main process stream, running slurries through
long sections of sampling loops to the central analyzer, and subsampling from the sam-
pling loops before presentation to the analyzer. This is a complex and expensive system.
X-ray tube analysis systems developed in the 1980s sequentially route the slurries from up
to ve process streams through a common ow cell viewed by an XRF analyzing unit
(Saarhilo, 1983). The analyzer is mounted in the plant near the process streams and thus
overcomes much of the mechanical complexity of the 14-stream system just discussed.
Both the x-ray tube crystal spectrometer system and the radioisotope XRF solid-state
detector system are routinely used with this new sample loop system. Both systems can
also be used for the continuous analysis of ne powders. The radioisotope system is
capable of determining elements of atomic number as low as 14 (silicon), because with the
short x-ray path length, the absorption of the low-energy x-rays in air is minimized.
The development of dierent systems for the on-stream analysis of mineral slurries
illustrates the strong inuence of sampling and sample presentation on the type of XRF
analysis system used. Various radioisotope (Table 6) and x-ray tube systems are now in
use, with about several hundred plant systems being installed in concentrators throughout
the world. The radioisotope systems, both in stream (Watt, 1985; Berry et al., 1983) and
using short sample loop, and the ve-stream x-ray tube system, are preferred for new
installations because they cost less and are mechanically less complex. Improvements in
plant control based on this analysis information have led to an increase in the recovery of
valuable minerals (Fig. 27), decreased reagent addition, and reduced need for assay and
sampling sta (Watt, 1985). Total savings per concentrator vary in the range from
US$100,000 to several million dollars a year.
E. On-Line Determination of the Ash Content of Coal
Continuous on-line determination of the ash content of coal on conveyors is required for
the control of coal mining, blending, sorting, and preparation operations. The coal is
carried by the conveyors, usually at the rate of 100600 tons=h, the speed of the conveyor
Figure 26 A system for the on-stream analysis of mineral slurries. The microcomputer outputs solids weight fraction and concentrations of
valuable minerals in the solids of each stream. (Courtesy of AMDL.)
is about 3 m=s, and the coal particle top size is in the range 10150 mm, depending on the
application. The process requirement for analysis time varies from 1 or 2 s for the fast
sorting of coal to 10 min for the steady-state control used in coal preparation plants.
Three x-ray or low-energy g-ray techniques have been developed: backscatter of
x-rays (H. Fraenkel, private communication, 1987), backscatter of low-energy g-rays
(Fauth et al., 1986; Cierpicz, 1986), and dual-energy g-ray transmission (Fookes et al.,
1983; Gravitis et al., 1987). Each relies on the photoelectric eect, which depends on
atomic number, and on the fact that ash (mainly SiO
2
and Al
2
O
3
with smaller con-
centrations of Fe
2
O
3
) has an eective atomic number, Z, greater than that of the coal
matter (carbon, hydrogen, nitrogen and oxygen).
The x-ray technique (H. Fraenkel, private communication, 1987) depends on the
scatter of approximately 17-keV x-rays from
238
Pu (or
244
Cm) source in the coal and, at
the same time, excitation of iron K x-rays in the coal to correct for the high absorption per
unit mass by Fe
2
O
3
compared with Al
2
O
3
and SiO
2
. Because the low-energy x-rays pe-
netrate only thin layers of coal, the coal is sampled from the conveyor, subsampled, and
ground to 5-mm top size particles, partially dried, and then presented in a moving stream
of controlled geometry to the radioisotope x-ray analysis system. This system compensates
for the eect of variations in Fe
2
O
3
in the ash, a signicant source of uncertainty in some
applications. However, it involves complex sampling, sample handling and processing,
and blockages occur when the coal is very wet.
The low-energy g-ray technique, using an
241
Am (60 keV) source, depends on mea-
surement of the intensity of g-ray scattered from thick layers (<15 cm) of coal. It was rst
used on a high-throughput sample line (Fauth et al., 1986). Although coal must be
sampled, there is no need for the coal to be subsampled and crushed because of the high
Figure 27 Improvements in recovery of mineral concentrators after installation of on-stream
analysis systems. The symbols refer to tin (diamonds), lead (square), zinc (circles) and copper
(asterisks).
penetration of g-rays in the coal. The technique has been adapted for use on-line (Cierpicz,
1986), the analysis head unit riding on a raft that is spring loaded so that it is always
touching the top of the coal on the conveyor. Its use is restricted to conveyor speeds of less
than 2 m=s and to minimum thickness of 15 cm of coal on the conveyor compared to the
normal practice of 520 cm.
The dual-energy g-ray transmission technique (Fookes et al., 1983; Gravitis et al.,
1987) measures coal directly on the conveyor belt (Fig. 28), eliminating the need for
sampling the coal. The ash content is determined independently of vertical segregation
of coal on the belt, and if segregation across the belt occurs, the narrow beam of g-rays can
be made to scan across the belt to obtain a representative sample. The coal mass per unit
area in the g-ray beam must be <3 or 4 g=cm
2
to achieve sucient sensitivity of analysis.
Variations of iron in the ash limits the accuracy of ash determination in some applications.
The choice of a suitable x- or g-ray analysis technique is highly inuenced by the
complexities in sampling of the coal on the conveyor and the subsequent subsampling and
grinding. Radioisotope techniques that measure directly on-line are preferred to those
involving sampling, and if sampling is necessary, preference is given to those that minimize
sampling and sample presentation.
Dual-energy g-ray transmission is now the preferred technique for the on-line
determination of ash content of coal, except for applications in which unacceptable un-
certainties in ash are caused by variations in iron in the ash. In this case, a high-energy
g-ray technique, which is based on the pair production interaction and is much less sen-
sitive to variations in iron, is preferred. Its main disadvantages are cost and that it must
operate on a sample line (Sowerby, 1986).
F. On-Line Analysis of Paper
Continuous on-line analysis of paper is required for control of the production process.
Paper consists of cellulose, water, and mineral llers. The characteristic and the quality of
various types of paper are, to a great extent, dependent on the quality, quantity, and
distribution of ller materials. These ller materials occupy the spaces between bers and
improve the printing properties of the paper. Filler materials include CaCO
3
, kaolin, talc,
and TiO
2
, and the concentrations of each may vary.
The analysis may be achieved by a combining XRF, XRA, and b-ray transmission
techniques (Kelha et al., 1983). The mass absorption coecients of x-rays in the 110-keV
region are shown in Figure 29, with abrupt changes in the K shell absorption-edge energies
of calcium (4.04 keV) and titanium (4.96 keV). X-ray preferential absorption measure-
ments are made at x-ray energies of 5.9 (
55
Fe), 4.51 (TiKa x-rays), and 3.69 keV (CaKa
x-rays), the latter two energies being contained by exciting a secondary target material
with
55
Fe x-rays (Fig. 30). The total mass per unit area of the paper is determined by b-ray
transmission. The distribution of the ller material through the paper is determined by
making XRF measurements, using
55
Fe x-rays to excite calcium K x-rays, to give the
dierence in CaCO
3
concentrations near the surface on each side of the paper. These
techniques can be used to determine the concentrations of cellulose, kaolin or talc, CaCO
3
and TiO
2
.
G. Determination of Sulfur and Chlorine in Oil
Sulfur in oil is a source of air pollution. Strict environmental controls are applied to limit
sulfur release into the atmosphere. Oil in sample lines from main pipelines is monitored
routinely by one of two radioisotope x-ray techniques. One technique combines XRF
(
55
Fe and a proportional detector) and b-ray transmission. The other combines XRA,
using 22-keV silver K x-rays that are absorbed equally per unit weight by both carbon and
hydrogen, with a nonnuclear technique to determine the density of the oil. In Japan alone,
more than 100 of the former gauges and several hundred of the latter are used (Table 6).
More recently, this application received an application boost from regulatory agencies
such as U.S. Environmental Protection Agency. Since October of 1993, no on-highway
diesel fuel the United States can contain more than 500 mg=kg of sulfur. This regulation
forced sulfur monitoring for compliance at reneries, distributorships, and local suppliers.
A proportional detector with neon gas lling and a thin, 13-mm Be window, coupled with a
1.48-GBq (40 mCi)
55
Fe isotope allows sulfur analysis in diesel fuel down to 50 mg=kg,
with a precision of 8 mg=kg (1s), in 300 s measurement time (Piorek and Piorek, 1993).
Figure 28 System for on-line determination of the ash content of coal based on dual-energy g-ray
transmission techniques.
A factor of 5 better results may be obtained by using low-power x-ray tube in the place of
the isotope. The issue of sulfur measurement in petroleum products for compliance with
the EPA regulations has been addressed by American Society for Testing and Measure-
ment (ASTM), with two ASTM Standard Test Methods, D2622 and D4294. Similar
regulations for sulfur in petroleum products for on-highway use are being implemented in
Europe and Asia.
Spent engine oil is burned as fuel in industrial boilers and home heating furnaces.
Because chlorinated solvents have routinely been mixed with much of this oil, there is a
danger that hazardous levels of these compounds or their derivatives will be released into
the atmosphere. The U.S. Environmental Protection Agency has banned the sale of used
oil for fuel if the total halogen level (interpreted as total chlorine level) exceeds 1000 mg=g.
If the total halogen level is more than 4000 mg=g, such oil has to be considered as
Figure 29 Mass absorption coefficients of the most frequently used filler materials, water and
cellulose, relating to the manufacture of paper. (From Kelha et al., 1983.)
Figure 30 Measuring principle used in the on-line analysis of paper: (a) XRF, (b) XRA, and (c) b-ray absorption. (From Kelha et al.,
1983.)
hazardous waste and cannot be reused. However, if the total halogen level is greater than
1000 but less than 4000 mg=g, it may be diluted with less contaminated oil to reduce the
halogen content below 1000 mg=g, after which it can be burned as fuel. Piorek and Rhodes
(1987) and Gaskill et al. (1987) showed that a portable XRF analyzer, with a high-
resolution proportional detector and a 0.74-GBq (20 mCi)
55
Fe source, can be used to
analyze for chlorine in oil. The used oil also contains phosphorus, sulfur, potassium, and
calcium, and the intensities of the K x-rays from all these elements were incorporated into
the calibration so that the measured chlorine K x-ray intensity could be properly corrected
for spectral overlap. The analysis time was 30 s per sample, and the overall accuracy
achieved was quite adequate.
H. Analysis of Environmental Samples
Perhaps the second most important group of applications well served by XRF is in the
analysis of a variety of environmental samples. This is especially true of portable XRF
analyzers, which, in a very natural way, drifted frommineral prospecting to soil screening for
metals; the two applications virtually dier only by name. Successes of XRF in analysis of
thin lms and coatings have been parlayed into measurement of air particulates collected on
lter media. Even much more analytically demanding analysis of water can also be per-
formed with XRF using ion-exchange membranes. All these applications will be discussed.
1. Air Particulatesin Ambient Air
The concentrations of particulates suspended in ambient air are determined to identify
sources of air pollution. The air particulates are collected by drawing large volumes of air
through a lter paper, which is then submitted to multielements analysis. Rhodes et al.
(1972) and Florkowski and Piorek (1974) showed that energy-dispersive XRF analysis
based on radioisotope sources and a silicon solid-state detector is a simple and cost-
eective method for determining the elemental concentrations on the lter paper. The
advantage of the solid-state detector is that simultaneous multielement analysis is achieved
with excellent sensitivity and short analysis time.
Analyses were made using 4.44 GBq (120 mCi)
55
Fe, 14.8 GBq (400 mCi)
238
Pu, and
444 MBq (12 mCi)
109
Cd, a 80-mm
2
64-mm-thick silicon detector (energy resolution of
180 eV at 5.9 keV), and counting for 10 min per lter paper with
238
Pu and
109
Cd and 5 min
with
55
Fe. The detection limit (3s of the background under the relevant peak) for the 19
elements measured varied in the range from 0.03 to 0.24 mg=cm
2
. This is more than adequate
for levels required in environmental pollution analysis. Rhodes and Rautala (1983) have
since shown that the same radioisotopes, with activities of 111370 MBq (310 mCi), can be
used with a high-resolution proportional detector to determine the same elements with de-
tection limits (3s) between 0.4 and 12 mg=cm
2
in 4 min. The main competitive techniques are
energy-dispersive techniques using x-ray tubes and solid-state detectors (Chapter 3) and
particle accelerators in proton-induced x-ray emission (PIXE) techniques (Chapter 12). The
energy-dispersive XRF have been used for the last 20 years by various governmental and
international institutions for routine monitoring of ambient air pollution.
2. Air Particulates Monitoringin Stack Emissions and Workplace Air
The dierence between ambient air monitoring and stack emission or workplace air is
only in the levels of concentrations to be measured and frequency of sampling. As in
analysis of ambient air by ltering the air onto a thin membrane substrate, a signicant
preconcentration of the sample is realized, resulting in improved sensitivity of the XRF
analysis. Although the concentrations of metals in stack emissions and in workplace air
are much higher than in ambient air, they can only be sampled and analyzed for short
periods of time. Nevertheless, despite these restrictions, the portable x-ray analyzer can
still provide sucient sensitivity of measurement. The typical application is analysis of
metals in deposits obtained with personal samplers for breathing zone air used by
workers occupationally exposed to polluted air. Samples of air particulates are col-
lected for 8 h by pumping air through a 37-mm-diameter membrane, at a rate of about
2 L=min. These deposits can then by analyzed by the same portable XRF analyzer which
was used for soil screening during remediation eort. Within the last 3 years, the issue of
metals monitoring in stack emissions from industrial incinerators has been the subject of
regulatory action in the United States and Europe. Regulations in the United States are
pending which will limit emissions of toxic metals from incinerators stacks and will
require continuous on-line monitoring for compliance. Of the several attempts at Con-
tinuous Emission Monitoring (CEM) Systems, XRF proved to be a viable and relatively
inexpensive alternative. The proof of principle experiment using XRF was performed by
Piorek et al. in 1995 (Piorek et al., 1995) during the EPA-sponsored eld test in the
EPAs own hazardous waste incinerator in Little Rock, Arkansas. The test showed that
particulate deposits obtained by ltering stack exhaust for 10 min on lter membrane
can be readily analyzed by the portable XRF system with radioisotopes as excitation
sources (Makov et al., 1968). Table 9 lists the capabilities of the portable analyzer for
metals ltered from air on a membrane substrate (Piorek, 1997). As can be seen, the
detection limits for air particulates collected on the lter are on the order of a micro-
gram per cubic meter of air. Further improvement of the performance is possible using
x-ray tubes as excitation sources and integrating the analyzer into an continuous on-line
monitor.
Table 9 Performance of a Si(Li)-Detector-Based Field Portable X-ray Analyzer in Monitoring
Air Particulates in Workplace Air and Industrial Incinerator Exhaust
Element
Detection limit
(mg/cm
2
)
Detection limit
a
(mg/cm
3
)
PEL
b
in air
(mg/cm
3
)
Detection limit
CEM
c
(mg/cm
3
)
Cr 0.43 3.0 1000 1.5
Mn 0.45 3.2 50 ND
Fe 0.45 3.2 10
4
(as Fe
2
O
3
) ND
Ni 0.29 2.0 1000 ND
Cu 0.29 2.0 1001000 ND
Zn 0.27 2.0 (15) 10
3
ND
As 0.16 1.1 10 1.5
Se 0.16 1.1 200 ND
Pb 0.24 1.7 50 3.1
Cd 0.07 0.5 1003000 3.1
Sb 0.06 0.5 500 1.5
Sn 0.05 0.4 2000 ND
a
For one cubic meter of air (gas) pumped through a Millipore SMWP membrane of 9 cm
2
area.
b
The OSHA Permissible Exposure Limit in work place air, PEL (as per 29 CFR 1910.1000, 1 Jan. 1977).
c
Hazardous waste combustors, revised standards, proposed rule, 40 CFR Part 60 et al., April 19, 1996. NDnot
determined; CEMcontinuous emission monitor. Source: From Piorek, 1997.
The same technique for analyzing thin-layer samples can be used for measurement of
metallic ions in water, by cycling the water through an ion-exchange membrane. Piorek
and Pasmore (1993) reported the detection limits for transition metals in water at less than
0.1 mg=L if 250 mL of water was cycled seven times through a 37-mm-diameter ion-
exchange membrane, followed by a 200-s analysis with a 0.37-GBq (10 mCi)
109
Cd source.
3. Soil Screeningfor Inorganic Contaminants
On-site analysis of metals in soils, sediments, and mine wastes is required as part of re-
habilitation studies at hazardous waste sites. The distribution of the hazardous metals is
heterogeneous owing to the exigencies of dumping and possible leaching by rainwater.
Many samples must be taken over the surface area and at depths to dene the zones of
metal accumulation and metal depletion. Chappell et al. (1986) and Piorek and Rhodes
(1987) demonstrated that the portable XRF analyzers based on a high-resolution pro-
portional detector and a 3.7-GBq (100 mCi)
244
Cm source can be used to determine
concentrations of arsenic, copper, zinc, and lead in soils in the range of approximately
from 10 to 10,000 mg=g, with an accuracy that is adequate for this type of investigation.
Rapid, on-site analyses can be incorporated immediately into a eld investigation pro-
gram, making it possible to change the density of sampling at any spot, depending on the
results of previous analyses. Since then, portable XRF analyzers have been improved to
include high-resolution semiconductor detector probes and extensively used to measure
in situ metals in soil, such as lead, zinc, copper, arsenic, nickel, chromium, and cadmium.
In the majority of reported cases, the correlation between the XRF and the conrmatory
method results [such as Atomic Absorption Spectrometry (AAS) or Inductively-Coupled
Plasma Atomic Emission Spectrometry (ICP-AES)] was very good (correlation coecient
greater than or equal to 0.9) (Piorek, 1994). Cole et al. (1993) report on an extensive lead
study conducted during the summer of 1991 in Leadville, Colorado, where over 3700
samples of soil were analyzed for lead using portable XRF analyzers. The accuracy of the
lead determination by the XRF in that study was estimated at about 8% relative. Another
very important observation from that study is that the accuracy of the determination of
spatial distribution of lead in the soil does not depend so much on the accuracy of the
individual result as on the total (large) number of samples. In other words, raising the
analytical quality of the individual data has very little eect on the total uncertainty;
however, increasing the number of samples will considerably improve the accuracy of the
determination of spatial distribution of lead. This conclusion has been conrmed by other
researchers as well (Raab et al., 1991).
The portable XRF analyzer has been successfully used during remediation eorts at
the cleanup of soil contaminated with chromium (Waligora, 1997). More than 3000
samples were measured in the eld, providing an immediate feedback to an excavating
crew which was working literally on the heels of the eld analytical team. Figure 31
illustrates typical performance parameters of the contemporary portable XRF analyzer
with a Si(Li) detector probe for metals in soil matrix. As it can be seen, the typical de-
tection limits are in the range 50100 mg=kg. The success of portable XRF in soil
screening led to coining of a new term of eld-portable x-ray uorescence (FPXRF),
probably to distinguish this application from the others.
The FPXRF analyzer oers an attractive, in situ alternative to the traditional la-
boratory analysis of contaminated soil. The operator equipped with the portable XRF
analyzer can perform a large number of multielement measurements in situ by placing the
probe directly on the soil surface, thus allowing for the decisions to be made in real time.
Moreover, the measurements can also be performed at any stage of the remediation
Figure 31 Typical detection limits (DLs) for metals in soil obtained with field portable X-ray analyzer equipped with a
Si(Li) detector probe. Conditions: Si(Li) detector, 30 mm
2
area; measurement time 200 s; sample matrix: silica sand. K series
excitation with
109
Cd and
241
Am isotopes. Open rectangles correspond to 1s uncertainty of counting; solid rectangles mark
the DL. The DLs for heavy metals determined via their L series x-rays, such as Pb, Hg, Bi, are numerically similar to those
from Zn to Br. (From Piorek, 1994.)
process to either verify that the cleanup is accomplished or that the work has to continue.
The results obtained with the XRF analyzer will reveal relative variations of contami-
nant(s), their spatial distribution, and pinpoint locations with elevated contamination
levels (so-called hot spots), thus making sampling plans realistic and ecient. This is
particularly important because any contaminated site is likely to have an extremely het-
erogeneous distribution of hazardous chemicals in the soil. For that reason, the sampling
strategies will mandate that many densely distributed samples are taken, in order to ensure
that hot spots are not missed. This type of analysis, which is referred to as screening,
is allowed by the EPA to have uncertainties as large as 50% relative (EPA, 1987). Most
recently, the ocial recognition of the FPXRF as a valid soil characterization method has
materialized in a form of a new EPA Method 6200, which has been published in June of
1997 (EPA, 1997).
4. Analysis of Liquid HazardousWaste
The analysis of liquid hazardous waste (LHW) is required prior to its treatment in order to
properly set up the treatment process and, also, after the treatment to determine the nal
disposition of the treated waste. Liquid waste is a mixture of solids suspended in a liquid
medium. Solid particles vary considerably in particle size and composition, whereas the
liquid phase is often a mixture of immiscible liquids. The sludge remaining after the
treatment of liquid waste is either transported to a waste dump or, preferably, utilized for
soil amendment in agriculture and forestry because it is often rich in nutrients. However,
depending on the origin of the waste, it may also contain a whole range of heavy metals,
which even at moderately elevated concentrations, are very toxic to plants and animals. In
order to avoid the accumulation of toxic metals in soil, the concentration of these metals in
the original waste, as well as in postprocess sludge, has to be known.
Traditionally, the liquid waste samples are analyzed by a ame or graphite furnace
AAS or ICP-AE. Those methods, while oering low detection limits, are slow and labor
intensive. Additionally, they call for rather involved sample preparation (digestion) and
are relatively expensive. Energy-dispersive x-ray uorescence spectrometry was considered
as an alternative analytical method for liquid waste due to its known features of speed,
multielement character, wide dynamic range, and little to no sample preparation re-
quirement. However, the diversity of form and composition makes LHW an extremely
dicult medium to analyze with XRF as a result of the severe matrix eects present in a
sample of LHW. The severity of matrix eects in liquid hazardous waste precludes the use
of many known calculational models correcting for absorption=enhancement phenomena
because mathematical models are valid only for physically and chemically homogeneous
materials. To overcome these diculties, a novel empirical approach was proposed for
stabilization of the sample matrix by dilution (ASTM, 1997; Piorek et al., 1997), For the
purpose of XRF analysis of liquid hazardous waste, a calcined alumina powder (Al
2
O
3
)
was used as a diluent. This powder is characteristic for its highly adsorptive properties
toward liquids. Thus, after adding a small amount of liquid to an aliquot of Al
2
O
3
, the
latter instantly absorbs the liquid. After brief mixing and shaking, the originally liquid
sample is converted to a homogeneous powder. The mass ratio of the diluent to sample has
to be maintained constant from sample to sample and should not be smaller than 3:1,
otherwise the sample=diluent mixture will behave more like a slurry than a powder. This
kind of sample matrix stabilization is eective for liquids as well as liquids with suspended
solids. By diluting and mixing, both the liquid as well as the suspended solids are now
suspended in alumina powder, which does not allow waste solids to settle. Another
important function of alumina is that it dominates the matrix of the sample and, therefore,
the composition dierences between the original samples of waste are reduced to easily
manageable levels. For calibration, a set of samples of alumina powder is prepared by
spiking with a known amount of standard solutions. The details of the technique are
described in the ASTM Standard Method D6052-97 (ASTM, 1997). Using a portable
Si(Li)-detector-based probe with a 0.74-GBq (20 mCi)
109
Cd source and a 1.11-GBq
(30 mCi)
241
Am source, the 200-s measurement time detection limits obtained with this
method for elements ranging from Cr to As were between 35 and 10 mg=kg, respectively.
For heavy elements such as Hg, Pb, Cd, and Sb, detection limits were 12, 8, 4, and
4 mg=kg, respectively.
5. Analysis of LeadinWall Paint
A prolonged exposure to low levels of lead may lead to serious health problems in young
children, including impairment of the central nervous system, behavioral disorders, and
mental retardation. Paint, dust, soil and, to a lesser extent, food, water, and air are all
potential sources of exposure to lead. After banning the use of leaded gasoline in the U.S.,
lead-based paint is recognized as the principal source of lead in dust and soil. From here it
can easily enter a childs system as the result of hand-to-mouth activity, typical for young
children. These concerns were addressed with federal regulations in the early seventies.
The essence of those regulations is that any applied lead-based paint exhibiting more than
1.0 mg of lead per square centimeter must be removed, as well as any applied to surface
paint that contains more than 0.5% lead by dry weight. In recent years the lead-based
paint danger became the focus of attention in European countries. France, for example,
introduced guidelines for lead levels in paint and followed with enforcement regulations
(Law No. 99-483 of June 9, 1999). It is expected that other countries will follow Frances
example in coming years.
The preferred method for testing applied paint for lead is FPXRF (McKnight et al.,
1989; Piorek et al., 1995). This is because XRF is nondestructive and fast and oers overall
good performance. Additionally, lead x-rays, either K or L series, have high penetrating
power (especially the Ks), and are not interfered with by the other elements which make up
the paint. As the result, the XRF method is quite selective for lead in leaded paint applied
on any substrate. A number of accounts on this subject has been published over the years,
and a number of portable XRF devices was designed for just lead in wall paint mea-
surements. The majority of the instruments used lead K shell x-rays, excited either with
57
Co or
109
Cd (the 88-keV g-rays of this isotope), but some have utilized L shell excita-
tion of lead. The latter approach has been reported to be able to measure lead with a
proportional detector and a 2.1-GBq (60 mCi)
244
Cm source with a precision of
0.05 mg Pb=cm
2
. Probably the most successful overall lead in paint analyzer has been
Model LPA-1 from Radiation Monitoring Devices. The self-contained instrument in a
shape of the lightweight pistol uses a
57
Co isotope and CdTe detector to determine the lead
concentration in applied paint at a 2s condence level in 5 s measurement time. The
analyzer automatically adjusts the measurement time to reach a preset level of total
measurement uncertainty. The instrument is an example of well thought out ergonomical
design, responding well to the needs of the market. The analyzer can be preset for a
specic, local lead abatement action level and it can generate a hard-copy analytical
report. Another interesting entry in the lead in paint market is the Model XL from the
Niton Corporation (1999). Although a marvel of miniaturization, its shape seems less
conforming to the requirements expected of a hand-held device operated continuously for
several hours. This is also the only commercially available analyzer which uses L shell lead
x-rays for analysis and the ratio of the lead La to Lb lines for determination of the depth at
which leaded paint is present under overcoats of other paint (Shefsky et al., 1997); in those
instances in which leaded paint may be buried under overcoats of paint, the instrument
uses K shell lead lines for measurement, as there are very little aected by top layers of
paint.
I. Analysis of Corrosion Products
An interesting on-line application has recently been reported by Connolly and Millet
(1994) and Connolly and Harvey (1995) for corrosion product monitoring in nuclear
power plant feedwater. By coupling the XRF analyzer probe to a specially designed
sample ow chamber, the authors realized continuous measurement of incremental ac-
cumulation of corrosion products such as iron. The feedwater is circulated through the
sample ow chamber, where it passes through the membrane lter. The solids present in
the water are collected on the lter surface and then measured with an XRF probe. The
measurement is incremental, so that the lter does not have to be removed for analysis
after each sampling cycle. A gas-lled proportional detector and 3.7-GBq (100 mCi)
244
Cm
source allow one to routinely achieve the detection limits for iron of 1 ppb, at a 300-s
sampling period followed by 300 s of measurement time. Further work is under way to
improve these performance and to extend the applicability of this method to other ele-
ments and liquid media.
VII. FUTURE OF RADIOISOTOPE-EXCITEDXRFANALYSIS
As we have stated in the Introduction, radioisotope x-ray analysis is mainly useful in
industrial and eld applications. This trend will continue, although the proportion of on-
line installations for process control to number of eld-portable x-ray analyzers will
constantly decrease. First, it will be the result of a more general contemporary trend in the
instrument industry of bringing the analytical method to the site. Second, the number of
applications that can benet from portable XRF analysis is much greater and more di-
versied than the number of installations for process control. Third, radioisotope-based
on-line installations will gradually be displaced by systems based on x-ray tubes. Last but
not least, on-line installations will face erce competition from new analytical technologies
based on lasers, which, in many cases, oer instantaneous results at a high repetition rate.
As a result, in the very near future, radioisotope x-ray analysis may become synonymous
with eld-portable XRF and, therefore, the future of radioisotope X-ray analysis will most
likely depend on the developments in eld-portable XRF.
The next designs of the portable XRF analyzers will feature new, high-resolution-
semiconductor, room-temperature detectors. Most likely these will be improved detectors
based on silicon diodes (p-i-n detector) or composite semiconductors such as ZnCdTe,
CdTe, GaAs, and so forth. A recently introduced x-ray detector (Xash Detector) built on
a silicon chip as a solid-state drift chamber oers count-rate capabilities well into
50,000 cps at an energy resolution still better than 200 eV (Ro ntec 1997). The portable
XRF analyzer of the future will incorporate a GPS (Global Positioning System) module,
whichif neededwill instantly locate the measurement site on the map andif properly
equippedwill transmit the measurement results via a wireless link to a central data
collection station. An instrument with a GPS chip installed will also be very easy to track
down if misplaced or stolen, a very desirable feature for a radioisotope-containing device.
The FPXRF will travel underground, as an analytical module built into the push-in
probe or in a cone penetrometer. The rst trials were very encouraging (Elam et al., 1997).
Technological progress will also bring us truly small x-ray sources, which will gradually
replace radioisotopes in applications requiring less than 35-keV-energy x-rays (Moxtek
Inc., private information, 1998). We should also expect an increased number of dedicated,
smart XRF analyzers customized to specic applications, such as the already mentioned
measurement of lead in wall paint. New portable instruments will be smaller, lighter, and
smarter than their predecessors. Perhaps the avor of the future direction of develop-
ment of portable, radioisotope excited XRF is best exemplied by Model XL by Niton
Corp. (Fig. 32), a one-piece, miniature XRF analyzer with built-in ADC=MCA, and
weighting only about 1.6 kg (Niton Corp., 1999).
VIII. CONCLUSIONS
X-ray uorescence spectroscopy is perhaps the rst spectroscopic technique to successfully
enter the eld and plant environments. Radioisotope x- and g-ray techniques have been
widely used for analysis in the laboratory, in industrial plants, and in the eld. Because of
their simplicity, they are preferred to x-ray tube analysis techniques in many applications,
particularly for more routine analyses involving a limited range of sample compositions.
The techniques are less sensitive, however, than those based on x-ray tubecrystal spec-
trometer systems and less exible to widely dierent analysis applications. Radioisotope
x- and g-ray techniques have had great impact on industrial and eld applications. Their use
Figure 32 Niton II, XRF Alloy Analyzer based on a silicon p-i-n diode. (Courtesy Niton Corp.)
for the continuous on-line analysis in the coating, mineral, coal, paper, and petroleum in-
dustries has led to better control of the industrial processes. This, in turn, has led to products
that more closely meet specications, with consequently large savings in production costs.
Portable XRF analyzers have been around for about 30 years, and during that
period, their design has been rened and their performance greatly improved. A con-
temporary, high-resolution, portable XRF analyzer brings to the eld site not only an
excellent performance often matching that of the laboratory instrument but also un-
surpassed savings in time and labor, contradicting the popular conviction about the in-
herent inferiority of portable instrumentation. The use of portable instruments in the eld
(e.g., for the sorting of alloys and for detection of hazardous waste materials) has led to a
much more rapid analysis of materials and, hence, to the much wider use of x-ray tech-
niques in eld analysis. Field-portable x-ray uorescence is an example of a well-balanced
compromise among portability, ruggedness, reliability, and analytical performance. There
are not that many analytical techniques that can rival FPXRF in simplicity, speed of
operation, and relaxed requirements of sample preparation. Whenever a fast and frequent
elemental analysis for inorganics is required, there is a place for the FPXRF analyzer.
This applies in particular to scenarios in which a quick verication type of analysis is
needed.
APPENDIX: LIST OF COMPANIES THAT MANUFACTURE RADIOISOTOPE-BASED
X-RAYANALYZERS ANDSYSTEMS
AMDL (Australian Mineral Development Laboratories), P.O. Box 114, Eastwood,
SA 5063, Australia
ASOMA Instruments, 11675 Jollyville Road, Austin, TX 78759, USA
BRGM, BP 6009-45060 Orleans, Cedex 02, France
Data Measurement Corporation, P.O. Box 490, Gaithersburg, MD 20877, USA
Detora Analytical, P.O. Box 2747, Alliance, OH 44601-0747, USA
Electrical Engineering and Automation (EMAG), Katowice, Poland
FAG Kugelscher Georg Schafer KG Auf Aktien, Tennenloher Strasse 41,
Erlangen, Germany
Harrison Copper Systems, Inc., AMF Box 22014, Salt Lake City, UT 84122, USA
Harshaw Radiation Detectors, Harshaw=Filtrol Partnership, 6801 Cochran Road,
Solon, OH 44139, USA
Humboldt Wedag, P.O. Box 2729, 4630 Bochum, Germany
Kevex Corporation, P.O. Box 4050, Foster City, CA 94404, USA
Metorex International Oy, P.O. Box 85, SF-02631 Espoo, Finland
Mineral Control Instrumentation Pty. Ltd., P.O. Box 64, Unley, SA 5061, Australia
Mitsubishi Corporation, 6-3, Marunouchi 2-chone, Chiyoda-Ku, Tokyo 100, Japan
Niton Corporation, 900 Middlesex Turnpike, Bldg. 8, Billerica, MA 01821, USA
Outokumpu Oy, PO Box 85, SF-02201, Espoo, Finland
Oxford Instruments, 20 Nueld Way, Abingdon, Oxon OXI4 1TX, UK
Paul Lippke GmbH & Co. KG, Postfach 1760, 5450 Neuwied 1, Germany
Radiation Monitoring Devices, 44 Hunt Street, Watertown, MA 02172, USA
Ramsey Ltd., 385 Enford Rd., Richmond Hill, Ontario, L4C 3G2, Canada
Rigaku Denki, 14-8 Akaoji, Takatsuki-shi, Osaka, Japan
Science Applications Inc., 1257 Tasman Drive, Sunnyvale, CA 94089, USA
Sentrol Systems Ltd., 4401 Steeles Avenue West, North York, Ontario, Canada,
M3N2S4
Sortex Ltd., Pudding Mill Lane, London E15 2PJ, UK
TN Technologies (Texas Nuclear Corporation), 2555 North Interstate Hwy 35,
Round Rock, TX 78689, USA
Tracor X-ray, Inc., 345 East Middleeld Rd., Mountain View, CA 94043, USA
Yokogawa Hokushin Electric Corporation, 9-32 Nakacho 2-chome, Musashino-shi,
Tokyo, 180, Japan
ACKNOWLEDGMENTS
The author thanks the many scientists, organizations, and companies who generously
supplied information used in this chapter and to the following for permission to reprint
gures used in this chapter: Pergamon Press (Figs. 2, 14, 18, 21, 22, and 28); EG&G Ortec
(Fig. 1); The Radiochemical Centre, Amersham (Fig. 4); the International Atomic Energy
Agency (Fig. 7); The Analyst (Fig. 20); Outokumpu Oy (now Metorex Int.) (Figs. 11 and
23); IEEE (Fig. 16); Automatica (Fig. 25); Australian Mineral Development Laboratories
(Fig. 26); The Australasian Institute of Mining and Metallurgy (Fig. 27); and Acta
Polytechnica Scandinavia (Figs. 29 and 30).
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8
Synchrotron Radiation-Induced
X-ray Emission
Keith W. Jones
Brookhaven National Laboratory, Upton, New York
I. INTRODUCTION
Elemental analysis using the emission of characteristic x-rays is a well-established scientic
method. The success of this analytical method is highly dependent on the properties of the
source used to produce the x-rays. X-ray tubes have long existed as a principal excitation
source, but electron and proton beams have also been employed extensively. The devel-
opment of the synchrotron radiation x-ray source that has taken place during the past 40
years has had a major impact on the general eld of x-ray analysis. Even after 40 years, the
science of x-ray analysis with synchrotron x-ray beams is by no means mature. Im-
provements being made to existing synchrotron facilities and the design and construction
of new facilities promise to accelerate the development of the general scientic use of
synchrotron x-ray sources for at least the next 10 years.
The eective use of the synchrotron source technology depends heavily on the use of
high-performance computers for analysis and theoretical interpretation of the experi-
mental data. Fortunately, computer technology has advanced at least as rapidly as the
x-ray technology during the past 40 years and should continue to do so during the next
decade. The combination of these technologies should bring about dramatic advances in
many elds where synchrotron x-ray science is applied.
A short summary of the present state of the synchrotron radiation-induced x-ray
emission (SRIXE) method is presented here. Basically, SRIXE experiments can include
any that depend on the detection of characteristic x-rays produced by the incident x-ray
beam from the synchrotron source as they interact with a sample. Thus, experiments done
to measure elemental composition, chemical state, crystal structure, and other sample
parameters can be considered in a discussion of SRIXE. It is also clear that the experi-
mentalist may wish to use a variety of complementary techniques for study of a given
sample. For this reason, a discussion of computed microtomography (CMT) and x-ray
diraction is included here.
It is hoped that this present discussion will serve as a succinct introduction to the
basic ideas of SRIXE for those not working in the eld and possibly help to stimulate new
types of work by those starting in the eld as well as by experienced practitioners of the art.
The topics covered include short descriptions of (1) the properties of synchrotron
radiation, (2) a description of facilities used for its production, (3) collimated micro-
probes, (4) focused microprobes, (5) continuum and monoenergetic excitation, (6) de-
tection limits, (7) quantitation, (8) applications of SRIXE, (9) CMT, and (10) chemical
speciation using x-ray absorption near-edge structure (XANES) and extended x-ray
absorption ne structure (EXAFS). An eort has been made to cite a wide variety of
work from dierent laboratories to show the vital nature of the eld.
There are many review articles and books that cover all aspects of the production
and use of synchrotron radiation (Kim, 1986; Kunz, 1979; Margaritondo, 1988; Winick
and Doniach, 1980). The early article on SRIXE by Sparks (1980) is a useful source of
information on various aspects of the use of SRIXE as part of a high-resolution x-ray
microscope (XRM) system. Several more recent review articles have covered new devel-
opments (Chen et al., 1990; Jones and Gordon, 1989; Kno chel, 1990; Vis, 1990; Vis and
van Langevelde, 1991).
Microscopy using x-rays can be carried out in several ways. A large eort is
aimed at producing extremely high-resolution maps of the linear attenuation coecient
for low-energy x-rays in biological materials (Sayre et al., 1988). Another approach is
based on the detection of electrons emitted from the specimen (Ade et al., 1990).
Elemental detection can be accomplished by mapping above and below the absorption
edge for the element. Rarback et al. (1987) have shown that this may be a preferable
method for elements lighter than calcium because of the small values of the uores-
cence yield. This approach has been used by Kenney et al. (1985) to study the
calcium distribution in a bone specimen using the Ca L absorption edge for the image
formation.
Image formation using uorescent x-rays is advantageous for the high-Z elements in
terms of attaining the best possible values for minimum detection limits (DLs) combined
with the best possible spatial resolution. It is not possible to use x-ray detection in some
situations where the thickness of the specimen is much larger than the absorption depth of
the uorescent x-rays. In this case also, the use of the above- and below-edge imaging
using the techniques of computed microtomography is possible. In the discussion that
follows, the use of all these methods is disscussed although the major emphasis is placed
on SRIXE.
Images may also be formed using other types of information obtained through
probing the sample. X-ray diraction can be used to determine crystal structure. In-
formation on the chemical state of the elements and position in the lattice can be obtained
by use of XANES or EXAFS. These are, of course, methods widely applied with both
conventional and synchrotron x-ray sources. A merging of these methods with technol-
ogies for producing micrometer-sized beams is a natural direction for the development of
the instrumentation to follow. This is beginning to happen now, and the rate of devel-
opment is bound to increase in the future.
No matter what mode is used for image formation or to characterize a single
volume element in a specimen, the work is dominated by the fact that only limited
numbers of atoms are present to produce a signal. As an example, consider the number
of zinc atoms present in an organic material as a function of the specimen volume
probed for a constant weight fraction of one part per million (ppm). Values are shown
in Figure 1, and it can be seen that there are only 10
4
atoms present in a 1-mm
3
volume.
The detection of such a small number is a technical challenge no matter what mode of
detection is used.
II. PROPERTIES OF SYNCHROTRONRADIATION
It has been known for almost 100 years that the acceleration of a charged particle will
result in the radiation of electromagnetic energy. The development of the betatron and
synchrotron electron accelerators 50 years later led to the experimental observation of
radiation from electrons circulating in a closed orbit (Elder et al., 1947) and to naming it
specically synchrotron radiation after the accelerator used to produce it. The rst re-
cognition of the unique properties of the synchrotron radiation by Tombulian and
Harman (1956) then brought about an explosive development of activity in constructing
improved sources for production of the radiation and using the radiation in experimental
science.
The original synchrotrons were designed for use in nuclear physics research. Later,
facilities were designed to optimize the conditions for production of x-rays. The compo-
nents of the new facilities include a source of electrons or positrons and an accelerator to
produce high-energy beams. This might be done by the use of a linear accelerator to
produce energies of around 100 MeV. These beams are then injected into a synchrotron
and boosted to energies in the GeV range. Finally, the beam is stored in the same accel-
erator used to attain the nal energy or in a separate storage ring. An acceleration eld in
the ring is used to supply energy to the beam to compensate for the radiation energy loss.
Figure 1 The number of zinc atoms contained in a given volume element is plotted as a function
of volume. A constant zinc concentration of 1 ppm contained in an organic matrix with a density of
1 g=cm
3
is assumed. This shows that the detection of trace amounts of an element at a given
concentration level becomes increasingly difficult as the probe decreases. (From Jones KW, Pounds
JG. Biol Trace Element Res 12:3, 1987.)
The lifetime of the stored beam is many hours, so that, in practice, the synchrotron source
is almost starting to become similar to a standard x-ray tube in use.
The synchrotron-produced x-ray beams have unique properties that make them
desirable for use. They have a continuous energy distribution so that monoenergetic
beams can be produced over a wide range of energies. The photons are highly polarized in
the plane of the electron beam orbit, which is extremely important for background re-
duction in SRIXE-type experiments in particular. The x-rays are emitted in a continuous
band in the horizontal direction but are highly collimated in the vertical direction. It is
therefore possible to produce intense beams with little angular divergence. The source size
is small and, as a result, the production of intense beams of small area is feasible. The
synchrotron source is a pulsed source because of the nature of synchrotron-type accel-
erators. The x-rays are produced in narrow bursts, less than 1 ns in width, and have a time
between pulses of around 20 ns or more.
The main parameters of interest in dening the synchrotron source are as follows:
1. Magnitude of the stored electron=positron current. Typically, currents are in the
range from 100 to 1000 mA. The lifetimes of the stored beam are many hours.
The lifetimes for stored electrons at the National Synchrotron Light Source
(NSLS) at Brookhaven National Laboratory, (Upton, NY) have typical values
of around 24 h. At Laboratoire pour LUtilisation de Radiation Electromagne-
tique (LURE), Orsay, France, where positron beams are used, the lifetimes are
even longer because the positive beam does not trap positively charged heavy
ions produced from the residual gases in the vacuum chamber.
2. Assuming that the size and angular divergence of the electron beam are not
important, the source brightness is dened as [in units of photons=s=mr
2
=(0.1%
bandwidth)]:
d
2
I
dy dc
1:327 10
13
E
2
GeViAH
2
o
o
c

1
where E is the energy of the electron beam (in GeV), i the current (in A), H
2
(o=o
c
) is a function tabulated in Kim (1986), o is the photon angular frequency,
and o
c
is the critical frequency which splits the emitted power into halves and is
given by the expression 3g
3
c=2r, where g is the electron energy in units of the
electron rest mass, c is the velocity of light, and r is the radius of curvature of the
electron path. The angles y and c are the angles of emission in the plane of the
electron orbit and perpendicular to that plane, respectively.
3. The total photon emission is found by integrating over c and is given by [in units
of photons=s
1
=mr
1
=(0.1% bandwidth)]
dI
dy
2:457 10
13
EGeV iA G
1
o
o
c

2
For electron beams with nonzero emittance (nite area and angular divergence), it is
necessary to dene another quantity, the brilliance, which is the number of photons
emitted into angular intervals dy and dc at angles y and c from an innitesimal source
area (in units of photons=s
1
=mr
2
=mm
2
=(0.1% bandwidth)]. The values of brilliance
and brightness are important in evaluating the performance expected for focused and
collimated x-ray microscopes. Kim (1986) provides a detailed discussion of the emittance
eects, polarization, and performance of wiggler and undulator insertion devices.
Values attained for these quantities at the 2.5-GeV x-ray ring of the NSLS are shown
in Figures 24. Its x-ray beams are typical of those produced by second-generation syn-
chrotron storage rings. The ring energy is high enough to produce x-rays over an energy
range sucient to produce K x-rays from elements to about Z40 with good eciency
and L x-rays throughout the periodic table. Thus, it is highly suitable for use as the basis of
a system for x-ray microscopy-based SRIXE.
The brilliance obtained from two third-generation synchrotrons is shown in Figures 5
and 6 as a function of the photon energy for several types of devices. The brilliance
obtained from an undulator insertion device at the 7-GeV Argonne National Laboratory
Advanced Photon Source is shown in Figure 5. The brilliance for dierent bending
magnet, undulator, and wiggler devices at the 8-GeV Spring-8 facility in Japan is given in
Figure 6. It can be seen that the third-generation storage rings have gained approximately
three to four orders of magnitude in brilliance when compared to that found from bending
magnets at the NSLS. Similar gains are found for third-generation rings operating at lower
energies although the spectrum of x-rays is naturally aected by the energy of the stored
electron=positron beam. This increase translates to a gain in x-ray intensity that enables
new types of x-ray uorescence experiments.
The high degree of linear polarization of the x-rays from the synchrotron source is a
major factor in making the synchrotron XRM a sensitive instrument. The physics describing
the interaction of polarized x-rays with matter is therefore an important topic. Hanson (1990)
Figure 2 The brilliance of the NSLS x-ray ring is plotted as a function of the x-ray energy
produced. The brilliance is important in defining limitations on production of x-ray images using
focusing optics. (From Jones KW, et al. Ultramicroscopy 24:313, 1988.)
has carried out an extensive examination of the scattering problem and given methods for
assessing particular geometries used in the XRM. A second point is the continuous x-ray
energyspectrumextending fromenergies inthe infraredtohardx-rays withenergies of several
hundred kiloelectron volts. The tunable energy is important for many types of experiments.
III. DESCRIPTIONOF SYNCHROTRONFACILITIES
There are nowmany synchrotron facilities located around the world that are suitable for use
in various types of x-ray spectrometry measurement. They fall roughly into three classes.
First-generation synchrotrons were built primarily as high-energy physics machines
and were used secondarily for synchrotron radiation production. The Cornell High En-
ergy Synchrotron Source (CHESS) at Ithaca, NY is an example.
Second-generation synchrotrons were optimized as radiation sources, and as a result,
produce x-ray beams with superior brilliance and brightness characteristics. The two rings
of the Brookhaven NSLS fall in this category.
Finally, the third generation of synchrotrons is now being designed. They will be the
rst sources intended to incorporate insertion devices, wigglers, and undulators in the design
phase. In some cases, the ring energy is increased to give better performance with the in-
sertion devices. Synchrotrons designed with these features will begin operation in the latter
part of the 1990s. The European Synchrotron Radiation Facility (ESRF) at Grenoble,
Figure 3 The brightness [defined in Eq. (1)] of the NSLS x-ray ring as a function of the x-ray
energy produced. The brightness is of importance in defining the usefulness of x-ray beams produced
by use of a collimator. (From Jones KW, et al. Ultramicroscopy 24:313, 1988.)
France, the Super Photon Ring-9 GeV (SPring-8) in Kansai, Japan, and the Advanced
Photon Source (APS) at Argonne National Laboratory, Argonne, IL, illustrate this case.
A listing of a number of synchrotron laboratories producing high-energy x-ray
beams suitable for use in SRIXE is given in Tables 13 (Fuggle, 1990; Jackson, 1990;
Winick, 1989, 1990). The number of XRM beam lines is growing rapidly and their em-
ployment for research as a result is becoming widespread.
IV. APPARATUS FOR X-RAYMICROSCOPY
The apparatus that is used for x-ray microscopy measurements varies substantially from
laboratory to laboratory. A schematic diagram of the components of a very compre-
hensive system is shown in Figure 7. All the components are not necessarily used in a
specic instrument. The most important dierences between systems lies in the treatment
of the incident beam. The simplest approach is to use the white beam (full-energy
spectrum) and a collimator. The more complex systems use focusing mirrors to collect
more photons and demagnify the beam and monochromators to produce monoenergetic
beams. At present, the performance of the various systems is quite comparable in terms of
spatial resolution and detection limits (DLs). Thus, a versatile and exible approach to the
Figure 4 The x-ray flux produced by the NSLS x-ray ring is plotted as a function of the x-ray
energy produced. The values are given after integration over the vertical opening angle of the beam.
The definition of the flux is given in Eq. (2). (From Jones KW, et al. Ultramicroscopy 24:313, 1988.)
Figure 5 The brilliance obtained from an undulator insertion device at the 7-GeV Argonne
National Laboratory Advanced Photon Source. (From Advanced Photon Source Research,
ANL=APL=TB-31 1(1):5, 1998. Argonne National Laboratory, managed and operated by The
University of Chicago for the U.S. Department of Energy under Contract No. W-31-109-ENG-38.)
Figure6 The brilliance for different bending magnet, undulator, and wiggler devices at the 8-GeV
SPring-8 facility in Japan. (From Kitamura H. SPring-8 Annual Report 1994, JASRI, 1995, p 47.)
choice and design of the components is advisable. A number of the dierent instruments
are described briey in the following subsections.
A. Collimated X-Ray Microscopes
A highly eective XRM system can be made by simply collimating the white beam
(continuous energy) of x-rays produced by the synchrotron. This approach has been fol-
lowed mainly by groups at the Hamburg storage ring (Kno chel et al., 1983), HASYLAB,
and at the Brookhaven NSLS (Jones et al., 1988). The use of white radiation is feasible
because the high brightness gives a high ux of photons in a small area, and the high
polarization of the synchrotron beams minimizes scattering from the sample into the de-
tector. White radiation also makes possible ecient multielement detection over a very
broad range of atomic numbers.
The collimators for the instrument can be made from a set of four polished tantalum
strips. The strips can be spaced apart with thin plastic or metal foils to produce apertures
usable to a beam size of 1 mm. Alternatively, the slits can be attached to individual stepper
Table 2 Second-Generation Synchrotron Light Sources
a
Storage ring (Lab) Energy (GeV) Location URL
CAMD (LSU) 1.4 Baton Rouge, USA www.camd.lsu.edu
DELTA (DU) 1.5 Dortmund, Germany prian.physik.uni-dormund.de
NSLS x-ray (BNL) 2.5 Upton, USA www.nsls.bnl.gov
Photon Fac. (KEK) 2.5 Tsukuba, Japan www.kek.jp
Synch. Rad. Source (SRS) 2.0 Daresbury, UK www.dl.ac.uk
Note: Lists of synchrotron sites can be found from many of the home pages listed.
a
This is the rst generation of machines built to be dedicated synchrotron radiation facilities. The use of bending
magnet ports is emphasized although some straight sections have insertion devices (e.g., undulators and wigglers)
[see Winick (1989, 1990), Jackson (1990), Fuggle (1990)].
Table1 First-Generation Synchrotron Light Sources
a
Storage ring (Lab) Energy (GeV) Location URL
ADONE (LNF) 1.5 Frascati, Italy
DCI (LURE) 1.8 Orsay, France www.lure.u-psud.fr
VEPP-3 (INP) 2.2 Novosibirsk, USSR
BEPC (IHEP) 2.22.8 Beijing, China
SPEAR (SSRL) 3.03.5 Stanford, USA www-ssrl.slac.stanford.edu=
welcome.html
ELSA (Bonn Univ.) 3.5 Bonn, Germany www-elsa.physik.uni-bonn.de
DORIS II (HASYLAB) 3.55.5 Hamburg, Germany www-hasylab.desy.de
VEPP-4 (INP) 5.07.0 Novosibirsk, USSR
CESR (CHESS) 5.58.0 Ithaca, USA www.chess.cornell.edu
Acc. Ring (KEK) 6.08.0 Tsukuba, Japan www.kek.jp
Tristan (KEK) 2530 Tsubuka, Japan
Note: Lists of synchrotron sites can be found from many of the home pages listed.
a
Most of these early facilities were built to do research with the primary electron or positron beams. Synchrotron
radiation research was parasitic. Today, all have become at least partly dedicated as synchrotron light sources [see
Winick (1989, 1990), Jackson (1990), Fuggle (1990)].
motors for producing variable-sized beams of size greater than about 10 mm. The col-
limation approach is ultimately limited by beam-spreading related to nite source and
pinhole dimensions and to diraction.
The collimated XRM (CXRM) was rst operated at the now defunct Cambridge
Electron Accelerator by Horowitz and Howell (1972). They used a pinhole made by the
evaporation of a thick gold layer around a 2-mm quartz ber, followed by subsequent
etching away of the quartz. The x-ray energy was about 2.2 keV, and image contrast was
achieved using determination of the linear attenuation coecient. The specimen was
moved past the incident beam, and uorescent x-rays were detected with a proportional
counter. A spatial resolution of 2 mm was measured with this pioneering apparatus.
Later versions of the CXRM have been put into operation at Hamburg and
Brookhaven. Some of the details of the operations are given to illustrate some of the more
important operational details.
It is often best to maximize the photon ux on the sample by employing a white
beam of x-rays. The ux available at a point 9 m from a NSLS bending magnet source is
shown in Figure 8. The ux from this source, integrated over the entire energy spectrum, is
about 3610
8
photons=s=m
2
with a 100-mA stored electron current.
For best operation of the CXRM, care must be taken in shaping the incident x-ray
spectrum using lters. The inuence of the beam lters has been studied by the Hamburg
group (Kno chel et al., 1983). Their results are shown in Figure 9. By varying the eective
energy, it is possible to tailor the beam to give the best possible DL for a given atomic
number. Filters on the detector can be used in some cases to reduce the eect of a major
Table 3 Third-Generation Synchrotron Light Sources
a
Light source Energy (GeV) Location URL
ALS 1.01.9 Berkeley, USA www-als.lbl.gov
ASTRID 0.58 Aarhus, Denmark www.dfi.aau.dk
BSRF 1.41.55 Beijing, China solar.rtd.utk.edu=$china=ins=
IHEP=bsrf=bsrf.html
CLS 2.52.9 Saskatoon, Canada sal.usask.ca=cls=cls.html
SLS 2.1 Villigen, Switzerland www.psi.ch=sls
SRC 0.81.0 Stoughton, USA www.src.wisc.edu
SRRC 1.3 Hsinchu, ROC 210.65.15.200=en=index.html
INDUS II 1.4 Indore, India
MAX II 1.5 Lund, Sweden www.maxlab.ln.se
BESSY II 1.52.0 Berlin, Germany www.bessy.de
ELETTRA 1.52.0 Trieste, Italy www.elettra.trieste.it
LNLS 2.0 Campinas, Brazil www.lnls.br
PLS 2.0 Pohang, Korea
SIBERIA II 2.5 Moscow, USSR
ESRF 6.0 Grenoble, France www.esrf.fr
APS 7.0 Argonne, USA www.epics.aps.anl.gov
SPring-8 8.0 Kansai, Japan www.spring8.or.jp
Note: Lists of synchrotron sites can be found from many of the home pages listed above.
a
This is the newest generation of dedicated synchrotron radiation facilities. The use of insertion devices (e.g.,
undulators and wigglers) is emphasized, but bending-magnet ports will also be available [see Winick (1989, 1990),
Jackson (1990) Fuggle (1990)].
element. In experiments that examine the distribution of trace elements in bone, a lter of
polyimide can reduce the high rates caused by the calcium in the bone, but it will not have
a large eect on the x-rays from iron, copper, and zinc.
An equally critical task is the alignment of the energy-dispersive x-ray detector.
Kwiatek et al. (1990) have reported on this phase of the optimization procedure. The
importance of aligning the detector in the horizontal plane can be seen by reference to
Figure 10. In addition, the energy spectrum and degree of polarization change as a
function of the vertical distance from the plane of the electron orbit in the storage ring.
Figure 11 shows the relative photon ux for the two polarization states. Examination of
the curves shows that the alignment needs to be made to an accuracy of better than a few
hundred micrometers to get the best reduction of scattered background.
Results of the experimental background=peak ratio determination as a function of
vertical displacement are shown in Figure 12 for elements from calcium to zinc in a gelatin
matrix and for palladium in a pyrrhotite matrix. The dependence on scattering angle in the
Figure 7 A comprehensive synchrotron beam line designed for use as a x-ray microscope. Not all
the components would be utilized at a given time in practice. The rather varied uses of the system
require a flexible approach to the design of the equipment.
Figure 9 Values for DLs obtained for a white-light XRM are shown as a function of atomic
number. The change in the DLs as a function of filtering of the incident beam using aluminum filters
is an important feature of this type of arrangement. (From Kno chel et al., 1983.)
Figure 8 Energy distribution of photon flux produced by a bending magnet on the NSLS x-ray
ring at a electron current of 100 mA. (From Jones et al., 1990b.)
Figure 10 Dependence of incoherent scattering cross sections for x-rays polarized parallel and
perpendicular to the plane of the stored electron orbit on the scattering angle. Observation at a
scattering angle of 90
gives optimum signal-to-background conditions. (From Jones KW, et al.

Ultramicroscopy 24:313, 1988.)
Figure11 Polarization of NSLS x-ray beams is given as a function of distance from the plane of
the electron orbit for x-ray energies of 10, 20, and 30 keV. (From Hanson AL, et al. Nucl Instrum
Methods Phys Res B24=25:400, 1987.)
horizontal plane is shown in Figure 13. The details of the methods used to make the
alignments are given by Kwiatek et al. (1990).
The Brookhaven work has shown that it is possible to achieve spatial resolutions
below the 10-mm range using the CXRM. The spatial resolution of the instrument has
been demonstrated by scanning a thin-evaporated gold straight edge through the beam
and recording the intensity of the L x-rays as a function of distance. The resolution in
this case was 3.5 mm. Some control over the resolution for a given collimator is obtained by
inclining the collimator with respect to the incident beam.
The Brookhaven device is routinely used for trace element measurements with a spatial
resolution of less than 10 mm. The sensitivity and DLs obtained under these conditions have
been reported by Jones et al. (1990b) and their results are displayed in Figures 14 and 15.
Figure 12 The background-to-signal ratio is shown as a function displacement of the detector
normal to the plane of the orbit of the stored electrons. The alignment becomes increasingly critical
at the higher x-ray energies. The curves shown (a) were obtained for Ca, Fe, Zn, Br and, Sr contained
in a gelatin matrix. The curve shown in (b) was obtained for Pd contained in a pyrrhotite matrix
(From Kwiatek et al., 1990.)
It is interesting to realize that an absolute determination of the elemental con-
centrations can be made based either on the theoretical estimates of photon ux or from a
direct determination using an ion chamber. Kwiatek et al. (1990) point out that the ex-
pected counting rate for a given element is given by
YE
Z
N
A
E
k
dO
4p
exp mE
Z
w
d
Z
1
E
ab
NE exp fmEws
fl
EgdE 3
where YE
Z
is the count rate for an element with a characteristic x-ray energy E
Z
; N
A
is
the number of target atoms within a beam spot, e
k
is the detector eciency, dO=4p is the
solid angle, NE is the photon ux [number of photons=(s mm
2
0.1-keV bandwidth)], mE
is the linear attenuation coecient for Al and mE
Z
that for polyimide, w is the Al
thickness, w
d
is the polyimide thickness, s
fl
E is the uorescent cross section, E
ab
is the
energy of the absorption edge, and E is the photon beam energy.
Results of a comparison of measured and calculated rates for a section of gelatin
with known amounts of iron and zinc are shown in Table 4 for three dierent incident
beam spectra. The results of the comparison are excellent for iron, less so for zinc. It is
clear, however, that it is feasible to make determinations of the abundances of the elements
without reference to standards.
B. Focused X-Ray Microscopes
Focused x-ray microprobes (FXRM) have been the subject of great interest over the years.
The rst version appears to have been developed by Sparks (1980) and was used at
Figure 13 The background-to-signal ratio is plotted as a function of scattering angle in the
horizontal plane. The curve was obtained by displacement of the detector and the equivalent angular
range spanned was roughly 4
. (From Kwiaek et al., 1990.)

Figure14 The sensitivity of the BNL collimated XRM is given as a function of atomic number for
K and L x-ray detection. Values are given for a beam size of 8 mm68 mm. A 3-mm-diameter Si(Li)
x-ray detector placed 40 mm from the beam was used as a detector. The curves were calculated from
basic principles. (From Jones et al., 1990b.)
Figure15 DLs measured for the BNL collimated XRM under the conditions described in the text
and for Fig. 14. (From Jones et al., 1990b.)
SPEAR. In an interesting application, it was used in a search for superheavy elements
(Sparks et al., 1978).
A variety of dierent schemes have been used in the intervening years. A summary of
recent approaches at dierent laboratories is given here to illustrate the directions now
being taken by this approach to the production of intense x-ray beams. Early estimates of
DLs for specic congurations have been given by Gordon (1982), Gordon and Jones
(1985), and Grodzins (1983).
1. LURE (1987)
The equipment used for SRIXE at LURE has been described by Chevallier et al. (1987)
and Brissaud et al. (1989). The white beam from the storage ring passes through a
beryllium window and is incident on a curved crystal of mosaic pyrolytic graphite. The
size of the incident beam is 2 cm, 1 cm before the monochromator, which produces a
nal focused beam of 14-keV photons with a size of 1 mm61 mm. The uorescent x-rays
are detected with a Si(Li) detector collimated using a 2.8-mm aperture. The DLs
achieved are around 1 ppm for thick geological specimens and much less for organic
matrices. The probe has only been used for measurements, which do not require high
spatial resolution.
2. Photon Factory (1990)
The group working at the Photon Factory in Japan has made seminal contributions to the
development of SRIXE and of SXRM. An early instrument used Wolter-type focusing
optics and achieved spatial resolutions of around 10 mm630 mm (Hayakawa et al., 1989).
A later version was developed to provide higher photon ux and give improved values for
the DLs (Hayakawa et al., 1990).
The design chosen was similar to one described by Jones et al. (1984), which has been
partially implemented at the NSLS. A schematic diagram of the Photon Factory appa-
ratus is shown in Figure 16. The platinum-coated ellipsoidal mirror was designed to
produce a demagnication of the beam of 1:9.5. The mirror accepted 0.6 mrad of beam in
the horizontal direction and 0.05 mrad in the vertical direction and was run at a grazing
angle of 7 mrad. A gain in intensity of a factor of 170 was found for a monoenergetic beam
of 8 keV. The system produced a photon ux of about 1.4 10
3
photons=(s mm
2
mA). The
ability to locate the system in close proximity to the electron beam is a key factor in
maximizing the photon ux.
Table 4 Experimental and Predicted Count Rates for Different Beam Filters
a
Beam lter
thickness (mm A)
Fe (cps) Zn (cps)
M
b
T
c
M T
50 86.5 75.6 77.7 53.7
100 54.8 48.5 59.1 43.2
200 24.7 23.6 37.0 28.8
a
Experimental errors at 1015%.
b
Measured values.
c
Theoretical values.
3. SRS (1990)
The instrumentation at the Daresbury SRS has been developed by a group of collaborators
from the Free University in Amsterdam and Warwick University at Coventry. The latest
device uses a silicon crystals as both a monochromator and focusing device (Van Langevelde
et al., 1990a, 1990b, 1990c). A diagram of the instrument is shown in Figure 17. The crystal
Figure17 Schematic diagram of the focusing XRM in operation at the Daresbury XRM. (From
Van Langevelde et al., 1990c.)
Figure 16 Schematic diagram of the focussing XRM used at the Photon Factory. (From
Hayakawa et al., 1990.)
is a 100-mm-thick silicon crystal bent with a radius of 100 mm in the sagittal plane and
5740 mm in the meridional plane. The beam is focused to a spot size of about 15 mm620 mm
at an energy of 15 keV. The demagnication is 1000 in the horizontal plane and 15 in the
horizontal plane, with a photon ux increase of greater than 10
4
. A ux of 15-keV photons
at the specimen of 10
4
photons=(S mm
2
mA) is obtained. This is an impressive result when it
is remembered that the device is located about 80 m from the electron beam.
4. Novosibirsk (1989)
Baryshev et al. (1989) working at the Novosibirsk VEPP-3 synchrotron have used both
monoenergetic and white beams of x-rays. A single-crystal pyrolytic graphite mono-
chromator was used to produce monoenergetic beams with energies between 8 and 35 keV.
The spatial resolution was 60 mm for the monoenergetic beam and 30 mm for the white
beam. The DL for the monoenergetic beam was 10 ppm for elements from iron to
strontium for a 13-s run.
5. LBL (1988)
The group at the Lawrence Berkeley Laboratory has developed a focusing system based
on the KirkpatrickBaez geometry (Giauque et al., 1988; Kirkpatrick and Baez, 1948;
Thompson et al., 1987; Thompson et al., 1988; Underwood et al., 1988, Wu et al., 1990).
A schematic diagram of their system is shown in Figure 18. The system uses a parallel
beam of photons to produce an image which is demagnied by about a factor of 100 to
produce nal images of a few micrometers. The use of multilayer coatings of tungsten
carbide on the mirrors gives a quasimonoenergetic beam with a bandwidth of about 10%
at 10 keV and a high throughput. Much of the experimental work has been carried out at
the NSLS in collaboration with the BNL group. It is thus possible to make comparisons in
performance between the CXRM and FXRM on the same storage ring.
Figure18 Schematic diagram of the focusing XRM of the Berkeley group used at the BNL X26
beam line. (From Thompson et al., 1988.)
The LBL FXRM has produced photon uxes of about 3610
5
photons=(s mm
2
mA)
at 10 keV energy. It is important to note that the use of a nal collimator is not required in
this apparatus. Improvements in the device will make it possible to reach higher x-ray
energies and provide easy tunability of the x-ray beam energy.
6. LBL at the Advanced Photon Source (ALS) (1988)
A much more elaborate imaging capability has now been developed by LBL at the ALS
(Warwick et al., 1998). A number of dierent beam lines can be used to do experiments
with energies ranging from 100 eV to 15 keV. The spatial resolutions vary from 0.1 mm to
about 2 mm, depending on the beam energy and imaging mechanism. Some of the tech-
niques used are Fourier transform infrared spectroscopy (FTIR), scanning transmission
x-ray microscopy, photoemission electron microscopy, x-ray microdiraction, and micro
x-ray uorescence. A schematic diagram of the apparatus developed to cover the x-ray
energy range from 2 to 15 keV is shown in Figure 19. The chosen hardware conguration
uses KirkpatrickBaez focusing mirrors, as did the earlier system described. Beam sizes as
small as 0.8 mm have been achieved with an experimental setup.
7. Cornell High Energy Synchrotron Source (CHESS)
Focusing of both monoenergetic and white x-ray beams can be accomplished by total
external reection of the x-rays in tapered glass capillaries (Bilderback et al., 1994a; 1994b;
1994c; 1995a; 1995b; Homan et al., 1994; Thiel et al., 1992). The Cornell group has been
one of the leading proponents of this approach over the past 10 years. It has also been
actively developed at other laboratories and installed on beam lines at several dierent
synchrotron facilities. One such installation at the ESRF is described in the following
subsection. The experiments at CHESS have shown that it is possible to produce beams
with a diameter as small as 0.05 mm (Homan et al., 1994). A scan across an edge de-
monstrating this spatial resolution is shown in Figure 20. The x-ray ux is increased by
factors of up to 1000. It seems fair to say that this experiment marks a major step forward
in x-ray microscopy techniques. The initial experiments showed that the capillary system
could be used for Laue diraction measurements and for x-ray radiography at this size
scale. Preliminary work done in 1994 at the BNL X26A beam line by Sutton, Homan,
Figure 19 Schematic layout of KB mirrors and a four-crystal channel-cut monochromator for
micrometer precision micro-x-ray absorption spectrometry and micro-diffraction developed by
Padmore et al. at the ALS. (From Warwick et al., 1998.)
Bajt, Jones, and Bilderback showed that SRIXE experiments can be successfully per-
formed with the capillaries. SRIXE experiments are made dicult by the large divergence
of the x-ray beam after it emerges from the capillary tip. In order to achieve the best
spatial resolution, it is necessary to place the sample within a few millimeters of
the capillary and at the same time arrange optimal detection geometry for the x-rays from
the sample at a 90
angle to the incident beam.

8. European Synchrotron Radiation Facility (1994)
The microfocus beam line on ID 13-1 developed by Riekel (personal communication,
1995) and collaborators is intended mainly for microdiraction experiments. It has also
been used for SRIXE and uorescent computed microtomography experiments. The beam
line uses an undulator x-ray source and is designed for operation between 6 and 16 keV.
The optics use either silicon or multilayer monochromators and an ellipsoidal mirror to
produce a focal spot in the experimental hutch. Collimation can be used to produce a 7-mm
full width at half-maximum focal spot with a beam ux of 2610
11
photons=s at 13 keV.
The silicon channel-cut monochromator can be combined with capillary focusing optics to
reduce the spot size to about 262 mm
2
. The photon ux is also about 2610
11
photons=s in
this conguration. A schematic diagram of the beam line optics is shown in Figure 21. The
photon ux that can be used for SRIXE experiments is around four orders of magnitude
higher than the values found for the NSLS X26A beam line. The expected detection limits
at the ESRF are then about two orders of magnitude lower. The high ux at the ESRF has
made it possible to achieve detection limits around 100 ag for transition elements
(K. Janssens, personal communication, 1998).
9. Advanced Photon Source (1998)
The University of Chicago Center for Advanced Radiation Sources is operating several
beam lines at the APS with capabilities for SRIXE, computed microtomography, EXAFS,
Figure 20 The experiments at CHESS have shown that it is possible to produce beams with a
diameter as small as 0.05 mm. A scan across an edge demonstrating this spatial resolution is shown.
(From Hoffman et al., 1994.)
XANES, and high-pressure experiments. The SRIXE apparatus is located on an un-
dulator beam line and uses cryogenically cooled Si monochromators to cover photon
energy ranges from 4.5 to 21 keV and 15 to 80 keV. The monochromator design and ar-
rangement is such that both can be used simultaneously. Focusing of both white and
monoenergetic beams is done with two 1-m-long silicon KirkpatrickBaez-type mirrors
that reduce the beam size by factors ranging from 3 to 10. Experiments on this beam line
will be microprobe experiments to study various parameters of geological and environ-
mental samples including compositions of uid inclusions and trace element partitioning.
The experimental techniques include SRIXE, EXAFS=XANES, and computed micro-
tomography.
10. Summary BeamLine Design Comments
Beam lines and experimental apparatus used for SRIXE and related experiments during
the past 25 years have been discussed here. It is clear that very major developments have
taken place in the experimental capabilities during that time. The obvious foundation for
the developments has been the rapid improvements in the synchrotron x-ray source
through the introduction of the wiggler and undulator insertion devices. However, the
parallel improvement in x-ray optics for focusing these beams and in x-ray detectors has
been necessary to make possible the most eective use of these beams for experiments.
Indeed, future progress in the latter elds may be the most important factor for the actual
application of these techniques in experiments.
C. Experiments at a Distance
The eects of the remarkable increase in computer communications through the Internet
and World Wide Web are visible everywhere. In the past few years, there has been a
development of interest in making use of these technologies to help make facilities useful
to researchers at remote locations. One example has been the DOE 2000 initiative of the
U.S. Department of Energy (US Department of Energy, 1997). There are two components
of this initiative that are related to use of synchrotron beam lines. First, there is the
Figure 21 ESRF schematic diagram of the beam line optics. (From C. Riekel, private
communication, 1995.)
concept of national collaboratories. These are laboratories without walls that unite ex-
pertise, instruments, and computers, enabling scientists to carry out cooperative research
independent of geography. The second is to set up pilot projects that are virtual la-
boratories that give scientists the technology to collectively observe and attack problems
using combinations of ideas, methodologies, and instrumentation that do not exist at any
single location.
Examples of this idea exist for several types of instrumentation. An example of the
application to a synchrotron beam line is that of the Spectro-Microscopy Collaboratory
at the Advanced Light Source: A Distributed Collaboratory Testbed (Agarwal et al.,
1997). This prototype of a collaboratory is supposed to enable operation of equipment on
an undulator beam line at the ALS from the University of WisconsinMilwaukee. Some of
the topics of concern for the collaboratory are security mechanisms, data dissemination,
remote monitoring and control, safety mechanisms for beam line operation, resource
arbitration to decide location of control, video conferencing and remote viewing, network
needs, and shared electronic notebooks for data handling. Another example involves the
University of Florida and the APS (CAT Communicator, 1998). This project is supposed
to allow remote operation of a materials research beam line. The computer components
needed are similar to those listed for the LBLWisconsin demonstration.
V. CONTINUUMANDMONOCHROMATICEXCITATION
Successful XRMs have been put into operation using both continuum and monoenergetic
synchrotron-produced x-rays. The continuum radiation is extremely convenient to use
because it is easy to construct a CXRM with a minimum of equipment and achieve ex-
cellent performance. Further, the broad-band excitation means that measurements can be
made for essentially all elements in the periodic table in a single exposure. Monoenergetic
radiation can be used at an energy optimized for production of the characteristic x-rays of
a given element, thus reducing radiation damage in organic materials. Counting-rate
limitations in energy-dispersive detectors are reduced because of the elimination of scat-
tered x-ray events. The energy can be tuned to eliminate interferences (e.g., leadarsenic)
and to eliminate excitation of elements with Z higher than that of the element of interest.
Maps can also be constructed by subtraction of images obtained above and below ab-
sorption edges.
Successful XRMs have also been produced in collimated and focused modes em-
ploying either continuum or monoenergetic radiation. The brute-force-type collimated
continuum radiation microprobe employed at Brookhaven and Hamburg has been
comparable to the other types of probe in terms of spatial resolution and DL. The per-
formance of the Brookhaven instrument has been compared with the performance of the
LBL KirkpatrickBaez XRM operated on the same NSLS beam line (Giauque et al.,
1988). A comparison of results obtained with the CXRM positioned at 10 m from the
source with the FXRM at 20 m from the source is given by Rivers et al. (1992). Figure 22
shows the results of the comparison. The DL obtained with the FXRM is somewhat better
than for the CXRM, but the wider energy range of the CXRM is a substantial advantage
in some cases. The quality of the KirkpatrickBaez optics makes it feasible to dispense
with the use of a collimator placed close to the specimen, which is an advantage in the
design of the experiments in some cases.
For ultimate performance in terms of the spatial resolution, FXRM might be the
best choice because the construction of good collimators on the 1-mm
2
size or smaller scale
is dicult. However, it is feasible to fabricate capillaries that act essentially as a collimator.
In that case, the beam divergence is reduced and the capillary can produce a small beam
without the need to place the sample close to its end.
The challenge is thus to the following:
1. To obtain better optics to improve the spatial resolution
2. To improve the eciency of the optics to get higher photon uxes
These goals can be addressed most eectively by use of focusing optics. An alter-
native to the capillary approach has been demonstrated by Padmore et al. (1997), who
used an elliptical focusing mirror and KirkpatrickBaez mirrors to obtain a white beam
with a size of 0.8 mm. SRIXE systems with submicrometer spatial resolution are not now in
use on a routine basis. However, it appears that the combination of improving x-ray optics
and the high-ux x-ray beams produced by third-generation synchrotron undulators will
bring this advance about in the next few years.
VI. QUANTITATION
Methods for making quantitative elemental determinations using x-ray uorescence have
been developed over many years. These approaches are discussed for conventional x-ray
sources in Chapter 5 and 6. Some of the approaches used at synchrotron sources are given
here to show how the methods developed for use with conventional tubes have been used
with the new radiation source.
Figure 22 Sensitivity of the BNL collimated white-light XRM compared with the sensitivity
obtained with the Berkeley focused XRM. (From Rivers ML, et al., 1992.)
Giauque et al. (1986) measured several U.S. National Bureau of Standards (NBS),
now National Institute of Standards and Technology (NIST), and the Japan National
Institute of Environmental Science (NIES) standard reference materials (SRM) at the 54-
pole wiggler beam line at the Stanford Synchrotron Radiation Laboratory. They referred
their measurements to a copper standard prepared by evaporation where the weight was
determined from gravimetric measurements. Multielement standards were prepared by
dissolving known weights of an element in an acidic solution. Monoenergetic radiation
was used for the work at energies of 10 and 18 keV. The beam size was dened by an
aperture 3 mm in size. The dierences in sample mass were accounted for by normalizing
to the intensity of the scattered radiation (Giauque et al., 1986). The results obtained for
three NBS materials are shown in Table 5.
The work of Giauque et al. (1986) addressed quantitation in thin biological speci-
mens where matrix eects were negligible and where the Compton scattering could be used
for normalization of masses. It is necessary to extend this approach if thick specimens are
to be investigated. There are many geological experiments where this situation holds.
Methods for quantitation have been discussed by Brissaud et al. (1989) and by Lu et al.
(1989). Corrections are made for attenuation of incoming and uorescent x-rays by the
sample matrix and by any lters employed as well as for secondary uorescence. The
composition of the major elements is generally known for geological materials; hence,
concentrations can be referred to that of one of the major elements.
Brissaud et al. (1989) compared the SRIXE results with several standards. The re-
sults are shown in Table 6. The table gives the recommended concentration and the
SRIXE value. It can be seen that agreement is quite good. In this case, as noted earlier, a
comparatively large 1-mm beam was used. Lu et al. (1989) used a microprobe with a beam
size of 30 mm660 mm to analyze dierent specimens of feldspars. They compared their
SRIXE results with values obtained using an electron probe and atomic absorption
spectroscopy. The agreement with the electron probe was good, but the atomic absorption
values tended to be systematically lower than the SRIXE values. Results for the com-
parison with the electron probe are shown for iron and strontium in Figure 23.
For thin biological specimens, concentrations can be established by use of a sensi-
tivity curve such as the one displayed in Figure 14. Corrections for dierences in thickness
can be made by normalizing to the intensity of the scattered incoherent peak if a mono-
energetic beam is used or to the continuum comprising both incoherent and coherent
scattering if white beam is used (Giauque et al., 1979).
Quantitation of SRIXE draws on many years of experience gained using tube-excited
x-ray uorescence. The main dierence between the x-ray sources occurs when SRIXE is
used with microbeams with dimensions on the micrometer scale. In this case, strict at-
tention must be given to the uniformity of the standards used and to the experience gained
in calibration of the electron microprobe (Hren et al., 1979) and proton microprobe
(Johansson and Campbell, 1988).
VII. SENSITIVITIES ANDMINIMUMDETECTIONLIMITS
The related questions of sensitivites and DLs have been addressed by calculations based
on the known physical parameters of the XRM systems and by empirical determinations.
The detailed understanding of the x-ray production process using synchrotron radiation
is helpful in assessing the sensitivities and DLs that can be achieved in SXRM. The
results cited for the sensitivities and DLs should be taken as representative of the current
Table 5 Results Determined for Three NBS Standard References Materials (mg=g)
Nonfat milk powder SRM 1549 disk
a
51 mg=cm
2
wt
b
37 mg wt
c
500 mg
Wheat our SRM 1567 disk
a
60 mg=cm
2
wt
b
43 mg wt
c
400 mg
Rice our SRM 1568 disk
a
60 mg=cm
2
wt
b
43 mg wt
c
400 mg
Element NBS XRF NBS XRF NBS XRF
K 16,900 3,000 17,800 2,000 1,360 40 1,220 130 1,120 20 1,360 160
Ca 13,000 500 12,000 800 190 10 174 10 140 20 158 14
Cr 0.0026 0.0007 <0.6 <0.3 <0.4
Mn 0.26 0.06 0.33 0.12 8.5 0.5 8.2 1.8 20.1 0.4 22.1 2.8
Fe (2.1) 2.30 0.16 18.3 1.0 17.1 4.8 8.7 0.6 9.1 1.2
Ni 0.24 0.06 (0.18) 0.11 0.06 (0.16) 0.18 0.06
Cu 0.7 0.1 0.65 0.04 2.0 0.3 1.88 0.12 2.2 0.3 2.21 0.22
Zn 46.1 2.2 46.9 0.9 10.6 1.0 10.3 0.4 19.4 1.0 21.9 1.8
As (0.0019) <0.05 (0.006) <0.03 0.41 0.05 0.42 0.09
Se 0.11 0.01 0.09 0.04 1.1 0.2 0.92 0.06 0.4 0.1 0.38 0.04
Br (12) 12.1 0.2 (9) 8.5 1.4 (1) 1.19 0.17
Rb (11) 13.1 0.2 (1) 0.94 0.06 (7) 8.4 0.9
Sr 3.69 0.10 0.82 0.04 0.19 0.04
Hg 0.0008 0.0002 <0.1 0.001 0.0008 <0.06 0.0060 0.0007 <0.08
Pb 0.019 0.003 <0.1 0.020 0.010 <0.1 0.045 0.010 0.10 0.09
a
Mass thickness of disks.
b
Weight of area scanned.
c
Recommended sample weight.
Source: From Giauque et al., 1986.
situation. The actual values depend on the particular experimental conditions, syn-
chrotron ring currents, spatial resolutions, and so forth so that exact comparisons are not
terribly meaningful.
Sparks (1980), Gordon (1982), Gordon and Jones (1985), and Grodzins (1983) have
presented calculations of the minimum detection limits to be expected using the second-
generation synchrotron radiation sources such as the NSLS to produce x-ray microbeams.
Many experimental determinations have been made for the two quantities. The results
obtained by dierent groups using dierent types of XRMs are given here.
Figures 14 and 15 show the values obtained by Jones et al. (1990b) using the colli-
mated microprobe at the NSLS. Their values are relevant to thin specimens with an or-
ganic matrix. Values for the calculated DLs extrapolated from the work of Gordon and
Jones (1985) are included in Figure 15. It can be seen that the experimental values are in
the same range as the calculations although the experimental system was not the same as
the one considered theoretically. The sensitivities that are shown in Figure 14 indicate the
agreement between predicted (solid curve) and measured (data points) counting rates. The
curves were calculated from knowledge of the experimental arrangement, synchrotron
energy spectrum, and specimen parameters. The experimental points show the measured
values assuming the same specimen parameters.
Table 6 16.6- and 21.7-keV SRXRF Analysis of Three International Geostandards
a
GSN BEN MICA-Fer
SRIXE SRIXE SRIXE
Element GST 16.6 21.7 GST 16.6 21.7 GST 16.6 21.7
K, % 3.84 3.54 3.34 1.15 1.05 0.86 7.26 6.10 5.89
Ca, % 1.78 1.68 1.66 9.85 8.98 8.74 0.31 0.15 0.07
Ti, % 0.41 0.41 0.38 1.57 1.54 1.49 1.50 1.35 1.47
V 65 125 188 235 185 360 135 42 257
Cr 55 45 117 360 346 407 90 125 134
Mn 433 479 551 1540 1662 1679 2695 3006 3200
Fe, % 2.63 3.13 3.12 8.99 9.66 9.20 17.96 18.95 19.15
Ni 34 36 35 267 320 278 35 39
Cu 20 16 25 72 62 85 4 14
Zn 48 60 66 120 117 129 1300 1320 1501
Ga 22 21 27 17 10 21 95 79 118
Rb 185 115 189 47 27 61 2200 1013 2696
Sr 570 469 905 1370 1550 1759 5 1 5
Y 19 22 30 34 25 50
Zr 235 296 265 343 800 1058
Nb 23 32 100 136 270 375
Ba 1400 1103
W 470 500 610 30 30
Pb 53 51 82 4 2 5 13 23 17
Th 44 11 13 11 2 3 150 51 50
U 8 4 2.4 2 60 33
a
GST are the admitted values. Units are in ppm or %. The abbreviations, GSN, BEN, MICA-Fer are the names
of standards as given in Gavindaraju K. Geostandards Newslett, 3:3, 1979; 4:49, 1980, 8:173, 1984.
Source: From Brissaud et al., 1989.
Figure 23 Comparison of concentrations for Sr and Fe in feldspar obtained using the NSLS
XRM with those obtained using an electron microprobe. The solid lines show the values expected for
exact agreement between the two methods. The good agreement validates the use of the XRM
method for geological analyses. (From Lu et al., 1989.)
Figure 24 shows the results obtained for the DLs by Giauque et al. (1988) using the
KirkpatrickBaez XRM at the NSLS. The sensitivity curve has been previously discussed
in comparing sensitivities for the collimated and focused instruments (see Fig. 22). Jones
et al. (1988) compared the DL values for the collimated-white-beam and monoenergetic-
focused-beam approaches and showed that the DL values were very similar. Ketelsen et al.
(1986) have also compared DL values for white beams and monoenergetic beams. The
results are shown in Figure 25 and also demonstrate that the two approaches give com-
parable results. The absolute values of the two experiments cannot be directly compared
because of the beam size and ring operating conditions.
Figure24 Relative sensitivity for determination of elements from K to Zn obtained using the LBL
KirkpatrickBaez XRM at the NSLS X26 beam line. NIST (NBS) thin glass Standard Reference
Materials 1832 and 1833 were used. (From Giauque et al., 1988.)
Few experiments appear to have been devoted to measuring detection limits at the
third-generation sources. Results from the ESRF have been discussed in comparison to the
values found at the NSLS in the survey of beam lines given in Sec. IV.B. Improvements in
spatial resolution and=or detection limits can be generally assumed. These improvements
should be by about a factor of 100 when comparing the use of undulator beam lines at the
new facilities with their bending magnet performance.
VIII. BEAM-INDUCEDDAMAGE
Passage of a photon beam through a specimen results in energy deposition through the
photoelectric eect and Compton-scattering processes. This energy deposition results in a
breaking of molecular bonds as the secondary electrons produced lose their energy by
further ionization or scattering processes with other atoms. The eects have been ex-
amined in great detail for electron beams used in electron microscopy. Much less has been
done for the XRM. This is not surprising because the eld is much younger and less ex-
tensively developed than is the eld of electron microscopy. Another important reason is
that the photon beam uences employed thus far have been substantially smaller than
those employed in the electron microscope, and as a result, the magnitude of beam-
induced damage has not been so important.
Biological and other organic materials are generally more susceptible to beam-
induced damage than are other materials. For this reason, the discussion is limited to these
materials. In the future, when more intense synchrotron x-ray sources are available, it will
be necessary to expand the list of materials considered.
Figure 25 Detection limits observed for aerosol samples using Hamburg synchrotron with a
70-mA stored beam of 3.7-GeV electrons for 300 s. The open triangles were obtained with a white
beam filtered with 8 mm of Al, filled circles for a 31-keV monoenergetic beam, and open circles for a
12.5-keV monoenergetic beam. (From Ketelsen et al., 1986.)
A qualitative calculation can also be done to illustrate the energy deposition for
photon beams of various energies. Assume that the photon ux used for a typical uor-
escence experiment is 10
6
photons=(s mm
2
). Typical run times are 10 min or less. The
maximum photon uence for current XRM instruments is thus about 6610
8
pho-
tons=mm
2
. It is interesting to note that these uences are now starting to approach
the range of the uences found in use of the electron microprobe. In order to estimate
the energy deposition, it is assumed that attenuation coecients can be represented by the
photoelectric process attenuation coecient only and that all of the energy of the pho-
toelectrons is absorbed in the volume considered. The Compton-scattering process is re-
latively small and can be neglected in a qualitative estimate of the dose. The results of the
calculation are shown for photon beams with energies less than 20 keV.
The x-ray dose needed to kill living biological systems has been examined in detail over
the years (Kirz and Sayre, 1980; Sayre et al., 1977, 1978; Slatkin et al., 1984; Themner et al.,
1990). Adose whichexceeds 1Gy is likely tocause serious damage toa biological cell or system.
Thus, there are limitations to the use of x-ray beams for the examination of living
systems, as there are, of course, for all other beams. The limitations depend on the ab-
sorbed dose. One way that this can be done is by measuring the linear attenuation coef-
cients in CMT or in projection-radiography-type experiments. Spanne (1989) has
calculated the dose given to an object in obtaining an image with a signal-to-noise ratio of
5 for a water phantom with a contrasting detail with a diameter 0.005 of the phantom
diameter. The results of Spanne for objects with dierent diameters and compositions are
shown in Figure 26a and 26b. It can be seen that the dose is strongly energy dependent and
Figure26 (a) Absorbed dose at the center of a circular water phantom for detection of an element
of fat with a signal-to-noise ratio of 5 as a function of photon energy. The cylinder diameters are
shown in the figure. (b) Absorbed dose at the center of 1-mm-diameter water phantoms for detection
of elements of fat, air and calcium with a signal-to-noise ratio of 5. The element diameter is 0.005 of
the phantom diameter or 5 mm. (From Spanne, 1989.)
for relatively small objects (1 mm), the observed dose at the optimum energy is about
10
2
Gy. Examination of living systems using CMT with resolution on a level of 510 mm
thus may not be practicable. However, relaxation of the resolution criterion would reduce
the dose at a point where in vivo examination of living systems is feasible. It can also be
seen from Figure 26 that the optimum energy for examining very thin specimens (cells)
becomes very low. This represents a separate eld of research and is not considered here.
The use of projection radiography methods should also be useful. The dose is much less
because fewer photons are needed to form an image. In this case, the examination of living
systems will be easier.
If x-ray beams are used to make uorescence measurements on nonliving systems, a
loss of mass and possibly of trace elements can occur. Slaktin et al. (1984) investigated
changes in the morphology of human leukocytes and showed that severe damage resulted
for uences of 15-keV photons of about 10
17
to 10
19
photons=cm
2
. Figure 27 shows a
photomicrograph of the leukocytes after bombardment by uences from 0.4610
19
to
2.4610
9
photons=cm
2
. Damage to thin sections of the kidney (10 mm) was much less. Mass
loss in other types of organic materials was measured by Themner et al. (1990). They
determined mass loss by measuring the change in scattered radiation counting rate as a
function of total dose. The results that they obtained for irradiation of a skin sample is
shown in Figure 28. It can be seen that changes can be observed at dose values comparable
to those used in many uorescence-type experiments. Mass loss, therefore, should be
carefully measured if the scattered radiation is used as measure of the specimen areal
density for quantitation purposes.
The eects discussed can lead to loss of trace elements and to errors in the assign-
ment of concentrations, as is well known from the case of electron or proton microprobes.
Just as in those cases, measurements need to be made of the yield of characteristic x-rays as
a function of photon uence for uorescence measurements. One such examination shows
the yield of chromium x-rays observed in the bombardment of a section of rat kidney
which was investigated in a study of the toxic eects of chromium. It can be seen that there
are no indications of loss of the chromium under the conditions used.
Diraction experiments are possibly one type of experiment that will be very sen-
sitive to radiation damage eects. Protein crystallography experiments at the NSLS (Sweet
et al., 1995) showed that focused bending magnet radiation from the NSLS was sucient
to render samples useless in a short period of time. Diraction of 13-keV x-rays by thin
sections of polyethylene was studied at the ESRF microfocus beam line. In this case, the
diraction patterns were essentially destroyed in 3060 s (Jones et al., personal commu-
nication, 1995).
In summary, although beam-induced damage can be observed, it does not seem to
have been a problem in experiments conducted to date for experiments that are not sen-
sitive to crystal structure. However, because much higher uences are to be expected as
focusing methods are improved and as the synchrotron source itself becomes more
powerful, the beam damage eects will become of more central importance. Further
studies of these eects should be conducted.
IX. APPLICATIONS OF SRIXE
There are now examples of the uses of the XRM in many dierent elds. A brief description
of the diverse applications is given here to illustrate the rapid development of the eld and to
give an idea of the ways the XRM may be used in the future. The examples presented cover
Figure 27 Morphology of red blood cells is shown as a function of the fluence of incident 15-keV
photons. The fluences for the different exposures are as follows: 0, 0.4610
19
, 1.1610
19
, 1.6610
19
,
2.0610
19
and 2.4610
19
photons=cm
2
for frames (a)(f), respectively. (From Slatkin et al., 1984.)
mainly activities during the past 10 years. The total number of experiments performed
during this time is very large. The intent is to give an example of work covering a variety of
topics. There is no intent to give an encyclopedic review of all applications.
A. Archaeology
Brissaud et al. (1989) made low-resolution measurements on a number of dierent ma-
terials. One case involved examination of three Gallic coins using synchrotron radiation
and a comparison with the results obtained using proton-induced x-ray emission and
neutron-activation analysis. The x-ray and proton beams probe material close to the
surface of the coin, whereas the activation approach gives the bulk concentration. The
results given in Figure 29 show dierences in the concentrations found with these methods
and also show that the activation approach is not applicable to all elements. This
straightforward example shows that the synchrotron can be used to good eect in studying
archaeological and other materials with spatial resolutions of the order of 1 mm. It is
however, a type of experiment that should be viewed as a bridge between the use of
conventional x-ray tube sources and the synchrotron sources with high brilliance.
B. Biology=Medical: Calcified Tissue Studies
The distribution of trace elements in bone and other calcied tissues is generally of great
interest since the concentrations of the essential trace elements are relevant to bone growth
Figure28 Mass loss observed for skin sample irradiated with a 66-keV beam of photons shown as
a function of the dose. The mass loss was determined by observation of the scattered radiation
intensity. (From Themner et al., 1990.)
Figure 29 Chemical compositions of coins determined using SRIXE, PIXE (solid bar), and neutron-activation analysis (open
bar). The SRIXE work was done at 17 keV (diagonal cross-hatch) and 35 keV (horizontal cross-hatch). (From Brissaud et al.,
1989.)
and disease. Therapeutic agents used to treat disease states may modify the trace element
concentrations and will deposit in particular patterns in the tissue themselves; nally, toxic
elements such as lead are stored in the bone in localized patterns. Several experiments can
be cited to illustrate these points.
Tros et al. (1990) have examined neonatal hamster tooth germs using both micro-
PIXE and the XRM approach. In this work, neonatal hamsters were treated with a
uoride compound commonly used to inhibit tooth decay. A tooth was obtained from the
hamster after a 1-day interval and thin sections were measured using the two types of
beam. The uorine concentrations were found using the proton microprobe at Amsterdam
and the zinc distribution by XRM at Daresbury. The XRM was chosen for the de-
termination of the essential trace elements because of its high sensitivity and low beam-
induced damage. The proton beam was suited to the determination of the uorine because
the cross sections for inelastic proton scattering are high. The combined use of the two
methods shows that ion beams can be used eectively in combination with the photon
beams to cover all elements in the periodic table. The results of the XRM measurement of
Zn and Ca are shown in Figure 30.
Gallium nitrate is another therapeutic element that is used to treat accelerated bone
resorption found in cancer patients. The mechanisms by which gallium interacts with the
bone are as yet poorly understood. Bockman et al. (1990) used the NSLS X26 XRM to
study sections of rat tibia obtained from animals treated with gallium nitrate. A scan
across the tibia from periosteum to endosteum giving the distribution of Ca, Ga, and Zn in
a 12-mm-thick section of bone is shown in Figure 31a. A two-dimensional map of the
gallium and calcium distributions in a fetal rat ulna bone that was exposed to gallium
(25 mm) in culture medium for 48 h is shown in Figure 31b. The bone structure is shown in
an electron micrograph in the center section of the gure. The noncalcied portion ac-
cumulates little gallium compared to the calcied portion, where the gallium accumulates
in the metabolically active regions where new bone matrix is being formed. The method
has been used to study the kinetics of gallium absorption in the bone for dierent dosed
and for dierent states of the bone metabolism. Changes in the concentrations of iron and
zinc as a function of the gallium treatment indicate that it may be possible to infer par-
ticular enzymes, which are targets for the gallium.
Lead can be used to show the uses of the XRM in the study of the eects of toxic
metals. Lead is a major public health problem in many countries. Most of the lead in the
body is stored in the skeleton and can be released to cause serious health eects under
certain conditions. It is known that it causes neurological and other problems in children,
and it is associated with kidney and cardiovascular disease in adults. Understanding the
deposition patterns and kinetics of lead in bone are therefore of great importance from a
particular standpoint. Jones et al. (1990b, 1992) have reported measurements on lead dis-
tributions in the human tibia and in sections of deciduous teeth. Figure 32 shows the dis-
tribution of lead in such a tooth. The end objective in this case will be to attempt to correlate
the distributions with the blood-lead concentrations at birth from examination of the en-
amel (formed by the time of birth) and the dentine (later exposures). Knowledge of the time-
integrated lead exposure can then be related to neurological decits and other eects.
An initial experiment to investigate the kinetics for the accumulation and desorption
of lead in bone was carried out in a controlled experiment that investigated chick tibia
(Jones et al., 1997). The measurements were performed the proximal end of thin (60 mm)
sections of tibia. Chicks raised on diets that contained normal amounts of Ca and Ca-
decient diets and lead were analyzed. Maps over the bone were made with a step size
between points of 60 mm. Analysis of these maps showed that Pb and Ca depositions in
bone are similar and that the eects on bone growth and mineralization caused by Pb
inuences the distribution of both cations. This experiment shows that SRIXE can be used
as a valuable complement to more standard techniques used in biomedical investigations.
The eect of lead on the developing brain has been investigated by Cline et al. (1996)
and Jones et al. (1997). They studied the retinotectal system of frog tadpoles as a function
of exposure to various levels of lead during growth. The lead content in the optic tectum of
the exposed tadpoles was measured using SRIXE at the NSLS X26 beam line with white
light and a collimated beam. Lead levels of about 200 ppb were successfully detected. Use
of SRIXE was advantageous because it can be used with the very small amounts of sample
Figure 30 Scan over a 2-mm section of a neonatal hamster tooth germ showing the variation of
zinc (a) and calcium (b). The zinc is located on the outside edge of the calcium distribution, but the
reasons for difference remain to be determined. (From Tros et al., 1990.)
material available. Atomic absorption spectroscopy could not be used for that reason. The
results of the overall experiment demonstrated the impact of lead on the developing brain
through the structure of the retinal axons. Further, work with the chelating agent 2,3-
dimercaptosuccinic acid showed that the eect of lead on the neuronal structure could be
reversed at a level superior to removal of the lead source alone. These conclusions are
relevant to lead-induced cognitive decits in humans. The results demonstrate that SRIXE
can be a useful measurement technique in many dierent types of biomedical applications
where it is necessary to measure trace concentrations of an element in thin tissue sections
where sample size or handling preclude other conventional approaches. Lower detection
limits at undulator beam lines will increase the scope of this type of analytical experiment.
Osteoarthritic degeneration of articular cartilage is a degenerative disease of major
importance which can be brought about by senescence and trauma. It causes changes in
the cartilage and in the bone. The metacarpal joints of horses aected by osteoarthritis can
be used as an animal model for study of the disease. Rizzo et al. (1995) have studied 5-mm-
thick cartilage slices obtained from normal and arthritic horses using x-ray microbeams
(10 mm in size) at the X26A beam line at the NSLS to map the spatial distribution of S, Ca,
and Zn along a line through the section. It was found that there were dierences in the
Figure 31 (a) Scan over a thin section of the tibia diaphysis of a rat which had been treated with
gallium nitrate showing the distribution of the Ca, Zn, and Ga. Some of the variations come from
irregularities in specimen thickness. The spatial distribution is a function of the gallium nitrate
treatment of the rat. The step size was 9 mm. (b) Map of the distribution of gallium (left) and calcium
(right) in a fetal rat ulna bone after exposure to gallium (25 mM) in a culture medium. The light
regions have the highest elemental concentrations. A scanning electron micrograph (center) shows
the bone structure in the same region. The dark portions at the top of the figure are the noncalcified
cartilaginous portions of the bone, which accumulate little gallium. Most of the gallium is distributed
in metabolically active regions of the metaphysis and diaphysis. (From Bockman et al., 1990.)
results for the normal and arthritic tissue for all three elements. It is argued that the zinc
may be contained in the metalloenzyme alkaline phosphatase. This result may be of use in
understanding the metabolic processes of importance in osteoarthritis.
C. Geology and Environmental Sciences
The XRM has been used for many dierent types of geological and environmental ex-
periments. A survey of geological and environmental applications of synchrotron
radiation has been given by several authors (Smith, 1995; Jones, 2000). A few examples of
dierent applications are given here.
Scientic questions related to the environment are generally very complex and re-
quire understanding on a number of spatial scales. Synchrotron radiation analytical
techniques can be used to eectively investigate many of these problems. This has been
recognized explicitly at the ALS (Robinson, 1997), where they have considered how to
integrate synchrotron techniques with environmental projects. A particular virtue of
photon use is ease of analyzing wet samples as compared with electron spectroscopy. It
was suggested that an appropriate name for the eld would be Molecular Enviromental
Science (MES) in the soft X-ray Region, although it could be argued that the use of
molecular is too restrictive. In any case, some of the experiments described here t well
into such a conceptual framework.
One topic that has been the subject of many investigations has been the uptake of
metals by plants and trees from contaminated soils and water. Experiments have recently
been carried out at the ESRF and at the NSLS, which are relevant to this topic. The ESRF
experiments were carried out using high-resolution beams formed by capillary focusing to
Figure 31
determine wood density and elemental composition. Figure 33 shows results obtained for
the distribution of Mn and the density in the region analyzed. The area examined is at the
boundary between winter and onset of growth in the spring. Measurements at the cellular
level make it possible to examine pathways for accumulation of toxic elements from the
environment. The experiments at the NSLS have been aimed at looking at accumulations
of metals over a long-term period at trees growing in close proximity to a metal smelter
(Martin et al., 1998). The focus of this work was to attempt to determine the relationship
between the time-varying environmental conditions and the composition of the wood. The
results obtained using SRIXE and secondary ion mass spectroscopy (SIMS) to examine
thick wood specimens showed that the distributions were very heterogeneous and that
growth cycles were not easily distinguished from the trace element concentrations.
In geology, many of the experiments used thin sections of rocks for studies of specic
types of minerals in a heterogeneous matrix. Examples of this type of application are
the study of zoned carbonate gangue cements found in Tennessee (Kopp et al., 1990).
The XRM measurements were used in an attempt to interpret the eects of trace amounts
Figure32 The relative concentrations of Ca, Zn, and Pb are for a scan across a section of a childs
deciduous tooth which was thick compared to the absorption of the characteristic x-rays. The
variation of the lead in the scan may be useful in the future in understanding the time dependence of
lead exposure and uptake by the child. The spatial resolution and step size were both about 10 mm.
(From Jones et al., 1992.)
of Mn and Fe on cathodoluminescence in carbonates. Further, the variations in the trace
element concentrations should aid in deducing the source and direction of ow of uids
responsible for the formation of dolomites.
Small particles can also be eectively examined using XRM. Sutton and Flynn
(1988) and Flynn and Sutton (1990) have carried out a series of experiments dealing with
analyses of extraterrestrial particles. These analyses were carried out on particles of sizes
less than 100 mm. Minimum detection limits less than 10 ppm were obtained for particles
less than 20 mm in size using the BNL X26 XRM. Tuniz et al. (1991) also used this
equipment for examination of y ash taken from dierent types of power plants and in-
cinerators. They measured elemental composition in individual y-ash particles with sizes
down to a few micrometers and also made two-dimensional maps of the distributions of
the elements in 10-mm-thick sections of particles produced by a lapping technique. The
results may be useful in verifying models for production of toxic compounds in in-
cinerators based on the presence of specic metals in the ash (Karasek and Dickson, 1987;
Hagenmaler et al., 1987; Altwicker et al., 1990).
D. Materials and Chemical Sciences
Fluorescence can also be used to advantage in the material sciences. For example, Isaacs
et al. (1991) have studied the concentration gradients produced in a solution during the
localized corrosion of stainless steel. The combination of high spatial resolution and ex-
cellent detection sensitivity enabled them to study the variation in the nickel concentration
above a stainless-steel surface immersed in a bulk chloride electrode. Figure 34 shows the
electrochemical cell used in the work and the observed variation of nickel concentration
above the stainless-steel surface. From a study of the concentration gradients, Isaacs et al.
(1991) were able to identify eects arising from silicon in the steel. In situ studies of kinetic
eects should be of increasing interest, not only in corrosion measurements, but also for
other types of chemical reaction.
SRIXE can also be applied to the measurement of relevant to supported catalysts. In
particular, it can be used to measure the distribution of Cr catalyst distributions in
polyethylene polymerization particles (Jones et al., 1997). The use of SRIXE makes it
possible to study the catalyst distribution at high yields that are not possible by other
methods. The experiments was done on microtomed sections of polyethylene particles
using the NSLS X26A XRM. A map of the Cr distribution is shown in Figure 35. Sharp
peaks observed at the periphery of the particle are consistent with observations made using
computed microtomography. The presence of rather uniform concentration of the catalyst
through the particle has not been observed previously. The observation shows that it is
possible to investigate the fragmentation of the catalyst during the polymerization process
by making sequential measurements as the polymerization process evolves. Use of higher
Figure 33 Results obtained for the distribution of Mn and the density in the region analyzed in
the ESRF experiments were carried out using high-resolution beams formed by capillary focusing to
determine wood density and elemental composition. (Rindby A, Engstro m, From ESRF
Highlights1996=1997, p 80.)
spatial resolution and improved detection limits feasible with new XRM equipment will
make it possible to substantially improve this type of investigation.
X. TOMOGRAPHY
Computed microtomography (CMT) is an important approach to nondestructive analysis
and has been extensively developed using conventional x-ray sources. The synchrotron
source gives substantial advantages because of its high brilliance and continuous x-ray
spectrum. The superior properties of the synchrotron source have led to CMT in-
strumentation capable of superior spatial resolution and shorter data acquisition times.
Almost all the work that has been done has concentrated on the use of CMT in the
attenuation mode where determinations are made of the linear attenuation coecients.
The absorption mode is a simple and eective approach to CMT imaging. It can be used
on samples with a variety of sizes and attenuation coecients by choosing the appropriate
x-ray energy. The use of SRIXE is more restricted because the specimen must be small
enough to allow the escape of the characteristic x-ray of interest. However, as is the case
with EXAFS and XANES, the absorption and emission (SRIXE) approaches are com-
plementary and both need to be available as part of the basic XRM.
Renements to the method are necessary in order to get better information on the
elemental composition of the materials. The absorption approach can be rened by pro-
ducing tomograms above and below an elemental x-ray absorption edge. Subtraction of
the tomograms gives the concentration of that element. The dierent technique is valuable
for the study of major and minor elements to the 0.1% level.
The imaging of trace elements often necessitates the use of SRIXE so that specic
elements are selected through the detection of their characteristic x-rays. The detection
system must be chosen for high eciency and high counting-rate capability. The type
of specimen, which can be investigated, is limited by the attenuation of the uorescent
x-rays in the sample being investigated. The sample dimension is strongly constrained
because of this.
Figure 34 The apparatus used for studying corrosion of stainless steel (S. S.) in a chloride
environment is shown on the left (a). The spatial distribution of nickel observed above the stainless is
shown as a function of distance above the metalliquid interface (b). (From Isaacs et al., 1991.)
Several groups have done CMT work with synchrotrons. Flannery et al. (1987)
developed a third-generation type system at the NSLS. They used a x-ray magnication
system with a scintillation detector coupled to an image intensier to produce images with
a claimed resolution down to 1 mm. A similar approach was used by Bonse et al. (1986)
and Kinney et al. (1988) at SSRL. Spanne and Rivers (1987) demonstrated at a rst-
generation system at the NSLS X26 beam line. Later work with the apparatus has pro-
duced images with a spatial resolution of 1 mm61 mm and a slice thickness of 5 mm, quite
comparable to the results from the third-generation devices. More recently, a third-gen-
eration apparatus has also been put into operation at BNL (Dowd et al., 1998). It can be
used for analyses with voxel sizes as small as 2.7 mm
3
.
The rst-generation approach takes longer to produce images but has the advantage
that beam scattering eects in the sample are eliminated and SRIXE measurements can be
performed to produce elemental maps. In the third-generation systems, elemental maps
are made by subtracting images taken above and below the absorption edge of interest.
The DL for such an approach is about 0.1%.
Spanne (1990) has carried out a pilot study with the aim of evaluating the potential
for mapping of light elements at the cellular level in the rat sciatic nerve using uorescence
CMT. A comparison of the mean free path for characteristic x-rays from potassium and
typical sciatic nerve sizes shows that it is feasible to make corrections for the attenuation of
the potassium K x-rays in the nerve. The computed emission tomogram of the distribution
of potassium in the epineurium of a rat sciatic nerve given in Figure 36 illustrates this
point. Note that the short escape depth for the potassium x-rays that are observed
Figure 35 Map of the Cr distribution. The experiment was done on microtomed sections of
polyethylene particles using the NSLS X26A XRM. Sharp peaks observed at the periphery of
the particle are consistent with observations made using computed microtomography. (From Jones
et al., 1997.)
necessitates special measures during the reconstruction of the image. Saubermann (per-
sonal communication, 1989) points out that uorescence CMT makes the studies of ele-
mental distributions in unsectioned samples possible. Examination of unsectioned samples
also makes in vitro analysis of sections of nerves several millimeters long feasible.
Figure 36 Computed emission tomogram showing the distribution in the epineurium of a freeze-
dried rat sciatic nerve. The pixel size was 3 mm63 mm and a slice thickness of 5 mm. The matrix size
was 1756175 pixels. (From Jones et al., 1990a.)
Longitudinal distributions of elements can then be conveniently studied by scanning at
dierent heights, and it is even possible to go back to a previously mapped region for a
more detailed examination if steep concentration gradients are discovered. Longitudinal
concentration gradients have been demonstrated in the rat sciatic nerve, although with a
very poor longitudinal resolution and may be of signicance in nerve injury (LoPachin
et al., 1988; LoPachin et al., 1990).
Exxon (Auzerais et al., 1996) and BNL (Spanne et al., 1994, Coles et al., 1996, 1998a,
1998b) groups have investigated topics related to the microgeometry of sandstones in
parallel experiments at the NSLS. In addition to measuring properties of the sandstones
such as porosity, premeability, tortuosity, and connectivity, attention was given to the
displacement of oil by water and modeling of ow through the experimentally determined
structures. A structure of Fontainebleau sandstone measured in the experiment of Spanne
et al. (1994) is shown in Figure 37. The structure was analyzed to give a theoretical re-
presentation of the structure that could be used for predicting uid owat larger sizes scales.
Feng et al. (1999) have examined the structure of micrometeorites using the BNL
equipment. Previous examinations of the particle have shown that there are void spaces
and small nuggets of Pt in the interior of some of these particles. This information was
gained by laborious sequential sectioning of particles with a diameter of about 400 mm.
The use of CMT to gain the same information represents a major step forward in the
analytical technique for the eld. A representation of a Pt nugget observed in a micro-
meteorite is displayed in Figure 38. The results show that it will be possible to system-
atically examine large numbers of specimens to obtain signicant information about the
nuggets and about the history of the particle as it passes through the Earths atmosphere.
Several groups at the ESRF and NSLS have been concerned with the development of
improved methods for obtaining contrast between materials with similar x-ray absorption
coecients (see, for example, Raven et al., 1997). Buere et al. (1998) have applied the
phase-contrast technique, based on diraction patterns produced at discontinuities in the
sample, to measure damage in metal matrix composites. This was an ingenious experiment
that investigated the development of cracks in the composite as a function of tensile forces
applied to the specimen in situ. The experiment revealed the cracking of SiC particles,
decohesion between sample phases, and propagation of pores.
The development of CMT at synchrotrons has been very rapid over the past 10 years
from the standpoint of instrumentation. Applications have also been developed, but
perhaps at a slower pace. This will change in the future, with an increase in the avail-
ability of the technique and improvements that can be made with the increasing use
of third-generation synchrotron undulators. It is apparent that both absorption and
emission approaches are needed and that both approaches are required at any synchrotron
XRM facility. The emission technique will be greatly assisted by the use of undulator
beam lines to obtain higher counting rates.
XI. EXAFS ANDXANES
Extended x-ray absorption ne structure and the related XANES have been widely applied
to give information on the chemical state of elements in many dierent materials (Winick
and Doniach, 1980; Koningsberger and Prinz, 1988). Many of the experiments that have
been carried out have used relatively large x-ray beams and thick specimens to make
absorption measurements on a timescale of minutes possible. This approach is not useful
for elemental concentrations less than about 0.11%. The use of EXAFS and XANES at
lower concentrations can be achieved by use of uorescent x-ray detection. Cramer et al.,
(1988) have developed at 13-element Si(Li) x-ray detector which gives a high eective
detection eciency for this type of application. Other workers have developed means of
acquiring EXAFS spectra on a millisecond timescale (Tolentino et al., 1990) and have
made measurements of chemical state on a ner spatial scale (Iida et al., 1989). The future
development of x-ray microscopy can thus be seen to include the use of SRIXE with
EXAFS and XANES and the development of new techniques to make it possible to work
with improved DLs and beam sizes at the micrometer level.
The NSLS X26 group has employed a simple channel-cut silicon monochromator
with an energy resolution of about 1.1 eV for several demonstration XANES experiments.
The beam was rst dened with a four-jawed aperture whose size could be adjusted using
computer-controlled stepping motor drivers. This was followed by the monochromator
placed about 10 cm upstream from the target. The beam moved vertically on the target by
about 60 mm during the scan. This was not important for the resolutions used, but could
be easily compensated for by a correlated motion of the target to keep the same spot under
the beam. The rst test used a thick specimen of NIST SRM 1570 spinach leaves, which
contained 550 ppm iron. The iron x-rays were detected with the XRM equipment de-
scribed earlier. The work was done with a beam size of 2 mm
2
. The results of a scan of
a pure iron specimen (beam size 200 mm6200 mm) and the spinach leaves are shown in
Figure 39. The spectra agree well with the results of a similar scan done on the NSLS X19
beam line using the 13-element Si(Li) detector. Extrapolation from these initial values
showed that work with beam sizes down to 100 mm and perhaps lower was feasible with
the existing equipment for this particular target.
Figure 37 View of the pore space of Fontainebleau sandstone obtained by CMT. The pore
structure is shown as white and the rock as black; that is, the pore structure is opaque and the rock
transparent. (From Spanne et al., 1994.)
A more stringent demonstration is the use of thinner specimens. For this purpose,
measurements were made on the chromium contained in olivine and pyroxene components
in a 30-mm section of lunar mare basalt 15555 from Apollo 15 and in a 10-mm section of a
rat kidney. The lunar basalt study was undertaken because the oxidation state of the
chromium could shed light on conditions existing at the time of the formation of the
mineral studied (Sutton et al., 1991). The rat kidney measurement was needed to cast light
on nephrotoxic eects resulting from environmental exposures. It is hypothesized that the
oxidation state of the chromium changed during its passage from lungs to kidneys with
related implications for health eects.
The basalt specimen contained chromium at a level of about 1000 ppm and the
kidney at a level of about 50 ppm. Figure 40 shows the XANES spectrum for chromium in
pyroxene and olivine contained in the lunar basalt taken with a beam resolution of
200 mm6200 mm. Figure 41 shows the spectrum obtained for the rat kidney, but in this
case with a 1-mm61-mm beam size. The beam was positioned over the medulla portion of
the kidney. The XANES spectra show that chromium exists primarily in the 2
and 3
states in the lunar olivines but as the 3
state in the kidney.

Figure 38 CMT three-dimensional image of the interior of type-I deep-sea spherule with parts of
the surface cut away. The compact bright spot in the upper right is a platinum group metal nugget.
The light mass in the foreground represents a hole in the interior of the spherule. (From Feng et al.,
1999.)
The application of SRIXE to EXAFS and XANES experiments has expanded
greatly on the X26 beam line since these initial experiments. This has been especially true
in the geological and environmental elds. Delaney and co-workers have continued their
examination of both geological and extra terrestrial materials (Delaney et al., 1996, 1998a,
1998b; Flynn and Sutton, 1990). A number of experiments have been performed that
Figure 39 Fluorescent XANES spectrum obtained for Fe at the 550-pm level in a thick NIST
SRM 1570 (spinach) sample compared to the spectrum obtained under the same conditions for an
iron foil.
relate to speciation of contaminants in soils and sediments (Bertsch et al., 1994; Bajt et al.,
1993; Sutton et al., 1994; Tokunaga et al. 1997, 1998). Ilman et al. (personal commu-
nication, 1996) have investigated the chemical state of Cr and As in wood treated with
chromated copperarsenate and the role of Mn in fungal diseases of wood. The work,
taken as a whole, serves as an actual demonstration of the concept mentioned in Sec. IX
for denition of a eld of Molecular Environmental Science (Robinson, 1997).
There are several examples of the way that these experiments can be extended at third-
generation synchrotron facilities. Sarret et al. (1998) used a bending magnet beam line at
the ESRF to do experiments with a spatial resolution of 300 mm6300 mm for examination
of trace elements at concentrations as low as 100 ppm. These parameters are similar to
those at the NSLS X26 beam line. Measurements were made to study uptake mechanisms
of Pb and Zn in lichens. Lichens were of interest because they are commonly used as a
biomonitor to assess environmental pollution. Analysis of these spectra made it possible to
reach an understanding of how Pb and Zn are transported and absorbed in the plant.
A demonstration experiment similar in intent to the work at the NSLS and ESRF
has been performed at the ALS (Warwick et al., 1998). In this example, measurements
were made with a much higher spatial resolution. The oxidation state of Cr in a soil sample
was determined by rst scanning a region of 60 mm680 mm. One region of high Cr con-
centration was found and chosen for examination with XANES. The spectrum obtained
Figure 40 Fluorescent XANES spectrum obtained for Cr at the 1000-ppm level in a 30-mm-thick
section of pyroxene and olivine contained in lunar basalt 15555. The spatial resolution was
200 mm6200 mm. (From Sutton et al., 1991.)
from this region with an area of a few square micrometers indicated that the Cr was in
both Cr(III) and Cr(VI) oxidation states. The results of this experiment are shown in
Figure 42.
Another example is given by the work of Cai et al. (1998) at the APS. They de-
scribe a beam line using a undulator source and zone plate focusing to obtain a beam
size of less than 0.25 mm and a photon ux of 5610
10
photons=s at a bandwidth 0.01%.
It is possible to do x-ray diraction, x-ray uorescence, and computed microtomography
Figure 41 Fluorescent XANES spectrum obtained for Cr at the 50-ppm level contained in a thin
section of rat kidney. The spatial resolution was 1 mm61 mm. The spectrum shows that there is little
Cr VI present in this portion of the kidney.
simultaneously on this beam line. Data are presented for spatial distributions of Mn, Fe,
Cu, and Zn in a root, hydrated P. lanceolata, infected by a fungus, mycorrhizal fungus
G. mosseae. A XANES spectrum for Mn obtained from a location in the root at a spatial
resolution of 1 mm63 mm is shown in Figure 43.
The examples of work that has been done at the NSLS, ESRF, ALS, and APS on
soils and metal transport in plants during the past decade illustrates the usefulness of the
synchrotron XRM for geological and environmental work. A similar collection of ex-
periments can be assembled to illustrate other applications of SRIXE=XANES=EXAFS
using both second- and third-generation facilities. It is clear that the scientic applications
of these techniques will increase dramatically in the future.
XII. FUTURE DIRECTIONS
What does the future hold for synchrotron XRM? Several dierent developments can be
predicted for the rst decade of the next millenium, 20002010, with some condence.
First, continuation of the present types of experiments will go on at an expanded rate
as thevirtues of themethodbecomebetter known. Theapplications will benet fromenhance-
ments in the facilities, which will bring spatial resolutions to 1 mm
2
for two-dimensional
maps or to 1 mm
3
for CMT. Relatively minor improvements to the existing systems are
needed to achieve this level of resolution. Detection-level (DL) values should also improve
somewhat with the introduction of improvements in the x-ray detector systems, again
using known techniques. There will be a further merging of XRM techniques with those
developed for EXAFS and XANES.
Second, development of new focusing methods will begin and this will lead to the
routine achievement of spatial resolutions of the order of 0.1 mm by 20002005. An ex-
ample is the production of zone plates suitable for focusing of 8-keV x-rays by Bionta et al.
(1990) and the application of capillary focusing by Bilderback et al. (1994a,b,c).
Figure42 Elemental mapping and chemical speciation of Cr in a soil specimen on the micrometer-
size scale. Measurements performed by R. Reeder et al. (Dept. of Geosciences, SUNY Stony Brook)
at the ALS. (From Warwick et al., 1998.)
Figure 44 The spatial resolution (expressed as the beam area) obtained with high-energy x-ray
microscopes is plotted as a function of time. The best spatial resolutions in 1990 are around 14 mm
2
.
If improvements had continued at the same rate, resolutions would have been close to atomic
dimensions around the year 2000. This did not happen.
Figure43 AXANES spectrumfor Mn obtained froma location in the root at a spatial resolution of
1 mm63 mm. (Cai et al., 1998. Argonne National Laboratory, managed and operated by The
University of Chicago for the U.S. Department of Energy under Contract No. W-31-109-ENG-38.)
Figure45 The average and peak spectral brightness as a function of photon energy for the LCLS as compared to the
values for other operating and proposed facilities. (From Cornacchia, 1998.)
Third, a new era in SRIXE research has been signaled by the operation of third-
generation synchrotron sources such as the Advanced Photon Source (APS) at Argonne
National Laboratory and the European Synchrotron Radiation Facility (ESRF) at
Grenoble. These systems produce beams with improvements of three to four orders to
magnitude when using undulator insertion devices and with higher energies when using
either bending magnets or wigglers. A general discussion of the impact of these new
rings on XRM has been given by Sparks and Ice (1990), who found detection limits of
10
8
atoms in a solid and of 10
3
free atoms for uorescence detection with a 1-mm
2
beam
and a data acquisition time of 1 s. An early discussion of the impact of the APS on the
geosciences was given by Sutton and Flynn (1988). It remains to be seen how close these
predictions will approach reality. It is presently clear that SRIXE is now a major
analytical method for the geological and environmental sciences and possibly to a lesser
extent for other scientic elds.
Figure 44 summarizes the time dependence for the synchrotron XRM spatial re-
solution. The area resolution has decreased exponentially over the past 15 years. Ex-
trapolating into the future assuming the same rate of improvement would lead to an
estimate of an area resolution corresponding to a beam size of roughly 1 nm by the year
2000. Looking at what has been accomplished for focusing low-energy x-rays with zone
plates and at the high-energy end with capillaries, it is probable that the XRM re-
solutions will approach a constant value of about 0.0250.05 mm.
We have already seen the characteristic of x-ray sources improved by many orders of
magnitude. There is a good probability that this rate of improvement is not about to come
to an end. There has been an intense eort to develop a free-electron laser at a number of
laboratories. For instance, the Stanford Linear Accelerator Center (SLAC) has developed
a design for a Linac coherent light source (LCLS) based on a 15-GeV linear accelerator
(Cornacchia, 1998). Figure 45 shows the average and peak spectral brightness as a func-
tion of photon energy for the LCLS as compared to the values for other operating and
proposed facilities. Improvements of three or more orders of magnitude should be at-
tained. Many new types of experiments should be possible, considering the time structure
of the photon beams and their intensity.
It seems very safe to conclude that SRIXE experiments should continue to be an area
of continuing high interest for the foreseeable future. This is based on the established value
of the analytical techniques and the prospectus for major improvements in its capabilities
from future improvements in the x-ray source, in x-ray optics and detectors, and in the
interfacing of computational methods with the experiments.
ACKNOWLEDGMENTS
I am particularly indebted to my colleagues for simulating discussions and interactions,
which have inuenced my views of x-ray microscopy over the years. Among them are
R. S. Bockman, R. D. Giauque, Y. Gohshi, L. Grodzins, A. L. Hanson, J. B. Hastings,
K. Janssens, J. G. Pounds, C. Riekel, M. L. Rivers, A. J. Saubermann, J. V. Smith,
P. Spanne, S. R. Sutton, A. C. Thompson, S. To rok, C. Tuniz, J. H. Underwood, and
R. D. Vis. I am particularly saddened to note that P. Spanne died in the crash of Swissair
Flight 111, September 1998.
This work was supported in part by the Oce of Basic Energy Sciences, U.S. De-
partment of Energy for development and application of analytical techniques under
Contract Nos. DE-AC02-76CH00016 and DE-AC02-98CH10886 and by the National
Institutes of Health Biotechnology Research Resources Grant No. P41RR01838.
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Methods Phys Res A292:719, 1990a.
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Instrum Methods Phys Res A291:146, 1990.
9
Total-Reection X-ray Fluorescence
Peter Kregsamer, Christina Streli, and Peter Wobrauschek
Atominstitut, Vienna, Austria
I. INTRODUCTION
The phenomenon of total reection of x-rays had been discovered by Compton (1923). He
found that the reectivity of a at target strongly increased below a critical angle of only
0.1
. In 1971, Yoneda and Horiuchi (1971) rst took advantage of this eect for x-ray
uorescence (XRF). They proposed the analysis of a small amount of material deposited
on a at totally reecting support. This idea was subsequently implemented in the so-
called total-reection x-ray uorescence (TXRF) analysis which has spread out worldwide.
It is now a recognized analytical tool with high sensitivity and low detection limits, down
to the femtogram range. TXRF is basically an energy-dispersive technique in a special
excitation geometry. This geometry is achieved by adjusting the sample carrier inclined
under angles of about 1 mrad (0.06
) to the primary beam. The incident beam thus im-

pinges at angles below the critical angle of (external) total reection for x-rays. Usually the
liquid sample, with a volume of only 1100 mL, is pipetted in the center of the reector. As
a result of the drying process where the liquid part of the sample is evaporated, the residue
is irregularly distributed on the reector (within an area of a few millimeters in diameter),
forming a very thin sample. (See Figure 1.)
Total-reection XRF oers the following advantages:
If the adjusted incident angle of the primary radiation is below the critical angle,
almost 100% of the incident photons are totally reected, so the primary
radiation scarcely penetrates into the reector and the background contribu-
tion from scattering on the substrate is drastically reduced.
The sample is excited by both the direct and the reected beam, which results in a
doubling of the uorescent intensity.
Due to the geometry, it is possible to position the detector close to the surface of the
reector where, in the center, the sample is located. This results in a large solid
angle for the detection of the uorescence signal.
Consequently, the peak-to-background ratio in TXRF is high and the detection limits are
drastically improved by several orders of magnitude as compared to conventional XRF.
The very distinct angular dependence of the characteristic x-ray intensities close to
the total-reection regime can be used to investigate surface impurities, thin near-surface
layers, and even molecules absorbed on at surfaces. The analysis of the composition,
thickness, and density of layers as well as the nondestructive in-depth examination of
concentration proles in the range of 1500 nm are possible.
Demands for TXRF are as follows:
Higher photon ux of excitation sources as compared to standard XRF
Small source size (typically 10 mm640 mm for x-ray tubes for TXRF)
Low divergence (in one direction below 1 mrad).
As most widely spread excitation sources, high-power Mo x-ray diraction tubes are
in use. Depending on the chemical elements of interest, other anodes might be preferred.
The insertion of a spectral modication device in the beam path of the primary radiation
improves the background; that is, a multilayer monochromator suppresses in the ideal case
all photons, except the ones with an energy range which covers the most intense char-
acteristic line of the anode material.
It was demonstrated that the optimum excitation source for TXRF is a synchrotron
storage ring. The routine determination of light elements (below Si) with TXRF is still a
challenging task: Both the excitation as well as the detection of the uorescence radiation
of interest are dicult. In this context, several spectrometers were constructed, based on
ultrathin entrance window and windowless detectors as well as synchrotron radiation and
new prototype x-ray tubes applied for excitation.
Typical applications of TXRF include analysis of drinking water, river water, rain-
water, seawater, wastewater, body uids, tissue, purity of chemicals (acids, bases, solvents,
etc.), oils and greases, aerosols, y ash, soils, forensic and art-historical objects, study of
thin layers and depth proles, and so forth.
II. PHYSICAL PRINCIPLES
The theoretical fundamentals of TXRF can be deduced in a way analogous to that applied
in light optics. One has to consider the interaction of an electromagnetic wave that hits the
plane boundary between vacuum and a medium described by its refraction index n, which
takes into account both scattering and absorption and can be calculated by quantum
mechanics:
Figure1 Scheme of TXRF.
n 1 d ib 1
It can also be expressed as function of atomic scattering factors f
1
and f
2
(see Fig. 2), which
are tabulated by atomic number dependent on the incident x-ray energy (Henke et al., 1993):
n 1 N
A
e
2
m
0
c
2
l
2
2p
r
A
f
1
if
2
2
where N
A
is Avogadros number, l is the wavelength of the incident radiation, r is the
density of the medium, A is the atomic mass, e and m
0
are the electric charges and rest
mass of an electron, respectively, and c is the velocity of light.
By comparing Eqs. (1) and (2), we obtain
d N
A
r
0
2p
l
2
r
A
f
1
3
where r
0
is the classical electron radius:
r
0

e
2
m
0
c
2
4
The real part of the complex refraction index (1 7d) is slightly smaller than unity with
d 10
75
10
76
in the energy range of x-rays. The minus sign reects the fact that the
bound electrons follow the exciting photons in the opposite phase. Consequently the re-
fraction index for x-rays is always smaller than 1 (except sometimes for the energies close
to absorption edges). The imaginary part b (usually smaller than d) is a measure of the
absorption and is related to the photoelectric mass absorption coecient t
m
:
Figure2 f
1
and f
2
for silicon as a function of the incident radiation energy. At the absorption edge
energy of 1838 eV, discontinuities in the scattering and absorption behavior are found. For energies
far above this energy, f
1
approaches asymptotically the value of its atomic number Z14.
b N
A
r
0
2p
l
2
r
A
f
2

l
4p
rt
m
5
According to Figure 3, the following rules are valid:
The incident, the reected, and the refracted beams span a plane that is
perpendicular to the boundary plane.
The angles of the incident beam j
0
and the reected beam j
R
are equal: j
R
j
0
.
The angles of the incident beam j
0
and the refracted beam j
T
follow Snellius law:
n
vacuum;air
n
reflector
cos j
T
cos j
0
6
For x-rays, the real part of n
reflector
is slightly less than 1, whereas the refraction index for
vacuum is 1 (in good approximation also valid for air). Consequently, the reector is the
optically thinner medium than vacuum (air), and the reected beam will be deected
toward the boundary, which is completely dierent as compared to usual light optics. Due
to the fact that the angles for which the total reection eect is observed for x-rays are
small, sine functions can be replaced by their argument sin j
0
!j
0
, and cosine by
1 j
2
0
=2.
The electromagnetic waves for the incoming, reected, and refracted beams can be
dened in the usual way for light optics, and Fresnels formulas will give the ratios of, for
example, the reected E
R
and incoming E
0
amplitudes:
E
R
E
0
j
0
j
2
0
2d 2ib
q
j
0
j
2
0
2d 2ib
q 7
For exact calculations, the polarization state of the primary radiation and the propagation
of the refracted beam as the so-called inhomogeneous wave have to be considered. It
appears, however, that the eects for MoKa primary radiation and a quartz reector are
negligible and can be ignored in the calculation of reection (R) and transmission (T)
coecients as well as of refraction angles j
T
:
Figure 3 The incident (I
0
), the reflected (I
R
), and the refracted (transmitted, I
T
) beams at the
interface of two media. The refraction index of the medium from the radiation comes (usually air or
vacuum) is greater than the one of the reflector.
R I
R

E
R
E
0
4x
2
T
x
0
x
T
2
y
2
4x
2
T
x
0
x
T
2
y
2
8
T
E
T
E
0
2
x
T
j
0
16x
3
T
x
0
4x
2
T
x
0
x
T
2
y
2
9
The parameters x
T
; x
0
, and y are dened as follows:
x
T

j
T
j
crit
10a
x
0

j
0
j
crit
10b
y
b
d
10c
The reection and transmission coecients fulll the following condition (as a direct
consequence of energy conservation):
R T 1 11
The refraction angle j
T
, given by
j
T

d
p
x
2
0
1

2
y
2
h i
r
x
2
0
1

s
12
is a function of the incidence angle and coincides with it for the angles well above the
critical angle. The refraction angle is very small, but does not vanish for an (hypothetical)
incidence parallel to the interface j
0
0 (see Fig. 4).
Figure 4 The refraction angle j
T
as a function of the incident angle j
0
for MoKa and a quartz
reflector. The critical angle for this configuration is at 1.8 mrad. Even for very small incident angles
close to 0
, the refraction angle is 5 mrad.

The so-called critical angle of total reection, j
crit
, can be written as
j
crit

2d
p
13
and is closed to the position of the respective inection points of the transmission and
reection coecient curves and also of the refraction angle. For energies well above the
reector materials absorption edges, a simple dimensional equation can be derived,
j
crit
mrad
28:8
E keV
Zr g=cm
3
A
s
14
showing that the critical angle is inversely proportional to the energy of the incident ra-
diation, which means that the higher the energy of the incident photons, the smaller the
angle of the reector has to be adjusted to observe total reection. Z is the atomic number,
r is the density, and A is the atomic mass.
The dependence of the reectivity on the critical angle of the reector material is
demonstrated in Figure 5: The lower the atomic number of the reector, the lower its
critical angle and the more step-function-like is its shape. For the combination of MoKa
incident radiation reected on quartz, j
crit
1.8 mrad ( 0.10
).
The Fresnel equations are based on classical dispersion theory and have been derived
assuming a perfectly at and smooth interface between homogeneous media. Even though
a real surface is, in general, rough on a microscopic scale, the experimental results have
shown sucient agreement.
The penetration depth z
P
for total reection, in accordance with the denition for
conventional XRF, is the distance measured normally to the interface at which the
Figure 5 Calculated reflectivities of several reflector materials for MoKa radiation. The values of
the critical angles j
crit
for C, Si, Ge, Nb, and Ta (1.75, 1.8, 2.5, 3.1, and 4.2 mrad, respectively) are
indicated by circles.
intensity of the (refracted) beam is reduced by a factor of e (i.e., to 37% of its value). It is
directly proportional to the refraction angle (for conventional XRF, this angle is equal to
the angle of incidence):
z
P

1
rt
m
j
T
15
As will be shown later, the penetration depth has no direct inuence on the background
intensity.
Only some years after TXRF was introduced as a spectrometric tool, the interference
eect on top of the reector between the incoming and reected beam was recognized. The
undisturbed coherent superposition of the plane electromagnetic waves results in a vari-
ation of the intensity pattern, depending on the distance above the surface, called a
standing wave.
Figure 6 displays the fundamental facts; the length D gives the distance between two
maxima of the standing wave with wavelength l,
D
l
2j
0
16
and is typically in the range of 10100 nm. The intensity of the standing wave is a function
of the height z above the reector surface and the incident angle:
Ij
0
; z I
0
1 Rj
0
2
Rj
0
p
cos Fj
0
2p
z
Dj
0
!
17
This intensity can vary between zero and four times the primary intensity I
0
. The phase
factor Fj
0
cos F 2x
2
0
1 18
was found by Bedzyk et al. (1989) for the case b 0 (i.e., when absorption was ne-
glected). For standard TXRF where granular residues deposited on a reector are
analyzed, a problem might arise that samples with dierent thickness (but smaller than
D) can give dierent uorescence intensities. For homogeneous residues for which many
of these maxima and minima of the standing waves occur within the sample thickness,
this eect will level out to a large extent. If an internal standard is homogeneously mixed
with the sample material, the ratio of the respective uorescence intensities will lead to
Figure 6 The interference (standing wave) zone between the incident (I
0
) and reflected (I
R
) plane
waves with wavelength l shows nodes and antinodes with a period of D.
an acceptable precision in any case. Therefore, the use of an internal standard is in-
evitable for TXRF analysis of the residues. (See Figure 7.)
For a broad range of elements, TXRF provides x-ray spectra characterized by high
sensitivities and low background. The background generated by the sample support can be
assessed from the transmitted part of the primary radiation.
One of the main features of TXRF is a strong dependence of both the scattered and
uorescence signals, which originate from the substrate itself, on the incidence angle. The
intensity of the scattered radiation I
scatter
(j
0
) is given by
I
scatter
j
0
/ j
0
Tj
0
ds
dO
1
m
m
E
0
19
The following factors had been considered:
For standard TXRF, the area on the reector, seen by the detector, is generally
smaller than the area hit by the primary radiation; therefore, a geometry factor
proportional to sin j
0
has to be used (de Boer, 1989) (and the sine can be
replaced by its argument).
Only those primary photons that are not totally reected on the surface are able
to penetrate and induce interactions. This leads to the transmission
coecient T.
Considering the phenomena of elastic and inelastic scattering, the dierential
scattering coecients ds=dO, which depend on the scattering angle (for TXRF
in the range of 90
) should be utilized (Kregsamer, 1991) (see Fig. 8).

Figure 7 Relative intensities of the standing waves for the incident angles of 0.9, 1.8, (j
crit
), and
3.6 mrad (primary radiation: MoKa, silicon substrate). The standing-wave effect above the
interface increases with decreasing incident angle. The dependence of the distance between maxima
D on the incident angle [see Eq. (16)] is also seen. Inside the medium, the refraction angle is
responsible for the intensity decrease in the direction normal to the surface; the propagation is very
shallow below the surface for small incident angles.
The attenuation of the refracted beam inside the substrate on the way to the location
where an interaction takes place may not be neglected. However, the
attenuation from this point to the surface toward the detector can usually be
ignored.
For the incident angles larger than the critical angle, the geometry factor is responsible for
the increase in the spectral background, whereas the sudden reduction for the smaller
angles originates from the almost perfect total reection; the reection coecient is nearly
1 in this range. (See Figure 9.)
III. INSTRUMENTATION
A. Excitation Sources forTXRF
The usual excitation source for TXRF is a high-power diraction x-ray tube with a Mo
anode with an electrical power of 23 kW. This type of x-ray tube is also available with Cr,
Cu, Ag, and W targets. The line focus of the anode has to be used so that the emitted
brilliance is in correlation with the slit collimation necessary to produce a narrow beam
with the divergence less than the critical angles involved. A higher photon ux on the
sample can be achieved by using rotating anodes, which can stand up to 18 kW. In all
cases, the focal size of the electron beam on the anode is a line with the dimensions of
0.468 mm
2
(ne focus) or 0.4612 mm
2
(long ne focus). The emission of the x-rays is
observed under the angle of 6
to the anode surface, so that the width of the focus is

reduced optically by the projection with sin 6
( 0.1) to 0.04 mm.

Figure 8 Differential coherent and incoherent scattering coefficients for the MoKa incident
radiation, scattered by amorphous silicon. The scattering angle is the sum of the incident and the
detection angles and is close to 90
for TXRF.
The emitted spectrum consists of the continuum (bremsstrahlung) and superimposed
are the characteristic lines of the anode material (e.g., MoKa and MoKb) (see Fig. 10).
Insertion of spectral modication devices in the path of the primary radiation beam im-
proves the background (see Fig. 11).
A so-called cuto reector, acting as a low-pass lter, suppresses the high-energy
photons (above the K lines of the anode material), whereas the low-energy part of the
primary radiation, including the characteristic lines, should be reected, improving the
backgroundin particular, in the low-energy region. High-energy photons of the con-
tinuum (although not of direct inuence to the background under the lines of interest) can
get to the front side of the detector and can be inelastically backscattered (Compton
backscattering). By-products of such events are the recoil electrons of the scattering atom,
which are registered in the detector. Their energy is a function of the scattering angle and
the primary energy. As a consequence, the spectrum shows a shelf (Compton edge),
starting from zero up to several kiloelectron volts.
The eect of inserting a cuto reector into the beam path between the x-ray tube
(collimation unit) and the sample reector can be seen from the dierence for the high-
energy parts of the spectra in Figures 12a and 12b; almost all photons above 20 keV are
suppressed for the latter. A proper alignment is fairly critical, because, otherwise, either
some high-energy photons can pass the device or, even worse, a part of the needed ex-
citation spectrum is suppressed (see Fig. 12c, where MoKb is drastically reduced in
intensity).
A typical resulting sample spectrum for a well-adjusted TXRF spectrometer (sample
reector also adjusted) is displayed in Figure 13. Unknown samples can be quantied
(referring to a given internal standard element) with sensitivity factors [for denition, see
Eq. (22)] (Fig. 14).
Figure 9 The angular dependence of the background intensity for TXRF measurements (MoKa
primary radiation under total reflection on a quartz reflector; the critical angle is 1.8 mrad). The
dashed line represents the case where no total reflection is observed.
Monochromators also can modify the primary radiation and they are usually set to
the energy of the most intense characteristic line of the anode material. For a Mo-anode
x-ray tube MoKa or for a W-anode x-ray tube WLb are selected, but a part of the
continuum can be monochromatized as well. Commonly used crystal monochromators
Figure 10 Measured primary spectrum of a fine-focus Mo diffraction x-ray tube (45 kV
acceleration voltage) as typically used for TXRF. The characteristic MoKa and MoKb lines are
superimposed on the bremsstrahlung background. In the energy range between 5 and 10 keV, several
additional lines resulting from anode contaminations and so on were present for this particular tube.
Figure11 Major components of a TXRF spectrometer.
Figure 12 (a) Scattered spectrum of a Mo x-ray tube (40 kV acceleration voltage) as used in a
TXRF module spectrometer; (b) scattered spectrum, under the identical conditions as above, but
with a cutoff reflector insertedadjusted to suppress primary photons between 20 and 40 keV.
(c) scattered spectrum, under the identical conditions as in (a) and (b), but with the cutoff reflector
slightly de-adjusted. As a consequence, the MoKb line is also suppressed.
have the disadvantage of a very narrow energy band transmitted (usually in the range of
few electron volts), whereas synthetic multilayer structures are characterized by higher
DE=E and reectivities of up to 75% for premium quality materials. (See Fig. 15.)
The excitation of an element is the most ecient when the energy of the exciting
radiation is close to its absorption edge. The search for anode materials for special ap-
plications has led to the development of Al- or Si-anode x-ray tubes which are suitable for
the determination of elements below Si, such as F, Na, Mg, and Al.
A spectrometer has been developed with a variable double multilayer pair used as a
tunable monochromator combined with an x-ray tube with an anode made of a homo-
geneous alloy of molybdenum and tungsten (Knoth et al., 1997). Three discretely ad-
justable excitation energies (9.7, 17.5, and 35 keV) are supplied by this combination and
cover a much wider range of the elements than the detectable with a single spectrometer.
The detection limits were determined to be 0.4 pg for Ni using WLb excitation, 0.6 pg
for Pb with MoKa excitation, and 8 pg for Cd (determined by using its K lines) with the
35-keV bandpass excitation.
The applicability of three congurations of curved multilayer mirrors as mono-
chromatizing and focusing elements has been studied theoretically (Stoev et al., 1998) and
the predicted theoretical results were compared with those obtained with a prototype
spectrometer (tunable between 9.7 and 17.5 keV, with the above-mentioned W=Mo alloy
anode) for the element Ni (Knoth et al., 1999).
Currently, synchrotron radiation is the most brilliant photon beam for XRF and it
has almost ideal features for TXRF. It is several orders of magnitude brighter than the
output of x-ray tubes and is naturally collimated and linearly polarized in the plane of
the orbit of the electrons of positrons. The spectral distribution is continuous; therefore,
Figure12
monochromatization is necessary and selective excitation is possible. Because scattering
and absorption of primary photons in air should be avoided, the use of a vacuum
chamber is recommended. As a result, the ArK line disappears from the spectrum and
the absorption of primary and uorescent photons is also avoided. If for any reasons
the measurements in vacuum are not possible, ushing the chamber with helium is
advantageous.
B. Sample Reflectors
For the trace analysis of granular residues, a carrier with high reectivity that serves as a
totally reecting sample support is required. Therefore, the mean roughness should be in
the range of only a few nanometers and the overall atness should typically be less than
l=20 (l 589 nm, the mean wavelength of the visible light). Furthermore, reectors
should be free of impurities so that the blank spectrum should be free from con-
tamination peaks and the carrier material must not have uorescence peaks in the
spectral region of interest. In addition, the carrier material must be chemically inert (also
against strong chemicals, which are often used for the sample preparation), easy to be
cleaned for repeated use. They should be commercially available and inexpensive.
Typically, they are disk shaped with a 30-mm diameter and a thickness of 35 mm. The
carrier materials commonly used are quartz glass in the synthetic form as Synsil, or
Suprasil, fused silica, and elemental Si. Heavier elements like Ti, Nb, and Ta were
Figure13 Spectrum of a multielement standard (25 ng of each element) prepared as residue sample
on a quartz sample reflector (well-adjusted cutoff reflector). Conditions: TXRF module, Mo tube,
50 kV, 40 mA, 100 s measuring time. S
Sr
and DL
Sr
are the sensitivity factor and detection limit for Sr,
respectively.
recently tested and showed a good performance. Boron nitride, glassy carbon, Plexiglas,
and Perspex (for single use) are suitable (e.g., for the determination of light elements).
All components of a TXRF spectrometer need to be adjusted (at least once) by
translation and rotation stages and tilters, either manually, or by using remote controllers.
To visualize the eect of total reection, one can use a proper charge-coupled detector
(CCD) camera where the x-rays are falling directly on the chip and become visible on a
monitor. In a more traditional approach, the x-rays can be observed on a ZnS screen.
C. Detectors
Total-reection XRF is an energy-dispersive XRF method (see also Chapter 3); the
radiation is measured mainly by Si(Li)-detectors. A good detector oers a high-energy
resolution [Full width at half-maximum (FWHM) in the range of 140 eV at 5.89 keV],
intrinsic eciency close to 1 for the x-ray lines of interest, symmetric peak shapes, and low
contribution to the background. Primarily, incomplete charge collection at the electrodes
leads to low-energy tailing. The detector escape eect creates escape peaks and thus an
increased background in certain spectral regions. An inherent advantage of semiconductor
detectors is the possibility of bringing the detector crystal very close to the sample, which
results in a large solid angle. Light elements emit uorescent lines in the range from 100
to 1000 eV. The usually used Be entrance window would completely absorb them, so new
window materials, oering better transmission characteristics, are used instead.
Figure14 Experimentally determined sensitivities (total) for the K lines of several elements for a
TXRF spectrometer with a cutoff filter. The excitation can be split (theoretically) into the
contributions from the characteristic MoK lines (MoKa Kb) and bremsstrahlung (continuum). The
ratio of the two sensitivity factors depends, among others, on the applied high voltage (in this case
45 kV). Zr and Nb (Z40, 41) have the K absorption edges already above the energy of MoKa.
The development of Peltier-element-cooled detectors is a step in the direction of
being independent of liquid-nitrogen supply. Energy-dispersive detectors with a Si p-i-n
diode and Peltier cooling are used as light hand-sized units with an acceptable resolution
of 160200 eV.
D. Manufacturers of TXRF Spectrometers
Atomika Instruments (Germany), spectrometers for chemical analysis (ch ) and
wafer surfaces (w); e-mail: sales@atomika.com
Atominstitut (Austria) (ch ); e-mail: wobi@ati.ac.at
Diraction Technology (Australia) (ch ); e-mail: rod@pcug.org.au
Italstructures (Italy) (ch ); e-mail: isinfo@italstructures.com
I.U.T. (Germany) (ch ); e-mail: i.u.t@t-online.de
Rigaku (Japan) (w); e-mail: rinttyo@rigaku.co.jp
Technos (Japan) (w); Fax: 0720-20 2002
IV. CHEMICAL ANALYSIS
In 1971, Yoneda and Horiuchi (1971) published an article with the rst experimental
data from an energy-dispersive x-ray uorescence measurement with a Ge detector in
Figure15 Two spectra of a sample with a total mass of 700 ng, containing Mg, Cl, Sc, and so forth
excited with a Cr tube, obtained with a cutoff reflector inserted into the beam path (Cut-off), as a
spectrum-modifying device, and a multilayer monochromator (ML). The spectral background and
the characteristic lines are smaller for the latter case; also the scattered CrKb line is suppressed.
total-reection geometry. The sample was a dried spot of 100 ng of Ni from a water
solution of NiCl
2
on an optical at. In 1974, Aiginger and Wobrauschek (1974)
published results using a Si(Li) detector and a Suprasil reector where 5 mL of Cr salts in
aqueous solution were dried and analyzed with a Cu-anode x-ray tube. A more detailed
publication (Wobrauschek and Aiginger, 1975) contained theoretical considerations,
details of the setup, calibration curves, steps for the quantication, and detection limits
of 4 ng for the element Cr. In 1977, Knoth et al. (1977) presented their rst prototype of
a total-reection XRF spectrometer and analytical results for a blood serum analysis.
From that time on, several groups worldwide participated in the further development of
this technique. From 1986 on, regular biannual TXRF user meetings have been held
(Proceedings of the TXRF Conference, 1989, 1991, 1993, 1995, 1997). The rst book
dealing exclusively with TXRF was written by Klockenka mper (1997).
A. Sample Reflectors and Their Cleaning
Various sample carrier materials have been used for chemical analysis with TXRF, as
mentioned in the previous chapter. Nonreecting residues on top of suitable surfaces give
a doubled uorescence intensity, when measurements are made at angles of incidence
smaller than the respective critical angle for the substrate, owing to the twofold excita-
tionby the direct beam (1) and the reected (2) one (see Fig. 16). The reector must be
long enough so that the latter can fully contribute.
The high sensitivity makes cleaning of the sample carriers critical, particularly in
routine operations when large numbers of them are in use. The following cleaning pro-
cedure has proven to be eective.
1. Mechanical removal of sample residues from previous analysis using tissue or a
brush.
2. Rinsing with water or, in case of organic residuals, with acetone.
3. Gentle boiling for 1 h in a detergent bath (e.g. diluted Extran neutral or acidic),
preferably in special carrier supports from Teon, in order to avoid scratching or
even breaking.
4. Gentle boiling for 1 h in diluted nitric acid (p.a. grade).
5. Rinsing with ultrapure water and subsequent drying.
Figure16 Twofold excitation of the sample for TXRF by the primary beam (1) and the reflected
beam (2), for a case where the reflector is long enough so that beam (2) is observed.
6. Nonhydrophobic surfaces, such as quartz, must be coated with a silicone
solution (e.g., available from Serva) and subsequently dried at 100
C for about
1 h to keep aqueous samples within a small spot.
7. After cleaning, a blank spectrum should be measured for each reector.
B. Special Sample PreparationTechniques for TXRF
Numerous samples have been prepared for TXRF by using sample preparation tech-
niques, which are basically the same as those applied for atomic absorption spectro-
metry (AAS) or ICPOES. There are, however, special cases where suitable sample
preparation techniques are required to take full advantage of the particular features of
TXRF (e.g., the capability of analyzing small samples and the advantage of an inert
sample carrier).
An example is the direct collection of air particulates on the sample carrier with the
aid of size-separating samplers (impactors). Plexiglas carriers can be used. If the collected
air is wet, the aerosols are reliably deposited on the carrier; when the air is dry, they can
be bounced o. This drawback can be prevented by coating the reectors with a thin lm
of suitable grease (Salva et al., 1993). The reectors loaded with collected aerosols can be
directly analyzed after adding an internal standard. Detection limits are in the range of
0.1 ng for a 1-h collection time and a sampling volume of 0.5 m
3
. Of course, aerosols also
can be analyzed after collection on a lter and subsequent digestion of the loaded lter
material (see Fig. 17). Due to direct analysis, systematic errors are avoided (Injuk and
Van Grieken, 1995).
Figure 17 Spectrum of an aerosol sample, which was collected in a Batelle impactor (stage 1)
directly on a polycarbonate sample carrier. On top 30 ng of Sc were pipetted as internal standard
element (Cr anode, 30 kV, 30 mA, multilayer monochromator, 500 s measuring time).
One of the inherent advantages of TXRF is the small sample volume required for
analysis; Only a few nanograms of sample mass (or a few microliters of sample volume)
are required, which might be considered as an advantage compared to some other sensitive
analytical methods for trace analysis.
For liquid samples, the easiest way of performing TXRF is the direct analysis.
A few microliters (of the sample solution mixed with the internal standard) are pipetted
on the sample reector and dried, either in a desiccator, with an infrared lamp, on a hot
plate, or in a (dedicated) oven. The sample support can be utilized to allow chemical
reactions in microliter volumes, for example, in the following way: Up to 100 mL solution
loaded with alkali and alkaline-earth salts are placed on the quartz carrier, previously
rendered hydrophobic by means of a silicone solution. The droplet on the carrier is
spiked with about 5 mL of a 1% sodium dibenzyldithiocarbamate solution. After allowing
the sample to dry for about 30 min, the reector is rinsed with ultrapure water. The
insoluble metal carbamates, including that of the internal standard element, remain xed
on the hydrophobic surface, whereas the soluble matrix is dissolved and removed by the
water. The resulting specimen gives substantially improved detection limits compared to
the unprocessed sample.
The properties of the sample support in combination with the high detection per-
formance of TXRF are also utilized in the analysis of thin sections of tissue (microtome
section). A small piece of tissue is frozen and cut by a microtome in thin sections of about
15 mm thickness. A section is then placed on a sample reector and spiked with an internal
standard. This method was applied to tissue of kidney, liver, and lung. Detection limits of
10 ng=g have been reported (von Bohlen et al., 1988).
C. General Sample Preparation
The detection limits obtained for a special sample depend very much on the sample pre-
paration. Figure 18 gives an overview of various common methods for sample preparation
in TXRF, depending on the kind of sample to be analyzed. Of course, one has to be aware
that sample preparation can cause loss of elements as well as contamination by other
elements, and the sample taken for analysis must represent the whole specimen; therefore,
homogenization might be required.
Solid samples can be crushed and then ground to a ne powder of micrometer grain
size. This powder can be mixed with a liquid to produce a suspension, which can be pip-
etted after adding an internal standard on the sample reector. The pulverized sample can
also be dissolved in a suitable solvent, and after adding the internal standard, an aliquot is
pipetted on the sample reector and dried.
For the decomposition of biological and environmental materials, various methods
have been utilized (e.g. with a low-temperature oxygen plasma asher, followed by dis-
solving the ash in an acid). The most popular method of decomposition of biological and
environmental samples like plants, tissue, sediments, and so forth is the wet digestion in
Teon vessels (Teon bombs) with acids like HNO
3
, HF, HNO
3
HCl, HNO
3
H
2
O
2
,
and so forth, in dierent proportions. Using the hydrouoric acid might be a problem if
quartz glass reectors are used. The use of a microwave oven for heating the Teon
bomb reduces the time of digestion to less than 1 h.
The volume of some sample solutions or any sample containing water can be
reduced by freeze-drying. The sample is frozen and the solvent is evaporated under
vacuum conditions. The dried residue can be dissolved in small volume of acid or wet
digested.
It is also possible to extract traces of certain elements by phase separation. To
a given volume of sample water solutions at appropriate pH and spiked with an internal
standard, an organic solvent is added and mixed thoroughly. Then, the two phases
are separated. The traces of metal ions stay in the organic phase, whereas the matrix
Figure18 Sample preparation methods for TXRF.
Table1 Inuence of Sample Preparation Methods on Detection Limits
Preparation
Sample Drying
Freeze-
drying
Chemical
matrix
separation
Open
digestion Ashing Suspension Solution
Pressure
digestion
Freeze-
cutting
Rain, river water 0.13 ng=mL 20100 pg=mL 320 pg=mL 13 ng=mL
Blood, serum Digestion:
230 ng=mL
2080 ng=mL 40220 ng=mL
Air dust, ash,
aerosols
5200 mg=g 10100 mg=g 0.13 mg=g
Air dust on lter 0.620 ng=cm
2
0.26 ng=cm
2
Suspended matter 325 mg=g 10100 mg=g
Sediment 10100 mg=g 15300 mg=g
Powdered
biomaterial
110 mg=g 0.22 mg=g
Fine roots 110 mg=g Digestion:
0.11 mg=g
High-purity acids 550 pg=mL
Tissue, foodstu,
biomaterial
0.55 mg=g
Mineral oil 115 mg=g
Mussel, sh 0.11 mg=g
High-purity water 1 pg=mL
Source: Data from Klockenka mper, 1997.
elements are left in the inorganic solution. The organic liquid can be directly pipetted
onto the reector. Also, the separation of traces by adding a chelating agent and pre-
cipitating the metal ions is a commonly used technique. The metal complexes are ltered
through a membrane lter and dissolved in a suitable organic solvent.
Generally, the selected sample preparation method has a tremendous inuence on
the obtainable detection limits, which is documented in Table 1. Details on sample pre-
paration procedures can be found in the works of Prange et al. (1989), Klockenka mper
and von Bohlen (1999), Holynska et al. (1996), Dargie et al. (1997).
D. Some Applications
Three main advantages characterize TXRF: simultaneous multielement capability, low
detection limits for many elements, and small sample volume. Additional advantages are
the absence of matrix eects, easy calibration, fast analysis, and comparatively low costs.
Table 2 gives an overview of various kinds of sample that have been already analyzed with
TXRF. Generally all kinds of aqueous or acidic liquids where the liquid matrix can be
evaporated, leaving a small amount on a sample reector, can be analyzed. Oils, alcohols,
whole blood, and blood serum can be analyzed after special treatment.
Typical for TXRF are water samples (Fig. 19). Pure water like rainwater or tap
water can be directly analyzed (Holynska et al., 1998; Barreiros et al., 1997); for riverwater
or seawater as well as wastewater, sample preparation is usually required to remove
Table 2 Applications of TXRF
Environment
Water: Rain water, river water, sea water, drinking water, waste water
Air: Aerosols, airborne particles, dust, fly ash
Soil: Sediments, sewage sludge
Plant material: Algae, hay, leaves, lichen, moss, needles, roots, wood
Foodstuff: Fish, flour, fruits, crab, mussel, mushrooms, nuts, vegetables, wine, tea
Various: Coal, peat
Medicine=biology=pharmacology
Body fluids: Blood, serum, urine, amniotic fluid
Tissue: Hair, kidney, liver, lung, nails, stomach, colon
Various: Enzymes, polysaccharides, glucose, proteins, cosmetics, biofilms
Industrial=technical
Surface analysis: Water surfaces
Implanted ions
Thin films
Oil: Crude oil, fuel oil, grease
Chemicals: Acids, bases, salts, solvents
Fusion=fission research: Transmutational elements Al Cu, iodine in water
Geology=mineralogy
Ores, rocks, minerals, rare earth elements
Fine arts=archeology=forensic
Pigments, paintings, varnish
Bronzes, pottery, jewelry
Textile fibres, glass, cognac, dollar bills, gunshot residue, drugs, tapes, sperm, finger-prints
suspended matter or the salt content. Detection limits are in the low nanograms per
milliliter range. To reduce the detection limits down to the 10-pg=ml level, freeze-drying
with additional leaching of the residue with HNO
3
has to be applied. To remove the salt
matrix from seawater, complexation, chromatographic adsorption, and subsequent elu-
tion have to be performed. This method was developed by Prange et al. (1985). Suspended
matter separated from ltrates can be analyzed by digesting the lter with HNO
3
(Prange
et al., 1993). For the analysis of sediments, microwave digestion is recommended
(Koopmann and Prange, 1991).
Environmental monitoring can also be done by analyzing appropriate plants like
moss or lichen (biomonitoring). The analysis of plants requires a proper sample pre-
paration. After cleaning, shredding, freeze-drying, and nally pulverizing, the powder is
mixed with HNO
3
and digested in a Teon bomb.
Vegetable oil is recommended to be diluted with toluene and an oil-based standard
should be added as internal standard (Reus, 1991). After pipetting an aliquot on the
sample reector, it is heated up to evaporate the volatile parts of the matrix. Detection
limits are in the range of 320 ng=g. Also, low-temperature oxygen plasma ashing is
suitable; the resulting residue has to be dissolved in HNO
3
.
Both depletion and accumulation of trace elements can inuence the biological
functions of human beings. Whole blood and blood serum, amniotic uid, organ tissue,
hair, and dental plaque have been analyzed by TXRF. Detection limits down to 20 ng=mL
for body uids after microwave digestion (Prange et al., 1989) were reported.
Quality control of ultrapure reagents, like acids, bases and solvents can be performed
by using TXRF (Prange et al., 1991). Crude oils (Ojeda et al., 1993), lubricating oils
(Bilbrey et al., 1987), motor oils (Freitag et al., 1989), and diesel fuel (Yap et al., 1988)
have also been analyzed. Light oils can be diluted with chloroform or toluene, the volatile
Figure 19 Spectrum of 10 mL of the NIST water reference standard SRM 1634c, analyzed in an
Atominstitut TXRF spectrometer (Mo anode, 40 kV, 50 mA, multilayer monochromator, vacuum
conditions, 1000 s measuring time).
matrix then removed by evaporation, and detection limits in the range of micrograms per
milliliter are achievable. If detection limits of nanograms per milliliter are required, low-
temperature oxygen plasma ashing is necessary. For forensic applications the micro-
analytical capability of TXRF is appreciated, because microsamples are usually available.
In recent years, several specic problems have been investigated, including analysis of hair
samples, glass particles, tape fragments, drug powder, semen traces, gunshot residues, and
textile bers (Ninomiya et al., 1995; Prange et al., 1995). Oil paints were investigated by
analyzing the pigments, which are characterized by a limited number of major elements.
Cotton tips can be used to remove an amount of about 1 mg from the paint and deposit it
on a sample reector (Klockenka mper et al., 1993).
E. Quantification
One of the inherent advantages of TXRF is the fact that the sample forms a thin lm on
the sample reector; thus, no matrix eects have to be considered and the so-called thin-
lm approximation is applicable (both absorption and enhancement eects can be neg-
lected). The intensity of the uorescent radiation for, the Ka line, for example, of an
element i with concentration c
i
in the sample (with mass m) is then given by
IE
i
Ka

Z
E
max
EE
i
abs
I
0
EG
m
sin j
s
i
Ka
Ec
i
f E
i
Ka
eE
i
Ka
dE 20
where E
abs
is the energy of the absorption edge of element i, E
max
is the maximum energy of
the excitation spectrum, E
i
Ka
is the energy of the Ka line of element i, I
0
E is the spectral
distribution of the exciting radiation, G is the geometry factor, s
i
Ka
is the uorescence cross
section for the K shell of element i, fE
i
Ka
is the absorption factor for the uorescence
radiation between the sample and the detector, and eE
i
Ka
is the relative detector eciency
for the energy E
i
Ka
. It is assumed that the sample is always completely irradiated by the
primary radiation.
In this special case, the relation between concentration and uorescence intensity is
linear. The so called sensitivity [counts=(second)(sample mass)] can be dened:
S
i

I
i
c
i
m
21
and S
i
depends only on fundamental parameters and the measuring conditions, which
usually can be assumed to be constant. When an element St is used as the internal standard
the relative sensitivity (sensitivity factors) for elements i dened as
S
i
rel

fE
i
Ka
eE
i
Ka
R
E
max
EE
i
abs
I
0
Es
i
Ka
E dE
fE
St
Ka
eE
St
Ka
R
E
max
EE
St
abs
I
0
Es
St
Ka
E dE
22
can be established experimentally with articially prepared standards (Fig. 20) or calcu-
lated theoretically. The determination of the concentration c
i
of the element i in an un-
known sample spiked with the same internal standard element is then simple:
c
i

I
i
I
St
1
S
i
rel
c
St
23
There is a linear correlation between intensity I
i
and concentration c
i
. The addition of
one element as the internal standard of known concentration to the sample is necessary
primarily because of the inhomogeneous excitation due to the standing-wave eld above
the sample reector surface, where the sample is positioned. Also, geometric and vol-
umetric errors can be canceled.
A sample is thin if its thickness does not exceed the critical thickness
(Klockenka mper, 1997), which is about 4 mm for organic tissue, 0.7 mm for mineral
powders, and 0.01 mm for metallic smears. Under the assumption that the matrix ab-
sorption for the analyte diers only slightly from that of the internal standard element,
these values can generally be higher by a factor of 10400. For the calculation of these
values, the standing-wave eld was not taken into account. This eect and the sample self-
absorption can lead to contradictory requirements for the sample thickness (de Boer,
1991a).
Figure 21 shows a comparison of detection limits for various analytical methods in
the trace element range, following the work of Klockenka mper (1997). Inductively coupled
plasmamass spectrometry (ICPMS) and INAA are more macro than micro methods. In
comparison, TXRF requires only very small sample volumes (in the range of microliters).
ICPMS provides lower detection limits, but both spectral interferences and matrix eects
make quantication more complex.
V. SURFACE ANALYSIS
In order to remain competitive, the semiconductor industry is being constantly forced to
increase the performance and reduce the cost of integrated circuits by shrinking device
Figure 20 Fitted calibration curve (relative sensitivities) for K lines (Atominstitut TXRF module,
Mo anode) with Ga as internal standard element. The circles represent the measured elements
actually used for the calibration (standard solutions with various concentrations). Other elements in
a sample can also be determined by interpolation (in this case, S, K, Mn, Br, and Rb).
Figure 21 Relative detection limits of INAA, TXRF, ET-AAS, and ICPMS, applied to trace
analysis of aqueous solutions. A 50 mL specimen was used for TXRF and ET-AAS; 3 mL were
needed for INAA and ICPMS. The individual values are approximated after the work of
Klockenka mper (1997).
dimensions and increasing the number of devices per unit area on chips. A strong
correlation has been found between the presence of metal contamination on the wafer
surface and process yields. Even very low concentrations of dispersed metals can create
defects at the atomic scale, which lead to leakage current, gate insulator breakdown, or
poor threshold voltage control. All of these can result in device failure or reliability
problems. With decreasing size of devices, the acceptable level of metal contamination
decreases as well. The ability to measure low levels of contamination is crucial for the
development of techniques to be used to remove these contaminations. The Semi-
conductor Industry Association (SIA) 1997 National Technology Roadmap for Semi-
conductors (NTRS; http:==www.sematech.org) projects that the required sensitivities for
the transition metals will be at the level of 3610
8
atoms=cm
2
in the year 2001.
One of the most important applications showing the analytical power of TXRF is
the analysis of impurities on the surface of Si wafers (Na, Al, Ca, Ti, Fe, Ni, Cu, Zn, etc.)
for the semiconductor industry (Knoth et al., 1989; Berneike et al., 1989; Weisbrod et al.,
1991; Schwenke et al., 1992). The sample is the wafer itself, with its polished plane surface
having already the quality required for total reection of x-rays (sometimes except at-
ness). With the attributes of TXRF [nondestructive analysis, multielement capacity,
mapping ability (Fig. 22), and excellent detection limits], this technique dominates over
Figure 22 Wafer mapping for the element Na of 7610 spots (1-mm scan steps, relative
coordinates). Synchrotron radiation excitation (SSRL, Beam line III-4), measuring time for each
pixel: 10 s.
others in this eld. Presently, the 10
9
-atoms=cm
2
level is reached by TXRF using standard
tube excitation (Atomika TXRF8030W, http:==www.atomika.com) or rotating anode tube
excitation (Philips TREX 630 T=S, http:==www.analytical.philips.com; Rigaku 3750
TXRF). The possibility to map a wafer [i.e., scan several points on the surface and de-
termine the level of contamination as a function of the coordinates (Berneike, 1993)], can
help to locate sources of contaminations uniquely.
To measure surface contaminations on wafers, a special setup is required, without
any front surface contact and with a possibility of making measurements at various
angles (Fig. 23). Correct quantication is strongly related to the glancing angle setting.
Measuring the angle dependence of the uorescence signal allows one to distinguish
the form of the contamination (i.e., if it is lm or particulate type). Figure 24 shows the
uorescence intensities of Si, Sc, and Ni as a function of the incident angle around the
critical angle. The steplike function (Sc) is obtained if the contamination is found in
particles on the surface of the wafer (equivalent chemical analysis TXRF). The peaking
curve (Ni) is obtained when the atoms are evenly distributed within a layer of a few
nanometers thickness placed on the wafer surface. Most of the real samples do not show
one of these extreme cases. Prange and Schwenke, (1992) rst gave some examples of
applications of TXRF for surface analysis. If one does not want to measure the complete
angle-dependent behavior, only a single measurement performed at the operating angle,
where the two curves (Sc, Ni) are crossing, allows accurate quantication. For com-
pleteness, the typical curve for the bulk material (silicon of the wafer) or bulk con-
tamination is given. Usually, the bulk Si signal is used for control of the angular
adjustment.
Figure 23 Typical components of a TXRF spectrometer for wafer analysis with all necessary
degrees of freedom for surface mapping (x and y movement), height control (z movement), and
rotation around the x axis (angle of incidence). The special detector and the evacuable sample
chamber allow also the detection of low-Z elements.
A. Quantification
For the case of granular residues on a substrate (particulate type), which is equivalent to
chemical analysis by using TXRF, the intensity above the critical angle is constant because
the thin, small sample is completely excited. The intensity doubles at the critical angle in
a steplike fashion and remains at the twofold value down to very small angles due to total
reection,
I
particle
i
j
0
k
particle
I
0
c
i
1 Rj
0
24
following the angular behavior of the reection coecient Rj
0
. This intensity is pro-
portional to the primary intensity I
0
and the interesting area-related concentration c
i
. For
incidence angles j
0
below j
crit
, Eq. (24) can be simplied to
I
particle
i
2 k
particle
I
0
c
i
24a
For buried layers (lm like) in a substrate, the intensity far above the critical angle becomes
constant. The asymptotic behavior of the intensities for the particulate and lmlike con-
taminations can even be equal if both concentration values are the same and the appro-
priate scaling factors k
particle
and k
lm
are chosen. However, the intensity for the buried
layers steadily increases with decreasing angle and can reach (theoretically) the fourfold
value at the critical angle. For the smaller incidence angles, the intensity is going to zero,
according to
I
film
i
j
0
k
film
I
0
c
i
1 Rj
0
j
0
z
P
k
film
I
0
c
i
Tj
0
j
0
j
T
j
0
rt
m
25
Figure24 Fluorescence intensities of Sc, prepared as a residue sample (conventional TXRF), Si of
the sample refractor substrate, as representative of bulk signal, and Ni, prepared as a thin-film
sample. The angles of incidence are normalized to the respective critical angles.
Z
P
is the penetration depth as dened in Eq. (15). The angular behavior is caused by the
countereect of the transmission coecient Tj
0
and the refraction angle j
T
.
The intensities of the characteristic x-rays for homogeneously distributed con-
taminations and major constituents(s) in an innitely thick and at substrate can be
described by
I
bulk
i
j
0
k
bulk
I
0
c
i
1 Rj
0
j
0
k
bulk
I
0
c
i
Tj
0
j
0
26
which is related to Eq. (19) with respect of the angular behavior. Due to the geometry
factor, represented by the direct proportionality to j
0
, there is a monotonous increase in
intensity for angles above the critical angle.
For practical purposes, the divergence of the primary beam should be considered.
The scaling (calibrating) factors k must be determined during the calibration of an in-
strument. Layer-type external standards produced by immersion or spin coating of a wafer
with a spiked solution are recommended (Torcheux et al., 1994; Mori et al., 1995);
however, particulate-type (Fabry et al., 1995) and bulk-type standards have been used
(Gutschke, 1991; Schwenke and Knoth, 1995). All types of standards are commercially
available. Calibration by internal standard is not permissible.
A common preconcentration technique used for the analysis of Si-wafer surfaces is
VPD (vapor-phase decomposition). The wafer is exposed to HF vapor, leading to dis-
solution of the SiO
2
surface layer of the wafer (Neumann and Eichinger, 1991). The
impurities can then be collected by scanning the surface systematically with a droplet of
a special liquid or water from the whole surface. The droplet can then be dried and
measured by TXRF. This leads to a detection capability of 10
8
atoms=cm
2
; the im-
provement is given by the area of the wafer (100 mm, 200 mm, 300 mm ) divided by the
area seen by the detector. The disadvantages of the wafer analysis with VPD pre-
concentration are the loss of the local information and the destructive character (Fabry
et al., 1994). Care must be taken to get a residue within an acceptable small area and to
place it just under the detector.
VI. THINFILMS ANDDEPTHPROFILES
In many technological applications, thin-layered materials and implantations have an
increasing importance. A characterization of such structures can be achieved with angle-
dependent x-ray uorescence analysis in the region around the critical angle of total re-
ection. As the penetration depth of the incoming x-rays changes from the nanometer to
the micrometer region when the angle of incidence passes the critical angle, information
can be obtained on depth distributions and thin lms in that range.
A. Depth Profiles
The uorescence intensity I
i
j
0
of an element i, implanted in a at smooth substrate, with
a depth prole c
i
z showing a variation of its concentration over depth z (normal to the
surface), is a function of the incident angle j
0
:
I
i
j
0
/ Tj
0
j
0
j
T
j
0
Z
1
z0
c
i
z exp
m
1
j
T
j
0
m
2

rz
!
r dz 27
which is the generalized form of Eq. (26). The mass-attenuation coecients m
1
and m
2
describe the absorption of the exciting and the uorescence radiation of the element i,
respectively; r is the density of the substrate. The transmission coecient Tj
0
takes into
account the refracted part of the incoming radiation and j
T
is the refraction angle inside
the substrate. Examples are given for Ni (Fig. 25) and Al (Fig 26) depth proles.
In practice, the general shape of a depth prole has to be given and some parameters
can be tted (Kregsamer et al., 1999) or dierent functions can be tested (Weisbrod et al.,
1991; Schwenke et al., 1997; Mori et al., 1997), although, theoretically, a Laplace trans-
formation is possible.
B. Thin Films
The composition, density, and thickness of single as well as periodic and nonperiodic
multiple lms can be analyzed (Weisbrod et al., 1991; Schwenke et al., 1992). The uor-
escence intensity I
i
j
0
of an element i (with concentration c
i
) embedded in a single thin
lm with thickness d on top of a at smooth substrate, is a function of the incident angle
j
0
and is described by (de Boer, 1991a, b)
I
i
j
0
/ c
i
jE
T
j
2
1 expm
1
=j
T
m
2
rd
m
1
=j
T
m
2
&
jE
R
j
2
1 expm
1
=j
T
m
2
rd
m
1
=j
T
m
2
2 Real part E
T
E
R
1 exp fi4pj
T
=lr m
2
grd
i4pj
T
=lr m
2
'
28
Figure 25 Calculated NiKa fluorescence intensities as a function of the incidence angle for Ni
depth profiles in quartz excited by MoKa (normalized to values at 10 mrad). As a depth distribution
for the Ni atoms, a step function was assumed. The maxima of the angle distributions with less than
50 nm are in the vicinity of the critical angle of quartz ( 1.8 mrad).
The electric elds E
T
(transmitted by the lm surface) and E
R
(reected from the substrate)
are derived from Fresnels equations and are complex quantities. The wavelength of the
exciting radiation is l. The formation of standing wave above a reecting surface is al-
ready taken into account by this formalism. An example is given for a Ni thin lm in
Figure 27.
The layer(s) and the substrate must be homogeneous, at, and smooth, with perfectly
sharp interfaces. With some eorts, even a certain roughness of the interfaces can be taken
into account in the calculations (van den Hoogenhof and de Boer, 1993; Nevot and Croce,
1980). A review on grazing incidence X-ray spectrometry and reectometry had been given
by Stoev and Sakurai (1999).
VII. SYNCHROTRONRADIATIONEXCITATION
There are dierent strategies to improve the detection limits, either by increasing the
sensitivity, by reduction of the spectral background, or extending the measuring time
(which, however, is limited for practical reasons).
One approach to reducing the spectral background it to use total-reection geo-
metry. A further possibility for reducing the background is the use of polarized primary
radiation (Ryon and Zahrt, 1993; Aiginger and Wobrauschek, 1974). Due to the ani-
sotropy in the intensity of scattered radiation, it is advantageous to place a detector in
such a position that almost only the isotropic emission of the uorescence signal is
detected. It is possible to combine TXRF with polarized primary radiation excitation.
Moreover, the use of monochromatic primary radiation improves the background
conditions, because only photons with one energy are scattered (incomplete charge
Figure 26 Angular dependence for the intensity of the AlK line obtained for 10
16
atoms=cm
2
Al
ions implanted in silicon at 80
to the surface normal. Fitted with an asymmetric triangular depth

distribution with several depths of the maximum as parameter (the best fit is for 10 nm).
collection still causes a background). Tunable monochromators enable the exciting en-
ergy to be adjusted slightly above the absorption edge of the element of interest (se-
lective excitation). Sometimes, it is even possible to set this energy below the absorption
edge of a matrix element with high concentration, with the drawback, however, of an
increased background due to Raman scattering if it is too close to this edge.
Highly intensive broad-band photon sources realized in the synchrotron radiation
facilities can increase the sensitivity by orders of magnitude as compared to conventional
x-ray tubes. Its outstanding properties oer new possibilities for TXRF. The intense
primary beam with a continuous spectral distribution from infrared to high-energy pho-
tons, the linear polarization in the orbit plane, the small source size, and its natural col-
limation are features best suited for the excitation in total-reection geometry. For
optimum excitation conditions, the spectral distribution can be modied by using elements
like cuto mirrors, crystal and multilayer monochromators and lters, and so forth
(Wobrauschek et al., 1997a, b).
Multilayer monochromators are well suited for synchrotron radiation-excited XRF
(Bilderback, 1982; Pianetta and Barbee, 1988). In comparison to crystal monochromators,
they oer a larger bandwidth (DE=E%0.01), which leads to higher photon ux on the
sample. The combination of TXRF with synchrotron radiation can be achieved by several
geometrical arrangements for the entrance slit, sample reector, and detector. Figure 28
shows three possibilities. For the uppermost geometry (Fig. 28a), the polarization eect is
fully utilized by positioning the detector axis in the plane of the orbit. Scattered radiation
is not emitted in that direction. The beam eciently and homogeneously illuminates the
Figure 27 Calculated NiKa fluorescence intensities as a function of the incidence angle for Ni
films on quartz substrate, excited by MoKa (normalized to values at 10 mrad). For a thickness
around 1 nm, the maximum of the distribution is found at the critical angle of quartz (1.8 mrad). For
around 25 nm film thickness, the maximum position coincides with the critical angle of nickel
(3.6 mrad).
Figure 28 Three possible geometrical arrangements of synchrotron radiation-excited TXRF.
sample with a certain width in the horizontal plane. There are no losses due to the entrance
slits particularly, because the beam is naturally collimated in the vertical plane (0.1
0.2 mrad, depending on the energy), whereas the detection of the uorescence signal is not
optimum, because the detector must be side-looking (to utilize the polarization eect). The
uorescent radiation has a long path in the sample itself before it reaches the detector.
The excitation conditions for the arrangement in Figure 28b are poor. Most of the
photons in the horizontal plane are stopped in the collimation system. The vertical in-
tensity distribution drops drastically and, therefore, the uorescence intensity also drops
with the deviation of sample regions from the plane of reference. However, the geo-
metrical detection eciency is very good. Good excitation and detection conditions will
be met with the arrangement in Figure 28c. Unfortunately, the polarization eect is not
used at all.
Experiments have been performed at HASYLAB, Beamline L, with a bending
magnet (Wobrauschek and Streli, 1997). The arrangement can be seen in Figure 29, fol-
lowing the geometry of Figure 28b, with the vertical reector and the side-looking de-
tector. The beam is collimated by a primary slit system and then impinges on a multilayer
monochromator. The nonreected part of the primary beam behind the monochromator is
absorbed in a beam stopper. The shielding of the vaccum chamber is extremely important
because of multiple scattering eects for high-energy photons. The beam is totally reected
on a rectangular Suprasil reector with a Ta plate at the front edge to prevent scattering
from the front edge into the detector (Rieder et al., 1995; Wobrauschek et al., 1997a, b;
Go rgl et al., 1997). For spectra, see Figures 30 and 31. Several other groups also per-
formed synchrotron radiation-excited TXRF experiments, for example, in Japan (Iida,
1991; Kondo et al., 1997), at NSLS (Pella, 1988), at SSRL (Brennan et al., 1994) and at
Frascati (Sanchez et al., 1994).
The semiconductor industry requires the analysis of wafer surface contaminations at
ultratrace-level detection limits in the 10
8
-atoms=cm
2
range (corresponding to femtograms
in mass units). Synchrotron radiation-excited TXRF has therefore become an interesting
tool for the task. Experiments have been performed at HASYLAB, leading to detection
limits of 13 fg for Ni in a droplet sample, simulating the VPD method (or 1.3610
8
atoms=cm
2
assuming an inspected area of 1 cm
2
) (Wobrauschek et al., 1997a, b).
A group at SSRL (Pianetta et al., 1995, Fischer-Colbrie et al., 1997) established a
spectrometer for routine wafer analysis at SSRL, Beamline 6-II (focused wiggler beam line
Figure 29 Experimental setup for TXRF experiments at HASYLAB, utilizing the radiation from
the DORIS III positron storage ring. Several slits and diaphragms and beam stoppers are used to
prevent the count-rate saturation of the detection system by direct and scattered radiation from
primary beam, transmitted photons through the monochromator and so on.
with a double multilayer monochromator). The measurements are performed under a
clean-room environment. The automatic handling for 150-mm and 200-mm wafers, the
possibility of wafer mapping, and detection limits of 3610
8
atoms=cm
2
for transition
metals meet the requirements of the semiconductor industry. The wafer is held by a
Figure 30 Spectrum of a 10-pg Ni sample on a Si-wafer substrate. Measured at HASYLAB,
Beamline L, with monochromatic excitation at 10 keV, 77 mA ring current, and measuring time
100 sec. A 10-mm-thick Al detector filter suppresses the SiK lines. Ca, Fe, and Cu originate from
contaminations. The extrapolated detection limits for Ni were determined as 13 fg.
Figure 31 Spectrum of a 200-pg Cd sample. Measured at HASYLAB, Beamline L, with
monochromatic excitation at 31.3 keV, 70 mA ring current, and 100 s measuring time. The
extrapolated detection limits are 150 fg.
combined vacuumelectrostatic chuck in the vertical position, the detector is side-looking,
and the measurements are performed under vaccum conditions.
A project is being implemented at ESRF on an undulator beamline (Comin et al.,
1998). A Si(111) double-crystal monochromator as well as a multilayer monochromator
will be used. The wafer will be held by a chuck in the horizontal position and two detector
arrays consisting of seven elements in a side-looking geometry will measure the uorescent
radiation (down to Na). Detection limits below 10
8
atoms=cm
2
are expected for 200- and
300-mm wafers.
VIII. LIGHT ELEMENTS
There is a lack of analytical methods performing nondestructive and rapid multielement
determinations of light elements at trace levels. TXRF can be suitable for these purposes
(Streli et al., 1991, Streli et al., 1993a, b) if a special spectrometer adapted to the specic
problems of the energy-dispersive detection of low-energy radiation is used. The detection
limits achievable are mainly inuenced by the kind of excitation source, which should
provide a large number of photons with the energy near the K absorption edge of these
elements (from 200 eV upward). Of determining inuence is the integral over the intensity
of the source spectrum I
0
E multiplied by the photoelectric absorption coecient t
i
E of
an element i
I
i
/
Z
I
0
Et
i
E dE 29
The absorption coecient drops steadily as the energy E increases above an elements
absorption edge. Therefore, (diraction) x-ray tubes with standard anode materials (Sc,
Cr, Cu, etc.) are poor exciters for light elements, as their characteristic emissions are far
above the absorption edges of the elements of interest. To improve the sensitivity for
light elements, it is necessary to use either an x-ray tube which emits intensive char-
acteristic radiation with an energy as close as possible to the absorption edge of the
interesting element, or synchrotron radiation with its continuous spectral range down to
low energies.
The spectrometer used for the experiments described in Sec. VIII is characterized
in detail in the works of Streli et al. (1993a, b). A special Ge(HP) detector which meets
all the requirements for low-energy detection is used. It has a thin entrance window
(diamond window, 0.4 mm thick, transmission for oxygen Ka 85%), an ion-implanted
contact layer, a thin dead layer, and a low electronic noise contribution (FWHM at
5.9 keV125 eV). Measurements were performed under vacuum conditions to reduce
absorption. The radiation of a Cr x-ray tube (1.3 kW) was monochromatized with a
W=C multilayer. Details are described in the work of Streli et al. (1995).
To improve the excitation conditions, a windowless x-ray tube was used. Recently,
various anode materials were tested after computational optimization of the takeo
angle of the x-ray tube to obtain a high photon ux on the sample. The calculation takes
into account the required brilliance and the self-attenuation of the emitted photons in
the anode. Al, Si (Fig. 32), and Mo were tested experimentally as anode materials.
Si oers the advantage of a high t value for Al, but a low one for Si itself, which is often
the major constituent of the reector substrate. For the analysis of impurities on
Si-wafer surfaces, this is a great advantage, because the high uorescence intensity of
Si is reduced (Streli et al., 1997a, b). Detection limits obtained dier very much with the
excitation conditions. The standard Cr x-ray tube provides about 90 pg for Mg, with the
windowless Si-anode tube, 7 pg were obtained.
Synchrotron radiation as an excitation source oers the advantage of an intensive,
naturally collimated x-ray beam of a wide spectral range, also in the low-energy region; it
is, therefore, the ideal source for light elements determination by TXRF. Experiments
have been performed at SSRL, Beamline III-4. This bending magnet beam line is equipped
with a horizontally deecting torroidal Au mirror to cut o photons with an energy higher
than 3 keV. A dierential pumping system oers the possibility of connecting the mea-
suring chamber directly, without any window. Various lters and a double multilayer
monochromator can be inserted into the beam path. The evacuable sample chamber was
connected to the monochromator chamber with a exible coupling and an interlock valve
that closes the main valve upstream if the pressure exceeds 10
73
mbar. Due to the down-
looking design of the used detector, the advantage of the linear polarization of synchro-
tron radiation for further background suppression could not be utilized (Streli et al., 1994,
1997a, b). In order to adapt the spectral distribution of the synchrotron radiation for the
analysis of Si-wafer surfaces, a 12-mm-thick Si lter was inserted into the beam path,
leading to quasimonochromatic radiation with a bandwidth of about 400 eV ( just below
the absorption edge of Si).
A promising application of low-Z TXRF is the quality control of Si-wafer sur-
faces. For the semiconductor industry, Al and Na are of special interest, because they
inuence the production yield of ICs negatively. It is important to have an analytical
method sensitive enough for the determination of ultratraces of these elements. Droplet
samples of 100 pg of Mg had been prepared on Si-wafer surfaces and analyzed with
synchrotron radiation excitation. The best results were obtained for the quasimono-
chromatic mode with detection limits of 60 fg for Mg (Fig. 33) (Streli et al., 1997a, b).
Figure 32 Spectrum of 4.5 ng of Na, Mg, and Al each. The sample was measured in an evacuated
TXRF spectrometer with a Si-anode windowless x-ray tube (20 kV, 25 mA, 200 s measuring time),
cutoff reflector, and a Ge(HP) detector with a diamond window.
Depth prole and thin-lm analysis of low-Z elements, usually not detectable by
conventional instruments, can be performed by synchrotron radiation excitation. An
angular scan for a thin lm of carbon (25 nm) on silicon demonstrates the power of
synchrotron-radiation-excitation XRF in total-reection geometryeven for low-energy
uorescent lines (Fig. 34).
Currently, there is only one TXRF spectrometer commercially available for the
determination of Na and Al, with a rotating W-anode x-ray tube (excitation by WM lines);
detection limits of 8610
10
and 3610
11
atoms=cm
2
for Na and Al, respectively, were ob-
tained (Fukuda et al., 1997).
IX. RELATEDTECHNIQUES
A. X-ray Reflectometry
X-ray reectometry is widely used for the analysis of surfaces and determination of
parameters of single-layer or multilayer thin lms. Usually a y2y scan with a gonio-
meter (monochromatic excitation) is performed in the regime of glancing incidence
with a proportional counter in order to obtain the characteristic intensity proles
(Kiessig fringes) and Bragg peaks for periodic structures (Leenaers et al., 1997). The
applications include measurements of layer thickness, surface and layer density, surface
and interface roughness, and the characterization of periodic (and nonperiodic) mul-
tilayer structures. In the case that all parameters are well specied, x-ray reectometry
can be used for the determination of the atomic scattering factor (Stanglmeier et al.,
1992).
Figure 33 Spectrum of a 100-pg Mg sample on a Si wafer. Measured at SSRL, Beamline III-4
with 12-mm-thick Si filter inserted into the primary beam path (ring current 54 mA, measuring time
100 s). The extrapolated detection limits are 60 fg. Na and Al were contaminations.
B. Grazing Emission XRF
In grazing emission XRF, the uncollimated, polychromatic excitation radiation hits the
sample (placed on a reecting substrate) normally to the surface and the uorescence
radiation (generated near the sample surface) is detected under exit angles equal to the
critical angle of total reection (Becker et al., 1983). According to Snellius law [Eq. (6)],
the scattered radiation cannot be detected for very small detection angles, due to the fact
that for x-rays, vacuum (air) is optically denser than the reector material, which will
result also in almost background-free spectra (de Bokx et al., 1997; Urbach and de Bokx,
1996; Claes et al., 1997a, b).
If a collimated or focused primary beam can be used, a lateral resolution of a few
micrometers can be obtained. The energy-dispersive detector (as used for TXRF) can be
replaced by a wavelength-dispersive detector, enabling a more reliable detection of the
characteristic x-rays of the light elements (because of the better energy resolution for
low energies). On the other hand, sample self-absorption eects become more severe,
because of the great path length of the emerging uorescence radiation of the low
energy.
Grazing-incidence and grazing-exit XRF is another modication of the angle-
dependent XRF method. When both the incident and the detected uorescent beams are
at grazing angles, the uorescent intensity can provide information on the chemical
composition of thin lms and vertical concentration proles. Both the incident and takeo
angles have to be controlled with high accuracy and are strongly restricted in their di-
vergence, which poses severe constraints to the intensity (Sasaki and Hirokawa, 1990;
Tsuji et al., 1993, 1994, 1995, 1996, 1997, 1999a, 1999b; Sato et al., 1996).
Figure 34 Carbon K fluorescence intensity as a function of the angle of incidence for a 25-nm
thin-film sample prepared on a Si substrate. Measured at SSRL, Beamline III-3, monochromator set
to 1.74 keV. The model used for fitting yielded a 18-nm thickness.
C. Total-Reflection Particle-Induced X-ray Emission
Ions with energies of a few megaelectron volts have been used to excite target atoms. The
de-excitation can result in the emission of uorescence radiation, which is known as
particle-induced x-ray emission (PIXE). Experiments with proton and a-beams at small
incident angles ( <35 mrad) have been performed (van Kan and Vis, 1996a, 1996b, 1997).
The determination of the angle at which such particles are being reected from a surface
requires the ionsurface interaction potential to be considered. For smaller angles, the
impulse component of the incoming particle perpendicular to the target surface becomes
too small to overcome the potential and the particle is reected. There is no well-dened
angle below which reection takes place.
D. Grazing-Exit EPMA and Grazing Exit PIXE
A new method of grazing-exit electron probe microanalysis (EPMA) was developed (in-
cident electron angle approximately 45
) (Tsuji et al., 1999a). The x-rays emitted under

grazing-exit conditions of samples with particles collected on a sample carrier from the
carrier surface and the particles were measured. It was found that surface-sensitive ana-
lysis with low spectral background was possible. Both wavelength-dispersive and energy-
dispersive detectors were tested for this purpose.
The grazing exit technique was also applied to PIXE analysis of thin lms and
aerosols deposited on Si wafers, where a 2.5-MeV proton beam bombarded the sample at
an incident angle of 90
(Tsuji et al., 1999b).

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10
Polarized Beam X-ray Fluorescence Analysis
Joachim Heckel
Spectro Analytical Instruments, GmbH & Co. KG, Kleve, Germany
Richard W. Ryon
Lawrence Livermore National Laboratory, Livermore, California
I. INTRODUCTION
In this chapter, we explore the sources of spectral background and show how polarization
eects can yield improved detection thresholds. In 1963, Champion and Whittem pointed
out that the detection of Co traces in aqueous solution can be improved signicantly
due to polarization of the background in a wavelength-dispersive x-ray uorescence
(WDXRF) setup. We see that the stationary arrangement of components used in energy-
dispersive x-ray uorescence (EDXRF) is ideally suited for geometrical congurations that
exploit polarization phenomena to reduce background and thereby improve signal-to-
noise ratios. The ability of simultaneously measure a wide range of elements is one of the
greatest advantages of EDXRF. This advantage is strongly reduced when the count-rate
limitation of the ED detection electronics is taken into consideration. This is due to si-
multaneous recording of the entire primary source radiation scattered on the specimen and
is especially true for examinations on samples with light matrices. Thus, the main purpose
of this chapter is to show that the multiple-element character of EDXRF can be ad-
vantageously utilized through the application of polarized x-rays.
Observed spectral background is caused by several interactions of radiation with
system components, the specimen, and the detector. A principal cause of background is the
scatter of source radiation by the specimen into the detector. The scattered radiation adds
directly to the background under analyte lines when broad-band primary radiation is used to
excite uorescence. Even when monochromatic radiation is used for excitation, the scatter of
this primary radiation adds indirectly to the background because of incomplete charge
collection in the detector. In addition, primary radiation carries with it uorescence fromthe
x-ray tube anode contaminants and collimator materials, and the scattered radiation causes
uorescence of collimator materials between the specimen and the detector, and the gold
contact layer on the surface of the detector. Scattered radiation also causes low-energy
background due to the residual electron kinetic energy when Compton scatter from the
detector itself occurs. All of these sources of spectral noise and interference can be reduced by
minimizing the scatter of source radiation into the detector by using polarized radiation to
excite uorescence. The most important advantage of this technique intrace element analysis
is that the intensity of the source radiation can be increased, thereby proportionally
increasing the intensity of analyte lines without exceeding the count-rate limitations of the
detection electronics due to the counting of unwanted scattered source radiation.
The following thought experiment demonstrates how the spectral background re-
duction stemming fromthe use of a polarized x-ray source leads to improved sensitivities and
detectionlimits. Polarizedandnonpolarizedradiationwiththe same spectral distributionare
used to excite uorescence and the two spectra are compared. The source intensities are
adjusted to give the same count rate in each case by adjusting the x-ray tube current. Then,
N B
np
i
np
N B
p
i
p
1
where N is the spectral sum of all net peak counts per second (cps) and per milliampere,
B is the spectral sum of all background counts per second (cps) and per milliampere, i is
the tube current (in mA) and the subscripts np and p indicate the nonpolarized case and
the polarized case, respectively.
Using excitation with polarized radiation with a degree of polarization of P
(0 P1), the background [see also Eq. (18)] is reduced to
B
p
1 PB
np
2
which leads to
N B
np

i
p
i
np
N 1 PB
np
3
The matrix-dependent ratio consisting of the net count rate and the background count
rate, V N=B
np
, is a deciding factor for the required increase in the current F i
p
=i
np
:
F
i
p
i

1 V
V 1 P
4
If one considers three practical examples, it is possible to recognize the advantages and
also the limits of polarized EDXRF (EDPXRF).
Example 1: Traces in polymers are measured using a polarization degree of 90%
P 0:9 that can be achieved in practice with EDPXRF. For this application,
V % 0, which leads to F 10. The net count rate, N, and, with it, the sensitivity
are improved by a maximum factor of 10 when polarization is used. The
spectral background is the same for both types of excitation when the current is
increased in the polarized case. In this example, the detection limits improve
proportionally to the sensitivity, also by a maximum factor of 10.
Example 2: Using synchrotron radiation with a polarization degree of approxi-
mately 97% P 0:97, the sensitivity and the detection limits can be improved
by a factor of about 33 for idealized applications from Example 1.
Example 3: In practice, a polarization degree of 90% P 0:9 can be achieved with
EDXRF and is used to measure elements in steel. For this application, V % a,
thus F 1, because the uorescence excitation is absolutely dominant
compared to the scatter in the specimen. Therefore, there is no advantage in
using polarized radiation for this example.
Example 1 demonstrates that the spectral background for EDPXRF can be identical with
the spectral background for unpolarized excitation. From this, it follows that an
additional improvement in the detection limits can be achieved through the use of
radiation lters with EDPXRF.
Polarized x-rays may be produced by various interactions of radiation with matter
(Howell and Pickles, 1974) or the source may be intrinsically polarized, as in synchrotron
radiation. When using conventional x-ray tubes, radiation caused by a single collision of
an electron with the anode is polarized. Examples are bremsstrahlung from thin targets
and radiation near the maximum energy for thick targets. X-rays passing through crystals
by Borrmann diraction are also polarized. However, scattering of x-ray tube radiation
from suitable materials has proven to be the most promising for EDPXRF facilities. With
x-rays, the index of refraction is very near to unity, so the corresponding angle required for
nearly complete polarization is p=2.
II. THEORY
A. Scattering of Nonpolarized Radiation
A decade after the discovery of x-rays by Roentgen in 1895, Barkla (1905) demonstrated
that this newly discovered radiation could be polarized by scattering, thus supporting the
hypothesis that x-rays are electromagnetic radiation (i.e., their wave nature). A few years
later, Friedrich et al. (1913) demonstrated x-ray diraction, which also substantiated the
electromagnetic hypothesis.
Thomson and Thomson (1933) found, based on the classical electromagnetic theory,
that the intensity of radiation scattered by a free electron is
I
S
I
0
1
r
2
e
2
m
0
c
2

2
sin
2
a 5
where I
0
is the intensity of the incident beam at the x-ray tube window, I
S
is the intensity
of the scattered beam at distance r, e is the charge of the electron 1:6 10
19
C, m
0
is the
rest mass of the electron 9:11 10
31
kg, c is the speed of light 3:00 10
8
m=s, r is the
distance to the point of observation (m), and a is the angle between the scattering electron
~
S (Pointing vector) and the direction of acceleration of the electron. The acceleration
vector is perpendicular to the direction of propagation of the incident radiation
~
S
0
and
parallel to the electric eld vector
~
E
0
of the incident radiation. If
~
S
0
is in the z direction
and
~
S is in the xz plane, the situation is as shown in Figure 1. For standard x-ray sources,
such as x-ray tubes,
~
E
0
of the photons incident on the scattering electron is random in
direction (but always perpendicular to the direction of propagation) so that on the
average
hE
2
0;x
i hE
2
0;y
i
1
2
E
2
0
6
To obtain the scattered intensity at a general scattering angle Y in the xz plane, it is
simply necessary to decompose the incident
~
E
0
into components and sum their individual
intensity contributions. Now,
~
E
0;y
causes the electron to oscillate in the y direction so that
the angle a p=2 and sin
2
a 1.
~
E
0;x
causes the electron to vibrate in the x direction,
so the angle a p=2 Y and sin
2
a cos
2
Y, where Y is the indicated scattering angle.
Combining these considerations of the dependencies of
~
E
0;x
and
~
E
0;y
on the scattering
angle a and recalling that the intensity of a wave is equal to the squares of its amplitude
I E
2
0
E
2
0;x
E
2
0;y
, the following result is obtained from Eqs. (5) and (6):
I
S
I
0
1
2r
2
e
2
m
0
c
2

2
1 cos
2
Y 7
From small-angle solid geometry, the quantity r
2
in Eq. (7) is equal to dA=dO, where dA is
the surface area of the expanding wave front of the solid angle dO at a distance r from the
point of scatter. Therefore,
I
S
I
0
dA
r
2
e
2
1 cos
2
Y dO
ds
e
dO
dO 8
If the intensity of the scattered radiation is summed over the surface area dA, the fraction
of the incident photon ux, which is scattered by the electron into the solid angle dO in the
direction Y, where r
e
e
2
=m
0
c
2
2:82 10
15
m is dened as the classical electron radius
and ds
e
=dO as the dierential cross section for scattering by a single electron,
ds
e
dO

r
2
e
2
1 cos
2
Y 9
This type of scattering is often referred to as Rayleigh scattering but is more appropriately
called Thomson Scattering. Note that, relative to the core atomic electrons, the valence
electrons are free in the Thomson sense. Corrections for electrons that are neither core
nor valence require the atomic structure factor.
Figure1 Geometry for Thomson scattering. E
0;x
is in the xz scatter plane and E
0;y
is perpendicular
to it. Y is the angle between the direction of the incident beam S
0
and the direction of the scattered
beam S in the xz plane. a is the angle between the electric field vector E
0
of the incident beam and the
direction of scatter S. b is the angle between the electric field vector E
0
of the incident beam and the
electric field vector E of the scattered beam.
Compton scattering is often taken to have the same cross section as Thomson
scattering, but Thomson cross sections are only low-energy approximations. At higher
energies, the inclusion of quantum mechanical considerations leads to the KleinNishina
formulation (Klein and Nishina, 1928), presented in Chapter 1, which is repeated here:
ds
KN
dO

r
2
e
2
1 cos
2
Y
1 g1 cos Y
2
1
g
2
1 cos Y
2
1 cos
2
Y1 g1 cos Y
!
10
where g is the incident photon energy=m
0
c
2
1:96 10
3
incident photon energy (keV).
Equation (10) presents the collisional cross section, which is also the approach of most
other authors. Because of the decrease in energy upon Compton scattering, the energy
scattered in a particular direction as a fraction of the incident intensity (Evans, 1958)
is needed. Thus, the dierential KleinNishina scattering cross section is ds
S
KN
=dO
n
0
=n
0
ds
KN
=dO. The wavelength shift due to Compton scattering is l
0
l h1
cos Ym
0
c, converting to frequency by the relationship ln c; n
0
= n 1=1 g1 cos Y
is obtained.
The fractional background reduction, even at a scattering angle of exactly p=2, is not
quite zero because of the KleinNishina limitation. The limitation to achievable polar-
ization is signicant when exciting K-line uorescence of heavy elements (Strittmatter,
1982). As g approaches zero in Eq. (10), the KleinNishina cross section approaches the
classical Thomson value in Eq. (9). The transition to description of the scattering on
the electron shell of an atom with the atomic number, Z, is carried out by introduction of
the scattering amplitude. If the small KleinNishina eect at lower energies is ignored,
it follows that unpolarized incident electromagnetic radiation scattered through an angle
of Y p=2 is linear
~
S S~e
x
polarized, with only E
y
surviving.
B. Scattering of Linear Polarized Radiation
Linear polarization of x-ray radiation is the predominant direction of the electromagnetic
eld vector in space. For scattering of the incident radiation presented in Figure 1, the
polarization P
0
in the yz plane is dened as
P
0

hE
2
0;x
i hE
2
0;y
i
hE
2
0;x
i hE
2
0;y
i
11
where hE
2
0;x
i and hE
2
0;y
i represent the mean intensity components I
0;x
and I
0;y
, respectively,
for all of the observed photons. The dependency of the coherent and incoherent scattering
cross sections for polarized radiation is exploited when using EDPXRF. The angle b (see
Fig. 1 with b p=2 a) between the electric eld vector of the incident radiation
~
E
0
and
the electric eld vector of the scattered radiation
~
E is introduced to describe the polar-
ization dependence of the scattering cross section. The following is obtained from Eq. (5)
(Hanson, 1986):
ds
e
dO
r
2
e
cos
2
b 12
The polarization dependency of scattering is determined using cos
2
b. This means that the
component E of the electric eld vector of the scattered photon is proportional to the
projection of
~
E
0
onto the plane which is perpendicular to the direction of propagation
~
S of
the scattered photon
E
2
$ E
2
0
cos
2
b 13
The orientation of
~
E corresponds to the projection of
~
E
0
onto the plane perpendicular to
~
S. Thus,
~
E
0
;
~
E, and
~
S lie in a single plane:
~
E
0
;
~
E;
~
S 0
~
E
0

~
S
0
0
~
E
~
S 0
14
The rst equation in Eq. (14) is also valid for Compton scattering, as g approaches zero
in Eq. (10). Using Eqs. (13) and (14), the mean electric eld vector is dened as
hE
2
i hE
2
x
i hE
2
y
i hE
2
z
i as a function of E
0;x
; E
0;y
; j, and d (see Fig. 1) (Brumme,
1990):
hE
2
i r
2
e
hE
2
0;x
i sin
2
d hE
2
0;y
i1 sin
2
d cos
2
j 15
With Eqs. (11) and (13), this leads to a description of the polarization-dependent scattering
cross section:
ds
dO

d;j
r
2
e
2
1 sin
2
d sin
2
j P
0
sin
2
d cos
2
j cos
2
d 16
Neglecting the atomic form factor and the scattering amplitude, the following is
obtained from Eq. (16) for the scattering cross section sP
0
; d
max
of a photon with the
direction of propagation
~
S
0
and the polarization P
0
in the solid-angle component
O 2p1 cos d
max
(see also Fig. 1):
s
O
P
0
; d
max

r
2
e
2
p 31 cos d
max

1
3
1 cos
3
d
max
P
0
cos d
max
cos
3
d
max
17
When a series approximation of Eq. (17) is conducted around d
max
0 for a scattering
angle Y p=2 to the second order in d
max
, the following is obtained:
s
O
P
0
; d
max

r
2
e
2
p1 P
0
d
2
max
18
drawing on Eq. (18) for the derivation of Eq. (2). For a polarization P
0
1, which ac-
cording to Eq. (11) is equivalent to
~
E
0
E
0;x
~e
x
, and a scattering angle of Y p=2; there is
no scattering in the x direction. With P
0
1, which is equivalent to
~
E
0
E
0;y
~e
y
; scat-
tering in the x direction reaches its maximum. In addition, it follows from Eq. (18) that the
radiation scattered in the solid-angle component O 2p1 cos d
max
is proportional to
the square of the scattering angle d
max
. The scattering angle d
max
is dened by the colli-
mator system.
The polarization P of the scattered radiation measured in the xz plane according to
Figure 1 is
P
hE
2
y
i hE
2
x
i hE
2
z
i
hE
2
y
i hE
2
x
i hE
2
z
i
19
When scatter in the solid angle O is also considered, in accordance with the above
observations the following is obtained:
P % 1
d
2
max
1 P
0
20
In the ideal case of scatter exactly around p=2 d
max
0, the polarization P of the
scattered radiation is independent of the primary polarization and has a value of unity.
The electric eld vector has exactly one component in the y direction. For greater scat-
tering angles (i.e. greater collimator diameters), the polarization is reduced as described in
Eq. (20). The primary polarization has a smaller inuence than d
max
. The best values of P
are achieved, as expected, with a primary polarization P
0
1
~
E
0
E
0;y
~e
y
.
C. Cartesian Geometry
In Barklas experiment (Compton and Hagenow, 1924) a source of x-rays is incident on a
scatterer S
1
, as shown in Figure 2. The scattered rays from S
1
intercepted by S
2
are nearly
linearly polarized, as the angle S
0
S
1
S
2
is p=2 plane. The electric eld vector is perpendi-
cular to the S
0
S
1
S
2
plane. Radiation from S
1
scattered by S
2
into I
z
also undergoes p=2
scattering, but it is in the same plane as the rst scattering and no further annihilation takes
place. However, scattering of the radiation from S
1
by S
2
into I
y
(also through p=2) anni-
hilates all remaining radiation. Thus, I
z
receives radiation, by I
y
does not. This discussion is
idealized; the measured value I
y
=I
z
depends on the tightness of collimation of the paths S
0
to
S
1
, S
1
to S
2
, S
2
to I
z
, and S
2
to I
y
, and also on the materials and thickness of S
1
and S
2
.
For the experimental determination of the degree of polarization (Brumme et al.,
1990) according to Figure 2, it is necessary to realize that the value P
eff
calculated with
Eq. (21) represents an eective polarization.
Figure 2 Schematic geometry for polarized beam XRF (PXRF). S
0
is the x-ray source, S
1
is the
polarizer, S
2
is the specimen, and I
y
is the intensity at the detector. I
z
is the intensity at an alternate,
in plane position for the detector, which does not eliminate source radiation.
P
eff

I
z
I
y
I
z
I
y
21
Multiple scattering in the scatterer S
1
and in the specimen S
2
, in particular, but also the
nite apertures of the two collimators C
3
and C
4
, lead to worsening of the degree of
polarization P > P
eff
. If the rst scatter occurs at some angle other than 90
, there will be a
component which can scatter a second time at a right angle relative to the initial incident
beam. The degree of polarization of such multiple scattering events is very low (P580%).
It is, therefore, necessary to consider the polarization unit (S
0
, S
1
, C
1
, and C
2
) as well as
the excitation unit (S
2
, C
4
, and the detector in the y direction) during optimization of
EDPXRF system.
The scattering target, S
1
in Figure 2 can, of course, be replaced by a secondary
target. In this case, the x-ray radiation emitted form the source, S
0
, is also polarized by p=2
through scattering on the target, S
1
. Because the ratio between scattering on the target and
emission of the characteristic radiation of the metal is very small for most metals, po-
larization of the source radiation plays as less decisive role than for typical scattering
targets. When a low-Z Barkla scatterer is used in an orthogonal geometry, marked im-
provements in the detection limits are possible [detection in the xy plane instead of xz
plane in Figure 2 (Bisga rd et al., 1981)]. An intermediate case is when Mg, Al, or Si
secondary targets are used for trace analysis. The polarization of source radiation becomes
more important in comparison to a planar excitation geometry, as the scattering eec-
tiveness of these metals cannot be neglected. In multiple-element analysis, however, sec-
ondary targets are disadvantageous, because only a limited number of elements can be
detected with good sensitivity. In orde
r
to react exibly to analytical applications with
Cartesian geometry, secondary targets are indispensable, in addition to Barkla and Bragg
polarizers. The eectiveness of this technique is shown in Figure 3.
III. BARKLASYSTEMS
Proof-of-principle experiments in the early 1970s (Dzubay et al., 1974; Howell et al., 1975),
using single collimators to dene the three orthogonal beams (Fig. 2), demonstrated im-
proved signal-to-noise ratios, but at severely reduced intensities. A few years later, it was
demonstrated (Ryon, 1977) that the way to maximize analyte intensities while minimizing
background is to open the apertures of the collimators until maximum systems throughput
is achieved while maintaining the orthogonal beam geometry. Such nonzero beam
divergence causes a small decrease in the degree of polarization, which is more than
compensated for by the increase in x-ray ux. Detection limits are improved in comparison
Figure 3 Comparison of excitation methods. The sample is an oil standard which contains 21
elements (e.g., Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Mo, Ag, Cd, Sn, Ba, and Pb) with concentrations
of 30 mg=g. The spectra (log scale) are (top) nonpolarized, direct excitation by radiation from
rhodium anode x-ray tube, (middle) molybdenum secondary excitation, and (bottom) polarized
excitation by scatter from a HOPG=Al
2
O
3
target. The measuring time amounts to 200 s for each
spectrum. The counting rate was first adjusted by increasing the tube current to its maximum value
and then increasing the collimator aperture to give a total count rate approximately 60,000 cps using
a Si(Li) detector with an active area of 25 mm
2
and a energy resolution of 166 eV for MnKa. In all
cases, a Rh end-window tube was used.
"
to either direct excitation or secondary uorescence (Ter-Saakov and Glebov; 1984,
Bertin, 1975).
Energy-dispersive x-ray uorescence analysis is ideally suited to measuring a wide
range of elements simultaneously because all photon energies are separately binned. When
the analytical goal is to exploit this capability of measuring many elements with good
sensitivity and low detection limits, a polarized polychromatic source is preferred. This is
in contrast to nonpolarized sources, for which the increased sensitivity due to ecient
excitation is oset by the increased background under the peaks.
To optimize polarization and scattering intensity, all inuencing factors, such as the
scattering material and its dimensions and form, multiple scattering in the polarizer and in
the specimen, scope of the collimator, and the nite dimension of the x-ray source and the
detector, must be taken into consideration. The primary intensity of the x-ray tube and the
optimized polarization equipment must be tuned so that, depending on the required re-
solution, the highest possible input count rate is achieved. This means that the loss in
intensity due to the geometry and scattering loss are balanced. Brumme (1990) examined
the above-mentioned inuencing factors using Monte Carlo simulations.
A. Scattering Material
The scattering eectiveness, e, of a planar target, S
1
(see Fig. 2) is dened as
eE
s
S
E
mE
1 exp
rmEd
sin 45
!
22
where mE is the mass-attenuation coecient of the target material for the x-ray energy E
(in cm
2
=g), s
S
is the scattering coecient (coherent incoherent) for the target material
for a scattering angle of p=2 and an x-ray energy E (in cm
2
=g), r is the density of the target
(in g=cm
3
), and d is the thickness of the target (in cm).
The quotient s=m of scatter and absorption must be a maximum for the scattering
target material. Materials with a very small average atomic number are especially suited
for this. They have a relatively small mass-attenuation coecient (m < 1 cm
3
=g) in the
energy ranges of interest, so that the thickness of the scattering target must be increased in
order to obtain a suciently high scattering intensity according to Eq. (22). Thick scat-
tering targets enable great variations in the scattering angle, which logically leads to poor
polarization (Table 1). Additionally, the probability of multiple-scattering processes in-
creases by increasing the thickness of the scattering target and, with it, the depolarization
(see Table 1). Polarization losses have been calculated by Zahrt and Ryon (1981).
Table 1 Scattering Target Effectiveness e and Polarization Calculated with Monte Carlo
Simulations Without P
0
and With P
MS
Consideration of Multiple-Scattering Processes in the
Target as a Function of the Thickness, d
T
, of a Planar Carbon Target (E 19:6 keV
d
T
(mm) e P
0
(%) P
MS
(%)
0.5 0.011 94.1 92.8
1.0 0.021 93.7 91.3
2.0 0.040 93.2 89.8
5.0 0.084 91.3 86.3
10.0 0.131 90.4 84.2
Source: From Brumme, 1990.
According to Table 1, the thickness of the scattering target should not be increased
unlimitedly to get a high scattering eectiveness. Therefore, the density r of the scattering
material plays a decisive role. For a constant thickness, the materials with a higher density
have the advantage of having a higher scatter eectiveness [see Eq. (22)] for a nearly
equal fraction of multiple scattering and degree of polarization. Materials with density
r < 2 g=cm
3
are not ideal Barkla polarizers. Because the scattering eectiveness is a function
of the energy, there energy ranges, E < 10 keV, 10 < E < 25 keV, and 25 < E < 60 keV, are
considered in the following. In the energy range E < 10 keV, photoabsorption dominates
compared with scattering so that the scattering eectiveness is too small, even for poor
polarizers (P < 0:7). Barkla polarization is therefore too ineective even using x-ray tubes
with anode materials that emit characteristic x-rays in this energy range (Cr, Cu, W, etc.).
In the mid-energy range, it is advantageous to use Barkla polarizers if the characteristic
radiation of the tube anode material lies in this energy range (Mo, Rh, Pd, and Ag). Boron
carbide (Ryon, 1977), pyrolitic graphite (Kanngieer, 1990; Kanngieer et al., 1992), and
boron nitride are particularly suitable as scattering target materials. Beryllium oxide and
boron can also be used. In the upper energy range, the bremsstrahlung emitted from x-ray
tubes withanode materials with Z > 40 canbe used for polarization. Corundum(Svoboda et
al., 1993), boron nitride, beryllium oxide, silicon nitride, and boron carbide are especially
useful as scattering materials. Because the average penetration depth of the scatter radiation
and the fraction of multiple scattering dier in both energy ranges, special optimization
examinations are necessary. Systems using layers of dierent materials are suitable as a
compromise for the entire energy range 10 < E < 60 keV.
In addition to the above-mentioned parameters, other material properties are of
practical interest:
Purity: Because the uorescence radiation excited in the scattering target is
nonpolarized, the smallest impurities in the target material lead to additional
background components in the measured spectrum. Elements with atomic
numbers Z > 20 should not be present with concentrations C>10 mg=g.
Resistance to high temperatures (x-ray tube exit window), air humidity, and x-ray
hardness.
Mechanical stability.
Availability.
B. Geometry of the Polarization Unit
In order to minimize as much as possible the geometric loss in intensity, it is necessary
to keep the distances between the tube and the target, the target and the specimen, and the
specimen and the detector small. It is, however, very important to prevent the sample from
directly irradiating by the primary radiation of the x-ray tube and also the detector from
directly detecting of scattered x-rays from the target or other parts of the unit.
The dimensions of the collimator system C
1
, C
2
, and C
4
(see Fig. 2) exercise the
largest inuence on the properties of the polarization unit. As can be seen in Table 2,
the scattering eectiveness increases by a factor of approximately 50 with variation of the
collimator diameter (d
1
d
2
) of the primary collimator C
1
, d
1
, and the secondary colli-
mator C
2
, d
2
, from 4 to 12 mm with a simultaneous loss in polarization from 0.938 to 0.8.
The ratio between single and multiple scattering events and with it the degradation of P
0
caused by multiple scattering (P
0
P
MS
) is not inuenced signicantly by increasing
collimator diameters (Brumme, 1990).
With a diameter d
1
d
2
d
3
5 mm for C
1
, C
2
, and C
3
a tube voltage of 50 keV
(Rh anode) and a tube power of 280 W, an input count rate at the detector of approxi-
mately 10
5
cps is obtained for the excitation of 4-g base oil (Conostan) specimen using a
Barkla target. The detected radiation consists mainly of incomplete polarized radiation
scattered at the sample. A further increase in the total scattering eciency is possible
through an increase in the target thickness [see Eq. (22)] or through an increase in colli-
mator diameters. Monte Carlo simulations indicate (Brumme, 1990) that the use of larger
collimator diameters is preferred to the use of thicker targets (see the dierence (P
0
P
MS
)
in Tables 1 and 2). The increase of the ratio between multiple-scattering events and single-
scattering events within the target, and the depolarization (P
0
P
MS
), coupled with it,
due to growing target thickness is the decisive factor.
The Monte Carlo simulations demonstrate that for a given target thickness, the
target area and, with it, the target volume can be extended beyond the volume, in which a
single-scattering event of primary radiation from the x-ray tube into the direction of the
sample can occur (Brumme, 1990). The increase of depolarization caused by the described
extending of the target area is insignicant.
C. X-rayTubes and Filters
All results of Monte Carlo simulations described so far are based on the assumption that
the focal spot of the x-ray tube is innitely small. The consideration of a nite focal spot
leads to a reduction of the polarization (see Table 3).
When mounting a side-window x-ray tube, it should be noted that the brems-
strahlung is slightly polarized in the plane dened by electron beam and x-ray beam from
the focal spot to the Be window of the x-ray tube. For this reason, the electron beam
and the specimen-detector axis should be parallel. When using line-focus x-ray tubes, the
Table 2 Inuence of the Collimator Diameter d
1
(Collimator C
1
) d
2
(Collimator C
2
) on the
Polarization Without P
0
and With P
MS
Consideration of Multiple Scattering and on the Total
Scattering Effectiveness G for a Planar Carbon Target with a Thickness of 2 mm
d (mm) G610
6
P
0
(%) P
MS
(%)
4 0.31 93.8 90.3
5 0.65 92.9 89.6
6 1.38 90.7 87.4
8 4.21 87.8 84.6
12 17.1 79.6 76.7
Note: Point Source S
0
, Distance S
0
S
1
: 36 mm, collimator length C
1
, l
1
2 mm; distance S
1
S
2
: 35 mm, collimator
length C
2
, l
2
12 mm.
Table 3 Inuence of the Dimensions of a Quadratic Anode Focal Spot on the Polarization
(Target Thickness: 1 mm)
Focus (mm) Point 161 363 666 868
P
0
0.957 0.957 0.954 0.936 0.918
line-shaped focal spot should lie in the scattering plane. For end-window x-ray tubes, the
diameter of the ring-shaped focal spot should be as small as possible. In practice, a
compromise among tube power, focal spot size, and distance between target and tube
anode should be found.
Except for the Compton shift, the spectral distribution of the tube primary spectrum
is approximately unchanged after Barkla scattering. Thus, the form of the spectral
background that is generated by incompletely polarized tube primary radiation approxi-
mately corresponds to the known background from direct excitation (see also Fig. 3). For
this reason, x-ray lters can be used to optimize the excitation of a limited number of
elements also in EDPXRF similarly to direct excitation EDXRF. Polarization measure-
ments show that lters between the x-ray source and target do not lead to worsening of the
eective polarization. In contrast, lters in the radiation path between the target and the
specimen cause a depolarization of up to 2%. Nonpolarized radiation that results from
contamination in the Barkla target can be absorbed by lters between the target and the
specimen. For example, Cr, Fe, and Ni contamination occurs in B
4
C due to the pressing
procedure; the uorescence radiation of these elements can be absorbed by a 30-mmRh
lter on its way to the specimen.
D. Multiple Scattering in the Specimen
In Sec. II.C, it was mentioned that the eective polarization, P
eff
, must be considered in
the description of the suppression of polarization. The dierences between P
MS
from Table
1 and P
eff
were caused either by x-ray lters between target and specimen or by multiple-
scattering processes in the specimen. The fraction of multiple scattering is dependent on
the matrix. Monte Carlo simulations (Brumme, 1990) show that polarization is reduced by
multiple scattering in a 0.5-mm-thick SiO
2
specimen from P
MS
1:0 to P
eff
0:96. In the
case of fully polarized radiation (P
MS
1:0), the ratio between multiple-scattering events
and single-scattering events within a 3-mm-thick SiO
2
specimen is 40%. This ratio
amounts to only 1520% for a typical polarization of 0:8 P
MS
0:9 and causes a de-
crease of polarization P
MS
P
eff
of 12%. Considering multiple scattering within the
sample and target, the eective polarization P
eff
amounts to 0.800.85 in the energy range
E < 25 keV and to 0.760.83 in the energy range E > 25 keV.
E. Multiple-Layer Scatterers
As later indicated (see Table 4), if a single element is determined, a monochromatic source
gives the lowest detection limits. However, a polychromatic source is desirable when
multielement analysis is performed. If polychromatic radiation is to be polarized by
scattering, high-Z scatterers absorb the low-energy portion of the incident spectrum,
whereas low-Z scatterers do not interact eectively with the high-energy components of
the spectrum (Zahrt and Ryon, 1986). In both cases, this limits the intensity over a broad
range of energies. In both of the examined energy ranges, E < 25 keV and
25 < E < 60 keV, B
4
C is well suited as the polarizer. However, optimized polarization
systems for both energy ranges dier from each other. Compared with B
4
C target, slight
improvements can be achieved using a combination of HOPG (highly oriented pyrolytic
graphite) on Al
2
O
3
. An HOPG target (d 1:2 mm) optimized for the energy range
8 < E < 25 keV is inecient in the upper energy range, due to its low density
(r 2:2 g=cm
3
). For the collimator diameters of 5 mm used here, the Bragg reection is
negligible (Kanngieer et al., 1992). When the target is glued to an Al
2
O
3
substrate,
the polarization decreases imperceptibly due to multiple scattering in the lower energy
range E < 25 keV. However, in the energy range E < 25 keV, the Al
2
O
3
substrate improves
the scattering eciency at the cost of polarization. On balance, such a multiple-layer
scatterer is useful for determining a wide range of elements simultaneously with very good
detection limits and sensitivities.
F. Applications
Based on Eqs. (3) and (4), Barkla targets are especially suited for multiple-trace-element
analysis in a light matrix. Typical applications include traces in organic substances
[polymers, oils, pharmaceuticals, biological materials (Heckel, 1995), etc.], traces in sili-
cates [rocks (Heckel et al., 1991), soils (Heckel et al., 1992), sludges, cinders, etc.], as well
as traces in Mg and Al alloys.
In a rst application, detection limits and sensitivities for traces in an oil matrix are
compared among direct excitation, secondary target excitation, and polarization excita-
tion (see Fig. 3). As mentioned several times earlier, the count-rate limitation of the de-
tection system is the deciding factor for optimization of the polarization system. It must
also be noted that the electronic noise and, with it, the energy resolution of the spectro-
meter are functions of the pulse peaking time of the pulse-processing electronics and,
through it, of the maximum possible pulse throughput rate. For multiple-element analysis
in the energy range between 1 and 50 keV, the energy resolution for MnKa should be
better than 180 eV. For the spectra displayed in Figure 3, a detection system with an
energy resolution of 166 eV at an input count rate of about 60,000 cps was used. It must be
noted that no x-ray lters are used to keep the goal of a multielement analysis in a short
measuring time. Especially in the case of polarized or direct excitation, the detection limits
of a limited number of elements can be improved by using x-ray lters signicantly. The
detection limits, DLs (see Chapter 2; condence level: 99.86%), for the excitation types
displayed in Figure 3 are summarized in Table 4; the analytical sensitivities, are
summarized in Table 5. A comparison of the numerical values in Table 4 indicates that
Table 4 Detection Limits (n.d. Not Detectable) for Some Elements in a Base Oil Using Direct
Excitation, Monochromatic Excitation Using a Mo Secondary Target, and Direct Excitation
with Linearly Polarized X-rays
Detection limits (in mg=g)
Element Direct excit. Mo second Polarization
Ca 13.0 8.8 4.1
Ti 3.8 2.9 1.6
Cr 3.1 2.0 0.78
Mn 2.6 1.2 0.51
Cu 1.7 0.31 0.34
Zn 1.7 0.30 0.33
Mo 2.3 n.d.
a
0.95
Cd 18.0* n.d. 1.6
Sn 12.0 n.d. 2.0
Pb 3.9 0.31 0.79
Note: 175 W for a Measuring Time of 200 s and an Incident Pulse Density of About 60,000 cps.
a
Overlapping with RhK
b2
.
the detection limits determined with excitation using polarized x-rays are, on average ve
times better than those determined with direct excitation. An improvement of only a factor
of 2.4 was achieved for the element Mo. In contrast to direct excitation using RhK ra-
diation, the Compton scattered RhKa line is unable to excite Mo. The detection limits for
the elements 46 < Z < 60 are worse than those for the elements 23 < Z < 41, because
these elements are only excited by bremsstrahlung. An improvement is possible when a
voltage >50 kV is used. The Rh tube is operated with a power of 175 W for polarization.
If a 2-kW tube is used, the eective polarization can be improved from P
e
%82% for the
Compton-scattered RhKa line to P
e
%87% for the same detector input count rate
through reduction of the collimator diameter. This clear increase in polarization results in
a 40% improvement of the detection limits displayed for polarization in Table 4.
If one compares the values for polarization equipment with those obtained with Mo
secondary targets, an improvement in the detection limits of a factor up to 2.5 is obtained
for all of the elements with absorption edges that are only slightly below the energy of the
MoKa line (e.g., Pb in Table 4). Similar improvements are expected for the elements Sr and
Zr. Detection limits of the polarization setup become better compared to those obtained
with Mo secondary target if the energy dierence between absorption edge of the elements
and the MoKa line becomes greater. Of course, not all of the elements can be determined
with the Mo secondary target. This reects an additional advantage of Cartesian excita-
tion geometry. A change in the targets is sucient to switch from a multiple-element
application with a polarizer to a single-element application when analyzing single
elements, such as Pb in oil, or a couple of elements with absorption edges that are only
slightly below the energy of the characteristic radiation of the secondary target. Changing
of the targets is computer controlled in commercially available instruments.
A comparison of the numerical values in Table 5 shows that, on the average, a
factor-of-4 improvement in the sensitivity is obtained using the polarization unit as
compared to direct excitation. The sensitivities are also improved by a factor of between 2
and 7 compared to those of the Mo secondary target.
Table 5 Analytical Sensitivity for Some Elements in a Base Oil Using Direct Excitation,
Monochromatic Excitation Using a Mo Secondary Target, and Direct Excitation with Linearly
Polarized X-rays
Sensitivity [in cps=(mg=g)]
Element Direct excit. Mo second Polarization
Ca 0.064 0.037 0.25
Ti 0.29 0.11 0.49
Cr 0.49 0.16 0.98
Mn 0.64 0.25 1.70
Cu 1.71 1.35 4.25
Zn 1.73 1.54 4.28
Mo 1.89 0.0 5.56
Cd 0.28 0.0 2.52
Sn 0.22 0.0 2.15
Pb 0.9 1.57 2.90
Note: 175 W for a Measuring Time of 200 s and an Incident Pulse Density of About 60,000 cps.
If the detection limits given in Table 4 are not sucient for the elements with atomic
numbers in the range 45 <Z<61, for example, then an improvement can be obtained by
optimizing the polarization unit for the respective energy range. For example, the de-
termination of Cd, Sn, and Sb with a concentration range C>0.1 mg=g in rocks represents
an interesting geological application. From the above discussion, it follows that an ad-
ditional improvement in the peak-to-background ratio can be achieved using an x-ray
lter. The result of the optimization is displayed in Figure 4 for the spectrum of the
standard granite AC-E. As can be seen in Figure 4, the peak-to-background ratios for Ag
and Cd are sucient for the determination of the elements in sub-ppm concentration
range. The root-mean-square deviation for the Cd calibration [see Eq. (28)], which is based
on 22 international rock standards, is 0.2 mg=g. The DLs are summarized in Table 6.
In contrast to the analysis of oil, which has been discussed earlier, when analyzing
geological samples with input count rates of 60,000 cps or more, it is necessary to take
pileup peaks into consideration at energies E<25 keV. This is because the concentration
of the elements K, Ca, Ti, and Fe may amount to % levels. A pileup peak from FeKa
FeKa at 12.8 keV near the PbLb line at 12.6 keV and near the ThLa line at 12.95 keV or a
pileup peak from FeKa CaKa at 10.09 keV near the HgLa line at 9.99 keV are typical
examples. These analytical problems can be contained using lters between the target and
the specimen or between the specimen and the detector, by reducing the input count rate
(see Fig. 5) or by improving the pileup rejection. With the given analytical conditions,
detection limits at sub-ppm levels were obtained for most of the trace elements in geo-
logical specimens (see Tables 6 and 7).
Because the iron content in many geological specimens amounts to the % levels,
an increase in the background in the energy region E<6.4 keV occurs due to incomplete
charge collection in the Si(Li) detector. This background worsens the detection limits,
particularly for V, Cr, and Mn. With a Co secondary target and an Fe lter between the
target and the specimen, only the CoKa line excites the specimen. This line is not able to
excite Fe. The detection limits of the elements V, Cr, and Mn are improved by using the
Co secondary target in an Fe-rich matrix (e.g. Fe ores). The secondary target is again
successfully combined with polarizers.
G. Limitations of Barkla Polarization
As established in Sec. III.A, the scattering eectiveness in the energy region E<10 keV
continually decreases in favor of photoabsorption. Thus, assuming a Cartesian excitation
geometry, it is necessary to examine other excitation possibilities. Using secondary targets,
the number of elements that can be excited with a sucient sensitivity decreases with
falling energy. Therefore, many dierent secondary targets must be used. In practice,
the measuring times would be unacceptably high. Bragg polarizers are an alternative to
secondary targets and are discussed in the following section.
IV. BRAGG SYSTEMS
A. Orthogonal System
Diraction oers an excellent means of obtaining both monochromatic and polarized
radiation. Synthetic multilayer materials that have very high reectivities can have a
d-spacing chosen virtually at will to give a diraction at 2y of p=2 for energies up to about
1.0 keV. For higher energies, crystalline materials must be used. Candidate materials for
Figure 4 Spectrum (log scale) of the standard specimen AC-E, excited using an Al
2
O
3
polarizer. A 180-mm Ta filter was placed between the
specimen and the target. Some of the certified concentrations are as follows: Ag, 0.1 mg=g; Cd, 0.6 mg=g; In, 0.1 mg=g; Sn, 12.0 mg=g.
Figure 5 Spectrum (log scale) of the standard specimen AC-E, excited using an B
4
C polarizer. A 50-mm Pd filter was placed between the
specimen and the target. Some of the certified concentrations are as follows: Ni: 1.5 mg=g; Cu: 4.0 mg=g; Sr: 3.0 mg=g; Tl: 0.9 mg=g.
use in a polarized-beam XRF experiment should have several characteristics. The rst
criterion is a material that has a reection of high diraction power (integral reectivity
>10
4
rad) at 2y near p=2 for the characteristic wavelength of the anode material used. In
addition, the material should be stable, must be free of contamination with characteristic
lines in the energy region 1 <E<15 keV, easy to orient and cut to the desired orientation,
obtainable at reasonable cost, and perhaps nontoxic.
The orthogonal triaxial geometry for Bragg-diraction polarization is similar to that
for Barkla scattering, shown in Figure 2. What is important here is the physics of the
diraction process and the parameters of the diraction crystal. There are two theories of
x-ray diraction; the wave kinematics (K theory) and the dynamic (D theory). The K
theory is valid for small crystals or mosaic blocks. The D theory must be used when
absorption and=or the interaction between incident and diracted beams becomes im-
portant. According to the theory of Zachariasen (1967), the integrated reectivity R
i
of an
ideal mosaic crystal in the symmetrical Bragg case has the following form:
R
i

r
0
V
2
1 cos
2
2y
B
2 sin 2y
B
jF
hkl
j
2
l
3
1
2m
0
exp
2B
sin
2
y
B
l
2
23
where
R
i
Integrated intensity compared to the incident beam
r
0
Classical electron radius
y
B
Bragg diraction angle
Table6 Detection Limits for Various Elements in Rocks Using Excitation with Linearly Polarized
X-rays
Element DL (mg=g) Element DL (mg=g) Element DL (mg=g)
Mo 0.32 Sb 0.25 La 1.4
Pd 0.24 Te 0.38 Ce 1.9
Ag 0.17 I 0.55 Pr 2.4
Cd 0.13 Cs 0.82 Nd 3.3
In 0.16 Ba 1.1 U 0.8
Sn 0.18
Note: Voltage: 59 kV; current: 33 mA; measuring time: 900 s; Al
2
O
3
polarizer; 180-mm Ta lter.
Table7 Detection Limits for Various Elements in Rocks Using Excitation with Linearly Polarized
X-rays
Element DL (mg=g) Element DL (mg=g) Element DL (mg=g)
Co 1.1 Se 0.2 Hf 1.9
Ni 0.9 Br 0.1 Ta 1.5
Cu 0.8 Rb 0.2 W 1.1
Zn 0.6 Sr 0.3 Tl 0.6
Ga 0.3 Y 0.3 Pb 0.5
Ge 0.2 Zr 0.3 Bi 0.5
As 0.2 Nb 0.4 Th 0.6
Note: Voltage: 38 kV; measuring time: 900 s; B
4
C polarizer; 50-mm Pd lter.
F
hkl
P
N
n1
f
n
exp2pihu
n
kv
n
lw
n
structure factor of the lattice plane hkl

u
n
; v
n
; w
n
Fractional coordinates 1=ax
n
; 1=by
n
; 1=cz
n
of the nth
atom in the unit cell
a; b; c Unit cell lengths
f
n
Atomic scattering factor
V Unit-cell volume
m
0
Linear absorption coecient
B Thermal Debye parameter at room temperature (B B
0 K
B
293 K
)
The atomic form factor f
n
is approximately half-Gaussian in shape with argument
sin y
B
=l and f
n
0 Z, the number of electrons in atom n. To maximize R
i
, we thus want
V to be small and F
H
large, which often means taking sin(y
B
)=l to be small, which, for
cubic crystals, implies low values for the Miller indices (h, k, l ), based on
1
d
2

h
2
k
2
l
2
a
2

4 sin
2
y
B
l
2
24
Equation (23) is only valid when the absorption and extinction eects within the mosaic
blocks are negligible. These eects may markedly reduce the integral reectivity.
Taking into consideration critical values for primary and secondary extinction as
well as true absorption, Beckho et al. (1992) give a detailed overview of possible Bragg
polarizers for MoKa, CrKa, CuKa, and AgKa radiation from the respective tube anode
materials. The integral reectivities of possible Bragg polarizers for MoKa, RhKa, and
AgKa radiation are comparable with the integral (energy and solid angle) Barkla-scat-
tering eectiveness in the energy region E>10 keV. On the other hand, experimental
comparisons (Kanngieer et al., 1991; Kanngieer et al., 1992; Ryon et al., 1982) have
shown that Barkla polarization is preferred in this energy region. At lower energies,
5 <E<10 keV, excellent detection limits are achieved by using Bragg polarization of
the CrKa and CuKa line (Aiginger et al., 1974; Aiginger and Wobrauschek, 1981;
Wobrauschek and Aiginger, 1985). Wobrauschek et al. (1988) obtained a detection limit of
66 ppb for Co in an aqueous solution (0.45 mL volume) using excitation with the CuKa
line (1.6 kW), for example, with a measuring time of 1000 s. The CuKa line was polarized
with a HOPG (006). Working with a suitable spectroscopy or diraction x-ray tube in-
volves interesting, special applications (e.g., compared to AAS or ICP) for trace detection
for a couple of elements. Assuming the possibility of simultaneous multielement analysis
with EDXRF, Bragg polarization of the L radiation from one of the Mo, Rh, Pd, or Ag
x-ray tubes (10400 W) normally used in EDXRF is, in practice, of greatest analytical
interest. In this energy range, the bremsstrahlung spectrum emitted from the tube has such
a weak intensity that Barkla polarization of this radiation is not useful from the practical
point of view.
Thinner Be windows (d 75 mm) can be placed in end-window x-ray tubes than
those used in side-window tubes, leading to the observation of clearly increased intensity
for the emitted low-energy L radiation. Crystals with an integral reectivity, R>0.001
rad, and a diraction angle, Y, near 45
for the L radiation from the above-men-

tioned end-window x-ray tubes are excellent Bragg polarizers. The calculation of the in-
tegral reectivity and, with it, the selection of a suitable crystal become more dicult due
to the expected absorption and extinction eects. The HOPG, which has already been
referred to as a Barkla scatterer and Bragg polarizer, is also an outstanding Bragg po-
larizer for the (002) reection of the RhLa radiation (y 43.2
). Beckho and Kanngieer

(personal communication, 1996) have calculated an integral reectivity of
R
i
0:0032 rad. The spectrum of a Rh end-window x-ray tube linearly polarized with an
HOPG crystal (FWHM mosaic spread: 1.7
) and measured in air is shown in Figure 6.

Because Barkla scattering prevails on the carbon target, the polarization spectrum from a
carbon target (displayed for comparison) enables a direct comparison of Bragg and
Barkla polarizations in a narrow beam geometry. As described in Sec. III, an increase in
the Barkla-scattering intensity shown in Figure 6 is possible by enlargement of the col-
limator diameter, for example. However, the optimized Barkla-scattering intensities do
not contribute greatly to the polarization spectrum in the energy region of the (002), (004),
and (006) reections.
The sensitivity of the elements with a critical excitation energy below the RhLa
energy, for example, may be improved by up to 30% when not only the RhLa line but also
the high-energy RhLb lines can be used for excitation. To do this, the polarization geo-
metry must be changed so that the diraction angle y
B
40:6
for reection of the RhLb

lines can be realized. The degree of polarization for Bragg polarization is reduced ac-
cording to Eq. (25) from P % 99% to P % 94%.
P %
1 cos
2
2y
B
1 cos
2
2y
B
25
However, as the degree of polarization worsens, there is an increased probability for
overlapping of sample element x-ray lines with escape lines, because scattering of non-
polarized L lines from the tube anode material on the sample may occur.
In addition to the polarization geometry, the focal spot size of the x-ray tube and the
mosaic spread (standard deviation of the Gaussian-shaped distribution of the mosaic
block orientations) of the mosaic crystal also pay a deciding role in optimizing the
Figure 6 Excitation spectrum of a flat HOPG crystal in comparison with graphite with a Bragg
angle of 43.2
(distance, tube crystal: 26 mm; distance, crystal detector: 28 mm; collimator diameter:
1 mm each; measurement in air; tube voltage: 30 kV). Logarithmic scale!
polarization unit. Equation (23) is valid assuming that the mosaic spread Z is much greater
than the critical value for secondary extinction:
Z4
2
p
r
R
i
26
A greater mosaic spread is advantageous for the collimator diameter (C
1
, C
2
, and C
4
in Fig. 2) 145 mm, normally used in EDXRF, as a larger angular acceptance is obtained.
On the other hand, the peak reectivity is reduced with increasing mosaic spread. In the
case of an HOPG crystal (R
i
0.0032 rad), the FWHM mosaic spread according to Eq.
(26) is much greater than 0.34
. The experimentally determined optimum for the FWHM

mosaic spread lies in the range between 1.7
and 2.1
.
The large angular acceptance desired for the HOPG (002) reection leads to an
increase in intensity of the (004) and (006) reections, as bremsstrahlung spectrum of
larger energy range can be reected. An eective excitation (K radiation) of the elements K
to Fe is possible with these reections so that the spectrum from Na to Fe, which can be
simultaneously excited with the three reections, becomes extremely interesting for many
applications. The product K
n, j
according to Eq. (27) is interesting for the analytical eva-
luation of the three reections (n 1, 2, 3):
K
n; j
R
i; n
o
j
r 1
r

j
27
where R
i,n
is the integral reectivity of the nth reection, n {1, 2, 3}, o
j
is the uorescent
yield of the element j, excited with reection n, and r
j
is the jump ratio for the element j.
When observing the K values for typical elements from the three excitation regions,
for example, Si, Ca, and Fe, similar values are found: K
1;Si
% K
2;Ca
% K
3;Fe
; that is, the
element specic sensitivities for the given excitations are similar. The very small uores-
cence yield for the light elements, such as Al and Si, is compensated for by higher integral
reectivity.
B. Curved Crystals
To increase the intensity at the sample, one may bend (Johann) or bend and grind (Jo-
hansson) the crystals (see Chapter 2). With a at crystal in a narrow-beam geometry, the
angular acceptance is essentially the rocking curve, generally !0.01
. With a bent crystal,

an angular acceptance of 5
10
is readily conceivable, with an increase in intensity

proportional to the size of the fan beam. Aiginger and Wobrauschek (1981) report an
intensity gain of 3.1 using Cu(113)CuKa in Johann geometry compared to the at crystal.
Calculations for Johann and Johannson geometries have been performed by Zahrt (1983,
1986). Although the calculations used the estimated values for a mosaic distribution
function and its full width at half-maximum, the reported gain is also calculated. Beckho
and Kanngieer (personal communication, 1996) calculated the intensity of the reected
RhL radiation on a spherically bent HOPG(002) crystal with a 32 mm radius of curvature
(1
C
1
1
C
2
1
C
3
12 mm according to Fig. 2) for various focal spot sizes of a Rh tube
and crystal positions using Monte Carlo simulations. When compared to a at crystal, it is
possible to have increases in the excitation intensity in a zone diameter 1
excitation
20 mm
(for example) on the sample by the factors of 17.2, 11.1, and 2.6 for focal spot diameters of
0.1 mm, 1 mm, and 6 mm of a Rh tube, respectively. Experimental examinations with a
focal spot diameter of 1
focus
% 1 mm have approximately conrmed this improvement by a
factor of 8.1 for the (002) reection. Focal spot diameters of 1
focus
% 1 mm can be realized
with the end-window x-ray tubes only in conjunction with reduced powers. However, even
tube powers of 50 W are sucient for the most applications.
C. Applications
Because only a limited number of elements can advantageously be excited with Bragg
systems, the range of applications of an EDPXRF instrument optimized exclusively for
Bragg polarization is limited. The determination of the thickness of Al layers on diverse
substrates (e.g., SiO
2
) is an interesting application of this kind. For a layer thickness of
d !90 nm, for example, reproducibilities [relative standard deviation (RSD)] <1%
(99.86% condence level) were obtained with a measuring time of 50 sec per measuring
point using a spherically bent HOPG(002). Due to the monochromatic excitation of Al
and Si, there were no disturbing peaks in the measured spectrum.
The optimization criteria described in Sec. III, for the generation of highly intense
Barkla polarized radiation, is crucial for optimization of the geometry of an EDPXRF
system for Bragg as well as Barkla polarization. Typical applications for Bragg systems
within the given framework include, for example, the determination of the elements from
Na to Fe in ceramics, refractory materials, cements, ores, ferro-alloys, slag, or additives
in oil.
The detection limits for 12 selected elements in base oil displayed in Table 8 de-
monstrate that EDPXRF is also well suited to the simultaneous trace detection of lighter
elements (see also Fig. 7).
Protective foils, 4 mm prolene, were used in front of the detector and between crystal
and sample for the measurements listed in Table 8. These easily replaceable protective foils
are necessary in routine work. It is, however, possible to obtain much better detection
limits for Na (120 mg=g) without the protective foils. The relatively poor detection limits
for Na is caused in part by an overlap of the NaKa line with the escape line from non-
polarized PdLa radiation backscattered from the sample. Greatly improved detection
limits and sensitivities can be obtained for Fe, Cu, and Zn by using a Barkla scatterer
analogous to that in Sec. III. F. However, these improvements are not required for the
given application, additives in oil; an additional measurement unnecessarily increases the
measuring time. The detection limits for P, S, and Cl, in particular, open the range of
possible applications for EDPXRF (e.g., the determination of S in diesel fuels and ga-
soline). The comparison shown in Table 9 demonstrates the brightness of curved crystals
in combination with ne focus x-ray tubes in EDPXRF.
Table 8 Detection Limits and Sensitivities, S, for Various Elements in an Oil Matrix Using
Excitation with Polarized Radiation
Element
DL
(mg=g)
S
[cps=(mg=g)] Element
DL
(mg=g)
S
[cps=(mg=g)] Element
DL
(mg=g)
S
[cps=(mg=g)]
Na 270.0 0.00288 S 0.6 1.81 Fe 0.9 1.66
Mg 28.0 0.0230 Cl 0.5 3.38 Cu 1.0 1.63
Si 1.6 0.341 K 5.5 0.243 Zn 1.2 1.63
P 0.7 0.823 Ca 0.7 0.424 Ba 1.4 0.332
Note: Pd tube; voltage: 15 kV; current: 14 mA; measuring time: 300 s; at HOPG polarizer; He environment;
4-mm prolene lters in front of the detector and between crystal and sample.
The polarization geometry described here is also suited to the analysis of fusion
samples. Preparation of lithium tetraborate glasses from oxidic samples, for example, is
utilized to conduct precise determination of major and minor elements and also, in some
cases, trace elements. Excellent sensitivity and reproducibility are required for simulta-
neous analysis of the elements from Na to Fe with dilution ratios from 1 : 6 to 1 : 20.
RSD0.12% for the reproducibility of major elements and root-mean-square deviations
RMSs for the calibration lines [see Eq. (28)], presented in Table 10 conrm the ad-
vantageous parameters of the analytical technique based on Bragg polarization:
Figure 7 Oil sample spectrum (log scale) excited by using an HOPG polarizer. Some of the
concentrations are as follows: Mg, 90 mg=g; P, 220 mg=g; S, 3650 mg=g; Cl, 70 mg=g; Ca, 480 mg=g;
Cu, 80 mg=g; Zn, 250 mg=g; Ba, 190 mg=g.
Table 9 Comparison of Sensitivities, S
N
, Normalized to Tube Current (mA) and Detector Area
(mm
2
) for Various Elements in Base Oil
S
N
10
2
S
N
10
2
S
N
10
2
[cps=(mg=g)=mA=mm
2
] [cps=(mg=g)=mA=mm
2
] [cps=(mg=g)=mA=mm
2
]
Element (1) (2) Element (1) (2) Element (1) (2)
Mg 0.014 0.350 S 1.08 32.6 Ca 0.252 5.73
Si 0.203 6.50 Cl 2.01 70.3 Ba 0.198 4.50
P 0.490 15.3 K 0.145 2.83
Note: (1): Pd tube with an approximately round focal spot of 8 mm in diameter (15 kV, 14 mA); at HOPG
polarizer; Si(Li) detector with an energy resolution of 164 eV for MnKa and a visible area of 12 mm
2
; (2): Pd tube
with a focal spot of 1 mm in diameter (25 kV, 1 mA); spherically bent HOPG polarizer (26 mm radius of
curvature); Si drift chamber with an energy resolution of 161 eV for MnKa and a visible area of 3 mm
2
. All
measurements are done in a He environment and with 4-mm prolene lters in front of the detector and between
crystal and sample.
RMS
P
M
i
C
certified
i
C
calibrated
i

2
M f
s
28
where M is the number of standards used (M35) and f is the number of regression
coecients determined.
V. BARKLA^BRAGGCOMBINATIONSYSTEMS
The HOPG crystals are characterized as very good Barkla targets in Sec. III and as ex-
cellent Bragg polarizers in Sec. IV. Polarization of the entire spectrum emitted from a tube
has been successfully performed with these crystals. Excitation by monochromatic Bragg
reections dominates the energy range E<10 keV; polychromatic Barkla polarized ra-
diation dominates in the energy range E>10 keV. Optimization of this BarklaBragg
combination system is matrix dependent due to the count-rate limitation of the detection
system and possible pileup lines. Using modern Si(Li) detectors or Si-drift chambers, it is
possible to process 10
4
10
5
cps so that optimization is facilitated by taking advantage of
the ability to control the tube current. Additional targets are only required for special
applications, because it is possible to excite all of the elements between Na and U with this
combination target. Of course, it is possible to optimize the excitation conditions using
radiation lters between the target and sample, analogously to direct excitation with
nonpolarized primary tube radiation. Being able to use air-cooled low-power x-ray tubes
(50 W) as the source of primary radiation is an important advantage of BarklaBragg
combination targets. The spectrum shown in Figure 8 was measured with an integral input
count rate of 25,000 cps (dead time: 18%) using a Peltier-cooled Si-drift chamber with an
active area of 5 mm
2
and an energy resolution of 159 eV for MnKa.
VI. SECONDARY TARGETS
The basic principles when working with secondary targets are to generate nearly mono-
chromatic radiation and to use it for excitation. Because the characteristic radiation of the
target material is nonpolarized, the detection system is burdened by backscattered char-
acteristic radiation from the target material, particularly when analyzing light matrices.
The advantageous application of secondary targets in the Cartesian excitation
geometry required for polarization is described by Bisga rd et al. (1981). The suppression of
Table10 Root-Mean-Square Deviation and Range of the Calibration Lines for Different Elements
in Lithium Tetraborate Glasses Using Excitation with Linearly Polarized Radiation
Element
Range
(g=kg)
RMS
(g=kg) Element
Range
(g=kg)
RMS
(g=kg) Element
Range
(g=kg)
RMS
(g=kg)
Na
2
O 070 0.34 P
2
O
5
010 0.23 TiO
2
01000 0.75
MgO 0970 1.1 SO
3
036 0.28 Cr
2
O
3
0160 0.58
Al
2
O
3
0890 1.0 K
2
O 0130 0.32 MnO 050 0.3
SiO
2
0990 1.1 CaO 0680 0.71 Fe
2
O
3
0560 0.95
Note: Rh tube; voltage: 15 kV; current 11 mA; measuring time: 300 s; at HOPG polarizer; no lter; vacuum.
primary tube radiation scattered on the target plays an important role, especially when
using secondary targets with low atomic numbers, such as Al. This is because radiation
lters cannot be placed between the target and the sample in this case. The detection limits
listed in Table 4 show that, compared to polarization targets, better results can be ob-
tained with a given x-ray tube for a limited number of elements. For example, a detection
limit of 0.2 mg=g was achieved for Hg in an organic solution using a measuring time of
500 s with a Zr secondary target.
Secondary targets in the Cartesian excitation geometry are often utilized to de-
termine trace elements with atomic numbers Z
trace
<Z
major
without exciting the major
element Z
major
. For example, a Co secondary target is used for the detection of Mn traces
in an iron matrix; an Fe lter is used to absorb the CoKb line that can excite Fe. A Si
secondary target is used for the trace detection of Na, Mg, and Al in a SiO
2
matrix.
A detection limit of 11 mg=g for Al in glass sand prepared as a pressed powder pellet is
achievable.
Thus, secondary targets are an ideal complement to Barkla and Bragg targets in a
Cartesian excitation geometry.
VII. CONCLUSION
In the fundamental publications in the 1980s and 1990s about the application of polarized
radiation in EDXRF by Ryon and Zahrt for Barkla polarization and Aiginger and Wo-
brauschek for Bragg polarization, tube powers in kilowatt ranges are a condition for
presentation of the advantages of EDPXRF over direct excitation with nonpolarized x-ray
radiation. In recent years, the development of Cartesian excitation geometries has been
Figure 8 Spectrum (log scale) of a geological standard sample, GnA, excited with the polarized
primary spectrum of a 50-W low-power Pd x-ray tube, measured with a Peltier-cooled Si-drift
chamber. Some of the concentrations are as follows: Si, 334 mg=g; K, 21.8 mg=g; Ca, 4.4 mg=g; Ti,
120 mg/g; Mn, 1.3 mg=g; Fe, 41.4 mg=g; Cu, 18 mg=g; Zn, 78 mg=kg; Rb, 2020 mg=g; Zr, 70 mg=g; Nb,
94 mg=g; Mo, 100 mg=g; Sn, 1900 mg=g; Bi, 220 mg=g.
propelled forward so that when coupled with powerful semiconductor spectrometers that
enable the processing of about 100,000 cps with resolution FWHM<200 eV, it is now
advantageous to use 50-W tubes in PXRF.
In practice, PXRF has asserted itself in many industrial laboratories and research
institutes as a powerful method for elemental analysis. The following typical applications
of EDPXRF instruments* have been identied:
Determination of heavy metals in soils and sludges
Major, minor, and trace element determination in geological samples
Precise major and minor element determination in ceramics and refractory materials
Trace elements determination in biological and organic samples
Analysis of aerosols
Analysis of additives in oils
Determination of trace elements in polymers and pharmaceutical products
Rapid determination of heavy metals and halogens in wastes
Analysis of slag
In the future, the adjustment of tube and crystal parameters will be additionally
improved so that new applications with EDPXRF will be possible (e.g., major, minor and
trace element determination within sample areas 1 mm
2
). It will be a long time before the
developments in the analytical elds become completed, especially the use of curved
crystals in EDXRF.
REFERENCES
Aiginger H, Wobrauschek P. J Radioanal Chem 61:281, 1981.
Aiginger H, Wobrauschek P, Brauner C. Nucl Instrum Methods 120:541, 1974; also in measurement,
Detection and Control of Environmental Pollutants. IAEA: Vienna, 1976.
Barkla CG. Trans Roy Soc (London) 204A:467, 1905; Barkla CG. Proc Roy Soc (London) 77:247,
1906.
Beckho B, Kanngieer B, Scheer J, Swoboda W. Adv X-ray Anal 35:1083, 1992.
Bertin EP. Principles and Practice of X-ray Spectrometric Analysis. 2nd ed. Plenum Press: New
York, 1975, p 117.
Bisga rd KM, Laursen J, Schmidt Nielson B. X-ray Spectrom 10:17, 1981.
Brumme M. Die BARKLA-Polarisationseinrichtung in der energiedispersiven Ro ntgenuoreszen-
zanalyse. PhD dissertation, TU Dresden, Dresden, Germany, 1990.
Brumme M, Heckel J, Irmer K. Isotopenpraxis 26:341, 1990.
Champion KP, Whittem RN. Nature 199:1082, 1963.
Compton AH, Hagenow CF. J. Opt Soc Am 8:487, 1924.
Dzubay TG, Jarrett BV, Jaklevic JM. Nucl Instrum Methods 115:297, 1974.
Evans RD. In: Handbuch der Physik. Springer-Verlag: Berlin, 1958, Vol 34.
Friedrich W, Knipping P, von Laue M. Ann Phys. 41:971, 1913.
Hanson AL. Nucl Instrum Methods A243:583, 1986.
Heckel J. J Trace Microprobe Tech 13:97, 1995.
Heckel J, Brumme M, Weinert A, Irmer K. X-ray Spectrom 20:287, 1991.
Heckel J, Haschke M, Brumme M, Schindler R. J Anal Atomic Spectrom 7:281, 1992.
Howell R, Pickles W. Nucl Instrum Methods 120:187, 1974.
Howell R, Pickles W, Cate Jr J. Adv X-ray Anal 18:265, 1975.
*Manufactured by Spectro A.I. GmbH & Co. KG, Kleve, Germany.
Kanngieer B. Die Anwendung von HOPG-Kristallen in der energiedispersiven Ro ntgenuor-
eszenanalyse. Diploma thesis, University of Bremen, 1990.
Kanngieer B, Beckho B, Scheer J, Swoboda W. X-ray Spectrom 20:331, 1991.
Kanngieer B, Beckho B, Scheer J, Swoboda W. Adv X-ray Anal 35:1001, 1992.
Klein O, Nishina Y. Z Phys 52:853, 1928.
Ryon RW. Adv X-ray Anal 20:575, 1977.
Ryon RW, Zahrt JD, Wobrauschek P, Aiginger H. Adv X-ray Anal 25:63, 1982.
Strittmatter RB. Adv X-ray Anal 25:75, 1982.
Svoboda W, Beckho B, Kanngieer B, Scheer J. X-Ray Spectrom 22:317, 1993.
Ter-Saakov AA, Glebov MV. Atomnaya Energiya 58:260, 1984.
Thomson JJ, Thomson G. The Conduction of Electricity Through Gases. 3rd ed. Cambridge
University Press: Cambridge, 1933.
Wobrauschek P, Aiginger H. Adv X-ray Anal 28:69, 1985.
Wobrauschek P, Aiginger H, Owesny G, Streli C. J Trace Microprobe Tech 6:295, 1988.
Zachariasen WH. Theory of X-ray Diraction in Crystals. Dover: New York, 1967.
Zahrt JD. Adv X-ray Anal 26:331, 1983.
Zahrt JD. Nucl Instrum Methods A242:558, 1986.
Zahrt JD, Ryon RW. Adv X-ray Anal 24:345, 1981.
Zahrt JD, Ryon RW. Adv X-ray Anal 29:435, 1986.
11
Microbeam XRF
Anders Rindby
Chalmers University of Technology and University of Go
te
borg, Go
tebo
rg, Sweden
Koen H. A. Janssens
I. INTRODUCTIONANDHISTORICAL PERSPECTIVE
Up to the end of the 1980s, elemental microanalysis based on the emission of characteristic
x-rays was largely restricted to charged-particle-beam techniques (electrons, protons, and
heavier nuclei). Although the use of primary x-rays for inducing the production of the
uorescent radiation was widespread in bulk x-ray uorescence (XRF) instrumentation,
the lack of brilliance of conventional x-ray tubes and the inherent diculties of focusing
x-rays in the 130-keV energy range hampered the development of the microscopic variant
of XRF as a microanalytical tool.
Nevertheless, Glockner and Schreiber (1928) quite early demonstrated the possibility
of doing chemical analysis by uorescence spectroscopy with small x-ray beams. In the
mid-1950s, Long and Cosslett (1957) reported detection limits at the picogram level from
an x-ray microbeam device. Zeits and Baez (1957) predicted a theoretical detection limit
from an optimal instrument to be below 10
14
g. They concluded that compared to the
electron microprobe, the x-ray microprobe was superior in relative sensitivity, but not in
terms of absolute detectability. Localization was also poor for x-rays; however, the energy
impact is much smaller in comparison to charged-particle beams.
In the early 1980s, the availability of highly intense radiation beams from syn-
chrotron sources increased the interest in using microscopic x-ray beams for performing
m-XRF experiments (Chapter 8); also around this period, capillary optics were being used
as simple, compact, and relatively inexpensive means of concentrating a beam of x-rays
down to a smaller size. This innovation lead to the development of microbeam XRF in-
strumentation employing (conventional) x-ray tubes as the source of primary radiation.
During the last two decades, monocapillary and polycapillary focusing devices have been
incorporated into a variety of m-XRF spectrometers; an overview of their characteristics is
provided in Table 1.
More recently, the introduction of commercially available compact minifocus and
microfocus tubes has considerably increased the potential of microbeam XRF, making
possible the use of microbeams in small-sized and easily transportable XRF equipment.
Another signicant development of recent years is the maturation of the techniques
Table1 Overview of Laboratory-Scale m-XRF Instruments Described in the Literature
Focal size
on anode
Distance
anodeoptics Optics
b
Tube power Brilliance
Anode X-ray source specication
a
(mm
2
) (mm) (diameters given) (W) (kW=mm
2
)
Diffraction tube (a) n.s. n.s. 10, 30, 100 mm coll. 1,000 n.s. Cu
W tube Mo secondary target (b) n.s. n.s. 200 mm str. cap n.s. n.s. W
Philips interchangeable tubes (c) n.s. n.s. 30 mm coll. 2,500 n.s. Cu
Fine-focus diffraction tube (d) n.s. n.s. 10, 30, 100 mm coll. 5001,000 n.s. Cu, Mo
n.s. (e) n.s. n.s. 22, 7.5 mm par. cap. n.s. n.s. Mo
Low-power tube (f) <0.25 0.25 n.s. 10, 30, 100 mm coll. 50 >0.8 Mo
Long, fine-focus diffr. tube (g,h) 0.4 12 $40 200 mm str. cap. 1,9003,000 0.40.6 Cr, W
Radiographic microfocus tube (i) 0.030 $5 10 mm str. cap. 1521 0.50.7 Mo, W
Diffraction tube ( j) 0.4 8 n.s. 18, 23, 27 mm str. cap. n.s. n.s. Cu, W, Mo
Low-power tube (k) 0.25 0.25 n.s. 70 mm coll. 50 0.8 Mo
Long, fine-focus 0.4 8 $40 18 mm con. cap. 1,000 0.3 Cr
diffraction tube (l,m) 7.5 mm ell. cap.
Idem (n) 15, 65, 70 mm con. cap. 1,500 0.5 Mo
Idem (o) 7.5 mm ell. cap. 1,000 0.3 Cr, Cu
n.s. (p) n.s. $40 15 mm con. cap. n.s. n.s. Mo
Radiographic microfocus 0.015 0.1 $5 4, 8, 29, 100 mm str. cap. 1.6 (Cu, W) 1.0 Cu, W, Mo
tube (q) 1.4 (Mo) 0.9
Rotating anode tube (r) 0.5 10 $70 10, 15 mm ell. con. cap. 18,000 3.6 Cu, Mo
Rotating anode tube (s) 0.5 10 $70 160 mm polycap. 18,000 3.6 Mo
Minifocus tube (t) 0.25 0.25 $40 50, 100 mm polycap. 60 0.96 Mo
Radiographic microfocus tube (u) 0.03 0.006 22 21 mm polycap. 12 67 Mo
a
(a) Nichols and Ryan, 1986; (b) Rindby, 1986; (c) Boehme, 1987; (d) Nichols et al., 1987; (e) Yamamoto and Hosokawa, 1988; (f ) Wherry et al., 1988; (g) Engstro m et al.,
1989; (h) Rindby et al., 1989; (i) Carpenter, 1989; Carpenter et al., 1989; Carpenter and Taylor, 1991; (j) Furata et al., 1991; Furata et al., 1993; Hosokawa et al., 1997;
(k) Pella and Feng, 1992; (l) Larsson et al., 1990; (m) Shakir et al., 1990; (n) Rindby, 1993; (o) Attaelmanan et al., 1995; (p) Holynska et al., 1995; (q) Carpenter et al., 1995b;
(r) Janssens et al., 1996a; (s) Vekemans et al., 1998; (t) Bichlmeier et al., 2000; (u) Gao et al., 1997.
b
str.cap., con.cap., par.cap., ell.cap.: resp. straight, conical, paraboloidal, ellipsoidal capillary; coll.: collimator; polcap.: monolithic polycapillary lens; n.s.: not specied.
for manufacturing monolithic polycapillary x-ray lenses. In addition to being used for
focusing tube-generated x-rays into microscopic spots, at synchrotrons, these devices are
now also being employed for performing m-XAS (x-ray absorption spectroscopy), m-XRD
(x-ray diraction), and x-ray radiography experiments.
The state of the art of m-XRF has recently been summarized in a special issue of the
journal X-ray Spectrometry (Carpenter, 1997) and in a book (Janssens et al., 2000a).
A. Development of Microscopic X-ray Emission Analysis
With the availability of an intense electron microbeam and an ecient detection system for
x-rays, a scanning x-ray microscope was quite an obvious development; one of the very
rst scanning x-ray microscopes was described by Duncumb (1957). The system used
electron excitation and was constructed as a microfocused x-ray tube. A proportional
counter was used for detecting the emitted x-rays. Proportional counters are very ecient
devices but are not able to separate the K x-rays of adjacent elements unless the counter is
combined with some kind of Bragg-reecting dispersion element. With the introduction of
the Si(Li) detectors in the late 1960s, the construction of XRF spectrometers in general
was simplied. One of the rst x-ray excitation scanning uorescent microbeams was
constructed by Long and Cosslett (1957) using a microfocused transmission tube in
combination with an aperture.
Next, by using highly brilliant sources of hard x-rays as provided by synchrotron
storage rings, microbeam spectroscopy became possible at a much more sophisticated
level. The basic instrumental arrangement employed during m-XRF experiments is shown
in Figure 1. The very rst synchrotron-based x-ray microbeam setup was described by
Horowitz and Howell (1972). Tabletop m-XRF devices have developed rapidly over the
last decade and the number of applications is growing. Today, m-XRF instruments are
used in forensic science, industrial quality control, and environmental science. They are
used in material science for analyzing polymers, composite materials, ber materials, soft
tissues from plants, and so forth. Several instruments are now commercially available and
most of these setups have a similar set of components.
A standard microbeam spectrometer consists of an x-ray source, some kind of fo-
cusing device (or just an aperture), a sample holder, and a detection system. The rst two
Figure1 Basic experimental scheme employed during m-XRF investigations.
components will dene the spectral properties of the primary beam (large or narrow
energy bandwidth). The sample holder should allow for an accurate remote control of the
sample position and the detection system for intensity measurement of uorescent,
transmitted, or=and diracted radiation. A conventional microscope (or just a camera and
a lens system) can be used as a monitoring system for identifying the part of the sample
that is to be analyzed. Normally, uorescence spectroscopy can be done in dierent
modes: point analysis, line scan, and area scan. In addition to uorescence spectroscopy,
absorption and diraction measurements can be done in the same modes. Other types of
spectroscopy can also be performed such as XANES (x-ray absorption near-edge spec-
troscopy) or EXAFS (extended x-ray absorption ne structure spectroscopy) (Bertsch
et al., 1994); however, these types of spectroscopy require the possibility to tune the pri-
mary energy to the absorption edges of element(s) of interest and, in most cases, are
performed only at synchrotron beam lines.
With the development of capillary optics, a considerable number of tabletop
microbeam instruments have been developed and described in the scientic literature
(see Table 1). These instruments normally use capillary optics in combinations with
conventional ne-focus x-ray tubes, where the virtual brilliance can be fully utilized, or
with micro-focused tubes, where the (actual) brilliance is very high. The sensitivity of these
instruments can be quite high: Larsson and Engstro m (1992) reported a detectable limit
(DL) for such an instrument of about 40 fg (4 10
14
g) of calcium in a paper specimen,
which is in agreement with the prediction of Zeitz and Baez (1957).
B. Development of Microfocusing X-ray Optics
The reason why x-ray spectroscopy has not been applied on the microscopic level as has
been the case with electron-probe x-ray microanalysis is mainly attributed to the di-
culties of optically controlling an x-ray beam as compared to an electron beam. Although
dierent types of optics for focusing and imaging in the x-ray region have been developed,
their eciencies are still inferior to those of conventional electron optical systems. How-
ever, even with poor optical eciency, the use of x-ray microbeams oers many ad-
vantages in comparison to electron beam excitation.
Also, for x-ray microscopy, there has been a great need for microfocusing optics. As
early as 1936, Sievert (1936) used a conventional aperture of a fewmicrometers to generate a
small x-ray source for x-ray microscopy. Although the resolution was good, the intensity
was poor and von Ardenne (1939) proposed an electron lens to generate small x-ray sources
for projection x-ray microscopy. A microfocus x-ray tube based on the idea of von Ardenne
was actually constructed by Cosslett and Nixon (1952) for this purpose. Although the
electron lens system constructed in the early 1950s was the starting point for a very rapid
development of electron microscopy, x-ray microscopy and microbeam spectroscopy did
not develop at the same rate due to the inability to generate ecient optical systems for
x-rays. With the introduction of synchrotrons in the late 1960s, a newinterest in x-ray optics
was created and several synchrotron-based x-ray microbeam setups are now in operation
(Iida, 2000). In recent years, also tabletop x-ray microbeam setups have been constructed in
which both conventional and nonconventional optics have been applied (Rindby, 2000).
1. First-Generation Focusing Systems
One of the very rst focusing devices used for x-rays was probably the von SeemanBohlin
(von Seeman, 1919) camera, which was a Rowland circle setup. The practical problem of
x-ray optics was recognized early when Compton (1923) demonstrated that although
x-rays have measurable optical properties, the refractive power of most materials in
the x-ray region is very low. This means that a conventional lens system for x-rays was very
impractical. However, in 1924, Larsson, et al. (1924) used the edge of a prism block to focus
x-rays. The system, which was rather inecient and had severe chromatic aberration, was
later used by Hink and Petzold (1958), but only to measure refractive indices. The technical
possibilities left for x-ray optics were Bragg reection and total external reection.
Bragg reection was used in the Johan (1931) and Johansson (1933) cameras. An
advantage with Bragg reection is that normal incidence can be used, thus reducing as-
tigmatism and aberrations. However, the system only works within a very small energy
band width and the rest of the radiation energy is completely lost. In order to construct
broad-band x-ray optics, total-reecting devices need to be employed.
Jentzsch (1929) established the essential geometrical principles for x-ray focusing
from total-reecting spherical surfaces. He pointed out the importance of using highly
nished surfaces but also concluded that glancing-angle incidence will always generate
severe astigmatism. Attempts were also made to form images from the inside of a glass
tube. Experiments were carried out by Ehrenberg and Jentzsch (1929) and by Na hring
(1930a, 1930b) and imaging properties were also discussed by Kellerman (1943), but no
result was ever reported. One of the very rst practical focusing devices was a total-
reecting curved crystal developed by Ehrenberg (1947).
In order to overcome some of the problems with astigmatism, another approach to
the imaging requirements was investigated by Wolter (1952a) and Herrnring and Wiedner
(1956). They suggested the use of cylindrical mirrors (i.e., the Wolter microscope). A more
practical method for astigmatism correction is the crossing of two cylindrical mirrors at
right angles. In general, large aberrations in cylindrical and spherical mirrors can always
be reduced by a second mirror. Pioneering work with this kind of compound system was
done by Kirkpatrick and Baez (1948). Other compound systems were proposed by
Herrnring and Wiedner (1956) and Wolter (1952b), suggesting combinations of
hyperboloid and paraboloid surfaces.
2. Second-Generation Focusing Systems
Today, the KirkpatrickBaez compound system as well as the Wolter mirror are in use at
dierent synchrontron-based microbeam setups. Due to the improved technique for de-
veloping highly nished and perfect surfaces, ellipsoidal and paraboloidal mirrors can now
be manufactured with high perfection. The multilayer technique has also improved the
reecting quality of modern mirrors.
The LBL (Lawrence Berkeley Laboratory) microbeam setup uses a Kirkpatrick
Baez system with two mutually perpendicular spherical mirrors coated with a WC
(tungstencarbon) multilayer. The system, when operating at the X-26C beamline at
NSLS (Upton, NY), provides a 50-fold demagnication and generates a 10-mm
2
x-ray
focus. At the NSLS X26A beamline, an elliposoidal mirror is used for focusing purposes.
A Wolter focusing mirror combined with a hyperboloidal and an elipsoidal surface is used
at the Photon Factory microbeam setup (Tsukuba, Japan). A bent crystal is used for the
SRS microprobe (Daresbury, UK). A comparison between dierent microprobe setups
and their sensitivity was given by Larsson and Engstro m (1992). Reviews of synchrotron
microprobes are given by Jones and Gordon (1989) and Rivers and Sutton (1991); Rindby
et al. (2000) provides an up-to-date overview of the technology that is currently used to
focus x-rays. See also Chapter 8.
3. X-ray Concentrators
Although improvements have been made in the fabrication of optical elements such as
mirrors and zone plates, the technique is limited by its basic imaging properties. Whatever
imaging system is used, the focal spot is nothing else than the image of the source; thus,
in order to produce an x-ray beam with small focal spot, one needs a small x-ray source.
Variation and instability of the primary source can induce a corresponding instability of
the focal spot, and small variation in the geometry of the reecting mirrors, due to thermal
gradients, can cause a large uctuation in the focal length and focal spot size. Many of
these problems can be circumvented by going beyond the conventional imaging optics and
apply nonimaging optics (NIO). If the optical system is only used to focus the beam, NIO
technology is normally superior to conventional imaging optics.
Nonimaging optics was born in the mid-1960s when Baranov, Ploke, and Winston
(see Winston, 1991) independently designed the rst compound parabolic concentrator. In
nonimaging optics, no focal plane can be dened, but the optical elements are designed
only to generate maximum (spatial) concentration of the radiation. These optical elements,
which are normally called concentrators, can generate intensities far better than any
conventional imaging system. A typical NIO technique for x-rays is the application of
small conical glass capillaries used for generating micrometer-sized x-ray beams.
The advantage of the x-ray concentrators (mostly referred to as capillary optics) is
their source independence. The beam size is dened by the capillary inner diameter
rather than the source size. As it is a NIO technique, a high virtual brilliance source (such
as the point focal output from a line-focus x-ray tube) can be used in an ecient way.
Instability and uctuations in the source position will not aect the position or the size of
the focal spot. As the beam is dened by the capillary opening, the beam position can
easily be established by an ordinary optical microscope. Due to its cylindrical symmetry,
thermal gradients will not aect the beam position even at high radiation exposure. Be-
cause it is a total-reection device, capillaries also have broad-band properties. They have
submicrometer capabilities, and compared to conventional x-ray optics, are very in-
expensive. One disadvantage, however, is that the highest intensity is achieved at the ca-
pillary opening so that the sample needs to be very close to the capillary output in order to
utilize the high photon density completely. Although the divergence of a capillary beam is
normally very small (it is of the order of the critical angles for total reection), this pro-
blem can be severe for near-mircometer or submicrometer capillary beams.
After the attempts of Ehrenberg and Jentzsch (1929) to form x-ray images from the
inside of a glass-capillary tube, Jentzsch and Na hring (1931) used straight glass capillaries
of dierent dimensions, of length 1075 cm and an opening of 0.12 mm in diameter, to
generate x-ray microbeams. Practical applications of glass capillaries began at the end of
the 1940s. Chesley (1947) designed a microcamera that used a short, straight glass capil-
lary; in the same year, Kreger (see Hirsch, 1955) used a 20-mm beam from a 1-cm-long
conical glass capillary to study the structure of the wax-rod coating of a sugar cane stem.
Hirsch and Keller (1951) used photographs of the emergent beam from a 35-mm capillary
to properly align the capillary. In the period 19521954, capillary-generated microbeams
were applied to the study of the deformation, recovery, and recrystallization of metals
(Hirsch, 1955). The smallest beam used was 8 mm. Mosher and Stephanakis (1976) de-
scribed the ecient transport of soft x-rays through hollow glass and metal tubing. A
bundle of such tubes was used to remotely image a weak plasma source of soft x-rays.
Comprehensive theoretical analysis of x-ray guides was conducted by Chung and
Pantell (1977) and by Pantell and Chung (1978, 1979), who investigated the transmission
and power enhancement of x-rays in cylindrical wave guides, the transmission of x-rays
through curved wave guides, and also studied the inuence of surface roughness on the
propagation of x-rays through capillaries.
Rindby (1986) measured the critical angle for total reection for x-rays inside a 200-mm
glass capillary. Inthe same year Nozaki andNakazawa (1986) describeda conical x-ray guide
tube (XGT). The XGT was used with the smaller opening nearest to the x-ray tube to obtain
an almost parallel x-ray beam. Carpenter et al. (1987) carried out several experiments to
determine the variation in beam prole, intensity, and spectrum with capillary size and
position. The rst focusing XGT was reported by Yamamoto and Hosokawa (1988), who
developed a parabolic inner-wall x-ray guide tube made of glass that focused the x-ray beam
into a 5.7-mm spot. The rst scanning x-ray microprobe with glass-capillary collimation,
which had a beam size of 10 mm, was described by Carpenter et al. (1988).
The rst capillary-generated submicron x-ray beam was reported by Engstro m et al.
(1991), from a synchrotron radiation source. Homan et al. (1994) reported a 50-nm x-ray
beam from a conical capillary, which was measured with energies up to 8 keV, using
synchrotron radiation.
Kumakhov (1986, 1990) and Kumakhov and Komarov (1990) performed extensive
research, both theoretical and practical, on the multireaction properties of glass capil-
laries, which led to the design of the Kumakhov or polycapillary x-ray lens, a type of
device now manufactured by several laboratories worldwide (Kardiawarman et al., 1995;
Ullrich et al., 1995; Kumakhov, 1998; Ding et al., 1998; Vekemans et al., 1998; Gao et al.,
1998). This optical technology possesses real imaging properties and has found broad
application areas in both pure and applied sciences. In combination with microfocus x-ray
tubes, beam sizes down to 1530 mm can now be achieved.
C. Chapter Overview
In this chapter, after providing some information on the basic x-raymatter interactions
which are employed for microfocusing x-ray and comparing the way in which x-ray and
charged-particle microbeams interact with matter, the instrumentation required for per-
forming microbeam XRF is discussed, with some emphasis on recent developments in this
eld (tubes, optics, detectors). Next, data acquisition strategies for point, line, and image
XRF analysis are described and the appropriate procedures for evaluating, segmenting,
and quantifying (large amounts of) spectral data are discussed. Finally, an overview of
applications of the microbeam XRF technique in various elds is presented: the latter
include the use of m-XRF in the industrial, environmental, cultural, and forensic sectors of
activity.
II. THEORETICAL BACKGROUND
A. PhotonVersus Charged-Particle-Induced X-ray Emission
When considering the (dis)advantages of microbeam XRF relative to other micro-
analytical methods, in the rst instance, it is relevant to consider the factors determining
the sensitivity of the microbeam XRF technique and its closest analogs, EPXMA (elec-
tron-probe x-ray microanalysis) and m-PIXE (proton-induced x-ray emission). For all
x-ray emission techniques that employ some form of photon counting in the detection
chain (mostly when energy-dispersive detectors are used), the lowest detectable con-
centration level c
DL
(DL: detection limit) for a given chemical element can be estimated
from the net photopeak intensity N and the corresponding background intensity B, which
are collected from a sample containing a concentration c of a given element, as:
c
DL
c
k
B
p
N

k

s
B
p
s
N
1
It
p 1
where k is usually a number in the range 15 (often k 3), s
N
N=cIt is the net x-ray yield
for this element and s
B
B=It is the corresponding background yield. The sensitivity of
any x-ray emission technique therefore can be increased by the following:
1. Decreasing the background abundance s
B
2. Increasing the elemental yield s
N
3. Increasing the beam intensity I and=or the collection time t
It is useful to consider the relative and absolute magnitudes of the above-mentioned
quantities when comparing the analytical characteristics of various x-ray emission tech-
niques. Because, in the present context, dierent microanlytical techniques are compared,
the achievable beam size S and the beam ux density F I=S (expressed, e.g., in photons,
electrons, or protons per second and per square micrometer) are also important gures of
merit.
a. Penetration Depth
In Table 2, the penetration depth of 20-keV x-ray photons and electrons and 2.5-MeV
protons are compared. The much larger penetrative power of photons in light matrices
(Z<20) relative to charged particles is immediately clear; protons take an intermediate
position between electron and photons. The penetration range for charged particles is
determined by the gradual energy loss that occurs as a result of many inelastic scattering
interactions with the sample material [quantitative described by the stopping power
function SE] and by the curvature of the trajectories (mainly resulting from many elastic
collisions between projectile and sample atoms). On the other hand, for x-ray photons in
the range 150 keV, the most probable interaction mechanism (for many sample materials)
is the photoelectric eect. For example, for 10-keV photons in Al, the probabilities for
photoionization and Compton (i.e., inelastic) and Rayleigh (elastic) scattering are 97.5%,
0.4% and 2.1%, respectively. Because the photoelectric eect causes the primary photon
to be annihilated, the majority of the primary photons will only be subject to a single
Table 2 Penetration Depth of Electrons, Protons, and X-ray Photons in Various Materials
Element
Atomic
number
Atomic
mass
Density
(g=cm
3
)
m
a
L
(cm
71
)
Penetration range (mm)
X
b
20 keV
e
7c
20 kV
p
c
2.5 MeV
C 6 12 1.9 0.79 12,000 5 55
Si 14 28.1 2.3 10 1,000 5 68
Fe 26 55.9 7.8 200 50 1.6 27
Ag 47 107.9 10.5 189 50 1.7 28
Pb 82 207.2 11.3 971 10 2 37
a
m
L
linear mass absorption coefcient.
b
1=e range.
c
Bethe range.
(scattering or photelectric) interaction; only a very small fraction will rst be (in)elastically
scattered by a sample atom before ionizing a second atom.
b. Phenomena Contributing to the Background
The consequence of this dierent behaviour is that samples irradiated with monochro-
matic x-ray photons of energy E
0
, next to the characteristic radiation of the sample atoms,
will only emit scattered photons in a limited energy window from a few kiloelectron volts
below up to the primary energy E
0
. In contrast, the irradiation of a material with charged
particles of energy E
0
will result in a bremsstrahlung continuum (primarily due to decel-
erating electrons) spanning the entire energy range from 0 to E
0
. This continuum is
especially noticeable in EPXMA spectra, where the continuum is generated at relatively
shallow depths (Reed, 1975) (typically $5 mm; see Table 2 and Fig. 2a). In case of PIXE,
the abundance of the continuum is supressed because it is caused by secondary electrons of
relative low energy generated by the primary protons (Johansson and Campbell, 1988)
(Fig. 2b). When a sample is irradiated with a polychromatic x-ray beam, also in XRF
spectra, a scatter continuum spanning the entire energy range can be observed (Fig. 2c). In
contrast to SR-based microbeam XRF instruments, in which linearly polarized radiation
is employed in order to reduce the scatter background level (Fig. 3a), laboratory m-XRF
instruments operate with unpolarized polychromatic radiation, giving rise to an appre-
ciable background continuum in the EDXRF spectra (Fig. 3b).
c. Production of Characteristic Radiation
In Figure 4, the cross sections for characteristic x-ray production by x-ray photons,
electrons, and protons are compared (Vis, 1990). Two important observations can be
made: (1) for the three projectile types, the overall probability for ionization is compar-
able; (2) for the charged particles, the ionization cross sections decrease with increasing
atomic number of the target atomsthe photoionization process favors heavier over
lighter elements.
Considering Eq. (1), it can therefore be concluded that for equal beam intensity I and
collection time t, the lower background levels that are recorded with monochromatic
photon-induced x-ray emission, together with the comparable or higher ionization cross
sections, will result in lower detection limits (DLs) for m-XRF than for EPXMA and
m-PIXE in the case of heavy elements (Z>25).
Unfortunately, whereas in conventional electron microprobes routinely currents of,
for example, 1 nA (i.e., about 6 10
9
electrons=sec) are focused in an area smaller than
0.001 mm
2
and whereas in m-PIXE apparatus, usually 101000 pA are concentrated into a
110-mm
2
spot (resulting in ux densities in the range of 10
6
10
9
protons=s=mm
2
),
equivalent photon ux densities cannot be straightforwardly achieved using conventional
x-ray sources. The reasons for this are twofold:
1. The spot emitting x-rays on the anode of a conventional x-ray tube is
comparatively large (one to a few tens of square millimeters), whereas the
generated photon beam is emitted into a broad cone.
2. It is not possible to focus x-rays as easily as charged particles or as radiation of
longer wavelengths.
The problem is even aggravated by the fact that x-ray tubes (based on electron-induced
x-ray emission) produce a continuum of x-rays rather than monochromatic radiation.
Typical primary ux densities on a sample surface achievable with a standard x-ray tube
are situated in the range of 10
4
10
5
photons=s=mm
2
(Cu tube, 30 mA, 45 kV, sample at
5 cm from the anode spot) when only the principal anode line intensity is considered.
Therefore, in order to take advantage of the inherently better peak-to-background
ratio of photon-induced x-ray emission relative to excitation by charged particles, either
much more brilliant x-ray sources than conventional tubes must be used or the radiation
from an x-ray tube must be focused into a microspot on the sample or both.
Figure 2 EPXMA, m-PIXE, and white beam SR-XRF (NSLS X26A station) spectra collected by
irradiating NIST SRM K961 glass microspheres.
Figure 3 ED-XRF spectra of NIST SRM 1577 Bovine Liver obtained using (a) an 8 8 -mm
2
polychromatic SR beam (220 s counting time) at the NSLS beam line X26A station, (b) a Mo-anode
x-ray tube using a conical capillary (300 s counting time). Dots: experimental spectra, lines: predicted
spectral distributions obtained by Monte Carlo simulation (see text).
In addition to the use of synchrotron sources (Chapter 8), in the laboratory,
microfocus or minifocus x-ray tubes may be used, either in combination with an aperture
or with focusing optics. Of the latter, in practice, only compact devices such as single-
capillary concentrators or monolithic polycapillary lenses are being used in laboratory
m-XRF instruments.
B. X-ray^Matter Interactions Employed for Microfocusing
1. Optical Theoryof X-rays
The description of the propagation of x-rays in any refractive medium is based on the
same concepts as used for describing ordinary optical light propagation. These types of
models rely on the fact that most materials can be described in terms of a refractive index n
which is related to its dielectric properties
n

e
r
p
2
where e
r
is the relatively dielectric constant. As in general, e
r
is a complex number and the
index of refraction can be written under the form: n 1 d where d a ib. a and b can
be written as
a
2pNe
2
m
e
o
2
f
0
; b
2pNe
2
m
e
o
2
f
00
3
where f
0
and f
00
are the real and imaginary parts of scattering factor, respectively, o is the
frequency of the x-ray, N is the number of atoms per unit volume, m
e
is the electron rest
mass, and e is its charge. The imaginary part of the index of refraction is also related to the
linear absorption coecient m
L
:
b
cm
L
2o
4
Figure 4 Cross sections for K-shell x-ray production by x-rays, protons, and electrons as a
function of target atomic number for various projectile energies.
For a multielectron atom, f
0
can be written as a sum of scattering factors for all the
electrons. For energies far below any absorption edge, the corresponding electrons will
only contribute in a minor way to the atomic scattering factor. However, for energies far
above the absorption edge, the corresponding electron will contribute with unity. Thus, for
energies far above the K edge, the scattering factor will be equal to the atomic number.
Close to any edge, the scattering factor will have a resonance structure, as shown in
Fig. 5.
2. X-ray Reflectivity
If a plane wave propagating in a medium characterized by the refractive index n
1
1 d
1
is incident on a smooth-plane boundary of another medium with refractive index
n
2
1 d
2
then if d
1
6 d
2
, a reected and a transmitted wave is generated. The reectivity
(R) as well as the transmittance (T) can be calculated from the Fresnel formula that simply
assumes the electric and magnetic eld components to be continuous at the boundary
interface (Azaro et al., 1974). Using Snells law, the parallel and perpendicular compo-
nents of the reectivity R
p
and R
s
can be expressed in terms of the incident angle y
i
and the
indices of refraction of the two media:
r
p

1 d
2
2
sin y
i
1 d
1
1 d
1
2
1 d
1
2
cos
2
y
i
1=2
1 d
2
2
sin y
i
1 d
1
1 d
2
2
1 d
1
2
cos
2
y
i
1=2
; R
p
r
p
r
p
r
s

1 d
1
2
sin y
i
1 d
2
2
1 d
1
2
cos
2
y
i
1=2
1 d
1
2
sin y
i
1 d
2
2
1 d
1
2
cos
2
y
i
1=2
; R
s
r
s
r
s
5
Figure 5 The real part of the atomic scattering factor times the number of atoms per cubic
centimeter for silver and for SiO
2
glass.
By assuming that the glancing angle is small, the parallel and perpendicular components
will become almost identical and, furthermore, by putting d
1
0 (incidence from air or
vacuum) and d
2
d, we can simplify the formulas for the reectivity to
r
s
r
p

y
i
y
2
i
2d
1=2
y
i
y
2
i
2d
1=2
6
Note that this expression becomes unity if y
2
2d, provided that d is real. This situation
corresponds to total reection of the incident wave front and thus the critical angle
y
c
2d
1=2
/ 1=E, where E is the x-ray energy. Because d, in general, is complex (taking
the absorption into account) the reection coecient will not be exactly unity. However,
for most of the optical materials considered here, the reectivity will be close to unity
within a small angular range from zero degrees up to a few minutes of arc and then
suddenly drop to about $d
2
=4 (see Fig. 6).
Because d is complex d a ib, the following substitution will be convenient:
y
2
2d
p

y
2
2a 2ib
q
p iq 7
Thus, R can be written as
Ry; E
y p
2
q
2
y p
2
q
2
8
where
p
2
1
2
y
2
2a
2
4b
2
q
y
2
2a;
q
2
1
2
y
2
2a
2
4b
2
q
y
2
2a
9
3. Geometrical Aberrations
As the reectivity for x-rays is extremely small except within a small range from zero up to
critical angle y
c
, most x-ray optics are based on the principle of grazing incidence, although
optical devices based on Bragg diraction are also in use (Ice, 1997). The dierent types of
geometrical aberration that occur for such an optical system can be described in terms of
spherical aberration, astigmatism, curvature of the eld, and coma. However, in contrast to
the imaging system of light optics, there is no axial symmetry. Thus, the normal optical
treatment cannot be applied and the classication of aberration will be somewhat dierent.
Spherical aberration arises when rays (originating from a point source), which will be
incident on the mirror surface at dierent angle, are not intercepting at the
same point. Thus, the image of a point object formed by such a nonideal
reector will become a disk on confusion rather then a point.
Astigmatism will arise if the meridian and sagittal rays are not focussed at the same
distance from the mirror.
Coma is a kind of eld aberration that is due to dierent magnications being
produced by dierent regions of the mirror.
Curvature of the eld means the focal plane is slightly curved due to dierences in
focal lengths at dierent position in the object plane. This type of aberration
will determine the physical depth of focus for the system.
Figure6 Left: The reflectivity for glass as a function of the glancing angle at E5.411 keV; the absorption coefficient was chosen to
be m
glass
(i.e., the normal value), 10m
glass
and 0.1m
glass
. Right: Calculated reflectivity of glass at two energies (CrKa and MoKa) while
using the normal value for absorption coefficient.
III. INSTRUMENTATIONFOR MICROBEAMXRF
Table 1 summarizes the characteristic features of several tabletop instruments recently de-
scribed in the scientic literature. A m-XRF setup essentially consists of four major parts:
1. An x-ray source
2. A focusing or collimation device
3. A motorized sample stage microscope
4. One or more detectors
As we can see from Table 1, capillary optics is, by far, the most popular type of optics for the
tabletop instruments. Most of the tabletop setups are equipped with either microfocused
tubes in combination with collimators or straight capillaries or high-ux tubes with conical
capillaries. When simple pinhole or cross-slit systems are used to aperture the beam, the
problemis toget close enough to the actual source in order to pick up the highest ux density.
Straight capillaries have beenused by many authors as a means of doing so andguiding it out
to the sample position without the 1=r
2
geometrical loss that occurs when conventional
collimators are employed. As shown in Figure 7, these setups may utilize specially designed
microfocused tubes where the capillary optics have been integrated in the tube construction.
By using conical capillaries, one can operate further away from the source, as the
squeezing of the beam will compensate for the reduced ux density. As a nonimaging
device, the conical capillaries can utilize virtual brilliance that is achieved in standard
diraction tubes by the projection of long ne-focal spots. For any focusing device,
accurate alignment is important; thus, the focusing element has to be completely in-
tegrated and permanently xed to the source or be mounted on a exible stage so that
realignment can be done. A more recent development is the use of polycapillary x-ray
lenses in combination with compact low-power tubes for generating x-ray beams in the
size range above 1530 mm.
Figure 7 Microbeam XRF setup with the capillary focusing unit built into a microfocus x-ray
tube. (From Carpenter et al., 1988.)
A. X-ray Sources Suitable for MicrobeamXRF
The dierent types of x-ray tube commercially available at present are discussed elsewhere
in this volume (Chapter 5). General information on the x-ray continuum produced in x-ray
tubes can be found in Bethe (1930), Webster et al. (1993), Mott and Massey (1949),
Metchnick and Tomlin (1963), Robinson (1974), and Go rgl et al. (1992). In the framework
of microbeam XRF, basically two types of tube can be distinguished: high-power and low-
power tubes. High-power tubes have a water-cooled anode, are normally equipped with a
side-looking x-ray exit window, and can operate up to several kilowatts. The limitation of
the source brilliance is due to the heat load on the anode that is a function of the power
load, focal spot size, cooling eciency, thermal conductivity, and so forth. The standard
type of diraction tube can take a power load up to 0.6 kW=mm
2
. For diraction tubes,
the focal spot is formed as a ne line allowing for both a line-focal output and a point focal
output, where the virtual high brilliance, from the projection of the line, can be utilized.
The rotating anode technique is a way to improve the cooling eciency of the anode and is
used for very high-power loads.
Low-power tubes can be side-looking, end-window, or transmission tubes. The low
power means that the total ux of radiation is low; however, the brilliance can still be high
when all photons emerge froma small focal spot. For most types of X-ray focusing optics (see
next subsection), the brilliance is the vital parameter and not the total ux. Thus, low-power
tubes are also very interesting in m-beam XRF. For side-looking, microfocused tubes (50
100 mm spot size and smaller), the brilliance is comparable or better than that of the high-
power tubes, although the total power is only a fewwatts. In transmission tubes, the radiation
is taken out in a direction parallel with the electron beam. Here, the anode is just a thin foil
that acts as a radiation window. For this type of tube, the power load is further limited by the
reduced heat conductivity in the anode. In Table 3, the characteristics of some microfocus
and minifocus tubes are listed. A comparison of the brilliance values listed in Tables 1 and 3
shows that all of these newly available minifocus and microfocus sources are well (if not
better) suited for micro-XRF setups than the more conventional sources used up to now.
B. X-ray Optics
As can be seen from Table 1, in laboratory m-XRF setups, monocapillary or polycapillary
optics is employed almost exclusively for beam focusing or concentration. At synchrotron
Table 3 Characteristics of Some Commercially Available Minifocus and Microfocus Tubes
Manufacturer=
model Anode
Nominal
focal size
(mm
2
)
Maximum
voltage
(kV)
Maximum
current
(mA)
Maximum
power
(W)
Nominal
maximum
brilliance
(kW=mm
2
)
Distance
anode to
Be window
(mm)
Kevex=PXS4-613 Mo 250250 60 1 60 0.96 15.8
Oxford=XTF5011 Mo 150150 50 1 50 1.2 17
Oxford=XTF5000HP Mo 100100 50 1 50 5 17
Oxford=XTF5000HP W 5050 50 1 50 20 17
Kevex=PSX5-724 W 1010 70 0.1 7 70 12.2
Hamamatsu=L673101 W 88 80 0.1 8 125 12
Oxford Ultrabright W (1540)
2
90 2 80 128 1.6
beam lines (having lower natural divergence and higher intensity), in addition to these,
more expensive and elaborate microfocusing X-ray optics are in use also. These devices
were reviewed by Ice (1997). Capillary optics is one of the fastest growing x-ray optical
technologies because of its capacity of generating high-ux-density beams in the
micrometer and submicrometer range. Due to its broad-band characteristics, nonimaging
properties, and simplicity, it is a very attractive optical device for microbeam XRF and
x-ray scanning microscopy.
1. Different Capillary Types
There are basically four major types of X-ray capillary concentrator available today:
straight, conical, and ellipsoidal (or parabolic) monocapillary concentrators and mono-
lithic polycapillary lenses. The principle of x-ray propagation inside these dierent types of
capillary shapes is schematically shown in Fig. 8.
Straight capillaries can be used for transporting the x-ray intensity from close to a
point source to the sample thereby eliminating the 1=r
2
loss from isotropic point sources.
Radiation propagating inside such a device will have a constant angle of incidence and
these types of capillary can easily be manufactured and are easy to apply to almost any
kind of source.
Conical capillaries operate in a similar way as the straight tubes but in addition to
transporting the radiation from the source to the sample, they also squeeze the x-ray
beam down to the dimension of the capillary output diameter. Upon each reection, the
Figure8 The principle of x-ray propagation inside straight, conical, and ellipsoidal capillaries and
in monolithic polycapillary x-ray lenses. In the ellipsoidal and polycapillary cases, a true focus is
formed by rays emitted from the focal point of the device. Any ray emitted outside the optical axis
will propagate inside the ellipsoidal by multiple reflections similar to the conical capillary.
angle of incidence will increase by an amount 2g, where g is the capillary cone angle. Thus,
photons propagating inside the cone will gradually be absorbed by the walls, because their
angle of incidence will approach the critical angle. Thus, for conical capillaries the max-
imum angular divergence will always be equal to the critical angle (at least for energies
above a certain threshold). In this sense, conical capillaries always tend to maximize the
output intensity. For conical capillaries, the transmission spectrum is more complicated
with a typical bandpass structure, as compared with straight tubes that just have a cuto
energy. By varying the length and cone angle, it is possible to optimize the design of the
capillaries for various energies within a wide range.
One drawback with conical shapes is that the maximum intensity is reached at the
capillary opening, and after that, the beam divergence is of the order of y. For borosilicate
glass, y
c
(mrad) %30=E (keV). Thus, the sample has to be put close to the capillary
opening if the high intensity is to be retained. For medium-sized capillaries (5010 mm),
this is normally not a problem; however, for very small capillaries or irregularly shaped
samples, this can be a problem. If the capillary is too close to the sample surface, it might
block some of the uorescent radiation on its way to the detector.
A more recent development is the ellipsoidal capillary where the divergence can be
reduced due to the imaging properties of ellipsoidals. In a perfect ellipsoidal, any ray
coming from one of the focal points will eventually be focused in the other focal point,
thus small objects placed in one of the focal points will generate an image in the other
point. If an ellipsoid-shaped capillary is placed so that the x-ray source is positioned in one
focal point, part of that source will be focussed in the other focal point. However, for any
source point far away from the optical axis, the radiation will propagate through the el-
lipsoidal capillary much the same as in a conical capillary. If such a capillary has its
opening just in front of its focal plane, the radiation coming out will consists of two
components, one nonimaging divergent beam and one imaging convergent beam.
The sum of the two components will somewhat balance each other up to the focal point.
After that point, both of them will be divergent. This means that there exists a short
distance, for the capillary opening to the focal point of the ellipsoidal, where the diver-
gence of the beam will be substantially reduced.
Monolithic polycapillary x-ray lenses consists of a very large number of straight
channels (from a few thousands up to 250,000) which are rst bundled into monolithic
strands; then, the thick multiber is pulled in such a way that radiation originating from
a focal source point S, which is located typically 25 cm from the lens, is transported by
the channels, changed in direction, and refocused into a focal spot F at the other side of
the lens. In contrast to monocapillaries, the marked advantage of polycapillary devices is
that a large solid angle of the x-ray source is captured and that the radiation is focused
into a point which is several centimeters from the X-ray lens itself, allowing this type of
optics to be used for noncontact=nondestructive types of investigations. Early ap-
proaches (Kumakhov, 1986, 1990; Kumakhov and Komarov, 1990; Kardiawarman et al.,
1995) to the manufacture of polycapillary lenses consisted in the use of individual
straight capillaries which were bent and kept in place by a series of perforated metal
disks; this resulted in fairly large devices [e.g., see Kumakhov (1990) for details].
Monolithic polycapillary lenses are more compact and consists of one or more bundles of
closely packed straight capillaries that, after consolidation into a monolithic bundle, have
been shaped in the desired form. As these lenses are the result of a fairly sophisticated
production process, only a limited number of laboratories in the world are able to
produce them (Ullrich et al., 1995; Kumakhov, 1998; Ding et al., 1998; Vekemans et al.,
1998; Gao et al., 1998).
2. X-ray Transport Inside Capillaries
X-rays entering into a capillary under a very small glancing angle can propagate inside the
device by successive reections without losing almost any intensity. If the intensity of
x-rays from such a capillary is compared with the intensity when no reections would
occur (which can be determined by replacing the capillary with a collimator with the same
diameter as the nal capillary crosssection), the reectivity of the capillary wall material
can be studied and the intensity gain can be determined.
For a straight capillary, the gain factor can be dened as the ratio between the ef-
fective solid angle DO
eff
seen by the x-ray source (corresponding to the critical angle) and
the solid DO when no reections occur (defned by the exit end), assuming the reectivity to
be unity up to the critical angle (I
g
DO
eff
=DO, as shown in Figure 9. The gain factor
shows the behavior of a low-pass lter. In Figure 10, E
min
corresponds to the smallest
angle of y
c
or the angle that corresponds to the entrance opening, and E
max
corresponds to
the exit end of the capillary. Note that the gain factor is proportional to 1=E
2
in the range
from E
min
to E
max
.
When calculating the transmittance of x-rays through the capillary, one has to know
the grazing angle of incidence and the number of reections. For a straight capillary, the
angle of incidence for each reection and hence the reectivity will be the same. This is not
Figure9 The capillary gain factor (I
g
) of a straight capillary is defined by the ratio of DO
eff
to DO.
Figure 10 The capillary gain factor versus x-ray energy for a straight capillary without any
absorption.
the case for a conical geometry, where the angle will increase for each reection, and one
has to calculate the reectivity for each reection.
In the model presented in next subsection, a perfectly shaped capillary and an x-ray
point source situated at the capillary symmetry axis are assumed. All y
i
and g are su-
ciently small to allow for the approximations: tan y
i
% y
I
and tan g % g. For a conical ca-
pillary geometry (as dened in Fig. 11), the glancing angle of the ith reection can be
written as (Stern et al., 1988)
y
i
y
0
2i 1g 10
From the geometrical constraints shown in Figure 11, one can easily deduce that the
number of reections N is given by
N
y
0
l l
0
d
1
1
2
11
The total reection coecient R
tot
can be written as the product of each individual re-
ection coecient Ry
i
; E at each successive angle of incidence y
i
encountered by the ray
when passing through the capillary:
R
tot
y
0
; E
Y
N
i1
Ry
i
; E 12
As long as the nal angle of incidence is below the critical angle, the x-rays propagate
inside the capillary by successive reections without losing almost any intensity. If the
intensity of the x-rays from such a capillary is compared with the intensity where no re-
ections occur, which can be determined by replacing the capillary with an aperture
positioned at the site corresponding to the far end of the capillary, the reectivity of the
capillary wall material can be determined. The intensity gain factor, which can also be
dened as the ratio of the intensity with and without reection, can then be written as
I
g

1
DO
Z
y
max
y
min
R
tot
y
0
; E2p sin y
0
dy
0
1 13
Figure11 Conical capillary geometry.
where DO is the solid angle seen by the x-ray when no reections occur, corresponding to
the far end of the capillary. The limits of integration, y
min
and y
max
, are the minimum and
the maximum glancing angles, respectively, for the x-rays inside the capillary as dened by
the geometric dimensions of the capillary and the x-ray sourcecapillary distance (l
0
).
3. Ray-Tracing Models
Although explicit expressions can be obtained for calculating the reection of radiation
inside a capillary (Engstro m, 1991; Lechtenberg, 1994; Vincze, 1995c), they are only valid
for perfectly shaped conical capillaries and can only be applied for point sources. Any
model that would intend to describe real capillaries applied to real extended sources
have to rely on some kind of Monte Carlo model where all the source and capillary
parameters are used as input data.
There are many dierent factors that have an inuence on the capillary performance
and it is hard to quantitatively assess the signicance of each individual factor by inter-
pretation of simple test experiments. This problem is augmented by the fact that the
manufacture of capillary optics is still very much an art rather than a well-controlled
technique, making it dicult to produce series of capillaries where one parameter is sys-
tematically varied. The need to gain insight into the relative importance of the various
above-mentioned factors has prompted the development of a detailed ray-tracing code
(Vincze, 1995c) that is able to simulate the beam-forming properties of realistic capillary
devices assuming various experimental conditions.
A number of dierent factors such as capillary material, surface roughness, devia-
tions in shape that real devices assume in comparison to the ideal straight, conical,
or ellipsoidal shapes, need to be properly described in such a simulation calculation.
In addition to that, the size, divergence, and distance of the x-ray source and the energy
distribution of the photons that enter the capillary also strongly inuence the performance
of the capillary beam and thus also have to be specied in detail. Such a full-scale ray
tracing simulation model has been described by Vincze et al. (1995c).
Because the capillaries in such a simulation are treated as truly three-dimensional
devices having numerically dened shapes, the only restriction on the modeled shape is the
assumed circular cross section in the plane perpendicular to the capillary axis. This allows
overall distortions of the capillary shape, such as bending of the capillary axis, to be
included in the model. Also, the composition of the capillary material as well as the
roughness of the reecting surface can be freely chosen. The implemented surface
roughness model describes both the attenuation of the specular reectivity and the eects
of diuse scattering by the rough surface. An additional feature of the program is that the
possible transmission of photons through the capillary wall is also taken into account. In
the case of a perfectly conical capillary coupled to a point x-ray source, the simulation is in
perfect agreement with the analytical models, as is demonstrated in Figure 12. However,
the ray-tracing models, is also able to simulate all kinds of capillarysource combination
which cannot be simplied so that they may be described by simple analytical models.
As we can see from Figure 12, the transmission eciency versus energy will appear as
a steplike function, where the steps represents the maximum number of reections that
can occur inside the capillary before the critical angle is reached. This distinct feature
disappears for an extended source, as the initial inclination angle will vary over a wide
range corresponding to the source size. The graphs in Figure 12 also show that the e-
ciency goes down for an extended source and the energy of maximum transmission
eciency will be shifted to lower energies.
The two-dimensional distribution of the outcoming photons can also be simulated by
the ray-tracing code. For a monochromatic beam, the dierent reection orders will appear
as clearly visible rings in the intensity distribution observed at a distance from the capillary
opening (see Fig. 13, left panel). However, even here, the impact of an extended source will
blur this feature (Fig. 13, center panel). Geometrical distortions or misalignment of the
capillary will be manifested by the appearance of asymmetric rings or crescents in the an-
gular distributions. (The intensity distribution shown in the right panel of Figure 13 was
recorded at a signicant distance from the capillary tip.) Intensity distributions recorded
or calculatedclose to the opening will normally show a rather homogeneous and sharp
distribution corresponding to the zero-order radiation, imaging the actual cross section of
the capillary itself. Thus, for elemental maps, recorded close to the opening, the spatial
resolution can be improved by the application of deconvolution methods. The technique
and possibilities for this enhanced resolution have been discussed by Attaelmanan (1995).
4. Practical Considerations
According to most models of capillary optics, almost any gain factor could be obtained if
there are no geometrical constraints on the capillary dimensions. However, in practice, the
capillaries have to be designed within a narrow range of geometrical limits. In most cases,
the source characteristics and the beam diameter is xed or dictated by the analytical
Figure12 Comparison of the analytical model and the ray-tracing model as applied to a perfect
conical-shaped capillary and a point source. The solid curve shows the transmission efficiency (out
going flux=ingoing flux) calculated for a capillary 5 cm away from a point source with the
dimensions l 7 cm, d
0
31 mm, and d
1
5 mm. The symbols correspond to ray-tracing calculations
for a point and mm extended x-ray source (100 100 mm
2
).
requirements and, thus, length, shape and capillary material can be optimized. In some
cases, the sourcesample distance is determined by the mechanical arrangement so that
only the shape (i.e., the capillary cone angle) can be varied. Figure 14 shows an example
Figure 13 Intensity distribution from a conical capillary 5 cm away from the opening. left; ray
tracing calculation for a point source, center; ray tracing calculation for an extended source
(400 400 mm
2
) and right; recorded image from a synchrotron set-up. The central spot represents the
direct beam and the rings correspond to different reflection modes (first ring one reflection, second
ring two reflections etc.).
Figure14 Calculated effective solid angle as a function of entrance diameter for different capillary
lengths. The calculation was performed at an energy of 7 keV and a fixed output opening of 5 mm
assuming a point source and a sourcecapillary distance of 5 cm. The surface roughness was
characterized by assuming a slope error of 30 A
(see Vincze, 1995c). The result was also obtained for

an ideal surface.
of how the lengths and cone angle will aect the ultimate gain factor at a given set of
experimental parameters.
These calculations were performed with the introduction of a realistic surface
roughness model. The impact of surface roughness is indicated in Figure 15 by showing
the gain factor with perfect reecting inner walls. Although the gain factor will be
dependent of the capillary length, the ux density will be about the same for all three
capillaries in Figure 15 and they will all have an optimum at an entrance opening of about
30 mm. If the distance between the source and capillary is substantially longer than the
capillary itself, then the optimum will be reached for a certain cone angle for any capillary
length, but the ux density obtained will depend on how long one can make the capillary.
If the source is extended, then the eective solid angle in Figure 14 will decrease, and
the maximum values will be reached at a slightly higher entrance diameter as the capillary
can pick up more of the o-axis rays emitted from the source (see Fig. 15).
5. Capillary Alignment
For (mono) capillary optics, it is necessary to have two linear and two rotational stages for
a complete alignment procedure (see Fig. 16). Most alignment procedures are monitored by
the output ux (normally recorded by some simple device such as an ion chamber, a diode,
etc.) and the operator has to nd the position for the maximum throughout. This is not a
straightforward task, as there always will be secondary maxima when operating the four
dierent stages. The secondary maximum problem can be avoided by combining the
linear and rotational stages in such a way that rotational axes are intercepting the x-ray
Figure15 The effective solid angle for various x-ray source sizes. The calculation was performed
for a 7-cm-long conical capillary with 5-mm opening placed 5 cm away from the source.
source. However, a simple systematic alignment procedure normally works well and
realignment is a matter of a few minutes if there is some measurable ux being transmitted
through the capillary. If the beam is completely lost, realignment will take a longer time.
In this case, prealignment of the optics holder with a wider capillary can be a solution.
In general, the alignment of polycapillary lenses is easier and less critical than that of
monocapillary tubes; this is due the larger acceptance angle of polycapillary lenses.
Normally, only a stage having two transational stages is sucient; in some cases,
alignment of the lens can even be achieved by using plastic spacers of various thicknesses
to appropriately position the lens relative to the anode focal point of the tube (Worley
et al., 1999).
C. Sample Movement and Visualization Equipment
Although x-rays can be focused into microbeams, they cannot be controlled in the same
way as charged-particle beams. Thus, scanning has normally to be promoted by the
movement of the sample rather than of the beam.
For monocapillary focused x-ray beams, the maximum intensity is achieved at the
outlet of the capillary; thus, in this case, the sample has also to be positioned very close to
the capillary. The precise positioning of the sample is normally achieved by a sample
holder which consists of two or three linear stagesand sometimes also a rotational
stagedriven by computer controlled dc or step motors. The motor position is usually
monitored by some kind of encoder. The minimum step size should be well below the
minimum lateral resolution of the spectrometer as dened by the beam size.
The sample position can be monitored by an optical microscope with a camera or
some simple lens system attached to a charge-coupled device (CCD) camera. The optical
features and quality of the monitoring system will depend on the resolution required. In
some setups, the camera is placed in a xed position aimed at a xed sample site. This is
possible with a pinhole or polycapillary beam or any beam where the focal plane is far
away from any bulky optical equipment. However, the sample has to be turned (away
from the plane perpendicular to the beam) in order to coincide with the focal plane of the
Figure 16 Photograph of the COX Analytical Instruments capillary holder and gimbal
mechanics. The capillary rest in a highly viscous liquid that has a high cross section for x-ray
absorption. The semiliquid efficiently damps out microvibration while preventing any x-rays from
passing the holder outside the capillary. The capillary and the liquid are encapsulated into a
stainless-steel tube which is put into the gimbal.
camera. In this position, the sample position is monitored directly by the camera. A
drawback is that the camera has to operate with fairly long-focal-length optics (>2 cm)
that will limit the magnication; sometimes, the illumination can be dicult to arrange
in a proper way.
For monocapillary focused beams, this direct inspection is often not feasible, as the
capillary is shadowing a large part of the sample due to the short distance between
capillary opening and sample surface. In these cases, the camera (or microscope) is placed
a bit away from the measuring position and the sample has to be brought into the cameras
focal plane by the sample stage (see Fig. 17). By combining linear and rotational move-
ments, the camera can be placed in almost any convenient position and operated with any
range of focal length and magnication. In this way, the sample inclination in the mea-
suring position is independent of the camera position. However, there will always be a time
delay while moving the sample between the measuring position and the camera position;
this may require a large-range linear stage and possibly an extra rotational stage
(see Fig. 18).
Figure 17 Photograph of the microbeam XRF setup at Chalmers University of Technology in
Go teborg. The picture shows a closeup of the capillary and sample stage with a rotational stage on
the top. The optical microscope is used for positioning the sample in the beam (Photo courtesy of
A. R.).
For the direct inspection camera setup, it is necessary to have at least one
(probably two) mechanical linear stage to adjust the camera focal plane so that it will
coincide with the sample surface plane. For the indirect inspection system, the camera
can be xed to the table, but it will be necessary to recalibrate the exact distance (in motor
steps) between the central point in the camera focal plane and the location of the beam at
the measuring position. The camera (or microscope) can be equipped with dierent types
of magnication lens, and optical micrographs from the sample are usually recorded
through a framegrabber to a video screen.
Figure18 Schematic drawing of the information flow in the microbeam XRF setup at Chalmers
University of Technology. Here, the microscope is looking right into the capillary opening; thus, the
sample has to be rotated 180
in order to see the front side. (From Engstro m, 1991).

D. Detectors
Most microbeam XRF tabletop systems are equipped with a conventional solid-state x-ray
detector such as Si(Li) or HP (high purity) Ge devices. For monocapillary-based mi-
crobeam XRF, it is important to have a large detector solid angle, as the primary photon
ux normally is very slow, especially for applications in trace element mapping. Thus, the
detector area needs to be large and the detector crystal should be close to the entrance
window (Fukumoto et al., 1999). It is important that the end-cap design is such that the
detector entrance window can come close to the sample. Normally, the count-rate cap-
ability is not critical; however, for fast mapping of mineral samples (or any material with
relatively high concentrations of heavy elements such as metal alloy samples), the count
rate can induce variations in the electronic dead time, generating a distortion in the ele-
mental maps. Deviations from the linear relation between the count rate of characteristic
radiation and the image gray-scale level will occur in areas where local concentrations are
high. This problem can be avoided by using the lifetime settings of the MCA (multi-
channel analyzer), but only when static scanning is used (see Sec. IV.A).
With the introduction of the solid-state drift-chamber x-ray detectors (Bertucci,
1992; Lechter et al., 1996; Stru der et al., 1998), the linear range can be extended for count
rates beyond 20,000 counts without any serious deviation and still with reasonable energy
resolution and low dead time. Other types of detectors that can be integrated in the sys-
tems are x-ray p-i-n diodes used for monitoring the primary intensity and for recording the
transmitted intensity. In this way, microradiographic images of the sample can be re-
corded and the sample thickness or density can be determined with high accuracy at each
image pixel (Attaelmanan et al., 1994). A large-area p-i-n diode is also useful for alignment
of capillary optics when the operator has to nd the transmission maximum. Standard
CCD detectors have also been used as beam monitors, especially for studying the prole of
the primary beam (Attaelmanan et al., 1993). This is important for precise and accurate
alignment of many types of x-ray optics. It is also necessary to have detailed information
of the beam prole in order to perform any kind of image deconvolution.
E. Analytical Characteristics of l-XRF Setups
1. Monocapillary Setups
a. Estimated Beam Flux and Sensitivity
The sensitivity from a tabletop m-XRF instrument can be estimated from the ux density,
beam size, and detector eciency. The ux density is just a function of the source bril-
liance and the eciency of the optical device used. The brilliance of characteristic radia-
tion from a Cu-anode tube can be estimated from the Metchnik and Tomlin formula
(1963). Assuming a voltage of 45 kV and a spot size of 100 100 mm
2
, the brilliance would
be about 3.7 10
12
Ka photons=s=mA=sr. Assuming that the anode is a large solid piece of
metal cooled by water, the maximum load would be about 100 W before the melting
temperature is reached. Thus, it is reasonable to assume that such a tube could operate up
to 1 mA (less than half of the maximum current).
The expected ux density from a 7-cm capillary with a 5-mm opening, at 5 cm away
from the focal spot, can be calculated to be 13.7 10
5
photons=s=mA, corresponding to
about 2 10
4
Ka photons=s=mm
2
. This is approximately the number being reported for
some of the monocapillary based tabletop instruments, although achieved with very dif-
ferent types of x-ray source (see Attaelmanan et al., 1994 and Carpenter et al., 1995b).
Carpenter et al. (1995b) reported an absolute DL below 10
13
g (corresponding to the ppm
range) from a 4-mm-capillary focused Cu beam with a ux density of 2 10
4
pho-
tons=s=mm
2
. Similar values were reported by Larsson and Engstro m (1992).
b. Spectral Distribution
Because the critical angle for total reection is smaller for lower energies inside a (non-
straight) capillary, for higher-energy photons, there is a greater chance for absorption
than for x-rays of lower energy (see Fig. 10). The wavelength dependence of the re-
ectivity decrease due to surface roughness even increases this trend (Vincze et al.,
1995c). This energy-dependent transmission eciency causes capillaries to act as high-
energy ltering devices which can introduce non-negligible changes in the polychro-
matic tube spectrum. Figure 19 illustrates this principle: Two EDXRF spectra obtained
by irradiating NIST SRM 1833 using microbeams obtained by means of a 200 200-
mm
2
pinhole and by using a conical capillary with approximate conical shape and a 40-
mm end diameter are plotted normalized to the Ti peak intensity. The high-energy
eect in the capillary spectrum can clearly be observed, and at the excitation energy
(17.5 keV), it results in a decrease in relative intensity by about a factor of 4 relative
to 4.5 keV (TiKa). It is obvious that during quantitative calculations based on fun-
damental parameters these changes in the excitation spectrum need to be taken into
account.
c. Elemental Yields and Detection Limits
In Figure 20a, the elemental yields obtained by irradiating NIST SRM 1832 and 1833
(thin-glass standards) using Mo-anode excitation in the m-XRF setup at the University of
Figure 19 EDXRF spectra of NIST SRM 1833 irradiated with Mo-anode-derived x-ray
microbeams.
Figure 20 (a) Thin target elemental yields (in counts=s=(mg=cm
2
) and (b) absolute DLs (in pg)
obtained for thin samples obtained by means of a conical capillary (15 mm effective beam diameter)
and several polycapillary lenses (160 mm beam diameter) using a Mo rotating anode tube m-XRF
setup and at the m-SRXRF station at NSLS beam line X26A; (c) relative DL (normalized to
1000 s) in mg=g derived from irradiation of a 100 mg=cm
2
NIST SRM 1577a bovine liver sample.
The absolute DL values for the synchrotron setup (not shown in Fig. 20b) situate themselves in
the femtogram range.
Antwerp (Janssens et al., 1996), employing a 10-mm tapered capillary (15-mm eective
beam diameter at the sample surface) are compared to values obtained for the NSLS beam
line X26A m-SRXRF spectrometer (8-mm beam diameter) (Jones and Gordon, 1989). For
the laboratory setup, net yield values which are lower by a factor of 3050 than those
obtained for the synchrotron setup. The absolute detection limits derived from the same
spectra (Fig. 20b) indicate that a comparable absolute detectability to that obtained with
other laboratory-scale m-XRF setups (Carpenter et al., 1995b) is obtained, situated at the
0.11.0-pg level. For thick samples, rather than the absolute DL values, the peak-to-
background ratios (P=Bs) found in experimental spectra determine, to a large extent, the
lowest measureable concentration levels.
Figure 3 compares the EDXRF spectrum of NIST SRM 1577a bovine liver ob-
tained using the above-mentioned monocapillary setup to the spectral distribution ob-
tained by using a polychromatic synchrotron (micro)beam of comparable cross section
at NSLS (Jones and Gordon, 1989) on the same sample. In Figure 20c, the corre-
sponding relative DLs corresponding to a 1000-s counting time are plotted. Clearly, in
the spectrum of Figure 3a (polychromatic synchrotron excitation), a much better peak-
to-background ratio is obtained: overall, the laboratory m-XRF spectrum features P=B
ratios which are about 1030 times worse (Fig. 3b). The abundant scatter background
in the region of 1016 keV makes fairly long counting times (>1000 s) necessary in order
to obtain information on elements present at or below the 10-ppm level (e.g., Br:
18 ppm). As can be seen in Figure 20c, for the elements Fe to Rb, DL values are
situated in the 310 ppm range for the lab-scale spectrometer, whereas they are about an
order of magnitude better in the case of polychromatic synchrotron excitation. One can
conclude that by means of the laboratory m-XRF instrument involved, trace-level
Figure 20 Continued
microanalysis at the 10-ppm=10-mm level is possible, provided that suciently long
counting times are employed.
2. Polycapillary Setups
In contrast to monocapillary concentrators, polycapillary lenses have the ability to actu-
ally collect divergent radiation in a fairly large solid angle and focus it onto a point which
is located several centimeters away from the other end of the lens (see Fig. 8).
a. Beam Size and Divergence
In Figure 21, the beam size by vertically scanning a 10-mm Cr wire through the beam
produced by two polycapillary lenses is plotted for dierent values of the lens-to-wire
distance d. Both lenses had an input and output widths of $5.5 mm and lengths in the
range of 5064 mm. The distance of the lenses to the Mo anode of a minifocus tube was
$4 cm so that they collect radiation in a solid angle of $0.015 sr. The lenses consist of
250,000 individual monocapillary channels, each with an internal diameter of 7 mm (35%
open area) (Vekemans et al., 1998). Lens A yields a focal spot with a diameter of $60 mm
at a distance d of 15.7 mm from the end of the lens; in the case of lens B, a focus of around
120 mm is reached at d %42 mm.
Figure 21 Beam FWHM obtained by perpendicular scanning of a 10-mm Cr wire through the
beams produced by two polycapillary lenses of different output lengths. Lens A has an output focal
length of $15 mm and focuses the radiation into a spot of $60 mm FWHM; lens B has an output
focal length of $42 mm and produces a focal spot of around 120 mm in diameter.
The beams produced by the polycapillary lenses are strongly convergent before
and strongly divergent behind the focal plane. If we consider that the Cr atoms in the
CrFeNi wire will preferentially be excited by radiation at or just above the Cr K
edge at 5.998 keV (say, with an average energy of 7 keV) and that this radiation leaves
the individual glass tubes (with 7 mm diameter) on average with an angle y %1.6 mrad,
it follows that at an average distance of 42 mm, the 7-mm beam will have spread to a
beam of $7 mm2 42 mm1.6 10
3
141 mm wide, a value which is quite con-
sistent with the experimental beam size of 120 10 mm found by Cr-wire scanning at
d 4043 mm. Similarly, at d 15 mm, a divergence of 1.6 mrad corresponds to a focus
of 7 mm2 15 mm1.6 10
3
55 mm wide. It therefore appears that the errors in
the orientation of the individual capillaries probably contribute only in a minor way to
the overall spot size and that primarily the natural beam spreading of the individual
cone beams denes the beam spot. One of the smallest polycapillary beam sizes re-
ported thus far (2000) was 21 mm (Gao et al., 1998) and was obtained by using a
combination of a 12-W microfocus tube (Mo anode) and a lens with 8.4 mm output
focal distance.
b. High-Energy Transparency
Figure 22a shows scan proles obtained by scanning a 10-mm bronze (Cu=Sn) wire
through the beam produced by polycapillary B (Fig. 21). These data illustrate the
transparency of the polycapillary lenses for the higher-energy radiation. Clearly, in both
cases, a focused beam $200 mm wide is present (Fig. 22a), but at high energy (which
excites the SnK level), this focused beam is surrounded by a halo several millimeters in
diameter. The abundance of the halo is tube-voltage dependent (see Pd wire data in Fig.
22b) and becomes very important when tube voltages above 40 kV are employed. For
practical purposes, it is therefore recommended to use the lenses at lower tube voltages
and to employ them for local analysis of elements with uorescent lines situated in the
520-keV range.
c. Lens Transmission and Gain Factors
The gain factor I
g
of a lens can be dened as the increase in beam ux density as a result of
using the lens (index L) instead of an aperture (index A) of comparable diameter as the
focal spot produced by the lens:
I
g

F
L
=d
2
L
F
A
=d
2
A
l
2
L
l
2
A
where F
L
and F
A
are the measured beam uxes at a distance l
L
and l
A
, respectively, and
d
L
and d
A
are the beam FWHM produced by both devices. Because sometimes slightly
dierent denitions for the gain factor are used in the literature, is it dicult to directly
compare the individually reported values; however, under optimal conditions, values of a
few hundred to several thousand have been measured (Gao et al., 1998). When due to
external constraints, the x-ray source or lens characteristics are less than optimal, gain
factors between 10 and 100 are obtained. An example of such situation was described by
Worley et al. (1999), where a polycapillary lens was designed to t into an existing m-XRF
spectrometer. The fact that the lens was only 29 mm long caused the gain factors to vary
between 124 (at 4 keV) and 2.5 (at 16 keV). When using a rotating anode as the x-ray
source (where the distance between anode spot and lens is of the order of 90 mm due to the
size of the anode tower), gain factors of 720 were observed (Vekemans et al., 1998),
despite the relatively high brilliance of the source (see Table 1). In a study to nd the
optimal match between various commercially available x-ray sources and polycapillary
lenses, Bichlmeier et al. (2001) obtained gain factors between 30 and 300 for dierent
lenses coupled to a Mo-anode minifocus tube.
d. Analytical Characteristics
In Figure 20a, the elemental yields [in counts=s=(mg=cm
2
)] obtained by irradiating
NIST SRM 1832 and 1833 (thin-glass standards) using Mo excitation at 40 kV ex-
citation and three polycapillary lenses are compared to values obtained for the NSLS
beam line X26A m-SRXRF spectrometer (8 mm beam diameter) and to those obtained
by means of the monocapillary concentrator. For the polycapillary lenses, net yield
Figure22 Fluorescent intensity profiles derived from a lens by perpendicular scanning of (a) a 20-
mm Cu=Sn wire through the beam at 50 kV tube operating voltage and (b) a 250-mm Pd wire at
various tube operating voltages in the range 3050 kV. The importance of the transmission halo
increases with tube voltage.
values which are a factor of 35 lower are obtained than for the synchrotron setup. In
the setup employed, the lenses yielded a beam size of $160 mm. Considering a ratio of
$(160=8)
2
400 in spot sizes, this indicates that by means of polycapillary lenses, a
ux density is obtained which is $10002000 lower than at the synchrotron beam line.
The absolute detection limits derived from the same spectra (Fig. 20b) are situated in
the 110-pg range, whereas the corresponding values for the monocapillary are one
order of magnitude better. Similar values were found by Bichlmeier et al. (2001),
whereas Gao et al. (1998) and Ding et al. (1998) reported absolute DL values in the
0.110-pg level. The relative detection limits (Fig. 20c) derived by irradiation of NIST
SRM 1577a bovine liver sample by means of the three lenses are situated at the 23-
ppm level (i.e., intermediate between the monocapillary characteristics and those of the
NSLS X-26A beam line). In a glass matrix (NIST SRM610), Bichlmeier et al. (2001)
reported relative DL values in the 10100-ppm range for the elements Ca to Rb. It can
be concluded from these measurements that the polycapillary lenses are able to pro-
duce highly intense beams with moderate ux density and relatively small size, per-
mitting the determination of minor and trace constituents with a lateral resolution in
the range 20150 mm.
F. Commercial Equipment
At present, four commercial companies market microbeam XRF instruments. Kevex-
Spectrace Inc. (Sunnyvale, CA) has been oering the Omicron instrument since 1986
(Nichols and Ryan, 1986; Yamamoto and Hosokawa, 1988), based on a 50-W minifocus
tube (250 250-mm spot on a Rh anode) and 10-, 30-, and 100-mm apertures. The
apertures are about 6 cm away from the anode spot and 3 mm from the sample; uor-
escent radiation is collected with a 50-mm
2
Si(Li) detector. Such a device can also be
retrotted with a polycapillary lens (Worley et al., 1999). Hosokawa et al. (1997) of
Horiba Ltd. (Kyoto, Japan) developed a scanning x-ray analytical microscope (the XGT
2000 instrument) based on capillaries with paraboloidal inner walls to focus radiation
produced in a compact Rh-anode x-ray tube with a 200 200-mm
2
spot size. A high-
purity Si(Li) detector collected uorescent radiation. The capillary and detector nose are
situated in a small vacuum chamber sealed with a thin resin foil so that the airpath that
primary and uorescent x-rays need to pass on their way to and from the sample is less
than 1 mm. Beams of 10 and 100 mm can be used in this device. The XGT 2000 is dis-
tributed in the United States and Europe by Oxford Instruments. COX Analytical In-
struments is a Swedish company (Go teborg, Sweden) that is marketing the
monocapillary-based ITRAX instrument oering m-beam XRF capacity down 5 mm; the
instrument is equipped with a high-ux x-ray tube (Attaelmanan et al., 1995). COX
Analytical Instruments also provides modular units for converting existing XRF equip-
ment into microbeam spectrometers. EDAX (Tilburg, The Netherlands) has introduced
the EAGLE m-probe device; this m-XRF instrument device uses a microfocus x-ray tube
and a polycapillary focusing unit to generate a 30-mm x-ray beam. All commercial
equipment includes a motorized scanning stage and optical microscopy system for sample
viewing (Haschke et al., 1998). More specically intended for thickness gauging and
(other) applications in the microelectronics industry, Veeco Inc. (Plainview, NY) oers
several microscopic and small-spot XRF systems, the smallest beam size available being
50 mm. Seiko Instruments (Torrance, CA) also oers small-spot XRF equipment for
use in the microelectronics industry.
IV. COLLECTIONANDPROCESSINGOF l-XRF DATA
There are three dierent types of measuring mode for the microbeamXRFinstrument: point
analysis, line scanning, and area scanning. The scanning procedure is promoted by a regular
movement of the sample in the beam with a simultaneous recording of the intensities of
dierent characteristic x-ray energies by the x-ray detector. The operator normally controls
the sample position by manually inducing precise movements of the dierent sample stage
motors while the camera is viewing the sample surface. When the desired sample position is
found, the operator can normally select a point, line, or an area of interest.
During line and area scanning, the important choices for the operator are the step
size and exposure time. These parameters are interdependent and the choice is related to
the type of analytical data required and the time available for the analysis. Normally, the
step size is set equal to the eective diameter of the beam and the exposure time is selected
from the expected concentration of the elements being analyzed. However, in some cases,
it might be wise to operate with smaller step sizes (increasing the number of pixels) and
decreasing exposure times. Attaelmanan et al. (1994) described a scanning system where
the step size is always set equal to the pixel size of the optical image from the monitoring
microscope. The uorescent data can then be superimposed directly on the micrograph
image (Rindby et al., 1992). This allowed the operator to check for correlations between
the distribution of certain elements and well-dened structures within the specimen.
As the amount of information obtained by the scan is entirely determined by the
time of analysis, no information is lost by scanning in steps smaller than the beam size.
The small step size might also allow for an increased image resolution by applying de-
convolution techniques if precise knowledge of the beam proles can be implemented into
the algorithms (Zahrt, 1989).
The simplest way of implementing coordinated sample movement and spectrum
collection is to employ a motorized stage and detector electronics, which are both con-
trolled via PC plug-in cards or the equivalent. From within a scanning program, syn-
chronized motor movement and data collection and storage commands can then be issued.
A. Static and Dynamic Scanning
When all necessary scan parameters are given, the scan starts by moving the sample into
position. The movement scheme should be such that the maximum resolution of the motors
is utilized and backlash problems are avoided. The software system can either move the
samples in steps corresponding to the selected step size and wait for the spectrum recording,
readout, and so forth (static scanning), or move with a predened constant velocity along a
line while spectrum collection and readout are done on the y (dynamic scanning).
The former method will always assure that the spectrum is recorded at the correct
position and with the correct exposure time. However, it will generate a lot of dead time in
the system as the sample movement and all other computer overhead time will occur when
the MCA is closed. For a short exposure time, the dead time and computer overhead time
can be up to 50% or more.
With the latter method, no dead time is generated because the MCA is open (almost)
all the time; however, there is no guarantee that the recordingreadout process will always
take the same time. Internal clock systems must be used to compensate for variations in
the exposure time; several authors have described such systems (Carpenter et al., 1995b;
Janssens et al., 1996a). By performing a number of such line scans in sequence, for ex-
ample, a 50 50-pixel image (called a frame) can thus be recorded within, for example,
50 50 0.25 625 s (i.e., in about 10 min). If after this period of time, (some of) the
obtained images are too noisy, one or more additional frame scans can be performed and
the collected x-ray distribution can be added to the one collected during the previous
frame(s) until images of sucient contrast and clarity are obtained. Usually, the number
of required frames is dierent for each elemental signal; as an illustration, Figure 23 shows
dynamically collected x-ray images using two, four, and ten 0.25-s=pixel frames obtained
from a sectioned piece of corroded Roman glass (see the electron micrograph shown in
Fig. 24a). Also shown are the corresponding images obtained using the static mode of
collection (60 s dwell time per pixel) to highlight the fact the both modes of operation in
the end yield essentially the same information.
Note that the images of Figure 23 result from integration of the spectral intensity
within various windows positioned around characteristic peaks and that, therefore, no
spectral background correction was performed; in Figure 24b, the complete set of
Figure 23 Dynamically collected x-ray images from polished piece of Roman glass sample using
two, four, and ten 0.25s=pixel frames and by static image collection (60s=pixel dwell time).
(background corrected) elemental maps is shown. These maps are obtained by recording
the intensity from characteristic lines in the spectra for each pixel and storing these values
as two-dimensional image les. Thus, these images les can later be subjected to any kind
of image processing (see the next subsection). The recording can be done directly by
reading the counts from operator predened ROIs (regions of interest) in the spectra or by
storing a complete spectrum from every pixel and doing peak-area evaluation and ele-
mental map reconstruction in a second phase.
B. SpectrumProcessing
The data-reduction procedures associated with m-XRF spectrometry share a number of
features with those for m-PIXE data. In contrast to their bulk equivalents, scanning
m-PIXE and m-XRF are able to rapidly produce massive amounts of raw data: The col-
lection of a 64 64-pixel x-ray image may involve, for example, the collection of 8 Mbyte
of raw data and the processing of 4096 separate x-ray spectra. Although, in principle,
the same spectrum evaluation procedures that are used for the bulk technique data can be
Figure24 (a) Backscatter electron micrograph of a polished section of Roman glass showing a cut
through a hemispherical corrosion growth. The complex morphology of the corrosion layer is
visible. The embedding resin and the original glass are visible in respectively the left bottom and right
upper corners. Scale bar length is 100 mm. (b) Full set of background-corrected m-XRF images
(see also Fig. 25).
employed, the large size of these microscopic data sets makes the adaptation of these
procedures mandatory so that they can operate in a reliable way with minimal user in-
tervention on large numbers of spectra.
In m-PIXE setups, which frequently employ list mode data acquisition strategies,
x-ray line scans and x-ray maps for a particular element can be obtained by sorting the
recorded events using an appropriate energy window, centered around the peak energy of
the element in question. A similar procedure is also often employed during on- or o-line
processing of m-XRF data. This simple procedure is very useful for explorative
data analysis but implicitly assumes that within the energy window used, a single,
nonoverlapped peak is present with a high peak-to-background ratio so that the integrated
intensity within the window is a good estimate of the net intensity of the peak. Un-
fortunately, both for m-PIXE and m-XRF spectra, in general, these assumptions are not
valid: peak overlap frequently occurs in energy-dispersive x-ray spectra, whereas, espe-
cially for peaks corresponding to trace constituents, the background intensity below the
peak may be of the same order or larger than the net peak intensity. In these cases, the use
of too simple spectrum evaluation procedures may negate all the eorts that are made
Figure 24 Continued
both during the data collection and during the further quantitative processing of the data
to increase the reliability of the nal (trace) element concentration proles or images.
As an example, in Figure 25, the result of processing in various ways the elemental
maps derived from the Roman glass sample of Figure 24 are shown. These images were
obtained respectively by plotting the integrated ROI intensities (Fig. 25a), by using a
simple straight-line background compensation interpolation approach between the ROI
boundaries (Fig. 25b), and by using net peak intensities obtained via least-squares tting
of the individual spectra (Fig. 25c) (Vekemans et al., 1994; Van Espen et al., 1986;
Vekemans et al., 1995). See Chapter 4 for a detailed discussion on spectrum evaluation and
nonlinear least-squares tting. During the latter processing, the evaluation of the spectra is
largely unsupervised: the tting model (containing a list of photopeaks to be tted and a
specication of the background modeling function to be used) is made a priori using a few
spectra from the set or by means of the sum spectrum. As a background compensation
algorithm, the use of a robust procedure is recommended when processing is unsupervised.
In this case, the background of each spectrum is described by linear combination of
mutually orthogonal polynomials, typically of the order of 1015 (Vekemans et al., 1994,
1995). This algorithm permits the calculation of the appropriate background shape of the
spectra while this shape changes throughout the series of spectra (e.g., for spectra collected
from dierent phases in the scanned area) and also results in correct background values in
case spectra with much noise are processed. In Figure 24b, the full set of x-ray maps
obtained via method c is shown.
The most striking dierence between the results of method a (no background
compensation) and methods b and c is that the high scatter background contribution in
the Ni and Br ROIs is eliminated. For images with much contrast between phases (see,
e.g., the Mn map), the three methods yield quasi-identical results. Method c resolves the
overlap between the KKb and CaKa signals, which results in a more detailed Ca map.
Similarly, instead of being a replica of the Mn distribution, the Fe-image appears quite
dierent in reality after proper processing. In the case of Ni, the use of the tting pro-
cedure results in a less noisy image than when the straight-line background (method b) is
used for background correction. Finally, from the Br image, one can conclude that in the
corroded area, in general, more Br is present than in the original glass but that the noise
level does not permit to discern details.
It can therefore be concluded that for m-XRF data, in addition to resolving peak
overlap and correct background compensation in the neighborhood of intense matrix
lines, especially the ability of the (unsupervised) software to do reliable background
subtraction below the x-ray peaks of the heavier trace elements (atomic number >26) is
valuable. Using current-day workstations or personal computers, the computational eort
associated with the nonlinear least-squares evaluation does not represent a large fraction
of the total time required for acquisition and processing of the x-ray image data. As de-
scribed by Janssens et al. (1996b), by proper synchronization of dierent tasks, the eva-
luation of a spectrum corresponding to a particular pixel may be accomplished on-line
while the spectrum of the next pixel is being collected.
C. Image Interpretation and Segmentation
1. Color Encoding
For visualizing the distribution of major components in a specimen, the intensity of
uorescent radiation is suciently high for generating elemental maps with large dynamics
within reasonable time. Structures within such an elemental map can normally be easily
Figure 25 Micro-XRF images obtained from a polished piece of corroded Roman glass shown in Figure 24. (a) Integrated ROI maps, (b) ROI
maps after straight-line background subtraction, (c) net intensity maps obtained via least-squares fitting of individual EDXRF spectra.
identied. However, for trace element distribution, the intensity is poor and only in-
dividual counts are recorded in each pixel, which makes it more dicult to identify any
structure in the sample. This is why it is so important to be able to correlate trace element
maps directly to the optical micrograph image. For trace element distributions in general,
the question is normally where rather than how much. Figure 26 shows a typical
example of the identication of a structure from the distribution of trace elements
(Stocklassa and Nilsson, 1993). For many of these maps, it is dicult to identify any
recognizable structure, but if you know what to look for (24), then most of the maps
show a signicant increase in trace element concentration for that particular structure.
Although the contrast from trace mapping can be very poor, it can normally be
enhanced by a standard type of image processing technique, such as dynamics optimi-
zation, gray-level histogram equalization, and so forth. With good pixel statistics, de-
convolution or simple smoothing techniques can be used in order to achieve higher
lateral resolution or to utilize the screen dynamics of a color screen in a more ecient
way. For example, by utilizing the full dynamic of a color screen, three dierent ele-
mental maps can be superimposed at the same time using the RGB channels as separate
gray-scale images, as shown in Figure 27. In this way, correlations between dierent
elements can be studied in a convenient way; for noncorrelating elements, however, the
color mixing will complicate the interpretation.
2. Automated Image Segmentation
A m-XRF image scan generates an n
chan
n
col
n
row
data cube (n
chan
is the number of
channels in the spectrum collected per image pixel; n
row
and n
col
are number of rows and
columns in the image). Evaluation (tting) of this series of n
col
n
row
spectra (Vekemans
Figure 26 Image reconstructions from different trace element distributions derived from ball-
point ink on paper. The figure shows the reconstructed text 24 that has been overwritten by
another ink quality. The reconstructions were done at the National Laboratory of Forensic Science
in Linko ping, Sweden. (From Stocklassa and Nilsson, 1993.)
et al., 1994) allows one to reduce this dataset (typically 1024 50 50 datapoints) to
dimensions n
el
n
col
n
row
, where n
el
is the number of elemental intensities derived from
each spectrum; n
el
typically has values in the range 520. In either case, the data cube can
be considered as a multivariate dataset, consisting of a number of objects (the pixels in the
image), each characterized by a number of properties (either n
chan
channel contents or a
vector of n
el
x-ray intensities).
Because during image scans, usually fairly short collection times are employed per
pixel (typically in the range 1100 s), the photopeaks in individual spectra are often buried
in the background noise. This results in noisy images for the corresponding elements (see
Figs. 2426). For performing quantitative analysis with a precision of the same order as
the accuracy oered by the calibration model employed, usually a better signal-to-noise
ratio is required.
The heterogeneous materials that are investigated in many cases are built up out of a
limited number of (quasi)homogeneous phases (Carpenter, 1997; Vekemans et al., 1997;
Rindby, 1993). Thus, m-XRF elemental maps usually can be segmented into a limited
number of regions, in which all pixels provided equal or similar compositional informa-
tion, or in the multivariate sense, they display a similar pattern of properties. After seg-
mentation of m-XRF images, it becomes possible to calculate the sum spectrum
corresponding to each region (by simply adding all spectra corresponding to each of the
pixels inside a region) having a much better signal-to-noise level than the spectra corre-
sponding to individual pixels. A similar approach is also employed in m-PIXE analysis
(Ryan et al., 1988; Svietlicki et al., 1993).
Segmentation of individual images can be done in various ways, by using, for
example, edge-enhancement lters or, on the basis of their corresponding, gray-level
histograms (Russ, 1995; Bonnet, 1995a). In the case of multivariate datasets (produced by
m-XRF or a similar technique), it is better to employ the information in all images
simultaneously during the segmentation process (Bonnet, 1995b; Geladi, 1995). This can be
done by employing appropriate mathematical procedures for (1) eliminating redundancies,
(2) distinguishing the signicant information from random noise, and (3) splitting the
information in mutually orthogonal (i.e., noncorrelated) components. Techniques for
doing this have been reviewed by Bonnet (1995a, 1995b) and illustrated with datasets
Figure 27 A comparison between the scanning electron backscattered micrograph of a sample of
malachite ore (left) and a color-combined microfluorescence image (right). (From Stocklassa and
Nilsson 1993.)
taken from electron probe microanalysis (Paque et al., 1990; Bright et al., 1988; Bright,
1995), auger electron spectrometry (Prutton et al., 1990), electron energy loss spectroscopy
(EELS) mapping (Jeanguillaume, 1985), and secondary ion microscopy (Van Espen et al.,
1992). For the specic case of m-XRF datasets, Cross et al. (1992) have described the use of
principal-component analysis (PCA) (see Geladi and Kowalski, 1986; Johnson and
Wickern, 1988; Press et al., 1992; Trebbia et al., 1995 for details) for colinearity removal
and dimensionality reduction.
By manually grouping pixels in the space of the resulting principal components
[a procedure called interactive correlation partitioning (ICP); see Paque et al., 1990],
semiautomated or supervised image segmentation was shown to be feasible for datasets in
which a limited number (three) of principal components were present. A procedure for
automated correlation partitioning (ACP) was proposed by Vekemans et al. (1997); this
method can also be applied to datasets in which more than three principal components are
present so that it is possible to automatically extract a small number of region-specic sum
spectra from a m-XRF image dataset.
Instead of attempting to reduce the dimensionality of the n
col
n
row
n
el
dataset by
looking for collinearity (or covariance) between the various elemental signals within the
images (as is done in PCA), in order to perform automated image segmentation, all
(n
col
n
row
) pixels can be considered as objects characterized by a vector of n
el
properties
(a multivariate ngerprint) and by using an algorithm such as K-means clustering
(KMC) (Bonnet, 1995a; Vekemans et al., 1997) to generate a limited number of pixel
groups having similar ngerprints.
A more sophisticated approach is to use a combination of PCA and K-means
pixel clustering: In a rst step, the eigenvalues and principal-component images (or
eigenimages) of the original dataset are calculated using PCA; this serves to separate
the meaningful structure in the data from the noise. Second, a limited number of
these (noise-free) eigenimages are used as input to the KMC algorithm, allowing the
original elemental maps to be segmented. A concise overview of the mathematical
background of the PCA and KMC procedures can be found in Vekemans et al. (1997),
in addition to a discussion on the behavior of this procedure with datasets of variable
complexity.
The usefulness of this combined procedure can be illustrated by again considering
the x-ray images derived from the glass sample shown in Figure 24. The elemental maps
and electron micrograph show quite a complicated picture: In addition to the Mn-rich
areas where precipitation occured, several bands of dierent composition can be dis-
tinguished. The top layer corresponds to the original glass (high Ca signal) and the bottom
layer is the embedding resin. Many of the trace element maps (e.g., Ti, Cr, Ni, Zn, Br, Pb),
however, have a noisy appearance.
In Figure 28, the rst nine principal-component images, resulting from PCA pro-
cessing of all the original maps of gure 24b are shown (step 1 in the procedure described
earlier). Images PC1PC7 are contrast-rich, whereas in the remaining PCs noise dom-
inates the pictures; PC1PC7 explain more than 99% of the variance in the data. When
considering score and loading scatterplots [see Vekemans et al. (1997) for details], it ap-
pears very dicult, if not impossible, to nd a pair of principal components where all pixel
clusters can be straightforwardly separated.
By using the seven meaningful PCA images as input for the KMC procedure, the
pixel grouping indicated in Figure 29 was obtained. The corresponding sum spectra are
shown in Figure 30. Cluster 7, which is associated with a high Compton scatter signal and
to none of the elemental signals, corresponds to the embedding resin; the corresponding
sum spectrum (Fig. 30) shows (almost) only background and a high Compton=Rayleigh
ratio. Sum spectrum 2 shows abundant Ca, Mn, and Fe signals, a clear Sr peak, and a
much lower Compton=Rayleigh ratio; this image segment corresponds to the original
glass. Cluster 3 shows a similar pattern but features clear Cu and Bi signals and probably
corresponds to a Bi-rich precipitate in the crack between the original glass and the cor-
roded layer. Clusters 6 and 9 contain only a few pixels of Bi hot spots but essentially
show the same pattern. Clusters 4 and 1 corresponds respectively to the MnO
2
pre-
cipitation area and the phase it originated from (high Mn and Fe signals), whereas clusters
8 and 10 refer to respectively the top part of the leached layer, parallel with the surface,
and the precipitate crust formed on top of the surface (high Ca signal associated with a
relatively low Sr signal).
Figure 28 Score images obtained by PCA of the x-ray maps of Figure 24b.
Comparison of the x-ray maps of Figure 24b and of the sum spectra in Figure 30
shows that although some of the x-ray maps show an excessively noisy distribution, most
of the sum spectra feature (sometimes weak but) predominatly noisy-free photopeaks,
allowing the corresponding major and trace constituents to be determined with an un-
certainty which mainly derives from the errors in the calibration model and not from
counting statistics.
D. Quantitative Analysis
1. General Considerations
X-ray uorescence is well known for its ability to yield reliable quantitative data and,
as such, is used in many (industrial and research) laboratories for routine analysis of a
variety of material types. In many cases, in order to ensure high accuracy, wavelength
dispersive instrumentation and an empirical form of quantitative calibration is employed.
Relative accuracies better than a few percent can be reached for specic matrix types
(see Chapter 13). In laboratories which are more research oriented and=or where the type
of material being analyzed is more diverse, qualication models which (1) allow a rapid
Figure 29 Individual and compound segmentation masks obtained by KMC on the first seven
score images shown in Figure 28.
changeover from one matrix type to another, (2) do not require many calibration stan-
dards, and (3) readily allow for quantitative analysis of samples of dierent and inter-
mediate thickness are preferred and the so-called fundamental parameter (FP) method
is often employed (Shiraiwa and Fujino, 1966, 1968b).
As explained in detail in Chapter 13, these models essentially attempt to correct
mathematically for all phenomena (of rst and higher order) that inuence the detected
intensity of the characteristic radiation emitted by the sample. Because in these corrections
Figure 30 Image and cluster sum spectra corresponding to the clusters shown in Figure 29.
a number of atomic constants of the elemental species involved are used (mass-absorption
coecients, photoelectric cross section, uorescent yields, transition probabilities, etc.),
the uncertainty on these fundamental parameters propagates into the uncertainty on the
elemental concentrations calculated with these methods. In addition, as the mathematical
expressions for the corrections are established for ideal(ized) geometrical conditions (e.g.,
parallel primary beam, perfectly at sample surfaces, etc.), systematic deviations may be
introduced by using these models when the experimental reality does not conform to their
implicit assumptions. When models of sucient sophistication are employed and
calibration is done with standards very similar to the unknown samples, accuracies of the
order of 25% can be obtained (He and Van Espen, 1991) for innitely thick samples. For
partially transparent samples, some of these models include the estimation of the sample
mass (rd from the energy-dispersive spectrum; because this introduces additional errors,
the accuracy in these cases is of the order of 510% (Shiraiwa and Fujino, 1966, 1968b).
For quantication of m-XRF spectra, which normally are collected from samples
featuring some form of heterogeneity (either in sample shape, composition, or both)
(Janssens et al., 1996c), the use of FP-based models rather than empirical calibration
schemes is the most appropriate. Examples of heterogeneous sample types are, for ex-
ample, particles on a lter backing, uid inclusions, in a geological material, multilayered
samples, and interfaces between two minerals inside a thin rock section.
2. Information Depth
As already mentioned (see Table 2), in most materials, x-rays have a much larger pene-
tration range compared to charged particles. The absorption corrections for the char-
acteristic x-rays are therefore much larger in the case of XRF than with EPXMA or
m-PIXE, at least when intermediate or thick samples are concerned. To correct for matrix
eects in EPXMA and m-PIXE, corrections have to be applied for the (continuous)
slowing down of the particles and for the attenuation of the x-rays on their way out of the
sample toward the detector. For protons, the slowing down does not strongly depend on
the matrix composition; also, the corrections due to this eect are partly compensated by
the self-absorption of the characteristic x-rays. In XRF, there is no such compensation,
as both the primary and uorescent x-rays are attenuated. In EPXMA and PIXE, usually
the penetration range of the primary projectiles determines the depth of information; in
XRF, this is not the case: Because the characteristic radiation is usually more strongly
absorbed than the primary radiation, the information depth in most nonthin samples is
strongly element dependent.
One way of dening the information depth for element i (with characteristic)
radiation of energy E
i
) is to equate it to the samples thickness d
99%,i
that would yield 99%
of the intensity that might be derived from an innitely thick target with the same com-
position. In the case of monochromatic excitation, d
99%,i
satises the equation
Z
d
99%;i
0
e
wrz
dz 0:99
Z
1
0
e
wrz
dz ,rd
99%;i

ln1 0:99
wE
0
; E
i
14
where wE
0
; E
i
mE
0
csca mE
i
cscb: mE
0
and mE
i
represent the mass
absorption coecients of the sample at the primary and uorescent energy. a and b are the
incidence and takeo angles, respectively (see Fig. 31). In the case of polychromatic
excitation, Eq. (14) needs to be integrated over the appropriate excitation energy range
and a value of d
99%,i
may be obtained numerically.
In Table 4, the information depth d
99%
is calculated for a few matrices, corre-
sponding to monochromatic MoKa excitation (E
0
17.4 keV); in addition to the energy
of the characteristic radiation, the major composition and density of the sample also
inuences d
99%
is a signicant way. This means that for a sample of given thickness, the
self-absorption can also vary considerably, the same sample being innitely thick for
low-energy radiation while being (partially) transparent for the more energetic lines. To
illustrate this, in Table 5, the absorption factors A
i
1 expw
i
rd =w
i
rd are listed for
a 100-mm-thick foil of the same materials as in Table 4. A
i
is the ratio of the elemental
intensity derived from this foil to that when no self-absorption would take place in it.
3. Self-Absorption Correctionin Heterogeneous Samples
In heterogeneous samples, consisting of several phases of dierent composition, instead of
modeling the attenuation by simple expressions as in Eq. (14), the total attenuation along
the path of the impinging and exiting x-rays must now be calculated as the line integral of
the absorption coecient m
L
. For example, for a sample which features a variable con-
centration c
i
(z) in the z direction (depth) but is homogeneous parallel to the surface,
Figure31 Size of area at beam impaction point required to be homogeneous to permit application
of conventional calibration models to heterogeneous samples.
Table 4 Information Depth (d
99 %
) for Different Elements in a Few Matrices (E
0
17.4 keV,
a b 45
) (in mm)
d
99%
ln100=wE
0
; E
i
r (mm)
Matrix
Density
(g=cm
3
)
CaKa
(3.7 keV)
FeKa
(6.4 keV)
PbLa
(10.54 keV)
SrKa
(14.16 keV)
MoKa
(17.54 keV)
Polypropylene 0.95 830 4,300 16,000 26,000 33,000
Soda-lime glass 2.5 43 150 540 1,000 1,500
Apatite, Ca
5
(PO
4
)
3
OH 3.2 42 60 200 400 550
Malachite, Cu
2
CO
3
(OH)
2
4 24 90 60 100 150
Brass, 70 % Cu, 30 % Zn 8.5 8 25 15 27 37
Lead 11.3 6 5 12 11 12
the concentration to the x-ray intensity of element i derived from an innitesimal sample
volume with thickness dz situated at a depth z would become (in rst order)
dI
i
dz
/ I
0
E
0
rzc
i
zt
i
E
0
exp
Z
z
0
m
L
E
0
; z
0
csca m
L
E
i
; z
0
cscbdz
0
!
I
0
E
0
rzc
i
zt
i
E
0
exp
Z
z
0
w
L
E
0
; E
i
; z
0
dz
0
!
15
where m
L
E; z mE; z rz is the (depth-dependent) linear absorption coecient. In the
case that this sample consists of a number of discrete layers (index k from 1 to N), each
homogeneous and which its own concentration c
i,k
, mass absorption coecient m
k
E,
density r
k
, and thickness d
k
, the contribution dI
i;k
to the intensity of element i from a slice
of thickness dz in the kth layer becomes
dI
i;k
dz
/ I
0
E
0
r
i
c
i;z
t
i
E
0
exp
X
k
j1
m
j
E
0
csca m
j
E
i
cscbr
j
z
j
" #
I
0
E
0
r
i
c
i;z
t
i
E
0
exp
X
k
j1
w
j
E
0
; E
i
r
j
z
j
" #
16
with
z
j

d
j
if j < k
z
P
k1
n1
d
n
if j k
8
<
:
For other heterogeneous samples with comparable (simple) heterogeneity, analogous ex-
pressions such as that of Eq. (16) may be established. As can be seen from this equation,
even for samples with limited heterogeneity, fairly complex expressions relate the observed
uorescent intensity I
i
to the characteristics of each layer. In the general case (sample
heterogeneous in three dimensions), the relation between I
i
and the sample structure can
only established by numerical integration of the sample concentration and absorption
characteristics over the interaction volume of the primary and uorescent x-rays.
What is important to note when considering Eqs. (15) and (16) (and their equivalents
for other cases) is that the magnitude of the exponential absorption factors depends very
Table 5 Absorption Factor (A
i
) for Different Elements in a Few Matrices (E
0
17.4 keV,
a b45
)
A
i
1 expw
i
rd=w
i
rd; d 100 mm
Matrix
Density
(g=cm
3
)
CaKa
(3.7 keV)
FeKa
(6.4 keV)
PbLa
(10.5 keV)
Sr-Ka
(14.2 keV)
MoKa
(17.4 keV)
Polypropylene 0.95 0.76 0.948 0.985 0.991 0.993
Soda-lime glass 2.5 0.09
a
0.3 0.67 0.8 0.86
Apatite (Ca
5
(PO
4
)
3
OH) 3.2 0.08
a
0.12
a
0.38 0.56 0.65
Malachite Cu
2
CO
3
(OH)
2
4 0.05
a
0.19
a
0.12
a
0.22
a
0.29
Brass (70=30 Cu=Zn) 8.5 0.02
a
0.05
a
0.03
a
0.06
a
0.08
a
Lead 11.3 0.01
a
0.01
a
0.03
a
0.02
a
0.02
a
a
d
99%
d (i.e., sample innitely thick).
strongly on how the total path of, for example, the uorescent x-rays [total length z csc(b)
in Eq. (16)] is distributed over the various phases. Small variations in this repartition may
cause large uctuations in the integrated absorption coecient along the total path. As an
example, in Table 6, for various thickness combinations the integrated attenuation
exp
P
j
m
j
E
i
r
j
z
j
cscb is listed of several characteristic line energies E
i
in a hypothe-
tical three-layered sample of 100 mm total thickness consisting of parallel layers of KAl-
Si
3
O
8
, NaAlSi
3
O
8
, and SiO
2
bottom layer), assuming that this radiation originates from a
depth of 90 mm.
The data in Table 6 illustrate that in order to reliably correct for strong self-ab-
sorption (CaKa, CrKa, and FeKa), the matrix composition and detailed spatial distribu-
tion of the various phases that make up a heterogeneous sample must be known with high
accuracy. Whereas, in many cases, the matrix of these phases may be approximately
known (e.g., from measurements on more homogeneous parts of the material or by using
other methods), the details on the spatial distribution of the various phases inside natural
samples (e.g., a rock sample composed of dierent minerals) is hard to nd. Table 6 also
shows that when the self-absorption is intermediate to weak (PbLa, SrKa, MoKa, in the
example), only an approximate knowledge of the repartition of phases is required.
In the former case (strong self-absorption), even when the sample geometry is known,
the position of the microbeam relative to this heterogeneous structure must also be known
in order to allow experimental spectra to be corrected for self-absorption. This is illustrated
for a very simple case in Figure 32. This gure shows experimental data collected
by scanning a NIST K961 glass microsphere of 32 mm diameter through a microbeam
of 8 8 mm
2
in the x and y direction( cf. Fig. 31). When the sample movement is done in the
beamsampledetector plane (x direction, see Figs. 32a and 32b), the characteristic ra-
diation of K, Ti, and so forth must pass through the body of the glass sphere on its way to
the detector and the intensity proles are strongly and assymetrically deformed by self-
absorption in the glass. [see Voglis and Rindby (1995) for a more detailed discussion]. Note
that the maxima of the K, Ti, and so forth proles do not coincide with each other or with
the geometrical center of the particle. Experimentally, it is therefore dicult to position the
beam exactly at the center of the particle because this position does not correspond with a
maximum in the detected count rate. The situation is simpler when the sample movement is
executed perpendicularly to the beamdetector plane ( y direction, see Figs. 32c and 32d);
in this case, the uorescent radiation leaves the particle sideways toward, the detector and a
Table 6 Variation of the Attentuation of Characteristic Radiation upon Leaving a Three-Layered
(SiO
2
, NaAlSi
3
O
8
, KAlSi
3
O
8
) Sample with Average Density of 2.5 g=cm
3
Characteristic
radiation
(keV)
25 mm KAlSi
3
O
8
45 mm NaAlSi
3
O
8
30 mm SiO
2
35 mm KAlSi
3
O
8
35 mm NaAlSi
3
O
8
30 mm SiO
2
45 mm KAlSi
3
O
8
25 mm NaAlSi
3
O
8
30 mm SiO
2
CaKa (3.7) 1.3 10
75
0.9 10
75
0.7 10
75
CrKa (5.4) 0.02 0.017 0.015
FeKa (6.4) 0.089 0.08 0.072
PbLa (10.5) 0.57 0.55 0.54
SrKa (14.2) 0.79 0.78 0.77
MoKa (17.4) 0.88 0.87 0.87
Note: The radiation takeoff angle b is 45
.
symmetrical response is obtained so that all prole maxima occur at the same position (i.e.,
when the beam irradiates the center of the spherical particle).
From the above considerations, it may be concluded that, with the exception of
samples having a simple and well-known spatial distribution and matrix composition of
the phases that constitute them, quantitative m-XRF analysis of truly heterogeneous
Figure 32 Experimental and simulated net intensity profiles resulting from scanning a 32-mm-
diameter K961 glass microsphere through a 8 8-mm
2
white SR beam (a, b) in the beamsample
detector plane (horizontal sample movement). (c, d) perpendicular to this plane (vertical sample
movement), (e) m-XRF spectra collected during scan (a) at 10 mm to the left (lower curve) and right
(upper curve) of the geometrical center of the particle.
samples is prone to error, especially when low-energy characteristic radiation is involved
for which the information depth is of the same order as the dimensions of the phases
present. Nevertheless, in many practical situations, quantitative measurements can be
performed provided these samples being analyzed are locally homogeneous.
Figure 32 Continued
4. Conditionsfor Local Homogeneity=Factors Determining Lateral Resolution
A sample may be dened as being locally homogeneous at a given location when both the
primary photons entering the sample at that point and the resulting uorescent x-rays
while leaving the sample on their way to the detector will pass through the same phase. In
this case, the spectral data derived from such a measurement can be quantitatively pro-
cessed as if they were obtained from a completely homogeneous sample. In Figure 31,
the three-dimensional size and shape of the area which must be homogeneous around the
beam-impact point is schematically drawn. Clearly, this area is much wider in the
beamdetector plane (L
x
) than in the direction perpendicular to it (L
y
). L
x
is determined
by the angles of incidence and takeo of the radiation and depends more on the in-
formation depth of the uorescent radiation being considered than on the actual beam size
d
beam,x
. For a parallel primary beam and a small detector far away from the sample, one
can derive that
L
x;i
L
z;i
cot a cot b d
beam;x
csc a
L
y;i
d
beam;y
L
z;i
mind
sample
; d
99%;i
17
In the case of radiation for which the sample is innitely thick, L
z;i
d
99%;i
; for more
penetrant radiation d
99%;i
> d
sample
, the sample thickness determines the lateral size L
x
of
the interaction volume in the x direction and therefore also the lateral resolution in this
direction. In the y direction and perpendicular to the beamdetector plane), only the beam
size d
beam,y
denes the size of the interaction volume, at least when the x-ray detector
Figure 32 Continued
subtends a small solid angle, as is usually the case at sychrotron m-XRF setups. In labo-
ratory instrumentation, sometimes large-area detectors are used (e.g., 80 mm
2
at a fairly
close distance to the sample (e.g., 2 mm) so that the detector solid angle O becomes quite
large. In this case, the conditions for local homogeneity are somewhat stricter and the
following expressions must used for L
x
and L
y
(with tan
2
g O=p):
L
x;i
L
z;i
cot a cotb g d
beam;x
csc a
L
y;i
L
z;i
2 tan gcsc b d
beam;y
L
z;i
mind
sample
; d
99%;i
18
Degradation of the lateral resolution due to spreading of the primary beam as a result of
scattering interactions (as is the case EPXMA) can be neglected in most cases.
From Eqs. (17) and (18), it follows that in order to maximize lateral resolution in
m-XRF, the highest possible incidence and takeo angles should be employed. Because
such an arrangement also corresponds to the shortest attentuation paths of both primary
and uorescent radiation and yields the smallest volume in which the sample must be
homogeneous, it is also recommended for obtaining the highest quantitative accuracy. The
only argument against the use of large incidence and takeo angles is that when their sum
is no longer 90
, the scatter peak intensity and spectral background will be higher than in
the 90
geometry. This is especially true for synchrotron setups employing linearly

polarized radiation where the scatter background intensity can increase by a factor 10 or
more when a nonoptimal detection geometry is used. In laboratory m-XRF, the implica-
tions will not be so important because unpolarized radiation is used and also because the
radiation is usually collected in a larger solid angle. Hence, for sample types that do not
excessively scatter the primary radiation, the use of perpendicular irradiation-detection
geometries may have more benets than disadvantages. Up to now, however, no sys-
tematic studies evaluating the eect of dierent geometries on instrument sensitivity,
lateral resolution, and accuracy of m-XRF instruments have been reported.
5. Predictionof the Spectral Response of m-XRFSpectrometers
For simplicity, in the derivation of Eqs. (15) and (16), only rst-order beamsample
interactions were considered. In reality, also other phenonema such as photon scattering
(Rayleigh and Compton) and higher-order interactions (e.g., enhancement) take place
which complicate the analytical treatment (He and Van Espen, 1991; Shiraiwa and Fujino,
1966, 1968b; Criss and Birks, 1968; Van Dyck et al., 1986).
One direct way of using all knowledge of the various interaction processes that can
occur between an x-ray photon and the material in which it is traveling is to implement it in
a Monte Carlo photon trajectory calculation program. Vincze et al. have published a
number of articles describing such a detailed computer model for predicting in detail the
spectral response of a generic EDXRF spectrometer (Vincze et al., 1993, 1995a, 1995b,
1999a, 1999b). This computer code takes as input parameter the excitation conditions, the
detection geometry, and the characteristics of the (heterogeneous) sample being irradiated
and generates the equivalent of experimentally collected EDXRF spectra. Using this code,
it is possible to systematically study all parameters inuencing experimentally recorded
EDXRF spectra and evaluate their signicance.
One can obtain an idea of the predictive power of this Monte Carlo model from
Figures 3, 32e, 33a, and 33b in which experimental and predicted XRF spectra are
compared corresponding to dierent experimental conditions and sample materials. A
Figure 33 Experimental and simulated EDXRF distributions of (a) NIST SRM 662 steel using
monochromatic 15-keV excitation and (b) NIST SRM 620 glass using polychromatic white-beam
excitation. Both experimental spectra were recorded at the NSLS X26A SR-XRF station.
high degree of similarity between experimental and simulated spectral data can be reached,
allowing the simulation to be used for quantication purposes (Janssens et al., 1993b), for
example, by varying the input parameters of the simulation program (primarily the sample
characteristics) until the resulting simulated spectral distribution shows the highest overlap
with the experimental spectrum that one wants to quantify (Vincze et al., 1993, 1995a,
1995b). In Table 7, some quantitative results obtained with the latter approach are
summarized for dierent excitation conditions and sample types (experimental data col-
lected at the Hasylab m-SRXRF station). In general, root-mean-square deviations between
certied and calculated concentrations in the range of 515% are observed; for laboratory
m-XRF spectrometers, similar deviations are observed.
An advantage of using this simulation program rather than the more conventional
analytical approaches to fundamental parameter-based quantication (see, e.g., He and
Van Espen, 1991) is that it is relatively easy to extend it toward the case of heterogeneous
samples (Janssens et al., 1996c; Vincze et al., 1999b, 1999c). As an example, in Figure 32,
in addition to the experimental data obtained by scanning over a 32-mm glass microsphere,
the corresponding Monte Carlo predictions (solid lines in Figs. 32b, 32d, and 32e) are
plotted also. The Monte Carlo model is clearly capable of predicting the self-absorption in
the glass sphere in a correct way. In Figure 32e, two experimental spectra collected during
the horizontal scan (Figs. 32a and 32b), corresponding to locations at 10 mm left and right
of the geometrical center of the sphere are shown. Table 8 lists the quantitative results
obtained from these two spectra while (erroneously) assuming in the calculation model
that they correspond to the being at center of the particle. When the beam strikes the
particle at the 10 mm position (see Table 8), the absorption path of the x-rays exciting the
particle is smaller than in the center-position. Accordingly, the concentration of low-Z
elements are seriously overestimated; because at this position, the amount of material
being irradiated is lower than at the center-position, high-Z elements [with x-ray energies
for which the glass is (nearly) transparent] will be slightly underestimated. In the reverse
case (10 mm position) the absorption paths are longer than assumed in the calculation,
resulting inan underestimation of the low-Z elements. Because in this position, less ma-
terial is being irradiated than at the center-position, the higher-Z constituents are also
underestimated.
However, the availability of a Monte Carlo model that is capable of reliably
predicting the spectral data that may be derived from a given heterogeneous sample in
specic experimental circumstances is, in general, not sucient to perform the reverse
operation (i.e., to derive from a set of experimental m-XRF data the composition of the
various phases that constitute such a heterogeneous sample). By means of such a model,
it is only possible to verify whether a given hypothesis about the structure=composition
of a particular sample is consistent with the experimental spectra data that were derived
from it. In many cases, however, where external information is available on the structure
and=or matrix composition of the sample (as in Fig. 32), this approach may be em-
ployed.
6. Analytical Model for m-XRFAnalysis of Particles
For the simpler situation when the x-ray beam is larger than the particle (i.e., when the
response is averaged out over the entire particle), Lankosz (1993), Lankosz et al. (1993),
and Lankosz and Pella (1994a, 1994b, 1995, 1997) developed a calibration model for
quantitative analysis that attempts to correct for the self-absorption eects in these
samples by using an analytical expression combined with the intensity of elastic and
Table 7 Results of Quantitative Analysis of Various Types of Material by Means of the Monte Carlo Model
Matrix Biological materials Metallic materials Geological materials
Material
NIST SRM
1571
NIST SRM
1577a
NIST SRM
1206
NIST SRM
1208 KL2 Basalt ATHO Rhyolite
Element
Cert.
(ppm)
Calc.
(ppm)
Cert.
(ppm)
Calc.
(ppm)
Cert.
(%)
Calc.
(%)
Cert.
(%)
Calc.
(%)
Cert.
a
(ppm)
Calc.
(ppm)
Cert.
a
(ppm)
Calc.
(ppm)
K 1.47% 1.41% 0.97% 0.92% 0.39% 0.53 0.16% 2.24% 1.64 0.17%
Ca 2.09% 2.1% 0.012 <DL 7.95% 7.1 0.2% 1.20% 0.94 0.09%
Ti 2.94 2.74 0.46 0.52 1.53% 1.4 0.1% 0.15% 0.11 0.02%
Cr 19.7 18.4 17.5 17.3 280 417 148 4 (180)
b
177 34
Mn 91 87 10.3 7.9 0.137% 0.18 0.03% 0.086% 0.10 0.02%
Fe 300 258 270 261 0.46 0.41 19.2 19.16 8.79% (ref ) 2.59% (ref )
Co 11.55 11.9 0.82
Ni 53.3 53.4 51.9 50.8 110 124 25 8
Cu 12 14.8 193 204
Zn 25 22.7 130 134 110 123 14 150 153 10
As 14 14.5 0.055 <DL
Br (10) 9.2 9
Rb 12 12.7 18.3 19.6 9 10 4 62 65 4
Sr 37 35.2 370 391 33 93 99 5
Y 26 22 6 102 105 4
Zr 155 177 29 540 557 15
Nb 5.38 5.30 15 13 5 59 52 3
Mo 10.3 10.4 3.24 3.35
Ba 121 153 43 600 592 16
La 13.0 12 7 52 57 3
Ce 32.5 34 13 119 125 5
Pr 4.6 5 4 14 13 2
Nd 21.3 29 11 58 72 3
Pb 45 48.9 0.34 <DL
a
The geological materials were irradiated as fused glass; the certied concentrations refer to the parent basaltic rocks.
b
Note: For details see Vincze et al., 1993, 1995a, 1995b.
inelastic beam scatter. The eective mass thickness of the particle is approximated by
an iterative technique that employs experimentally detected elastic and inelastic scat-
tered intensities. The method is restricted to particles with homogeneous element dis-
tributions. In addition, the beam size had to be greater than the size of the particle and
the method worked best with light-element matrices. When used to analyze the NIST
glass standards K-411 and K-3267, over the particle size range, 50150 mm, the results
for K-411 showed reasonable agreement with certied values. For K-3267, however, the
results for Si and Ca were nearly 30% dierent from the certied values. The poor
results for K-3267 were attributed to the more irregular and elongated shape of those
particles.
7. Detectionof SystematicVariationsin m-XRFData Dueto Topological Effects
In the fundamental parameter approach, the uorescent intensity from an element in a
material is dependent not only on the corresponding concentration of that element in the
sample but also on a number of other parameters which can be divided into three groups:
(1) spectrometer-dependent parameters such as primary intensity, beam size, detector
eciency, and so forth, (2) element-dependent parameters such as the photoionization
cross section, uorescence yield, and so forth, and (3) sample-dependent parameters such
as the sample thickness, attenuation coecients for primary and secondary radiation,
and the sample geometry (e.g., the inclination of the sample surface plane relative to the
beam and detector).
In order to be able to apply the conventional FP approach, all of the sample-
dependent parameters have to appear constant over the interaction volume (sample
volume aected by the beam exposure). If this is not the case, it will be necessary to apply
Table 8 Quantitative Analysis Results (in % w=w) Obtained from Different Locations on a 32 mm
Diameter Glass Microsphere Assuming the Beam to Point at the Particle Center
Beam position
At center 10 mm O-center 710 mm O-center
Element
Actual
conc.
Calculated
conc.
Relative dev.
%
Calculated
conc.
Relative dev.
%
K 2.49% 3.36% 35 1.49% 740
Ca 3.57% 4.51% 26 2.27% 735
Ti 1.2% 1.38% 15 0.88% 726
Mn 0.32% 0.34% 6 0.27% 716
Fe 3.5% 3.58% 2 3.0% 714
Ni 100 ppm 100.7 ppm 0.7 87.3 ppm 713
Zn 100 ppm 98.6 ppm 71.4 89.1 ppm 711
Br 100 ppm 97.0 ppm 73 94.1 ppm 76
Zr 100 ppm 96.3 ppm 74 94.4 ppm 76
dierent types of explicit models describing the variation of these parameters, at least over
the exposed volume.
It is convenient to distinguish between compositional and topological variations.
Thus, in this context, the concept of topological variations is dened as any variation
(except compositional ones) of the sample-dependent parameters that will induce variation
in the detected uorescent intensities.
A topological model could be a mathematical function that describes the topology
over a certain sample volume. From the general mathematical features of the FP theory,
the topological models necessary for describing the variation in uorescence intensity can
be reduced to a nite set of variables modeling the sample thickness variation, slope
variation, and so forth. Thus, the intensity (versus elemental concentration) from any
characteristic line can be written as a function f of these topological parameters {p} and
the attenuation coecient for the corresponding characteristic energy:
I
i
c
i
f fpg; m
i
Accordingly, in situations where there is only one independent topological parameter p

(provided f is strictly monotonous), there will exists a well-dened inverse function f
1
relating this single topological parameter with the intensity of a characteristic line from
one element:
p f
1
I
i
c
i
; m
i

Thus, the intensity from another element can be described as a function of the intensity
from the rst element through its dependence of the topological parameter. In this case,
it will be possible to write an explicit expression for how the intensity of element i will
depend on the intensity from element j. These types of correlation between pairs of
elements can be used to verify the chemical homogeneity in samples that have a simple and
well-known topological structure (such as small spheres or wedge-shaped fragments of
glass) or to identify specic topology structures in smples where the chemical homogeneity
has already been established.
In general, this kind of reduced topological parameter space (or interdependency
between the parameters) cannot be expected and, normally, some of the topological
parameters will appear explicity in the correlation functions. Thus, in order to determine
the explicit relation between intensities from element i and j, the exact scan path (in terms
of topological parameter values) has to be known.
However, in some special cases, it will be possible to formulate explicit expressions of
correlation functions entirely independent of the particular scan path taken. For example,
the intensity from samples which are innitely thick will only depend on the slope of the
surface and intensity from samples which are very thin will entirely depend on the
thickness variation. In these types of single-topological-parameter samples, the correlation
functions between dierent elements can easily be demonstrated. Rindby et al. (1996)
obtained explicit expressions for the correlation functions at dierent conditions, showing
that they could be written as second-order polynomial and that the linear term for thin
samples was completely independent on any sample parameters.
Somogyi et al. (2000a, 2000b) used binary correlation plots to distinguish between
m-XRF data sets obtained by two-dimensional scanning of homogeneous and (partially)-
heterogeneous particles and to select the most appropriate mathematical model to be used
during quantication of the raw x-ray intensities.
8. Microheterogeneity Characterizationof Reference Materials
Appropriate reference materials are essential for quantitative calibration of m-XRF
spectrometers. Because during m-XRF experiments, only a very small sample mass
(sub-microgram) is being analyzed, in principle, reference materials of high homogeneity
are required. With the exception of glass, for most matrix types, highly homogeneous
reference materials with certied levels of one or more trace elements are not available.
In addition, due to a lack of suitable techniques that allow one to measure the micro-
heterogeneity of (trace) constituents inside a material, information on the micro-
heterogeneity of existing references materials is either not available or very approximate.
In a few articles, the suitability of m-XRF for investigating the microheterogeneity of
existing reference materials has been evaluated (Wegrzynek et al., 1999; Kempenaers et
al., 2000). An important advantage of the use of m-XRF in this respect is that the method
is nondestructive, so that surface enrichment or other changes in the microheterogeneity
of the material that may be induced by the use of other microbeam methods can be
avoided.
E. Fluorescent X-ray Microtomography
As outlined earlier, in some situations, the very large penetration and sampling depth of a
microscopic photon beam can limit the practical applicability of the m-XRF method.
However, by using another data collection method, this penetrative character can also be
exploited to gain information on the three-dimensional distribution of medium-to-heavy
elements inside small samples. The conventional XY manner of scanning a sample through
the microbeam yields two-dimensional images which actually are projections of the three-
dimensional compositional structure of this sample parallel to the direction of the primary
beam. In order to obtain information on this three-dimensional structure, the same sample
may be irradiated under various dierent observation angles, thus creating dierent two-
dimensional projections of the same three-dimensional structure.
As an example, Figure 34 shows m-XRF maps collected from an oil y-ash particle
(Janssens et al., 1998). Fly ash is formed when fossil fuels such as coal, lignite (brown
coal), or oil are burned in power plants; it is a complex heterogeneous mixture of partially
burned hydrocarbons (forming a hollow carbon skeleton) and the chemically and physi-
cally altered remains of the mineral fraction of the fuel. Oil y ash usually takes the form
of spongelike hollow spheres, into and onto which (volatile) metals such as V, Ni, Cu, and
Zn condense during the cooling of the gases in the power plant chimney stack. Although
the large-sized particulates are too heavy to become airborne or inhaled and therefore do
not present a direct health risk, the ash which is produced in a power plant may be subject
to water-induced leaching during long-term storage, causing the metals to be released in the
environment. It is therefore relevant to study where inside the particles the heavy metals
are concentrated and what physical and chemical changes take place during leaching
processes.
As can be seen in Figure 34, y-ash particles, when investigated with a 4-mm x-ray
beam, show a markedly heterogeneous structure: in addition to a relatively homogeneous
S distribution, especially the metallic constituents of the particulate appear to be con-
centrated in specic areas. From one set of XRF maps, it is not possible to determine
whether these hot spots are situated on the surface (i.e., the most prone to leaching) or
are inside the particle (where they might be more shielded from chemical attacks by
moisture or other chemical agents by the carbon skeleton). When another image scan is
performed on the same particle after it was rotated over 90
relative to the beam,

equivalent maps are obtained which show, as expected, the hot spots at other locations
in the projection maps. In a simple case, two perpendicularly collected elemental views
may be sucient to triangulate the approximate position of the metal-rich areas inside
the particulate (see, e.g., the Cr and Fe maps in Figures 34a and 34b). However, when the
distribution of the element involved is more complicated, it is recommended to collect
more than two views.
If, instead of collecting XRF spectra while the samples is moved according to an XY
scanning pattern, the sample height Y is xed and instead a XY scan is performed, during
which the horizontal position and orientation angle of the particle relative to the beam are
varied, instead of elemental maps, one obtains so-called sinograms. Figure 35 shows a
photograph and schematic drawing of the sample environment during XRF tomography
experiments. During tomographic data collection, the sample (mounted on a goniometer
head and on a rotation stage) is translated in a stepwise manner through the microbeam
(with a horizontal increment Dx of, e.g., 4 mm), after which the sample=goniometer head
assembly is rotated (with angular increment Dy of, e.g., 3
) around the vertical axis and

the translation movement starts again until an angular range of 180
or 360
has been
covered.
In this manner, instead of performing a conventional XY scan, yielding multiple XY
elemental maps, an XY-scanning movement of the sample through the beam is executed,
which results in several elemental sinograms (see Fig. 36). Through the use of the ap-
propriate reconstruction algorithms, the latter can be back-projected into XZ maps of the
internal distribution of chemical elements in the horizontal plane through the sample at a
particular vertical position Y on the sample.
Figure 34 XRF maps of various elements in a large fly-ash particle obtained using two different
sample-detector orientations: (a) 0
, (b) 90
. Image size: 40 35 pixels; pixels size: 4 4 mm,

spectrum collection time per pixel: 1 s.
As an example, Figure 36 (middle panel) shows the sinograms obtained from the
particle shown in Figure 34 at the indicated height by employing an angular increment of
3
and a horizontal translation increment of 5 mm while the sample was kept at constant
height. In this way, the distribution of elements inside a plane situated at $35 mm above
the lower edge of the particle can be determined. From the elemental sinograms, by means
Figure 35 Photograph and schematic drawing of the sample environment during XRF
tomography experiments: The sample is placed at the end of a thin glass tube mounted in a
manually adjustable goniometer head. This allows the center of the sample to be aligned with the
rotation axis of the motorized XYZY stage and with the capillary.
Figure 36 Conventional elemental XY maps, elemental sinograms (or XY maps), and elemental
tomographs (or XZ maps) of the fly-ash particle shown in Figure 34. Size in sinograms: 30 120
pixels, pixel size: 5 mm3
; size of resulting tomograms: 30 30 pixels size: 5 5 mm. T.B.

tomographic back-projection.
of a mathematical technique called weighted back-projection, the equivalent elemental
tomograms (i.e., the distributions of the elements in the XZ plane through the particle at a
specic vertical coordinate) may be obtained (Fig. 36, right panel). For a more detailed
discussion on tomographic data collection strategies and back-projection theory and al-
gorithms, see, for example, Herman (1980) and Russ (1995).
As can be seen from the superposition of the S, V, and Cu tomograms, the metal-rich
areas of the particulate appear to be located on the outside of the particle. From the S
tomogram, it also appears that this particle is hollow and that the sulfur is distributed in a
shell around a central cavity. This type of structure has also been observed during other
experiments (Rindby, 1997a, 1997b). The hot spots apparently are small, quasi spherical
metal-rich particles which have become attached to this S-rich shell. However, not all hot
spots contain the heavy metals in the same relative amounts: for example, the three
enriched areas visible in the tomograms of Figure 36 all contain the elements Ca, V, Cr, Ni
and Mo, but only two show a detectable Cu signal. It is clear that by varying the height of
the sample relative to the beam, equivalent tomograms at various vertical positions inside
the particle may be obtained allowing a full three-dimensional visualization of the dis-
tribution of various chemical elements throughout the entire particle volume and this with
a spatial resolution equal to the primary beam size.
Whereas the example shown in Figure 36 highlights some of the analytical possi-
bilities the use of small, penetrant photon beams may have for three-dimensional in-
vestigation of certain sample types, it is appropriate also to point to some of the present
limitations of the technique in its current state. First, the technique is limited to fairly
small samples: Because it is the intensity of the uorescent signals which is used to
construct the elemental tomograms, obviously only samples which are smaller or of
the same diameter as the sampling depth of the uorescent radiation can be studied in
this way. In the case shown in Figure 36, this presents no problem, as the eective
density of the y-ash sample (mainly consisting of a carbon skeleton and hollow areas) is
fairly low.
However, in the metal-rich areas, although they are fairly small in diameter
($1015 mm), the local density and atomic number is much higher and considerable self-
absorption occurs, especially for the uorescent radiation of the lighter elements (e.g., S
and Ca). This can be seen in the S sinogram in Figure 36 in which the sinuous bands that
correspond to specic S-rich area in the XZ cross section under observation do not show
the same intensity under all angles, as parts of the particle that absorb the SKa radiation to
a dierent extent rotate into the path of the SKa x-rays on their way to the detector. The
self-absorption, which inuences both the intensity of the primary beam on its way to a
particular volume element inside the particle and the intensity of the emerging uorescent
radiation, must be corrected for in order to obtain quantitatively reliable tomographic
maps. In order to perform such a quantitative correction of the experimentally corrected
sinograms, the variation of the linear absorption coecient m
L
(x, z, E) within the slice
under consideration (x, z) and at the primary and various uorescent energies (E) involved
must be known, or, equivalently, the (heterogeneous) matrix composition within the slice
must be approximately known.
Studies with simulated data indicate that under such conditions, via the use of an
iterative correction procedure, self-absorption phenomena may be corrected and the initial
compositional distribution iteratively rened, provided that the self-absorption of the
uorescent signals is not too severe (Nellessen, 1996; Vincze et al., 1999b, 1999c); con-
siderable eorts, however, still are necessary to solve this heterogeneous calibration pro-
blem in a general way (Simionovici et al., 2000). Because, at the moment, such correction
algorithms are not (yet) available in validated form (Sakellariou et al., 1997a, 1997b), the
tomograms in Figure 36 can only be used in a semiquantitative manner (by implicitely
assuming either a nonexistent or a constant self-absorption inside the particle) (Vekemans
et al., 2000).
Note: The elemental XY projection images, sinograms, and XZ tomograms show in
Figure 36 were obtained at the m-SRXRF setup at HASYLAB Beamline L by means of an
ellipsoidal lead glass capillary, providing a beam of $45 mm diameter (Janssens et al.,
1998). Similar measurements, but with less good lateral resolution, could also be per-
formed by employing a monocapillary-based laboratory m-XRF spectrometer using at
15-mm x-ray beam from a Mo anode operated at 40 kV.
V. APPLICATIONS
Although laboratory m-XRF instruments in their current conguration, have limitations
with respect to the net detectable count rate, the fact that elements in the range K to Zr can
be determined down to the 10-ppm level makes it a valuable tool for investigating pro-
blems where trace element information is useful and=or required, where the in-air op-
eration of the technique, its local analysis possibility, and=or the penetrative character of
the primary and uorescent radiation can be advantageously applied.
A. Industrial Applications
X-ray uorescence has been used in the industrial laboratory and on the factory oor to
analyze small specimens or small areas for many years (Adler et al., 1960; Miller, 1961;
Shiraiwa and Fujino, 1968a; Stebel and Silverman, 1984). By simply restricting the x-ray
beam with vendor-supplied apertures or other special attachments, spatially resolved
quantitative data could be obtained without using expensive electron beam equipment.
Special attachments for conventional XRF instrumentation reduced beam sizes to 100 mm
for application to a variety of problems in the industrial laboratory. It became obvious
that many materials problems such as plating and lm thickness measurement could be
solved with the lower resolution of the m-XRF technique.
In the mid-1980s, two developments occurred which led to increased industrial ac-
ceptance of m-XRF. The rst instrument specically designed for energy-dispersive m-XRF
was developed and marketed in 1986 (Wherry and Cross, 1986). Perhaps more sig-
nicantly, it was capable of element imaging, allowing the user, instead of simple point
analysis, to superimpose elemental maps and optical images. The availability of specialized
instrumentation led to applications involving microelectronic devices, industrial waste
screening, forensics, wood, paper, and other problems in materials science. The other
signicant innovation in the mid-1980s was the development of more intense laboratory
sources using glass-capillary optics.
1. Plating Thickness=Composition Gauging
The plating industry has used XRF to measure and control lm thickness for many years
(Seaman, 1985; Bush and Stebel, 1985; Czechanski, 1986; Anderson et al., 1991; Asher
and Ruiz, 1986). The m-XRF technique has largely replaced beta-backscatter in the
measurement of lm thickness in small areas. Beta-backscatter requires contact with the
surface; thus, the correct placement of small areas in the beam is dicult. The stando
in a m-XRF instrument allows the use of precise alignment techniques such as microscopes
and=or lasers. In addition, for beta-backscatter, the substrate atomic number must be at
least 20% dierent from that of the substrate lm, whereas XRF can resolve signals from
adjacent elements in the periodic table. XRF is also the only technique that can si-
multaneously measure the composition of a lm [e.g., Sn=Pb on Cu substrate (Stebel and
Silverman, 1984)] or of high-temperature superconductor tape (Cross and Wherry, 1988)
and its thickness.
Individual lm layer thicknesses in multiple lms can be measured by XRF, be-
cause each element produces a distinctive signal and absorption corrections can be
made from a knowledge of the order in which each lm is laid down. A common
example in the microelectronics industry in Au over Ni on a Cu substrate, a combi-
nation which cannot be measured with beta-backscatter. The characterization of plating
and coating layers in microelectronics, jewelry, and small coated wires requires mea-
surements of lm thickness in areas on the order of several hundred microns or on
curved parts where small beam sizes are needed to reduce the eects of surface cur-
vature. Examples of coatings are Au=Ni=Cu stacks in connector pins (Stebel and Sil-
verman, 1984) or in microelectronic lead frames (Nakazawa, 1983), coated wires (Ni or
Sn on Cu, Cd or Zn on steel) (Stebel and Silverman, 1984) or switch components (Au
on Ag; SnPb, Ag, Sn, Ni on Cu; Zn on steel), and Cd or Ni layers on steel fasteners.
In heat sinks, integrated circuit strips, and alloy transistors (Cross and Wherry, 1988),
NiP coatings on Al, Cu, and Fe are characterized by m-XRF. For this type of in-
vestigations, XRF instruments with apertured x-ray tube are used, with beams down to
100 mm in diameter.
2. Microelectronics Industry
In the microelectronics industry, thin-lm technology is being used to solve a number of
connector and packaging problems that have developed with the downsizing of in-
tegrated circuits. The lead counts on VLSI (very large-scale integration) circuits have
increased in proportion to the increase in the number of components per chip. Close
tolerances and narrow statistical quality control parameters have placed great demands
on the characterization of these thin lms, m-XRF is the method of choice for the
measurement of lm thickness and composition in the small areas involved in electronic
devices.
Wherry and Cross (1986) described a m-XRF instrument that had several advantages
over conventional small-spot, proportional detector systems with respect to applications
in the microelectronics industry. The instrument used a solid-state Si(Li) detector and had
imaging capabilities for revealing hidden chemistry information and qualitative in-
formation on lm thickness homogeneity. Anderson and co-workers (1991) presented
several examples of the utility of the new m-XRF analyzer to support the manufacture of
integrated circuits. Tape Automated Bonding (TAB) is a method for bonding
input=output leads to VLSI circuits. They accurately measured the Sn lm thickness on
TAB tape by monitoring the SnKa line with a 100-s counting time. The m-XRF technique
was said to be superior to Auger and SEMEDXRF analyses because of the larger
thickness range covered, lower detection limits for impurity elements, and simplied
measurements procedure (no sample preparation needed and ability to operate in air,
helium, and=or low vacuum). They also demonstrated the possibility of monitoring the
Cu=Sn intermetallic formation by measuring the CuK and SnL lines via the use of a thin-
window solid-state detector.
3. Waste Characterization
The characterization of industrial wastes in an area of concern because of potential en-
vironmental pollution due to improper wastes disposal. The identity and quantity of
hazardous elements present must be determined before disposal. In addition, new disposal
methods must be developed to contain hazardous materials and prevent leaching into the
soil. m-XRF has played a role in both of these areas.
a. Electronic Components
Tissot and Boehme (1994) suggested the use of m-XRF as a replacement for the Toxic
Characterization Leaching Procedure (TCLP) in the classication of waste from electronic
components. TCLP is an expensive (US $2000=sample) wet-chemical process that is re-
quired by the United States Environmental Protection Agency as the basis for compliance
with the Resource Conservation and Recovery Act (RCRA). It involves leaching the waste
material with dilute acetic acid; if specic toxic element concentrations exceed as pre-
scribed amount in the leachate, then sample and leachate must be disposed of in a ha-
zardous landll. In the m-XRF-based procedure, large areas of fractured waste are scanned
in air; samples required essentially no special preparation. No other analytical imaging
method could have been used to obtain the required data.
Electronic components from dismantled nuclear weapons at Sandia National La-
boratory were broken up using an industrial forge hammer to create samples having
particle sizes in the 210 mm range. These samples were used for the TCLP and for m-XRF
analysis. Sample chambers (4 in. 5 in., lled one layer deep with granulate) were scanned
with a 100 mm x-ray beam from a Mo-target x-ray tube (50 kV). In a sample in which
TCLP found Cd (10 1 ppm) and Pb (30 10 ppm) levels above the regulatory limit (1 and
5 ppm, respectively), these elements were also detected by means of m-XRF. In addition,
Cr was found to be present by m-XRF, but this element was not present at hazardous levels
in the leachate. Though present at relatively low concentration levels in the sample as a
whole, the presence of these elements could readily be determined by m-XRF because in
the crushed electronic components, they are concentrated in small areas that are still
signicantly larger than the beam. Thus, one small particle containing a large con-
centration of Pb would yield a large XRF count rate and that could correspond to pm
quantities for the entire sample. Furthermore, element associations in the electronic
component waste, determined by comparing m-XRF element maps, were used to estimate
the relative toxicity of the hazardous elements. For example, Cr, associated in stable form
with Fe and Ni as stainless steel, was not expected to toxic and, therefore, was not
leachable in the TCLP, Pb, on the other hand, was associated with Sn as solder and was
expected to readily undergo acid attack.
b. Evaluation of Industrial Waste-Disposal Methods
Carpenter and co-workers described two studies of new waste-disposal methods in which
m-XRF was used along with m-x-ray diraction (m-XRD) to determine the phases resulting
from procedures designed to prevent leaching of toxic elements into the soil and
groundwater (Carpenter et al., 1995a). In the rst study, the goal was to determine the
eect of lead oxychloride phases on the volatility of lead from lead oxide in toxic-waste
repositories. To determine what phases of lead oxychloride would form, a stimulation
consisting of suspending PbO pellets in HCl gas was conducted. The reaction zone, an
approximately 1 mm-thick surface layer, was relatively uniform except in regions in which
the Cl concentration was relatively high. Atomic Cl=Pb ratios in the range 0.5 (inner edge
of reaction zone) to 0.72 (edge of specimen) were found.
Micro-XRD measurements revealed the presence of Pb
2
O
2
Cl. In the reaction zone,
Cl=Pb ranged between 0.85 and 1.3. m-XRD data in this region revealed Pb
5
O
2
Cl
6
as the
major phase, along with PbO and Pb
2
O
2
Cl as intermediate to minor phases; the range of
Cl=Pb values could be accounted for by changing proportions of these phases within the
area included by the x-ray microprobe beam, at least up to Cl=Pb 1.2 (corresponding to
Pb
5
O
2
Cl
6
). Although m-XRD patterns provide direct information on the mineralogical
phases present, the value of the m-XRF quantitative line scans in this analysis was that
detailed chemical information could be obtained in a shorter period of time (300 s per
spectrum) than required by m-XRD (several hours per pattern). This analysis emphasized
the complementary nature of the two microbeam techniques.
In another study involving the development of new waste-disposal techniques, MgO
powder was mixed with dilute HCl solutions of sludge from an industrial wastewater-
treatment plant in order to form a hardened cement. It was anticipated that metal ions
incorporated into the lattices of the cement phases would be contained in a stable en-
vironment for long-term storage. The material was studied using m-XRF, m-XRD, and
SEM and was found to consist of large Mg(OH)
2
particles and Mg
3
(OH)
5
Cl5H
2
O. Other
particles contained signicant amounts of the metal constituents and were thought to be
undissolved sludge. However, the diuse distribution of Fe, Cr, and Ni throughout the
matrix phase was indicative of the desired solid-solution formation.
Presumbly, a greater eort to more thoroughly dissolve the sludge might produce
more complete encapsulation of the waste metals. The diuse distribution could be easily
seen in the Fe m-XRF map. On the other hand, in the corresponding SEM maps, only the
Fe in the particles at the surface of the sample was visible and showed no Fe in association
with the matrix phase. This dierence illustrates one of the advantages of m-XRF over
energy-dispersive x-ray analysis in the SEM: due to the larger penetration depth of the
x-ray photons and the higher sensitivity to Fe by the CuKa exciting radiation, the lower
concentration of Fe in the matrix was detectable by m-XRF and not by SEM. This
complementary nature was recognized early in the development of modern m-XRF tech-
niques. SEM analysis produces backscatter images, as well as light-element maps. Com-
bining these data with m-XRF images of heavier elements results in a more complete
analysis of, for example, ceramics, composites, and biological materials.
4. Homogeneity Testing
Wide-area scans, using beam sizes ranging from a few hundred micrometers to 1 mm, are
used in the steel industry to determine gross element segregation. Welfringer and co-
workers described the m-XRF analysis of an area 150 150 mm
2
on as cast 100C6 steel
using a spot size of 1 mm
2
(Welfringer et al., 1992). The authors pointed out that the easily
detectable Cr and Mn tend to cosegregate with the minor elements P and S, which undergo
extensive segregation during melting. The detection and characterization of segregation
allows the metallurgist to predict the properties of the product and make adjustments to
the continuous casting machine. Quantitative maps of Cr and Mn were produced from
calibration curves. It was found that a milled surface nish was adequate for the m-XRF
technique and that the data were as good as or better than that obtained by metallographic
etching or the more expensive and complicated electron microprobe technique.
5. Materials Analysisinthe Industrial Laboratory
The use of m-XRF as an analytical tool in failure analysis and in the investigation
of production problems is also becoming more prevalent in the industrial laboratory.
The technique provides unique information that cannot be obtained with other analytical
methods. As with any other technique, the data provided by m-XRF are best used in a
complementary manner with data from other microanalytical tools, such as scanning
electron microscopy, x-ray diraction, and x-ray photoelectron spectroscopy.
Carpenter (2000) describes (1) the use of a 10-mm x-ray beam for analysis of stain-
less-steel spray nozzles (1 mm in diameter), revealing that the investigated orice had
undergone extensive corrosion (resulting in local Cr enrichment) during the spraying of
molten ceramic material, (2) the use of m-XRF instead of SEM for analysis of volatile
materials (which can contaminate the vacuum system of a SEM) e.g., for establishing the
rate of amalgamation between Cu and Zn powders and Hg contaminated with radioactive
waste, and (3) the analysis of Zr=Mo coating-hardened metal pins, allowing to qualita-
tively compare the thickness and composition of the coatings and of the base alloy of the
pins used by various manufacturers. Pella and Feng described the analysis of a MnO
2
coating on the wash-coat surface of a cylindrical automobile catalyst by m-XRF to de-
termine the eect of a fuel additive on the catalyst (Pella and Feng, 1992). The use of
electron beam methods was not appropriate because thickness measurements were re-
quired. The m-XRF technique was also advantageous because no sample preparation was
required to make the sample electrically conductive. After longitudinal sectioning, a scan
parallel with the cylindrical axis revealed that the coating thickness was reduced by about
a factor of 2 at about 8 mm from the inlet side of the catalyst.
Worley and Havrilla (1998) characterized mixed-oxide (MOX) fuel feed material
surrogates composed of Ga
2
O
3
in CeO
2
. MOX fuel contains trace level of Ga
2
O
3
that can
potentially damage the fuel cladding. Because the majority of the Ga
2
O
3
is extracted
during MOX fuel feed processing by reduction to volatile and mobile Ga
2
O, spatially
resolved spot analyses, line and image scans were performed by means of m-XRF to de-
termine the gallium distribution in surrogate pellets. A CeO
2
matrix was used because it is
easier to handle than PuO
2
and because it exhibits chemical properties similar to those of
plutonium. The gallium (as a volatile suboxide) was found to migrate to the exterior of the
pellets when reduced with hydrogen; it also followed a thermal gradient in the reducing
oven and moved toward the pellet tops at high reduction temperatures.
B. Environmental Applications
An overview of environmental application of laboratory and synchrotron-based
microbeam XRF can be found in Osan et al. (2000). In what follows, primarily the
applications that can be realized with laboratory m-XRF setups are briey outlined.
1. Individual Particulate Analysis
Because the atmosphere, the soil, and the groundwater are recipients of industrial and
other antropogenic pollutants, the regulation of these emissions is based on the monitoring
of their presence. Traditionally, XRF has been one of the prime and analytical methods
for the determination of many elements at reasonable cost in a large series of samples. A
considerable number of elements and a profusion of organic compounds are emitted into
the atmosphere; of these, more than 50% is preferentially present in particulate matter
form rather than in the gas phase. Many methods are in use for the elemental analysis
of aerosols; most methods provide the average composition of the total amount of
particulate matter collected on, for example, an air lter with or without size fractionation.
In general, a distinction is made between the ne (respirable) aerosol fraction (0.12.5 mm
diameter) and the coarse (2.5100 mm) fraction (sedimentation-type particles). By ana-
lyzing particles individually, after a classication step, the contributions and composition
of each particle source at the sampling location may be determined directly.
Especially EPXMA (e.g., Van Borm et al., 1990) and to a lesser extent m-PIXE
(Jaksic et al., 1991) and microbeam XRF (Janssens et al., 1992, 1993a; Rindby et al.,
1997a, 1997b; To ro k et al., 1994; Osan et al., 1997) have been used in the last decade for
characterization of individual particles. EPXMA has sucient lateral resolution in the
relevant size range to allow fast and automated major analysis of coarse- and ne-mode
aerosols; even for large particles, however, it is limited to the determination of the major
components. To allow determination of trace concentrations (110-ppm level) in very
small sample volumes (a 1-mm-radius aerosol typically has a mass $10 pg), a detection
power in the (sub)femtogram range is required. Therefore, m-PIXE and m-SRXRF are
mostly applied to coarse-mode aerosol.
A comparison of sensitivities using glass microspheres of 2030 mm, (Janssens et al.,
1992; Gordon and Jones, 1993) revealed that synchrotron microbeam XRF (NSLS mi-
croprobe) provided the best relative detection limits (110-ppm range for the elements K
to Zn in 100 s), that m-PIXE (University of Amsterdam setup) took up an intermediate
position, and that EPXMA was limited to concentrations above 0.10.2%. However,
when EPXMA and m-SRXRF were compared in terms of absolute detectability for par-
ticles of comparable size to the x-ray microbeam (4-mm radius), the performance of both
methods was not very dierent (DLs in the 0.050.5-pg range for m-XRF; 0.55 pg for
EPXMA). It is expected that a third-generation synchrotrons, where absolute detection
limits in the ag (10
18
g) range were reported already (Rindby et al., 1997b), trace analysis
of ne-mode aerosols will be feasible.
Another type of information that can be obtained from individuals aerosol particles
by means of an x-ray microbeam of tunable energy is the chemical state of minor and trace
constituents of environmental materials. Because of the changeover from nuclear to
conventional fossile-fuel-burning power plants, interest in the characterization of y ash
has increased in recent years in view of the possibility of direct public exposure to toxic
metals enriched on the surface of y-ash particles or the released into the environment of
these metals due to leaching. To obtain a better understanding of the toxicity of some of
the metals, their oxidation state can be determined by uorescent-mode XANES (x-ray
absorption near-edge structure spectroscopy). By means of a 100 100-mm
2
tunable
monochromatic beam, it was possible to establish that most of the As in single y-ash
particles, collected from a Hungarian power plant, was present as As
5
and not as the
more toxic As
3
(To ro k et al., 1994; Osan et al., 1997). More recently, Janssens et al.
(2000c) used a polycapillary lens to focus bending magnet radiation down to 4050 mm to
collect XANES proles of trace elements such as As and Se, present at the 40-ppm level in
y-ash particles. Also, the local oxidation state of U and Ni in microscopic particles has
been studied in this manner.
2. Tree Ring Analysis
A wide range of living organisms can be used for biomonitoring of the quality of the
environment (Burton, 1986; Markert, 1993). They can reect the varying circumstances by
growth reduction or decrease of biological activity. The immobilized chemical components
incorporated in these organisms are historical records of the environment. Moreover,
some of the trace pollutants can be enriched in their tissues, thus facilitating the analysis of
lower concentrations. The history of the environment of a given area can be studied using
biological materials spending their whole lifetime in the studied territory. Trees are ideal
plants to study because their lifetime is long enough to range several decades but is usually
too short to use other physical or chemical techniques for their dating. In the temperate
zone, trees usually grow one ring during one vegetation period, which is easily identiable
by simple optical methods. Growth variations can reect meteorological, ecological, and
environmental changes.
Microbeam XRF is an ecient and nondestructive method for studying both the
trace element composition and the density variations of wood; when the analysis of a
single tree ring is aimed for, XRF analysis of sucient lateral resolution or mechanical
separation (cutting) of the sample is needed. Experiments in the last decade, attempting to
use bulk XRF for the trace element determination in the tree rings, required chemical
preconcentration and therefore were destructive (Nagj et al., 1987). The precise identi-
cation of the rings and their physical separation is cumbersome and the obtained con-
centrations can hardly be correlated to the date. m-PIXE and EPXMA were also applied to
obtain data on individual rings; theses methods are not very suitable in this case because
energy deposition by the charged particles can cause loss of volatile components and
damage to the plant material. Nagj et al. (1987) studied the same tree samples by both
XRF and PIXE and claimed that PIXE sulfur values are ve times lower than the XRF
values, which is due to local heating of the sample caused by the proton beam. The
concentration values for other elements are slightly higher when determined by PIXE,
which is probably caused by the loss of matrix induced by charged-particle heating.
Experiments aimed at establishing the trace element composition of tree rings were
performed by several groups. Hayakawa et al. (1990) were the rst to show the applic-
ability of SRXRF for analysis of cedar tree rings using a collimated 200-mm beam of
10 keV energy. The Ca distribution could related to the structure of the tree ring, whereas
Fe, Cu, and Zn maps (ppm level) showed that these elements are localized in small regions
of the sample. They also concluded that (external beam) PIXE analysis causes strong
sample damage due to the low thermal conductivity of the sample. Gilfrich et al. (1991)
used both conventional and synchrotron x-ray sources for the analysis of the sassafras
southern red oak. The conventional XRF measurements were carried out with a colli-
mated and unltered Rh-anode beam of 0.5 mm0.7 mm in vacuum. Because the size of
tree rings is larger than the beam size, the limitation of the experiment was the relatively
low peak=background. The SRXRF analysis was carried out at the NSLS X-23B beam
line by using a 10-keV beam apertured to 50 mm1 mm. The radial distribution of nine
elements in the tree ring samples was established. The study showed that year-to-year
variations of trace elements can be obtained by the SRXRF analysis in reasonable time
(long-range scans can be done within 1 h), but, from the environmental point of view,
a great deal of research is still required in order to establish the correlation between the
pollutants in the soil, water, and air to which the tree has been exposed.
Selin et al. (1993) reported on a tabletop system which used a 0.1 1-mm beam from
a Mo secondary target for trace element analysis of tree rings. The rings to be analyzed
were identied optically. They showed that a minimum detection limit of the order of a
few ppm for thick samples (tree biopsies) can be reached within the 300-s measurement
time. Long-term variations of the Zn and Mn levels in spruce, pine, and birch from central
Sweden were indicative of the occurrence of stress to all trees around 1980, attributed to
changes of the general environmental conditions in the area caused by extensive cutting of
wood. Some elements such as zinc, iron, and lead showed dramatic variations (four to six
times) in the long-term period and also within 1 year. Lead and zinc were in high corre-
lation, which could indicate a direct inuence from air pollutants.
a. Density Variations Between and Within Individual Rings
In the temperature zone, the tree rings have dark and light areas resulting from seasonal
dierences in biological activity and growth rate. The rings therefore have dierent den-
sities and dierent structures but are made of approximately the same organic material. A
microscopic x-ray beam can be eciently used to determinate the density variations of the
wood material even within a single year ring. Microbeam-based densitometric analysis has
two approaches; the density variations can be studied (1) by transmission or (2) by co-
herent scattering measurements.
1. Transmission method. The intensity I
tr
of the transmitted beam is proportional
to exp
P
i
w
i
m
i
rz expMr, where M denotes the product of the total
mass-attenuation coecient m and the sample thickness z. (Because the
composition of the wood is approximately constant, the total mass-attenuation
coecient
P
i
w
i
m
i
can be simply written as m, and z is assumed to be constant
due to the sample preparation.) I is the intensity of the primary beam and I
r
is
the intensity of the transmitted radiation. As a result, the intensity of the
transmitted x-rays is a simple function of the density r (Kuczumow et al.,
1995).
2. Scatter method. Assuming constant thickness z, the scattered intensity is also a
monotonous function of the density r. The scatter intensity can be used for
studying density variations, or via a series of appropriate standards (Vincze,
1995), the density can be determined quantitatively. The most important
advantage of the use of the scattering signal is that in addition to information on
the density also the chemical composition can be obtained simultaneously and
from the same ED XRF spectrum. Also, the sample preparation is not as
demanding as for transmission measurements.
Kuczumow et al. (1995) aimed to obtain density variational data within one in-
dividual growth ring (using 20 mm resolution) and to record long-range density changes
(80 mm resolution). The primary intensity obtained from a conventional x-ray tube (Cu
anode) with capillary focusing (7-, 18-, 23- and 79-mm openings) was sucient for
transmission and coherent scattering measurements. Core samples of two similar tree
species (Pinus silvestris from Poland and Picea abies from northern Sweden) but growing
in dierent climatic conditions were analyzed. Ten-year scans showed that the transmis-
sion data and the temperature distribution were in good correlation; each increase in
ambient temperature caused a density decrease. From the long-range densitometric
measurements, year rings with extremely high mean density could be selected, as an evi-
dence of low-temperature years (Jones et al., 1995) (e.g., as a result of volcanic explosions,
causing a global temperature decrease due to dust emission into the atmosphere). By
means of a 18-mm capillary beam (Kuczumov, 1995), within individual year rings sig-
nicant dierences between the Polish and Swedish wood were found. In the former wood
type, a typical yearly density variation of pine growing in the temperate zone was found
showing a thick layer of dense late wood. The Swedish wood lacked this layer; its
density rapidly decreased in spring and sharply increased in autumn. When the densito-
metric measurement was carried out in the scattering mode, Attaelmanan et al. (1994)
demonstrated that some nutritional elements such as Ca and Mn followed the density
variations, whereas others (K, Cl) were completely uncorrelated. Kuczumow et al. (1999a,
1999b) also studied dierences in density and in composition of year rings in petried
wood by means a combination of techniques.
Laboratory x-ray tube systems have also been used for biomedical applications. This
type of investigation was reviewed by Fukumoto et al. (1999). Already in 1990, Fukumoto
et al. (1990) demonstrated the possibility of performing trace element mapping on tumor
tissues and living plant leaves by means of a 200-mm beam extracted from a conventional
x-ray tube. Trace element mapping on tree leaves was later demonstrated by Carpenter
(1995b), whereas Voglis et al. (1993) performed high-resolution mapping of Ca in bone.
C. Applications in Art and Archaeometry
According to Lahanier et al. (1986), the ideal method for analyzing objects of artistic,
historic, and archaeological value should be (1) nondestructive, (2) fast, (3) universal,
(4) versatile, (5) sensitive, and (6) multielemental. Because XRF meets a number of these
requirements, analysis of objects of this type with XRF is fairly common and is, in fact,
one of the most applied ways of obtaining qualitative and semiquantitative information on
the materials of which these objects are made. However, the use of conventional XRF for
reliable quantitative analysis is severely hampered by the fact that the irradiated area
usually is too large (preventing details of decorations, shapes, and so forth to be analyzed
separately), whereas also the irradiation geometry and sample surface are usually nonideal
and=or not well dened, possibly introducing systematic errors in the quantication. Some
of the limitations can be circumvented by using smaller x-ray beams. Motorized sample
movement also allows to extend the local analysis capability toward two-dimensional
imaging of certain elements on the surface of (decorated) artifacts. Because many objects
of artistic and=or archaeological nature are fairly large and bulky (e.g., statues, oil
paintings, vases, treasury objects), instrumentation operating in air atmosphere that can
accommodate various object shapes is very useful.
More recently, polycapillary lenses have also been used for the local and non-
destructive analysis of artistic objects. The fact that polycapillaries only produce beams of
100200 mm diameter does not present a limitation in investigations where mostly sub-
millimeter-sized (or larger) features of macroscopic objects are analyzed. The marked
advantage polycapillaries have over monocapillaries is the fact that they form a focal spot
at a considerable distance from the end of the lens, whereas with monocapillaries the
smallest beam diameters are reached at the point where the beam leaves the capillary. This
allows for a completely noncontact and nondestructive kind of investigation and makes
polycapillary lenses ideal for local analysis of sensitive, precious, and=or unique objects of
macroscopic size such as statues, miniature paintings, coins, utilitarian objects in glass or
metal (goblets, vases, etc.), and the (often multicolored) decorations which are applied
to them.
In what follows, a few examples of the application of monocapillary- and poly-
capillary-produced submillimeter x-ray beams to the above-described type of problems are
given (Janssens et al., 2000b).
1. Trace Element Mappingin Corroded Roman Glass
The backscattered electron micrograph and x-ray maps shown in Figures 2429 were
collected from a fragment of Roman glass that had been buried in moist Jordanian soil for
about 1900 years; details on the nature and history of this material can be found elsewhere
(Janssens et al., 1996c, 1996d). As a result of the interaction with groundwater during this
period, a leached or corroded layer was produced, in which a number of the original
cations of the glass (mainly Na
, K
, and Ca
2
) were replaced by protons and other
cations dissolved in the groundwater. Due to a number of other physical and chemical
processes that have occurred inside the leached layer and in the surface crust on top of the
original surface, a chemically and physically complex multilayered structure was formed.
For example, in Figure 24a, a parallel corrosion front next to a hemispherical corrosion
body can be distinguished. In order to obtain a better understanding of the mechanisms
that lead to the formation of these complex structures, the distribution and migratory
patterns of various (trace) elements (e.g., Mn, Bi, Sr, Zr, etc.) must be determined and
correlated to their ionic size and bonding nature to the glass network structure in the
various layers (Newton and Paul, 1980). A comparison of m-XRF- and m-PIXE-generated
elemental maps obtained (Janssens et al., 1996a) showed that both techniques provide
approximately equivalent information on the distribution of trace constituents such as Cr,
Ni, Cu, Zn, Pb, Bi, Sr, and Mo, although, generally speaking, the noise level in the m-XRF
images is higher. Also, the achievable resolution in state-of-the-art m-PIXE setups is sig-
nicantly better than what is now possible in lab-scale m-XRF instruments. In cases,
however, where complementary information on matrix elements can be obtained by, for
example, EPXMA and a lateral resolution of $10 mm is sucient, the maps in Figure 24b
suggest that lab-scale m-XRF can be considered as a valuable (and less expensive) alter-
native microanalytical trace-level technique.
2. Local Analysis of Decorationsin Japanese18th-Century PorcelainVases
An area in which authentication of art(istic) objects is of considerable (economical)
interest in that of Oriental china ware. Since until the 17th century, high-quality por-
celain was exclusively manufactured in China and Japan; imported chinaware were
highly valued and expensive. In the later periods up to now, an extensive production
system of counterfeit Chinese and=or Japanese porcelain both in Europe and in Asia has
come into existence. Some of these reproductions are very sophisticated and cannot
easily be distinguished from the original counterparts by visual inspection alone.
However, objective ways of distinguishing between original period pieces and more
contemporary reproductions have up to now focused predominantly on the porcelain
base material itself (Yap and Tang, 1984, 1985). An alternative approach is to con-
centrate on the variation of the composition of the enamel paints used to decorate the
objects. In view of the size and shape of the pieces, this type of analysis is dicult to
perform using SEMEDX (scanning electron microscopy equipped with energy-dis-
persive x-ray detection) and the intricacy of the decoration patterns usually preclude the
use of conventional XRF except when only averaged analysis results are required (Yu
and Miao, 1997, 1999); m-XRF analysis of individual decorations is feasible however. As
detailed in Janssens et al. (1996a), by employing a monocapillary-base setup, it is pos-
sible to record large-scale m-XRF maps of these decorations and to determine which
transition elements (e.g., Mn, Fe, Cu) were employed to color the PbO-based enamel
paint; it was also possible to distinguish between originally present and add-on dec-
orations of the same color on the basis of the local XRF spectra. Also, polycapillary
lenses, yielding a beam size of approximately the same dimensions as the details of the
decorations, have been used to perform local analysis of this type of material (Vekemans
et al., 1998).
3. Local Analysis of Bronze Statues
In the 19th century, a great interest arose for the ancient Egyptian civilization; many
museums in the world currently own a collection of small Egyptian statues of religious
nature in stone or bronze (Oost, 1995). To a varying extent, most metal statues have
developed a corrosion layer which prevents reliable analysis of the Cu-based alloys of the
objects were made of (Robbiola et al., 1988; Robbiola and Fiaud, 1993). Nevertheless, this
information is of interest because it can be used to trace the evolution of metallurgy in the
period 30000 BC (Wuttmann, 1986, 1996). Analyses of this type can also be used to
distinguish between original pieces and contemporary forgeries (Vekemans et al., 1998) or
to establish, for example, whether all parts of a statue originate from the same workshop.
By employing microbeam or millibeam XRF, several parts of a statue can be examined in
reproducible conditions (e.g., by avoiding strongly curved surfaces) whereas for quanti-
tative analysis of the underlying metal, only small areas of the corrosion layer (e.g., on the
base of a statue) need to be removed.
As an example, Table 9 lists quantitative analysis results obtained from a statue of
the god Nefer-Hotep represented in Figure 37 (about 40 cm high, from the collection of
the Museum Vleeshuis, Antwerp, Belgium (Oost, 1995) of exceptional quality, dated to
the XXIIXXIII dynasty ($1000 BC) (Vittiglio et al., 1999)]. It was nondestructively
analyzed by means of a simple milli-XRF setup consisting of a collimated low-power
minifocus tube (250 mm focal spot on Mo anode), yielding a pencil beam of $300 mm in
diameter and a 30-mm
2
Si(Li) detector. A fundamental parameter method was used to
obtain quantitative results; analyses of brass and bronze standards revealed that the
elements Cu, Zn, Sn, and Pb (the elements most informative of Cu metallurgy in this
period) could be determined with an accuracy of $10%. Whereas the body of the statue is
copper-colored, has a very smooth surface, and shows only a very thin corrosion layer,
the double crown and base of the statue are darker in color and have a rougher texture,
suggesting the presence of a thicker corrosion crust and possibly the use of different alloy
composition. Both crown and base were made separate from the body. Because the data
in Table 9 suggest a difference in composition between the body of the statue (legs, front
of body) and its crown and base, on the bottom side of the base, a few square millimeters
of the corrosion layer were polished away, exposing the original metal. The results ob-
tained after polishing are also shown in Table 9 and indicate that there is, in fact, no large
difference in composition between base and body and that probably all parts of the statue
were made using a similar alloy composition and in the same workshop. The compositions
found after polishing are consistent with literature data on this type of material and
period. It is clear that the nondestructive analysis possibilities of m-XRF in this case can
contribute signicantly to a better understanding of ancient metallurgical techniques
employed in the period involved.
4. Document Forgeries
The ability to analyze materials in air and in a nondestructive manner makes m-XRF an
excellent technique for the analysis of valuable documents (e.g., to determine their au-
thenticity). Typically, dierent inks, while having the same visible appearance, will have
dierent chemical compositions. Although m-PIXE and m-SRXRF has been used to ex-
amine documents such as the Gutenberg Bible and other early printed works (Cahil, 1981,
1984; Mommsen, 1996), the relative simplicity and nondestructive nature of m-XRF make
it an attractive analytical alternative.
Larsson (1991) and Stocklassa and Nilsson (1993) described analysis by m-XRF of an
500-year-old Swedish possession letter (dated April 1, 1499). The document, a sales
contract for an estate, showed signs of alteration. It is suspected that the alteration was
made in the 1530s when the Swedish king gave land back to certain nobles, who had been
Table 9 Quantitative Results on Local Analysis of Different Locations on the Nefer-Hotep Statue Shown in Figure 37
Body Base (unpolished) Base (polished)
% (w=w)
Right
leg Front
Head
band
Crown
Front Back Bottom A Bottom A Bottom B Bottom C Lower Upper
Fe 0.12 0.14 0.25 0.09 0.09 0.11 0.11 0.15 0.09 0.07 0.08
Cu 81.2 82 76.5 72.8 75.8 72.6 70.7 71.4 80 84.9 84.8
Ag 0.05 0.04 0.12 0.18 0.13 0.17 0.19 0.13 0.07 0.06 0.06
Sn 13.7 12.9 14.8 19.8 17.5 22.3 21.6 21 15.3 12.2 12.2
Pb 4.8 4.5 7.6 6.5 6.2 4.3 7 6.7 4.6 2.5 2.5
Figure 37 Photograph of a bronze statue of the Egyptian god Nefer-Hotep (collection of the
Museum Vleeshuis, Antwerp, Belgium), dated to the XXII-XXIII dynasty (ca. 1000 BC).
stripped of their estates by an earlier ruler. Although alteration was suspected by visual
inspection (the original name of the estate was removed by scraping), the original text was
unreadable. By employing m-XRF-generated Zn maps (a trace constituent of the original
ink), the original name could be established however. In Figure 38, m-XRF scans of Ca
and Zn are shown across a selected area of the parchment. In the Ca map, the (falsied)
visible text can be seen, featuring the family name Ga smestad i Bo re; in the Zn map of
the same area, however, a completely dierent text reading Btinge i Asbo becomes
visible. Obviously, the forger used a dierent ink for the alteration, accounting for the
dierent chemical makeup.
In a forensic (see next subsection) rather than a historically oriented study (Stock-
lassa and Nillson, 1993), a comparison analysis of 10 blue ball-point inks of similar color
by m-XRF analysis revealed the presence in some inks of Fe and Rb, of W, of Fe and Cu,
or of Fe, Cu, and Zn patterns, indicating the possibility to distinguish between the various
inks used by dierent manufacturers. A text (the number 24, see Fig. 26) was written on
a piece of paper with one pen and completely overwritten with another ball-point pen of
Figure 38 The Ca (bottom panel), Mn, Fe, and Zn (top panel) maps of an area of a Swedish
possession letter. In the Ca map, the family name Ga smested i Bo re is visible, corresponding to the
visible (but falsified) writing; in the Zn map of the same area, however, a completely different name
reading Btinge i Asbo is visible.
similar color but dierent brand. By using the appropriate elemental image specic for the
ink of the rst pen, the original text could be easily visualized.
D. Forensic Applications
In view of the nondestructive nature of m-XRF and the minimal specimen preparation
required, it is an ideal tool for the analysis of material found at crime scenes and for the
investigation forgeries. The use of m-XRF permits to avoid the destructive of valuable
evidence, as is the case for many other methods commonly employed in forensic analytical
chemistry. In Stocklassa et al. (1992), the analysis of various forensic materials such as
single hair bers, paint chips, glass particles, and ball-point pen ink using m-XRF is de-
scribed.
1. Hair Analysis
With respect to the analysis of trace elements in hair, m-XRF has the advantage of being
nondestructive, quick, and able to map element distributions both along the length of the
ber and across its thickness.
Trace elements in hair originate from both internal (endogeneous) and external
(exogeneous) sources (Chatt and Katz, 1988). Exogeneous elements originate from en-
vironmental sources such as tap water or air pollution. The assumption is generally made
that exogeneous elements will be concentrated nearer the surface of hair strands and the
concentrations of those elements will increase with length, as long as the external de-
position continues; in contrast, endogeneous elements should be distributed relatively
uniformly throughout the thickness of the ber, the relative amounts of each element
determined by diet and individual metabolism.
In a few studies, the claim is made that within a persons hair, the compositional
ngerprint among individual hair is relatively constant and that this patterns is unique to a
single individual (Toribara et al., 1982; Seta et al., 1982, Valkovic et al., 1973); thus,
(m-XRF) analysis of a single hair strand could potentially provide the forensic scientist
with unique information to match hair bers found at crime scenes. Engstro m et al. (1989)
showed that detection limits of 1 ppm were possible in the analysis of trace elements in a
single hair ber using a m-XRF analyzer with a 200-mm beam. With the same instrument
and a small (19 mm) Cr-anode beam, Larsson et al. (1990) obtained self-absorption cor-
rected radial distributions of sulfur and calcium from single hair bers without cross
sectioning the ber. The Ca distribution was maximum at the surface of the ber and
showed a minimum in the center of the ber, consistent with other work indicating the
presence of signicant amounts of exogenous Ca in hair from washing in tap water and
with PIXE observations by Cookson and Pilling (1975).
Toribara (1987) constructed an XRF analyzer for the analysis of single hair bers in
12-mm steps along the length of the hair. The authors pointed out that the data obtained
from multiple hair samples from a single individual did not appear to vary signicantly
and that forensic applications were possible. Detection limits were found to be similar to
those for PIXE, or less than about 30 ppm. The longitudinal distribution of Hg in the hair
of an Iraqi woman who had consumed wheat produced by seed that had been treated
with methyl mercury insecticide was determined. From the fact that hair grows at an
average rate of about 1 cm per month, the period of ingestion of the Hg could be de-
termined. This is similar to PIXE data used to show slow poisoning of Napolean by As,
except that it was done faster and with higher spatial resolution (Forshufvud et al., 1961;
Smith et al., 1962). The same instrument was also used to determine trace elements in
brous materials: chemical dierences could be found in carpets made by dierent
manufacturers, pointing to the possibility to match=identify single textile bers found on
victims and=or criminals.
2. Individual Particle Analysis
The analysis of microscopic particles found on a suspect can potentially place the suspect
at the scene of a crime. Particles may originate from bullets passing through clothing, from
gun shot residue or from glass breakage.
a. Glass Fragment Analysis
The elements present in glass vary depending on the type of glass involved and the
manufacturing lot. A group of European forensic laboratories (Sto cklein et al., 1997)
compared various analytical techniques for discriminating between various types of oat
glass (as used, e.g., in shop windows). Float glass is one of the major types of evidence
encountered in crimes such as burglary, road accidents, and vandalism. A rapid and
widespread manner of distinguishing between the dierent oat glass manufacturers is to
determine the index of refraction of the glass (usually in the range 1.5171.520). However,
due to the globalization of trade and because narrow limits are set for the major com-
ponents used in the manufacturing process of oat glass (i.e., Na
2
O, K
2
O, CaO, and SiO
2
),
the ability of this method to discriminate between glass samples of dierent origin in the
future will be reduced.
Two varieties of m-XRF (employing a unltered, collimated Rh tube and capillary
focused Cu-anode beam, respectively), SEMEDX and ICPMS (inductively couple
plasmamass spectrometry) were used to analyze various standards glasses, some of which
with the same refractive index. Of these, only capillary m-XRF and ICPMS were able to
distinguish between glass samples made in the same furnace but produced in an interval of
9 months; these methods also detected minor inhomogeneities within individual pieces of
glass. Both varieties of m-XRF, with DL values in the range 1100 ppm, were able to
dierentiate between glass manufactured in dierent plants, by making use of the tran-
sition element ngerprints of the glass. Other quoted advantages of the use of m-XRF for
glass fragment ngerprint were its multielemental character, the simple sample prepara-
tion, and its nondestructive character (as compared to ICPMS). Disadvantages are its
limitations with respect to light-element determination and (for irregularly shaped frag-
ments) its semiquantitative character.
b. Gunshot Residue Analysis
When a gun is red, a pattern of residue is distributed on the person ring the weapon and
on the target. Analysis of particles (taken from the clothing or skin of the suspect=victim)
in this case is typically done using scanning electron microscopy and automated routines
may be used to search over large areas, identify particles, and carry out quantitative
analysis on them (Nilsson and Stocklassa, 1993), provided the particles are on the surface
of the material. m-XRF has been used to directly map the residue distribution on fabrics
where the particles have penetrated into the material. In a case where a man was shot
during hunting, the same authors describe the automated search and analysis of metallic
particles deposited into textile fabric by passage of a bullet; the bullet itself was not
available for analysis. All particles were found to contain the same concentrations of Ni,
Cu, and Zn; it could be concluded that the bullet fragments could only have come from
one of two weapons suspected to have red the bullet.
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12
Particle-Induced X-ray Emission Analysis
Willy Maenhaut
Ghent University, Ghent, Belgium
Klas G. Malmqvist
Lund University and Lund Institute of Technology, Lund, Sweden
I. INTRODUCTION
In 1970, Johansson et al. (1970) demonstrated that the bombardment of a specimen with
protons of a few megaelectron volts (MeV) gives rise to the emission of characteristic x-rays
and that this can form the basis for a highly sensitive elemental analysis. This landmark
article formed the starting point of the x-ray emission analysis technique which became
known as particle-induced x-ray emission analysis (PIXE). Although PIXE is sometimes
considered a variant of x-ray uorescence (XRF), such a classication is not correct in a
strict sense, because the technique does not rely on excitation of the sample by x-rays.
Instead, heavy charged particles (i.e., protons, a-particles, or heavy ions) are used in PIXE
to create inner-shell vacancies in the atoms of the specimen. As in XRF and electron-probe
microanalysis (EPMA), the characteristic x-rays produced by deexcitation of the vacancies
can be measured by either a wavelength-dispersive or an energy-dispersive detection sys-
tem. However, whereas the two detection systems are employed in both XRF and EPMA,
an energy-dispersive spectrometer with a Si(Li) detector is almost exclusively used in PIXE.
The incident charged-particle beams in PIXE are invariably generated by particle accel-
erators. For the great majority of PIXE work, protons of 14MeV, which can be produced by
small accelerators (e.g., Vande Graaaccelerators or compact cyclotrons), are employed. Such
small accelerators are also used in other analytical techniques that utilize ions of a few mega-
electron volts per mass unit, such as Rutherford backscattering spectrometry (RBS), nuclear
reaction analysis (NRA), charged-particle activation analysis (CPAA), and accelerator mass
spectrometry (AMS). Because of their common use of ion beams, these techniques and PIXE
are often jointly referred to as ion beam analysis (IBA) techniques. Furthermore, because
the same incident particle type and energy may be used in several of the techniques, the
simultaneous analysis of a sample by PIXE and some other IBA techniques (particularly RBS
and NRA) is often feasible, so that the elemental coverage may be increased down
to the very light elements and=or information on the depth distribution may be obtained.
Compared to x-rays, protons or other heavy charged particles have the advantage
that they can be focused by electrostatic or (electro)magnetic lenses and may be trans-
ported over large distances without loss in beam intensity. As a result, incident uence
densities (expressed as the number of impinging particles per square centimeter and per
second) are generally much higher in PIXE than in ordinary tube-excited XRF. Moreover,
focusing of particle beams down to micrometer sizes is possible, so that PIXE allows an
analysis with high spatial resolution. The microbeam variant of PIXE has become known
as micro-PIXE, whereas the common variant, which makes use of a millimeter-sized beam,
is now often referred to as macro-PIXE. Focusing to micrometer sizes is also possible with
electrons and has given rise to the powerful EPMA technique, but heavy charged particles
have the clear advantage that they give rise to much lower continuum background in-
tensity in the x-ray spectrum. As a result, the relative detection limits (micrograms per
gram) are typically two orders of magnitude better in micro-PIXE than in EPMA.
After the initial experiment by Johansson et al. (1970), the favorable characteristics
of PIXE were rapidly realized by many researchers, particularly within the nuclear physics
community. Its applicability and potential for solving numerous trace element analytical
problems were extensively examined and abundantly demonstrated. In addition to the
traditional bombardment in vacuum, external beam approaches (with the specimen either
in the laboratory air or in a nitrogen or He atmosphere) were also attempted and were
found to be useful, particularly in examining delicate and=or large objects. The progress of
PIXE over the years can be followed from the proceedings of the eight international
conferences exclusively dedicated to the PIXE technique and its applications (Johansson,
1977, 1981; Martin, 1984; Van Rinsvelt, 1987; Vis, 1990; Uda, 1993; Moschini and
Valkovic , 1996; Malmqvist, 1999) and of the ve conferences on nuclear microprobe
technology and applications (Grime and Watt, 1988; Legge and Jamieson, 1991; Lindh,
1993; Yang et al., 1995; Doyle et al., 1997), which contain numerous papers on micro-
PIXE. By now, PIXE has evolved into a rather well-used and mature technique, as is
demonstrated by the increasing numbers of research papers in which PIXE provided the
analytical results and by the publication of the two textbooks on the technique (Johansson
and Campbell, 1988; Johansson et al., 1995). For a comprehensive treatment of PIXE and
its applications, a reading of these books is highly recommended.
II. INTERACTIONS OF CHARGEDPARTICLES WITHMATTER,
CHARACTERISTICX-RAYPRODUCTION, AND CONTINUOUS PHOTON
BACKGROUNDPRODUCTION
A. Interaction of Charged Particles with Matter
1. Slowing Downof Charged Particlesin Matter: Stopping Power
When a beam of heavy charged particles of a few megaelectron volts per atomic mass unit
penetrates into matter, it loses its energy gradually with depth, until it is nally stopped.
The energy loss occurs mainly through inelastic Coulombic encounters with bound elec-
trons, and in contrast to the case of electron beams, the direction of travel of an ion beam
is scarcely altered during the slowing-down process.
The stopping power S(E) of an ion with energy E is dened as the energy loss per
unit mass thickness traversed:
SE
1
r
dE
dx
1
where r is the density of the stopping material and x is the distance. As dened here, S(E)
is expressed in units of kiloelectron volt per gram per square centimeter.
Numerous experimental measurements of stopping powers are available. They
formed the database to t the parameters of semiempirical equations (Anderson and
Ziegler, 1977; Ziegler et al., 1985), which are now commonly used to obtain the stopping
powers for all elements of the periodic table. For the energy range of 14 MeV, which is
most important in PIXE, the uncertainty of the values calculated with the semiempirical
equations is estimated at less than 3%.
The stopping power for compounds or more complex matrices is obtained from
those of the constituent elements through the BraggKleemann additivity rule:
S
matr
E
X
n
i1
w
i
S
i
E 2
where w
i
and S
i
E are the mass fraction and stopping power of constituent element i,
respectively.
The total path length R of an ion may easily be obtained by integration of the
stopping powers:
R
Z
0
E
0
dE
SE
3
where E
0
is the incident ion energy. Although the total path length is larger than the
projected range, the dierence between the two is smaller than 1% for incident protons of
a few megaelectron volts.
2. Inner-Shell Vacancy Creation: Ionizationand X-ray Production Cross Sections
Many of the Coulombic interactions between protons or heavier ions and matter result in
the ejection of inner-shell electrons. It is those interactions and their cross sections that are
of importance in PIXE. Three basic theoretical approaches have been used to calculate the
cross sections for inner-shell vacancy creation: the binary encounter approximation (BEA),
the semiclassical approximation (SCA), and the plane-wave Born approximation (PWBA).
The PWBA model, which applies perturbation theory to a transition from an initial
state (plane-wave projectile and bound atomic electron) to a nal state (plane-wave pro-
jectile and ejected continuum electron), has been most elaborated, particularly by Brandt
and co-workers. These researchers incorporated a series of modications in the model to
correct for its inherent approximations, and this resulted in the so-called ECPSSR treat-
ment (Brandt and Lapicki, 1979, 1981) of K and L shell ionization cross sections. The
ECPSSR treatment deals with the deection of the projectile due to the nuclear Coulomb
eld (C), perturbation of the atomic stationary states (PSS) by the projectile, relativistic
eects (R), and energy loss (E) during the collision.
Cohen and Harrigan (1985) used the ECPSSR model to produce an extensive ta-
bulation of K and L subshell ionization cross sections for most target elements and for
protons and helium ions between 100 keV and 10 MeV. As in the original ECPSSR version
of Brandt and Lapicki (1981), Cohen and Harrigan (1985) employed nonrelativistic hy-
drogenic wave functions to describe the atomic electrons. More elaborate relativistic
DiracHartreeSlater (DHS) wave functions within a Brandt and Lapicki (1979) form-
alism were used by Chen and Crasemann (1985, 1989) to produce K, L, and M shell io-
nization cross sections for protons of a few selected energies from 100 keV to 5 MeV and
for a narrow range of selected target elements.
For K shell ionization with protons, the cross sections as predicted by the ECPSSR
and other theories were thoroughly compared with experimental data by Paul and co-
workers (Paul and Muhr, 1986; Paul, 1987, 1989; Paul and Sacher, 1989) and a set of
reference cross sections was derived (Paul and Sacher, 1989). Although no theory emerges
that will predict the experimental data within a few percent for all target elements and
energies (Paul, 1989), it is generally agreed (Johansson and Campbell, 1988; Cohen, 1990;
Campbell et al., 1990) that both the tables of Cohen and Harrigan (1985) and of Chen and
Crasemann (1985, 1989) are adequate for most K shell proton PIXE work. For the case of
the L ionization, the situation is less satisfactory, however, as is discussed in detail by
Johansson and Campbell (1988), Campbell (1988), Cohen (1990), and Johansson et al.
(1995). Orlic and co-workers compared a large number of experimental L shell ionization
cross section data for proton impact with the ECPSSR theoretical predictions (Orlic et al.,
1994) and derived reference cross sections (Smit and Orlic , 1994) in a similar manner as
was done for the K shell by Paul and Sacher (1989).
For practical purposes, one requires x-ray production cross sections for individual
x-ray lines (i.e., s
X
p
with p the x-ray line used for analysis). The x-ray production cross
sections are related to the ionization cross sections through the following equations. For K
x-rays,
s
X
Kp
s
I
K
o
K
G
Kp
G
K

4
where the index K refers to the K shell, s
I
K
is the K shell ionization cross section, o
K
is the
uorescence yield and G
Kp
=G
K
is the fractional radiative width for line p.
For L x-rays,
s
X
Li;p
s
X
Li
G
Li;p
G
Li

5
where Li (with i 1; 2; 3) refers to the ith L subshell, s
X
Li
is the x-ray production cross
section for the subshell Li whose vacancy is lled up by the radiative transition, and
G
Li;p
=G
Li
is the fractional radiative width. The x-ray production cross sections s
X
Li
are
related to the L subshell ionization cross sections s
I
Li
through
s
X
L1
s
I
L1
o
1
6
s
X
L2
s
I
L2
s
I
L1
f
12
o
2
7
s
X
L3
s
I
L3
s
I
L2
f
23
s
I
L1
f
13
f
12
f
23
f
0
13
o
3
8
where o
i
denotes the uorescence yield, f
ij
denotes the CosterKronig probability, and f
0
13
is the small radiative intrashell vacancy transfer probability.
Calculation of the x-ray production cross section from the ionization cross sections
thus involves additional atomic parameters; that is, uorescence yields and fractional
radiative widths in the case of the K shell and uorescence yields, CosterKronig yields,
and fractional radiative widths for the L shell. As to the K fractional radiative widths,
either the experimental data of Salem et al. (1974) or the theoretical values of Scoeld
(1974a) that are derived from DiracHartreeFock (DHF) calculations are considered
accurate within 1%. There is, however, a small failure of the theory in the atomic number
region 22 < Z < 30, where experimenters (Perujo et al., 1987) agree on a deviation of a
few percent. The K uorescence yields are usually taken from Krause (1979). These data
are quite accurate for atomic numbers above Z 20, but the situation for the lighter
elements is less clear (Maenhaut and Raemdonck, 1984; Paul, 1989). For these lighter
elements, one currently prefers the data from Hubbell (1989). For the case of the L x-rays,
Cohen and Clayton (1987) and Cohen (1990) suggest employing the fractional radiative
widths of Salem et al. (1974) and the Krause (1979) uorescence and CosterKronig yields,
and Cohen and Harrigan (1986) used this approach to convert their table of ECPSSR L
ionization cross sections (Cohen and Harrigan, 1985) into a very useful table of produc-
tion cross sections for up to 16 individual L x-ray lines. Campbell (1988), however, ad-
vocates the use of the DHF radiative widths of Scoeld (1974b) and of the DHS
uorescence and CosterKronig yields of Chen et al. (1981) in combination with the
tabulated DHS L ionization cross sections of Chen and Crasemann (1985, 1989).
A very practical alternative to tabulated theoretical ionization and x-ray production
cross sections, particularly with computer calculations in mind, are parameterized or
analytical formulas which are obtained by tting polynomial expressions to theoretical or
empirical cross-sectional data. The equations derived by Johansson and Johansson (1976)
have been widely used by PIXE analysts in the past, but it is now known that they pro-
gressively underpredict cross sections with increasing Z of the target element. More ac-
curate formulas, in which similar functions were often used as in the Johansson and
Johansson equations, have been presented by Paul (1984), Cohen and Clayton (1987),
Miyagawa et al. (1988), Johansson and Campbell (1988), and Sow et al. (1993).
For the proton energy range of 14 MeV typically used in PIXE, the ionization (and
x-ray production) cross sections increase with increasing proton energy and decrease with
Figure 1 K and L shell ionization cross sections in barns (1 barn 10
724
cm
2
) as a function of
proton energy and target atom. The values are theoretical ECPSSR predictions (Cohen and
Harrigan, 1985). (From Johansson and Campbell, 1988. Copyright John Wiley & Sons, Ltd.
Reproduced with permission.)
increasing atomic number of the target atom. This is illustrated in Figure 1, which displays
theoretical K and total L shell ionization cross sections (Cohen and Harrigan, 1985) for
selected target elements. The very steep fall in the K ionization cross section with Z is
particularly notable.
3. Elastic Encounters
Protons or other heavy charged particles that pass near atomic nuclei can be scattered
elastically (i.e., without causing nuclear or atomic excitation). The cross section for the
elastic scattering is strongly dependent on the scattering angle and on the atomic number
(Z) of the scattering nuclide; it decreases with increasing angle and increases with increasing
Z. The energy of the scattered particles also increases with Z. By measuring the elastically
scattered particles, information can be obtained on the elemental composition of the sample
and on the distribution of the elements with depth. This has given rise to the widely used
technique of Rutherford backscattering spectrometry (Chu et al., 1978), which can often be
elegantly employed in combination with PIXE to provide complementary information. On
the other hand, the energetic scattered particles can also cause problems in PIXE. Indeed,
when they enter the Si(Li) detector, their large energy is deposited there, and this gives rise
to serious resolution deterioration and other electronic problems in many x-ray pulse
processing systems (Mingay, 1983). A solution to this problem is to interpose a light-ele-
ment absorber (preferably Be) between specimen and Si(Li) detector (e.g., Maenhaut and
Raemdonck, 1984), but this invariably results in loss of sensitivity for the light elements.
4. Nuclear Reactions
In addition to elastic encounters between incident particles and target nuclei, various in-
elastic interactions or nuclear reactions are possible. They include ( p, g), ( p, p
0
g), and
( p, ag) reactions when protons are used as incident particles. The cross sections for those
reactions vary in a rather irregular way with target nuclide and with incident particle
energy. They generally increase with increasing energy but may exhibit intense resonance
peaks at particular energies. Also, because of the Coulomb barrier, the cross sections are
smaller for the heavier target elements than for lighter ones. By detecting the promptly
emitted g-rays or charged particles for these nuclear reactions, elemental analysis and
depth proling of certain elements is possible. The analytical technique that employs these
possibilities is referred to as nuclear reaction analysis. A comprehensive treatment of this
technique can be found in the Handbook of Modern Ion Beam Materials Analysis (Tesmer
et al., 1995). The technique is also briey presented in Sec. VII.B.
5. Other Interactions
As indicated earlier, the interactions of charged particles and matter occur mainly through
inelastic Coulombic encounters with bound electrons. This results in electron excitation
and ionization but also in secondary phenomena that contribute to the continuous photon
background in the PIXE spectrum. Another interaction which contributes to that back-
ground is projectile bremsstrahlung. All these interactions are discussed in some detail here.
B. Continuous Photon Background Production
1. Electron Bremsstrahlung
The characteristic x-ray lines in a PIXE spectrum are superimposed on a continuum
background that has a strong resemblance to that observed in EPMA. In both cases,
electron bremsstrahlung is the major background component. Although this originates
from primary electron interactions in EPMA, secondary phenomena are at its origin in
PIXE. In the mid-1970s, Folkmann and various co-workers made very signicant con-
tributions to our understanding of the continuum background in PIXE [e.g., Folkmann
et al. (1974a, 1974b), Folkmann (1976)]. This work was later complemented and extended
by Ishii and Morita (1984, 1987, 1988, 1990). It is by now clear that the electron brems-
strahlung in PIXE originates essentially from three processes: quasi-free electron brems-
strahlung (QFEB), secondary electron bremsstrahlung (SEB), and atomic bremsstrahlung
(AB). SEB is formed by a two-step process: the incident particle rst ejects an electron
from a target atom, and the secondary electron is subsequently scattered in the Coulomb
eld of a target nucleus, thus producing the bremsstrahlung. The photon spectrum of SEB
is characterized by an end-point energy T
m
4m
e
E
p
=M
p
, with m
e
and M
p
the electron
and projectile masses and E
p
the projectile energy. Above T
m
, the intensity of SEB de-
creases rapidly. QFEB is emitted when an electron of a target atom is scattered by the
Coulomb eld of the projectile (this is a process in the projectile frame). The QSEB end-
point energy T
r
is equal to T
m
=4. The process AB occurs when a bound target electron is
excited to a continuum state by the projectile and, returning to its original state, emits a
photon. The relative contributions of QFEB, SEB, and AB to the electron bremsstrahlung
background are schematically shown in Figure 2. As can be seen from Figure 2, AB
predominates in the high-energy part of the spectrum (i.e., for photon energies above T
m
),
whereas QFEB becomes the prevailing component at low photon energies (below T
r
). As
both T
r
and T
m
increase linearly with increasing projectile energy E
p
, the PIXE spectrum
(which typically extends from 0 at about 2030 keV) has a quite dierent appearance
depending on the value of E
p
. In addition to E
p
, the matrix composition of the target also
plays a critical role in both the shape and intensity of the electron bremsstrahlung back-
ground. The intensity of this background per unit mass thickness is roughly proportional
to the average Z of the matrix.
The electron bremsstrahlung is emitted anisotropically and is lower at forward and
backward angles than at 90
. For this reason, the Si(Li) detector is frequently positioned at

an angle of 135
in an experimental PIXE chamber.

Figure 2 Schematic representation of the relative contributions of QFEB, SEB, and AB to the
electron bremsstrahlung background. For an explanation of the acronyms and symbols, see the text.
(From Ishii and Morita, 1987; with permission from Elsevier Science.)
2. Projectile Bremsstrahlung
While passing through the target, the incident charged particles may be decelerated in
the Coulomb eld of atomic nuclei and thereby give rise to the emission of projectile
bremsstrahlung (PB). Although this process is negligible within the context of the pro-
jectile energy loss, it contributes to some extent to the continuum background in the PIXE
spectra. For a detailed treatment on PB in PIXE we refer to the papers by Folkmann and
co-workers (Folkmann et al., 1974a, 1974b; Folkmann, 1976). The PB is much less im-
portant than the electron bremsstrahlung and becomes only signicant at photon energies
above 1020 keV.
3. g-Ray Background
The prompt g-rays emitted as a result of nuclear reactions between the projectiles and the
target atoms are generally quite energetic and are therefore far outside the 030-keV
energy range typically observed in PIXE. However, through Compton interactions of
these g-rays with the Si(Li) detector, a wide spectrum of electron energies is generated,
and this, in turn, gives rise to a slowly varying continuum in the PIXE spectrum. This
Compton-scattering background is not predictable in the sense that the bremsstrahlung
background is predictable, as it does not depend on the matrix composition of the
target alone but rather on the presence of particular elements with large cross sections
for nuclear reactions yielding g-rays. Na and, particularly, F are examples of elements
that are often responsible for a noticeable or even signicant g-ray background. A large
fraction of the g-ray background in the PIXE spectrum may originate from nuclear
reactions that do not take place in the specimen but instead in the beam collimators,
Faraday cup, or various other parts of the PIXE irradiation chamber [even the x-ray
absorber placed in front of the Si(Li) detector]. As discussed by Johansson and Campbell
(1988) and Johansson et al. (1995) and briey indicated in Sec. III.B.1, the materials
for the collimators and various other parts of the chamber should therefore be selected
with care.
4. Other Sources of Background
In many cases, intense characteristic x-ray peaks are present in the PIXE spectrum. This is
particularly true when the matrix consists of element(s) with atomic number above
Z 11. These intense peaks and their escape and pileup peaks seriously hamper (or even
preclude) the detection of other elements with characteristic x-rays of similar energy.
Furthermore, incomplete charge collection in the Si(Li) detector and other processes
(Johansson and Campbell, 1988; Johansson et al., 1995) have the eect that each x-ray
peak exhibits low-energy tailing, which typically consists of two major components,
namely an exponential tail and a at shelf with height up to 1% of the peak height.
Consequently, tailing associated with very intense peaks forms a substantial component of
the total background. Because of the intense peaks and associated tails for higher-Z
matrices, and because, in addition, the electron bremsstrahlung intensity increases with
increasing Z of the matrix, PIXE is much more suitable for analyzing trace elements in
light-element matrices than in heavy-element matrices.
When heavy ions are used as projectiles, processes other than those discussed thus
far also contribute to the continuum background. According to Folkmann (1976),
radiative electron capture and molecular orbital x-rays are important.
5. Enhancement of Signal to BackgroundinTotal-Reflection PIXE
The angle of incidence y (i.e., the angle between the incident proton beam and the
specimen surface) in a normal PIXE setup is typically either 45
, 67.5
, or 90
. When a
much smaller angle (035 mrad) is used, the MeV proton (or a-particle) beam can be
totally reected from the surface (Vis and Van Langevelde, 1991). This phenomenon
forms the basis of total-reection PIXE (TPIXE). In TPIXE, characteristic x-rays and
bremsstrahlung (and g-ray) background are only produced from a very shallow surface
layer. This feature can advantageously be used to increase the ratio of the characteristic
X-ray signal intensity to the background when analyzing thin layers on a thick substrate,
such as top layers on Si wafers or dried solutions on a backing lm. In normal PIXE,
the bulk of the Si wafer or the backing lm will also provide a substantial contribution
to the background intensity, whereas this contribution is absent or at least much reduced
in TPIXE. The principle and applicability of TPIXE are similar to those of total-
reection XRF (TXRF). Pioneering work on TPIXE was done by the Amsterdam PIXE
group and further details on the technique can be found in several publications
from that group (Vis and Van Langevelde, 1991; van Kan and Vis, 1995, 1996, 1997;
van Kan, 1996).
III. INSTRUMENTATION
A. Accelerators
The ion beams used for PIXE analysis are produced in an accelerator. The energy range
required, 14 MeV=u, means that relatively small accelerators are sucient. Electrostatic
accelerators or cyclotrons are suitable sources (Scharf, 1989). Electrostatic accelerators are
most commonly used. They may be of a regular or modied Van de Graa type, in which
a high-voltage terminal is charged by a belt or a metal chain. A second type of electrostatic
accelerator uses a high-frequency voltage multiplication stage to charge the terminal, the
ions being accelerated in the electrostatic eld created by the terminal. Cyclotrons have
been employed at some laboratories. These are particularly suitable for PIXE at higher ion
energies (Durocher et al., 1988; McKee et al., 1989; Peisach and Pineda, 1990) and in
certain combinations of PIXE with complementary techniques, such as particle elastic
scattering analysis (PESA) or forward alpha scattering (FAST) (Cahill et al., 1984).
In most analytical situations in which PIXE is applied, the choice of accelerator is
governed by access to a particular machine rather than by free choice. When a dedicated
accelerator can be selected, however, usually a single-ended or tandem electrostatic ma-
chine of 23 MV is chosen. Such accelerators may also favorably be employed for a
combined use of ion implantation and ion-beam analysis, including PIXE.
Certain types of analysis, such as analyses by microbeam techniques, impose special
requirements on ion source brightness, energy stability, beam emittance, and minimum
scattering of the ion beam. Such requirements may play an important role in selecting an
accelerator.
It is often stated that the need for an accelerator in PIXE is a major drawback, for
reasons or both technical complexity and economy. Although such objections contain
some truth, it should be pointed out that the prices of small electrostatic accelerators are of
the same order as those for complex traditional analytical equipment, such as mass
spectrometers or electron microscopes, and that a comparable technical skill is required
of the operator. It is therefore unjustied to rule out the PIXE method for such reasons.
B. BeamHandling and Target Chambers
1. Macro-PIXEinVacuum
Commercially available vacuum chambers used as scattering chambers in nuclear physics
experiments are generally not well suited for PIXE. Their shapes and dimensions hamper
obtaining large solid angles for detection and introducing multispecimen holders and
sample changers. As a consequence, few existing PIXE chambers are of commercial origin.
There are exceptions to this rule, however, and certain chambers have been built entirely
from commercially available components.
Figure 3 shows the design and principal components of a hypothetical typical
setup for macro-PIXE analysis. In the following, the details of such a system are outlined.
The ion beam emerging from the accelerator rst passes through an analyzing
magnet, which sorts out the ions of the correct mass and velocity, and is then normally
focused by electrostatic or magnetic quadrupole lenses onto the specimen.
A typical experimental facility for macro-PIXE analysis employs a system for pro-
ducing a homogeneous beam so that the specimen is evenly irradiated. This is required for
quantitative analysis of heterogeneous samples. There are various methods of achieving
this:
1. Focusing the beam onto a scattering foil, which distributes the ions homo-
geneously over the cross section selected by a diaphragm. The foil material
should be able to withstand the ion beam for long times. It is often made of thin
metal, such as gold, which is an excellent scatterer with low stopping power for
the ions.
2. Rastering the beam over the sample by electrostatic deection, for example.
This does not give a genuinely homogeneous distribution and may, therefore,
produce high instantaneous count rates in heterogeneous samples. On the other
hand, this method has the advantage of relatively low loss of beam intensity,
whereas such a loss may be more than 90% in the case of method 1.
3. After the initial alignment of the beam, straightforward symmetric defocusing by
the quadrupole magnets.
After homogenization, the beam is dened by a pair of collimators (diaphragms), which
are normally circular with diameters between 1 and 10 mm and placed approximately
Figure 3 Typical experimental arrangement for routine PIXE, with detectors for x-rays and
g-rays. Normally, the collimators can be changed between 1 and 10 mm diameter, and the x-ray
absorber holder would contain 510 different filters.
100200 mm apart, just before the entrance to the irradiation chamber. The collimator
material should preferably withstand bombardment by the ions over long periods and
produce low background in the PIXE spectra. This can be achieved by using a material
containing nuclei with low cross sections for producing g-rays at the ion energy interval in
question. Common choices of collimator materials are tantalum and graphite (Johansson
et al., 1995). To measure the beam uence on the target accurately, the collimators should
be grounded and electrically shielded from the irradiation chamber in which the target is
placed, and secondary electrons generated at these collimators should be prevented from
entering the target chamber. A target holder denes the proper position of the sample
during analysis. In a typical setup for PIXE analysis, in vacuo, several samples are si-
multaneously inserted into the vacuum, so that a high sample throughput is facilitated.
The normal slide frame format (565 cm
2
) is a standard target frame in many laboratories,
and often 3680 target frames are contained in vacuum. The samples are irradiated at an
angle suitable to detect the x-rays, and often the detector views the sample from a
backward angle to 135
or more, as this produces higher peak-to-background ratios in the

PIXE spectra (see Sec. II.B.1).
In contrast to energy-dispersive XRF (EDXRF) spectra, PIXE spectra have most
of their x-ray intensity in the low-energy region, so that the spectral shape can ad-
vantageously be modulated by placing an x-ray absorber between sample and detector.
The aim of absorbers invariably is to reduce or eliminate unwanted continuum back-
ground and=or intense x-ray peaks and their associated pileup peaks and at the same time
to allow bombardments at higher beam intensities, so that the elements of interest can be
measured in shorter bombardment times and with fewer spectral interferences. The ab-
sorbers are usually made from organic material (e.g., Mylar) or from light-element metal
foils (Be and Al). Plain absorbers are employed if complete elimination of the low-energy
part of the spectrum is desired. In many cases, however, it is preferable to allow a certain
fraction (e.g., a few percent) of the low-energy x-rays to pass on onto the detector. This
can be realized elegantly by resorting to pinhole absorbers (usually called funny lters
within the PIXE community). Also, more sophisticated designs consisting of a combina-
tion of various layers with dierent thicknesses and pinhole diameters have been used
(Carlsson and Akselsson, 1981). Figure 4 illustrates the eect of some absorbers on the
appearance of the PIXE spectrum for a biological reference material (Maenhaut, 1990a).
In the acquisition of the top spectrum, a funny lter, consisting of a 52-mm-thick Be foil
and a 324-mm Mylar lter with 5.54% hole, was placed in front of the detector, and even at
a beam current of 10 nA, the count rate exceeded 2000 cps. For acquiring the bottom
spectrum of Figure 4, a 660-mm Mylar absorber was interposed between specimen and
detector. This had the eect a allowing a beam current of 150 nA, and the count rate
remained below 1000 cps. If one wants to analyze samples with high concentrations of
elements whose lines severely interfere with nearby lines of the elements of interest, it is
useful to resort to bandpass absorbers. For instance, in the PIXE analysis of steel, a
chromium absorber selectively suppresses the strong FeK lines (Ahlberg et al., 1975b).
Other examples in which such complex absorbers are advantageous are the analysis of
metal alloys in archaeology [e.g., of bronzes (Swann, 1983; Swann and Fleming, 1990)] and
various analyses in material studies.
When one is interested in measuring the light element (Z<13) by PIXE, only a very
thin x-ray absorber may be used, and for the very light elements, a windowless detector or
a detector with an ultrathin polymer window (Quantum X-ray detector, Kevex Corp.,
1987) would even be advisable. However, as indicated in Sec. II.A.3, bombardment of a
sample with charged particles also gives rise to backscattered particles, and a fraction of
these may penetrate into the Si(Li) detector and cause problems. Hence, it is advisable to
use an absorber that is suciently thick to stop all scattered particles, but this hampers or
precludes the detection of those light elements. According to Musket (1986) and Nejedly
et al. (1995), placing a magnetic deection trap between the sample and the detector crystal
is a viable alternative to an absorber for removing the scattered ions. However, the
installation of such system also results in a lower solid angle of detection.
The Si(Li) detectors used for PIXE are the same as those in EDXRF (see Chapter 3).
They typically have a sensitive area from 10 to 80 mm
2
, but this area is often reduced by
inserting an x-ray collimator in front of the detector. The aim of such collimator is to
minimize the low-energy peak tailing that results from incomplete charge collection at the
edge of the detector crystal.
In TPIXE, the special geometry with a very small angle of incidence allows one to
position the x-ray detector very close to the specimen (van Kan and Vis, 1997), similarly as
in TXRF. Consequently, a very large solid angle can be obtained, thereby increasing the
sensitivity. This increased sensitivity in combination with the reduced bremsstrahlung
background is at the origin of the low limits of detection in TPIXE (van Kan and Vis, 1997).
The ampliers=pulse processors in energy-dispersive x-ray spectroscopy require large
time constants for optimum energy resolution (see Chapter 3). Unfortunately, large time
constants also imply that pulse pileup already becomes a serious problem at relatively low
count rates. It is therefore common practice to incorporate an electronic pileup rejector
Figure 4 PIXE spectra for a 5-mg=cm
2
NIST bovine liver specimen. Incident proton beam of
2.4 MeV. Top spectrum: taken with funny filter (see text); beam current 10 nA, x-ray count rate
2200 cps, and preset charge 20 mC. Bottom spectrum: taken with a 660-mm Mylar absorber; beam
current 150 nA, count rate 900 cps, and preset charge 200 mC. The ordinate scale applies to the top
spectrum. All marked peaks are K lines (Ka and Kb). Most of the unmarked peaks in the top
spectrum are sum peaks. (From Maenhaut, 1990a.)
and its associated dead-time correction circuitry in the pulse processing chain. Such so-
lution reduces the throughput of signals to the analyzer (i.e., it decreases the ratio of
output signal count rate to beam current) and this forms a drawback when analyzing
samples that deteriorate during bombardment. To minimize beam-induced damage during
PIXE analysis, an on-demand beam excitation system is recommended. Such a system
employs a set of deection plates placed in the beam path upstream of the sample; when an
x-ray event is detected, the beam is deected immediately and then held o until the event
has been processed (Malmqvist et al., 1982). It should be indicated here that pileup peaks
(or sum peaks) are not entirely eliminated by pileup rejectors or on-demand beam excita-
tion, because such systems have a nite pulse pair resolving time or beam-switching time.
In PIXE of thin specimens, the ions pass through and are dumped in a Faraday cup
(see Fig. 3) for charge integration. To minimize the g-ray background originating from
nuclear reactions in the Faraday cup, long cups in which the particles are collected far
from the detector are preferable. Furthermore, the escape of secondary electrons from the
cup as well as the entrance of secondary electrons from the specimen should be prevented
by placing a negatively biased ring in from of the cup. The charge integration itself is
accomplished by connecting the Faraday cup to a sensitive current integrator=digitizer.
When the samples are thick enough to stop the ions, the beam current must be measured
either on the whole irradiation chamber or through some indirect approach. One possible
method is to place a thin foil in the beam path upstream of the target and to measure the
intensity of the particles scattered from it with a surface barrier detector (Mitchell et al.,
1980). Another, related method uses a beam chopper (e.g., a thin metal strip, which
periodically passes through the beam) (Volvo et al., 1983).
The bombardment of an insulating thick (or semithick) specimen in vacuum gen-
erally gives rise to charge buildup, and the specimen may reach a positive potential of up
to several tens of kilovolts before breakdown and sparking. The high potential accelerates
electrons up to tens of kiloelectron volts, and as a consequence, a huge bremsstrahlung
background is produced in the PIXE spectrum. The peak-to-background ratios then de-
crease signicantly (Ahlberg et al., 1975a). To avoid this, various methods can be used:
1. Increased pressure in the chamber (Ahlberg et al., 1975a)
2. Thin carbon coating of the specimen (Cabri et al., 1985), as is commonly done in
EPMA
3. Placing a thin carbon foil just in front of the sample (Chaudri and Crawford,
1981)
4. Spraying with electrons from an electron gun (Ahlberg at al., 1975a)
5. Using strong permanent magnets (Mingay and Barnard, 1978)
These methods either avoid the buildup of a high potential by conduction of the positive
charge or by producing electrons to neutralize the positive charge or avoid the eects from
the electrons impinging on the sample (magnets).
In addition to the equipment used for quantitative PIXE analysis, target chambers
also often include equipment necessary for the complementary IBA techniques presented
in Sec. VII, such as surface barrier detectors of measuring charged particles or Ge de-
tectors for measuring prompt g-rays.
2. NonvacuumMacro-PIXE
As has already been indicated, it is sometimes advantageous to use atmospheric pressure or
moderate vacuum instead of high vacuum during analysis (Williams, 1984). The advantages
are that the heat conductivity is increased and the target temperature decreased, the charge
is conducted from the target, and the vacuum requirements are less, thus making it easier to
design a low-cost chamber. Because the accelerator requires a good high vacuum, the ion
beam must be extracted into the moderate vacuum or atmospheric pressure region through
a thin exit foil. The beam eventually deteriorates this foil, and, therefore, its material has to
be carefully selected. The best choice is the polyimide foil Kapton, which withstands high
intensities and a high radiation dose before mechanical breakdown. Supporting the foil by a
carbon grid and direct ow of liquid-nitrogen-cooled helium gas allows the use of high
beam intensities over extended time intervals (Hyvonen-Dabek et al., 1982). The chamber
gas is normally helium or nitrogen. In addition to its better cooling properties, helium
produces less bremsstrahlung than nitrogen. Some x-ray detector windows are not leak
proof to helium, however, and this has disastrous consequences for the cryostat vacuum
unless the detector is separated from the chamber gas by an additional window.
The choice of chamber atmosphere is determined by the objectives of the analysis
and by the samples to be analyzed. A rather low pressure of helium gas, for example,
suces to improve the heat conductivity and to reduce thermal losses of elements or
compounds (Martinsson, 1987). On the other hand, an external beam in air is needed when
large objects are to be analyzed without sectioning of subsampling. This is very important
in archaeology and art science, for example. The disadvantages of bombardment in air are
that there is a danger of sample oxidation during irradiation and interfering argon x-ray
lines are present in the spectrum. The strong argon lines may also be used to monitor the
beam uence, however, which is otherwise dicult to do in nonvacuum PIXE. In fact, one
generally relies on some indirect method of beam current measuring (Mitchell et al., 1980;
Volkov et al., 1983); although with special precautions, it is possible to measure the beam
current directly (Wookey and Rouse, 1987).
The advantages of using higher pressure during irradiation have been demonstrated
in various applications. For example, in studies on volatile organic compounds, using a
combination of PIXE and complementary techniques (PESA), it was shown that sig-
nicant losses of certain constituents occurred when bombarding in high vacuum, whereas
the losses were insignicant for bombardments of similar beam intensity in helium at a
pressure of 100 torr (Martinsson, 1987).
When using external beams, some safety precautions are necessary. Besides the
obvious hazard of direct exposure, there is the potential exposure to the scattered beam
and the activation of the air to form positron-emitting radionuclides. These hazards are
discussed in detail by Doyle et al. (1991) in a review of external beam work with various
analytical techniques.
3. Nuclear Microprobes
In nuclear microprobe or micro-PIXE analysis, the particle beam is collimated and=or
focused down to dimensions in the range of 150 mm. With the regular equipment used in
accelerator-based ion-beam analysis, beam sizes down to typically a few tenths of a milli-
meter diameter are easily obtained, but to produce a genuine microbeam, specially de-
signed equipment is required.
The simplest way of producing a microbeam is to employ a pinhole collimator
(Horowitz and Grodzins, 1975). For very small collimator sizes, however, the beam in-
tensity obtainable is much too low for practical use. In addition, a substantial fraction of
the ions are scattered at the edge of the collimator, and this gives rise to a halo (with an
intensity of several percent of the beam current) around the central beam. In most micro-
PIXE systems developed since the early seventies, collimation is therefore combined with
an electrostatic or magnetic demagnication system, such as quadrupole doublets, triplets,
quadruplets, or superconducting solenoids (Legge, 1997). The initial collimation in an
object aperture normally provides a beam with dimensions of 5100 mm, and this beam is
then demagnied by a factor of 5100. New-generation microprobes with enhanced de-
magnication power (2003006) are under development in a few laboratories (Breese
et al., 1999). The best systems currently available are able to produce a spatial resolution
of about 0.5 mm at the specimen while maintaining an ion current that is useful for PIXE
analysis ( >100 pA). Figure 5 shows the layout of a nuclear microprobe. Although the
exciting particles form the only dierence between micro-PIXE and energy-dispersive
EPMA, much better peak-to-background ratios and, consequently, lower detection
limits are obtainable by micro-PIXE. This is illustrated in Figure 6, where x-ray spectra
for a biological specimen obtained by both techniques are compared. The much better
peak-to-background ratio, particularly for the heavier elements (Z>20), justies the use
of the much more complex analytical equipment of the nuclear microprobe. In addition,
the high resolution of the nuclear microprobe makes it possible to combine PIXE with
several other analytical techniques for imaging and quantitative analysis.
As shown in Figure 5, the normal components of a nuclear microprobe comprise the
following:
1. A particle accelerator (normally electrostatic) with a very bright ion source
2. Precision collimators
3. Magnetic or electrostatic quadrupoles for focusing
4. A scanning system to raster the beam over the sample, as in a scanning electron
microscope
The detection system is, in principle, identical to that for macro-PIXE but usually includes
complementary surface barrier detectors for scattered particles and for particles emitted in
nuclear reactions to extend the analytical arsenal (Malmqvist, 1995a). Sometimes, a de-
tection system for secondary electrons (Kneis et al., 1982) and=or a detection system for
near-visible light, ionoluminescence (Yang et al., 1993) are also included, for imaging
of the specimen (see Sec. VII.C). Facilities for accurate positioning of the beam on the
specimen area of interest are also required. Hence, an optical viewing system with high
magnication and good resolution is needed, as well as a precision sample holder con-
trolled by stepping motors or piezoelectrical crystals with a position accuracy below 1 mm.
The data are acquired in dedicated computer systems that can produce both quantitative
results and qualitative elemental maps.
Various types of object collimators can be used. The collimator design should
minimize the contribution of scattered ions to the specimen. Such devices with precision-
polished cylinder surfaces (Fischer, 1988) to dene the ion beam and local or remote
control of the collimator width are commercially available and are employed in most
nuclear microprobe setups. Other laboratories prefer to use xed apertures of the same
design as for electron probes (Legge et al., 1982). The precision parts of the collimators are
normally protected against beam damage and excessive heating by adding a slightly larger
precollimator in which most of the energy is dissipated.
Each conguration of demagnication devices has its advantages and drawbacks.
The rather complex Russian quadruplet, which was used in the rst micro-PIXE system at
Harwell (Cookson et al., 1972), produces a symmetric image but is dicult to align
mechanically and has an increased risk of parasitic aberrations. Because of its simpli-
city, some laboratories use the doublet conguration, although it requires rectangular
collimation for obtaining a symmetric image. The most common system, at present, is the
commercially available triplet system from Oxford Microbeams
TM
Ltd. (Oxford, UK).
When more than two quadrupoles are used, two magnets are connected in series to the
same current supply. Whatever conguration is used, the current supplies should be very
stable ( <10
74
), to reduce distortions due to chromatic aberrations.
The image size at the specimen is easily determined from rst-order calculation. For
small apertures, however, the rst-order calculation does not suce and second- and third-
Figure 5 Base components (not to scale) of a typical nuclear microprobe system: (a) electrostatic
particle accelerator; (b) primary object aperture; (c) secondary collimator; (d) focusing system;
(e) scanning system; (f ) video camera and microscope; (g) surface barrier detector for scattered
particles; (h) x-ray detector; (i) specimen; ( j) surface barrier detector for transmitted particles
(STIM); (k) front-end CAMAC with data bus; (l) main computer and display with elemental map.
order calculations are required. The lens aberrations can be calculated if the details of the
conguration are known. For more information on this subject, the reader is referred to
the book by Grime and Watt (1984), which provides a comprehensive compilation of
various magnetic quadrupole systems. It should be noted here, that among the intrinsic
aberrations, the third-order, spherical (angular) aberrations are the dominating ones in
most nuclear microprobes. Hence, some systems make use of octupole magnets to reduce
the spherical aberrations (Jamieson and Legge, 1988). Other important factors are the
mechanical precision (to reduce parasitic aberrations) and, particularly, the rotational
defects in the magnetic elds (these can severely distort the image).
To allow full use of its powerful analytical capabilities, a nuclear microprobe setup
should include a scanning system for rastering the ion beam over the specimen surface.
Figure 6 X-ray spectra from a thin biological specimen (human brain) obtained with electron (a)
and nuclear microprobe (b) excitation. Note the very large difference in peak-to-background ratio,
particularly from about 3 keV (channel 100) up. (From Johansson and Campbell, 1988. Copyright
John Wiley & Sons, Ltd. Reproduced with permission.)
The scanning system could be installed before focusing ( predeection), but such a system
deects the beam out of the optical axis and could therefore, for large deection angles,
signicantly increase the aberrations. By proper selection of the position of deection,
however, the beam can be made to pass through the optical center of the lens system so
that the aberrations are minimized. The scanning system can also be installed after the
demagnication lenses. Because of the short distance between lens and specimen, however,
scanning systems using electrostatic deection plates require a high electric eld (with
concomitant risk of electric discharges) to obtain a suciently large deection amplitude.
An alternative is to employ magnetic scanning. By using scanning coils with ferrite cores,
a reasonably large amplitude and a scanning frequency of more that 5 kHz can be ob-
tained (Tapper et al., 1988). Such systems provide a good compromise between scanning
speed and amplitude. The scanning system is usually computer controlled and connected
to the data acquisition system (see Sec. III. C.2).
The detailed design of the irradiation chamber for the nuclear microprobe is beyond
the scope of this chapter. We will therefore limit ourselves to giving some recommenda-
tions for the essential components. The sample-positioning system may be a commercially
available x-y-z precision translator as designed for scanning electron microscopes. The
sample holder should preferably take many samples to avoid the need for frequent
opening of the vacuum chamber. The microscope used for viewing the specimen should
have a magnication of 2004006 and preferably be equipped with a zoom lens. In ad-
dition to the x-ray detector, surface barrier detectors should be entered in the forward and
backward directions. Such detectors are needed for extending the elemental coverage and
for determination of the specimen thickness. The specimen thickness is of paramount
importance for PIXE quantication in thin and semithick samples (see Secs. IV.B. and
IV.C). The specimen thickness may also be provided by measuring the energy loss in each
specimen pixel, as is done in scanning transmission microscopy (STIM) (Bench et al.,
1992). Finally, it is recommended to install a secondary electron detector and to allow for
detection of visible light to facilitate imaging of the specimen surface.
A good high vacuum is crucial to reduce residual gas scattering that would de-
grade the beam quality. A high vacuum close to and in the specimen chamber is
maintained by direct pumping with oil diusion, turbomolecular, or cryopumps. Al-
though they have many advantages, the two latter types may transmit vibrations and
magnetic disturbance to the demagnication lens system and to the specimen holder.
Hence, it is crucial to arrange those pumps to minimize such eects. The focusing of
small beams is adversely aected by these or other vibrations. It is therefore common to
place the whole microprobe system on a rigid optical bench on a fundament with good
damping. The accurate positioning of the optical elements on this bench is realized by
high-precision mechanical controls. Furthermore, to avoid the eects of the Earths
magnetic eld and stray elds from surrounding equipment, beam tubes are sometimes
shielded by m-metal foils.
As is the case for macro-PIXE, micro-PIXE may also be carried out under non-
vacuum conditions (see Sec. III.B.2). Because of scattering of the beam by the gas, however,
nonvacuum micro-PIXE is only feasible for moderately small beam sizes (20100 mm).
After collimation and=or focusing, the beam is passed to the nonvacuum region through a
pinhole or an exit foil. In the rst approach, the high vacuum in the beam line is maintained
by means of dierential pumping. If the spatial resolution requirements are not too high,
the nonvacuum micro-PIXE technique is rather straightforward and simple to use. It is very
useful when examining large samples or sensitive art objects, such as bronze gures and
ancient documents, and may, hence provide unique information (Swann, 1983).
C. Data Acquisition
1. Macro-PIXE
The data acquisition systems used in PIXE show great similarity with the EDXRF data
acquisition systems discussed in Chapter 3. For x-ray detection, a high-resolution solid-
state detector is virtually always employed. This could be either a Si(Li) or high-purity Ge
(HPGe) detector, but the former is highly preferable in most PIXE work. Ge detectors give
rise to much more intense escape peaks than Si(Li), and this can render the spectra un-
acceptably complex. The higher detection eciency of Ge for energies above 20 keV is not
very useful in 14-MeV PIXE because of the very rapid decrease in K ionization cross
sections with increasing Z (see Sec. II.A.2). On the contrary, the higher detection eciency
may be a disadvantage, as the background contribution resulting from Compton-scattered
g-rays is larger than with Si. Most PIXE chambers contain only one Si(Li) detector for
x-ray detection. However, to improve the sensitivity for the heavier elements while re-
taining the capability of measuring the light elements during the same bombardment, the
use of two Si(Li) detectors has been advocated (Wa tjen et al., 1990), and such a system is
now employed in an increasing number of PIXE facilities (Johansson et al., 1995). The
second Si(Li) detector, used for measuring the heavier elements, is provided with a thick
absorber to cut down the high count rate from the light elements and has a larger solid
angle of detection than the rst Si(Li). As an alternative to such a second Si(Li), a Ge x-ray
detector is well worth considering. In addition to the Si(Li) detector(s) for x-rays, PIXE
chambers generally also contain detectors for the complementary IBA techniques (i.e.,
surface barrier detectors for scattered particles or for particles resulting from nuclear re-
actions and a Ge detector for measuring prompt g-rays). Hence, the acquisition system
must include several analog-to-digital converters. Furthermore, because the spectral in-
tensity in PIXE is proportional to the number of incident particles, the measurements are
generally carried out for a preset charge (or some parameter related to it in the case of
indirect beam current measurement) instead of for a preset live time. The charge (or re-
lated parameter) is usually measured by an external counter, and this unit forces the data
collection to stop when its preset is reached. For acquiring the spectra, either a personal-
computer (PC)-based multichannel analyzer (MCA) or a classical MCA may be used, but
the latter should be interfaced to a computer so that the spectra can be saved on disk and
evaluated by appropriate computer programs.
2. Micro-PIXE
The data acquisition in scanning nuclear microprobe analysis is more complex than in
macro-PIXE and is invariably controlled by computers. As in more advanced systems for
macro-PIXE, signals from several detectors must be handled, but, in addition, the posi-
tional information must be recorded. In Figure 7, a typical modern design of a data
acquisition system is outlined (Elfman et al., 1997). Two main principles are employed:
on-line display of elemental maps and event-by-event acquisition with o-line sorting of
data. Sometimes, a combination of both is used. Elemental maps on-line are obtained by
setting energy windows for the characteristic x-ray lines of interest (and for background
regions) and reading out the count rate within each window for each position of the beam.
The line intensity values (with or without background subtraction) for each beam position
(pixel) are stored in a computer, and maps are generated on-line with intensity modulation
by gray or color codes. This technique gives good feedback, so, that, during analysis, one
can concentrate on the more interesting regions of the specimen. This is quite important
Figure 7 Schematic outline of a comprehensive data acquisition system for a nuclear microprobe including several detectors. A CAMAC system is
used as front end and several personal computers interact with the system control and the data acquisition. (Courtesy of M. Elfman.)
in micro-PIXE analyses, because they are often very time-consuming. However, a
disadvantage of on-line elemental mapping is that truly quantitative information on the
elemental concentrations is normally not provided. However, in a further development of
this technique, dynamic analysis, on-line quantitative elemental maps are produced (Ryan
and Jamieson, 1992). Using a spectral decomposition transform, that closely approximates
the time-consuming nonlinear least-squares method, quantitative PIXE analyses can be
performed in live time, continuously updating as the data accumulate. This dynamic
analysis approach is able to accumulate on-line PIXE elemental maps that are inherently
overlap-resolved and background-subtracted.
In the event-by-event or list-mode type of analysis, data acquisition is normally
handled by the same computer that controls the beam scanning. When an event (x-ray,
scattered particle, g-ray, or secondary electron) is registered in a detector, the computer is
triggered, and the detector label, the energy of the radiation, and the coordinates of the
pixel where the event occurred are recorded on disk. The same procedure is repeated for
each event detected. It is also possible to record the dead-time losses and the accumulated
charge for each pixel. The data obtained for all events can be sorted or analyzed o-line in
any selected manner. The use of modern very powerful personal computers or work-
stations has facilitated rapid evaluation of spectra generated from the data in each pixel,
group of pixels, or whole maps, so that quantitative results of high accuracy may be
obtained.
IV. QUANTITATION, DETECTIONLIMITS, ACCURACY, ANDPRECISION
A. Analysis of PIXE Spectra
Once a PIXE spectrum has been acquired, the rst step in the quantitation is the extraction
of the net peak intensities for the elements of interest. This task is similar to that to be
carried out in all other x-ray emission analysis techniques with energy-dispersive detection,
and we therefore refer to Chapter 4 for a detailed discussion on the subject. By far the
most common spectrum analysis approach in PIXE is to model the spectrum by an analytic
function. This function includes modied Gaussians to describe the characteristic x-ray
peaks and a polynomial or exponential polynomial to represent the underlying continuum
background (Campbell et al., 1986). An alternative to analytical background modeling is
to use some kind of mathematical background removal method (Maxwell et al., 1989,
1995). A third approach is to employ a peak-clipping algorithm to remove all peaks from
the measured spectrum, thus generating a numerical background spectrum. The model
spectrum is then built by adding Gaussians to this background (whose overall height is a
single variable) (Ryan et al., 1990a, 1990b).
Because of the low continuum background in PIXE (particularly when compared to
energy-dispersive EPMA), the range of peak heights in a PIXE spectrum can be up to ve
to six orders of magnitude. This leads to PIXE spectra that often exhibit ne details, such
as escape and sum peaks, and low-energy tailing for intense peaks. Whereas escape peaks
and low-energy tailing may also be quite important in EDXRF spectra, sum peaks tend to
be a minor problem in the latter, because the most intense peaks are generally located in
the upper part of the spectrum. In PIXE, however, the most intense peaks are usually
situated in the lower part of the spectrum (this results from the fact that cross sections
increase with decreasing Z), and sum peaks therefore show up when high count rates are
used during spectrum acquisition. An illustration of the importance of sum peaks is given
in Figure 8. The presence of the many ne details in the PIXE spectra places stringent
requirements on the spectrum model. As far as the modeling of the sum peaks is con-
cerned, this is generally done by representing them by a single pileup element, according to
an approach rst proposed by Johansson (1982). Despite the many ne details, accurate
modeling of PIXE spectra is quite feasible, as was demonstrated in an intercomparison
exercise of ve dierent PIXE spectrum analysis programs (Campbell et al., 1986). It is
also illustrated by the good agreement between modeled and experimental spectrum in
Figure 8.
B. Quantitation for Thin Specimens
When protons of 14 MeV are used in PIXE, elements with Z up to about 50 are generally
determined through their K x-rays (typically the Ka line), and the heavier elements are
measured through their L x-rays (La line). The basis for a quantitative analysis is that
there is a relationship between the net area of an elements characteristic K or L x-ray line
in the PIXE spectrum and the amount of element present in the sample. For proton
bombardment and an innitely thin specimen (by this is meant a specimen that is su-
ciently thin so that matrix eects become negligible), the relation is given by
Y
p
Z
N
0
s
X
pZ
E
0
E
p
NC
Z
rt
A
Z
sin y
9
Figure 8 PIXE spectrum obtained for a NIST orchard leaves specimen [incident proton energy
2.4 MeV, funny filter in front of Si(Li) detector, x-ray count rate 2200 cps]. The marked peaks are K
lines, except where indicated otherwise. The unmarked peaks between FeKb and CuKa are sum
peaks. The dots represent the experimental spectrum, the curve through the dots is the modeled
spectrum, as obtained from a nonlinear least-squares fit, and the dashed line is the modeled
background. (From Maenhaut, 1990a.)
where Y
p
Z is the number of counts in a characteristic x-ray line p of the analyte element
with atomic number Z, N
0
is Avagadros number, s
X
pZ
E
0
is the x-ray production cross
section for line p at the incident proton energy E
0
, E
p
is the absolute detection eciency
(including the solid angle) for x-ray line p, N is the number of incident protons, C
Z
is the
concentration of the analyte element in the specimen, r is the specimen density, t is the
specimen thickness, A
Z
is the atomic mass of the analyte element, and y is the angle be-
tween the incident proton beam and the specimen surface. In formulating Eq. (9), it is
implicitly assumed that the specimen is uniform and that the beam size is smaller than the
specimen area. For a formulation of the situation where the beam size is larger than the
specimen area, the reader is referred to Johansson and Campbell (1988).
In deriving the analyte concentration from its x-ray yield, several approaches are
possible (Johansson and Campbell, 1988). One can solve Eq. (9) for C
Z
, and thus employ
the absolute or fundamental parameter method. This requires accurate knowledge of all
parameters involved. The most critical parameters are the x-ray production cross sections
and the absolute detection eciency. The accuracy of the x-ray production cross sections
was addressed in Sec. II.A.2. The absolute detection eciency of a Si(Li) detector has been
the subject of numerous research papers. Its determination poses no problems for photon
energies in the 530 keV region (Campbell and McGhee, 1986), in which use can be made
of accurate long-lived radionuclide standards and the relative detection eciency can be
accurately modeled. Unfortunately, no such standards are available for the 15 keV range,
where there is a steep decrease in eciency. The best solution for characterizing this region
is to use a strong radionuclide source in combination with secondary uorescers, and some
laboratories (Denecke et al., 1990; Lepy et al., 1992) have developed carefully calibrated
devices for this purpose.
Because of the diculties with the absolute quantitation method, many PIXE
workers prefer to rely on a relative approach, and they calibrate their experimental PIXE
setup using thin lm standards [e.g., Johansson et al. (1981), Maenhaut and Raemdonck
(1984), Borbe ly-Kiss et al. (1985)]. This method yields so-called thin-target sensitivities
k
p
Z which combine several of the quantities of Eq. (9):
k
p
Z
N
0
s
X
pZ
E
0
E
p
A
Z
sin y
10
The units of k
p
Z are x-ray counts per unit proton charge (usually mC) and per mg=cm
2
.
Both the absolute and relative quantitation methods generally require the knowledge
of the specimen mass thickness if the results are to be obtained as concentrations in the
specimen material. As discussed by Johansson and Campbell (1988), there are a variety of
ways to determine the specimen thickness. They include direct weighing, thickness mea-
surement via ancillary photon transmission measurements, thickness measurement via
energy loss of transmitted protons, and energy loss determination by means of a beam
stop.
The requirement for knowing the specimen mass thickness can be avoided by spiking
the sample with a known amount of an internal standard element before specimen pre-
paration. Such spiking is easily done for liquid samples and is also feasible when one deals
with powdered solid materials, but it is, of course, impossible in the nondestructive ana-
lysis of solid samples. Another advantage of spiking is that the number of incident par-
ticles (beam uence or preset charge) need not be measured accurately. Indeed, when a
spike is used, the quantitation involves division of Eq. (9) for the analyte element by the
same equation for the internal standard, so that the number of incident particles N as well
as the mass thickness rt cancel out.
C. Quantitation for Specimens of IntermediateThickness and for Infinitely
Thick Specimens
In practice, specimens are rarely thin enough that matrix eects are entirely negligible. For
example, in 2.5-MeV-proton PIXE of a 0.5-mg=cm
2
-thick US National Institute of
Standards and Technology (NIST) bovine liver specimen, and when basing the analysis on
the Ka x-ray line, the matrix correction factor is 1.031.05 for the elements K to Sn, and it
increases strongly with decreasing Z for the light elements (e.g., it is 1.1 for S, 1.2 for Si,
and 1.5 for Mg).
For specimens of intermediate thickness and for innitely thick specimens (the latter
are specimens that are thicker than the particle range), Eq. (9) has to be replaced by
Y
p
Z
N
0
E
p
NC
Z
A
Z
Z
E
f
E
0
s
X
pZ
ET
p
E
SE
dE 11
where E
0
ad E
f
are the incident proton energy and the energy of the protons after passage
through the target (E
f
0 for an innitely thick specimen), respectively, E is the proton
energy, T
p
E is the transmission of the x-rays from successive depths in the specimen, and
SE is the matrix stopping power. T
p
E is itself given by
T
p
E exp
m
p
sin y
sin f
Z
E
E
0
dE
SE
0
B
@
1
C
A 12
with m
p
the mass attenuation coecient for line p in the sample matrix, and f the angle
between the specimen surface and the specimendetector axis (i.e., the x-ray takeo angle).
It should be noted here that the relation between the analyte element line intensity
Y
p
Z and the concentration C
Z
, as expressed by Eqs. (11) and (12), does not include
secondary or tertiary uorescence enhancement eects. Detailed treatments of these eects
were given by Campbell et al. (1989, 1993). Although enhancement eects are less pro-
nounced in PIXE than in XRF and are, in fact, often negligible, secondary uorescence
should be accounted for when the analyte elements are lighter than the matrix elements.
For example, in 3-MeV-thick target PIXE of stainless steel (with y and f both equal to
45
), the CrKa intensity is raised by about 50% as a result of the secondary uorescence
from the FeK x-ray lines (Campbell et al., 1989).
As for thin specimens, several quantitation approaches are possible for thick spe-
cimens. If one relies on the fundamental parameter approach and thus solves Eqs. (11) and
(12) for C
Z
, other parameters are needed in addition to those already required for the thin-
specimen case. These additional parameters are m
p
and SE, the mass attenuation co-
ecient for line p in the sample matrix and the matrix stopping power, respectively. The
values of those parameters for the sample matrix can be obtained from those for the
matrix constituents by employing Braggs additivity rule, as already indicated in Sec.
II.A.1 for the matrix stopping power. Such calculations require knowledge of the matrix
composition and databases for the mass-attenuation coecients in the various elements
and for the elemental stopping powers. The stopping power database and its accuracy
were dealt with in Sec. II.A.1. The problem of selecting an accurate database for the mass-
attenuation coecients is the same as in all other x-ray emission techniques and will not be
discussed here. The matrix elemental composition places the major burden on the calcu-
lations and usually contributes most to the uncertainty in the calculated m
p
and SE
values for the sample matrix. For heavier-element matrices, in which all matrix elements
are detected in the PIXE spectrum, iterative procedures can be applied to obtain the
matrix composition, but for light-element matrices, one must resort to a priori information
(e.g., obtained by other techniques) or certain assumptions have to be made (e.g., that the
elements are present as oxides). In any case, this problem of the matrix composition
is common to all x-ray emission analysis techniques. When specimens of intermediate
thickness are analyzed, the transmitted proton energy E
f
(or rather the energy loss
E
0
E
f
) is also needed for evaluating the integral in Eq. (11). This implies knowledge (or
determination) of the specimen mass thickness, because the energy loss is related to the
latter through the matrix stopping power. Alternatively, the energy loss can be measured
experimentally. It is evident that any uncertainty in the specimen mass thickness (or in the
experimental energy loss) will also be transmitted to the value of C
Z
. The magnitude of
this uncertainty transmission increases with decreasing specimen thickness and, ultimately,
a given relative uncertainty in the specimen mass thickness produces an identical relative
uncertainty in the value of C
Z
, as is, in fact, also the situation for the innitely thin
specimens just discussed. The uncertainty transmission from the matrix composition, from
the databases, and for intermediately thick specimens also from the specimen mass
thickness can be much reduced by the use of an internal standard element. Indeed, the
uncertainty transmitted in the integral of Eq. (11) is, to a large extent, in the same sense for
the analyte and the spike, so that a signicant uncertainty reduction occurs when dividing
the two integrals.
An alternative to the pure fundamental parameter quantitation approach is to make
use of experimental thin-target sensitivities k
p
Z, as dened by Eq. (10), so that Eq. (11)
can be written as
Y
p
Z
k
p
ZNC
Z
s
X
pZ
E
0
= sin y
Z
E
f
E
0
s
X
pZ
ET
p
E
SE
dE 13
By solving this equation for C
Z
, one basically uses a relative method (relative to thin-lm
standards), but the correction for matrix eects is made by a fundamental parameter ap-
proach. As in the relative quantitation method for thin specimens, this mixed approach
requires no knowledge of the absolute detection eciency or of the radiative transition
probabilities and uorescence yields [the latter two parameters cancel out in the ratio of the
x-ray production cross sections in Eq. (13)], but ionization cross sections and Coster
Kronig yields are still required. However, the division of the x-ray production cross sections
also has the eect that the impact of the CosterKronig yields is marginal and that for
ionization cross sections, essentially only their dependence on proton energy is needed,
which has a much smaller uncertainty than the absolute value of the ionization cross section.
In the analysis of innitely thick specimens, one can also utilize experimental thick-
target calibration factors instead of relying on the fundamental parameter approach or on
experimental thin-target sensitivities. The thick-target calibration factors incorporate the
integral of Eq. (11) and are usually expressed in x-ray counts/mC and per mg=g. They are
commonly derived from PIXE measurements on samples with known trace element
composition (standards). In a strict sense, the thick-target factors are only valid for the
analysis of unknown samples with identical (matrix) composition to the standards, but in
practice, some variability in composition can be tolerated or corrected for. The necessary
correction factor is, in this case, the ratio of the integral of Eq. (11) for the standard to the
corresponding integral for the unknown.
As discussed by Johansson and Campbell (1988) and Johansson et al. (1995), still
other quantitation approaches are possible, for example, making use of thick single-
element standards.
Before closing this section on quantitation for semithick and innitely thick speci-
mens, it should be warned that Eqs. (11)(13) are, in a strict sense, only valid for perfectly
at homogeneous samples and that, for specimens made up of particulate material, the
particle size should be as small as possible (ideally below 1 mm when quantifying light
elements, such as Na through Si). The surface roughness eects in PIXE were dealt with by
Cookson and Campbell (1983). With regard to particle size eects in PIXE, these are
especially of concern when analyzing deposits of atmospheric particulate material (aero-
sols) on lter or cascade impactor samples. Model calculations for proton-induced x-ray
generation in a monolayer of spherical particles having realistic matrix compositions were
presented by Jex et al. (1990). In aluminosilicate particles of 2 mm diameter, the attenua-
tion is over 20% for the elements Na to P.
D. Detection Limits inThin- and Thick-Target PIXE
As in other spectrometric techniques, the detection limits in PIXE are determined by the
sensitivity (calibration) factors, on the one hand, and by the spectral background intensity
where the analyte signal (x-ray line) is expected, on the other hand. Various denitions for
the limit of detection (x
L
) were proposed in the early years of PIXE (Johansson and
Campbell, 1988), but it is now general practice to dene x
L
as that amount (or con-
centration) of analyte element that gives rise to a peak area which is equal to three times
the standard deviation (square root) of the background intensity N
B
in the spectral in-
terval of the principal x-ray line. The spectral interval for integration of N
B
is usually
dened in terms of the full width at half-maximum (FWHM) of the principal x-ray line,
but regions of one, two, and three FWHMs have been used in the PIXE literature; this
range of choice introduces a variation of 1.7 in detection limits deduced from the same
dataset.
For thin specimens, the relationship between line intensity Y
p
Z and analyte con-
centration C
Z
was given by Eq. (9). If we represent the probability for the production of
continuum background radiation per unit of x-ray energy by s
B
and if we further assume
(to keep the formulation simple) that the background originates from a single matrix
element with atomic mass A
B
, the following relation can be written for the background
intensity N
B
:
N
B

N
0
s
B
E
0
nFWHME
p
Nrt
A
B
sin y
14
where nFWHM indicates the spectral interval used for summation of the background, and
all other symbols have the same meaning as in Eq. (9). By setting Y
p
Z equal to 3N
1=2
B
and
solving Eqs. (9) and (14) for the x
L
value of C
Z
, one obtains
x
L
Z
3A
Z
s
X
pZ
E
0
s
B
E
0
nFWHM sin y
N
0
A
B
E
p
Nrt
s
15
It thus appears that x
L
is proportional (or inversely proportional) to the square root of the
experimental parameters FWHM, E
p
; N, and the specimen mass thickness. Hence, to op-
timize x
L
, a detector with very good resolution has to be used, and, rather obviously, the
solid angle of detection should be made as large as possible, but improvement in this
parameter is limited by the area of the detector and by the fact that the detector can only
get to about 2 cm from the specimen. Much more exibility is provided by the number of
incident protons N (preset charge), which can be increased either by a longer measurement
time or by an increase in beam current.
Both theoretical calculations and experimental measurements have been performed
to obtain x
L
values for thin specimens [e.g., Folkmann (1976), Johansson and Johansson
(1976), Ishii and Morita (1988)]. In most of this work, one adopted (or employed) a light-
element matrix (typically carbon or an organic polymer) and a specimen mass thickness of
1 or 0.1 mg=cm
2
. Johansson and Johansson (1976) produced a very useful contour plot of
x
L
values as a function of incident proton energy and atomic number of the analyte ele-
ment for the case of 0.1-mg=cm
2
-thick carbon matrix. Their plot, reproduced here in
Figure 9, was based on experimental measurements of the continuum background, and it
was further assumed that elements with atomic number up to about 50 are determined
through their Ka x-ray line and the heavier elements through their La line. As can be seen
in Figure 9, there is a valley of optimum detection limits for both the K and L cases, with
the best Kx
L
values (less than 0.5 mg=g) obtained at lower proton energy than the best Lx
L
values (0.51 mg=g). Furthermore, within either the K or L case, the bombarding energy for
optimum detection limits depends on the atomic number of the analyte elements of
interest, with higher bombarding energies favoring the heavier elements. Selection of the
energy should thus be made with the objective of the analysis in mind, but, in practice,
some compromise is necessary. Johansson and Johansson (1976) concluded from their
contour plot that the optimum proton energy is about 2 MeV for the analysis of trace
elements in biological and environmental samples. Such bombarding energy also has the
advantage that the x
L
values show rather little variation (about one decade only) for the
analyte elements with Z between 15 and 90. More recently, Ishii and Morita (1988)
produced a contour plot similar to that of Johansson and Johansson (1976), but they
based it solely on theoretical calculations and adopted a pure oxygen matrix (which was
considered representative for biological samples). The conclusion of this study was that the
Figure 9 Contour plot of the limit of detection (x
L
) as a function of incident proton energy and
atomic number of the analyte element for the case of a 0.1-mg=cm
2
-thick carbon matrix.
Experimental conditions: detector FWHM 165 eV, solid angle of detection 38 msr, collected charge
10 mC. The background interval selected for calculating x
L
was equal to one FWHM. (From
Johansson and Johansson, 1976, with permission from Elsevier Science.)
best detection limits were obtained with about 3 MeV protons. Considering these in-
vestigations on x
L
values, it is thus no surprise that most PIXE laboratories employ
proton energies in the range of 23 MeV. Several laboratories actually consistently use the
same bombarding energy (e.g., 2.5 MeV) for their typical applications.
Detection limits have also been examined for other projectiles than protons, but the
results were generally not very encouraging. A noteworthy exception is given in the de-
tailed study by Johansson (1992) on the use of 5-MeV helium ions (a-particles). It was
found that these oer signicantly improved detection limits (about three times better than
protons) for thin organic specimens.
The detection limits in Figure 9 are expressed in relative units (concentrations), but
they are easily converted into absolute units (masses) by multiplying by the specimen mass
probed by the beam. Because this mass is invariably small (e.g., for a 0.1-mg=cm
2
-thick
specimen as in Figure 9 and a typical beam size of 0.2 cm
2
, the probed mass is 0.02 mg),
it follows that the absolute detection limits are in the range of 10100 pg for the case of
2-MeV protons and the experimental parameters of Figure 9.
As indicated by Eq. (15), the concentration limit of detection improves with the
square root of the mass thickness. However, this relation remains only valid as long as the
thin-specimen criterion holds. Because of the existence of matrix eects (i.e., the decrease
in s
X
pZ
and in the cross sections for bremsstrahlung production with decreasing proton
energy and the attenuation of the characteristic x-rays and continuum radiation by the
sample matrix), x
L
rapidly approaches its optimum value. In general, the improvement in
x
L
is quite limited above a few mg=cm
2
. Depending on the origin of the continuum
background and the energy dependence of its production cross section, x
L
may actually
deteriorate somewhat beyond a certain specimen thickness. Such situations may occur for
analyte lines in the spectral region where prompt g-radiation forms the major background
source (typically above about 10 keV).
Whereas x
L
studies for thin specimens have concentrated on light-element matrices,
in similar investigations for innitely thick targets, heavy-element matrices were also
considered. Teesdale et al. (1988) conducted a comprehensive experimental study of x
L
values for 15-MeV proton bombardment of pure single-element matrices of carbon,
aluminum, silicon, titanium, iron, germanium, molybdenum, silver, tin, ytterbium, and
lead. They paid particular attention to the choice of appropriate x-ray lters for sup-
pression of the matrix characteristic x-ray lines and their pileup peaks and to the choice of
the optimum proton energy. It was found that increase of energy up to 3 MeV is protable,
but that a further increase confers only small benets. Increasing absorber thickness were
suggested for increasing atomic number of the matrix up to Z 40. Under these condi-
tions and using a beam charge of 1 mC, the x
L
values were a few micrograms per gram for
the light-element matrices (C and Al) and 1050 mg=g for the intermediate matrices Ti
through Ge.
By using an optimized PIXE setup and a preset charge of 100 mC (which corresponds
to a 15-min bombardment with 100 nA current), x
L
values down to a few tenths of mi-
crogram per gram may be obtained for light-element matrices. The detection limit, ex-
pressed as concentration in the original sample, can be further improved by a physical or
chemical separation of the material of interest or by a chemical separation of the analyte
element(s) from the bulk of the sample. Drying or freeze-drying is an obvious pre-
concentration step for natural water samples, but also for biological tissues (which typically
contain 80% water). For natural waters with high mineral content, such as seawater, che-
mical preseparation schemes are advantageous, and detection limits of 1 ng=L (or 1 pg=g)
have been obtained by such an approach (Johansson and Johansson, 1984). For dried
biological tissues, further preconcentration may be realized by resorting to high- or low-
temperature ashing. As demonstrated by Pallon and Malmqvist (1981) and Maenhaut et al.
(1984), however, the gain in detection limits remains limited to a factor of about 2.
In this entire discussion on x
L
values, it was assumed that the PIXE analyses were
carried out in a vacuum chamber. In external beam or nonvacuum PIXE (in air or in a
helium or nitrogen atmosphere), poorer x
L
values are expected because of the background
contribution from interactions in the beam exit foil material and in the air or chamber gas
and, for the light elements, also because of the substantial attenuation of their soft x-rays
by the same gases. However, practical x
L
values in nonvacuum PIXE appear to be rather
comparable to the x
L
values in vacuum PIXE, at least for analyte elements with atomic
number above 25 (Ra isa nen, 1986).
E. Precision and Accuracy inThin- and Thick-Target PIXE
As in any other analytical technique, high precision and accuracy should be aimed for in
PIXE. It is therefore essential that careful attention be given to all stages of the analysis.
These include sample and specimen preparation, specimen bombardment, spectral data
processing, quantication, and correction for matrix eects. For a discussion of the critical
facets in the various stages, the reader is referred to the specic section dealing with each
stage. As far as the specimen bombardment stage is concerned, it should be added here
that one should be aware of the danger of radiation- or heat-induced losses during PIXE
bombardment. Such losses are particularly feared for volatile analyte elements (e.g., the
halogens, S, As, Se, and Hg) and, in the case of organic or biological specimens, also for
certain matrix elements (mainly H and O). The current density applied during analysis
plays a major role, and the danger for losses is therefore more severe in micro-PIXE than
in macro-PIXE. In any case, it should be determined which irradiation conditions are safe
for a particular application. More information on this subject can be found in a tutorial
paper by Maenhaut (1990a) and in research papers of Legge and co-workers (Legge and
Mazzolini, 1980; Cholewa and Legge, 1989; Kirby and Legge, 1991), Themner and co-
workers (Themner et al., 1990; Themner, 1991), and Van Lierde et al. (1995, 1997).
The reproducibility (precision) of an entire PIXE analytical procedure (including the
contribution from sample processing and specimen preparation) can be examined by
preparing several specimens from the same material, subjecting these to PIXE, and cal-
culating a standard deviation (s) from the spread in the results obtained. Under optimum
conditions, this standard deviation should be the same as that expected on the basis from
counting statistics alone (s
c
). However, when the percentage standard deviation from
counting statistics (%s
c
) approaches values smaller than about 12%, dierences between
s and s
c
are often unavoidable because of the limitations in sample and specimen homo-
geneity. It should indeed be realized that, even in macro-PIXE of innitely thick speci-
mens, the probed sample mass is at most a few milligrams, so that only nanogram amounts
of analyte elements are actually examined for concentration levels of a few micrograms per
gram. Particularly in the analysis of biological, geological, and atmospheric aerosol
samples, a %s of 12% is often the ultimate practical limit of precision. Such precisions
were obtained by Maenhaut et al. (1987), for example, in PIXE analysis of biological
reference materials.
The accuracy of a PIXE procedure should be evaluated by analyzing (certied) re-
ference materials or through comparisons with other analytical techniques. Ultimately, the
accuracy will depend on the extent of spectral interferences and matrix eects and on how
well these can be controlled or corrected for. Several PIXE analyses of reference materials
and other accuracy investigations have been reported in the literature, and selected studies
dealing with the analysis of trace elements in biological, environmental, and geological
samples were reviewed by Maenhaut (1987). The book of Johansson et al. (1995) also
reports on several accuracy studies and presents some ne examples of investigations in
which micro-PIXE was used. As an example of a macro-PIXE accuracy investigation on
biological materials, the study by Maenhaut et al. (1987) can be cited. A total of 18 ele-
ments were measured in up to 14 (certied) reference materials, and from a comparison of
the PIXE results with the reference values (when available), it was concluded that the
accuracy was better than 5%. For assessing the accuracy in macro-PIXE of atmospheric
aerosol samples, one has to rely on comparisons with other techniques. Good examples
of such intercomparisons are the work by Wa tjen and co-workers (Wa tjen et al., 1983;
Bombelka et al., 1984) and more recently by Nejedly et al. (1995).
V. SAMPLE COLLECTIONANDSAMPLE ANDSPECIMENPREPARATION
FOR PIXE ANALYSIS
A. General
In this section, general aspects of sample collection (sampling) and sample and specimen
preparation are discussed. Methods or procedures which only apply to samples of a
specic type (e.g., biological and environmental) are touched upon in Sec. VI, which deals
with the applications of PIXE. Furthermore, the present section discusses aspects that are
of general importance in both macro- and micro-PIXE. Points that are relevant for micro-
PIXE only are dealt with in Sec. V.B.
Particle-induced x-ray emission can, in principle, be applied to any type of sample.
Considering that the bombardments are normally done in vacuum, however, it is evident
that the technique is more suitable for analyzing solids than liquids. PIXE analysis of
liquids normally involves some preconcentration by drying (which can be as simple as
drying a drop of the liquid on a suitable backing lm) or some other physical or chemical
separation of the analyte elements from the liquid phase. As far as the analysis of solids is
concerned, it should be kept in mind that even in macro-PIXE of innitely thick samples,
the mass actually probed by the beam is at most a few milligram. Determination of the
bulk composition of a solid sample without any preliminary sample preparation is
therefore only possible for samples that are homogeneous in all three dimensions. Hence,
before deciding on analyzing a sample by PIXE, it should be carefully examined whether
the analytical problem is not much better solved by some other technique. The analysis of
liquid samples and the bulk analysis of large heterogeneous samples are clearly problems
for which PIXE may not be most appropriate. However, as concluded in a paper by
Maenhaut (1990b) in which PIXE and various nuclear and atomic spectrometric techni-
ques were compared, there are numerous analytical problems for which PIXE is the most
suitable technique or, at least, among the more suitable. Examples of such are the mul-
tielemental analysis of milligram-sized samples consisting of a light-element matrix (e.g.,
biomedical and atmospheric aerosol samples), the nondestructive analysis of millimeter-
sized areas on a large sample or of thin supercial layers on a bulk sample, and various
problems that require sensitive analysis with high spatial resolution.
When it has been decided to tackle an analytical problem by PIXE, full use should be
made of the inherent characteristics of the technique, particularly of its nondestructive and
instrumental character. Therefore, if possible, sampling should be done in such a way that
subsequent sample preparation can be avoided or kept to a strict minimum. The collection
of suspended atmospheric particulate material (atmospheric aerosols) is a good example
where such strategy should be adopted. For unique samples or samples of high commercial
or historical value, sample preparation or subsampling may even not be allowed because
the sample generally must be returned unaltered after the analysis. Examples of such
samples are historical documents, various objects of art, and extraterrestrial dust particles.
In many situations, however, some sample preparation is required. This may vary
from simple cleaning of the sample (to remove surface contamination), polishing (to
eliminate surface roughness eects), and powdering (to homogenize the sample and to re-
duce the particle size), to digestion or physical or chemical preconcentration or separation.
Furthermore, the last step in the sample preparation usually consists of preparing specimens
that are suitable for PIXE bombardment. Such specimen preparation may involve depos-
iting a drop of a liquid (e.g., of an acid digest) or a few milligrams of powdered material on a
clean, strong substrate lm (for thin and intermediate specimens) or pressing a certain
amount of sample into a pellet (for innitely thick specimens). The prepared specimen is
often mounted or held in a target frame (e.g., a 25-mm-diameter plastic ring or a square
target frame that ts in a standard 35-mm slide tray holder). Overall, the sample and spe-
cimen preparation procedures in PIXE are quite similar to those in the other x-ray emission
analysis techniques (see Chapter 14). As far as the backing lms for thin and semithick
specimens are concerned, an additional requirement in PIXE is that such lms should be
able to withstand the irradiation by the particle beam. More detailed information on
specimen backing lms for PIXE is given by Johansson and Johansson (1976) and Russell
et al. (1981).
Considering that PIXE analyses often aim at measuring microgram per gram levels
of trace elements and that the absolute amounts of analyte elements actually examined are
then in the nanogram region or below, contamination control is very important. Hence,
acid-cleaned plastic (e.g., polyethylene or Teon) or quartz containers and tools should be
employed during sampling and sample processing. The chemicals, acids, and water used in
sample preparation (e.g., for digestion or dissolution) should be of high purity. Also, all
critical manipulations should be done in a clean bench with laminar airow. When ap-
plying thin-specimen procedures, realistic blank specimens should always be prepared.
This should be done by applying the same procedures and using the same substrate lms
as for the actual sample specimens. Another point of concern is potential losses of analyte
elements during sample storage, sample processing, and specimen preparation. During
storage of aqueous samples, analyte elements may be deposited on the container walls.
Perhaps more important is that some analyte elements (e.g., the halogens, S, As, Se, Hg,
and Pb) may be volatilized by drying of the sample at elevated temperature and especially
in sample preparation methods which involve high- or low-temperature ashing or acid
digestion in an open vessel.
For more information about general aspects of sample and specimen preparation for
PIXE, the tutorial paper by Mangelson and Hill (1990) can be recommended. This paper
also provides a ne overview of the various physical and chemical methods of sample
preparation.
B. Specimen Preparation for Micro-PIXE
Because of the similarity between micro-PIXE and EPMA, the specimen preparation
techniques developed for EPMA are generally also applicable in micro-PIXE. However,
the dierence in ionizing particles (typically 1020-keV electrons in EPMA versus MeV
protons in PIXE) has the eect that the depth probed in the analysis is signicantly greater
in micro-PIXE. For example, this depth amounts to several tens of micrometers for 3-
MeV protons. In order to obtain meaningful results, the specimen should be homogeneous
throughout the depth analyzed, and for optimum use of the lateral capability of the nu-
clear microprobe, the specimen thickness should preferentially be of the same order as the
size of the focus of the microbeam. On the other hand, the specimen has to be suciently
thick (0.11.5 mg=cm
2
) in order to obtain a high x-ray yield. It should also be realized that
the support material (backing lm or other support material) may cause interference in the
x-ray spectrum, and it should therefore be selected with care.
The actual specimen preparation will, to a large extent, be determined by the ma-
terial to be studied. For biological materials, cryosectioning of frozen samples followed by
freeze-drying and mounting of the material on a thin clean plastic foil is often the method
of choice. For minerals, the specimens may consist of thin, polished, or ion-milled disks
mounted on a glass plate or an electron microscope grid. Finally, the preparation of thin
or semithick specimens should be done in such a way that the sample mass examined in
each pixel can be determined. This mass thickness is required in order to allow expressing
the results as elemental concentrations (see Secs. IV.B and IV.C).
VI. APPLICATIONS
The applicability of PIXE to various analytical problems has been amply demonstrated in
many publications. Furthermore, numerous studies have been carried out in which PIXE
provided part or all of the requested trace element concentration data. This section pre-
sents a brief selection of the applications of PIXE and is mainly based on publications
from the period 1992 through mid-1998. Many more examples can be found in the pro-
ceedings of the international conferences on PIXE (Johansson, 1977, 1981; Martin, 1984;
Van Rinsvelt, 1987; Vis, 1990; Uda, 1993; Moschini and Valkovic , 1996; Malmqvist, 1999)
and nuclear microprobe technology (Grime and Watt, 1988; Legge and Jamieson, 1991;
Lindh, 1993; Yang et al., 1995; Doyle et al., 1997), in the proceedings of the international
symposia on Bio-PIXE (Ishii et al., 1992; Zheng et al., 1996), in two textbooks on the
PIXE technique (Johansson and Campbell, 1988; Johansson et al., 1995), and in the
chapter on PIXE in the rst edition of this Handbook of X-Ray Spectrometry (Maenhaut
and Malmqvist, 1992).
A. Biological and Medical Samples
Most samples of biological origin are composed of essentially organic material, so that its
matrix elements are light and do not give rise to characteristic x-ray lines in the PIXE
spectrum. Furthermore, the electron bremsstrahlung background is lower for an organic
matrix than for a matrix of heavy elements. Biomedical samples are therefore well suited
for trace element determinations by PIXE. The disadvantage is that the organic matter is
sensitive to radiation damage and to heating eects. As discussed in Sec. IV.E, the light
matrix elements, especially H and O, but also some analyte elements may be lost to some
extent, in particular in micro-PIXE.
The elements of interest in biological materials are either essential minor or trace
elements (e.g., K, Ca, Mn, Fe, Cu, Zn, and Se) or toxic trace elements (e.g., Cd and Pb).
A comparison of the detection limits in PIXE (see, e.g., Fig. 9) with the levels of the minor
or trace elements in biological tissues [e.g., Iyengar et al., (1978), Iyengar (1989)] reveals
that most elements of interest in physiology or pathology, with a few exceptions, such as
Cd, can suitably be determined by PIXE in most tissue types. Consequently, ever since the
development of PIXE started, biological and medical applications have been prominent.
In the last decade, however, competition from new ultratrace techniques and the need for
high-sensitivity measurements in bioscience have resulted in growing diculties to pro-
mote PIXE and other x-ray spectrometric techniques. Furthermore, in recent years, the
emphasis has shifted from total element determination toward elemental speciation (i.e.,
measuring of the chemical compound or biological molecule to which the element is bound
or associated). PIXE and the other x-ray techniques lend themselves much less to this
speciation work than some of the new atomic spectrometric techniques. In applying PIXE
to biomedical problems, one should therefore look for cases where one can fully utilize the
special advantages of PIXE, such as high spatial resolution, accurate quantitative analysis,
and small samples. Particularly micro-PIXE, as used in the nuclear microprobe, is in-
valuable in biomedical trace element research.
1. Sampleand Specimen Preparation
The preparation of biomedical samples for PIXE analysis depends on the type of sample,
its composition, the information looked for (bulk concentrations or spatially resolved
data), the elements of interest, and the mode of irradiation (vacuum or nonvacuum). For
nuclear microprobe analyses, special requirements apply, as indicated in Sec. V.B.
Many elements exhibit suciently high concentrations in biological material that a
simple physical sample preparation method may suce in order to obtain the requested
concentration data. Several of the purely physical sample preparation methods are dis-
cussed in detail by Mangelson and Hill (1990). They include drying or freeze-drying,
homogenizing and pulverizing, and cutting of thin sections. In some cases, however,
particularly for natural levels of toxic elements and for levels of some essential elements in
certain tissue types, preconcentration by destruction of the organic matrix or some other
chemical preconcentration or preseparation is required. This may be performed in various
ways (Mangelson and Hill, 1990). The most common methods are (1) wet digestion in
acids, either in open or closed vessels, (2) dry ashing in an oven, (3) low-temperature
ashing in a plasma asher, and (4) biochemical separation techniques.
In wet digestion, the organic sample matrix is decomposed by concentrated strong
acids, normally nitric and=or hydrochloric acid. As the acid has to be removed by eva-
poration prior to PIXE analysis, the use of hygroscopic acids (i.e., sulfuric, perchloric, and
phosphoric acid) should denitely be avoided. Moderate heating in an oven or microwave-
assisted digestion signicantly increases the decomposition rate. The digestion rate may be
further increased by performing the digestion in a closed pressurized vessel [e.g., in a
Teon bomb in a regular oven (Duou et al., 1987) or in a closed vessel in a microwave
oven (Pinheiro et al., 1990)]. Such a procedure has the additional advantage that losses of
volatile analyte elements are greatly reduced. Unfortunately, losses of certain elements
(particularly of the halogens) may still occur while opening the vessel and during the
drying of the digest on the backing lm while preparing the PIXE specimen.
Dry ashing provides a greater mass reduction factor than wet ashing, with high-
temperature ashing even being better in this respect than low-temperature ashing. By dry
ashing at 550
C, preconcentration factors of up to 500 have been obtained for certain

biological materials (Saurela et al., 1995). However, the very severe risk of loosing volatile
analyte elements may prohibit the use of a high temperature. The more complex low-
temperature ashing in an oxygen plasma is therefore often preferred, but also this tech-
nique involves a serious risk of loss (Maenhaut et al., 1984; Maenhaut, 1990a).
Biochemical separation techniques are used in research on elemental speciation.
Pallon et al. (1987) developed a gel ltration method to separate a blood serum sample
into 100 fractions for subsequent analysis by macro-PIXE in order to examine the asso-
ciation of trace elements with serum proteins. Szo kefalvi-Nagy et al. (1990, 1993) per-
formed several studies using gel electrophoresis to localize and quantify metals in various
enzymes. They worked with polyacrylamide and cellulose acetate gels and separated the
proteins according to electrical charge. Polyacrylamide gel electrophoresis (PAGE) was
also used by Weber and co-workers (Weber et al., 1996; Strivay et al., 1998). Vogt et al.
(1996) coupled PIXE on-line with capillary-zone electrophoresis (CZE). A Japanese group
(Hirokawa et al., 1991; Hu et al., 1992) applied isotachophoretic separation.
After the physical or chemical sample preparation, or even when no sample pre-
paration is used, specimens for the actual PIXE bombardment generally have to be pre-
pared, as indicated in Sec. V.A. When preparing specimens by pipetting a drop of a liquid
(e.g., of an acid digest) on a backing lm, the uniformity of the deposit can be enhanced by
pretreatment of the lm (Mangelson et al., 1981; Duou et al., 1987), by adding lecithin or
some other suitable additive to the liquid prior to pipetting (Campbell et al., 1985;
Mangelson and Hill, 1990), and by rapid drying of the pipetted solution (e.g., by placing
the targets in a vacuum desiccator) thereby favoring the formation of ne crystallites
(Maenhaut, 1990a).
2. Examples of Macro-PIXE
The macro-PIXE application examples presented here were chosen somewhat arbitrarily.
However, their selection was guided by the aim of demonstrating the particular potential
of the PIXE technique. Furthermore, most examples were taken from the medical eld.
a. Body Fluids
Blood, blood plasma, and serum have always been popular study objects for PIXE, despite
the fact that only a few real trace elements (Fe, Cu, Zn, Se, Br, Rb) can be measured in
these sample types. Compared to the early days of PIXE, there is now increasing com-
petition from other highly sensitive analytical techniques, such as inductively coupled
plasmamass spectrometry (ICPMS), which are more suitable for analyzing liquid
samples. Therefore, it becomes hard to justify the use of PIXE. The motivation often is
that one has a good-running and cost-eective bio-PIXE research program set up at a
small accelerator or baby cyclotron and that the blood, plasma, or serum samples form
part of a wider variety of sample types which are studied in the research project. When
working with blood or blood components from small experimental animals (e.g., mice or
rats), the small sample size provides additional justication for the use of PIXE.
Shenberg et al. (1995) used a combination of PIXE and instrumental neutron acti-
vation analysis (INAA) for measuring K, Fe, Zn, Se, Br, and Rb in blood and blood
fractions (plasma and red cells) of colorectal patients. It was concluded that the two
techniques complement each other. The mean values for K, Fe, Se, Br, Rb, and the Br=Rb
ratio were signicantly lower for cancer cases than for healthy individuals, and it was
suggested that this may be applicable as additional information for dierentiating ma-
lignant cases from normals. It was also found that the Br=Rb ratio was much lower in
Belgium than in Israel, which was explained by the inuence of dierences in dietary
habits and environmental factors on the Br level in the blood of both populations. Miura
et al. (1996) used PIXE for measuring 7 elements in serum of patients with acute myo-
cardial infarction (AMI), and they examined the correlations between the elements and the
vascular cell adhesion molecule-1 (VCAM-1), which is closely related to various types of
inammation. Soluble VCAM-1 was markedly enhanced in the sera of the patients with
respect to controls, and two of the elements measured (i.e., Ca and Zn) were signicantly
correlated with it. The authors suggested that there was an interaction between the di-
valent cations Ca
2
and Zn
2
and VCAM-1, but concluded that further investigations
are needed to elucidate the actual mechanism of the alterations.
Blood plasma samples from experiments with animal models were analyzed by PIXE
by Sato et al. (1995) and Tamanoi et al. (1995). The study of Sato et al. (1995) dealt with
the eects of diethyleneaminepentaacetic acid (DTPA). This chelating agent is re-
commended for eliminating several kinds of radionuclides from persons contaminated
with them. It is generally administered as calcium-trisodium salt (Ca-DTPA) or zinc-tri-
sodium salt (Zn-DTPA), but both compounds have been reported to induce injuries, be it
that Zn-DTPA is less toxic than Ca-DTPA. Male Wistar rats were intraperitoneally (i.p.)
injected with the salts, and blood was collected from the tail vein just before and at 3, 6,
and 24 h after the injection. Na, K, Ca, Fe, Cu, and Zn were measured in the plasma. Ca-
DTPA signicantly lowered the concentration of Zn, whereas no signicant changes were
observed for the other metals. Zn-DTPA did not lower any metal concentrations, but
a signicant increase of plasma Zn was observed. Tamanoi et al. (1995) used PIXE to
measure Cl, K, and Ca in blood plasma of mice in which EL-4 lymphatic tumor cells had
been transplanted. The motivation for employing PIXE was that blood samples were
taken at several intervals after the transplantation and that it was desirable to collect
samples as small as possible in order to induce no stress. A sample size of 5 mL plasma was
used for the PIXE analysis.
Certain body uids, such as cerebrospinal uid (CSF), exhibit very low concentra-
tions of trace elements, even for Fe, Cu, and Zn. PIXE of CSF requires special sample
preparation and analysis procedures. Kupila-Rantala et al. (1996) used ultrathin (20
30 mg=cm
2
) Formvar lms as sample support and a 625-mm-thick Kapton foil with a
pinhole as the x-ray absorber. The detection limits for Fe, Cu, Zn, and Br were 6, 4, 8, and
18 mg=L, respectively, for a CSF sample size of 50 mL.
b. Soft Tissues and Organs
The fact that PIXE only requires a small amount of sample makes it possible to investigate
the regional distribution of trace elements in large heterogeneous tissues, such as human
brain. Following up on earlier work by Duou et al. (1989), Hebbrecht et al. (1994a)
measured the concentrations of two minor (K, Ca) and six trace elements (Mn, Fe, Cu, Zn,
Se, Rb) and the dry-to-wet weight ratio in 50 dierent structures of additional normal
brains. The datasets were combined and examined with chemometric techniques (Maen-
haut et al., 1993a). Mn and Cu were higher in the gray matter of the cerebellum than in the
gray matter of the cerebrum. Both elements and also Fe were elevated in the nucleus
caudatus, putamen, and globus pallidus. The substantia nigra exhibited elevated levels of
Fe and, particularly, Cu. Hierarchical cluster analysis indicated that morphologically si-
milar regions or structures involved in the same physiological function often con-
glomerated in the same cluster. This strongly suggests that there is some relationship
between the trace element prole of a brain structure and its function. Hebbrecht and
colleagues also examined alterations in trace element levels and water content in hemor-
rhagic and nonhemorrhagic cerebral infarcts (Hebbrecht et al., 1994b) and they studied
the inuence of neurotropin for human brains that were aected by recent middle cerebral
artery infarcts (De Reuck et al., 1993). The most striking nding of the latter study was a
less signicant increase in the water content in the white matter of the infarcts of
patients who had been treated with neurotropin. In addition, decreases in intracytoplasmic
elements, such as Rb and Cu, and increases in Ca were more clearly present in the infarcts
of patients who had been treated with placebo compared to neurotropin.
In comprehensive study, Vandenhaute and Maenhaut (1994a, 1994b) used acute and
chronic intoxication by i.p. injection of CCl
4
to induce liver injuries (liver necrosis, stea-
tosis, and cirrhosis) in female Wistar rats. Liver, kidneys, and blood serum were collected
from the experimental animals and from controls and analyzed for up to 12 elements (i.e.,
K, Ca, Mn, Fe, Cu, Zn, As, Se, Br, Rb, Sr, and Mo). The acute intoxication (leading to
necrosis and steatosis) caused denite alternations of many trace element levels.
As expected, the alternations were most pronounced in the liver. In this organ, Ca
exhibited a strongly increased concentration. Important alterations for the elements K,
Zn, and Se were also observed. For virtually all elements, however, the concentration
alterations showed an idiosyncratic character. This means that the intensity and sometimes
the direction of the alterations are hard to predict. Furthermore, it turned out that the
concentration dierences resulting from the liver disorders were often of the same order as
those between various populations of the control animals. As a result, it is very hard to
assess the physiological condition of an organ solely on the basis of its elemental con-
centrations. This nding also seems to preclude the use of trace element alterations for
diagnostic or prognostic purposes in liver injuries in humans.
c. Human Hard Material
Hard human material includes materials as varied as hair, nails, human stones, calcied
tissues, teeth, and bone. As solid materials, they have in common that direct analysis using
in vacuo or external-beam analysis can normally be used. It should be taken into account,
though, that the direct irradiation of a solid sample gives concentration data that are only
representative for the supercial layer of 100 mm at most. If bulk data are required, the
samples are usually crushed and pulverized, followed by pelletizing or depositing a small
amount of the powder on a backing lm.
Shizuma et al. (1991) used in vacuo millibeam PIXE to examine the distribution of
Cl, K, Ca, Mn, Fe, Cu, and Zn in ve dierent types of gallstone. They sandwiched
sections of the stones between two aluminized Mylar lms in order to eliminate charging
eects and scanned the sections with a beam of 0.5 or 1 mm diameter. The Ca concen-
tration was high in the central region of nearly all gallstone samples and it was also high in
the outer layers of the combination stones.
Lane and Duy (1996) analyzed dental enamel from human teeth collected from the
Oxfordshire area of the United Kingdom. Elements heavier than Ca were correlated to a
number of parameters, including the health of the teeth and age and gender of the donor.
The concentrations of Fe, Sr, and Cu were found to correlate with dental health, and the
mean concentration of Pb was found to be 7 mg=g for those under 25 years of age and
increased with age. Archaeological samples of human teeth originating from Peru, Venice,
and a Roman site were examined by Buoso et al. (1992). The depth proles from enamel to
the tooth interior were determined for elements heavier than Ca in order to understand
their postmortem diusion with time. Solis et al. (1996) analyzed human teeth from pre-
Columbian, colonial, and contemporary population groups in Mexico in order to evaluate
elemental changes. For Mn, Fe, Cu, Zn, and Sr, no dierences between the three popu-
lations were detected. Pb, in contrast, was higher in colonial teeth than in contemporary
ones, and it was below the detection limit for pre-Columbian teeth. The high Pb in the
colonial period was attributed to the introduction of glaze pottery by the Spaniards.
Bone acts as a repository for many trace elements, so that it may provide in-
formation on the long-term trace element status of an individual. In a study on the role of
trace elements in Alzheimer disease (AD), Robertson et al. (1992) used external-beam
thick-target PIXE for analyzing cortical and trabecular bone autopsy samples from 4 AD
patients and 12 age-matched controls. The results indicated a possible imbalance in Zn,
Br, and Rb for the AD patients.
d. Zoology, Botany, and Environment
Fish is a very important food in many coastal regions and in several national cuisines
(e.g., in Japan). Changing environmental conditions may aect both the quantity and the
quality of the sh stocks. Arai and colleagues (Arai and Sakamoto, 1993; Arai et al., 1994)
used PIXE for analyzing otoliths (i.e., ear stones) in several species of teleost sh, and they
examined relationships between trace element concentrations and environmental para-
meters, such as water temperature and salinity. It was found that Sr and Zn concentrations
increased with increasing seawater temperature. In addition, there were signicant dif-
ferences in trace element composition between otoliths of reared red sea bream and
rocksh and otoliths of wild ones (Arai et al., 1994). Furthermore, the Sr=Ca ratio for red
sea bream otoliths varied among rearing stations (Arai et al., 1995), so that it can be used
for sh stock discrimination. Similar investigations, but on statoliths from squids, were
performed by Ikeda et al. (1995). Kakuta et al. (1995) studied the changes of blood and
urine parameters of carp that was exposed to diluted (20%) raw sewage for 30 min. Blood
and urine samples were taken before and just after the exposure, and at 4, 12, and 36 h
after the exposure. The changes in trace element levels were largest at 4 h after exposure,
with signicant increases in blood S, Cl, and Br and in urine S, Cl, K, Ca, Zn, and Br.
After 36 h, the levels had essentially returned to normal.
The PIXE technique is very well suited for studying the distribution of trace elements
in small botanical samples. Yokata et al. (1994) applied it to study alterations in Al, P, K,
and Cl of alfalfa root tip that was exposed to low pH or aluminum stress. One or two
pieces of root tips were sucient for the analysis. Short-term (within 4 h) decreases in K=P
and Cl=P ratios were observed under the stress conditions. Yukawa et al. (1995) studied
the distribution of elements in soybean seedlings (beam sprouts). Soybeans were germi-
nated in a dark box using pure water without any mineral supplement. After 20, 40, 65,
and 137 h, the seedlings were harvested and each sprout was separated into cotyledons,
hypocotyls, leaves, and root. Each bean sprout part was freeze-dried and analyzed by
PIXE. It was observed that K, Mn, Fe, Cu, and Zn moved from the cotyledons and the
primary root to the hypocotyls and rst leaf, whereas Ca in the seed hardly moved.
Naturally growing moss and lichens are often used as biomonitors (or bioindicators)
of atmospheric deposition of trace elements. They are normally collected at dierent sites
within a large region or country in order to study regional dierences in that deposition.
The basis for their use is that biomonitors obtain most of their supply of chemical sub-
stances directly from precipitation or from dry deposition of airborne particles. Williams
et al. (1996) analyzed lichens from several sites in the intermountain western United States
for up to 21 elements by PIXE. Certain samples had high concentrations of S, Cu, As, and
some other elements. It was concluded that some wilderness areas are impacted by
emissions from industrial plants. Reis et al. (1996) applied a combination of PIXE and
INAA for measuring 43 elements in 250 lichen samples from Portugal. The dataset was
subjected to Monte-Carlo-aided target-transformation factor analysis and the geo-
graphical distribution of the factor values was assessed.
Acidication of forests is a major ecological threat as well as important economic
factor in forestry. By stepping or scanning a millimeter-sized beam over a core radially
bored from the stem of a living tree and following the changes in the trace element content
along the core, it is expected that changes in the environment can be followed. However,
due to diusion before and during this kind of analysis, there have been some doubts
about the reliability of data; hence, micro-PIXE studies have been used for a more detailed
understanding (Malmqvist, 1995b). Examples of trace element analyses of trees by macro-
PIXE in recent years are those Glass et al. (1993), Harju et al. (1996), and Aoki et al.
(1998). Glass et al. (1993) extracted four cores (at two heights and two positions) from a
60-year-old water oak. Substantial dierences were found in elemental distributions for
the dierent cores. The dierences were not due to sample preparation, but possibly to
dierential deposition in the tree. The results indicate that caution must be exercised when
attempting to link trace element studies of tree rings to pollution chronology of the sur-
rounding environment. Harju et al. (1996) used thick-target PIXE in air to study the
seasonal variation of trace elements within tree rings of Norway spruce and Scots pine.
The samples were scanned with a 1-mm-diameter beam. The highest concentrations for
most elements were obtained for earlywood in the beginning of the growth season and the
lowest values for latewood, thus reecting the biological activity.
3. Examples of Micro-PIXE
The fact that one can focus the ion beam to small groups of cells or even single cells as well
as to dierent cell strata in various tissue, in combination with the high analytical sensi-
tivity and accuracy of the PIXE technique, makes the nuclear microprobe a strong ana-
lytical tool in biomedicine. Its high lateral resolution represents an obvious advantage for
studies on the role of elements in cellular functions. By selecting some good examples, we
will try to illustrate the great importance of micro-PIXE in biomedicine.
a. Single Cells
The elemental composition of single cells can be studied on cells that are either present in
their natural surrounding tissue or are grown free in cell cultures. In most studies of modern
biology, human or animal isolated cells are used as experimental models. The advantage of
analyzing normally grown cells is that one can assume that they are not perturbed ele-
mentally. Cultured cells, due the diculties of exactly simulating normal growing condi-
tions, may display some elemental deviations. However, the study of individual cells in a
living organism is impracticable because of the diculty in identifying the revelant cells, in
manipulating their behavior in a controlled manner, and in separating eects due to in-
trinsic properties of the cells from eects due to the interaction among the many cell types
present in the tissue. Hence, the use of cell cultures has increased during the last decades, in
particular for studies with x-ray microanalysis, including micro-PIXE by using the nuclear
microprobe. The purpose of working with isolated cells as a experimental models is to
check, in vitro, consequently in reproducible conditions, a cellular function or the eect of
any molecule with a biological activity (Moretto and Llabador, 1997).
One limitation of PIXE, other x-ray techniques, or most other elemental analysis
techniques is that no information on the ionic form or speciation of the element is obtained.
For instance, analysis of calcium ions in cells is important for the understanding of cell
physiology. Also, although micro-PIXE is more sensitive than traditional x-ray micro-
analysis as used in an electron microprobe, both techniques provide information only on
total Ca and not on the Ca
2
concentration, which is the relevant physiological parameter.
In the studies by Pa lsga rd et al. (1994) and Pa lsga rd and Grime (1996) on the role of Ca
2
as the second messenger, this problem has been overcome by using a Ca analog. In se-
cretory cells, such as the insulin-synthesizing b-cells, a rise in the Ca
2
level triggers the
exocytosis of secretory vesicles and the release of insulin. To discriminate between
endogenous Ca
2
and Ca
2
entering as a result of stimulation, Sr was used as a tracer.
Due to its chemical anity, Sr
2
is known to enter the Ca
2
channels and to mimic the
role of Ca
2
in the secretory process (Wroblevski et al., 1989). This elegant approach
makes use of the multielemental character and high sensitivity of PIXE. To assure that this
analog substitution works as assumed, Pa lsga rd et al. (1995) performed another study in
which they examined whether a dierent analog (Ba
2
) behaves the same.
When one is interested in measuring trace metals rather than electrolytes in cells,
micro-PIXE has particular relevance. Examples are research on heavy-metal intoxication,
but also studies on elemental changes induced by the physiological or pathological state of
the cells. In a study of Menkes disease, the Melbourne nuclear microprobe group in-
vestigated the intracellular Cu concentration in cultured Menkes broblasts by means of
individual cell microanalysis (Allan et al., 1994). There was a highly signicant dierence
of a factor of 6 between the Cu levels of Menkes and normal broblasts. By using the
individual cell analysis, it was also found that there was large biological variability be-
tween the individual cells, despite the fact that they were grown under uniform conditions.
Some transition metals delay important regulatory roles in gene expression. The
disturbance of their cellular levels could be involved in oncogene expression and tumo-
rigenesis. In a study by the Bordeaux nuclear microprobe group (Ortega et al., 1997),
micro-PIXE was used to measure Mn, Fe, Cu, and Zn in cultured human neuroblastoma
cells. The study indicated that the nuclear microprobe is a useful tool for investigating
transition metal concentrations in cultured cells and that further research is required to
investigate the detailed role of these trace elements.
Another interesting example of single-cell analysis is that of individual marine
plankton. The occurrence of annual marine phytoplankton blooms is becoming a global
problem. Within a European Union-funded project, it is investigated if the unbalanced
nutrient composition of the water promotes the dominance of harmful phytoplankton
species. A combination of new advanced methods is used to allow simultaneous de-
termination of toxin content, elemental composition, genetic expression, and bio-optical
properties of toxic phytoplankton at the species level in natural communities. One of the
tasks is the determination of the elemental composition of single phytoplankton cells. This
is carried out with the Lund nuclear microprobe, using both micro-PIXE and nuclear
reaction analysis (NRA) with deuterons, with a special focus on C, N, P and K. The
method used to isolate single living cells while reducing their salt environment is an im-
portant part of the analytical procedure. Figure 10 shows elemental maps obtained by
nuclear microprobe analysis of a phytoplankton. Also, the results from STIM measure-
ments and an optical micrograph are shown (J. Pallon, personal communication, 1999).
b. Soft Tissues
With the nuclear microprobe, one can raster the focused ion beam over selected areas on
various biological structures and form elemental or structural maps which are displayed
on-line. This facilitates the combination of overall analysis and detailed spot investiga-
tions. By overlaying a video image or an optical micrograph, it is possible to localize and
identify particularly interesting regions or cell strata. Because of the stringent requirements
on the sample preparation in order to preserve biological trace element information, the
tissue specimens are normally not stained but only freeze-dried. Hence, the lack of contrast
in optical mode of such specimens makes it necessary to combine all means of imaging and
analysis available (Malmqvist, 1995a).
The central nervous system has been extensively studied using the nuclear micro-
probe. Starting in Oxford and continuing at the National University of Singapore (NUS),
Watt and co-workers have carried out several studies on brain tissue taken postmortem
from diseased patients diagnosed as suering from Alzheimer disease. The presence of
elevated levels of certain elements, especially Al, in neurobrillary tangles and neuritic
plaques from such patients has been the subject of great controversy (Jacobs et al., 1989;
Landsberger et al., 1992). In a recent study on neurobrillary tangles, Makjanic et al.
(1997) used freeze-dried samples for analysis by both micro-PIXE and STIM. The results
indicated that the elevated Al concentration measured is an artifact introduced during
sample preparation. Using animal models, the Lund group performed several studies on
rat brains in order to understand the mechanisms behind cell death in special cell strata of
the brain as a consequence of stroke or epileptic seizures. The micro-PIXE results for
groups of cells in the substantia nigra indicated that the onset of the cell death was
characterized by a change in Ca concentration, and this before any histopathological ef-
fects could be observed (Themner et al., 1988; Inamura et al., 1989; Tapper et al., 1991).
Atherosclerosis is a major cause of death in the Western world. The understanding of
mechanisms behind the calcied depositions on the artery wall is of paramount im-
portance. Several studies using micro-PIXE and the nuclear microprobe have been carried
out on this subject (Rokita et al., 1991; Pinheiro et al., 1996). The detailed information
obtained, including data on several trace elements, provides clues on the atherogenesis.
Being a very well-stratied tissue, skin lends itself very easily to microprobe analysis.
Many studies have been carried out with the Lund nuclear microprobe by Forslind and co-
workers (Pallon et al., 1992, 1996, 1997). Both normal skin and pathological states (e.g.,
Figure 10 Elemental maps and an off-axis STIM map from a single phytoplankton, Dinophysis
sp., obtained by nuclear microprobe analysis with 2.5-MeV protons. P to Ca are determined by
micro-PIXE, and C and N with backscattering. The scan size is 64 mm. (Courtesy of J. Pallon.)
atopic and psoratic skin) have been extensively investigated. The trace elemental proles
across the various skin strata are also useful in the basic understanding of the skin barrier
function. This is a very essential mechanism of epidermal skin to protect the body while
still being permeable. Perturbations of the barrier have recently been investigated using a
nuclear microprobe by the Lawrence Livemore Laboratory group (Mauro et al., 1998).
Figure 11 shows the Ca distribution before and after acetone-induced barrier disruption.
Another type of tissue that has been studied frequently using the nuclear microprobe
is kidney cortex. In an attempt to understand the etiology of Menkes disease, Kirby et al.
(1998) used an animal model (mice) and studied the distributions of Cu, Fe, and Zn in
kidney cortex. The tissue specimens were prepared by cryosectioning and freeze-drying.
Localization was facilitated by enzyme histochemical staining of adjacent sections. The
micro-PIXE technique clearly showed how the three elements in question were distributed.
c. Hard Tissue
Due to the convenience in sampling (hair, nails), the elemental long-term stability (mi-
neralized tissues), time-recorder capability (hair, nails, shells), and stability under the
ion beam, hard tissues have been rather popular specimens for nuclear microprobe stu-
dies. Besides sh scales, various aragonite structures in sh and squid have been analyzed,
in particular for Ca and Sr (Tang et al., 1997). The elemental variations in the slowly
growing statoliths or otoliths (ear stones) reect variations in living conditions. In most
countries with extended coastlines, shing is of great economical importance, and hence
the migration patterns of sh are obviously of great economical as well as ecological
interest. Lipinski et al. (1997) studied squid statoliths using micro-PIXE. The results were
Figure 11 Calcium distribution in skin as measured by micro-PIXE with and without acetone
provocation. A 3-mm microbeam of 3-MeV protons was used for analysis. (From Mauro et al., 1988,
by permission of Blackwell Science, Inc.)
not easily interpreted, and further investigations were suggested using also techniques that
can reveal the crystal structure of the aragonite. In studies of sh migration, one has
already made extensive use of nuclear microprobe analysis of otoliths (Halden et al.,
1996). The good retention of absorbed elements in otoliths has been demonstrated, and
hence they can serve as reliable life-history records. The Sr concentration will be de-
pendent on the salinity of the water in which the sh is living and migration from
freshwater to bracken water or seawater, as, for instance, salmon might carry out, can
then be seen as variations in Sr concentration. Figure 12 shows two elemental maps
obtained by micro-PIXE analysis of a brown trout (Salmo trutta) otolith. The maps
clearly show how dierent the elements Zn and Sr are taken up during the otolith growth.
Zn shows clear seasonal ring patterns, whereas Sr has a strong peak in the center, at the
time of birth of the sh. The interpretation would be that a marine (saltwater) mother has
grown the egg at sea and thereby transferred a high Sr amount to it, and then migrated to
freshwater where the egg was laid and the trout remained until it was caught. The Zn is
incorporated with highest concentrations during the cold season (K. Limburg, Stockholm
University, personal communication, 1999). The shells from several other species (e.g.,
pearl mussels, abalone, and oysters) have also been tried as bioindicators of environ-
mental and climatic changes. The success in doing so has been limited, mainly because
of the complexity of the mechanisms involved and the diculties in interpreting
obtained data.
Human bone and teeth represent another material that has been investigated in great
detail with nuclear microprobes (Mitani et al., 1997). Bone and teeth dentine act as good
and relatively stable recorders of exposure and have therefore been used to assess the
exposure to Pb. More recently, however, more interest has been directed toward basic
growth patterns and the eects of metal implants (Pa lsga rd et al., 1997). Trace element
detection is used in the investigations of leaching of metal from, for instance, titanium
implants (Ektessabi et al., 1997). In this kind of work, electron and nuclear microprobes
can complement each other well, as was recently demonstrated in a study on implanted
articial hips (Jallot et al., 1998).
Figure12 Elemental maps (Zn and Sr) from an otolith from brown trout. Analysis was done by
2.5-MeV protons and the scan size was 4 mm. Dark areas indicate high concentration and light areas
indicate low concentration. (Courtesy of K. Limburg.)
d. Botany and Environment
The relatively high, but still limited, lateral resolution of the nuclear microprobe makes it
ideal for studying plant material. The cells are often rather large and it is possible to
examine subcellular structures even with the modest beam resolution. Przybylowicz and
co-workers performed several studies on plants, with special emphasis on the accumula-
tion of metals, and they also made a comprehensive review of the botanical applications of
the nuclear microprobe (Przybylowicz et al., 1997). They are using a combination of
micro-PIXE, backscattering spectrometry, and STIM, and they use the dynamical
quantitative elemental mapping technique to produce accurate distribution maps on-line.
They conclude that the nuclear microprobe is almost ideal for extensive characterization of
plant tissues, but that there are some limitations due to beam-induced damage of the
specimen. The Oxford scanning proton microprobe (SPM) has also been used for studies
of hyperaccumulation of metals in plants (Kra mer et al., 1997). A special plant (Alyssum
lesbiacum) was selected because it is known to concentrate heavy metals in the leaves and
because such species might be used for the cleanup of contaminated soil. It was found that
the plant clearly concentrated Ni in the epidermal trichomes.
The nuclear microprobe, with micro-PIXE as the most important tool, also has great
potential in studies of environmental problems (Malmqvist, 1996). A few selected examples
are studies of Al proles in plant roots (Schoeld et al., 1998), metal uptake in lichens
(Watkinson and Watt, 1992), and heavy-metal uptake in bracken (Watt et al., 1991).
B. Atmospheric Aerosols
The multielement analysis of airborne particulate material (atmospheric aerosols) has been
a very popular and highly successful application of PIXE since the early days of the
technique. Actually, the pioneering paper of Johansson et al. (1970) already presented a
PIXE spectrum of such material. A more recent spectrum, obtained from the bombard-
ment of an urban aerosol sample (Campbell et al., 1986), is shown in Figure 13.
Considering that atmospheric aerosols are often collected as a thin-sample layer on
some thin lter or substrate lm, that such samples can be analyzed nondestructively by
PIXE without sample preparation, that the sample matrix consists of light elements, and
that a 510 min bombardment suces to detect up to 20 elements, including interesting
anthropogenic elements such as S, V, Ni, Cu, Zn, As, and Pb, the analysis of aerosol samples
forms almost an ideal application of PIXE. Compared to EDXRF, which shares several
favorable characteristics, PIXE oers sensitivities (expressed as characteristic x-ray count
rate per microgramof element actually exposed to the analysis) that are typically at least one
order of magnitude better (Maenhaut, 1989), so that it requires much less sample mass and
thus allows the use of compact samplers with high time and size resolution. Another ad-
vantage of PIXE over EDXRF is that it can be complemented with other ion-beam analysis
techniques (Cohen, 1993, 1998; Cahill, 1995; Swietlicki et al., 1996a), so that the light ele-
ments (H, C, N, and O) that make up most of the aerosol mass can be measured as well.
Motivation for the study of atmospheric aerosols and of their physical and chemical
characteristics is that they reduce visibility, aect human health, contribute to acidication
of terrestrial and aquatic ecosystems, and cause damage to structures and buildings (Elsom,
1992; Boubel et al., 1994; Cahill, 1995; Seinfeld and Pandis, 1997). During the past decade,
renewed interest in the health risks of aerosols has been generated by the nding of strong
correlations between increased mortality and the concentrations of (ne) airborne particles
in metropolitan areas in the United States (Pope et al., 1995). Furthermore, it has become
clear that aerosols play a much more important role in climate than previously thought
(Charlson and Heintzenberg, 1995). At the same time, one has come to realize that there
remain serious gaps in our knowledge of atmospheric aerosols. With regard to the observed
correlations between aerosols and increased mortality, it is uncertain whether these are due
to the particles as a whole or to certain specic components, such as ne sulfate, the car-
bonaceous aerosol (organic carbon and elemental carbon), or heavy metals. There is
consensus, though, that the ne particles are more harmful to human health than the coarse
ones and this has led to the replacement in 1997 in the United States of the PM10 (parti-
culate matter smaller than 10 mm) standard by the PM2.5 (particulate matter <2.5 mm)
standard for aerosol measurements in atmospheric monitoring networks. As to the climatic
eect of aerosols, this stems from the fact that they physically aect the heat balance of the
Earth, both directly by reecting and absorbing solar radiation and by absorbing and
emitting some terrestrial infrared radiation and indirectly by inuencing the properties and
processes of clouds, and, possibly, by changing the heterogeneous chemistry of reactive
greenhouse gases (e.g., O
3
) (Charlson and Heintzenberg, 1995; Schwartz, 1996). Changes in
the heat balance due to anthropogenic or externally imposed changes are referred to as
forcings. There is a very large uncertainty associated with the aerosol forcing estimate, and
this is essentially due to our poor state of knowledge regarding the sources, spatial and
temporal variability, and chemical, physical, and optical properties of atmospheric aero-
sols. As for the impact on human health, ne (submicrometer-sized) particles are more
important than the coarse ones for both the direct and indirect eect on climate. However,
there is still much unknown about the formation, evolution, and composition of the ne
particles. Quite often, all measured aerosol constituents in ne-aerosol characterization
projects do not add up to the measured ne-particulate mass (PM), and a major fraction of
it remains unexplained. The recent ndings about the eects of aerosols together with the
realization of the serious gaps in our knowledge have given a strong new impetus to aerosol
Figure 13 PIXE spectrum of an urban aerosol sample. (From Campbell et al. 1986, with
permission from Elsevier Science.)
research. The PIXE technique can continue to provide an invaluable contribution to this
research by giving data for major, minor, and trace elements in large numbers of ne and
highly size-resolved aerosol samples. The data for the major elements (S, Na, Cl, Al, Si, Fe)
are needed for assessing the climatic eect of aerosols, for estimating the contributions of
important aerosol types (e.g., sea salt, crustal material), and for arriving at chemical mass
closure, whereas the multielemental data set as a whole (which comprises data for various
anthropogenic tracers) can be used for resolving the contributions from dierent source
categories. On the other hand, one should realize that PIXE only provides part of the
desired information. With regard to the chemical composition, it is highly desirable to
perform also measurements for important ionic species (e.g., ammonium, nitrate) and for
organic carbon (OC) and elemental carbon (EC). Furthermore, in order to arrive at a
complete aerosol characterization, the chemical measurements have to be complemented
with physical and optical (radiative) aerosol measurements.
Recent insights in the importance and role of atmospheric aerosols were provided by
Andreae and Crutzen (1997). The chapter by Cahill (1995) in the textbook of Johansson
et al. (1995) gives a comprehensive overview of the applications of PIXE to aerosol
research up to the early 1990s and gives valuable information on various aspects of
aerosols. In a review paper by Maenhaut (1992), PIXE applications of the early 1990s to
aerosols and other environmental samples are discussed.
1. Sampling Devices and Collection Surfaces
Sampling of atmospheric aerosols for chemical analysis is usually carried out by means of
lters, cascade impactors, cyclones, or a combination of these devices [e.g., Hinds (1982),
Spurny (1986), Lodge (1991), Willeke and Baron (1993)]. Similar to XRF (see also
Chapter 14), samplers that collect the particulate material on the surface of a lter or
substrate lm are also most suitable for PIXE. Although it is highly preferable for XRF
that the particles be present as a uniform layer, PIXE can also easily handle nonuniform
samples, such as those collected by single-orice or some other cascade impactors.
The collection of the aerosol by ltration is done in single-lter samplers (high-vo-
lume or low-volume samplers) which may be provided with a PM10, PM2.5, or PM1 inlet,
but also in certain devices that fractionate the aerosol in two size fractions, such as the
dichotomous sampler or virtual impactor (Dzubay and Stevens, 1975; Loo et al., 1976)
and the stacked lter unit (SFU) (Parker et al., 1977; Cahill et al., 1977). A recent example
of the latter type is the Gent PM10 SFU sampler (Maenhaut et al., 1994a; Hopke et al.,
1997). This device utilizes double NILU-type open face 47-mm-diameter lter cassettes
[Norwegian Institute for Air Research (NILU), Kjeller, Norway], operates at a ow rate
of 16 L=min, and separates the aerosol in two size fractions of 210-mm equivalent aero-
dynamic diameter (EAD) and <2 mm EAD, respectively. In most types of lter devices,
membrane or brous lters may be used, but the former, in particular Nuclepore poly-
carbonate lters, are preferred for analysis by PIXE. With brous lters and, in fact, with
certain membrane lters, a large fraction of the aerosol particles penetrates into the lter
material, so that cumbersome corrections for matrix eects are required (Kemp, 1977).
For certain applications, Teon membrane lters may be preferable to Nuclepore lters.
Unfortunately, their high uorine content gives rise to a pronounced prompt g-ray
background in the PIXE spectrum. Furthermore, some Si(Li) detection systems, when
exposed to high rates of such prompt g-rays, may exhibit resolution deterioration and
other electronic problems similar to those encountered when scattered particles penetrate
the detector. As it is impossible to nd a lter type that is suitable for every kind of
chemical analysis, systems have also been developed, such as the IMPROVE modular
aerosol monitor (Eldred et al., 1990), whereby four PM2.5 samplers with dierent lter
types are operated in parallel.
Single-lter samplers, dichotomous samplers, and stacked-lter units allow collecting
samples that may be analyzed by several techniques, including PIXE, but they do not
make full use of the favorable characteristics of PIXE, in particular its small mass re-
quirement. Several PIXE groups have therefore spent considerable time and eort in
designing innovative samplers that combined several of the following features: light
weight, battery powered, automated, and providing good time and size resolution. Nelson
and co-workers (Nelson et al., 1976; Nelson, 1977; Baumann et al., 1981) developed the
linear streaker and its successors: the circular and two-stage circular streaker. In these
devices, a Nuclepore polycarbonate lter surface is continuously moved over a sucking
orice, so that the particulate material is collected as a linear or circular streak on the lter
material. The rate of movement is typically 1 mm=h, so that subsequent analysis of the
Nuclepore strip with a 2-mm-wide beam provides a time resolution of 2 h. In recent years,
Annegarn et al. (1996) developed a variant of the streaker that can be deployed on a small
aircraft. Another example of a compact sampler is the SMART (solar monitoring of
aerosols in remote terrain), which can operate for 2 weeks at a time unattended, giving
PM10 and=or PM2.5 size cuts (Malm et al., 1994a).
In order to obtain ner size resolution than with the above samplers, the 1 L=min
single-orice Battelle-type cascade impactor, as modied and commercialized by PIXE
International Corporation (Baumann et al., 1981), can be used. This unit dierentiates the
aerosol in up to 10 size fractions and can be operated from small battery-powered pumps.
A more sophisticated design that combines both good time and size resolution is the
DRUM impactor, developed by the University of California at Davis (Raabe et al., 1988).
Cascade impactors that are widely deployed in conjunction with other analytical techni-
ques, such as the Berner low-pressure impactor (Berner, 1984) and the micro-orice uni-
form deposit impactor (MOUDI) (Marple et al., 1991), can also be used to collect samples
for subsequent analysis by PIXE (Maenhaut et al., 1993b, 1993c). These devices have the
advantage that they have several stages in the submicrometer size range and that they
operate at a ow rate of 25 or 30 L=min. However, as the aerosol particles are deposited on
a rather large area, the PIXE detection limits (in nanograms per cubic meter and per stage)
are not much better than with the 1-L=min PIXE Int. impactor (Maenhaut et al., 1993b).
An impactor which combines high size resolution with improved PIXE detection limits is
the small-deposit-area low-pressure impactor (SDI) (Maenhaut et al., 1996d). The SDI
was especially designed for aerosol collections with subsequent PIXE analysis. It provides
12 size classes (down to about 50 nm), operates at a ow rate of 11 L=min, and is a
multinozzle device, but the total aerosol deposit for each stage remains conned to an area
with diameter of less than 8 mm, so that it can be entirely enveloped by the PIXE beam.
A cross section of the SDI is shown in Figure 14.
The collection surfaces in cascade impactors are typically thin polyester (Mylar) or
polycarbonate (Kimfol) lms. To reduce particle bounce-o eects during sampling, the
lms are commonly coated with vaseline or paran.
2. Examples
There is a wealth of examples on the application of PIXE to atmospheric aerosol samples.
It is comforting to note that publications in which PIXE was used are not only published
in key journals on PIXE and the IBA techniques, such as Nuclear Instruments and Methods
in Physics Research B and the International Journal of PIXE, but also in atmospheric and
environmental chemistry journals, such as Atmospheric Environment, Journal of Geophy-
sical Research (section Atmospheres), and others. The aerosol samples analyzed by PIXE
range from those collected indoors (e.g., in work environments) or near specic pollution
sources to samples dealing with urban, regional, and global air-pollution problems, and to
samples collected in areas as remote as the Arctic and Antarctic.
a. Work Environments and Near Specic Sources
An example of a study in a work environment is that of Formenti et al. (1998b). These
researchers collected aerosols inside an arc-welding shop with a single-stage streaker
sampler, using a time resolution of 1 h. By examining the temporal variability and the
correlations among the airborne particulate elements, they extracted an arc-welding source
prole (i.e., the composition of the emitted particles). It was also found that the welding
shop activities gave rise to concentrations of up to 100 mg=m
3
for Fe and up to 7 mg=m
3
for
Cr. Studies on heavy metals in the atmosphere near copper, zinc, and steel smelters were
conducted in Chile (Romo-Kro ger et al., 1994), China (Zhu and Wang, 1998), and Italy
(Prati et al., 1998). The study near the copper smelter in Chile (Romo-Kro ger et al., 1994)
was done over a period of 1.5 months, but because of a major labor strike, there was a
total shutdown of the smelter during 22 days. It was found that S, Cu, Zn, and, especially,
As were quite enriched in the air during normal working periods relative to the strike
period. The average ne ( <2.5 mm EAD) As level at the sampling site (at 13 km from the
smelter) during normal operation was 240 ng=m
3
.
Also, the aerosol emissions from nonindustrial and larger-scale sources, such as the
1991 Kuwaiti oil res and tropical forest and savanna biomass burning, have been in-
vestigated using PIXE [e.g., Cahill et al. (1992), Reid et al. (1994), Echalar et al. (1995),
Gaudichet et al. (1995), Maenhaut et al. (1996c)]. However, in most of these studies, the
PIXE measurements were complemented with other analyses [e.g., for black carbon (BC)]
in order to arrive at a more complete characterization of the emitted particles. Some of the
collections for the Kuwaiti oil res (Cahill et al., 1992) were done with SFU samplers that
were installed on an aircraft. The samples were subjected to optical, gravimetric, scanning
electron microscopy (SEM), and PIXE analyses, yielding information on the morphology,
mass, and composition of the aerosols. It was found that the mass in the coarse size
fraction was dominated by soil-derived particles. In the ne fraction, organic matter and
Figure14 Cross section of the SDI. Only 4 of 12 impaction stages are shown. (From Maenhaut
et al., 1996d.)
ne soils each accounted for about one-fourth of the mass, whereas salt and sulfates
contributed about 10% and 7%, respectively. The work on the aerosol emissions from
tropical forest and savanna biomass burning (Echalar et al., 1995; Gaudichet et al., 1995;
Maenhaut et al., 1996c) resulted in source proles which can be used in chemical mass-
balance receptor (CMB) modeling work on ambient aerosol datasets in order to apportion
the contribution from biomass burning to the PM and various aerosol constituents
(Maenhaut et al., 1996a, 1996c).
b. Urban Areas
Numerous PIXE application papers have dealt with the study of atmospheric aerosols in
urban areas. Considering the renewed interest in the health risks of aerosols in such areas
(Pope et al., 1995), PIXE may continue to nd an important application niche in this eld.
Miranda (1996) presented an overview of the studies in large urban areas in which PIXE
was used and which were published up to 1995. Besides assessing the airborne levels of the
heavy metals and of important elements such as S, major objectives in most studies are to
identify the major sources (source types) of the heavy metals and elements and to ap-
portion them to the sources. For this source identication and apportionment, one mostly
relies on multivariate techniques, such as absolute principal-component analysis (APCA),
absolute principal factor analysis (APFA), and multiple regression analysis. Occasionally,
these approaches are complemented or compared with CMB analysis and wind direction
analysis.
Several urban aerosol studies with PIXE were carried out in Latin America, parti-
cularly in Mexico City, Santiago de Chile, and Sao Paulo city (Miranda et al., 1994, 1998;
Andrade et al., 1994; Cahill et al., 1996; Aldape et al., 1996). Andrade et al. (1994) applied
APCA to their coarse and ne aerosol data from Sao Paulo city and also to a dataset of
various meteorological variables, and they subsequently performed a correlation analysis
between the various matrices with absolute principal-component scores (APCS). This
indicated, for example, that the industrial components of both size fractions were posi-
tively correlated with the northeast wind direction. For Mexico City and Santiago de
Chile, the aerosol data were compared with those from Los Angeles, California (Cahill
et al., 1996). A rather surprising result was the rough equivalence among the three cities in
terms of several classes of ne particles. Coarser particles were, however, far more pre-
valent in Mexico City and Santiago than Los Angeles.
In Europe, extensive work with PIXE has been done on urban aerosols from
Hungary (Molna r et al., 1993; Ali et al., 1994; Borbe ly-Kiss et al., 1996; Salma et al.,
1998). In a study by Molna r et al. (1993), data for downtown Budapest were compared
with those for suburban Budapest and for rural air, and selected suburban and rural data
were subsequently used in a sourcereceptor model for estimating the dry deposition for a
number of elements. Urban aerosol studies in which PIXE was used were also done
in several other European countries (Climent-Font et al., 1994; Luis-Simon et al., 1995;
Braga Marcazzan, 1996; Swietlicki et al., 1996b; Harrison et al., 1997; Maenhaut and
Cafmeyer, 1998; Wrobel and Rokita, 1998). Swietlicki et al. (1996b) combined their PIXE
data for Lund, Sweden with results of gaseous species (SO
2
, NO
2
, O
3
) and examined the
combined dataset with APCA. About one-third of the SO
2
, most of the ne particulate S,
and about half of the ne Zn and Pb were attributed to a regional background source
originating from ferrous and nonferrous smelters. Also, Harrison et al. (1997) used PIXE
aerosol data together with results from other measurements and examined the combined
datasets with receptor modeling. In addition to two European cities (Birmingham, UK,
and Coimbra, Portugal), Lahore, Pakistan was included in this study. It was found that
there were considerable similarities between the two European cities, but large contrasts
with Lahore, with its dryer climate and poorly controlled pollution sources. Other cities in
Asia where aerosol studies with PIXE have been performed are Singapore (Bao et al.,
1995) and Kyoto, Japan (Kasahara and Gotoh, 1995).
An example of a comprehensive study on urban aerosols from Australia is the work
by Chan et al. (1997). PM10 samplers were used during 1 year at ve sites in Brisbane (and
a dichotomous sampler at one of the sites), and the samples were analyzed by a variety of
techniques, including PIXE, other IBA techniques, ion chromatography (IC), and atomic
spectrometry. The major components in the PM10 aerosols were crustal matter (25% by
mass), organics (17%), sea salt (12%), elemental carbon (10%), and ammonium sulfate
(7%). Furthermore, apart from signicant local inuences at some of the sites (such as a
cement factory), most anthropogenic emissions appeared to be rather evenly and widely
distributed in Brisbane. Also, urban aerosols from Africa have been analyzed by PIXE
[e.g., from Khartoum, Sudan (Eltayeb et al., 1992, 1993), from Lagos and Ile-Ife, Nigeria
(Ogunsola et al., 1993), and from Soweto, South Africa (Formenti et al., 1998a)].
c. Rural Areas and Regional Aerosol Studies
Particle-induced x-ray emission has been extensively employed for analyzing aerosols from
rural areas and in regional aerosol studies. Similar to in urban and local air pollution
studies, the investigations on rural and regional scales often aim at identifying and as-
sessing the sources of the particulate matter. However, whereas the urban=local-scale
studies deal with individual sources and=or source types, the emphasis in the rural=
regional-scale studies is placed on the source regions. To aid in this work, one often relies
heavily on air mass back-trajectories and wind sector data. In the United States, on the
other hand, the major objective in the regional-scale studies has been the examination of
the relationship between ne aerosol constituents and visibility degradation.
Scandinavia is a receptor region for long-range transported gaseous and particulate
pollutants from various European source regions. Research on this subject is ongoing for
several decades, and PIXE has contributed to much of our knowledge about aerosols for
Denmark and southern Sweden [see, e.g., Maenhaut and Malmqvist (1992)]. Also in the
1990s, PIXE has continued to be used for work in Denmark (Kemp, 1993, 1996). In
addition, it has been utilized in both campaign-type and long-term aerosol studies at some
sites in southern Norway (Pakkanen et al., 1996; Maenhaut et al., 1997b). In the long-term
study (Maenhaut et al., 1997b), Gent SFU samplers were employed for the continuous
collection of coarse and ne aerosols at Birkenes and Skrea dalen during a 4-year period.
The samples were analyzed for the PM, BC, and over 40 elements (by a combination of
PIXE and INAA). Seven air mass transport sectors were dened, and the air mass tra-
jectories for each individual sample served as the basis to classify the sample in one of the
sectors (or to leave it unclassied). For each sector, median coarse and ne concentrations
were then calculated for each element. Fine PM, S, BC, and various metals (V, Mn, Ni,
Zn, As, Sb, Pb) were highest for air masses coming from sectors E, SE, and S (Russia,
Poland, Germany, Benelux). For air masses from sector WSW (UK), the medians were
lower by a factor of 2 or more, and for air from the sectors WNW and NNW (Atlantic
Ocean and Norway), the median levels were 510 times lower. Substantial dierences were
also found in the multielemental proles of the dierent sectors. For example, the ratios to
noncrustal V (an indicator for heavy oil burning) varied by over a factor of 4 for As and Se
and by over a factor 10 for noncrustal Mn. Somewhat related to the research on the long-
range transport from continental Europe to Scandinavia is that on the transport to and
over the North Sea. PIXE was used for analyzing aerosol samples that were collected
above the North Sea using a small aircraft or aboard ships (Injuk et al., 1992; Rojas et al.,
1993; Franc ois et al., 1993).
As part of the Great Dun Fell Cloud Experiment 1993 in the United Kingdom,
Swietlicki et al. (1997) collected ne aerosols on lters with a 2-h time resolution and
performed analyses for soot, for elements by PIXE, and for anions and cations by IC.
Examination of the resulting dataset by APCA revealed three major source types, long-
range transport (LRT), sea spray, and a local source. LRT accounted for most of the soot,
S, Zn, sulfate, and ammonium. The results were largely consistent with those from APCA
on a separate cascade impactor dataset and with the other observations used in the source
identication.
Several rural=regional aerosol studies with PIXE were conducted in central and
eastern Europe (Molna r et al., 1995; Swietlicki and Krejci, 1996; Jagielski et al., 1996;
Amemiya et al., 1996). In the study by Molna r et al. (1995), total lter PIXE datasets for
three Hungarian sites were complemented with Cd data obtained by atomic absorption
spectrometry (AAS), with AAS data from cascade impactor samples, and with inductively
coupled plasmaatomic emission spectrometry (ICPAES) data from precipitation sam-
ples in order to derive the atmospheric budget of several particulate elements over
Hungary. It was found that the country is a net source for elements that are mostly
produced by fossil fuel combustion (V, Ni), whereas it is a net sink for elements released
during industrial processes and automotive transport.
As indicated earlier, the regional-scale studies in the United States have concentrated
on the relationship between ne aerosol constituents and visibility (Eldred and Cahill,
1994; Malm et al., 1994a, 1994b, 1996; Cahill, 1995; Malm and Pitchford, 1997). Using a
large network of IMPROVE samplers that were placed in remote areas, national parks,
and monuments, long-term collections of ne (<2.5 mm EAD) aerosol were made. PIXE
was used for measuring S, Si, K, Ca, Ti, Fe, Na, Cl, and other elements, and the data
obtained were employed to estimate the concentrations of sulfate, mineral dust, and some
other aerosol types. Another IBA technique [i.e., particle elastic scattering analysis
(PESA)] provided data for H, from which organic matter was derived. In addition, PM
was obtained by weighing, OC and EC were measured with a thermal optical reectance
(TOR) technique, anionic and cationic species were determined by IC, and the optical
absorption of the aerosol collected on lters was measured with the Laser Integrating Plate
Method (LIPM). At a number of the sites, the normal IMPROVE work was com-
plemented with measurement of the light scattering of the ambient (in situ) aerosol by an
integrating nephelometer or with DRUM aerosol collections for obtaining the detailed
size distribution of sulfate (derived from PIXE S). In examining the relationship between
light scattering, absorption, or extinction (the latter is the sum of scattering and absorp-
tion) and the concentrations of the various aerosol types, two approaches were used. The
rst (multivariate) approach relied on factor analysis or on multiple linear regression of
the optical data on the concentrations of the aerosol types (or species). In the second
approach, the particle scattering (or absorption) is estimated from the species con-
centrations and published mass-scattering (or absorption) eciencies and then compared
with the directly measured scattering (or absorption). From their examination of the re-
lationship in the Grand Canyon area, Malm et al. (1996) concluded that using EC, as
derived from TOR, to estimate the aerosol absorption may signicantly underestimate
absorption. In addition to EC, OC and soil provided substantial contributions.
Finally, as examples of rural=regional studies outside of Europe and the United
States, those of Romo-Kro ger and Llona (1993) and of Liu et al. (1996) can be mentioned.
Romo-Kro ger and Llona (1993) employed battery-powered SFUs on the slopes of the
Los Andes mountain range to collect aerosols for subsequent PIXE. Liu et al. (1996)
examined the spatial patterns of ne-particle S and Pb concentrations in New South
Wales, Australia. The data for the latter study were obtained from a network of 24 ne-
particle monitoring sites.
d. Tropical, Subtropical, and Polar Regions, and Very Long-Range Transport
In the past decades, there has been an increasing recognition that equatorial and tropical
regions, and in particular the South American and African continents and the large
Southeast Asian=Australian region, play a very important role in regional and global
atmospheric chemistry. Especially the atmospheric eects of tropical biomass burning
(res in savannas, deforestation, the burning of fuel wood and of agricultural waste) have
received much attention [e.g., Crutzen and Andreae (1990)]. The emission of particulate
matter during biomass burning occurs mainly in the form of submicrometer, accumula-
tion-mode particles (smoke). These ne particles are ecient scatterers of solar radiation,
and, as a consequence, they have often a large impact on local and regional visibility and
contribute to the planetary albedo, thus aecting regional and global climate. Moreover,
many of the pyrogenic particles can act as cloud condensation nuclei (CCN) and thereby
change the radiative properties of clouds. Outside of the burning season, natural biogenic
emissions from the vegetation provide a very substantial contribution to the atmospheric
aerosol burden, and a signicant fraction of the biogenic aerosol in the ne-size range may
be produced by oxidation and gas-to-particle conversion of volatile organic compounds
which are emitted by the vegetation.
During the 1990s, several aerosol studies were conducted in Brazil, in which one relied
heavily on PIXE (Artaxo et al., 1994; Artaxo and Hansson, 1995; Gerab et al., 1998a;
Maenhaut et al., 1996a). Artaxo et al. (1994) presented results from a long-term study on
the ne-aerosol composition at three sites in the Amazon Basin. The samples were obtained
with SFUs and analyzed for the PM, BC, and up to 20 elements. APFA on the resulting ne
datasets identied four components: soil dust, biomass burning (with BC, K, Cl), natural
primary biogenic particles, including a gas-to-particle component (with K, S, Ca, Mn, and
Zn), and marine aerosol. The biogenic and biomass burning components provided the
largest contribution to the ne PM. In southern Africa, aerosol studies with PIXE (Salma
et al., 1994; Maenhaut et al., 1996c) were conducted as part of the Southern Africa Fire-
Atmosphere Research Initiative (SAFARI-92), for which the eld work took place in
AugustOctober, during the dry season. In the study by Maenhaut et al. (1996c), aerosols
were simultaneously collected with Gent SFU samplers at three sites in the eastern
Transvaal, South Africa. In addition to PIXE, INAA was employed for the multielement
analysis, and the resulting data sets were examined by APCA and CMB receptor modeling.
Four components were identied in the ne size fraction (i.e., mineral dust, sea salt, bio-
mass burning products, and sulfate). The pyrogenic component was the dominant con-
tributor to the atmospheric concentrations of the ne BC, K, Zn, and I. About 40% of the
ne PM was, on the average, attributed to the pyrogenic particles and about one-third of it
to the sulfate component. The relation of the time trends of the various components with
three-dimensional air mass back-trajectories indicated that elevated levels of pyrogenic
products were mostly found in air masses arriving from the north.
The original stimulation for intensive aerosol research in the Arctic came from work
on the sources of Arctic haze in the 1970s (Rahn et al., 1977). In the 1980s, the nding of an
inverse relationship between non-sea-salt Br and surface O
3
during polar sunrise (Barrie
et al., 1988) provided an additional impetus. More recently, the increasing recognition that
the Arctic is a very sensitive environment and is highly important for regional and global
atmospheric chemistry and climate is giving further motivation for continued aerosol re-
search in the region. During the 1990s, long-term aerosol studies involving PIXE were
continued in Alaska (Polissar et al., 1996, 1998a, 1998b). It was found that the ratio of the
aerosol optical absorption coecient to the S concentration can be used as an indicator of
smoke from forest res (Polissar et al., 1996). Furthermore, the long-term ne-particle
datasets from seven sites were examined using a new type of factor analysis, positive matrix
factorization (PMF) (Polissar et al., 1998b). Four main sources contributed to the observed
concentrations at the more northerly locations in Alaska: long-range transported anthro-
pogenic aerosol (Arctic haze aerosol), sea salt, local soil dust, and aerosol with high BC
concentrations from regional forest res or local wood smoke. Also in the European Arctic,
long-term aerosol research involving PIXE has been conducted. Results from several years
of aerosol collections at the Zeppelin mountain station in Spitsbergen were presented
(Maenhaut et al., 1994b, 1997c; Havranek et al., 1996). The relative contributions from
natural and anthropogenic sources to the non-sea-salt (nss) sulfate were assessed, and
about one-third of the nss sulfate during summer was attributed to natural marine biogenic
emissions (emission of dimethylsulde by phytoplankton) (Maenhaut et al., 1994b). The
PIXE technique also contributed to the characterization of the atmospheric aerosol during
the International Arctic Ocean Expedition 1991 (Maenhaut et al., 1996b).
Particle-induced x-ray emission was extensively used for measuring the detailed size
distribution of particulate S, sea salt, crustal and other elements above the Greenland Ice
Sheet (Hillamo et al., 1993; Jarezo et al., 1993; Bergin et al., 1995; Kerminen et al., 1998).
The major objective in these studies was to obtain information that is needed for calcu-
lating the dry deposition velocities of the elements and to contribute to a better under-
standing of the air-to-snow transfer. At Dye 3, an 8-stage PIXE Int. cascade impactor was
used for the aerosol collections (Hillamo et al., 1993; Jarezo et al., 1993), but for the
subsequent work at Summit, 12-stage SDIs were deployed (Bergin et al., 1995; Kerminen
et al., 1998). The contributions of snow, fog, and dry deposition to the summer ux of a
number of elements and species at Summit were assessed. For S, and the crustal and sea
salt elements, dry deposition accounted for around 15% of the summer ux (Bergin et al.,
1995). Antarctic aerosol studies involving analysis by PIXE were also done (Artaxo et al.,
1992; Mittner et al., 1996; Correia et al., 1998).
That gaseous air pollutants and also natural and anthropogenic aerosols can be
transported over several thousands of kilometers fascinates atmospheric scientists for
more than three decades. During SAFARI-92, it was documented by PIXE and other
techniques that pyrogenic, biogenic, and mineral aerosols from southern Africa can be
transported to the central tropical South Atlantic (Swap et al., 1996). Perhaps a more
surprising nding derived from PIXE aerosol data is that desert dust from North Africa
may, under certain conditions, be transported to central Illinois and the eastern United
States (Gatz and Prospero, 1996; Perry et al., 1997).
e. Micro-PIXE
Whereas normal macro-PIXE is very extensively used for analyzing atmospheric aerosols,
the application of micro-PIXE and complementary nuclear microprobe techniques to this
sample type has been much more limited. The emphasis in contemporary aerosol research
is clearly placed on the submicrometer-sized particles, and to examine individual aerosol
particles of such sizes, a nuclear microbeam of 0.1 mm with an intensity of 100 pA would be
very welcome. However, progress in the development of such beam sizes has been slow.
Also, atmospheric aerosols consist of a heterogeneous population of particles of widely
variable size and composition. In order to obtain results that are representative for the
aerosol as a whole, thousands of individual particles should preferably be analyzed.
However, due to the fact that the nuclear microprobe analysis is rather time-consuming, at
most a few hundred particles are analyzed in micro-PIXE analyses of aerosols. For the fast
multielemental analysis of large numbers of submicrometer-sized particles, EPMA is
certainly to be preferred over micro-PIXE, and this is despite the fact that its detection
limits (in micrograms per gram) are about two orders of magnitude worse and that ac-
curate quantication in it is much more problematic. Rather than trying to compete with
EPMA in the analysis of aerosols, micro-PIXE should be used as a complementary
technique, for example, for obtaining additional information and=or for special aerosol
samples or problems where accurate quantitative results and=or data for real trace ele-
ments are needed.
Orlic (1995) reviewed the nuclear microprobe work on atmospheric aerosols that was
carried out up to about 1994. Examples of micro-PIXE applications on ambient (outdoor)
aerosols since then are the studies by Orlic et al. (1995) on particles from Singapore, of
Maenhaut et al. (1997a) on aerosols from Israel, of Gerab et al. (1998b) on Amazon Basin
aerosols, and of Rajta et al. (1998) on aerosols from Debrecen, Hungary. In the study by
Maenhaut et al. (1997a), micro-PIXE was used in combination with micro-Rutherford
back-scattering (RBS) to determine the quantitative composition of individual particles
and to dierentiate, for calcareous aerosols, between particles consisting of pure com-
pounds and of simple mixtures. For the latter type, the contribution from each compound
was quantitatively determined. In the study by Rajta et al. (1998), a quantitative PIXE
analysis was performed on 412 single particles (of 212 mm in diameter). The resulting
dataset was examined by hierarchical cluster analysis, and several types of soil particles
were identied. De Bock et al. (1996) employed micro-PIXE as a complement to EPMA in
their study on indoor aerosols from the Correr museum in Venice, Italy. They used the
Oxford SPM to produce elemental maps for giant particles ( >8 mm). Because of the better
detection limits, micro-PIXE allowed the detection of elements such as Ti, Cr, Fe, and Zn.
C. Other Environmental and Earth Science Applications
In addition to atmospheric aerosols, various other types of environmental sample have
been analyzed by PIXE. The applications to biological samples for environmental pur-
poses, including the use of bioindicators, were already addressed in Sec. VI.A. Here, we
will present examples of applications to samples collected from various combustion units,
such as y-ash particles, and samples from the aqueous environment, including rainwater,
river water, and river sediments. In addition, the potential of PIXE and in particular of the
nuclear microprobe for mineral prospecting and for improving our understanding of basic
geological processes will be illustrated.
1. Combustion Sources
The physicochemical characterization of particles from combustion units is of importance
from a purely environmental viewpoint, but also to understand and improve the com-
bustion technology. The environmental impact comes from particles that are emitted
through the stack into the atmosphere, but also from the particulate material that is
collected by electrostatic precipitators (ESPs) or other cleaning devices, or is recovered as
bottom ash. For ESP ash and bottom ash, the levels of heavy metals are of critical im-
portance for making decisions on their use as construction material, their distribution to
agricultural or other land, or their disposal as waste.
Several studies involving micro-PIXE have been done on particles from coal com-
bustion (Jaks ic et al., 1993; Caridi et al., 1993; Bogdanovic et al., 1994, 1995; Cereda et al.,
1995a, 1995b, 1996; Rousseau et al., 1997; Hickmott et al., 1997). The PIXE groups from
Zagreb and Milan, in cooperation with the Oxford SPM group, have been especially active
in this area. The y-ash and other ash particles usually had sizes of several micrometers,
which makes them more appropriate objects for nuclear microprobe investigations at the
individual particle level than, for example, submicrometer-sized atmospheric aerosols.
Bogdanovic et al. (1994) used STIM in combination with micro-PIXE in order to obtain
information on the areal density and topology of individual y-ash particles and to be able
to convert the elemental intensity maps into actual concentration distributions. Cereda
et al. (1995b) examined about 100 particles that were collected at the outlet of a pilot ESP
of a coal-red power plant. As a result of the combustion of the dierent components of
the mineral matter in the parent coal, seven particle classes with characteristic matrix
compositions and dierent trace element concentrations were observed. The trace elements
were found to be nonuniformly distributed over the particles. Elements which are asso-
ciated with volatile compounds, such as S, Ni, Zn, and Ga, were clearly more concentrated
in the smaller particles ( <2 mm) than in the larger ones.
Macro-PIXE in combination with other techniques has been used for the analysis of
cascade impactor samples that were collected at various locations in the ue gas stream of
coal burners (Maenhaut et al., 1993c; Lind et al., 1994, 1996) and recently also of biomass
combustion units. In their study on the volatilization of heavy metals (Cu, Zn, Cd, Pb)
during circulating uidized bed combustion of forest residue, Lind et al. (1999) found that
none of these metals were enriched in the ne particles at the inlet of the ESP. In order to
obtain source proles from the combustion of herbaceous and wood fuels, Turn et al.
(1997) conducted biomass burning experiments in a wind tunnel, collected the emitted
particles with a variety of samples, including DRUM impactors, and analyzed the samples
by PIXE, XRF, and some other techniques.
2. Aqueous Environment
Liquid samples are not very suitable for direct analysis by PIXE. They are often analyzed
after pipetting a fraction on a suitable backing lm, letting it dry, and then bombarding the
residue. However, in order to obtain detection limits that can compete with those in ICPMS
or AAS, one has to resort to preconcentration techniques. Savage et al. (1995) experimented
with dried algae for preconcentrating metallic trace elements from water for subsequent
PIXE analysis. For the preconcentration of precipitation samples, Tschierch et al. (1996)
built a spray-drying apparatus that was similar to that developed by Hansson et al. (1988).
Examples of applications of PIXE to rainwater are the work of Ghorai et al.
(1993) in Alabama (USA) and of Kasahara et al. (1996) in Kyoto, Japan. In the latter
study, rainwater was collected with 0.1 mm of rainfall from the start of each rain, and the
samples were ltered through a 0.2-mm pore-size Nuclepore lter, so that the soluble and
insoluble components could be determined. In accordance with earlier studies, it was
found that the concentrations of the elements in the rain decreased quickly until about
0.5 mm of rainfall. Si, Ti, and Fe were mainly present in the insoluble component of the
rain, whereas virtually all the S and Cl was soluble. River water from India and Portugal
was analyzed by PIXE (Kennedy et al., 1998; Araujo et al., 1998). Cecchi et al. (1996) gave
an overview of their comprehensive study on the Venice Lagoon. Somewhat special water
samples are ice cores drilled from glaciers or inland ice. Such samples are collected
to investigate variations in their composition and trace element content with depth
(e.g., along the core) and, by doing so, to obtain information on past environmental or
climatic changes or to assess the impact of major volcanic eruptions. PIXE oers the
possibility of analyzing ice cores with millimeter resolution, so that the seasonal and an-
nual elemental variation can be studied in great detail (Hansson et al., 1993). Samples for
PIXE may be prepared by placing ice sections on a thin backing lm and removing the ice
by sublimation. Hansson et al. (1993) used this approach for samples from a deep core,
which was drilled at Dye 3, South Greenland. The spatial (and thus temporal) variations in
the elements measured by PIXE were used to assist in the dating of some sections from the
core. Laj et al. (1996) coupled macro-PIXE with EPMA for characterizing atmospheric
aerosol particles and soluble species in ice cores from Summit, Central Greenland.
Several PIXE studies have been devoted to the study of sediments in rivers, estuaries,
or the sea (Randle et al., 1993; Limic and Valkovic , 1996; Valkovic and Bogdanovic , 1996;
Mart n et al., 1996, 1998a, 1998b; Benyaich et al., 1997; Dutta et al., 1998; Tang et al.,
1998), mostly to assess the anthropogenic input of heavy metals and other elements. Randle
et al. (1993) compared INAA and PIXE for the determination of heavy elements in es-
tuarine sediments and concluded that the two techniques should be regarded as com-
plementary rather than competitive. Valkovic and Bogdanovic (1996) used a combination
of PIXE and XRF. A total of 19 elements were measured by PIXE and 12 by XRF. For
elements that were determined by both techniques, reasonable agreement was observed.
Also, Benyaich et al. (1997) made a comparison of PIXE and XRF, and they concluded
that the two techniques are complementary. Dutta et al. (1998) analyzed ferromanganese
oxide deposits from dierent locations of the Indian Ocean by PIXE. Based on the Mn=Fe
ratio, the deposits were classied into hydrogenous and hydrothermal types, and the dis-
tribution of various minor and trace elements in both types were studied. Several elements
exhibited higher concentrations in the hydrogenous deposits than in the hydrothermal
ones. This was attributed to suitable physicochemical oceanic conditions prevailing at the
depositional sites and the growth rate of the deposits. The concentrations of Co, Ni, and Cu
were dependent on ocean depth. It was also found that the hydrothermal processes seem to
be more controlling in the uptake of V and As than the hydrogenous processes.
3. Mineral Prospectingand Geology
In addition to sediments in aqueous systems, there exists a very large variety of other
geological materials. During the past decade, macro-PIXE sometimes in combination with
complementary IBA techniques has been applied for analyzing soils (Cruvinel and
Flocchini, 1993), mineral grains (Vogt et al., 1992; Pillay et al., 1993), microspherules in
bedded chert (Miono et al., 1993), emeralds (Ma et al., 1993), and vein quartz from the
Tasmania gold mine (Russell et al., 1996). In the latter study, it was found that gold-
bearing quartz has higher Ge, Li, As, Mn, Fe and Al contents and lower K, S, Na and Cl
than barren quartz samples.
Because of its unique ability to provide quantitative trace element information on a
micrometer scale, micro-PIXE oers great potential for mineral prospecting and for im-
proving our understanding of basic geological processes. Actually, the nuclear microprobe
could serve as an excellent complement to the electron microprobe in these areas. The
capabilities of micro-PIXE are increasingly recognized by scientists in mineralogy and
geology, and some major research programs have been running over a long period (Cabri
et al., 1985; Sie, 1997).
The mineral sample preparation techniques used for other microscopic techniques
(e.g., for the electron microprobe) are, to a large extent, also suitable for micro-PIXE.
Great care should be taken to reduce surface roughness, however, as otherwise accurate
quantitative data cannot be obtained. For realizing a smooth surface, grinding or pol-
ishing are normally used, but in applying such procedures for PIXE, contamination
control is much more stringent than for the case of the electron microprobe. Hence, it is
recommended to use diamond powder for polishing, because this contains only carbon.
Furthermore, to take full advantage of the spatial resolution of the microbeam, it is ne-
cessary to prepare specimens that are less than a few micrometers thick. This can be done
by using an ion-milling technique.
The complex matrix composition of many geological specimens means that accurate
correction for projectile slowing and x-ray attenuation is quite complicated. Also, the
PIXE spectra of such specimens are often complex, so that special evaluation codes are
required (Ryan et al., 1990a). Finally, it should be realized that because of the relatively
large range of protons in matter, underlying layers of possibly quite dierent composition
may also contribute to the PIXE spectrum for certain specimens. To improve the accuracy
of nuclear microprobe analysis, it is almost always preceded by electron microprobe
analysis from which the matrix composition can be inferred. However, in a study to check
the quantication of the matrix elements, Campbell et al. (1997) investigated silicates and
glasses using only micro-PIXE. They used two x-ray detectors simultaneously to be able to
also measure the very light elements, and they showed that, with good calibration, one can
obtain the matrix composition with adequate accuracy.
The micro-PIXE analysis can be done either point-by-point or by performing a two-
dimensional scan over a selected area. The latter method provides ne maps for the major
and minor elements but is normally not sensitive enough at the trace element level. The
two-dimensional image can be used for selecting interesting spots for subsequent point-by-
point analysis. Alternatively, the pixels in arbitrary regions of interest can be added and
quantied o-line. As will be discussed in Sec. VII.C.2, a complementary technique, io-
noluminescence, is preferably combined with micro-PIXE for imaging and for analysis of
the geologically very important rare earth elements. Figure 15 shows elemental maps (from
micro-PIXE) and the distribution of the ionoluminescence (IL) obtained by scanning over
a 0.2560.25-mm
2
area of a zircon. The combination of optical viewing through a
microscope and the IL imaging technique signicantly facilitates orientation on the spe-
cimen and guides the geologist to nd the relevant spot for detailed microanalysis.
One important eld of application for micro-PIXE is ore mineralogy. In particular,
microanalysis of suldes has been extensively used. Grin et al. (1996) employed micro-
PIXE to analyze polished tourmaline sections collected in massive sulde deposits and
demonstrated the usefulness of trace element data for mineral exploration. A combined
electron and nuclear microprobe study of uid inclusions in quartz crystal from a por-
phyry copper deposit has contributed to the understanding of the metallogeny of the
deposit, even though only qualitative micro-PIXE data were obtained (Damman et al.,
1996). Other examples of successfully using micro-PIXE are studies on meteorites (Vis,
1997), patina layer analysis on rock artifacts in South Africa (Pineda et al., 1997), analysis
of platinum-group metals and gold (Maetz et al., 1997), and studies of fossil uids in rocks
(Volnger et al., 1997). The great potential and future of nuclear microprobes in geo-
science have recently been comprehensively discussed by Sie (1997).
As indicated in Sec. III.B.3, micro-PIXE can also be done in an external beam setup
in air and this possibility is also useful for analyzing some geological specimens. Accurate
elemental maps for areas of several hundreds of square millimeters can be produced by
mounting the specimen, which may be very large, on a simple xy plotter table controlled
by the normal beam-scanning electronics (Lo vestam and Swietlicki, 1989).
The most spectacular use of PIXE in the past few years has undoubtedly been the
deployment of the portable a-proton x-ray spectrometer (APXS) on Mars (Rieder et al.,
1997a, 1997b). The APXS was a compact (600 g) device installed on board the Sojourner
rover of the Mars Pathnder. Alpha-particles from a 50-mCi
244
Cm source were used for
the excitation, and the x-rays were detected with a thermoelectrically cooled Si p-i-n de-
tector with a resolution (FWHM) of 250 eV at 6.4 keV. Besides PIXE, RBS and NRA
[using (a, p) reactions] were employed with the APXS. The PIXE results indicated that the
Martian rocks were high in Si and K, but low in Mg compared to Martian soils and
Martian meteorites. The analyzed rocks were similar in composition to terrestrial ande-
sites and close to the mean composition of the Earths crust. Addition of a mac com-
ponent and reaction products of volcanic gases to the local rock material is necessary to
explain the soil composition.
D. Applications in Arts and Archaeology
One application of PIXE and, in particular, of micro-PIXE that has been unexpectedly
successful is the analysis of archaeological and art objects. Recently, Swann (1997) gave a
comprehensive review of the applications of nuclear microprobes in this eld. Recognition
of the potential of PIXE and other IBA techniques for art investigations has led to the
installation of an ion-beam analysis facility in the scientic laboratory of the Louvre
Museum in Paris (Menu et al., 1990), with a subsequent inclusion of a nuclear microprobe.
Such probes are currently used in several other laboratories specializing in archaeology.
Figure 15 Nuclear microprobe analysis of a natural zircon using 2.5-MeV protons. Elemental
maps obtained from micro-PIXE (Zr, Hf, Fe) and a map of ionoluminescence (IL). Scan size:
250 mm.
Because nondestructiveness is more important here than in other applications, there must
often be a trade-o between beam size and intensity in order not to damage an object.
Larger probe sizes and lower intensities than in other elds of application are normally
used. External-beam microprobes are particularly useful. Because of the heterogeneous
structure of many archaeological artifacts, using a highly collimated=focused ion beam is
somewhat problematic as the elemental data obtained depend very much on the position
of the beam. Many objects may contain inclusions and grains which are not representative
of the bulk. Consequently, the data must be very carefully scrutinized and one should be
careful about drawing conclusions from a few single-spot analyses. Although metallic
objects are not very sensitive to radiation damage, problems for non-noble metals may
arise from the presence of a patina or thick layers of corrosion. The shallow analytical
depth of the nuclear microprobe requires the removal of any such layers if one wants to
obtain results that are representative for the bulk material. Removal may be prohibitive in
some cases, but the situation is generally even worse when using most other analytical
methods. Several large-scale studies have been performed on copper-based alloys, mainly
antique bronzes. In such studies, especially great care has to be taken to avoid erroneous
analytical data due to surface eects caused by corrosion.
The Schonland nuclear microprobe in Johannesburg was used to characterize Iron
Age tin artifacts following bulk trace element analysis by INAA and ICP-MS (Przyby-
lowicz et al., 1993). The heterogeneity revealed by the nuclear microprobe provided a
plausible explanation for the large discrepancies between the bulk analysis techniques. In
addition, the microanalytical results yielded information on smelting, crafting, and mi-
neral composition of the local ores (Przybylowicz et al., 1993).
Noble metals, such as gold and platinum, are much less aected by deep corrosion
over long time spans, so that problems of surface layers are less pronounced. Demortier
and colleagues (Demortier et al., 1991; Demortier and Morciaux, 1994) used the external
nuclear microprobe at Namur, Belgium in extensive systematic investigations of gold
jewelery with the aim of determining the age and manufacturing processes. For ancient
artifacts with a gold surface, the nuclear microprobe is an ideal tool to characterize narrow
regions, in order to understand the skill of ancient goldsmiths. The presence of Cd in
ancient soldering processes is discussed, with many details on the interpretation, in old
metallurgical handbooks. In the 19th century, Cd was used as an additive to lower the
melting point when soldering gold. Its presence has therefore been regarded as a sign of a
modern object. However, the correlation between Cu and Cd is reversed in the newly
manufactured material. By he multielemental character of the PIXE method, forgeries of
ancient gold items can thus be revealed. Also, the Bartol group (Weldon et al., 1996)
performed studies of gold jewelery using an external nuclear microprobe, with the aim of
dating the manufacturing of some golden pendants.
Microanalytical techniques allow one to study pigments in paintings in greater
detail, for instance, for authentication of suspect forgeries or for understanding ancient
painter technologies. If samples can be collected without interfering with the visible parts
of a painting and there is a strong enough interest to make a detailed study, the nuclear
microprobe is a good complement to nondestructive techniques and to electron mi-
croprobes. By removing small pieces of pigments from a leadtin yellow region of a
painting, Grime et al. (1991) were able to produce elemental maps both by PIXE and
RBS. The conclusion drawn from this work was that, due to the deep penetration of the
ions and the risk of reaching layers below those relevant, micro-PIXE work on pigments
should, whenever possible, be combined with the depth-resolving ion-backscattering
technique.
In the eld of osteology, the Oxford SPM group has carried out some studies, both
looking at the uptake mechanisms of trace elements by bone under laboratory conditions
and studying the eects of environmental chemistry on human bone from a variety of sites
(Elliot and Grime, 1993). Ca and Fe distributions were determined within the matrix of an
unprovenanced human clavicle from the Mary Rose shipwreck of 1563. The results (see
Fig. 16) clearly show an accumulation of Fe at the bone surfaces that is attributed to
Fe-xing marine micro-organisms. Another nding of the study was the presence of a
surface enrichment of Pb. These results and others from terrestrial burials indicate that the
interactions between buried bone and its surroundings are extremely complex and that it is
dicult to distinguish the uptake of trace elements during a lifetime from the alterations
that occurred after burial. Another nuclear microprobe study on a skeleton was performed
at the Pierre Su e laboratory in Gif sur Yvette (Boscher-Barre and Trocellier, 1993). A 6th-
century womans skeleton buried in a lead sarcophagus was excavated near Lyon. Femoral
transverse sections were analyzed using micro-PIXE, NRA, and particle-induced g-ray
emission analysis (PIGE). A comparison was made with similarly prepared samples from a
newly deceased female. Carbon, O, Ca and Pb proles were determined across the sections.
This study was made possible by the high lateral resolution of the nuclear microprobe.
The dark black ink used in the Gutenburg bibles has fascinated other printers and
scientists through the centuries. Even after 500 years, the printing is very clear and distinct.
At the University of California Davis, the milliprobe PIXE system was initially designed
with the main purpose of characterizing the ink used in the Gutenburg bible (Kusko et al.,
1984), and it was later used for studying the Vinland map (Cahill et al., 1987). The
Davis group has improved the system over the years, providing enhanced security systems.
The results from analyzing large numbers of individual letters show that the main reason
for the high printing quality is the high concentration of Pb and Zn in the pigment. In
addition to determining the ink composition, the composition of individual paper sheets
was determined also. At Lund, an external semimicroprobe was used to examine portions
Figure 16 Elemental maps of an archaeological human bone sample collected in a marine
environment. The deposition of iron (Fe map) on the surface in the voids of the bone structure
(Ca map) is clearly shown. Dark areas indicate high concentration and light areas indicate low
concentration. (From Elliot and Grime, 1993, with permission from Elsevier Science.)
of handwriting on a 2000-year-old papyrus. By scanning the microbeam, maps of several
elements were produced for regions with faded writing. The multielement dataset was then
treated by a multivariate statistical technique in order to improve the contrast, and by
doing so, a two-dimensional pattern was obtained which revealed the actual letters
(Lo vestam and Swietlicki, 1990).
More recently, several groups have followed with similar studies. In Florence,
a system for document analysis using an external nuclear microbeam has been set up
(Lucarelli and Mando` , 1996). The emphasis has been on detailed characterization of
ancient inks in order to support theories on technology and trade routes of raw material.
Systematical methodological examinations were performed which showed that relevant
information can be obtained for medieval inks (Cambria et al., 1993). Among the docu-
ments investigated were some from the famous father of modern experimental physics,
Galileo (Giuntini et al., 1995). An external nuclear microprobe with special arrangements
for document analysis has also been set up at Oxford (Grime, personal communication,
1999). In these systems, it is crucial that the precious old documents are not damaged in
any way by the ion beam. Furthermore, it is important to aim the nuclear microbeam
accurately at the region of interest, which is normally facilitated by laser beams.
In addition to micro-PIXE, macro-PIXE has also been extensively used in arts and
archaeology and found to provide very useful information. Actually, the distinction be-
tween micro- and macro-PIXE is dicult to make in this eld of application, as much
work is carried out with (external) miniprobes or milliprobes, which have beam sizes
ranging from a few tens of micrometers to about 1 mm. Also, one often applies both
micro- and macro-PIXE analyses on the same samples. The multielement character of
PIXE and the speed of analysis are very useful in provenance studies of pottery and
earthenware [e.g., Lin et al. (1992), Hamanaka et al. (1994), Pio et al. (1996a, 1996b),
Cheng et al. (1996), Gosser et al. (1998), Zucchiatti et al. (1988)]. Cheng et al. (1996) found
that the trace elements Rb, Sr, and Zr can be used to trace the place of production of
ancient porcelain. By measuring major, minor, and trace elements in white glaze by PIXE,
they could distinguish a precious Chinese Qing dynasty porcelain from a fake. Also, ob-
sidians and prehistoric int tools have been examined by PIXE and other IBA techniques
(Murillo et al., 1998; Smit et al., 1998). Murillo et al. (1998) characterized obsidian
samples from dierent mineral sites in Mexico. Oxygen was determined by means of the
16
O(d, p)
17
O reaction, and the elements from K to Br by PIXE using an external-beam
facility. The light elements Na, Al, and Si were measured by PIGE, and RBS, using a-
particles, was employed to determine O, Si, and Fe. Smit et al. (1998) performed a study
on the usewear-induced deposition of polish on prehistoric int tools. They concluded that
the concentration of the elements Ca and P in the polish can be used to determine whether
the tool was used for work on bone or wood.
Cast iron, ancient iron slag, archaeological bronzes, ancient Greek copper coins,
precious metals, and gold artifacts have also been the subject of studies with macro-PIXE
and other IBA techniques (Kallithrakas-Kontos et al., 1993, 1996; Narayan et al., 1996;
Miono et al., 1996; Climent-Font et al., 1998; Guerra et al., 1998; Salamanca et al., 1998).
Narayan et al. (1996) used external-beam PIXE to examine cast-iron sow bars which had
been produced in the mid-1600s at Saugus, Massachusetts. Saugus is one of the few sites
where colonial Americans manufactured iron at that time, and a local rock gabbro served as
replacement for the limestone uxing agent traditionally used in England. The study
showed that gabbro introduced P and Ca in the iron, so that the levels of these elements can
be used as a ngerprint for Saugus iron. Climent-Font et al. (1998) employed a combi-
nation of PIXE, PIGE, RBS, and Auger electron spectroscopy (AES) for examining
archaeological bronzes. They found that the joint use of these techniques was quite useful,
as complementary information was obtained on elemental composition and chemical state.
The possible disturbance of the patina as a mask for the determination of the original
underlying bronze composition was also studied. Kallithrakas-Kontos et al. (1996) applied
external-beam PIXE for analyzing ancient Greek copper coins. In this work, the patina was
removed prior to analysis, as described in detail in an earlier publication (Kallithrakas-
Kontos et al., 1993). Gold jewelery artifacts of Tartesic origin (700500 BC) were examined
by external-beam PIXE by Salamanca et al. (1998). Collimators along the incident proton
beam path allowed the artifacts to be irradiated in narrow regions down to 350 mm in
diameter. Special attention was paid to the procedure of soldering in various narrowregions
of the bindings of ligrees, twisted wires, narrow strips, and granulations on nely deco-
rated items. The relative concentrations of Au, Ag, and Cu in such regions were determined.
The results seemed to indicate that the solderings were made by local fusion and brazing.
No procedure of solid-state diusion bonding like in Etruscan jewelery was identied.
E. Materials Analysis
Materials analysis is a vast eld of application for ion-beam analysis (IBA) techniques.
A comprehensive treatment of the various IBA techniques (with the exception of PIXE) in
the eld of materials analysis can be found in the Handbook of Modern Ion Beam Materials
Analysis (Tesmer et al., 1995). Rutherford backscattering spectrometry (RBS) in particular
is very commonly used for examining surface layers and determining elemental depth
distributions in various materials. PIXE generally serves only as a complementary tech-
nique. Because most matrices in this area are made up of elements with relatively high
atomic number, the characteristic x-rays of the matrix elements show up in the PIXE
spectra, thereby worsening the detectability of the trace elements. When the matrix is
rather light, however, as in the case of polymers, some semiconductor materials, and
cellulose bers, PIXE can provide concentration data down to the microgram per gram
level. For microscale characterization of materials, the nuclear microprobe has emerged as
an important technique (Breese et al., 1996), in particular when micro-PIXE is combined
with complementary IBA techniques. It has therefore also been implemented in the in-
dustrial environment (e.g., in development and production plants in the microelectronics
industry). Although the micro-PIXE technique provides essentially only elemental maps
and=or concentration data, the combination with various imaging techniques makes the
nuclear microprobe an invaluable tool in materials analysis. It forms a ne complement to
the vast array of surface and near-surface characterization techniques, such as Auger
electron spectroscopy, photoelectron spectroscopy, scanning electron microscopy, sec-
ondary ion mass spectrometry (SIMS), and many other techniques (Brune et al., 1997).
1. Semiconductor Materials
The majority of analyses on this type of material are performed as routine PIXE and RBS
measurements in semiconductor plants, with the aim of monitoring wafer processing.
However, PIXE and nuclear microprobes are also frequently used in research and de-
velopment environments for the characterization of silicon-based and other semi-
conductor materials, such as GaAs. Examples of macro-PIXE studies on the latter
material are the work by Kuri et al. (1996) and Wendler et al. (1996). Kuri et al. (1996)
used PIXE and XRF to study the eect of MeV Au ion implantation on the composition
of GaAs upon vacuum annealing. Practically no As loss was observed from the implanted
region, whereas such loss was signicant for the unimplanted region. Optical micrographs
taken on both regions showed the formation of Ga droplets on the unimplanted region
above 600
C annealing. No such features were observed in the implanted region up to

850
C. This indicated that MeV Au ion implantation inhibits the As release from GaAs.
For a given annealing temperature and duration, the amount of As loss was dependent on
the dose of implanted Au. Wendler et al. (1996) measured displacements in 2-MeV Se
implanted GaAs by RBS and PIXE channeling experiments. It is also possible to combine
micro-PIXE and micro-RBS with channeling. Under channeling conditions (i.e., when the
projectiles are guided along crystal axes or crystal planes), the interaction probability is
decreased and this leads to a reduced yield of induced x-rays or scattered particles.
By comparing the yields obtained for channeling and for random orientation, information
on the crystal structure and on interstitial atoms may be obtained (King et al., 1993;
Tesmer et al., 1995). To visualize the results from micro-PIXE and micro-RBS channeling
experiments, channeling contrast microscopy (CCM) can be used. The Microanalytical
Research Centre (MARC) in Melbourne is very active in studies on frontier materials,
mainly semiconductors (Jamieson, 1997). It applied micro-PIXE, micro-RBS, and CCM
in a study on diamond ion implantation and annealing. A diamond specimen was im-
planted with 4-MeV P
ions, whereafter the implanted region was laser annealed and

regrown, and examined with the nuclear microprobe. Figure 17 shows the channeling
angular yield curves from the center of the laser-annealed and regrown region, together
with the CCM images. The reduction in the yield of PKa x-rays in the channeling
Figure17 Yield of PIXE and RBS versus the tilt angle from the channeling direction in diamond.
CCM images are shown for both scattered particles and P x-rays. The CCM images cover an area of
1006100 mm
2
. (From Jamieson, 1997, with permission from Elsevier Science.)
orientation indicates that at least 50% of the implanted P atoms are substitutional on the
lattice sites.
2. High-Temperature Superconductor Materials
Ever since the discovery of the high critical temperature (high-T
c
) superconductors, ion
beams have been widely applied to study this new class of materials. For composition
analysis, RBS and non-Rutherford backscattering are commonly used. Tang et al. (1993)
explored the potential of deuteron-induced x-ray emission (DIXE) in combination with
the simultaneous measurement of the prompt g-rays from the
16
Od; pg
17
O reaction for
the complete stoichiometric analysis of YBaCuO superconductors. They found that the
technique was very sensitive to particle size eects, but concluded that good results should
be obtained for high-quality bulk specimens and thin-lm samples. S
andrik et al. (1993)

applied macro-PIXE in combination with RBS for the determination of the composition
of high-T
c
superconducting lms of YBaCuO and compared the results with those
obtained by ICPAES and XRF. It was concluded that the PIXE=RBS combination yields
concentration data for the matrix elements with 5% accuracy and a precision better than
3%. In a subsequent study, S
andrik et al. (1996) examined the stoichiometry and lateral

homogeneity of thin lms deposited from aerosol on MgO substrates. RBS and PIXE
analyses distinguished areas that were found to dier in the critical temperature values.
The PIXE results conrmed the dierences in composition between those areas. Variations
in layer thickness were found by means of RBS. Also, Ishii and Nakamura (1993) used a
combination of macro-PIXE and RBS in their analyses of thin lms of oxide super-
conductors, but in addition to the matrix elements, some impurity elements such as Fe, Cr,
and Ni were determined. Ecker et al. (1996) performed channeling studies of YBaCuO thin
lms with combined RBS and PIXE and they concluded that valuable additional in-
formation was obtained on the properties of epitaxially grown lms. This is of particular
interest for the thicker lms needed in microwave devices. Ahmed et al. (1997) performed
nondestructive depth proling on a small single crystal (1.5 mm6 1.3 mm60.1 mm) of an
YBaCuO superconductor by scanning its thickness with a proton microbeam and ana-
lyzing the micro-PIXE spectra obtained. Elemental composition spectra, two-dimensional
elemental distribution maps, and one-dimensional line-scan spectra from several parts of
the thickness were produced.
3. Metals
In most of the nuclear microprobe studies on metallurgical samples, use was made of NRA
in order to determine the low-Z elements (Doyle et al., 1991; Breese et al., 1991). Because
metals and metal alloys consist generally of high-Z elements, they are far from ideal
specimens for PIXE. Nevertheless, by optimizing experimental conditions, it is possible to
study, for instance, corrosion processes and diusion proles in such materials. One ex-
ample of a micro-PIXE study is that done on proposed superconducting wires for magnets
in the International Thermonuclear Experimental Reactor (ITER). These wires contain Sn
and Nb in a matrix of ultrapure Cu, and they are plated with Cr. Micro-PIXE was used to
study the diusion of Cr into the Cu matrix as a function of the temperature (Morse et al.,
1997). Already at rather low temperature, unexpectedly high Cr concentrations were
found in the Cu, and this was interpreted as being due to the formation of precipitates.
Other examples of metal analysis using micro-PIXE are the study of nodular cast in order
to draw conclusions regarding the nodularization process (Songlin et al., 1995) and the
investigation of lead in a chill-cast aluminum ingot of a bearing alloy (Breese et al., 1992).
In the latter case, a combination of PIXE, backscattering spectroscopy, and STIM was
used in addition to traditional techniques, such as an electron microprobe. The lead
precipitates could be identied and localized.
There are also examples of the application of macro-PIXE to metals and alloys.
Feng et al. (1996) used it to determine the antinodularizing elements Al, Pb, and Bi in
nodular cast iron. Wa tjen et al. (1996) used a combination of PIXE, RBS, and resonant
elastic backscattering to determine the depth proles and doses of Y implants in Cr and
NiCr alloys, the mass contents of Cr and Ni, and the oxygen concentration in surface
layers of the alloys before and after implantation. Only through the simultaneous use of
PIXE was a severe error in the alloy preparation revealed. One of the nominal binary
alloys was found to contain about 5% Fe, which inuences the corrosion behavior of this
material signicantly. Nakae et al. (1994) used a combination of PIXE channeling and
RBS channeling for characterizing single crystals of type 304 stainless steel. He
particles
were used as incident ions for both types of measurements. The study indicated that a
solution annealing process is absolutely necessary for producing a good single crystal. It
was further found that the P atoms were mostly on substitutional sites of the face-centered
cubic (fcc) structure and that the MeV He
ion irradiation induced segregation of Si and S

atoms to the (110) surface. In a subsequent study (Kawatsura et al., 1996), the radiation-
induced segregation was further examined.
4. Cellulose Fibers
The quality and properties of paper used for printing and various other purposes are
highly variable, depending on the particular demand from the industry which uses the
produced paper. One eld of great economical importance worldwide is the newsprint
industry, where extensive use is made of recycled ber material and where very tight time
constraints exist in the printing phase. There is great demand for an enhanced under-
standing on the right combination of printing technique and paper quality. At Lund, a
project involving the nuclear microprobe, and partially funded directly from industry, was
initiated as part of a larger project on physical characterization methods for newsprint
Figure18 Copper and STIM map from investigation of newsprint paper by a nuclear microprobe.
The Cu distribution reflects the pigment distribution and the STIM reflects the mass areal density
of the cellulose fibers. Dark areas indicate high concentration and light areas indicate low
concentration. Scan size: 0.5 mm. (Courtesy of P. Kristiansson.)
paper (Kristiansson et al., 1997). The basic problem of interest is the transfer of pigment to
the paper material in the printing process. The micro-PIXE technique can be used to
produce elemental maps of printed dots on various quality papers, and by interpreting the
patterns, it is possible to provide suggestions for appropriate modications in the pro-
duction process of the printed paper. The interpretation of the micro-PIXE results is fa-
cilitated when combined use is made of STIM to characterize the brous structure of the
newsprint paper. This is illustrated in Figure 18, where an elemental map of Cu and a
corresponding STIM map are shown. The Cu intensity is proportional to the pigment
concentration, and the STIM map shows the paper density.
VII. COMPLEMENTARYION-BEAM-ANALYSIS TECHNIQUES
On several occasions in this chapter, it has already been indicated that the MeV ion beams
employed for PIXE are also very useful for other ion-beam analysis (IBA) techniques. The
main interaction of MeV ions are close encounters, but also shallow encounters leading
to recombinations in the outer electron shells can be used by detecting the near-visible light.
In this section, the various IBA techniques are briey presented. In particular, it is shown
through examples of applications that the other IBA techniques can provide information
that is complementary to that obtainable by PIXE (e.g., by extending the elemental
coverage down to hydrogen) and that such analyses may often be done simultaneously with
the PIXE analysis. This represents an important advantage of PIXE over other x-ray
spectrometric techniques. For comprehensive accounts on the various complementary IBA
techniques, we refer to a number of textbooks (Chu et al., 1978; Ziegler, 1975; Thomas and
Cachard, 1978; Bird and Williams, 1989; Tesmer et al., 1995; Breese et al., 1996) and the
proceedings of the biennial IBA conferences [see Gyulai et al. (1994), Culbertson (1996),
and da Silva et al. (1998) for the last three conferences in the series].
A. Elastic Scattering Spectrometry and Related Techniques
Elastic scattering spectrometry involves the detection of the elastically scattered incident
particles or the elastically recoiled target nuclei. The rst approach is used in such tech-
niques as Rutherford backscattering spectrometry (RBS), Rutherford forward-scattering
spectrometry (RFS), particle elastic scattering analysis (PESA), and forward a-scattering
(FAST). Strictly speaking, the terms RBS and RFS imply that the scattering process is
purely Coulombic (i.e., according to the Rutherford law), but they are often used in a
broader sense and also include non-Rutherford scattering. RBS is a very prominent
technique in materials analysis, in which one generally applies 2-MeV a-particles and large
scattering angles. With such particles, deviations from the Rutherford cross section are
small for all target elements. In scattering spectroscopy using protons with an energy of a
few megaelectron volts, as is often done when combined with PIXE, quite substantial
deviations occur for the lighter target elements (up to about Ti) because of nuclear in-
terference. As the incident particle energy increases, the deviations become greater both
for protons and a-particles. The energy of the scattered particles depends on the scattering
angle, the energy and mass of the incident ion, and the mass of the target element. When
the specimen is not innitely thin, the scattered particle energy also depends on the in-
teraction depth. Incident particles lose energy as they penetrate into the specimen and the
scattered particles, in turn, lose energy on their way out to the detector. Elastic scattering
spectrometry therefore allows us to obtain information on both the elemental composition
of a sample and the distribution of the elements with depth, which is a very important
asset for materials research. However, the dependence of scattered particle energy on the
interaction depth also has the eect that RBS spectra, in contrast to PIXE spectra, may
contain broadened peaks (in the case of semithick samples), consist of a staircase of nearly
rectangular shelves (for innitely thick specimens of homogenous composition), or exhibit
a more complicated appearance. Furthermore, even for innitely thin specimens, the
scatter peaks from analyte elements (nuclei) of neighboring mass become less and less
resolved with increasing mass. For complex specimens, such as aerosol samples or bio-
medical or geological samples, RBS can only provide information on the lighter elements
(up to about Si), and extraction of the requested concentrations is generally dicult. The
reasons for the successful application of RBS for examining medium and heavy elements
in materials research is that substantial a priori information about the specimen is gen-
erally available and only a very limited number of medium- or high-Z constituents are
present in detectable concentrations.
To improve the elemental mass discrimination (and at the same time, ease the
spectral analysis) in elastic scattering spectrometry of the light elements in atmospheric
aerosol samples, Nelson and Courtney (1977) resorted to 16-MeV protons as incident
particles and called this variant of the technique Particle Elastic Scattering Analysis
(PESA). The disadvantage of using 16-MeV protons for PESA is that the measure-
ments cannot be performed concurrently with the PIXE measurements. A separate ion
bombardment and also a higher-energy accelerator are required. Other groups have
therefore developed PESA techniques that are more compatible with PIXE and with 1
4 MeV accelerators. Martinsson (1986) performed careful investigations on the depen-
dence of the scattering cross section on incident proton energy and detection angle, with
the measurement of H, C, N, and O in thin aerosol samples in mind, and he proposed
employing 3.58-MeV incident protons with detectors set up at 170
(for C, N, and O) and

at an angle between 29
and 59
(for H).
Whereas elastic scattering spectrometry is a very useful tool in aerosol analysis, its
applicability as a complement to macro-PIXE for analyzing biological and geological
samples is more limited. As far as biological samples are concerned, scattering analysis is
generally only employed to obtain information on the mass thickness of the specimen
and=or to determine the beam uence. These types of applications are especially useful
in nuclear microprobe investigations, in which the local mass thickness of, for instance,
a microtome slice must be measured to convert the x-ray intensities from the PIXE
spectrum into concentration values (Heck and Rokita, 1984; Themner and Malmqvist,
1986).
As indicated, the depth-proling capability of RBS is an important asset for mate-
rials research. This characteristic is also very useful in investigations related to art and
archaeology. For example, RBS can be employed to measure depth proles in samples
where surface uniformities may be of high signicance, as in patina, corrosion and surface
segregation processes, glass aging, and polishing procedures (Amsel et al., 1986).
For very light elements, in particular hydrogen, it is advantageous to detect the
elastically recoiled target nuclei instead of the scattered projectiles. The technique using
this approach is termed elastic recoil detection (ERD). Because of the kinematics of the
scattering process, the particle detector has to be placed in the forward direction in ERD,
and it therefore implies that thick specimens must be bombarded at a glancing angle.
Time-of-ight techniques are very suitable for energy determination of the recoiling par-
ticle (Rijken et al., 1992). ERD is particularly useful in materials research, but it has also
been employed in other applications, such as for depth proling of hydrogen in obsidians
(volcanic glasses) (Pretorius et al., 1988), with the aim of dating them.
In addition to the elastically scattered particles, the transmitted beam may also be
employed to extract valuable information on thin specimens. Indeed, by placing a surface
barrier downstream from the sample and measuring the energy loss of the incident par-
ticles, the local mass thickness may be derived. Because of the small beam currents re-
quired, this approach is particularly useful in nuclear microprobe work, where it has given
rise to the technique of scanning transmission ion microscopy (STIM). This technique is
employed for high-resolution imaging of a specimen, and because an extremely low beam
dose is sucient, eects of beam induced damage can also be studied in the virgin and
damage state (Saint and Legge, 1997). By judicious optimization, it is possible to obtain
images with a spatial resolution of better than 100 nm.
B. Nuclear Reaction Analysis
Nuclear reaction analysis is based on the detection of the prompt g-rays or prompt par-
ticles emitted as a result of nuclear reactions between the incident beam and the target
nuclei (Tesmer et al., 1995). As indicated in Sec. II.A.4, the cross sections for such reac-
tions vary in a rather irregular way with target nuclide and with incident particle energy.
When using light ion beams of only a few megaelectron volts, nuclear reaction cross
sections are only important for light- and medium-weight target nuclei. Of the two forms
of NRA, the one in which the prompt g-rays are detected is by far the most common. It is
usually referred to as particle-induced g-ray emission analysis (PIGE). The prompt g-ray
measurement has the advantage over the detection of the promptly emitted charged
particles that it allows for greater exibility in the experimental setup, and for thick
samples, the PIGE spectra are much less complicated and far more easily analyzed than
the prompt particle spectra.
Proton-induced g-ray emission analysis, which employs ( p, g), ( p, p
0
g), or ( p, ag)
reactions, lends itself easily to concurrent use with PIXE for virtually all specimen types.
Moreover, it is able to provide good detection limits for several elements that are not
accessible by PIXE, so that it is a truly complementary technique. Ra isa nen (1987) carried
out extensive investigations on the applicability of PIGE for analyzing thick biomedical
specimens and reported that, under favorable conditions, the detection limits are down to
the submicrogram per gram level for Li, B, F, and Na, about 1025 mg=g for N, Mg, and P,
and 100300 mg=g for C, O, and Cl. Unfortunately, however, the optimum proton energies
for all these elements are not the same. Moreover, the detection limits in PIGE depend
strongly on the sample composition and may be much worse when some of the elements
for which the sensitivity of the method is highest (e.g., Li, B, F, and Na) are present in
elevated concentrations.
The most popular application of PIGE on biomedical samples is unquestionably
the determination of uorine. Either the reaction
19
F p; p
0
g
19
F or
19
F p; ag
16
O may be
used for this purpose, but the former oers about ve times better detection limits
(Ra isa nen, 1987). Particularly favorite study objects for PIGE uorine analyses are
teeth. For example, Coote et al. (1997) used a nuclear microprobe to measure Ca and F
in teeth from sheep by a combination of PIGE and PIXE. The enhanced F con-
centrations due to exposure in conjunction with a volcanic eruption were investigated,
and in Figure 19, results from these measurements are shown. Nuclear microprobes were
also used in several studies on human teeth. It was possible to determine the uorine
prole across the entire thickness of the enamel layer (Svalbe et al., 1984a) and across
precarious and articially induced lesions (Svalbe et al., 1984b; Coote and Vickridge,
1988).
Particle-induced g-ray emission is also useful as a complementary technique to PIXE
in the analysis of atmospheric aerosol samples. Several groups have examined the opti-
mum bombarding energy and=or presented procedures or systems for measuring several
light elements in such samples by PIGE (Robaye et al., 1985; Asking et al., 1987; Boni
et al., 1989). Asking et al. (1987) conclude that two proton energies, 2.64 and 2.96 MeV,
are most suited for measuring Na in thin (<0.25 mg=cm
2
) aerosol samples, and they report
Figure19 Two-dimensional distributions of fluorine, as determined by the
19
F( p, ag)
16
O reaction,
for sections of sheep incisor, with the enamel to the left: (a) nonexposed sheep; (b) sheep with teeth in
developing phase during fluorine exposure; (c) sheep with teeth in the mature state during exposure.
Dark areas indicate high concentration and light areas indicate low concentration. (From Coote
et al., 1997, with permission from Elsevier Science.)
a detection limit of 100 ng=cm
2
. To smooth out the variations in the cross-section curves,
Boni et al. (1989) advocate spreading out the beam energy, and they propose an incident
proton beam of 3.23.5 MeV, with rectangular energy distribution. The detection limits
obtained with their setup are 1 ng=cm
2
for Li, 3 ng=cm
2
for F, 25 ng=cm
2
for Na, and of
the order of 100 ng=cm
2
for B, Mg, Al, Si, and P.
Simultaneous PIGE=PIXE analyses of thick geological samples have been done
by Carlsson and Akselsson (1981) and by Carlsson (1984). Carlsson (1984) used
PIGE for measuring Li, F, Na, Mg, and Al, whereas heavier elements were determined by
PIXE.
Archaeological specimens are often examined by a combination of PIGE and PIXE.
Such combination was, for example, used for provenancing obsidian artifacts (Duerden
et al., 1986). The determination of 11 elements by PIXE and 3 by PIGE provided a very
good characterization of the samples, as concluded from applying principal-components
analysis on the dataset obtained. Tuurnala et al. (1986) applied external milliprobe
PIGE=PIXE to check the authenticity of oil paintings. A relatively high beam energy of
4 MeV was used to raise the penetration depth, and Na, Mg, and Al were measured by
PIGE. Still other examples of applications of PIGE in art and archaeology are given by
Demortier (1989). For analyses in this eld, the depth-proling capacity of PIGE is also
quite useful.
Although PIGE is almost exclusively performed with proton beams, deuterons are
more commonly used as incident particles when the nuclear reaction analysis is based on
the detection of the promptly emitted charged particles. Consequently, this form of NRA
is less suitable for concurrent use with PIXE. Furthermore, as indicated earlier, prompt
particle spectra are often much more complex than PIGE spectra, thus making the
technique less attractive for routine use.
As far as biomedical materials are concerned, NRA with particle detection can be
used for measuring nitrogen (an indicator of protein content). For example, Go nczi et al.
(1982) applied the
14
Nd; p
15
N nuclear reaction, with 6-MeV deuterons, to measure the
nitrogen depth prole in 1000 individual wheat grains. The nitrogen distributions showed
striking correlations with parameters describing the nitrogen content of the fertilizer, the
time of harvesting, the grain position in a head, and the analyzed variety. The (d, p) re-
actions on
12
C and
14
N were used in combination with deuteron-induced x-ray emission
(DIXE) measurements to determine the N=C and S=N ratios along a single hair (Varga
et al., 1984). Some general aspects of NRA with particle detection using protons as in-
cident particles have been discussed by Ra isa nen (1987).
As an example of the application of (d, p) reactions for analyzing atmospheric
aerosol samples, the work by Braga Marcazzan et al. (1987) can be cited. In this work,
oxygen, nitrogen, and carbon were measured in particulate matter collected on a silver
lter. In nuclear microprobe investigations on meteorites and cosmic dust particles, a (d, p)
reaction was used to measure the carbon content (Vis et al., 1987). The applicability of
particle detection NRA in art and archaeology was addressed by Amsel et al. (1986) and
Demortier (1989).
Similarly to RBS, NRA (including PIGE) is particularly useful in materials analysis.
In such applications, the depth-proling capacity of NRA (e.g., by making use of strong
resonance peaks in the cross-sectional curves) is often quite valuable. As indicated in
Sec. VI.E, however, PIXE, if applied at all, generally serves as the complementary tech-
nique, whereas the essential information is obtained by RBS or NRA. For examples of
applications of NRA (including PIGE) to materials research, the reader is referred to the
textbooks and proceedings mentioned at the beginning of this section.
To improve the detection limits in NRA, Martinsson and Kristiansson (1993) and
Kristiansson and Martinsson (1997) have developed a new technique, photon-tagged
NRA (pRNA). By using fast coincidence electronics and applying stringent timing criteria
between photons and charged particles, the background in the particle energy spectra is
much reduced and better detection limits are obtained for several elements. In subsequent
work, the principles of the pRNA technique were implemented in a nuclear microprobe
setup (Sjo land et al., 1997d; Kristiansson et al., 1998). Figure 20 shows the schematic
design of such a system. The technique was further developed for the microanalysis of
special light elements (e.g., H, Li, and F) (Sjo land et al., 1997a, 1997b, 1997c).
C. Chemical and Structural Information
In biomedical and environmental research, considerably more insight may often be gained
by determining the chemical species or chemical association of minor or trace elements
than merely their elemental concentrations. For example, to understand the source and
transformation processes that are responsible for particulate nitrogen in the atmosphere, it
is of interest to nd out what fraction of total nitrogen is present as ammonium, nitrate, or
some other N-containing species, and whether the ammonium is associated with the
nitrate or sulfate, for example. Similarly, chemical and=or structural data on crystalline
specimens in mineralogy are of great importance to geoscientists. The close-encounter
reactions used in PIXE and most other IBA techniques do not provide any chemical or
structural information. Such information can, however, be obtained by making use of
other interactions or by employing special experimental conditions.
Figure 20 Schematics of experimental arrangements for photon-tagged nuclear reaction analysis
in a nuclear microprobe. P: the incoming ion beam; SBD: surface barrier detector; PMT: photo-
multiplier tube. (From Sjo land et al., 1997d, with permission from Elsevier Science.)
1. Ion-BeamThermography
To obtain speciation information with IBA techniques and IBA-compatible aerosol
samplers, Martinsson and Hansson (1988) developed the technique of ion-beam ther-
mography (IBT). This technique consists of an ingenious use of controlled heating of the
aerosol sample, whereby its temperature is gradually raised, with concurrent analysis by
PIXE and PESA. The technique has been further developed and integrated with a data
acquisition and specimen control computer system (Mentes et al., 1996). In principle, also
simultaneous PIGE measurements are possible. To reduce or eliminate vacuum- or beam-
induced losses of compounds or analyte elements from the sample, the measurements are
performed at a prevacuum pressure ( p < 10
2
mbar) or in a 10-mbar He atmosphere. The
sample is heated by passing an electrical current through the sample substrate, which
consists of a 0.8-mm-thick aluminum foil. The temperature of the sample is monitored by
determining the change in relative resistivity (dened as the ratio of the resistance of the
heated sample to that of the unheated sample). To achieve time resolution in the data
acquisition so that the course of sample deterioration during the thermographic treatment
can be followed, a special data acquisition program has been developed. The IBT results
are presented as a set of thermograms, one for each element, which show the amount of
element remaining in the sample as the temperature increases. From these thermograms,
the chemical compounds and their concentrations are inferred. Figure 21 shows the set of
thermograms obtained for a mixture of equal amounts of NH
4
NO
3
and (NH
4
)
2
SO
4
. The
rst 10 data points, at relative resistivities between 0.9 and 1, were taken without heating
Figure 21 Thermograms from a mixture of NH
4
NO
3
and (NH
4
)
2
SO
4
. Amounts inferred:
m(N) 4.1 mg=cm
2
, m(O) 4.3 3.6 mg=cm
2
, m(S) 1.8 mg=cm
2
, m(NH
4
NO
3
) 7.2 mg=cm
2
,
m((NH
4
)
2
SO
4
) 7.4 mg=cm
2
. (From Martinsson and Hansson, 1988, with permission from Elsevier
Science.)
the sample and are listed in chronological order. The elemental amounts inferred from the
thermograms are given in the legend to Figure 21 and are in good agreement with those
expected on the basis of stoichiometry.
The especially interesting features of IBT are that chemical compounds (not ions) are
determined, that it is a multicompound technique, that it requires no pretreatment of the
sample, and that some compounds may be measured down to trace levels under favour-
able conditions.
2. Ionoluminescence
When a signicant amount of energy is transferred to a crystalline material, be it by elec-
trons, photons, or charged particles, near-visible light is emitted due to luminescence in the
material. The well-known techniques of photoluminescence (PL) and cathodoluminescence
(CL) are widely used in material science and geology in order to study the chemistry,
structure, or electrical properties of the material. The exact character of the impinging
radiation does not matter very much for the basic interaction mechanisms involved in lu-
minescence. As a consequence, much of the physical understanding from the PL and CL
techniques can be directly incorporated in the ionoluminescence technique (IL) that was
introduced and developed in a collaboration between the nuclear microprobe groups of
Lund and Melbourne (Yang et al., 1993). The intensity and wavelength of the ionolumi-
nescent light provide information concerning the nature of luminescence centers, such as
trace substituents and structural defects, present in the matrix. This makes IL a useful
complement to other IBA techniques, such as PIXE and, to a some extent, also RBS.
Luminescence can be divided into two subgroups (intrinsic and extrinsic) according
to its origin. The intrinsic luminescence, which usually contributes in emission through
crystal structural defects, is not related to impurities but to crystal-lattice properties. The
extrinsic luminescence depends on the impurities in a crystal through the processes acti-
vation, sensitization, and quenching. Luminescence phenomena are common in many
solids, yet the use of the light produced is restricted because of the complex physical
mechanisms behind the emission. For insulators, to which many minerals belong, crystal-
eld theory can be used to explain luminescence (Henderson and Imbusch, 1989), whereas
for semiconductor crystals, band theory is often employed (Yacobi and Holt, 1990). As
long as no secondary eects such as lattice damage or crystal modication occur, the
general luminescence properties of a material are not dependent on the nature of the
excitation source. For excitation by energetic particles, the processes leading to lumines-
cence take place in three steps. First, the energy of the MeV particles is dissipated into the
excitation volume mainly through electronic stopping and partially through nuclear
stopping processes. Ionization takes place in the excitation volume. Recombination of the
electrons and the excited ions allows the crystal lattice to absorb the energy released and
the optical system becomes highly excited. The second stage involves the de-excitation of
the states of high excitation through radiationless transitions. The third stage, lumines-
cence emission, occurs when the atoms de-excite from a low-excitation state to the ground
level. The term activation is used when trace impurities cause a material to produce ex-
trinsic luminescence. Transition metal ions, with an electron conguration of 3d
(19)
, can
interact strongly with the crystal eld. This results in changes in the energy level structure
of the free ion. Usually, the luminescence activated by transition metal ions is char-
acterized by a broad peak width and a peak position strongly dependent on the host
matrix. The centroid and width of the peak are sensitive to the chemical surroundings in
the crystal and may be used to distinguish the host matrices involved. For example, with
Mn
2
(3d
5
) ions located in a crystal with a strong crystal eld, the luminescence produced
tends to be of longer wavelength. The luminescence of Mn
2
-activated calcite (Mn
2
ions
in octahedral coordination), for example, is orange, whereas the luminescence of Mn
2
-
activated willemite (Mn
2
ions in tetrahedral coordination) is greenish.
Trivalent rare-earth element ions and most divalent rare-earth element ions, except
for those of Ce, Gd and Lu, have the electron conguration 4f
(k)
[5s
2
5p
6
]. These special
electron congurations give rise to characteristic narrow luminescence emission bands for
rare earth element (REE) ions with the conguration 4f
(k1)
f
1
* through a f

! f tran-
sition. The narrow luminescence emission band of the REE ion (trivalent or divalent)
originates in the 4f subshell, which is partially shielded by [5s
2
5p
6
] electrons. Therefore, for
REE ions with a 4f
k1
f
1
conguration, the structure of the energy levels in the free REE
ions is basically the same in dierent host matrices. Figure 22 shows an IL spectrum from
a natural zircon grain, where three peaks from REE are superimposed on a broad intrinsic
luminescence band.
Experimentally, the IL light is detected by using mirrors or lenses and either directly
counting the photons in a PM tube or analyzing them in a spectrometer. The detailed
spectrum (see Fig. 22) provides information on the crystal structure and can be used to
determine the REE. A scanning grating spectrometer is a very slow system. Variation in
beam current, beam-induced lattice damage, and so forth can adversely aect the acquired
spectrum. The situation can be improved by implementing a photodiode-array detector
with, for instance, 1024 detector elements, each with a size of a few tens of micrometers.
Such a system allows the simultaneous recording of all wavelengths and can signicantly
improve the analytical capacity, speed up the analysis, and reduce beam damage eects.
Furthermore, because ion-beam bombardment of a solid material modies its properties
and changes its luminescence characteristics, the rapid spectrum acquisition makes it
possible to perform a detailed study of these transformations.
The most common experimental facility for IL is the nuclear microprobe, where the
imaging capability of IL is an invaluable asset, especially in studies on geological samples.
Figure 22 Ionoluminescence spectrum from a natural zircon with peaks, emanating from various
rare earth elements, superimposed on a broad yellow intrinsic luminescence band.
The very high cross sections for IL processes make it possible to employ extremely low
beam doses. Synergistic eects of the simultaneous use of PIXE and IL enhance the
capability of both techniques (Malmqvist et al., 1996). Because of L-line interferences,
PIXE is not very suitable for trace determination of the REE which are of great im-
portance in geoscience. The elemental information obtained by IL (on the REE) and by
PIXE (on many other elements) complement each other and the PIXE data can facilitate
the interpretation of the IL spectrum, so that both techniques enhance each other.
VIII. CONCLUSIONS
Particle-induced x-ray emission is undoubtedly an invaluable and very powerful x-ray
emission spectrometry technique. It has truly multielemental capability, covering a large
part of the periodic system (from Na to U), with detection limits that vary smoothly as a
function of atomic number. The use of x-ray absorbers can improve this Z dependence
further. The sensitivity of PIXE is high and detection limits are low, although they do
depend on the particular material being analyzed. The most favorable situation is the
determination of trace elements in a light-element matrix (Z<11), where detection limits
are of the order of 0.11 mg=g. For samples with appreciable amounts of heavy and
mediumheavy elements, the detection limits are somewhat higher; for example, typically
a few micrograms per gram for elements between Z20 and Z50 in geological mate-
rials. In absolute terms, the detection limits are even more pronounced, down to 10
12
g in
macro-PIXE and down to 10
17
g in micro-PIXE. Other favorable features of PIXE are
the ability to analyze tiny samples (1 mg or less in macro-PIXE, and much less in micro-
PIXE), the speed of the analysis (110 min bombardment time per specimen), and the
possibility for automation. The degree of specimen preparation needed in PIXE varies
from zero at one extreme (e.g., aerosol samples and archaeological materials) through
modest (e.g., mineralogical samples and materials science) to signicant at the other ex-
treme (e.g., some biomedical specimens). The specimens are normally in solid form, and
the irradiated target material is, in general, not aected by the particle beam at the current
densities needed for conventional macro-PIXE, so that the technique is nondestructive.
Even delicate materials such as paper or parchment are unaected by so-called millibeams,
although in these cases, special precautions such as low beam intensity and=or external
beams are necessary. In micro-PIXE, the larger current densities incident on the specimen
can cause damage and alteration, but, in practice, analyses are often conducted at current
densities that do not cause such problems. However, as beam diameters become smaller
and current densities higher, damage will become more important.
Particle-induced x-ray emission is extremely versatile in terms of the size of sample
that it can accommodate. Depending on the size, dierent experimental arrangements may
be used: a conventional macrobeam in vacuum (with beam size of the order of several
millimeters), an external macrobeam or millibeam, or a genuine microbeam. The variety of
specimens analyzed to date is enormous, ranging from a large painting to a single blood
cell. They have in common, though, that they are normally in solid form. Micro-PIXE as
used in the nuclear microprobe makes it possible to perform analyses with excellent spa-
tial resolution (down to 1 mm or better), high sensitivity (detection limits of the order of
1 mg=g), and good accuracy. The importance of this can hardly be overestimated. For
example, microscopically small grains in minerals or single cells in biological tissue can be
analyzed. If the microbeam is used in the scanning mode, as is often done, elemental maps
can be produced, giving a much more detailed picture of trace element distributions than
measurements made at single points.
Another favorable feature of PIXE is that it can be complemented with other IBA
techniques, such as RBS and other forms of elastic scattering spectrometry, NRA, and
PIGE. As a result, a simultaneous measurement of the light elements (H, Li, B, C, N, O,
and F), which cannot be measured by PIXE, is feasible. This is an important asset when
analyzing atmospheric aerosol samples, as discussed in detail by Cohen (1993, 1998),
Cahill (1995), and Swietlicki et al. (1996a), but also for various other sample types. Some
of the other IBA techniques, such as RBS and NRA, predate PIXE, and in certain elds of
application (e.g., materials analysis), RBS is the major IBA technique, and PIXE generally
serves only as a complementary technique. Some of the ancillary IBA techniques (e.g., o-
axis STIM and ionoluminescence) have been developed in the last decade as adjuncts to
micro-PIXE, demonstrating the continued development of the IBA eld overall.
Particle-induced x-ray emission combines a particular and unique set of advanta-
geous features, but as any technique, it has also it limitations. Limitations which are also
shared by XRF are that it suers from spectral interferences and matrix eects and that it
does not allow the direct measurement of ultratrace elements that are present at nano-
grams per gram levels. Unlike in some other techniques, however, the matrix eects are
well understood and can be corrected for. Consequently, PIXE can provide results with an
accuracy better than 5% relative. The most serious drawbacks of the technique are that it
requires a MeV particle accelerator and that commercial PIXE apparatus are not readily
available (the great majority of PIXE laboratories have built their own setup, and com-
mercial systems are usually custom-built). Most PIXE laboratories have been set up in
nuclear physics institutes, and although there have been interesting developments during
the past decade, with the installation of dedicated PIXE laboratories and nuclear micro-
probes, the growth in PIXE has remained slow. There are currently more than 100 PIXE
groups worldwide.
Part of the reason for the slow growth of PIXE is, of course, that the technique has
to compete with a wide plethora of other analytical techniques and that there have been
substantial advances in several of these techniques over the past 1015 years, for example,
in ICPMS. It is therefore worthwhile to compare the characteristics and capabilities
of PIXE with those of the other techniques and to assess for what sample types and=or
problems PIXE is most appropriate. Maenhaut (1990b) made such an evaluation for
macro-PIXE 10 years ago, which was retained in the Conclusions section in the chapter on
PIXE in the rst edition of Handbook of X-Ray Spectrometry (Maenhaut and Malmqvist,
1992). Although many of the conclusions still stand, that evaluation is now somewhat
outdated. A more recent evaluation is that of Johansson and Campbell (1995) in the
chapter Comparison with Other Methods: Future Prospects in the textbook Particle-
Induced X-Ray Emission Spectrometry (PIXE). In the present Conclusions section, we have
drawn heavily on that excellent and insightful chapter of Johansson and Campbell (1995).
As indicated by them, any comparison with other techniques is fraught with risk. The
range of techniques available means that it is not an easy matter to select the most ap-
propriate for a particular task. It is often the case that proximity, familiarity, and ease of
access play just as large a role as the matching between task and technique. Furthermore,
because of the rapid progress in analytical techniques, any comparison becomes dated
after a few years. The recent progress in x-ray emission spectrometry techniques can be
judged from the various chapters in this handbook. For continued updates on this, the
biennial fundamental review on x-ray spectrometry in the June issue (of every even year) of
the journal Analytical Chemistry can be recommended [see To ro k et al. (1998) for the most
recent one in the series]. That same June issue of Analytical Chemistry also contains
fundamental reviews on many other analytical techniques. Furthermore, some other
analytical chemistry journals, such as Journal of Analytical Atomic Spectrometry, also
publish technique-oriented reviews on a regular basis.
A natural starting point in a comparison of PIXE with other analytical techniques is
conventional tube-excited XRF. In actual numbers, the relative detection limits of PIXE
for thin samples and a light-element matrix vary within the range 0.11 mg=g for the ele-
ments of greatest interest (the transition metals and the heavy metals around Pb). With
careful optimization (a-particle excitation, tight geometry, and heavy shielding), detection
limits as low as 0.02 mg=g can even be reached in PIXE (Johansson, 1992). In EDXRF, the
corresponding detection limits are of the order of 110 mg=g. Even more pronounced is the
dierence in detection limits in absolute terms. To obtain optimum relative detection limits
in XRF, the sample weight has to be at least 10100 mg, which means that the absolute
detection limits are of the order of some hundred nanograms. In macro-PIXE, the amount
probed by the proton beam can be 0.1 mg or even lower, and the corresponding absolute
detection limits are of the order of a few picograms. However, as discussed by Johansson
and Campbell (1995), besides sensitivity and detection limits, several other factors have to
be considered. There are certainly many sample types and=or problems where EDXRF is
to be preferred over macro-PIXE as the technique of choice.
One substantial dierence between PIXE and XRF is that with micro-PIXE, the
spatial distribution of trace elements can be studied down to the submicrometer level,
whereas conventional XRF does not oer this possibility. In the mid-1980s, the use of
glass capillaries for the concentration of the primary radiation from an x-ray tube was
introduced into XRF (see Chapter 11). This and subsequent developments have led to
micro-XRF and desktop x-ray microprobes, whereby a spatial resolution down to 10 mm
with reasonable incident x-ray intensity may be obtained. These are important technical
advances, conferring on tabletop XRF some, although not all, of the abilities of micro-
PIXE. Another signicant step forward in XRF was the introduction of TXRF (see
Chapter 9). However, this technique is much more suitable for the analysis of dilute
aqueous solutions than of solid samples. It tends to compete more directly with other
techniques (e.g., optical atomic spectrometry) than with PIXE. There appears, for ex-
ample, to be little potential for high-throughput nondestructive analysis of aerosol par-
ticulate samples. A third far-reaching change in the XRF technique has occurred through
the introduction of synchrotron radiation (SR) as the primary source, which has led to
SRXRF (see Chapter 8). The main limitation of this technique is the same as for PIXE,
but to a much greater extent, namely the availability. In the case of PIXE, it is quite
feasible to set up an accelerator laboratory to be used solely for PIXE and related IBA
work, whereas it is clearly out of the question to use a SR source mainly for elemental
analysis. One is therefore limited to using existing facilities, whose number is small. The
potential of SRXRF undoubtedly lies in its microbeam capability. However, it seems
unlikely, for example, that the continued development and success of SRXRF will aect
the rapid growth of routine micro-PIXE analysis of mineral grains or the growing use of
micro-PIXE and associated IBA techniques in art and archaeometry. Perhaps the main
competition oered to micro-PIXE will be for in situ problems where the energy de-
position in the irradiated specimen is an important issue. Thus, microbeam SRXRF can
complement micro-PIXE by extending in situ microbeam analysis to specimens that
cannot withstand micro-PIXE.
Beyond doubt, the greatest competition for the nuclear microprobe and micro-PIXE
comes from electron probe microanalysis (EPMA) and other electron microscopic tech-
niques (see Chapter 13). Micro-PIXE has the advantage over EPMA that it oers relative
detection limits that are typically two orders of magnitude better, that it is easier to
quantify, and that it can be complemented with other IBA techniques. EPMA and other
electron microscopic techniques, on the other hand, have as advantages that the in-
strumentation is more compact and is commercially available and that they oer a much
higher speed of analysis, better spatial resolution, and better imaging capabilities. It is
clear that EPMA will be preferred over the nuclear microprobe in many studies. However,
rather than being competitors of each other, EPMA and the nuclear microprobe can very
well complement each other, whereby micro-PIXE is used for problems where its excellent
detection limits and other specic advantages are required or at least highly desirable.
The majority of bulk element analyses are carried out by optical atomic spectrometry
or atomic mass spectrometry, in particular ICPMS. In most of these techniques, the
sample material has to be introduced into the instrument as a liquid, and in ICPMS, a
dilute solution is even preferred. Solid samples must therefore be dissolved, which means
an extra preparation stage with the risk of incomplete dissolution, losses, or contamina-
tion. The dissolution also implies that the analysis is destructive. Although some techni-
ques allow one to analyze powdered materials [e.g., electrothermal atomization atomic
absorption spectrometry (ETAAAS)] or can handle various types of solid samples (e.g.,
laser ablation mass spectrometry), and continued research is done on the introduction of
powders in other techniques, there are overall serious limitations with the analysis of solid
samples by optical atomic spectrometry or atomic mass spectrometry. Such analyses suer
from severe matrix eects and diculties in obtaining accurate quantitative results for a
wide range of elements, and they are invariably destructive. Also, certain techniques, such
as ETAAAS, can only measure one element at a time and require the addition of an
appropriate matrix modier. It is clear that the optical atomic spectrometry and atomic
mass spectrometry techniques dier very much from PIXE. Also, the optical atomic
spectrometry techniques do not oer any equivalent of microbeam capability. Such cap-
ability does exist in some atomic mass spectrometry techniques [e.g., in secondary ion mass
spectrometry (SIMS)] and laser ablation inductively coupled plasmamass spectrometry
[LAICPMS], but their spatial resolution is clearly worse than in micro-PIXE and
accurate quantication is dicult.
One way to answer the question of which sample types or analytical problems are
better handled by PIXE and micro-PIXE than by other techniques is to survey the various
applications. Section VI provides such a survey, from which one can identify certain
applications where it appears dicult to nd alternatives. To a large extent, these are
applications involving solid and particulate sample material and having minimum or
zero sample preparation.
Because of its inherent characteristics, macro-PIXE has been very much applied for
measuring trace elements in various types of biomedical samples. However, for several of
such samples and for ultratrace determinations, the optical atomic spectrometric and ICP
MS techniques are now better suited. Also, in recent years, the emphasis has shifted from
total element determination toward elemental speciation. PIXE and the other x-ray
techniques lend themselves much less to this speciation work than some of the other
techniques. In applying PIXE to biomedical problems, one should therefore look for cases
in which one can fully utilize the special advantages of PIXE, such as spatial resolution,
accurate quantitative analysis, and small samples. Particularly micro-PIXE, as used in the
nuclear microprobe and complemented with other IBA techniques such as STIM, is in-
valuable in biomedical trace element research.
One area of application where macro-PIXE has been and continues to be highly
successful is in the analysis of airborne particulate material (atmospheric aerosols). For the
analysis of very large numbers of small aerosol deposits, as collect by compact samplers
which provide good time or size resolution, or both, there is virtually no competition to
PIXE. Conventional tube-excited EDXRF cannot be used because its absolute sensitivity
is too low. TXRF has the absolute sensitivity but is not physically appropriate and
SRXRF is much more expensive and not really applicable for routine analysis of large
numbers of samples. The optical atomic spectrometric techniques and ICPMS require
dissolution, which is time-consuming and may be incomplete for certain important matrix
elements. Conventional ICPMS also suers from spectral interferences, causing the
problem that some important elements cannot be measured. PIXE provides at the same
time data for the major elements (S, Na, Cl, Al, Si, Fe), from which the concentrations of
important aerosol types (sulfate, sea salt, crustal material) can be estimated, and for
several anthropogenic and natural minor and trace elements (P, V, Mn, Ni, Cu, Zn, As,
Se, Br, Rb, Pb) that can be used in source type identication and apportionment. Fur-
thermore, by complementing PIXE with other IBA techniques, concentrations can be
obtained for the light elements (H, C, N, O) that make up most of the aerosol mass, and
the hydrogen concentration can then be used to estimate the concentration of the im-
portant organic aerosol type (Cahill, 1995). Considering the current interest in the eects
of ne particles on human health and in the role of aerosols in climate, it is expected that
the analysis of atmospheric aerosol samples will remain a successful application for PIXE
for many years to come. However, as indicated in Sec. VI.B, one should realize that PIXE
provides only part of the desired information. With regard to the chemical composition, it
is highly desirable to also perform measurements for important ionic species (e.g., am-
monium, nitrate) and for organic carbon (OC) and elemental carbon (EC). Also, in order
to arrive at a complete aerosol characterization, the chemical measurements have to be
complemented with physical and optical (radiative) aerosol measurements. PIXE re-
searchers should try to complement their work with these various other measurements or
otherwise cooperate with other groups who are involved in such research, and they should
try to become integrated in larger atmospheric aerosol and atmospheric chemistry research
projects. Fortunately, this is increasingly realized within the PIXE community.
Earth science is another eld in which the use of PIXE or specically micro-PIXE
has increased dramatically during the past decade. Here, however, there are some powerful
competing techniques (e.g., the x-ray spectrometric techniques of micro-XRF and
SRXRF). Furthermore, other physically based analytical techniques continue to develop,
such as SIMS and LAICPMS. SIMS provides spatial resolution of a few micrometers
and relative detection limits that are frequently below 1 mg=g; it is clearly superior to
micro-PIXE for the rare earth elements. LAICPMS routinely oers a spatial resolution
of 2040 mm and detection limits of 0.5 mg=g. These two techniques also oer isotopic
discrimination, which is not an option with PIXE. However, in each of these two tech-
niques, the matrix eects are much more complex and quantication more dicult than in
PIXE. Micro-PIXE still maintains its advantage as a truly multielemental, in situ, non-
destructive technique with detection limits of a few micrograms per gram, 1 mm spatial
resolution, and straighforward matrix corrections based on simple, well-understood
physics. It can be used for surveys involving a large number of samples for ore pro-
specting, and for the detailed study of minerals. In the latter case, complementary use of
EPMA and micro-PIXE has turned out to be very fruitful. EPMA is a standard technique
in mineralogy for the determination of major and minor elements, and micro-PIXE allows
these studies to be extended in seamless fashion to trace elements. In studies of extra-
terrestrial materials, such as micrometeoritics and interstellar particles, the high sensitivity
and nondestructiveness of micro-PIXE are a prerequisite. Similarly, the study of ore body
emanations gives samples of extremely small mass and any other technique than PIXE
seems to be excluded. Micro-PIXE is ideal for investigations of mineral and melt inclu-
sions in many materials (e.g., diamonds). Meanwhile, in the quite dierent context of
multielement bulk rock analysis with sub-microgram per gram detection limits, INAA,
ICPAES, and ICPMS remain the techniques of choice.
Because PIXE and related IBA techniques allow the analysis of delicate samples
without giving any visible damage and without introducing any radioactivity, they can
also very advantageously be used in studies in art and archaeology or for analyzing other
unique samples of which subsampling is impossible. XRF is often the natural choice for
the nondestructive analysis of for example, archaeological artifacts, but PIXE has other
advantages due to its somewhat better sensitivity and imaging capability. A situation in
which the greater sensitivity is desired is the determination of the trace element prole in
various items, which can help in the characterization and identication of material for
addressing questions such as provenance, manufacturing procedure, and trade routes.
Perhaps, the greatest asset of PIXE in these elds is its versatility. Bulk analysis can be
carried out with macro-PIXE, and microscopic details can be studied with a microbeam.
A very useful arrangement is an external beam with a cross section of 0.11 mm, called a
millibeam. This can be used for studies of details in paintings or the ink of single letters in
books and other documents. However, the developments in micro-XRF and microbeam
SRXRF will give rise to strong competition for PIXE in this type of application.
Finally, PIXE will certainly nd further application in the eld of materials research.
However, as indicated earlier, RBS is the major IBA technique in this eld, and PIXE
generally serves only as a complementary technique. The complementarity of PIXE resides
in the fact that it is able to detect elements that are present at levels that are too low for
RBS or for which RBS does not oer sucient Z discrimination.
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B136138:893, 1998.
13
Electron-Induced X-ray Emission
John A. Small, Dale E. Newbury, and John T. Armstrong
National Institute of Standards and Technology, Gaithersburg, Maryland
I. INTRODUCTION
The current trend in many technology-related elds such as electronics and materials
science is toward miniaturization and increased spatial resolution well below the micro-
meter scale. The corresponding requirements for microanalytical instruments needed to
meet the demands of this trend require analytical instruments that are capable of analyzing
micrometer and submicrometer regions of samples. A schematic diagram outlining the
generic features of a microanalytical instrument is shown in Figure 1. In such an instru-
ment, the primary radiation (ions, photons, or electrons) is focused to form a beam from
about 1 mm down to about 0.5 nm in size. The interaction of the primary beam with the
specimen results in the emission of secondary radiation that is then analyzed with a
spectrometer system to provide information on the structure and composition of the
sample. For the analysis of micrometer and submicrometer domains, the electron-probe
microanalyzer (EPMA), scanning electron microscope (SEM), and analytical electron
microscope (AEM) use electron beams as their primary radiation source and incorporate
electron-induced x-ray emission as one of the primary spectroscopies for obtaining ana-
lytical information.
In electron beam instruments, the electron beam is generated from a tungsten la-
ment, a lanthanum hexaboride (LaB
6
) electron source, or a eld-emission electron source.
The emitter serves as the cathode in the electron gun and is maintained at a negative
potential with respect to ground as shown in Figure 2 for a tungsten-lament source. In
systems employing a tungsten lament, the source of choice for quantitative electron probe
analysis due to its stability, the electron beam is produced by the thermal emission of
electrons from a hairpin lament consisting of a tungsten wire bent in a V shape. The tip
of the V is approximately 200 mm in diameter, as shown in Figure 3. The tungsten wire is
directly heated to a temperature of 27002900 K, resulting in an electron emission current
density of about 10 A=cm
2
.
Note: Certain commercial equipment, instruments, or materials are identied in this report to specify
adequately the experimental procedure. Such identication does not imply recommendation or
endorsement by the National Institute of Standards and Technology, nor does it imply that the
materials or equipment identied are necessarily the best available for the purpose.
Figure1 A generic microanalytical instrument.
Figure2 Schematic of a W-filament electron gun. (From Goldstein et al., 1975a. Reproduced with
permission of Plenum Press.)
In systems that employ the LaB
6
electron source, the cathode consists of a rod of
solid LaB
6
that is milled on one end to a tip with a diameter of approximately 10 mm. The
LaB
6
source is heated to a temperature of about 1950 K. At this temperature, the emission
current density for the LaB
6
source is on the order of 100 A=cm
2
, a factor of 10 greater
than the current density for the tungsten lament. The higher current density of the LaB
6
enables the use of smaller primary beams for a given current than the tungsten lament. In
the past, the LaB
6
emission source has found only limited use in EPMA, primarily because
of instability in the emission current. Recent advances in electronics and gun design have
increased the stability of the electron emission from the LaB
6
source to a level that allows
the analyst to perform relatively high-quality x-ray analysis. The LaB
6
source, however,
is rapidly being replaced by eld-emission sources.
In systems that employ a eld-emission electron source, the emitter consists of a
single-crystal tungsten rod, the end of which has been formed into a sharp tip with a radius
less than 100 nm. In a cold eld-emission source, a strong electric eld is applied through a
series of extraction lenses to the tip, causing the emission of electrons without heating. In a
thermally assisted eld-emission source, the tip is heated to 1800 K, increasing the beam
stability and eliminating the need to ash or clean the tip prior to each use. The main
advantage of the eld-emission source is its inherent brightness on the order of 10
5
A=cm
2
,
a factor of 10
4
greater than the conventional tungsten wire that allows the formation of a
very small diameter probe on the order of 0.5 nm. This makes the eld-emission source
particularly useful for x-ray analysis with low acceleration voltages and soft x-rays.
After emission, the electrons in an electron probe with a W or LaB
6
lament are
focused through an initial crossover by the presence of the Wehnelt cap, which surrounds
the lament as shown in Figure 2. The cap is biased several hundred volts negative
compared to the lament, which creates an immersion eld that focuses the electrons to a
crossover with a diameter d
0
of approximately 50 mm for a conventional tungsten lament.
In a elid-emission instrument, the crossover is done with the extraction lenses. After
passing through the initial crossover, the electrons are accelerated by an anode plate
Figure 3 Photomicrograph of a W filament.
biased from 1 to 400 kV positive with respect to the cathode. Next, the initial electron
crossover or spot is demagnied by a series of apertures and electron optical lenses, in-
cluding both condenser and objective lenses. The nal probe diameter used to interrogate
the sample is dependent on lament material, accelerating voltage, and emission current.
Figure 4 shows a plot of probe diameter versus probe current for dierent laments at
30 kV acceleration potential. As the acceleration potential decreases, the probe diameter
increases as shown in Figure 5 (which shows a plot of probe diameter versus probe current
for 1kV acceleration potential). A schematic of an electron-probe microanalyzer is shown
in Figure 6. An excellent discussion of electron sources, optics, and electron probe for-
mation is given by Goldstein et al. (1992b).
Castaing developed the rst successful EPMA and outlined the fundamental physical
concepts of quantitative analysis (Castaing, 1951). The electron microprobe that he de-
veloped made use of a focused beam of electrons to excite x-rays from a microscopic
domain on a sample surface.
In classical electron-probe microanalysis, the acceleration potential is on the order of
1030 kV and the samples are polished at, homogeneous, and opaque with respect to the
electron beam. The characteristic x-rays emitted as a result of the primary electron beam
interaction with the atoms in the specimen are analyzed by either wavelength-dispersive
spectrometry (WDS) or energy-dispersive spectrometry (EDS) to determine elemental
compositions. The volume of the specimen that is excited depends on the specimen
composition and the energy of the primary electron beam. Because the absorption path
lengths for x-rays are considerably greater than those for secondary electrons used for
electron imaging, the spatial resolution for classical x-ray microanalysis is 12 mm, com-
pared to 35 nm for electron imaging. This is shown schematically in Figure 7, in which the
x-ray emission volume is compared to the electron beam diameter of 15 nm. Specimens
that are inhomogeneous at dimensions below the x-ray resolution cannot be readily
analyzed by conventional microprobe analysis. These samples are best analyzed with low
Figure 4 Probe diameter versus probe current for different electron gun designs, plotted for a
30-keV accelerating potential. (From Goldstein et al., 1992a. Reproduced with permission of Plenum
Press.)
Figure 6 Schematic of the modern electron-probe microanalyzer: Gelectron gun, An anode
plate, CLcondenser lens, Ap column aperture, OLobjective lens, Sspecimen, Cr diffrac-
tion crystal, and Dx-ray detector. (From Heinrich, 1981a. Reproduced with permission of Van
Nostrand Reinhold.)
Figure 5 Probe diameter versus probe current for different electron gun designs, plotted for a
1-keV accelerating potential. (From Goldstein et al., 1992a. Reproduced with permission of Plenum
Press.)
acceleration voltages and soft x-rays, or in the analytical electron microscope at high
voltages, 100 kV or more, as thin specimens.
II. QUANTITATIVE ANALYSIS
In this seminal paper on quantitative probe microanalysis, Castaing (1951) proposed
that quantitative elemental analysis could be carried out in the electron probe by
comparing the x-ray intensity generated from a given element i in an unknown to the
x-ray intensity of the same element i generated in a standard containing a known
amount of the element. The ratio of the intensity of i in the sample to i in a pure element
standard, Eq. (1), was referred to as the k ratio by Castaing and forms the basis for
quantitative analysis:
I
sam
i
I
std
i
k
i
1
In this equation, the intensities must be corrected for background, peak interference, and
dead time dierences by the methods described in Chapters 2 and 3. Ideally,
k
i

C
i
all j
C
j
C
i
since
all j
C
j
1 2
where C refers to the elemental concentrations, expressed as weight fractions, and the
subscript j refers to all of the elements in the sample.
Equation (2) only applies to a system in which the sample and the standard are
identical and have been measured under identical experimental conditions. In practice,
as the similarities between the sample and the standard decrease, Eq. (2), even as an ap-
proximation, fails and a series of corrections must be applied to the k ratio to obtain an
Figure 7 Relative dimensions of the primary electron beam, the electron excitation and emission
volumes, and the x-ray emission volumes in a Cu target. (From Goldstein et al., 1981a. Reproduced
with permission of Plenum Press.)
accurate quantitative analysis. The corrections that must be applied to the k ratio include
the following:
1. The atomic number correction for the dierence between the electron scattering
and penetration in the sample and the standard
2. The absorption correction for the dierence in the absorption of the x-rays as
they pass through the sample or standard before reaching the detector
3. The uorescence correction for the uorescence of x-rays induced by
the absorption of characteristic and continuum x-rays that are generated in
the sample by the primary electron beam and which propagate out from this
source
These corrections are applied to the various k ratios as part of theoretical or empirical
correction procedures in order to obtain quantitative results.
A. Analytical Corrections for Quantitative Electron-Probe Microanalysis
1. ZAFCorrections
In the rst correction procedures that were used to obtain quantitative elemental analysis
from electron-probe data, the various corrections were applied to the k ratios as separate
multiplicative terms:
C
i
k
Z
k
A
k
F
k
i
3
where the terms k
Z
, k
A
, and k
F
refer to the atomic number, absorption, and uorescence
corrections, respectively. The methods based on Eq. (3) were appropriately referred to as
ZAF methods. In the remainder of this section, each of the corrections will be discussed
separately.
a. Atomic Number Correction, k
Z
The atomic-number correction in electron microprobe analysis is applied to the k ratio to
compensate for the dierence in the electron retardation and electron backscattering be-
tween the sample and standard. Both the electron retardation and backscattering are
dependent on the average atomic number of the sample
"
Z, Eq. (4). Therefore, any dif-
ference between the average atomic number of the sample and the standard should be
addressed by this correction. As a general rule, ignoring the eects of the atomic-number
correction will result in an underestimation of the concentration of high-Z elements in
low-Z matrices and the overestimation of concentrations of low-Z elements in high-Z
matrices (Goldstein et al., 1981b). The average atomic number
"
Z for the sample is given by
"
Z
i
C
i
Z
i
4
The general formulation of k
Z
for element i is given in Eq. (5):
k
Z
i

R
sam
i
R
std
i
_
E
0
E
c
Q
i
S
sam
i
_ _
dE
_
E
0
E
c
Q
i
S
std
i
_ _
dE
5
where the R and the S terms refer to the electron backscattering and the electron stopping
power, respectively, and Q is the ionization cross section. The limits on the integral are
from the incident electron energy, E
0
, to the critical excitation energy, E
c
for the x-ray line
of interest.
Electron stopping power. The electron stopping power S is dened in Eq. (6) as the
energy lost per unit electron path length in material of density r (Widdington, 1912):
S
1
r
_ _
dE
dX
6
One of the most commonly used terms for S is the approximation by Bethe (1930) and
Bethe and Ashkin (1953), which assumes a continuous function for the electron energy
loss:
S 78;500
Z
i
A
i
_ _
1
E
ln
1:166E
J
i
_ _
7
where S is in keVcm
2
=g and E is in keV.
The value for the mean ionization potential, J, in Eq. (7) is not directly measured and
several dierent expressions have been used in the literature for the calculation of J.
Various literature values for J are listed in Table 1 and are plotted as a function of Z in
Figure 8. The various expressions for J all yield similar results for elements above Z10
with relatively large discrepancies among expressions for Z<10. The BergerSeltzer ex-
pression for J is one of the most widely used in quantitative analysis procedures (Berger
and Seltzer 1964).
There are also several models in the literature that have been used to calculate Q,
all of which have the general form described by Bethe (1930):
Q C
ln U
UE
2
c
8
where U is the overvoltage dened as E
0
=E
c
.
Heinrich and Yakowitz (1970), however, have shown that the dierence in the
various models resulted, in negligible changes in the nal elemental concentrations for
elements with Z > 10.
Duncumb and Reed (1968) simplied the integration in Eq. (5), eliminating the need
for the numerical integration Eq. (5) and the evaluation of Q. In their procedure, they
assumed that the values for (1=S) dE were constant for the sample and standard over the
electron range used in electron-probe analysis and, therefore, could be removed from the
integral. As a result of this assumption, the integration of Q is unnecessary because it
appears in both the numerator and denominator and is the same for the unknown and the
standard. The stopping power factor can then be expressed as
Table1 Different Values for J
Equation (in eV) Reference
J=Z 13 Bloch (1993)
J=Z 11:5 Wilson (1941)
J=Z 9:76 58:82Z
1:19
Berger and Seltzer (1964)
J=Z 9:01 Z
0:67
0:03Z Springer (1967)
J=Z 12:4 0:02Z Heinrich and Yakowitz (1970)
J=Z 14:01 e
0:1Z
75:5=Z
0:13Z
Z=100 Z Duncumb et al. (1969)
J=Z 10:04 8:25e
Z=11:22
Zeller (1975)
Source: From Heinrich, 1981b.
S
Z
A
_ _
ln
1:166E
J
_ _
9
where A is atomic weight, and J, from Duncumb et al. (1969), equals
J
Z
141 exp0:1Z
75:5
Z
Z=7:5
Z100 Z 10
Equation (9) is one of the most commonly used formulations for classical ZAF micro-
analysis. Duncumb and Reed (1968) have shown from experimental work that the stop-
ping power for a multielement specimen can be expressed as a weighted sum of the
stopping power factor for each element:
S
i

j
0
C
j
S
ij
11
Figure 8 Different formulations for the mean ionization potential, J, plotted as a function of the
atomic number of the target. (From Goldstein, 1981c. Reproduced with permission of Plenum Press.)
where S
i
is the stopping power for element i; S
ij
is the stopping power for element i in the
presence of element j, and C
j
is the weight fraction of element j.
In addition to Eq. (9), alternate formulations for S have been proposed by Philibert
and Tixier (1968), Pouchou and Pichoir (1991a), and Love et al. (1978). Philibert and
Tixier derived an exact analytical solution to Eq. (6) that denes S in terms of a loga-
rithmic integral:
1
S

1
m
U
0
1
ln w
w
hLiwU
0
Liwi
_ _
12
where
w
1:1666E
c
"
J
m
alli
C
i
Z
i
A
i
ln
"
J
alli
C
i
Z
i
=A
i
ln J
i
m
U
0

E
0
E
c
The logarithmic integral Li of a variable Y expressed as an innite series is
LiY ln j ln Yj
1
F1
ln Y
F
FF!
D 13
where D is Eulers constant, which equals 0.577.
Love et al. (1976) noted that the Bethe expression (Bethe, 1930) for S is valid only if
E ) J and, as a result, modied the Bethe expression . . . to give better limiting behavior
as E approaches J. Their work results in the following formulation for S:
1
S
1 16:05
"
J
E
c
_ _
1=2
U
1=2
0
1
U
0
1
_ _
1:07
_
_
_
_
alli
C
i
Z
i
A
i
_
_
_
_
1
14
Similarly, Pouchou and Pichoir (1991), to avoid problems with the limiting behavior as E
approaches J in the Bethe expression, dened S as
S
1
"
J
_ _

alli
C
i
Z
i
A
i
_ _
_
_
_
_
1
f V
_ _
15
where V E=
"
J,
"
J is same as Philibert and Tixier (1968), and J
i
is from Zeller (Table 1).
f V

k3
k1
D
k
V
p
k
with D
1
6:6 10
6
, D
2
1:12 10
5
1:35--0:45
"
J
2
, D
3
2:2
10
6
=
"
J, p
1
0:78, p
2
0:1, and p
3
0:50:25
"
J .
Electron backscatter factor. The electron backscatter factor Rin Eq. (5) is dened as
R 1
I
b
I
t
_ _
16
where I
b
is the x-ray intensity lost due to backscattered electrons and I
t
is the x-ray in-
tensity if there are no electrons backscattered.
The fraction of electrons that are backscattered from a sample is known as the
electron backscatter coecient Z, and is given by
Z
_
1
0
dZ
dw
dw 17
where w is the ratio of the energy of the backscattered electron, E
b
, to the beam energy
E
0
i:e:; E
b
=E
0
. An empirical expression for Z, Eq. (18), was obtained by Reuter (1972)
from a t to Heinrichs data (Heinrich 1966):
Z 0:0254 0:016Z 1:86 10
4
Z
2
8:3 10
7
Z
3
18
The number of ionizations generated in a sample by an electron with energy E is given,
for a characteristic X-ray line with critical excitation energy E
c
, by
_
E
c
E
Q
dE=drs
dE 19
I
b
can then be obtained by multiplying Eqs. (17) and (19):
I
b

_
1
w
0
dZ
dw
_
E
c
E
Q
dE
_
drs
dEdw 20
where the integration limit for Z is w
0
E
c
=E
0
because electrons with energies less than E
c
cannot excite the x-rays of interest.
Similarly, I
t
can be calculated from Eq. (21) with integration limits of E
0
to E
c
:
I
t

_
E
c
E
0
Q
dE=drs
dE 21
Finally, substituting Eqs. (20) and (21) into Eq. (16) results in the following formulation
for R:
R 1
_
1
w
0
dZ
dw
_
E
c
E
Q
dE=drs
dEdw
_
E
c
E
0
Q
dE=drs
dE
_
_
_
_
_
_
1
22
Several tabulations of R have been made for pure elements as a function of Z and U
(Duncumb and Reed, 1968); Green, 1963; Springer, 1966. Duncumb and Reed produced a
table of R values for various elements and several dierent overvoltage values. Their
values were determined indirectly from Bishops (1966) measurements of the energy dis-
tributions of backscattered electrons and were in agreement with the direct measurements
of R made by Derian and Castaing (1966). Figure 9 shows a plot of the DuncumbReed R
values versus Z at dierent overvoltages.
Duncumb derived an algebraic expression for R in terms of w
q
and Z from his
calculated values; Eq. (23) is still used in many analytical procedures (Heinrich, 1981c):
R 1 0:581 2:162w
q
5:137w
2
q
9:213w
3
q
8:619w
4
q
2:962w
5
q
10
2
Z
1:609 8:298w
q
28:791w
2
q
47:744w
3
q
46:540w
4
q
17:676w
5
q
10
4
Z
2
5:400 19:184w
q
75:733w
2
q
120:050w
3
q
110:700w
4
q
41:792w
5
q
10
6
Z
3
5:725 21:645w
q
88:128w
2
q
136:060w
3
q
117:750w
4
q
42:445w
5
q
10
8
Z
4
2:095 8:947w
q
36:510w
2
q
55:694w
3
q
46:079w
4
q
15:851w
5
q
10
10
Z
5
23
where w
q
E
c
=E
0
.
Yakowitz et al. (1973) obtained a simplied expression for R from a t of the
Duncumb and Reed values:
R
ij
R
0
1
R
0
2
lnR
0
3
Z
j
25 24
where
R
0
1
8:73 10
3
U
3
0:1669U
2
0:9662U 0:4523
R
0
2
2:703 10
3
U
3
5:182 10
2
U
2
0:302U 0:1836
R
0
3
0:887U
3
3:44U
2
9:33U 6:43=U
3
In this Eq. (24) i represents the element being measured and j represents the elements in the
specimen, including i. R
ij
is therefore the backscatter correction for element i in the pre-
sence of element j.
Figure 9 Duncumb backscatter correction factor R versus Z and overvoltage (From Heinrich,
1981c. Reproduced with permission of Van Nostrand Reinhold.)
Myklebust (1984) further simplied the expression for R:
R 1 0:0081512Z 3:613 10
5
Z
2
0:009582Z expU 0:00114E
0
25
This expression represents a t of the R values obtained from the NBS Monte Carlo
program (Myklebust et al., 1975). Figure 10 shows the behavior of various R values from
dierent authors as a function of Z for selected x-ray lines. Myklebust and Newbury
(1991) suggest that the dierent formulations of R produce only small dierences in the
quantitative results. However, they recommend the formulation of R in Eq. (26), which
uses the cross section from Fabre delta Ripelle (1949) with Eq. (22), as the best for-
mulation, including the extreme conditions of very high or very low overvoltages:
R 1
_
1
w
0
dZ
dw
_
wE
0
E
c
A
B
dEdw
_
_
_
_
_
_
_
E
0
E
c
A
B
dE
_
_
_
_
_
_
1
26
where A lnE=E
c
and B 1=E
c
1:32=E ln1:166=J E.
In a multielement system, the factor R for element i can be calculated from Eq. (27),
which was proposed by Duncumb and Reed (1968):
R
i

j
C
j
R
ij
27
Myklebust and Newbury (1988) compared results from Monte Carlo calculations to re-
sults from Eq. (25) for a 10% CuAu alloy to determine the accuracy of mass con-
centration averaging in multielement targets. Their results indicate that Eq. (27) is valid
for the alloy studied. A detailed discussion of the R factor can be found in Myklebust and
Newbury (1991).
Evaluation of k
Z
. The results of analysis for copper in 2 wt% CuAl alloy have
been used by Goldstein et al. (1981d) to demonstrate the magnitude of the atomic-number
correction. The authors used both pure elements and a 46% AlCu alloy as standards for
the analysis. The results, given in Table 2, indicate that the atomic-number correction for
this analysis at 30-keV incident electrons is as high as 16% for the pure-element standards
and is reduced to 8% when the alloy is used as the standard.
b. Absorption Correction, k
A
The primary electron beamgenerates x-rays at varying depths within the sample. As a result,
the x-rays must pass through that portion of the specimen that lies between the x-ray gen-
eration point and the detector before they escape the sample and are measured. As shown
Figure 11, the distance ABis referred to as the absorption path length because a percentage
of the generated x-rays undergo photoelectric absorption, interacting with specimen atoms
prior to escape. The eect of this absorption is an attenuation of the generated x-ray in-
tensity that is measured by the detector. Note that inelastic scattering of the x-rays is not a
signicant process over the path lengths involved. The energy of the unabsorbed char-
acteristic x-ray is not modied during its passage through the specimen. The magnitude of
the attenuation is dependent on the composition of the specimen and a correction must be
considered when the sample and the standards used for the analysis are dissmilar.
Castaing (1951) described the characteristic x-ray intensity (without absorption)
generated in a layer of thickness dz, at a depth z below the specimen surface, in a sample of
density r as
dI frz drz 28
Figure10 Comparison of different functions for R versus Z for K (a), L (b), and M (c) x-ray lines.
(From Myklebust and Newbury, 1991.)
where frz is the distribution of characteristic x-rays as a function of depth [density 6
distance (mg=cm
2
)] in the sample. A typical curve for CuKa radiation is shown in
Figure 12. The total generated x-ray intensity for a given line can be obtained by in-
tegrating the area under the curve over the entire x-ray range:
I
_
1
0
frz drz 29
The introduction of x-ray absorption into Eq. (29) results in the following expression for
the x-ray intensity after absorption, I
0
:
I
0

_
1
0
frz expm=rrz cscC drz 30
where rz cscC is the absorption path length for the x-rays in the specimen, C is the
detector emergence angle, and m=r is the mass absorption coecient of the specimen for
the characteristic line of the element of interest.
The absorption term for EPMA is referred to as fw or f
p
, where w m=r cscC
and fw I
0
=I. From Eqs. (29) and (30), fw can be expressed in terms relating to the
specimen as
fw
_
1
0
frz exp
m
r
rz csc C
_ _ _ _
drz
_
_
_
_
_
_
I
1
_
1
0
frz drz 31
Table 2 k
Z
Correction for Copper in a 2 wt% Copper in Aluminum
Alloy
15 keV 30 keV
Standard k
Z
(Cu) k
Z
(Cu)
Elemental Cu 1.16 1.11
Alloy 1.08 1.05
Source: From Goldstein et al., 1981d.
Figure11 X-ray absorption path length.
The absorption correction for EPMA can then be expressed as
k
A

fw
std
fw
sam
32
The basic formulation of the fw term was derived by Philibert (1963), who considered the
number of ionizations produced in a layer of element i with thickness dz at some depth z
within a specimen:
fw
1
f0hw
4f0hs
1 w=sf1 h=1 hw=sg
33
In this equation, f0 is the surface ionization function, s is Lenards (1895) coecient for
a given incident electron energy, and h is given by
h 1:67 10
6
A
Z
2
sE
2
0
34
Figure12 A f(rz) curves for CuKa radiation. The solid line are measurements by Castaing and Des-
camps and the dashed line is based on Philiberts f (w) with the DuncumbShields s. (From Criss, 1968.)
Noting that fw was not sensitive to either f0 or s, Philibert (1963) simplied Eq. (34)
by setting f0 0 and h 1:2A=Z
2
. This results in the following expression for fw:
1
fw
1
w
s
_ _
1
h
1 h
w
s
_ _
35
where s 4:5 10
5
=E
1:65
0
E
1:65
c
.
Duncumb and Shields (1996) modied s to take into account that electrons with
energies less than E
c
cannot generate x-rays from the line associated with E
c
. They pro-
posed the following expression for s:
s
2:39 10
5
E
1:5
0
E
1:5
c
36
Heinrich (1970) t experimental values of fw from Green (1962) and proposed the
following formulation for s:
s
4:5 10
5
E
1:65
0
E
1:65
c
37
The most common form of the absorption term found in the various analytical schemes is
Eq. (35) with h 1:2A=Z
2
and Heinrichs s. This form of Eq. (35) is often referred to as
the PhilibertDuncumbHeinrich equation.
Heinrich et al. (1972) empirically derived a simplied absorption term that was based
on experimental data and the Philibert equation. In the formulation of this term, it was
noted that the compositional dependence in Philiberts h term was small compared to the
scatter in the available experimental data. The resulting formulation for fw, given in
Eq. (38), is referred to by Heinrich as the quadratic model. In this equation, the
compositional dependence in the h term has been eliminated, making the model in-
dependent of the atomic weight and atomic number of the target:
1
fw
1 1:2 10
6
gw
_ _
2
38
where g is the quantity E
1:65
0
E
1:65
c
.
In Eq. (35), h is dependent on target composition and must be averaged for the
various elements in multielement targets. A compositionally weighted average for h,
Eq. (39), is generally employed in analytical procedures:
h
t

j
C
j
h
j
39
In addition, the mass absorption coecient, m=r, for the characteristic line of element i
in a multielement target is the weighted sum over all elements in the target including i:
m
r
_ _
sam
i
j
C
j
m
r
_ _
j
i
40
where m=r
j
I
is the mass absorption coecient for the line of element i in element j and C
j
is the concentration of element j.
The calculation of x-ray absorption from Eq. (35) is most accurate when the value of
fw is greater than 0.7. Toward this end, it is important in setting up an experiment to
minimize the degree of x-ray absorption by the following:
1. Minimizing the absorption path length by selecting a low overvoltage E
0
=E
c
2. Selecting high-energy x-ray lines that have low-absorption cross sections. It is
important to note that selecting a high-energy x-ray line requires a high
acceleration potential and will, therefore, increase the absorption for elements in
the sample that have relatively low-energy analytical lines
3. Measuring the intensities at the highest possible x-ray emergence angle (which
typically is xed for any given instrument)
A study was done by Small et al. (1991) comparing experimental measurements of fw
with four dierent absorption models. The experimental data were collected for Si at both
20 and 30 kV and for Fe and S in FeS
2
at 20 kV acceleration potential. The models studied
included the following:
1. Heinrichs quadratic model, Eq. (38) (Heinrich, 1972)
2. Heinrichs duplex model, Eq. (41) (Heinrich, personal communication, 1987)
3. Philiberts model, Eq. (35) (Philibert, 1963)
4. Pouchou and Pichoirs model, Eq. (42) (Pouchou and Pichoir 1991a)
Duplex model:
fw
1 1:65 10
6
gw
2
1 a1:65 10
6
gw
41
where a 0:18 2=g 8 10
9
E
c
0:005
Z
p
with E
c
in electron volts.
Puchou and Pichior model:
fw
F
1
w F
2
w
F
42
where the formulation for F, F
1
, and F
2
are given in Pouchou and Pichoir (1991a).
Acomparison of the dierent models and the experimental data is shown in Figure 13.
The results of the study indicated that no one model is best for all targets and conditions.
The analyst interested in the highest accuracy should select the absorption correction that
works the best for the particular type of sample and experimental conditions.
c. Fluorescence Correction, k
F
The characteristic uorescence correction is necessary when the analysis involves the
following conditions:
1. The characteristic x-ray peak from element j at energy E
j
is greater than the
critical excitation potential E
c;i
for element i.
2. The energy dierence E
j
E
c;i
< 5 keV.
When these conditions exist, the characteristic line of element j will excite the characteristic
line of element i in the specimen as shown in Figure 14. This uorescence results in an
increased intensity for element i that must be taken into account in obtaining a quanti-
tative analysis. In this case, the excitation is caused by x-rays and not electrons; hence, the
generation of the secondary x-rays will originate from a much larger volume of the sample
that if it were generated directly by electrons. In addition, the measured intensity of the
uorescence radiation is proportional to the x-ray emergence angle.
The basic formulation of the uorescence correction is given by
F
i
1
j
I
f; j
I
i
_ _
std
1
j
I
f; j
I
i
_ _
1
sam
43
Figure13 Plots of the experimental data and literature models for f (w), where the residuals 100f f w
model
f w
experimental
=
f w
experimental
g and high absorption w>10,000, medium1000<w<10,000, and loww<1000. (From Small et al., 1991.)
The factor I
f
=I
i
is the ratio of the x-ray-excited intensity for the characteristic line of
element i to the electron-excited intensity. The summation over j is required because the
total correction must be summed over all the elements in the specimen.
The most commonly used uorescence correction factor was originally developed by
Reed (1965) and is given in Eq. (44) [from Reed (1997)]:
I
f
I
i
0:5C
j
m
i
j
m
j
_ _
r
i
1
r
i
_ _
o
j
A
i
A
j
_ _
U
j
ln U
j
U
j
1
U
i
ln U
i
U
i
1
_ _
ln1 m
m

ln1 n
n
_ _
44
where C
j
is the concentration of element j; m is the mass absorption coecient, r is the
absorption jump ratio dened as the ratio of m=r on the high-energy side of the ab-
sorption edge to m=r on the low-energy side, the factor r
i
1=r
i
is 0.88 for K line
uorescence and 0.74 for L line uorescence, o
j
is the uorescent yield of element j,
A
i
is the atomic weight, U is the overvoltage, m m
i
cosec c=m
j
and n s (Lenards
coecient)=m
j
.
In practice, when calculating the uorescence correction from Eq. (43), the standard
is either a pure element or there is no signicant uorescence of element i by other elements
in the standard. For this situation, Eq. (43) reduces to
F
i
1 1
j
I
f; j
I
i
_ _
1
sam
45
which is the most common form of the correction found in analytical procedures. Gold-
stein et al. (1981e) demonstrated the magnitude of the uorescence correction with the
analysis of a 10 wt% Fe90 wt% Ni alloy. The results of the analysis are summarized in
Table 3 and show that the intensity of the uoresced iron, I
f
=I
Fe
ranges from 16.8% to
34.6% of the observed iron x-ray intensity. The magnitude of the correction is lower at the
smaller accelerating potential and detector takeo angle.
Figure14 Secondary fluorescence in a specimen.
In addition to the secondary excitation by characteristic x-rays, x-rays can also be
excited by the continuum x-rays produced in the sample. The continuum x-rays are the
result of the deceleration of beam electrons in the Coulombic eld of the specimen
atoms. This radiation forms an x-ray background that is slowly varying with energy
and ranges from E
0
to zero. Although there has been some eorts by Heinrich (1987) to
simplify the calculations for determining continuum uorescence, the basic formulation
for the added intensity from the continuum uorescence, I
c
, was derived by Henoc
(1968):
I
c
f
"
Z; o; r;
m
r
_ _
; C
_ _
46
The calculation of the continuum uorescence is relatively complicated, involving
integration over the range of E
0
to E
c
for each element in the specimen. Because the
correction can be as large as 24%, it should be included for highest accuracy. Myk-
lebust et al. (1979), investigating the continuum uorescence, determined the following
experimental conditions for which a correction for the uorescence by the continuum is
required:
fw > 0:95
C
i
< 0:5
"
Z from the standard much dierent from
"
Z of the sample
These requirements translate to a signicant continuum uorescence correction in
the analysis of a small amount of an element with a high-energy x-ray line such as zinc, in a
light matrix such as carbon. In Figure 15, Heinrich compared the uorescence intensities
caused by the x-ray continuum to the intensities generated by the primary electron beam
for Al and Cu at dierent electron beam energies and takeo angles.
2. Analysis Method Based on Integrationof frz Curves
In the classical ZAF procedures, the absorption correction, as mentioned earlier, was
based on Philiberts parameterization of a limited set of frz curves, including several
simplications. The shape of his curve, although not correct, works well for higher-
energy x-rays for which the shape of the curve is not critical due to the relatively long
absorption path lengths. However, for light elements in specimens with high absorption,
Al in Cu, or elements with low-energy x-rays, such as B, C, N, and O, where absorption
is signicant, the shape of the frz curve is critical. As a result, the classical ZAF
routines based on the simplied Philibert model produce large errors in the concentra-
tions for these elements.
Table 3 Fluorescence of FeKa by Ni in 10 wt% Fe90 wt%
Ni alloy
C (deg) E
0
(keV) I
f
=I
Fe
F
Fe
52.5 15 0.263 0.792
15.5 15 0.168 0.856
52.5 30 0.346 0.743
15.5 30 0.271 0.787
Source: From Goldstein et al., 1981e.
Several researchers, including Love (1983), Love and Scott (1988), Bastin et al.
(1986), Pouchou and Pichoir (1988), and Sewell et al. (1985a) have made experimental
measurements of x-ray depth distributions, frz curves, in a large number of targets,
including pure elements, alloys, and oxides. In addition, other researchers [e.g., Heinrich
et al. (1988), Gauvin et al. (1995), Murata et al. (1983), and Karduck and Rehbach (1988)]
have made Monte Carlo calculations of x-ray depth distributions. The increased knowl-
edge regarding the behavior of these curves for dierent materials has made it possible to
empirically develop corrections based on the integration of frz curves. These procedures
are particularly attractive for the analysis of low-energy x-ray lines from the elements
boron through uorine, where fw is much less than 0.7 and the accuracy of the ZAF
method is low. In these procedures, frz refers to the depth distribution of x-rays in a
bulk sample normalized to the x-ray intensity produced in an innitely thin, unsupported
lm of the same composition. In principle, the frz curve as described by Castaing (1951)
contains the information necessary to correct experimental data for both the atomic-
number correction, Z (integrated area under curve), and absorption correction, A (shape
of the curve). The Gaussian model proposed by Packwood and Brown (1981) combines
the Z and A corrections in their model for frz producing a single emitted intensity. It
should be noted, as pointed out by Armstrong (1988a), that the use of frz expressions
Figure15 Comparison of x-ray intensities fluoresced by the x-ray continuum to the intensities gen-
erated by the primary electron beam. I
0
c
=I
0
p
refers to the relative emergent fluorescent intensity at a
given angle and I
c
=I
p
refers to the relative generated fluorescent intensity. (From Heinrich 1981d. Re-
produced with permission of Van Nostrand Reinhold.)
for the correction of x-ray absorption requires only that a given expression produce the
correct shape for the frz curve. The use of the frz expression for the atomic-number
correction is risky because this requires that the thickness of the tracer lms and the
normalizing thin lms in the frz experiments for dierent matricies be known to a high
degree of accuracy (Armstrong 1988a).
In practice, several of the frz methods use of the shape of the frz curve for the
absorption correction and combine that with separate Z and F corrections. Independent of
the procedure used, the analysis of specimens using the frz correction method is de-
pendent on the derivation of an accurate expression that describes the experimental frz
curves and the degree to which that expression can be universally applied to systems with
unknown frz curves.
a. Analytical Expressions for frz
Listed below are a series of parameterizations that have been used by various authors to
represent the shape and area of frz curves.
Packwood and Brown. Packwood and Brown (1981) proposed a modied Gaussian
function to describe the shape of frz curves. In their procedure, both the atomic-number
correction and the absorption correction are parametrized by the model. The Gaussian is
centered at the sample surface and modied by a transient function that was introduced to
model the near-surface x-ray distribution. Figure 16 is a plot of the modied Gaussian
function showing the inuence of the various parameters a; b; g
0
, and f
0
. In the model given
in Eq. (47) [from Packwood (1991)], the a term related to the width of the Gaussian and g
0
relates to the amplitude. The b termin the transient is related to the slope of the curve in the
near-surface region (i.e., the rate at which the focused electron beamis randomized through
scattering in the target and the y intercept, f
0
, is related to the surface ionization potential):
frz g
0
expa
2
rz
2
..
Gaussian term
f1 g
0
f
0
=g
0
expbrzg
..
Transient term
47
The formulas for the dierent terms can be found in Packwood (1991).
Figure 16 Modified Gaussian function for fitting f(rz) curves. (From Packwood and Brown,
1981. Copyright John Wiley & Sons Limited. Reproduced with permission.)
Pouchou and Pichoir. Pouchou and Pichoir (1991b) proposed a frz procedure,
PAP that was designed to provide a broad range of analytical capabilities including bulk
and stratied sample analysis. In this procedure, the authors separate the parameters that
dene the shape of the frz curve (i.e., the absorption correction) from the parameters
that dene the total integral of the frz curve (i.e., the generated primary intensity or
atomic-number eect). The authors refer to their procedure as neither like a ZAF
structure with separate Z, A, and F corrections nor like a global structure such as the
model of Packwood and Brown (1981) in which the emerging intensity is obtained directly
from the parametric description of frz.
Area parameter: In the PAP procedure, the authors dene the integral of the frz
curve from zero to innity, Eq. (29), as F. The analytical expression for F which
is used for the atomic-number correction is given in Eq. (48), where R is the
backscatter factor based on the mean-backscatter coecient and the mean-
reduced backscattered electron energy for the electrons, 1=S is the deceleration
factor, and Q
A
1
E
0
is the cross section for x-ray production at level 1 for
element A and voltage E
0
:
F
R
S
_ _
Q
A
1
E
0
48
A detailed description of the analytical expression used to calculate F is given
in Pouchou and Pichoir (1991b).
Shape parameter: For their procedure, Pouchou and Pichoir placed the following
conditions on their analytical expression for the shape of the frz curve:
The integral of the shape function must be equal to F.
The shape function must have a nite value for f0.
The parameterization of the function must have a maximum, designated
as R
m
.
The function must vanish with a horizontal tangent at a predetermined
range, R
x
.
The shape of the frz curve is dened by a pair of intersecting parabolas. For this
model, the curve is dened by the following parameters:
f0 the surface ionization function
R
m
depth at which the maximum in the frz curve occurs
R
x
the x-ray range
The area under the frz curve (i.e., the total generated intensity)
The equation for the rst parabola nearest the target surface is given in Eq. (49) for
values of rz between 0 and R
c
and the second parabola by Eq. (50) for values
of rz between R
c
and R
x
:
f
1
rz A
1
rz R
m
2
B
1
49
f
2
rz A
2
rz R
x
2
50
where the parameters A
1
; A
2
, and B
1
are functions of R
m
; R
x
, and f0, and R
c
is the crossover point of the parabolas. The equation for R
c
is a function of the
generated X-ray intensity, I, which is the integral of the area under the frz
curve, Equation (29). Figure 17 is the plot of the double-parabola curve with
the various parameters located on the curve. Pouchou and Pichoir (1991b)
introduced a simplied version of their model based on
frz Aexparz Brz f0 A expbrz 51
The coecients A; B; a, and b can be determined from the following parameters:
1.
_
1
0
frzdrz
A
a

f0 A
b

B
b
2
2. f0 is the surface ionization.
3.
"
Rmean ionization depth,
"
R
A
a
2

f0 A
b
2

2B
b
2
4. The initial slope B aA bf0 A.
Merlet. Merlet (1994) developed a parameterization of frz based on a double
partial Gaussian expression for the description of the frz curve as shown in Figure 18.
The parameterization is dependent on dening the depth distribution at three points of the
frz curve, the surface at 0; f0, the curve maximum at rz
m
; fm, and the x-ray
range at rz
x
; fm=100. Equation (52) denes the partial Gaussian f
1
for rz values
between the surface and rz
m
, and Eq. (53) denes the partial Gaussian f
2
for rz values
from rz
m
to rz
x
:
f
1
f
m
exp
rz rz
m
b
_ _
2
_ _
52
where
b
rz
m
lnfm=f0
0:5
and
f
2
f
m
exp
rz rz
m
a
_ _
2
_ _
53
where
a 0:46598rz
x
rz
m
A detailed description of this procedure is given in Merlet (1994).

Figure 17 PAP double-parabola function for fitting f(rz) curves. (From Pouchou and Pichoir,
1991b. Reproduced with permission of Plenum Press.)
Bastin. Bastin and Heijligers (1991) modied the Gaussian model of Packwood and
Brown combining the a and g terms with a b term based on the PAP F term or area
parameter. In Bastins PROZA program (Bastin et al., 1984), the b term is adjusted, for
given a and g, so that the integral under the frz curve is equal to the PAP area para-
meter F, and the peak of the frz curve is optimized with respect to position and height.
The a term is a function of the beam energy E
0
, the critical excitation energy E
c
, the
overvoltage for the x-ray line of interest U
0
, the atomic number Z, atomic weight A, and
ionization potential J of the matrix. The g term is determined from one of two equations,
depending on whether U
0
is greater than 6. Both equations are functions of U
0
and Z. The
b term is derived from a; g and F and is divided into nine dierent segments based on the
value of Rb=2a. The equation f
0
is taken from the PAP model. The various equations
for the parameterization of a; b, and g are given in Bastin and Heijligers (1991).
In addition to PROZA, Bastin et al. (1998) have developed a new parameterization
based on the double partial Gaussian model of Merlet (1994), called PROZA96. The
formulation of the two Gaussian functions are as follows:
For 0 rz rz
m
f
l
rz f
m
expb
2
rz rz
m
2
54
For rz
m
rz 1
f
r
rz f
m
expa
2
rz rz
m
2
55
Figure18 Double partial Gaussian for fitting f(rz) curves. (From Merlet, 1994). Data points are
taken from the work of Castaing and Henoc. (From Castaing and Henoc, 1965; Reproduced with
permission of Springer-Verlag.)
In this case, the b term in Eq. (54) refers to the Gaussian rate of increase from 0 to rz
m
and
is dierent from the b term in the PROZA formulation. Likewise, the a term in Eq. (55) is
the Gaussian rate of decrease from rz
m
out to innity.
Bastin et al. adopted the new PROZA96 formulation for frz because of the
constraints placed on the position and height of the maximum in the frz curve by the g
term in the PROZA formulation. The area under the frz curve in PROZA is xed by
the F term. The main advantage of the new formulation is in absorption. The shape of the
frz curve in PROZA96 results in an increased exibility for analyzing ultralight ma-
trices such as Be, B, and C, particularly for thin-lm calculations where the shape of the
frz curve is critical, and at high overvoltages, the maximum will be shifted deeper into
the sample.
Armstrong. Armstrong (1991) developed a frz model, Eq. (56), based on the
Gaussian equation from Packwood and Brown:
frz g
0
e
a
2
rz
2
1 qe
brz
56
where
a 2:97 10
5
"
Z
1:05
"
AE
1:25
0
ln1:166E
0
=J
E
0
E
c
_ _
0:5
b
8:5 10
5
"
Z
2
"
AE
2
0
g
0
1
g
0

5pU
0
U
0
1 lnU
0
lnU
0
5 5U
0:2
0

q
g
0
f0
g
0
"
Z and
"
A are the atom-concentration weighted atomic number and atomic weight,
respectively. The surface ionization function, f0, can be determined from the expression
of either Reuter (1972) or Love and Scott (1978).
Love and Scott. Love et al. (1984) proposed a frz method in which they in-
troduced a separate atomic-number correction. With the separate treatment of the atomic-
number correction, the frz curve is used only for target absorption. As mentioned
earlier, target absorption requires only that the shape of the curve be correct and not the
absolute height. The authors proposed a quadrilateral prole, Figure 19, to t the shape of
the curve. The quadrilateral is dened by the y intercept f0, the position and amplitude
of the peak, rz
m
; fm, and the x-ray range, rz
r
. From the quadrilateral model, the
analytical expression for fw can be written as
fw 2A
1
B C 57
where
A rz
r
rz
m
rz
m
hrz
r
w
2
B expwrz
m
h expwrz
r
wrz
r
rz
m
h 1
C
expwrz
m
rz
r
hrz
r
hrz
r
rz
r
rz
m
h
fm
f0
To constrain the quadrilateral model when fw values exceed 0.5, the authors expressed
both rz
m
and rz
r
in terms of the mean depth of x-ray generation, " rz (Scott and Love,
1991). In conjunction with the quadrilateral t to the frz curve for target absorption,
the atomic-number correction combines the stopping power factor from Eq. (14) with the
backscatter factor R, Eq. (58), from Love et al. (1978):
1 R
Z
_ _
0:6
IU
0
ZGU
0
58
where U
0
is the overvoltage, Z is the backscatter coecient,
IU
0
0:3
1
U
0
exp1:5 1:5U
0:25
0

_ _
and
GU
0
0:368 0:075 ln U
0
exp1 2:3U
4
0

A full description of the quadrilateral model can be found in Scott and Love (1991).
3. Evaluationof ZAFand frz Analytical Correction Procedures
The relationship describing a ZAF or frz correction procedure gives the impression that
the concentration of a given element can be calculated directly from the k ratio. This,
however, is not the case because the parameters used in the dierent correction schemes
are dependent on the composition of the sample, including the element of interest. For a
simple binary system, the analyst could construct a calibration curve relating measured
x-ray intensity to concentration. However, this does not apply to more complicated sys-
tems and the primary method used in correction procedures is an iterative method.
A general owchart for a typical ZAF or frz correction method is shown in
Figure 20. The measured k ratio is used as the initial estimate of composition by taking
C
i

i
k
i
=C
i
. The dierent ZAF or frz corrections are then applied to the initial es-
timate of concentration to obtain the corresponding estimate of k. Next, a hyperbolic
iteration, Eq. (59), is used to obtain a value for a:
Figure 19 Quadrilateral function for fitting f(rz) curves. (From Scott and Love, 1991. Repro-
duced with permission of Plenum Press.)
Figure 20 General flowchart for a typical ZAF or f(rz) correction method.
k
i

a
i
C
i
a
j
C
j
59
The a value is then used with the measured k ratio to obtain a new estimate of con-
centration that is then normalized and the iteration continued. Convergence with the
hyperbolic function is rapid and seldom requires more than three iterations.
The practical lower limit for quantitative x-ray microanalysis is on the order of
0.01% by weight for an element homogeneously distributed in an innitely thick, polished
specimen. The x-ray excitation cross-sections and the signal-to-noise ratio of the x-ray
detection systems primarily set this limit. The accuracy of a classical ZAF electron-probe
analysis is shown in Figure 21, which is a histogram of the relative errors from 264
analyses of binary metal alloys.
The accuracy of several dierent analytical models, including both ZAF and frz
models is shown in Figures 2224, which are adapted from a table compiled by Pouchou
and Pichior (1991b) for 826 analyses of binary compounds. In these gures, the horizontal
line for a given model is 1 standard deviation for the mean value of k (calculated)=k
(experimental), which is represented by a lled circle. The length of the horizontal line for
a given model is an indicator of the variation in the accuracy for the performance of that
model on the given dataset. Similarly, the proximity of the mean with respect to unity is an
indicator of any systematic bias in the model.
Figure 22 displays the results from the entire 826 analyses. The frz models 1 and 2
have the lowest variations in accuracy, both less than 2%. frz models 3 and 4 and ZAF
model 5 are similar with variations less than 3%. The remaining two ZAF models (6 and
7) have variations greater than 4%. The systematic biases for the techniques are small and
fall within 1%, except for the ZAF method 5, which has a systematic bias of about
1.5%. Figure 23 displays the results of 577 of the 826 analyses involving samples where
the atomic-number eect is greater than the x-ray absorption eect. The variances for all
the models are similar generally less than 2%, except the frz model 4, which has a
variance of about 3%. The biases are also small, except for model 4, which has a positive
systematic bias of about 1.5%. Figure 24 shows the result for 242 analyses involving
samples where x-ray absorption is the predominate correction. For these samples, there is
a signicant dierence between the ZAF and frz models. Three of the fz models (1, 2
and 4), have variances in accuracy less than 3% and biases less than 1%. ZAF model 5 and
frz model 3 are similar for both variation, about 4%, and systematic bias, about 2%.
The remaining two ZAF models (6 and 7) have signicantly larger variances, about 6%,
and systematic biases of around 4%.
In addition to the above dataset, Pouchou and Pichior (1991b) also compiled data
for a series of boride analyses, the results of which are given in Figure 25. The variance in
accuracy for the dierent methods range from about 4% for several of the frz methods
to about 25% for the worst ZAF method. Five of the seven methods show a slight sys-
tematic bias of 12% with models 7 and 8 having signicant positive biases of 8% and
15%, respectively. Finally, Table 4 lists the results from the analyses of compounds
containing ultralight elements with PROZA96 from Bastin et al. (1998).
B. Empirical Approach to Quantitative Analysis
Ziebold and Ogilvie (1964) developed a quantitative analysis procedure for emitted x-rays
that is based on Castaings third approximation for generated x-rays given in Eq. (59)
(Castaing, 1951). In this empirical procedure, the relationship between the k ratio and
Figure 21 Histogram of the relative errors for a classical ZAF analysis from Goldstein et al.
(From Goldstein et al., 1975b. Reproduced with permission of Plenum Press.)
Figure 22 Results from the analysis of 826 binary compounds with several different quantitative
analysis procedures. (Adapted from Pouchou and Pichoir, 1991b.)
Figure23 Results for 577 of the 826 binary compounds where the atomic-number effect is greater
than the x-ray absorption effect. (Adapted from Pouchou and Pichoir, 1991b.)
Figure 24 Result for 242 analyses involving samples where x-ray absorption is the predominate
correction. (Adapted from Pouchou and Pichoir, 1991b.)
concentration, expressed in Eq. (2), can be expanded to include real samples by the in-
troduction of an eciency factor a for element a in a sample:
k
a

a
a
C
a
Sa
i
C
i
where the summation is over all elements in the sample.
Ziebold and Ogilvie, using Eq. (59), expressed the relationship between C and k for a
binary system containing elements i and j as
C
i
k
i
a 1 aC
i
60
or
k
i
C
i
1
a
1
1
a
_ _
k
i
61
where a for the binary is referred to as the a factor and equals a
j
=a
i
.
Figure 25 Results from the analysis of a series of borides. (Adapted from Pouchou and Pichoir,
1991b.)
Table 4 Performance of PROZA96 on Ultralight Element Data: Comparison of the Calculated k
ratio (k
0
) with the Measured One (k)
Element No. of measurements Mean k
0
=k Root mean square deviation (%)
Boron 192 1.0033 3.3114
Carbon 117 1.0001 3.2092
Nitrogen 144 0.9989 3.6820
Oxygen 294 1.0004 2.0090
Source: From Bastin et al., 1998.
Finally, solving for a yields Eq. (62) which is the formulation for the hyperbolic
approximation because the plots of the calibration curves of C versus k described by this
equation are hyperbolas:
a
C
1 C
_ _
1 k
k
_ _
62
Equations (60) and (61) indicate a linear relationship between C=k and C, and k=C
and k so that a plot of C=k versus C or k=C versus k are straight lines. The slope of the line
will be positive if a is greater than 1 and negative if a is less than 1. Experimental con-
rmation of the hyperbolic approximation is shown in Figure 26, which is a plot of k=C
versus k for experimental measurements on AgLa x-rays from four dierent AgAu alloys
at several dierent beam energies. Except for the 5-keV line, the plots for the dierent
alloys as predicted by the hyperbolic approximation are straight lines.
The concentrations C
i
and C
j
, for elements i and j in an unknown binary, can be
determined from Eq. (62) if the appropriate values for a
i
; a
j
; k
i
, and k
j
are known. In
theory, the k values do not present a problem because they are experimentally measured.
The determination of a
i
and a
j
, however, requires the analysis of a standard binary con-
taining the same elements as the unknown. In the procedure for determining the a factors,
k
i
and k
j
are obtained for the standard binary by comparison to pure-element standard of i
and j. Because the values of C
i
and C
j
, in the standard binary are known, it follows that a
i
Figure 26 k=C versus k for AgAu alloys at various electron beam energies. (From Goldstein
et al., 1981f. Reproduced with permission of Plenum Press.)
and a
j
can be calculated from Eq. (59). In the case of a binary, Eq. (63) can be used to
calculate the concentration for element i in the unknown binary:
C
i

k
i
a
1 k
i
a 1
63
The values for a are specic for a given experimental setup, and if the analysis
parameters are changed, the a values must be recalculated. As long as the analyst is
concerned with measurements on a given binary system under constant conditions, then
Eq. (63) provides a very rapid and easy method for the determination of elemental
composition with an accuracy that is comparable to that of the full ZAF procedure.
In addition to their work on binary systems, Ziebold and Ogilvie (1964) also derived
the analytical expression for a ternary system. The basic equation for the ternary remains
Eq. (63), except that the combined a factor for element 1 in a ternary compound con-
taining elements 1, 2, and 3 is given by the following expression:
a
1;2;3

a
1;2
C
2
a
1;3
C
3
C
2
C
3
64
An important aspect of the ternary derivation is that the combined a factor for the ternary
system in Eq. (64) can be expressed as a combination of the individual a factors for the
dierent binaries.
Bence and Albee (1968), building on the work of Ziebold and Ogilvie, extended the
application of the hyperbolic approximation to multielement systems containing six to
eight elements. They were interested in obtaining a rapid, accurate procedure for the
analysis of specimens of geological origin. In such specimens, it was not practical in 1968
to apply the full ZAF corrections due to the limited computational resources available.
Even with modern computer capabilities, the empirical approach oers a simple,
straightforward approach to quantitative analysis that can be programmed and executed
on a small pocket calculator. In addition, because of its simplicity and speed, it can be used
for real-time processing of spectra image data (see, Sec. V). The general formula for ele-
ment i in a system of n components is given by
C
i
k
i
b
i
65
where
b
i

k
2
a
i2
k
3
a
i3
k
n
a
in
k
2
k
3
k
n
In Eq. (65), the a
i2
factor refers to the a factor for element i in a binary of element 2 and
element i. Similarly, k
2
refers to the intensity ratio of element 2 in the specimen to the
element 2 in the standard. In practice, the analyst is required to measure nn 1 values
for a, which requires nn 1 binary standards.
The owchart for the empirical method of quantitative analysis is shown in Figure 27.
The analyst, having determined the needed a values, measures the appropriate k values for
the unknown and calculates the b termfromEq. (65). The b values are then used to calculate
a rst approximation of the elemental concentrations. From Eq. (65), a second set of b
values are determined with the approximate concentrations used for the ks. The iteration
loop is continued until the dierence in successive b terms is below a predetermined limit.
As previously mentioned, the analysis of multielement systems requires nn 1
standards. Because the large number of standards for the determination of a factors in a
complex system may not be available, a combination ZAF, frz, or Monte Carlo a factor
approach has been developed. In this procedure, the analyst calculates the necessary a
factors by assuming an appropriate composition and then running a ZAF, frz, or
Monte Carlo procedure to back-calculate the corresponding k ratios. The a factors can
then be determined from Eq. (60). It is important that the analyst realize that the total
uncertainty in this combined approach includes the uncertainties of both the empirical and
the ZAF methods. Albee and Ray (1970) have used this procedure to determine the a
factors for 36 elements relative to simple oxides. Laguitton et al. (1975) and Bence and
Holzwarth (1977) proposed additional corrections along with more elaborate polynomial
representations of the a factors. Armstrong (1988b) calculated a large number of oxide a
factors using a combination of ZAF, frz, and Monte Carlo methods combined with a
second-order polynomial for the a factors, Eq. (66):
a
i
i; j
c d
C
i
C
i
C
j
_ _
e
C
i
C
i
C
j
_ _
2
66
where C
i
and C
j
are the oxide weight fractions of elements i and j in the binary and c; d,
and e are the coecients of the polynomial t. The results indicated that the C=k values
Figure 27 An empirical analysis procedure.
from the second-order polynomial a factor were essentially identical to the ZAF, frz, or
Monte Carlo method they were based on and the results can be expected to have the same
accuracy and precision as the conventional procedures.
The empirical method of analysis is most accurate when the dierence between the
sample and standards is mainly the result of x-ray absorption. The procedure is less ac-
curate when there are large dierences in atomic number and is least accurate when there
is a signicant contribution from uorescence. Given these limitations, the empirical
procedure works best for the analysis of materials such as geologic specimens and oxide
systems that have relatively low mean atomic numbers and minimal secondary uores-
cence.
C. Standardless Quantitative Electron Probe X-ray Microanalysis with EDS
An increasing trend in recent years in performing quantitative electron probe x-ray
microanalysis with energy-dispersive x-ray spectrometry has been the substitution of
standardless methods in place of the traditional approach of measuring standards
containing the elements of interest on the same analytical instrument under the same
excitation and detection conditions (Russ, 1974). In standardless methods, the appropriate
standard intensities necessary for quantication are either calculated from rst principles,
considering all aspects of x-ray generation, propagation through the solid target, and
detection (true standardless), or else standard intensities are derived from a suite of
experimental measurements performed remotely and adjusted for the characteristics of the
local instrument actually used to measure the unknowns (tted standards). With either
route to standard intensities, the resulting k values (unknown=standard) are then
subjected to matrix corrections with one of the usual approaches [ZAF, frz, etc.].
The apparent advantages of standardless analysis are considerable. Instrument op-
eration can be extremely simple. There is no need to know the beam current, and, indeed,
it is not even necessary for the beam current to be stable during the spectrum accumu-
lation, a real asset for instruments such as the cold-eld-emission gun scanning electron
microscope (SEM), FEG-SEM, where the beam current can be a strong function of time.
Moreover, the detector solid angle is of no consequence to the quantitative procedure.
Both the beam current uncertainty and the detector solid angle uncertainty are eectively
hidden by forcing the analytical total to a predetermined value (e.g., unity when all
constituents are measured). When the spectrum has been accumulated to the desired level
of statistical precision, the analyst needs to specify only the beam energy, the x-ray takeo
angle, and list of elements to be quantied (of this list can be derived from an automatic
qualitative analysis). The software then proceeds to calculate the composition directly
from the spectrum, as described below, and in the resulting output report, the con-
centration is often specied to three or four signicant gures. The measurement precision
for each element, calculated from the integrated peak and background counts, is also
reported. The precision is really only limited by the patience of the analyst and the stability
of the specimen under electron bombardment, so that precision values below 1% relative
(1s can be readily achieved, even for minor constituents. Although such excellent precision
is invaluable when comparing dierent locations on the specimen, the measurement pre-
cision is independent of the accuracy of the analysis. For the traditional approach of
measuring standards and calculating matrix corrections, there exists an extensive literature
describing testing of the quantitative procedures. These test results are usually presented in
the form of error histograms, which the analyst can use to make an estimate of the ac-
curacy of the result. The relative error is dened as
Rel: error 100%
Measured True
True
_ _
67
An example of such an error histogram is shown in Figure 21, from which it can be de-
duced that, under the particular conditions used [binary alloys measured against pure
element standards with NISTZAF matrix corrections (1975 formulation)], 95% of the
analyses lie within 5% relative of the correct value. Unfortunately, such error histo-
grams are virtually never available for standardless analysis procedures as implemented in
commercial EDS systems. Recent work indicates that these standardless analysis proce-
dures may, in fact, be subject to large errors (Newbury et al., 1995; Newbury, 1998).
1. First-Principles Standardless Analysis
Calculating an equivalent standard intensity from rst principles requires solution of
I
std

rN
0
A
_ _
o
_
E
c
E
0
Q
dE=ds
dE
_
_
_
_Rfwe 68
where the terms in brackets represent the excitation function: r is the density, N
0
is
Avogadros number, A is the atomic weight, o is the uorescence yield, Q is the ionization
cross section, dE=ds is the stopping power, E is the electron energy, E
0
is the incident beam
energy, and E
c
is the critical excitation energy. The other terms correct for the loss of x-ray
production due to electron backscattering (R), the self-absorption of x-rays propagating
through the solid fw, and the eciency of the detector, e. It is useful to consider the
condence with which each of these terms can be calculated.
a. Excitation
Three terms are critical in the excitation function: the ionization cross section, the uor-
escence yield, and the stopping power.
1. Ionization cross section: Several parameterizations of the K shell ionization cross
section are plotted in Figure 28. The variation among these choices exceeds 25%.
Although we cannot say that any of these is correct, it is certain that they cannot
all be correct. Moreover, because of the continuous energy loss in a solid target,
the cross section must be integrated from E
0
to E
c
, through the peak in Q and
the rapid decrease to U1. This region of the cross section is poorly
characterized, so that it is dicult to choose among the cross-section
formulations based on experimental measurements. The situation for L and M
shell cross sections is even more unsatisfactory.
2. Fluorescence yield: Various experimental determinations of the K shell
uorescence yield are plotted in Figure 29. Again, a variation of more than
25% exists for many elements. The situation for L and M shell transitions is
substantially more incomplete.
3. Stopping power: The classic Bethe formulation of the stopping power becomes
inaccurate at low beam energies (<5 keV), and eventually with decreasing
energy, it becomes physically unrealistic with a sign change. The accuracy of the
stopping power matters for calculating Eq. (68) because the cross section must
be integrated to E
c
, which for low-energy x-rays (e.g., C, N, O, F) involve
electron energies in this regime. As discussed earlier in this chapter, several
authors have suggested modications to the Bethe formulation to correct for the
low beam energy regime. Unfortunately, the base of experimental measurements
necessary to select the best choice is just being developed.
b. Backscatter Loss
The backscatter-loss correction factor R was initially formulated based on experimental
measurements of the total backscatter coecient and the dierential backscatter coe-
cient energy. Although careful, extensive measurements of total backscatter were available
in the literature, the database of the dierential backscatter coecient as a function of
energy, a much more dicult experimental measurement, was limited to a few elements
and was available at only one emergence angle. The development of advanced Monte
Carlo simulations has permitted the rigorous calculation of R over all scattering angles
and energy losses so that this factor is probably known to an accuracy within a few percent
across the periodic table and the energy range of interest.
c. X-ray Self-absorption
The self-absorption of x-rays in the hypothetical standard is calculated with the for-
mulation of the absorption factor used in matrix corrections. Fortunately, the absorption
correction is generally small for the x-rays of a pure element, so that at least for higher-
energy characteristic x-rays (e.g., greater than 3 keV), there is little uncertainty in this
factor. However, the self-absorption increases both as photon energy decreases and in-
Figure 28 Ionization cross section as a function of overvoltage U, as formulated by different
authors.
cident electron energy increases, so that the error in calculating the intensity emitted from
an element emitting low-energy photons (e.g., carbon) could be signicant.
d. Detector Eciency
The last term in Eq. (69) is one of the most dicult with which to deal:
e exp
_

m
r
_ _
win
r
win
t
win

m
r
_ _
Au
r
Au
t
Au

m
r
_ _
SiDL
r
Si
t
SiDL

m
r
_ _
con
r
con
t
con

m
r
_ _
ice
r
ice
t
ice
_
1 exp
m
r
_ _
Si
r
Si
t
Si
_ _
69
In the traditional k-value approach, the detector eciency cancels quantitatively in the
intensity ratio because the same x-ray peak is measured for the unknown and the standard
under identical (or at least accurately reproducible) spectrometer conditions. When
standardless analysis is performed, this cancellation cannot occur because x-ray peaks of
dierent energies are eectively being compared and, therefore, accurate knowledge of the
detector eciency becomes critical. Detector eciency is mainly controlled by absorption
losses in the window(s) and detector structure. The expression for detector eciency, Eq.
(69), consists of a multiplicative series of absorption terms for each component: detector
window (win), gold surface electrode (Au), semiconductor dead layer (DL, actually a
partially active layer below the electrode and the source of incomplete charge phenomena),
and a transmission term for the detector thickness. Additionally, for most practical
measurement situations, there may be absorption contributions from contamination on
Figure 29 K Shell fluorescence yield as a function of atomic number.
the detector crystal, usually arising from ice buildup due to pinhole leaks in the window or
support (ice) and from contamination on the detector window usually deposited as hy-
drocarbons from the microscope environment (con).
An example of the detector eciency as a function of photon energy for several
window materials is shown in Figure 30. The choice of the window material has a strong
eect on the detector eciency for photon energies below 3 keV, and accurate knowledge
of the window and detector parameters is vital for accurate interelement eciency cor-
rection across the working range of the detector, typically 100 eV to 12 keV. The change in
the detector eciency with the accumulation of ice is illustrated in Figure 31. The buildup
of ice and other contaminants and the resulting loss in eciency is referred to as detector
aging. Detector aging can result in a signicant loss of the low-energy photons (<3 keV)
relative to the higher-energy photons (312 keV) (Fiori and Newbury, 1978).
2. Fitted Standards Standardless Analysis
The tted standards technique is the more widely used approach for implementing
standardless analysis on commercial computer-assisted EDS analyzer systems. In the
tted standards technique, a suite of pure-element standards covering K-, L-, and M- family
x-rays is measured at one or more beam energies on an electron beam instrument equipped
with an EDS detector whose eciency is known fromindependent measurements or at least
can be estimated. An example of such a measurement for a portion of the Kseries frompure
Figure 30 Detector efficiency for various windows (Al window coating 0.02 mm; Au electro-
de 0.01 mm; Si dead layer 0.03 mm): (a) beam energies 05 keV; (b) beam energies 01 keV.
elements measured at 20 keV is shown in Figure 32. Missing elements can be calculated by
simply tting the available peaks and interpolating (e.g., in Figure 32, the intensity for
gallium could be estimated by tting the smoothly varying data and interpolating). From
the smooth change in peak height with atomic number seen in Figure 32, such an inter-
polation should be possible with reasonable accuracy. The situation is not as satisfactory in
the L and M families, as illustrated in Figures 33 and 34, respectively, because the uor-
escence yield is a much more complicated function of atomic number.
If the analysis must be perfomed at a beam energy other than that of the spectral
database, then Eq. (68) must be used to shift the intensities appropriately. Similarly,
if a dierent EDS detector is used, the detector eciency must be corrected using Eq. (69).
The tted standards standardless procedure is expected to be more accurate than the
rst-principles standardless procedure because it is tied to actual experimental measure-
ments which directly incorporate the eects of the cross section and the uorescence yield,
at least over the range of the elements actually measured.
a. Testing the Accuracy of Standardless Analysis
The accuracy of standardless analysis procedure has been tested by carrying out analysis
on microhomogeneous materials of known composition: NIST Microanalysis Standard
Reference Materials (SRM), NIST Microanalysis Research Materials (RM), stoichio-
metric binary compounds (e.g., IIIV compounds such as GaAs and IIVI compounds
such as SrTe), and other materials such as ceramics, alloys, and minerals for which the
Figure 30 Continued.
composition was available from independent chemical analysis and for which micro-
homogeneity could be established. Compositions were carefully chosen to avoid serious
spectral overlaps (e.g., PbS, MoS
2
). Light elements such as B, C, N, O, and F were also
eliminated from consideration because of large errors due to uncertainties in mass ab-
sorption coecients. In oxidized systems, the oxygen was calculated by means of assumed
stoichiometry, but the resulting oxygen values were not included in the error histograms
because of their dependence on the cation determinations.
Figure 35 shows an error histogram for the rst-principles standardless analysis
procedure embedded in the National Institute of Standards and TechnologyNational
Institutes of Health Desktop Spectrum Analyzer (DTSA) x-ray spectrometry software
engine (Fiori et al., 1992). The error distribution shows symmetry around 0% error, but in
comparing this distribution with that for the conventional standards=ZAF procedure
shown in Figure 21, the striking fact is that the error bins are 10 times wider for the rst-
principles standardless analysis procedure. Thus, the 95% error range is approximately
50% relative rather than 5% relative.
The error distribution for a commercial standardless procedure based on the tted
standards approach is shown in Figure 36. This distribution is narrower than the rst-
principles standardless approach, but the error bins are still ve times wider than those of
the conventional standards=ZAF procedure, so that the 95% error range is 25%
compared to 5%. It must be emphasized that this distribution represents a test of only
one of the many implementations of standardless analysis in commercial software systems
and more extensive testing is needed.
Figure 31 Effect of ice buildup on the detector.
3. Using Standardless Analysis
Given the width of these error distributions for standardless analysis, it is clear that re-
porting composition values to three or four signicant gures can be very misleading in the
general case. At the same time, the error distributions show that there are signicant
numbers of analyses for which the errors are acceptably small. Usually, these analyses
involve elements of similar atomic number (e.g., Cr, Fe, and Ni in stainless steel) for which
the x-ray peaks are of similar energy and are therefore measured with similar eciency.
The user of standardless analysis must be wary that any condence obtained in such
analyses does not extend beyond those particular compositions. The most signicant er-
rors are usually found when elements must be measured involving a mix of K, L, and M
shell x-rays. The errors in the tails of the distributions are so large that the utility of any
such concentration values is limited in terms of solving problems.
Standardless analysis does have legitimate value. If a microhomogeneous material
with a known composition similar to the unknown specimen of interest is available, then
the errors due to standardless analysis can be assessed and included with the report of
analysis. For example, if the FeS system is to be studied, then the minerals pyrite (FeS
2
)
and troilite (FeS) would form a good test to challenge the standardless analysis procedure.
The analyst should never attempt to estimate relative concentrations merely by in-
specting a spectrum. There are simply too many complicated physical eects of relative
Figure 32 K-Family peaks from transition elements; E
0
20 keV.
excitation, absorption, and eciency of detection to allow a casual inspection of a spec-
trum. Standardless analysis incorporates enough of the corrections to allow a sensible
classication of the constituents of the specimen into broad categories:
Major: greater than 10 wt%
Minor: 110 wt%
Trace: less than 1 wt%
In the absence of a known material to test a standardless analysis procedure, it is
recommended to use broad classication categories instead of numerical concentration
Figure 33 L-Family peaks; E
0
20 keV.
Figure 34 M-Family peaks; E
0
20 keV.
Figure 35 Error distribution for the first-principles standardless analysis procedure embedded
in the NISTNIH Desktop Spectrum Analyzer x-ray spectrometry software system.
values, which may imply far more apparent accuracy than is justied and which may lead
to a loss of condence in quantitative electron-probe microanalysis when an independent
test is conducted.
III. MICROANALYSIS AT LOWELECTRONBEAMENERGY
A. What Is to Be Gained at LowBeamEnergy?
1. Lateral and Depth Resolution
Throughout the history of electron beam x-ray microanalysis, analysts have relied upon
the strong dependence of the electron range (R
0
) on the incident energy to control the
spatial resolution of analysis, which is critical in such problems as characterizing inclu-
sions in a matrix or a thin layer on a substrate:
R
0
kE
n
0
E
n
c
70
where k depends on matrix parameters [atomic number (Z), atomic weight (A), and
density (r)], E
0
is the incident beam energy, E
c
is the critical excitation energy (critical
ionization potential), and the exponent n is in the range 1.51.7. The conventional
energy range for quantitative electron beam x-ray microanalysis can be thought of as
beginning at 10 keV and extending to the upper limit of the accelerating potential, typically
3050 keV, depending on the instrument. The lower limit of 10 keV for the conventional
operating range is selected because this is the lowest incident beam energy for which there
is at least one satisfactory analytical x-ray peak excited from the K, L, or M shells for every
element in the periodic table that is accessible to x-ray spectrometry (Goldstein et al.,
1992c). Only H, He, and Li are excluded due to a lack of x-ray emission or, in the case of
Li, because the photon energy is so low (54 eV) that it is completely reabsorbed in the
Figure 36 Error distribution for a fitted standards standardless analysis procedure embedded
in the commercial x-ray spectrometry software system.
target or the components of the x-ray spectrometer. Electron-excited x-ray microanalysis
thus extends from Be (E
K
0.116 keV) to the transuranic elements. This elemental range
is based on establishing the minimum acceptable overvoltage as U E
0
=E
c
! 1:25. At
E
0
10 keV, this overvoltage criterion involves the use of K lines for 4 (Be) Z27 (Co)
L lines for 28 (Ni) Z67 (Ho), and M lines for 68 (Er) Z to the transuranics, as il-
lustrated by the periodic table in Figure 37, shaded according to the appropriate shell for
analysis with E
0
10 keV and U!1.25. This broad elemental coverage of electron beam
x-ray microanalysis is one of its most important features.
No strict denition exists as to what energy value constitutes the beginning of the
low-beam-energy microanalysis regime, but from the previous discussion, the low-energy
regime can be considered those beam energies below 10 keV, and especially below 5 keV.
Figure 38 shows the excitation range for several characteristic x-rays in a silicon matrix as
a function of incident beam energy from 0 to 10 keV, as calculated with the Kanaya
Okayama formulation of the excitation range (Kanaya and Okayama, 1972):
Rmm
0:0276A
Z
0:89
r
_ _
E
1:67
0
E
1:67
c
_ _
71
Near E
0
10 keV, the excitation range is substantially greater than 1 mm for the various
elemental lines plotted, whereas at 5 keV and below, the range for these x-rays is below
500 nm. The excitation range as a function of overvoltage is shown in Figure 39. The range
is less than 150 nm for AlK in Si for an overvoltage of 2 and diminishes sharply as the
overvoltage is reduced, so that for an overvoltage of 1.25, the excitation range is
approximately 2030 nm.
Figure 37 Selection of x-ray peaks available for analysis with E
0
10 keV for conventional EDS.
Note that elements in black squares either do not emit x-rays or else are too low in energy for prac-
tical detection.
Low-electron-beam-energy microanalysis below E
0
5 keV has been possible for
many years with scanning electron microscopes (SEMs) based on tungsten and LaB
6
lament electron guns. However, the relatively low brightness of these sources severely
limits resolution in the low-beam-energy regime. The emergence of the high-performance
FEGSEM which can still achieve nanometer-scale beam diameters at low energy, has
made it possible to actually make use of the potential analytical resolution given by
Eq. (71), and this has greatly increased interest in low-energy x-ray microanalysis. The
typical analytical FEGSEM as currently delivered is equipped with a semiconductor (Si
or Ge) energy-dispersive x-ray spectrometer with a limiting spectral resolution of 125
150 eV. Although useful analyses can certainly be performed with the semiconductor EDS,
the limited resolution of EDS (approximately 50100 times the natural x-ray linewidth)
and aspects of the physics of x-ray generation with low-energy excitation impose some
severe constraints. As the electron beam energy is reduced, x-ray microanalysis becomes
insensitive to certain elements because of these factors.
B. What Are the Negative Aspects of Low-Beam-EnergyAnalysis?
1. Limits of Detection
At high overvoltage U ! 3, experience with semiconductor EDS x-ray spectrometry has
shown that the concentration limit of detection, C
MDL
, for most elements in most matrices
is approximately 0.001 mass fraction in the absence of peak interference (Goldstein et al.,
Figure38 Range of excitation of various lines (AlK, FeL, and AuM) in a silicon matrix as a func-
tion of the beam energy, as calculated with the KanayaOkayama range.
1992d). The limit of detection depends strongly on the characteristic peak-to-brems-
strahlung background (P=B) and upon the characteristic x-ray peak counting rate (P)
(Ziebold, 1967):
C
MDL

3:29a
ntPP=B
1=2
72
where a is the zieboldOgilvie factor in the expression relating concentration to measured
intensity ratio [unknown sample to pure-element standard (Ziebold and Ogilvie, 1964); a
can be taken as approximately unity for general estimation purposes], n is the number of
measurements, t is the integration time per measurement, P is the peak counting rate, and B
is the background counting rate. As the overvoltage is lowered, both the peak counting rate
and the peak-to-background decrease. Figure 40a shows the experimentally measured
behavior of P=B and C
MDL
as a function of overvoltage for SiKa from pure silicon.
Figure 39 Range of excitation of AlK in silicon.
Figure 40 (a) Experimental measurement of the P=B for copper as a function of overvoltage and
calculation of the concentration limit of detection for SiKa in a matrix of similar atomic number
(e.g., Al). Detector: Si EDS (150 keV); 100 s integration. The vertical arrow designates the low-
keV SEM regime. (b) Calculated limit of detection (mass fraction), derived from experimental mea-
surements of P=B and peak counting rate, as a function of overvoltage, U. Si EDS (150 eV FWHM)
operated at 3040% dead time. Three different accumulation times (nt) of 100 s, 200 s, and 1000 s are
plotted. The vertical arrow designates the low-keV SEM regime.
"
Measurement conditions were 100-s accumulation times (nt product) with a beam current
and detector solid angle chosen so that the EDS system dead time was approximately 30%
(total spectrum) for a 30-mm
2
Si detector with a resolution of 150 eV (MnKa). As can be
seen in Figure 40a, operation at low overvoltage results in restrictions on the concentration
limit of detection. Although major (arbitrarily dened as C>0.1 mass fraction) and minor
(dened as 0.01 C0.1 mass fraction) constituents can still be detected with over-
voltages as low as U2 at an accumulation time of 100 s, trace constituents (dened as
C<0.01 mass fraction) cannot be reliably measured with U below 9.0. To reduce the
overvoltage requirement to U3 for trace levels above 0.001 mass fraction requires an
accumulation time of 1000 s, as seen in Figure 40b. A higher-resolution semiconductor
EDS detector (e.g., 130 eV at MnKa) would improve the situation by a factor of 1020%.
Any peak interferences would serve to make the detection situation much more un-
favorable.
2. Limitations Imposedby FluorescenceY|eld
When an energetic electron scatters inelastically with a bound atomic electron resulting in
the ejection of the atomic electron, the ionized atom is left in an excited state. The atom
returns to the ground state through processes that involve electron transitions. The
dierence in energy between the electron states can be released in the form of an x-ray
photon, or the energy can be transferred to another atomic electron, which is ejected as an
Auger electron. The fraction of ionizations that leads to photon emission is called the
uorescence yield, o, which is related to the Auger yield, a:
o a 1 73
For low-electron shells with low binding energy, the Auger process is strongly favored
over x-ray emission. For example, for carbon K shell ionization (E
K
0.284 keV), the
uorescence yield is 0.00198. Table 5 lists some typical values of the uorescence yield for
low-ionizaiton-energy shells. Examination of these data reveals that an important con-
sequence of having to select low-energy L and M shells to analyze for intermediate and
heavy atoms is that the uorescence yields are substantially lower than those of similar K
shells, a factor of 35 poorer for L shells and 1030 poorer of M shells. Thus, the x-ray
spectra of these elements with low-beam-energy excitation are likely to have characteristic
peaks with low intensity relative to the background (x-ray bremsstrahlung), a problem that
is further exacerbated by the poor resolution of the semiconductor EDS, which acts to
spread the available peak information over a wide range of background.
Table 5 Fluorescence Yields
Element Shell Edge energy (keV) o
C K 0.284 0.00198
Na K 1.080 0.0192
Mg K 1.303 0.0265
Si K 1.848 0.0603
Zn L 1.022 0.00736
Ga L 1.117 0.00875
Ge L 1.217 0.0103
Sm M 1.080 0.00133
Eu M 1.130 0.00137
The combination of low overvoltage and the low yield from L and M shell x-ray
peaks can result in spectra which look extremely unfamiliar to analysts who are used to
spectra excited in the conventional beam energy range. As an example, Figure 41 shows
the situation for (a) SiO
2
and (b) SiO excited with an incident beam energy of 5 keV and
measured with a Si EDS (150 eV FWHM at MnKa). Both O and Si are measured with K
lines, and peaks for both are prominent in the spectrum, with the O peak reduced relative
to the Si due to stronger absorption eects. By comparison, Figure 42 shows the spectrum
for GeO
2
. The GeL family of peaks (unresolved) is much reduced in intensity relative to
the OK and SiK peaks due to the relative uorescence yield dierences, despite the fact
that the overvoltage is actually greater for the GeL edge (E
LIII
1:217 keV) than the SiK
edge (E
K
1:848 keV). Similarly, Figure 43 shows the situation for CaF
2
excited with an
electron beam energy of 3 keV, which is below the CaK edge (4.038 keV). Note that the FK
peak is very prominent, but the Ca can only be detected through the CaL peak, which is a
factor of 10 lower relative to FK, due to both the lower uorescence yield from the L edge
and the increased absorption of the lower-energy CaL radiation.
An extreme example of the eects of excitation and uorescence yield is shown in
Figure 44, which presents the spectrum of BaCO
3
excited at 5 keV and measured with a Si
EDS (150 eV FWHM at MnKa). The BaM family of peaks is just visible above back-
ground. In fact, the series of BaM peak structures is partially a result of the BaM
absorption edges, which exist as discontinuities in the x-ray continuum (bremsstrahlung)
and which are broadened into peaklike features as a result of the action of the detector
broadening function.
An overall assessment of the impact of both low excitation and the uorescence yield
on elemental accessibility with a 5-keV incident beam is presented in Figure 45 and the
situation with 2.5 keV is shown in Figure 46. At 5 keV, a few intermediate and heavy
elements are inaccessible (black squares), whereas at 2.5 keV, the situation is much worse,
with extensive sections of the periodic table eectively lost to SEM=semiconductor EDS
measurement.
3. Quantitative Analysis at LowBeamEnergy
Quantitative analysis procedures for the low-beam-energy regime is a subject of some
controversy and ongoing development. The classic ZAF methods are based on a combi-
nation of empiricism and physical theory which were developed in the conventional high-
beam-energy regime and should not be expected a priori to work well in the low-energy
regime (Goldstein et al., 1992e). Very often, the analyst must employ x-ray peaks for which
there are little data on mass absorption coecients and ts to the available data are
subject to signicant error. The more recently developed frz quantitation methods have
the advantage that at least some of the database of experimental measurements on which
the algorithms are based were indeed measured with low incident beam energy for low-
energy photons, so that these methods should be inherently better for quantitation in the
low-energy regime. An example of the analysis of transition metal suldes at 5 keV with
conventional ZAF matrix corrections is given in Table 6. Signicant relative errors
(overestimates) are found in the measurement of the metal components; consequently, the
totals are anomalously high. By comparison, under conventional beam energy analysis
(20 keV), the relative errors are less than 2% for this system.
A particular problem in performing analysis at low beam energy is the actual
structure of the specimen being measured. Most specimens have a surface layer that is
dierent from the interior due, for example, to surface oxidation, a conductive coating
applied to minimize charging, or contamination. At high beam energy, this surface layer
Figure41 (a) SiO
2
excited with a beam energy of 5 keV and measured with a Si EDS (150-eV FWHM at MnKa). (b) SiO excited
with a beam energy of 5 keV and measured with a Si EDS (150 eV FWHM at MnKa).
Figure 42 GeO
2
excited with a beam energy 5 keV and measured with a Si EDS (150 eV FWHM at MnKa).
Figure 43 CaF
2
excited with an incident electron beam energy of 3 keV and measured with a Si EDS
(150 eV at MnKa).
Figure 44 BaCO
3
with minor Sr ($0.05) excited at 5 keV and measured with a Si EDS (150 eV at MnKa). The BaM and BaL
lines are marked. Note the low peak intensity for the BaM series; the BaL lines are not excited.
0
5 keV for conventional EDS.
Note that elements in black squares are not sufficiently excited to be practically measured.
0
2.5 keV for conventional EDS.
Note that elements in black squares are not sufficiently excited to be practically measured.
thickness is a small fraction of the excitation range, so the eect on quantitation is neg-
ligible. However, at low beam energy, the total sampling depth becomes so shallow that a
surface layer constitutes a signicant fraction of the analyzed depth. The specimen should
thus be considered as a case of special geometry, that of an overlayer of C (or oxide,
etc.) on a substrate that is actually the specimen composition of interest.
Rigorous testing for the accuracy of low-beam-energy microanalysis is similarly
aected by the issue of proper test specimens. The situation is dicult enough at high
beam energy, where the lateral homogeneity is the key issue. At low beam energy, the
measurement becomes profoundly sensitive to the surface region of both the specimen and
the standards, especially if these are dierent. Thus, any testing of quantitation procedures
can only sensibly proceed when a suitable series of test specimens and standards has been
produced that do not suer from limitations imposed by the quality of the surface.
C. What Future Developments Are Possible?
The physics of electron-excited x-ray production and propagation is determined by the
choice of beam energy, the element(s) to be measured, and the matrix composition. Once
the analysts room to maneuver is restricted through the choice of low beam energy, the
only possible route to improve the measurement process is to improve the x-ray spec-
trometry. From Eq. (72) and the spectra presented in Figures 4144, it is clear that im-
proving the spectral resolution will increase the peak-to-background ratio, thereby
improving the visibility of low-uorescence-yield peaks, reducing interferences, and low-
ering the limit of detection. Increasing the detector eciency (i.e., solid angle) and redu-
cing the pulse processing time will improve the peak counting rate, also contributing to
improving the limit of detection.
1. ImprovementstoWavelength-Dispersive Spectrometry
Wavelength-dispersive x-ray spectrometry, based on Bragg diraction of x-rays from a
crystal, is the oldest form of x-ray spectrometry and is commonly incorporated in the
instrument conguration referred to as the electron-probe x-ray microanalyzer. The WDS
is a high-resolution (10 eV or less), single-channel, narrow-bandpass spectrometer that
must be mechanically scanned to cover a range of x-ray wavelengths (energy). The higher
resolution of the WDS results in a higher P=B, yielding a lower limit of detection than
semiconductor EDS. Typically, the WDS limit of detection is 10
74
10
75
mass fraction.
Table 6 Low Beam Energy (5 keV) Analysis of Metal Suldes
True Analyzed Rel. error (%)
FeS (meteoritic troilite)
Fe 0.635 0.667 5.0
S 0.365 0.365 0
CuS
Cu 0.665 0.730 9.8
S 0.335 0.334 0.2
ZnS
Zn 0.671 0.732 9.1
S 0.329 0.320 2.7
The high spectral resolution has the added advantage of diminishing the likelihood of
spectral interferences, although interferences may still occur for certain combinations of
x-ray lines. However, the quantum eciency of the WDS is signicantly lower than the
EDS due to the relative ineciency of the diraction process. Consequently, beam cur-
rents of the order of 100 nA or more are normally used to achieve adequate peak counting
rates. Such current requirements are incompatible with small beam size, even with the
thermally assisted eld-emission gun. Additionally, when low-beam-energy excitation is
considered, another problem becomes signicant. Low-energy x-rays are emitted as a
result of electron transitions involving electron energy levels whose energy and population
can be altered due to chemical bonding eects. These chemical bonding eects are man-
ifested in the x-ray spectrum as shifts in the peak position and shape (Bastin and Heijligers,
1991). Because the WDS only detects a narrow band of energy, for an accurate mea-
surement of a peak that is subject to alteration due to chemical bonding eects, it is ne-
cessary to scan across the peak to accurately determine its position and the total intensity
under the peak above background. This requirement for scanning further reduces the
measurement eciency and increases the need for beam current. Thus, WDS at low beam
energy is normally performed under conditions that result in poorer spatial resolution than
EDS.
Two developments may lead to improved WDS eciency, which can benet low-
beam-energy x-ray microanalysis. First, the WDS is a focusing device, wherein the x-rays
diracted at various points along a curved crystal are brought to a focus within the en-
trance slit of a gas proportional detector placed on the focusing circle of the spectrometer
(Rowland circle). If the focused rays are allowed to diverge beyond the Rowland circle,
they form a spatially dispersed image of the peak (with a single focusing geometry
WDS). By placing an imaging detector array o the Rowland circle in the dispersion
plane, a wider energy window could be simultaneously measured, providing a direct image
of the full peak and adjacent background regions (Fiori et al., 1991). Second, the eciency
of the WDS can be improved by increasing its solid angle of collection. For low-energy
x-rays (01 keV), a parabolic reective x-ray optic has been described that gathers a wide
solid angle and presents a parallel beam to a at crystal diractor that scatters x-rays into
a large-window proportional gas detector. With this augmented WDS, limits of detection
as low as 10
5
mass fraction have been reported for light elements, such as C (Agnello
et al., 1997).
2. Microcalorimetry Energy-Dispersive Spectrometry
The ideal x-ray spectrometer would have the resolution of the WDS combined with the
energy-dispersive character of EDS over the useful analytical range, 100 eV10 keV. This
seemingly impossible requirement has actually been realized with the development of a
practical fast microcalorimeter EDS at NIST, Boulder (Wollman et al., 1998). In the
microcalorimeter spectrometer (see also Sec. III.F.4 of Chapter 3), the energy of an
individual photon is measured as the temperature rise in an absorbing target maintained
near 100 mK. The NIST microcalorimeter design incorporates critical features such as
the use of an absorber maintained in the normal conducting state and a temperature
sensor based on a superconducting transition sensor which both contribute to a faster
pulse response than earlier microcalorimeters. A novel superconducting quantum in-
terference device (SQUID) is used as a stable, fast, high-gain amplier. With regard to
analysis, the chief operating characteristics of the NIST microcalorimeter EDS are the
following:
1. Energy resolution <10eV. As an example of the energy resolution applied in a
dicult analytical situation, Figure 47 shows the separation of the BaLlines fromthe
TiK lines in BaTiO
3
achieved with the NIST microcalorimeter EDS and compares it
with the unresolved peaks in the spectrum obtained with a semiconductor EDS.
2. Limiting count rate (with beam blanking) $1 kHz.
3. Photon energy coverage: 250 ev10 keV. An example of this energy coverage is
given in Figure 48, which gives a spectrum for YBa
2
Cu
3
O
7
obtained with the
microcalorimeter EDS, showing L line detection for Cu, Y, and Ba and K line
detection for O. Carbon K shell x-rays at 0.282 keV have been successfully
measured, as shown in Figure 49.
The NIST microcalorimeter EDS represents the leading edge of a revolution in x-ray
spectrometry. In particular, microcalorimeter EDS technology should have a major and
immediate impact on the application of the FEGSEM to microanalysis at low beam
Figure 47 Comparison of spectra of BaTiO
3
obtained with the microcalorimeter EDS
(FWHM10 eV) and with the semiconductor EDS (FWHM140 eV).
Figure 48 Microcalorimeter EDS spectrum of YBa
2
Cu
3
O
7
; E
0
10 keV.
Figure 49 Microcalorimeter EDS spectrum of carbon; logarithmic scale. Note the carbon coinci-
dence peak, and the discontinuities in the background due to absorption in the spectrometer materi-
als (Al window thermal protection coating and AG absorber).
energy, for example, in the analysis of particles during defect review in simiconductor
processing. As an example, Figure 50 shows the spectrum obtained at 5 keV from WSi
2
with a 10-eV microcalorimeter EDS. The separation of the SiKa line from the WM family
is virtually complete, thus eliminating the severe interference encountered with semi-
conductor EDS. The high P=B ratios evident in the spectra in Figures 4750 will result in
limits of detection similar to WDS. Finally, the resolution of the microcalorimeter EDS
will make it possible to actually detect low-energy L and M lines that have low uores-
cence yield. As an example, Figure 51a demonstrates the detection of several of the low-
yield peaks of the titanium L family and the barium M family in BaTiO
3
, which can be
compared to Figure 51b, obtained with semiconductor EDS. With conventional EDS, the
TiL peaks are unresolved from the OK peak, and the BaM peaks, although visible, are
actually convolved with the BaM edge discontinuities in the background.
Figure 50 Microcalorimeter EDS spectrum of WSi
2
; E
0
5 keV.
Figure 51 (a) Microcalorimeter EDS spectrum of BaTiO
3
, low-energy region. Note detection of
BaM-family members; E
0
10 keV. (b) Si EDS spectrum of BaTiO
3
, low-energy region. Note detec-
tion of BaM-family members; E
0
10 keV.
"
IV. ANALYSIS OF SAMPLES WITHNONSTANDARD GEOMETRIES
As mentioned earlier, in classical electron-probe microanalysis, the samples are polished
at, homogeneous, and opaque with respect to the electron beam. Although these con-
straints on sample geometry enable the analyst to perform high-quality quantitative
analysis on a wide variety of samples, there are many samples which cannot be prepared
with the classical geometry. These samples include, among others, layered samples, thin
sections from samples that have inclusions ore phase domains smaller than the excitation
volume of a 1030-keV electron beam, particles, and samples with rough surfaces. To
obtain some degree of quantitative information from these samples, the analyst must
modify the analytical schemes outlined in the previous sections.
A. Quantitative Analysis of Layered Specimens
In the early days of electron microbeam analysis, characterization of specimens that were
compositionally nonuniform within the analytical volume (the volume excited by the
primary electron beam), such as particles, thin lms, or layered specimens, was either not
attempted or involved use of simple empirical correction procedures. For example, it was
noted that the thickness of thin lms (particularly single-element lms) on a common
substrate could be determined by measuring two or more lms of the same composition as
the unknown with dierent known thicknesses and then using the results to construct a
linear calibration curve [e.g., Sweeney et al. (1960), Bolon and Lifshin (1973)]. This pro-
cedure has reasonable accuracy as long as the lms are quite thin with respect to x-ray
absorption and electron penetration and if the standards substrate compositions are
identical or very similar in atomic number to those for the samples.
As microprobe instrumentation and correction procedures continued to develop, the
importance of considering the eect of surface coatings (such as surface oxide layers or the
thin conductive lms evaporated onto insulating samples) on analytical results obtained at
low accelerating potentials was noted [e.g., Sweatman and Long (1969)]. At the same time,
thin-lm analysis progressed by using variable accelerating potential analysis to estimate
the thickness of the lms and by using low accelerating potential analysis conditions to
analyze only the surface lm [e.g., Hutchins (1966), Colby (1968), Warner and Coleman
(1973)].
With the development of increasingly more accurate algorithms expressing the re-
lative production of x-ray intensity as a function of depth in the sample, it is possible to
derive theoretical correction methods that enable accurate quantitative analysis of thin-
lm or layered samples. Today, a number of laboratories are actively engaged in routinely
analyzing complicated layered specimens and in developing and rening the correction
procedures that enable the quantitative determination of both layer thicknesses and
compositions for such materials. A variety of through review papers have been recently
written on layered-specimen analysis [e.g., Pouchou and Pichoir (1991a), Packwood and
Remond (1992), Willich (1992), Pouchou (1993), Karduck, 1997]. One particularly de-
tailed and cogent treatment of the subject can be found in the textbook by Scott et al.
(1995).
The two most commonly used approaches to correct for electron scattering, electron
energy loss, and x-ray absorption in the quantitative analysis of thin lms and layered
specimens are those based on (1) analytical expressions of the relative production of x-rays
as a function of depth, f(rz) and (2) Monte Carlo modeling of electron scattering. In their
typical development, neither of these approaches predicts the contribution of secondary
x-ray uorescence, either by characteristic lines or the continuum. Several authors have
separately described corrections for secondary uorescence in layered specimens that can
be incorporated with either of the two approaches. The following subsections will outline
the current status of these approaches and give examples of the types of results that can be
obtained by their use.
1. Methods Based on Calculationof f(rz)
The most commonly used procedure used to analyze thin lms or layered specimens is to
measure the emitted x-ray intensity from the line(s) of interest in the sample and compare
them with the emitted intensities of those lines from one or more thick, polished standards.
In the simplest case, the standards employed are pure elements. In that case, when
uorescence by characteristic lines and the continuum can be ignored, the relative intensity
can be related to concentration and layer composition by the equation
k
A

I
thin
I
bulk std
C
A
_
rt2
rt1
f
0
A
rz expw
0
A
rz drz
_
1
0
f
A
rz expw
A
rz drz
_
_
_
_
1
74
where f
0
A
and f
A
are the x-ray depth distribution functions for the layer of interest in
the specimen and the bulk standard, respectively, w
0
A
and w
A
are the respective ab-
sorption factors, and rt1 and rt2 are the depths from the surface of the top and
bottom, respectively, of the layer of interest (i.e., rt1 0 for the topmost layer, rt2 1
for a bulk substrate). Only in a case in which the layer of interest is very similar in
average atomic number both to its underlying (and overlying) layer(s) and to the bulk
standard will f
0
A
and f
A
be similar. In most cases, f
0
A
needs to be modied from ex-
pressions developed for bulk specimens to account for the variable composition within
the excited volume of the electron beam. Similarly, w
0
A
and w
A
are seldom identical, and
w
A
for all underlying layers needs to be modied to account for the dierent degrees of
absorption in the various overlying layers. If the order, thicknesses, and compositions of
the various layers in the specimen are known, it is simple algebra to determine the
absorption factor [cf. Pichou and Pichoir (1991a), Scott et al. (1995)]. However, even if
the sequence of thickness and compositions were known, conventional parameteriza-
tions of f(rz) for bulk specimens cannot be used for layered specimens without sig-
nicant modication.
The fundamental dierence between f
0
A
rz and f
A
rz lies in the number and en-
ergy distribution of the electrons that scatter through the layer rz Drz; these, in turn,
depend on the average atomic number, distance, and thickness of the layer(s) that lie
above and below rz Drz. For example, at the top of a reasonably thick surface layer
(with respect to the electron beam depth of penetration) on a substrate of considerably
dierent Z, both the upward traveling and downward traveling electron components of
the f(rz) are similar for both f
0
A
rz and f
A
rz. At the bottom of a relatively thin surface
layer over a bulk substrate, the downward-traveling electron component of f
0
A
rz is
similar to a bulk specimen of the surface lm composition, whereas the upward-traveling
component is similar to a bulk specimen of the substrate composition. The situation gets
increasingly complex as the layers get thinner and=or more numerous.
A number of investigators have tried to come up with simplied expressions to ac-
count for the dierences in electron scattering between layered samples and thick speci-
mens, with varying degrees of success. Hutchins (1966) tried to modify the original
Castaing expression for bulk with expressions involving the initial slope of frz curves
and the backscatter coecient, whereas Colby (1968) modied Castaings expression with
functions relating to the dierences in the backscatter coecients, backsatter correction
factors, and stopping powers between lm and substrate compositions [cf. Scott et al.
(1995)]. Warner and Coleman (1973) modied Hutchins methods to apply it to biological
materials, and Duzevic and Bonefacic (1978) modied his procedure to measure alloy lm
compositions on elemental metal substrates. Oda and Nakajima (1973) modied Colbys
procedure and showed good results in analyzing AgCu alloys on FeNi substrates. None
of these early attempts, however, resulted in widespread application.
As more realistic models for frz for bulk specimens were developed, further at-
tempts were made to apply them to thin-lm and layered-specimen analysis. Reuter (1972)
modied the frz parameterization of Philibert (1963) to better t experimentally de-
termined frz curves and applied it to the determination of the thickness of elemental
lms on single-element and multielement substrates. His frz parameterization was a
function of the electron backscatter coecient, Z. In order to account for the eects of
variable average atomic number in the dierent layers, he introduced an eective back-
scatter coecient, Z
eff
, which varied between the limiting values of the backscatter coef-
cient of a bulk specimen of the composition of the lm, Z
F
, and the backscatter coecient
of the bulk substrate, Z
sub
:
Z
eff
Z
sub
n
rz
n
0
_ _
Z
F
1
n
rz
n
0
_ _ _ _
75
Where n
rz
=n
0
is the ratio of the number of electrons transmitted through layer rz com-
pared to the number of electrons passing through an innitely thin lm at the surface of a
sample and is expressed by
n
rz
n
0
expsrz or 1
4 10
4
Z
0:5
rz
E
1:7
0
76
whichever is larger (the Lenard coecient s 4:5 10
5
=E
1:65
0
; Z is the average atomic
number of the layer, E
0
is the accelerating potential in kiloelectron volts). As noted by the
author, this approximation accounts for dierences between the number of backscattered
electrons from lm and substrate, but not for dierences in their energy distributions.
Nevertheless, the author showed good agreement between calculated and experimental
results for elemental lms on substrates, both having a wide range in Z. A number of
investigators implemented various versions of this correction [e.g., Armstrong and Buseck
(1975) in their original frz expressions for thin lms and particles].
Love and Scott (1978) modied the square frz model of Bishop (1974) for
application to thin lms on substrates:
k
A

I
thin
I
std
1 expwrt
1 exp2wrz
m
77
where I
thin
and I
std
are emitted intensities from a thin lm and bulk standard of the same
material, t is the lm thickness, and z
m
is mean depth of x-ray penetration which Scott et al.
(1995) proposed should be expressed by the equation of Sewell et al. (1985b):
rz
m

rs
m
2:4 0:07Z 1:04 0:48Z= ln U
0
78
where, in turn, rs
m
is the mean electron range given by
rs
m

7:87E 6J
0:5
E
1:5
0
7:35E 7E
2
0
C
i
Z
i
=A
i
79
Bushby and Scott (1993) reported results of analyses of oxide lms on metallic substrates
using these corrections. The authors noted that this procedure is limited to analysis of
lms on substrates of similar atomic number, as the procedure does not correct for
dierences in electron scattering. This correction, however, is particularly easy to calculate
and is thus useful for back of the envelop calculations during experiment design.
The various forms of the modied, surface-centered Gaussian frz expression
[see Eq. (46)], as originally developed by Packwood and Brown (1981), have been widely
adapted for thin-lm and multilayer-specimen analysis. As described earlier, these
equations have the general form
frz g
0
expa
2
rz
2
g
0
f0 expa
2
rz
2
brz 80
with a variety of functions proposed for a; b; g
0
and f0. Packwood et al. (1987) noted
that for very thin lms on substrates, the eect of the lm(s) on the x-ray distribution
would be negligible and, thus, to a rst approximation, a frz expression for a sample of
the average atomic number of the substrate could be used for all layers. Similarly, for very
thick homogeneous lms on substrates (or lms analyzed at an accelerating potential low
enough so that few, if any, energetic electrons penetrate to the substrate), the frz ex-
pression for a sample of the average atomic number of the lm could be used for both lm
and substrate. The problem lies in the formulation of frz expressions for layers of in-
termediate thickness between the two extremes.
Packwood and co-workers (Packwood et al., 1987; Packwood, 1991; Packwood and
Remond, 1992) note that most expressions for the g
0
termin the Gaussian frz equationare
not functions of sample atomic number and so do not need to be modied for intermediate-
layer analysis. They further note that most expressions for the a term are only weakly de-
pendent on the atomic number of the specimen and that, in most cases, simply using an a
term calculated for a sample of the average atomic number of the substrate is sucient
(assuming most electrons in the analysis penetrate into the substrate). They propose two
alternate formulations of the b and f0 terms and one formulation of the backscatter
coecient, Z, to account for the change in electron scattering across layer boundaries:
b
specimen
b
layer
rd
1=2a
_ _
b
substrate
1 rd
1=2a
_ _
81
and
f0
specimen
f0
layer
rd
1=2a
_ _
f0
substrate
1 rd
1=2a
_ _
82
(where any layer of thickness greater than 1=2a is considered innite), or
b
specimen
b
layer
erf ard b
substrate
erfcard 83
and
f0
specimen
f0
layer
erf 2ard f0
substrate
erfc2ard 84
Z
specimen
Z
layer
erf 2ard Z
substrate
erfc2ard 85
(where the layer and substrate contributions are weighted under the electron distribution
curve). In these equations, d is the thickness of the layer, r is the density, and a is the term
in Eq. (80). Using Eqs. (83)(85), Packwood et al. (1987) [based on the original work of
Packwood and Milliken (1985)] proposed the following general expressions for the emitted
x-ray intensities for the various types of layered specimens:
I
surface layer
C
A
sqrtp
2a
_ __
g
0
exp
w
2a
_ _
2
erf ad
w
2a
_ _ _ _
erf
w
2a
_ _ _ _
g
0
f0 exp
w b
2a
_ _
2
erf ad
w b
2a
_ _
erf
w b
2a
_ _ _ __
86
I
buried layer
C
A
sqrtp
2a
_ __
g
0
exp
w
2a
_ _
2
erf ad
w
2a
_ _ _ _
erf ad
0

w
2a
_ _ _ _ _ _
g
0
f0 exp
w b
2a
_ _
2
erf ad
w b
2a
_ _
erf ad
0

w b
2a
_ _ _ __
expd
0
w
0
w 87
I
covered substrate
C
A
sqrtp
2a
_ __
g
0
exp
w
2a
_ _
2
1 erf ad
0

w
2a
_ _ _ _ _ _
g
0
f0 exp
w b
2a
_ _
2
1 erf ad
0

w b
2a
_ _ _ __
expd
0
w
0
w 88
compared to their expression for conventional thick, at specimens:
I
bulk specimen
C
A
sqrtp
2a
_ __
g
0
exp
w
2a
_ _
2
1 erf
w
2a
_ _ _ _
g
0
f0 exp
w b
2a
_ _
2
1 erf
w b
2a
_ _ _ __
89
where d is the mass thickness of the analyzed layer, d
0
is the mass thickness of the overlying
layer, w is the absorption term ( m
Aby specimen
csc c for x-rays in the analyzed area, and w
0
is the absorption term by the overlying lm(s).
Bastin and co-workers [e.g., Bastin et al. (1992, 1998), Bastin and Heijligers (1991)]
proposed modifying their PROZA formulation of the surface-centered Gaussian f(rz)
model to enable layered-specimen analysis in a manner similar to that done by Packwood
and co-workers. They noted, in agreement with Packwood et al. (1987), that the f(rz)
expression for a thin layer lies between the two extremes of a very thin layer, that has a
f(rz) expression consistent with a composition with the surface layer elements dissolved
in the substrate, and a very thick layer (with respect to electron penetration), whose f(rz)
is similar to a bulk specimen having the lms composition. Similar to Packwood et al.,
they proposed modifying the expressions for the a, b, g
0
, and f(0) terms in the f(rz)
equation for surface layers of intermediate thickness by empirical smoothing functions
accounting for the dierences in electron scattering among the dierent layers and sub-
strate:
a a
bulk layer
a
dissolved
a
bulk layer
exp1:5a
bulk layer
T 10
6
2
90
b b
bulk layer
b
dissolved
b
bulk layer
exp1:5a
bulk layer
T 10
6
91
g
0
g
0;bulk layer
g
0;dissolved
g
0;bulk layer
exp2:0a
bulk layer
T 10
6
2
92
f0 f0
bulk layer
f0
dissolved
f0
bulk layer
exp2:5a
bulk layer
T 10
6
2
93
where bulk layer refers to a bulk specimen with the same composition as the analyzed
layer, dissolved refers to the composition that would be calculated from an analysis as-
suming the elements in the surface layer(s) were dissolved in the substrate, and T is the
layer thickness (in mg=cm
2
). Unlike Packwood et al., Bastin and co-workers assume that
the composition of the surface layer(s) has no eect on the f(rz) expression for the
substrate. This latter assumption is certainly a source of error in cases of surface layers and
substrates of dissimilar average atomic number analyzed under conditions where a sub-
stantial fraction of the electron trajectories occur in the surface layers.
The f(rz) model of Pouchou and Pichoir [e.g., Pouchou and Pichoir (1985, 1987,
1991a), Pouchou (1993)] was initially designed to include the analysis of layered speci-
mens. As discussed earlier, the model is treated in two parts, each of which is expressed by
a parabolic function:
frz
1
A
1
rz R
m
2
B
1
94
frz
2
A
2
rz R
x
2
95
where R
m
is the depth at which f(rz) is at a maximum and R
x
is the x-ray range. These
terms need to be modied for layered specimens, along with F, the total integral under the
f(rz) curves, and f(0), the surface ionization potential. The expressions given by Pouchou
and Pichoir for these terms were briey discussed earlier and can be found extensively
derived in their articles. To account for layered samples of intermediate thickness, they
suggested modifying these expressions in order to calculate the f(rz) for a ctitious
homogeneous composite sample having an appropriate average atomic number to produce
electron scattering similar to that which occurs in the real multiphased sample. They utilize
a weighting law of the form
frz Nrz L
2
rz R
2
96
where L and R are the low and high rz intercepts of the f(rz) expression with L<0 and
N is a normalizing factor so that the area under the f(rz) curve equals F. The various
parameters are sequentially calculated using various estimates of L and R, and compo-
sitions of the dierent layers are then calculated by an iterative process. For the details of
this weighting procedure, see Pouchou and Pichoir (1991a).
Willich (1992) proposed modifying the weighting procedure of Pouchou and Pichoir
with a simple eective atomic number, Z
combination
, for a ctitious homogeneous sample
with the same electron scattering properties as the real multilayered specimen. Based on
the work of Willich and Overtop (1988), he proposed
Z
combination
Z
substrate
Z
film
Z
substrate
rT
film
2rz
max
_ _
0:65
97
where Z
substrate
and Z
lm
are the average atomic numbers of the substrate and lm, rT
lm
is the mass thickness of the lm, and rz
max
is the x-ray range.
In all of the above procedures, the layer and substrate thicknesses and composi-
tions are calculated by an iterative procedure. Typically, elements are assigned to each of
the layers; rst, estimates of the layer compositions are determined by running con-
ventional bulk corrections and normalizing to 100%. Next, the thin-lm expressions are
evaluated to determine the thickness at which the corrected k-ratio data would yield
concentrations summing to 100%. Finally, using this thickness for a new estimate of
layer compositions, followed by reiteration until convergence in both thickness and
composition is achieved.
If elements are present in more than one layer, it is necessary to either assign pro-
portionality of the element among the various layers on some basis or to collect data at
more than one accelerating potential and try either by trial and error or by simultaneous
solution of the f(rz) expressions at the various E
0
s. Public-domain and commercial
computer programs exist that utilize these corrections [e.g., Waldo (1988), Bastin et al.
(1992), Pouchou (1993)].
2. Methods Based on Monte Carlo Calculations
The Monte Carlo procedures that have been used by numerous investigators to calculate
electron deceleration trajectories in compositionally homogeneous bulk materials can be
readily adapted to simulate x-ray emission from multilayer samples. The algorithms em-
ployed inconventional Monte Carlocalculations for thick specimens [e.g., Joy (1995)] donot
have to be modied in any signicant way for thin lms or layered specimens. Only the
boundary conditions need to be changed. In a layered specimen, each time an electron
trajectory is calculated, the programneed to be changed. In a layered specimen, each time an
electron trajectory is calculated, the program needs to determine in which layer(s) the
electronis moving andthen use the appropriate scattering, emission, and absorption data for
the assumed composition of that layer. The nature of the equations used for scattering,
energy loss, ionization probabiliity, and so forth does not change. Unlike the case for the
analytical expressions for f(rz) described earlier, no assumptions need be made regarding
dierences inthe nature andamount of electronbackscattering fromthe various layers; these
are directly and independently calculated for each electron in the Monte Carlo method.
Thus, at least to a rst approximation, the analytical accuracy of thin-lm and layered-
specimen analysis using Monte Carlo methods is comparable to that for bulk specimens.
Calculations of x-ray emission from Monte Carlo calculations are made by de-
termining a f(rz) curve based on the number, directions (path lengths), and energies of
electrons that are calculated to pass through the layer rz D(rz):
frz
C
A
o
A
N
AV
A
A
_ __
E
c
E
0
nE; rzQ
A
E
drz
drs
_ _
drs
dE
_ _
dE 98
[e.g., Armstrong (1991)]. For a multilayer specimen, a series of f(rz) functions are cal-
culated, one for each element of interest in each layer. These are constructed by keeping
track of the arrays of summed electron path lengths through each rz layer corresponding
to the dierent array components of energy. For details of the procedures, consult Joy
(1995) or Armstrong (1991).
One of the rst groups to utilize Monte Carlo calculations for thin-lm analysis was
Bolon and Lifshin (1973). Utilizing the multiple scattering Monte Carlo method of
Curgenven and Duncumb (1971), they produced calculated calibration curves of relative
intensity versus thickness for thin elemental lms on elemental substrates (e.g., Au on Si)
and showed good agreement with experimental data. Kyser and Murata (1974, 1976) used
the single-scattering Monte Carlo model of Murata et al. (1971) to construct similar ca-
libration curves for both elemental and compound (alloy) lms on elemental and com-
pound targets. Using the examples of Mn
x
Bi
y
and Co
x
Pt
y
lms on SiO
2
, they were able to
show self-consistent agreement in both concentration and lm thickness between mea-
sured and Monte Carlo data.
Numerous groups more recently have used Monte Carlo calculations to predict
emitted x-ray intensities from a wide variety of layered samples, including thin surface
coatings, thin and thick multiple-layer structures, surface layers containing implanted
species, surface and depth diusion proles, and surface-layer analysis during ion sput-
tering [e.g., Amman and Karduck (1990), Amman et al. (1992), Karduck and Rehback
(1991), Armstrong (1991, 1993), Armigliato et al. (1996), Valamontes and Nassiopolos
(1996), Karduck (1997), Chan and Brown (1997a, 1997b)]. These studies have emphasized
the advantage of analyzing the same specimens at dierent analytical conditions (such as
electron beam accelerating potential and incidence angle) in order to elucidate their
structure. If there are no elements in common in the dierent analyzed layers, then each of
these measurements is an independent estimate of layer thickness and composition. If
there are elements that are present in more than one layer, then multiple measurements are
essential to deconvolve the composition and structure. Joy (1995) and co-workers and
Gauvin and co-workers (e.g., Hovington et al., 1997a,b; Drouin et al., 1997) have de-
veloped public-domain Monte Carlo programs that are easily adapted to the analysis of
layered specimens.
3. Correction for Secondary Fluorescence
All of the above discussion of quantitative analysis of layered specimens has only con-
sidered the case of electron excitation of inner-shell ionization resulting in production of
characteristic x-rays. However, characteristic x-rays can also be produced by uorescence
from any absorbed x-ray photons (characteristic or continuum=bremsstrahlung) having
energies greater than the inner-shell ionization potential. These uorescing x-rays can be
produced from any of the layers in the specimen. Because the range of energetic x-rays
typically greatly exceeds that of the beam electrons, x-rays may be uoresced in layers
(e.g., the substrate) that are considerably deeper than the electron range.
As noted above, uorescence by characteristic or continuum x-rays can contribute
up to 60% or 70% of the total x-ray emission from bulk specimens in extreme cases.
Typically, secondary uorescence contributes to 10% or less of the emitted intensity. In
the case of layered specimens, the amount of secondary uorescence will depend on the
thicknesses and relative positions of the layers containing the uoresced and uorescing
species. The typical x-ray mean free path between absorption=uorescence events is much
greater than the typical electron mean free path between inelastic scattering=inner-shell
ionization events. As a result, the relative contribution from secondary uorescence events
will be small if either the uorescing or uoresced x-ray line is from even a major element
in a very thin layer. The greatest contribution from secondary uorescence occurs for a
minor element in a thick layer from a major element in that or another thick layer or
substrate. Thus, in many applications, just as in the case of particles, correction for sec-
ondary uorescence can be safely ignored.
Several investigators have proposed corrections for uorescence by characteristic
lines and=or the continuum in layered specimens. Armstrong and Buseck (1985) derived a
rigorous, theoretically based general expression for a variety of layersubstrate conditions.
This expression requires numerical integration in multiple dimensions and is too lengthy to
show here. The reader is referred to the original paper for the details. Waldo (1991)
simplied these equations and adapted them for use in his public-domain thin-lm analysis
software (Waldo, 1988). Cox et al. (1979) developed a simplied characteristic uorescence
correction for multielement thin lms on multielements substrates. Their method was
based on the assumptions that the lm was thin with respect to the mean depth of x-ray
generation, and that the x-rays were generated isotropically from a point source located in
the substrate at a distance from the lmsubstrate boundary equal to the mean depth of
x-ray production. The details of the procedure can be found in the original paper and a
good summary can be found in the original paper and a good summary can be found in
Scott et al. (1995). Armigliato et al. (1982) incorporated this procedure into there thin lm
correction and reported improved results in selected cases. However, by its nature, it is
inappropriate for the analysis of thick lms on substrates or multiple uorescing layers.
More recently, Pouchou and Pichoir (1991b) proposed corrections for uorescence
by both characteristics lines and the continuum in layered specimens. The authors make
some simplifying assumptions regarding the depth distribution of the primary x-rays and
relative line intensities. Their derivation is beyond the scope of this book, and the reader is
once again referred to the original paper for the details. Their corrections are employed
in the commercial versions of their program. The continuum uorescence correction has
been integrated as well into the public-domain program of Walso (1988, 1991).
a. Analytical Results: Testing the Methods
X-ray emission analysis, particularly involving wavelength-dispersive detectors at
microprobe beam currents (i.e., 11000 nA) can produce thin-lm analysis results of very
high precision. Detection limits of less than 10% of an atomic monolayer can be measured
[e.g., Packwood and Remond (1992)]. Film thickness variations can be measured at a level
of 0.1 nm. Compositional variations of 0.2% for major and minor element concentrations
at a level of 100 ppm can be detected, under favorable conditions, in lms as thin as 10 nm.
(For examples of the measurement sensitivities and detection limits, see the review papers
of Pouchou and Pichoir (1991b), Packwood and Remond (1992), Willich (1992), Pouchou
(1993), and Karduck (1997)]. Thus, x-ray emission analysis provides an important
complementary tool to the more conventional techniques used in thin-lm and layered-
specimen characterization, such as Auger electron spectrometry (AES), Rutherford-
backscattering spectrometry (RBS), and secondary ion mass spectrometry (SIMS) [e.g.,
Cazaux (1992)] and, in certain circumstances, approaches or exceeds their detectability.
X-ray emission analysis has the potential to be a more accurate, routine technique
for quantitative determination of thin-lm=layered-specimen composition (and, in some
cases, layer thickness) than techniques like AES, RBS, and SIMS. However, a serious
problem in evaluating the comparative accuracy of thin-lm analysis with any of these
techniques is the lack of certied thin-lm standards (both in terms of composition and
thickness). Most of the papers cited above that have proposed quantitation schemes for
lm analysis or reviewed the applications of thin lm=layered specimen analysis showed
examples of the accuracy or consistency=plausibility of the technique by results of ana-
lyses of laboratory samples of unknown composition and thickness. In some cases, the
samples were analyzed and thicknesses were determined by another analytical technique.
In other cases, an expected range of composition and thickness was stated and the results
compared to that range. In no case that we have discovered, have thin lm or layered
specimens of known, certiable pedigree (i.e., having been analyzed and had thicknesses
measured by more than one analytical procedure that also included analyses of certied
reference materials for which limits of accuracy could be given) been used to evaluate the
proposed correction procedures. In most instances, the lm=layer composition is assumed
from the starting materials and the thickness may be measured by wet chemistry or RBS.
Many of the papers containing raw thin-lm and layered-specimen data that have been
used to formulate and evaluate the analytical procedures discussed above date back to
when RBS was a new technique with relatively large uncertainties and when evaporation
and sputtering techniques for thin lm manufacture did not have nearly the precision and
accuracy that exists today.
Although the necessary published data does not exist to make a precise evaluation of
the relative accuracy of the various proposed thin-lm analysis techniques, we present
several examples of published raw data from the literature processed through various of
the correction procedures we have discussed to give an idea of the variation of the pro-
cessed results. Three types of thin lm=layered specimen analysis are given.
Table 7 presents the results of thickness determinations for monoelemental thin lms
deposited on monoelemental substrates, taken from the raw data of Reuter (1972) and
processed through various thin-lm correction procedures. The procedures used for this
table are the f(rz) correction procedures of Reuter (1972), Pouchou and Pichoir (1991a)
[PAP], Bastin et al. (1986), Bastin and Heijlingers (1990) [both using implementation of
Table 7 Experimental Data of Reuter (1972) Processed Through GMRFilm and CASINO
Film and x-ray line: AlKa AlKa AlKa AlLa
Substrate: B B Be Fe Au Pt
Accelerating potential (keV) 12 12 4 30 30 30 30
Film thickness (mg=cm
2
)
Chemical measurement 14.5 4.4 4.4 73.0 73.0 73.0 77 193
Thin-film corrections
Reuter (1972) phi(PZ) 14.2 4.3 4.3 75.0 83.0 85.0 94 198
Monte Carlo (CASINO) 100 207
PAP w contin. fluor. corr. 13.0 4.2 4.2 81.3 79.0 73.5 109 233
PAP w=o contin. fluor. corr. 13.0 4.2 4.2 81.3 79.0 73.5 103 217
Bastin (1986) 12.3 3.7 4.4 79.2 80.4 79.9 102 224
Bastin (1990) 13.2 4.2 4.7 82.1 79.1 59.6 107 225
Packwood and Brown 11.6 3.9 4.8 72.5 74.7 74.2 (138) (303)
Mean 12.9 4.0 4.5 79.3 78.4 72.1 104 221
Std. dev. 0.9 0.2 0.3 3.9 2.2 7.5 3.7 9.8
% Sigma 6.8% 5.7% 6.3% 5.0% 2.8% 10.4% 3.6% 4.4%
Meanchem. 11.1% 8.2% 1.4% 8.6% 7.5% 1.2% 35.3% 14.6%
Film and x-ray line: CuKa CuLa AuLa
Substrate: SiO
2
Au SiO
2
Au Pt
Accelerating potential (keV) 30 30 10 10 15 18 22 30
Film thickness (mg=cm
2
)
Chemical measurement 83.0 83.0 83.0 83.0 26.0 26.0 26.0 26.0
Thin-film corrections
Reuter (1972) phi(PZ) 72.0 85.0 71.0 82.0 23.0 23.0 24.0 23.0
Monte Carlo (CASINO)
PAP w contin. fluor. corr. 89.2 82.4 77.6 86.4 26.4 24.5 26.6 26.1
PAP w=o contin. fluor. corr. 85.3 82.3 77.6 86.4 25.0 23.4 25.4 25.1
Bastin (1986) 82.9 89.1 78.1 93.0 26.5 24.9 26.6 26.0
Bastin (1990) 86.5 82.1 86.1 73.8 26.1 24.2 25.9 25.2
Packwood and Brown 84.7 96.0 80.8 95.9 30.6 26.5 26.8 24.1
Mean 83.4 86.4 80.0 87.1 26.9 24.7 26.3 25.3
Std. dev. 6.0 6.1 3.6 8.5 2.1 1.1 0.6 0.8
% Sigma 7.2% 7.1% 4.5% 9.8% 8.0% 4.6% 2.2% 3.2%
Meanchem. 0.5% 4.1% 3.6% 4.9% 3.5% 5.0% 1.0% 2.7%
Bastin et al. (1992)], Packwood (1991), and the Monte Carlo procedure of Gauvin and
co-workers (Hovington et al., 1997a, 1997b; Drouin et al., 1997) (CASINO). The results of
the Reuter procedure were taken from the article. The Monte Carlo results were de-
termined by developing calibration curves of k
el
versus thickness from simulations using
the public-domain CASINO program of Gauvin et al. The other procedures were tested
using a modied version of the public-domain GMRFilm program of Waldo (1991).
Examples are chosen to include cases of elements of very dissimilar atomic number as lm
and substrate, cases of both soft and hard x-ray lines, and cases of variation of accelerating
potential. None of the cases shown involve a large correction for uorescence either by the
continuum or by characteristic lines. The results show (with the exception of a few out-
liers) an agreement of about 1015% relative among the thicknesses calculated by the
various correction procedures and an agreement of about 510% relative between the
mean corrected value and the thickness determined by wet chemistry.
Table 8 shows the results of the next more complicated type of thin-lm analysis,
multielement thin lms on a multielement substrate of dissimilar average atomic number.
The data were taken from the work of Kyser and Murata (1974). The data were processed
through the same correction procedures as used for Table 7, except the Monte Carlo re-
sults of Kyser and Murata were used instead of the CASINO program and the early f(rz)
expression of Reuter was not evaluated. The alloy lms deposited on SiO
2
substrates were
of composition Mn
x
Bi
y
and Co
x
Pt
y
. To conserve space, only the Mn and Co concentra-
tions are shown in the Table 8; the Bi and Pt concentrations can be determined by dif-
ference from 100%. As was the case in Table 7, the PAP expression was evaluated with
and without a continuum uorescence correction; all other expressions were evaluated
without correction for continuum uorescence. The data in Table 8, indicates only a minor
dierence in calculated thickness and composition (typically 1%) due to continuum
uorescence in these cases. The agreement among the various corrections in the alloy
compositions is better than 5% relative; the agreement in thickness is better than 8%. The
agreement in the lm composition between the mean of the correction procedures and the
RBS measured value is better than 5%; the agreement in thickness is typically better than
15%, perhaps reecting the larger uncertainties in these early RBS thickness measure-
ments.
Table 9 gives the results of a still more complicated type of analysis, two multi-
element layers of dissimilar average atomic number over a monoelemental layer with an
atomic number signicantly dierent from both of the layers. The data were taken from
the work of Pouchou (1993). The data were processed through the same corrections as
employed for Table 8, except the STRATA data from the article is given instead of results
from the Monte Carlo expressions of Kyser and Murata. (STRATA, as described in the
article, is a commercial program that does a best-t determination of data collected at
multiple accelerating potentials using the PAP correction method.) The case studied is a
NlCr lm deposited on a layer of FeGdPt that has been deposited on Si. There are
small corrections for characteristic uorescence but no signicant continuum uorescence
eects. Data have been collected at three dierent accelerating potentials to show the eect
of electron range. In most cases, agreement among the various models for data collected
at a given E
0
exceeds that for the same correction procedure at varying E
0
s. Agreement in
both calculated composition and thickness among the various procedures at a given
accelerating potential is typically similar to those measured in Table 8. The agreement
between RBS and calculated compositions and thickness is typically better than that
observed in Table 8, possibly reecting improvements in the accuracy of RBS measure-
ments in this later work.
Close examinations of Tables 79 reveals dierences in the levels of agreement of the
various correction schemes, both with respect to the independent measurement data and
with respect to internal consistency (e.g., giving the same answer for data collected at
dierent accelerating potentials) that might be used to choose one procedure over another
as providing superior accuracy. However, due to the absence of independently analyzed
and certied reference standards as well as to the absence of comparable raw data col-
lected by more than one laboratory on these samples, no best correction scheme can be
unambiguously determined. The internal agreement of the various procedures, however,
is generally reasonably goodtypically at a level of about 5% relative. This level is ap-
proximately twice what might be expected for these types of materials if they were
Table 8 Experimental Data of Kyser and Murata (1974) Processed Through GMRFilm
MnBi lms
X115-3 X115-5 X115-7
CMn rt CMn rt CMn rt
RBS measurement 26.6 48.2 53.5 33.0 80.1 26.2
Thin-film corrections:
Monte Carlo (Kyser & Murata) 25.5 53.0 51.0 38.0 80.0 29.0
PAP w continuum fluorescence correction 26.5 52.1 52.1 37.2 80.0 28.6
PAP w=o continuum fluorescence correction 26.3 51.4 51.8 36.5 79.9 27.9
Bastin (1986) 26.8 49.0 52.7 35.4 80.5 27.6
Bastin (1990) 26.8 51.8 52.5 36.7 80.3 28.3
Packwood and Brown 26.4 53.5 51.7 37.6 79.7 28.5
Mean 26.4 51.8 52.0 36.9 80.1 28.3
Std. dev. 0.5 1.6 0.6 0.9 0.3 0.5
% Sigma 1.8% 3.0% 1.2% 2.5% 0.4% 1.8%
MeanRBS 0.8% 7.5% 2.9% 11.8% 0.0% 8.1%
CoPt Films
10-2 13-2 Mn lm Bi lm
CCo rt CCo rt rt rt
RBS measurement 19.4 49.0 9.6 33.6 40.1 48.6
Thin-film corrections:
Monte Carlo (Kyser & Murata) 18.5 53.0 10.1 40.0 42.0 54.0
PAP w continuum fluorescence correction 19.0 52.5 10.0 39.5 41.2 54.7
PAP w=o continuum fluorescence correction 18.6 51.7 9.7 39.1 40.1 54.1
Bastin (1986) 19.0 49.5 10.1 37.6 39.6 51.3
Bastin (1990) 19.0 52.3 9.9 39.0 41.3 54.3
Packwood and Brown 19.6 54.0 10.3 40.4 41.2 56.6
Mean 18.9 52.2 10.0 39.3 40.9 54.2
Std. dev. 0.4 1.5 0.2 1.0 0.9 1.7
% Sigma 2.1% 2.9% 2.0% 2.5% 2.2% 3.1%
MeanRBS 2.4% 6.5% 4.3% 16.9% 2.0% 11.5%
Note: Concentration in element weight %, lm thickness (rt) in mg=cm
2
. Analyses performed at 20 keV, with
psi 52.5. MnKa and CoKa, BiMa and PtMa lines measured. Films are on SiO
2
substrates.
Table 9 Experimental Data of Pouchou (1993) Processed Through GMRFilm
Layers on Si
Layer 1 Layer 2
E
0
CNi CCr T (nm) CFe CGd CPt T (nm)
RBS meas. 14.4 85.6 68.3 51.4 28.6 20.0 24.6
STRATA pgm 14.7 85.4 67.1 52.0 28.7 19.3 24.2
StrataRBS 2.1% 0.2% 1.8% 1.2% 0.3% 3.5% 1.6%
20 keV PAP 15.0 85.0 70.8 51.0 29.1 19.9 24.6
Bastin (1990) 15.2 84.8 72.2 51.4 29.3 19.3 26.3
Bastin (1986) 15.5 84.5 69.8 52.3 27.8 19.9 22.7
Packwood 16.1 83.8 73.1 50.6 30.4 19.0 27.2
Mean 15.5 84.5 71.5 51.3 29.2 19.5 25.2
Std dev. 0.5 0.5 1.5 0.7 1.1 0.5 2.0
% Sigma 3.1% 0.6% 2.0% 1.4% 3.7% 2.3% 7.9%
MeanRBS 7.3% 1.3% 4.6% 0.1% 1.9% 2.4% 2.4%
25 keV PAP 14.6 85.4 69.6 50.8 29.8 19.6 24.1
Bastin (1990) 15.4 84.6 68.3 51.8 28.9 19.6 22.5
Bastin (1986) 14.7 85.3 69.3 51.0 29.9 19.4 24.8
Packwood 15.5 85.5 67.4 49.9 31.3 19.4 25.0
Mean 15.1 85.2 68.7 50.9 30.0 19.5 24.1
Std dev. 0.5 0.4 1.0 0.8 1.0 0.1 1.1
% Sigma 3.1% 0.5% 1.5% 1.5% 3.3% 0.6% 4.7%
MeanRBS 4.5% 0.5% 0.5% 1.0% 4.8% 2.5.% 2.0%
30 keV PAP 14.3 85.7 68.8 51.1 29.3 19.6 24.2
Bastin (1990) 13.5 86.5 67.2 51.9 28.5 19.6 22.7
Bastin (1986) 14.4 85.6 68.3 51.2 29.4 19.4 24.4
Packwood 15.0 85.0 64.0 49.9 30.7 19.4 24.0
Mean 14.3 85.7 67.1 51.0 29.5 19.5 23.8
Std dev. 0.6 0.6 2.2 0.8 0.9 0.1 0.8
% Sigma 4.3% 0.7% 3.2% 1.6% 3.1% 0.6% 3.2%
MeanRBS 0.7% 0.1% 1.8% 0.7% 3.1% 2.5.% 3.2%
Means PAP 14.6 85.4 69.7 51.0 29.4 19.7 24.3
Std dev. 0.4 0.4 1.0 0.2 0.4 0.2 0.3
% Sigma 2.4% 0.4 1.4% 0.3% 1.2% 0.9% 1.1%
MeanRBS 1.6% 0.3% 2.1% 0.8% 2.8% 1.5% 1.2%
Bastin (1990) 14.7 85.3 69.2 51.7 28.9 19.5 23.8
Std dev. 1.0 1.0 2.6 0.3 0.4 0.2 2.1
% Sigma 7.1% 1.2% 3.8% 0.5% 1.4% 0.9% 9.0%
MeanRBS 2.1% 0.4% 1.4% 0.6% 1.0% 2.5% 3.1%
Bastin (1986) 14.9 85.1 69.1 51.5 29.0 19.6 24.0
Std dev. 0.6 0.6 0.8 0.7 1.1 0.3 1.1
% Sigma 3.8% 0.7% 1.1% 1.4% 3.8% 1.5% 4.7%
MeanRBS 3.2% 0.5% 1.2% 0.2% 1.5% 2.2% 2.6%
Packwood 15.5 84.8 68.2 50.1 30.8 19.3 25.4
Std dev. 0.6 0.9 4.6 0.4 0.5 0.2 1.6
% Sigma 3.5% 1.0% 6.7% 0.8% 1.5% 1.2% 6.4%
MeanRBS 7.9% 1.0% 0.2% 2.5% 7.7% 3.7% 3.3%
Note: Concentration in element weight %, layer thicknesses in nm. Continuum uorescence correction applied in
all cases. Lines analyzed: NiKa, CrKa, FeKa, GdLa, PtMa.
prepared and analyzed as bulk specimens. The level of agreement between the corrected
electron microbeam data and that determined by other techniques ranges from about 5%
to 15% relative and certainly includes a considerable component of uncertainty from the
comparative technique. In both cases, the level of agreement in the layer composition
appears to be somewhat better than the level of agreement in the layer thickness. The data
certainly suggest that electron microbeam analysis has the potential for determining thin-
layer compositions and thickness with comparable accuracy to the more conventionally
employed surface techniques, particularly when appropriate certiable standards be-
come available for correction procedure evaluation.
B. Quantitative Analysis of Thin Specimens at HighVoltages
The quantitative analysis of thin samples such as thin lms, thin sections of samples
that are inhomogeneous on a submicrometer scale, or small particles with dimensions less
than about 0.5 mm represents a unique class of analysis that must be considered separately
from conventional probe analysis. Unlike conventional electron-opaque samples, this
class of sample is best analyzed in the analytical electron microscope by a high-energy
electron beam with an accelerating potential in excess of 100 kV. If the sample is thin
enough, there is minimal electron backscattering and the electrons lose very little of their
energy in the sample (Goldstein, 1979). As a result, the atomic number correction k
Z
can
be neglected and the generated x-ray intensity, f
Drt
a
, from a characteristic line of element a
in an isolated thin lm of mass thickness Drt can be calculated from Eq. (99) according to
Williams and Goldstein (1991):
f
Drt
a
N
o
a
a
a
Q
a
A
a
_ _
C
a
Drt 99
where N is Avagadros number, C
a
is the weight fraction of element A, o
a
is the uor-
escence yield for the analytical line of element A, a
a
is the fraction of total K, L, or M line
intensity measured, A
a
is the atomic weight of element A, Q
a
is the ionization cross section
of the analytical line of element a, and t is the lm thickness.
In addition to a simplied generation expression, if the sample can be approximated
as an innitely thin lm, the eects of x-ray absorption and uorescence can be neglected.
This condition is often referred to as the thin-lm approximation and makes it possible
to express the relationship between the measured I
a
and the generated x-ray intensities for
element a by Eq. (100):
I
a
f
Drt
a
e
a
100
where e
a
is an eciency factor related to the overall eciency of the Si(Li) detector for the
detection of x-rays from element a (Goldstein et al., 1986). Because the determination of
sample thickness at each analytical point is impractical and the value of e
a
is not constant,
the analysis schemes for thin samples involve the measurement of elemental ratios in which
the relative concentration of one element to another can be expressed by the following
equation:
C
a
C
b
k
ab
I
a
I
b
_ _
101
The sensitivity factor approach to analysis is common to many analytical techniques and
the factor k
ab
in Eq. (101) is referred to as the CliLorimer factor or k
ab
factor (Cli and
Lorimer, 1975; Nasir, 1976). It is related to the generation and eciency terms for element
b ratioed to those for element a. In many analytical schemes, the analyst determines, from
binary standards, a set of k
ab
factors. Then, for a binary system containing unknown
concentrations of elements a and b, C
a
and C
b
can be determined from Eq. (100) and the
knowledge that C
a
C
b
1. In ternary and higher-order systems, the relative con-
centrations for the various elements can be determined if the k
ab
factors are known for
combinations of various binary compounds as shown in the following equations for a
ternary system:
C
a
C
b
k
ab
I
a
I
b
_ _
102
C
c
C
b
k
cb
I
c
I
b
_ _
103
C
a
C
b
C
c
1 104
In analytical electron microscopy, particularly in analyses related to geological speci-
mens, the convention is to express the k
ab
factors relative to silicon (i.e., k
aSi
). In this
form, they are referred to as simply k factors and are related to the k
ab
factors as shown
in
k
ab

K
aSi
K
bSi
K
a
K
b
105
Figure 52 shows the k
aSi
values from the work of Wood et al. (1984) and Schreiber and
Wims (1981).
In addition to the k factors relative to silicon, several researchers, particularly those
involved in metallurgy, have found it useful to report the k factors relative to iron. Table 10
lists the k
aFe
for the K and L lines of several elements.
It is also possible to calculate k factors from Eq. (99). A detailed discussion of the
equations used to calculate the various terms inEq. (99) canbe foundin Williams and Goldstein
Figure 52 Measured k
aSi
factors for thin-sample analysis from Wood et al. (From Wood et al.,
1984. Reproduced with permission of Blackwell Science Ltd.)
(1991) and Goldstein et al. (1986). Figures 53 and 54 show a comparison of the calculated and
measured k factors for K and L line radiation from various elements (Wood et al., 1984).
Sheridan (1989) has determined a large set of experimental k
aSi
factors for a wide
range of Ka, La, Ma lines. The measurements were performed on a series of sub-
micrometer particles ground from NBS multielement research glasses. After applying an
absorption correction, the experimental results were compared to theoretical k
aSi
factors
determined with several dierent ionization cross sections.
As the thickness of the sample increases, the electron transparency of the thin sample
or small particle decreases, eventually reaching a thickness for which the sample no longer
Table10 Experimental k
aFe
Factors for Various Elements
K Lines
Lorimer et al. (1976, 1977) McGill and Hubbard (1981) Wood et al. (1984)
Element (100 keV) (100 keV) (120 keV)
Na 2.46
Mg 1.23 0.08 1.16 0.96 0.03
Al 0.92 0.08 0.8 0.86 0.04
Si 0.76 0.08 0.71 0.76 0.004
P 0.77 0.005
S 0.83 0.03
K 0.79 0.77 0.86 0.014
Ca 0.81 0.05 0.75 0.88 0.005
Ti 0.86 0.05 0.86 0.03
Cr 0.91 0.05 0.90 0.006
Mn 0.95 0.05 1.04 0.025
Co 1.05 0.98 0.06
Ni 1.14 0.05 1.07 0.06
Cu 1.23 0.05 1.17 0.03
Zn 1.24 1.19 0.04
Nb 2.14 0.06
Mo 3.38 3.80 0.09
Ag 6.65 9.52 0.03
L Lines
Wood et al. (1984) Goldstein et al. (1977)
(120 keV) (100 keV)
Sr
a
1.21 0.06
Zr
a
1.35 0.01
Nb
a
0.90 0.06
Ag
a
1.18 0.06 1.04
Sn 2.21 0.07 2.39
Ba 2.18
W 2.43
Au 3.10 0.09 3.27
Pb 4.14
a
k Factors for these elements are for combined La and Lb lines.
Source: From Goldstein et al., 1986.
Figure 53 Calculated and measured k
aFe
factors for K line radiation from several elemental thin
films. Solid lines represent range of theoretical values. (From Wood et al., 1984. Reproduced with
permission of Blackwell Science Ltd.)
Figure 54 Calculated and measured k
aFe
factors for L-line radiation from several elemental thin
films. Solid lines represent range of theoretical values. (From Wood et al., 1984. Reproduced with
permission of Blackwell Science Ltd.)
conforms to the thin-lm criteria. Under these circumstances, corrections for x-ray
absorption should be included in the analysis scheme. According to Williams and
Goldstein (1991), the limits for the failure of the thin-lm criterion are an x-ray absorption
correction, A, <0.97 or >1.03 and=or a uorescence correction >5%. For these cases,
Eq. (101) can be expanded to include absorption and uorescence:
C
a
C
b
k
ab
I
a
I
b
_ _
F
abs
1
1 F
fl
_ _
106
where F
abs
is the absorption factor given in Eq. (107) and F
fl
is the ratio of the uoresced
to primary intensity, I
a
=I
0
, given in Eq. (108):
F
abs

m
r
_ _
a
sam
m
r
_ _
b
sam
_
_
_
_
_
_
1 exp w
a
rt
1 exp w
b
rt
_ _
107
I
a
I
0
C
b
o
b
r
a
1
r
a
_ _
A
a
A
b
m
r
_ _
b
a
E
c
a
E
c
b
_ _
lnU
b
lnU
a
_ _
rt
2
0:932 ln
m
r
_ _
b
sam
rt
_ _
sec c 108
where r
a
is the absorption jump ratio for element a and A
a
and A
b
are the atomic numbers
for a and b, respectively.
The absorption factor was derived by Goldstein et al. (1986) from the work of Tixier
and Philibert (1969) and Konig (1976). Williams and Goldstein (1991) calculated the
thicknesses of materials above which the absorption of x-rays was outside the 0.971.03
limits. The results of these calculations are given in Table 11.
As pointed out by Williams and Goldstein (1991), the eect of uorescence must be
investigated in cases where the concentration of the uoresced element is at a minor to
trace level, <10 wt%, in a sample composed mainly of the exciting element. In a study of
Fe10 wt% Cr (Nockolds et al., 1980), the uorescence correction was only about 5%.
The equations for the absorption and uorescence involve the measurement of the
lm or particle thickness and the calculation of the mass absorption coecients for ele-
ments a and b in the specimen. As the result, it is necessary to measure the thickness at
each analysis location and to calculate the concentrations in an iterative loop similar to
that used for the conventional ZAF schemes.
C. Quantitative Analysis of Particles with Energy-Dispersive X-ray
Spectrometry
Although some initial particle studies were done on the electron probe using wavelength-
dispersive spectrometers (WDS), the variablity and complexity of many particle
compositions coupled with the high currents necessary for WDS made elemental analysis
Table 11 Calculated Maximum Thickness of Thin Samples for
Which the Absorption Correction Is Less Than 3%
Element of interest=x-ray line Sample t
max
nm
AlKa NiAl 9
PKa Fe3P 22
MgKa, OKa MgO 25
Source: Data from Williams and Goldstein, 1991.
of particles by WDS dicult at best (Armstrong and Buseck, 1978). In addition, the use of
multiple spectrometers, each with a dierent view of the particle and, therefore, a dierent
particle geometry, as shown in Figure 55, limited the quantitative capabilities of the
technique. The evolution of the various quantitative procedures resulted in the separation
of particles into roughly three size categories that are based on the procedures and in-
struments used for analysis (see Fig. 56). The particles less than 0.5 mm in diameter are best
analyzed in the analytical electron microscope using the procedures described in the
previous subsection. The particles with dimensions below about 0.1 mm require very little,
if any, particle-geometry corrections for elements with atomic numbers greater than about
11 and can be analyzed as innitely thin lms using k
AB
factors. As the particle size in-
creases, approaching 0.5 mm and larger, the eects of particle geometry must be included in
the analysis procedure (Goldstein, 1979).
Once the particle dimensions are greater than approximately 0.5 mm, the particles are
too large to be analyzed in the AEM and are best analyzed in the electron-probe or
scanning electron microscope. From 0.5 to about 20 mm in diameter, particle geometry
may have a pronounced eect on the generation and emission of x-rays and can sig-
nicantly aect quantitative analytical results. Many dierent analytical schemes have
been developed for the analysis of the particles in this size range. Finally, when the dia-
meter of the particle is greater than about 20 mm, the particle is large enough with respect
to the electron beam than it is essentially a bulk sample and classical analytical corrections
apply. The remainder of this subsection is concerned with the quantitative analysis of
particles in the 0.510-mm size range.
Figure 55 Images of a particle taken at the angles for three different WD spectrometers.
Figure 56 Particle size ranges and associated analytical techniques.
In classical electron-probe analysis, schemes employing either a ZAF, bulk-sample
f(rz), or BenceAlbee approach, both sample and standard must be innitely thick with
respect to the penetration of the electron beam and have at surfaces. By controlling
sample dimensions and shape, the corrections for the interaction of the electron beam with
the sample and the subsequent x-ray emission can be calculated from simple geometric
relationships. In the quantitative analysis of particles, the shape and thickness of the
specimen often cannot be controlled or measured. the diculties in quantitative analysis of
particles result from three dierent eects that inuence the generation and measurement
of x-rays from these samples (Small, 1981).
The rst eect is the result of the nite size (mass) of the sample. The mass eect is
related to the elastic scattering of the electrons and is strongly aected by the average
atomic number of the sample. The mass eect is important when the sample thickness or
particle size is smaller than the range of the primary electron beam so that a fraction of the
beam escapes the sample before exciting x-rays. This is shown in Figure 57, which is a
Monte Carlo simulation of electron trajectories. The majority of the primary electron
trajectories terminate within the boundaries of larger sphere, but very few terminate within
the boundaries of the smaller sphere. As the size of the sample decreases, the mass of
material from which x-rays are excited drops and results in a reduction of x-ray intensities
from the specimen compared to a bulk sample of the identical composition. The mass
eect can be demonstrated by comparing the x-ray emissions from a bulk target to the
emissions from a particle of the same composition. This eect can be seen in Figure 58,
which is a plot of the BaLa x-ray intensity from particles normalized to the intensity from
a bulk material of the same composition plotted versus particle diameter. The energy of
the Ba x-rays is 4.47 keV, which is high enough so that the absorption eects are minimal.
The mass eect is demonstrated by the decrease in the intensity measured on the particles
compared to the bulk for particles less than 3 mm in diameter. The net result of not
Figure 57 Monte Carlo simulation of electron trajectories in a large and small particle. (From
Small, 1981.)
correcting for the mass eect in the analysis of particles less than about 3 mm in size will be
an underestimation of the composition for all elements analyzed in the sample.
The second eect that must be corrected for is the absorption eect. In the analysis
of most particles, the x-ray emergence angle and, therefore, the absorption path length
cannot be predicted accurately as it can for polished specimens. The magnitude of this
eect is largest when there is high absorption, as is typically the case for soft x-rays from
elements like Al or Si that have energies less than 2 keV. The dierence between the ab-
sorption path length in a particle and a bulk at sample can result in widely dierent
values of emitted x-ray intensities. For the particle shown in Figure 59, the path length A
B in the particle is less than the path length AC in the polished sample. The path length
A*D in the particle, however, is greater than the path length AC in the polished sample.
The result of the varying absorption path lengths is shown in Figure 60, which is the SiKa
x-ray intensity from particles normalized to the intensity from a bulk material of the same
composition plotted versus particle diameter. For these spherical particles, the absorption
path lengths in the particles are less than the bulk material, resulting in a higher emitted
x-ray intensity form the particles compared to bulk. This eect is detectable primarily for
the lower-energy x-ray lines, such as that of aluminum at 1.49 keV, which are highly ab-
sorbed. This increased intensity for the low-energy x-rays results in an overestimation of
the concentration for these elements and a corresponding underestimation of elements
with high-energy x-rays for which absorption is not signicant.
The third eect is caused by the uorescence of x-rays by either the continuumor other
characteristic x-rays. Because x-ray absorption coecients in solids are relatively small
compared to electron attenuation, the secondary x-ray uorescence occurs over a much
Figure 58 Normalized BaLa x-ray intensity plotted as a function particle diameter. (From Small,
1981.)
larger volume than the primary electron excitation. In bulk samples and standards, the
x-rays, for the most part, remain in the specimens. In the case of particles however, the
particle volume may be only a small fraction of the x-ray excitation volume. As a result, the
exciting x-rays will uoresce relatively few x-rays before leaving the particle. In those
samples where the uorescence is important, the eect of comparing a particle to a bulk
standard may be signicant. This eect is shown in Figure 61, which is a plot of the range for
NiKa x-rays causing uorescence of FeKa x-rays in a NiFe alloy. The net eect of not
correcting for the secondary excitation of x-rays in particle analysis is as follows:
Figure 59 X-ray absorption in a particle compared to the absorption in bulk material. (From
Small, 1981.)
Figure 60 Normalized SiKa x-ray intensity plotted as a function particle diameter. (From Small,
1981.)
1. An underestimation of the concentration for elements that have a signicant
contribution to their characteristic line or lines from excitation by other
characteristic x-rays
2. In the case of continuum uorescence, an underestimation of the concentrations
for all elements, particularly those with higher-energy lines, which are excited by
the higher-energy, longer-range continuum
1. Normalization
One of the simplest methods for the quantitative analysis of particles is to normalize to
100% the concentrations, determined with bulk standards, from a conventional procedure
such as ZAF Eq. (109) (Wright et al. 1963):
C
n
a

C
a
i
C
i
109
where C
n
a
is the normalized concentration of element a, C
a
is the concentration of a de-
termined from the analytical procedure, and
i
C
i
is the sum of the concentrations for all
elements in the sample.
The analyst, in selecting this method of correction, makes the assumption that x-ray
absorption and uorescence are the same for the particle as for a bulk specimen and that
the mass eect is the same for all elements. No elements can be determined by dierence;
that is, oxygen must be analyzed or calculated from an assumed stoichiometry. In addi-
tion, the analyst cannot determine, by obtaining an analysis total of less than 100%, the
presence of any undetermined elements. In practice, normalization of results is most
eective for the correction of the mass eect because the decrease in intensity as a function
of particle size is nearly the same for all elements. Figure 62 shows that the dierent
elemental curves merge together for particle diameters less than about 2 mm. Because this
Figure 61 Range of secondary x-ray fluorescence in a NiFe alloy. (From Small, 1981.)
procedure does not accurately compensate for the absorption and uorescence eects, the
most accurate results will be obtained on particle systems that meet the following con-
ditions: (1) systems for which all the analytical lines for the elements are above 4 keV
where the absorption eects are minimal; (2) if any of the analytical lines are below about
4 keV in energy, then the lines for all the elements should be as close together in energy as
possible so that the matrix absorption is approximately the same in all cases; (3) systems
for which there is no signicant uorescence.
Table 12 lists the results from the analysis of lead silicate glass particles. The rst set of
results are taken fromthe analysis of the PbMa line at 2.3 keV, which is close in energy to the
SiKa line at 1.74keV. Because the absorption and mass corrections are similar for these two
lines, the lead and silicon concentrations are in good agreement with the true values. The
second set of results were determined by analyzing the PbLa line at 10.6keV. In this case, the
two analytical lines have very dierent energies and the particle absorption eect is not similar
inmagnitude. As expected, the errors associatedwiththis analysis are considerablyhigher than
those associated with the PbMa analysis. The lack of an eective absorption correction by
simple normalization can also be seen in Figure 63, which shows the relative error distribu-
tions, by element, for the analysis of K-411 glass microspheres (Roberson et al., 1995) with a
bulk K-411 glass standard. The error distributions showthat the concentration of Mg with the
lowest energy x-ray, 1.25keV, is overestimated, Si at 1.74keV is centered at about zero error,
and the elements with harder x-ray lines (Ca, 3.7 keV and Fe, 6.4 keV) are underestimated.
2. Particle Standards
The analyst can use a conventional analysis scheme and substitute particle standards for
the normal polished standards (White et al., 1966). In this procedure, the assumption is
Figure62 Normalized x-ray intensities from several elements plotted as a function of particle dia-
meter. (From Small, 1981.)
that the particle eects, particularly the absorption eect, will be approximately the same
for the sample and standard. This assumption is reasonably valid, providing the sample
and standard are close in composition and shape, and the particle diameter is above about
2 mm. Below 2 mm, as shown in Figure 60, any dierence in size and shape between un-
known and standards will be critical because a small change in eective diameter will result
in a large change in x-ray intensity. Figure 64 shows the results of using particle standards
for the analysis of a series of K-411 glass microspheres. Figure 64a is the error distribution
for the normalized analysis of a population of spheres ranging in size from about 1 to
10 mm analyzed with a piece of bulk K-411 glass as the standard. The error distribution in
Figure 64a shows three distinct modes that correspond to the overestimation of under-
estimation of dierent elemental concentrations because of the lack of an eective ab-
sorption correction (see Sec. IV.C.1). In contrast, Figure 64b is the error distribution for
the normalized analysis of the same particle spectra used in Figure 64a, except a 5-mm
sphere was used as the standard rather than a piece of the bulk glass. The distribution in
Figure 64b has a single maximum, is centered on zero, and is narrower, 0.1, than the
distribution in Figure 64a.
3. Geometric Modelingof Particle Shape
The procedure for the quantitative analysis of particles by geometric modeling of particle
shape is based on Eq. (110), which denes the emitted x-ray intensity of element a from a
layer at depth z in the sample, I
0
a
rz (Armstrong, 1991):
I
0
a
rz f
a
rz exp m
a
csc Crz 110
where r is the density, f
a
rz is the generated primary x-ray intensity from a layer at depth
z in the sample, m
a
is the mass absorption coecient for element a, and C is the take-o
angle.
Table12 Analysis of Lead Silicate Glass K-229 by Normalization of ZAF Results
Analysis Si (wt%) % Error Pb (wt%) % Error
Analysis done with PbMa line (meets conditions)
1 0.155 10.7 0.620 4.6
2 0.144 2.9 0.643 1.0
3 0.136 2.7 0.658 1.2
4 0.138 1.1 0.653 0.5
5 0.127 9.0 0.675 3.8
6 0.170 22 0.588 9.5
7 0.137 2.5 0.657 1.1
Analysis done with PbLa line (does not meet conditions)
1 0.134 4.5 0.663 1.9
2 0.177 26.3 0.578 11
3 0.159 14 0.612 5.8
4 0.166 18 0.602 7.4
5 0.017 88 0.894 37
6 0.100 29 0.731 12.4
7 0.157 12.3 0.616 5.2
Note: Nominal composition: Si 0.140; Pb0.650.
Figure 63 Relative error distributions, by element, for the analysis of K-411 glass with a bulk K-411 glass stan-
dard.
Modifying Eq. (110) to take into account the particle absorption eect and the loss
of x-ray intensity due to the mass eect, this equation becomes
I
a
rz
_
a
2
rz
ya
1
rz
_
b
2
r
y;r
z
xb
1
r
y;r
z
f
a
r
x
; r
y
; r
z
exp m
a
gr
x
; r
y
; r
z
dr
x
dr
y
111
for particles, where gr
x
; r
y
; r
z
is the distance from the point of x-ray generation to the
particle surface in the direction of the detector and f
a
r
x
; r
y
; r
z
is the generated x-ray
intensity in the particle. Calculation of f
a
r
x
; r
y
; r
z
requires the determination of the
number of x-rays, DI of element a, product per electron path length Ds as shown in
Eq. (112), which is identical to Eq. (99) except Ds is substituted for D(pt):
DI
C
a
o
a
p
ia
N
A
a
Q
a
Ds
112
Introducing the integration limits for the particle volume and electron energy into
Eq. (112) yields Eq. (113) for the calculation of fr
x
; r
y
; r
z
:
fr
x
; r
y
; r
z

C
a
N
A
a
o
a
p
ia
_ _ _
E
c
E
0
_
2p
y0
_
2p
g0
nE; r
x
; r
y
; r
z
; y; g
drs=dV
Q
a
E
dE=drs
_ _
dg dy dE 113
where nE; r
x
; r
y
; r
z
; y; g is the number of electrons of energy E, scattering at angle y, the
angle relative to the beam axis, and at angle g, the azimuthal angle in plane normal to beam
axis, dE=drs is the mean electron energy loss over distance drs, and drs=dV is the distance
traveled by the electron going through the volume element dV at point x; y; z. The equation
for including secondary uorescence is complex and is given in Armstrong (1991).
The emitted x-ray intensity for element a, corrected for particle mass and adsorption,
can be determined from Eqs. (111) and (112) if the function dening the particle shape=
volume is known. For irregular particles, this is not the case and the method developed by
Armstrong and Buseck (1977, 1978) is based on the determination of a simple geometric
shape or combination of shapes such as a square or pyramid which denes the boundaries
of the particle of interest. The various particle eects are then calculated for the chosen
geometric shapes dening the shape of the particle. The procedure back-calculates the
x-ray production from the particle to an appropriate value for an innitely thick sample
for which all primary electrons remain in the sample and which has the same composition
as the unknown. The various mechanisms responsible for x-ray are corrected as follows:
1. Electron transmission: The amount of primary radiation lost as a result of electron
transmission through the particle and sidescatter requires an analytical expression
for fr
x
; r
y
; r
z
. This expressionis calculated fromthe frz expression developed
by Armstrong (1991) (see Sec. II.2 in this chapter). In the modied form, the
Armstrong frz expression can be used to calculate x-ray production as a
function of position within a particle by setting the integration limits of x; y, and z.
Figure 64 (a) Error distribution for the normalized analysis of a population of spheres ranging in
size from about 110 mm analyzed with a piece of bulk K-411 glass as the standard. (b) Error distri-
bution for normalized analysis of the same particle spectra used in (a), except a 5 mm sphere was used
as the standard rather than a piece of the bulk glass.
3
2. X-ray absorption: The correction for x-ray absorption is done by numerical
integration of Eq. (111), where x, y, and z are determined for the geometric
shape or shapes which dene the overall particle. The shapes which have been
included in the program include cube or rectangular prism, tetragonal prism,
triangular prism, square pyramid, cylinder, hemisphere, and sphere.
3. Atomic number: The expression of Duncumb and Reed (1968) can be used to
calculate the loss of x-rays as a result of electron backscatter. The standard
equation for bulk materials can be used because this correction is applied at a
point where the eects of particle shape have been removed.
4. Secondary uorescence: Armstrong and Buseck (1985) showed that the ratio of
the emitted, uoresced x-ray intensity to the primary x-ray for a particle relative
to the ratio for a thick polished sample of the same composition was about 0.5
for a 10-mm particle, 0.33 for a 5-mm particle, and 0.1 for a 1-mm particle. In
addition, they also found the ratio to be insensitive to beam energy and mostly
dependent on absorption of the excited and exciting x-rays.
Based on the series of polynomial ts to calculated particle data, Armstrong and
Buseck (1985) proposed Eq. (114) to calculated the ratio of the emitted, uoresced x-ray
intensity to the primary x-ray intensity for a particle relative to the ratio for a thick po-
lished sample of the same composition, R
f
:
R
f
A Bx Cx
2
114
where X 1 expm
bj
rr, A0.0260, B 1:1409 0:2012y; C 0:2471 0:2741y
0:01315y
2
; y w
ak
=m
bj
, r is the particle radius, r is the density, m
bj
is the mass absorption
coecient for the exciting element by matrix, and w
ak
is the mass absorption coecient for
the excited element by matrix.
Armstrong (1991) and Myklebust (1975) (see Figs. 57, 58, and 60) have also used
Monte Carlo procedures to study the generation and emission of x-rays from particles.
These calculations involve setting boundary limits for the Monte Carlo calculations based
on particle shapes. Armstrong has also proposed using Monte Carlo calculations based on
the particle shapes in his ZAF program to develop analytical procedures for the analysis of
the particles based on working curves or on a-factor approach (Armstrong, 1982, 1991).
For this procedure, the particles are assumed to be homogeneous and are analyzed
by scanning over the electron beam rather than positioning the beam at a single spot on
the particle. The required input includes the following:
Elements and lines analyzed
Beam voltage and takeo angle
Standards and compositions
Standard morphology (i.e., bulk polished, thin lm, or particle of a particular shape
as described earlier)
Size, estimated shape (as described earlier), an estimated density of the unknown
particle
Measured standard and unknown x-ray intensities for the analyzed elements
The program will also accept elemental k ratios. The performance of the geometric
modeling procedure is shown in Figure 65. Figure 65a is the relative error distribution for
particles analyzed with a thick-specimen ZAF procedure (results normalized to 100%).
The distribution is quite broad with the majority of the analyses falling between 30%
relative error. In contrast, Figure 65b calculated from the geometric-modeling program is
much narrower with almost the entire set of analyses falling within 10% relative error.
Figure 65 (a) Relative error distribution for particles analyzed with a thick-specimen ZAF proce-
dure (results normalized to 100%). (b) Relative error distribution for particle concentrations calcu-
lated from the geometric-modeling program. (From Armstrong, 1991.)
4. Peak-to-Background Ratios
A fourth method for the quantitative analysis of particles was developed by Small et al.
(1978) and Statham and Pawley (1978). This method, derived from work on biological
specimens by Hall (1968), is based on the following observation: To a rst approximation,
the ratio of a characteristic x-ray intensity to the continuum intensity of the same energy
for a at, innitely thick target is equivalent to the ratio from a particle or rough surface of
the same composition.
In the form of an equation, this observation can be expressed as
I
B
_ _
particle
I
B
_ _
bulk
115
where I is the background-corrected peak intensity and B is the continuum intensity for
the same energy window as the peak. It is assumed that the spatial distribution of char-
acteristic x-ray excitation is identical to the distribution for continuum x-ray excitation. As
a result, the eects of particle shape and size on measured x-ray intensity will be the same
for the continuum and the characteristic x-rays. It therefore follows that by taking the
ratio of the two intensities, the particle mass and absorption eects will cancel each other.
In the procedure developed by Small et al. (1978), Eq. (115) is rearranged and the
peak intensities for the particle or rough surface are scaled up to values similar to a bulk
material of the identical composition:
I
particle
I
bulk

I
particle
B
bulk
B
particle
116
The values of I
for each element in the unknown can then be used as input for a standard
quantitative analysis scheme. In practice, a bulk material will not exist for particle of
unknown composition and the value of B
bulk
at any given characteristic peak energy must
be estimated as part of the analysis scheme. In the procedure, B
bulk
is determined from
Eq. (117), and for each characteristic peak energy, it must be summed over all elements in
the unknown:
B
bulk

i
F
"
Z
bulk
F
"
Z
std
B
std
fw
bulk
fw
std
117
The F
"
Z terms describe the continuum intensity as a function of the concentration-
weighted average atomic number for the hypothetical bulk material and standards. For
the simplest case, Kramers relationship (Kramers, 1923), the rst part of Eq. (117) would
be
"
Z
bulk
=
"
Z
std
, where the current estimation of concentration from the iteration loop in the
ZAF procedure is used for the calculation of
"
Z
bulk
B
std
is the measured continuum in-
tensity for a given standard at the energy of the analyzed x-ray. For multielement stan-
dards, B
std
must be multiplied by the weight fraction of the element of interest. Once the
values for B
bulk
are determined, they can be used in Eq. (116) to obtain the rst estimates
for I
. A set of k ratios can then be calculated and used as input to the ZAF routine. The
set of concentrations from each iteration is used to calculate new values of B
bulk
and the
sequence is repeated until successive iterations agree within a predetermined limit.
Various mineral particles have been analyzed with the peak-to-background method,
FRAME P, (Small et al., 1979a). The results of these analyses are reported in Table 13
along with the result from the conventional ZAF routine, FRAME C (Myklebust et al.,
1979). In all cases, the analyses with the peak-to-background routine are within 10% and
usually better than 5% relative error of the stoichiometric values. In contrast, the errors
with the conventional ZAF routine range from 7.9% for S in ZnS to 47% for Mg and Si in
talc. In addition, standard deviations for individual measurements are less for the peak-to-
background routine than they are for the conventional ZAF routine.
In the analysis of particles, the assumption that the generation volumes for char-
acteristic and continuum x-rays are identical is only valid for particles larger than about
2 mm in diameter. Below this size, the anisotropic generation of the continuum results in a
signicantly dierent excitation volume for the continuum compared to the isotropically
generated characteristic x-rays (Albee and Ray, 1970). This eect is shown in Figure 66,
in which isotropic and anisotropic cross sections have been used to calculate peak-to-
background ratios from K-309 glass particles normalized to bulk glass. The composition
of K-309 is 7.9% Al, 18.7% Si, 10.7% Ca, 13.4% Ba, and 10.5% Fe. These plots show that
the introduction of an anisotropic cross section for the continuum results in signicantly
higher peak-to-background ratios for the smaller particles. As a result, it is necessary to
introduce a correction for anisotropic generation of the continuum for quantitative ana-
lysis with peak-to-background procedures.
In the peak-to-background method developed by Statham and Pawley (1978), the
peak-to-background ratio from a given element is compared to the ratio from a second
element:
C
a
C
b
f
ab
P=B
a
P=B
b
118
In this case, f
ab
is a correction factor that should have a minimal dependence on particle
size and can be calculated or determined empirically from standards. Table 14 lists the f
ab
Table13 Analysis of Mineral Particles by the Peak-to-Background Method
Talc (Mg
3
[Si
4
O
10
](OH)
2
)
Wt% Mg % Error
a
Wt% Si % Error
Nominal 19.3 29.8
Normalized FRAME C 19.4 0.5 29.7 0.3
PB FRAME P 18.5 4.0 29.7 0.3
FeS
2
Wt% S % Error Wt% Fe % Error
Nominal 53.4 46.6
PB FRAME P 52.9 0.9 46.4 0.4
ZnS
2
Wt% S % Error Wt% Fe % Error
Nominal 32.9 67.1
PB FRAME P 36.0 9.0 67.7 0.7
Note: The results are the average from seven analyses.
a
% Error {[(nom.calc.)]=nom.}6100.
Source: From Small, 1979a.
values for ve particles of K-961 glass, the composition of which is listed in Table 15.
These results show that the f
ab
values do not exhibit any noticeable trend with particle size
and the standard deviation of f
ab
is less than 8% relative for elements with a concentration
greater than 1 wt%. For the elements Mn and P, with concentrations less than 1%, the
standard deviation in f
ab
is small considering the relatively poor counting statistics.
Figure 66 Peak-to-background ratios from glass spheres normalized to bulk ratios showing the
effects of isotropic and anisotropic cross sections for continuum generation. (From Small, 1981.)
D. Analysis of Rough Surfaces
Results from the FRAME P analysis of rough surfaces show a similar improvements in
accuracy with the peak-to-background method compared to conventional ZAF. Table 16
lists the results of analyses on fracture surfaces of AuCu alloys and a Fe3.22% Si alloy.
A micrograph of one of the AuCu fracture surfaces is shown in Figure 67. The use of the
peak-to-background method for the analysis of rough surfaces can lead to signicant
improvement in accuracy and precision for the analysis of these types of samples.
V. SPATIALLYRESOLVEDX-RAYANALYSIS
A. xy Mapping
In spatially resolved x-ray analysis, the position of the electron beam on the sample is
couple to the output of an x-ray spectrometer. The x-ray spectrometer, in turn, is coupled
to the output of the display on a cathode-ray tube, photographic plate, or computer
memory such that when the beam is interrogating a point on the sample, the output from
x-ray spectrometer is displayed or stored at the corresponding point on the storage
medium. In this way, multiple analyses can be taken on a sample and the spatial
Table14 f
ab
Values for K-961 Microspheres
a
Diameter (mm) Mg Al Si P K Ca Ti Mn Fe
2 1 1.24 1.74 1.72 2.43 3.12 3.01 3.77 3.06
3 1 1.36 1.68 1.57 2.44 3.46 3.13 2.56 2.90
4 1 1.30 1.66 1.95 2.63 3.36 3.16 3.29 3.21
6 1 1.48 1.83 1.43 2.96 3.56 3.14 3.81 3.06
9 1 1.27 1.51 1.74 2.72 3.17 3.06 3.28 3.33
Ave. 1 1.33 1.69 1.68 2.64 3.33 3.10 3.34 3.11
s (%) 0 6.8 7.1 12. 8.3 5.7 2.2 15. 5.1
a
Na was not included in the results because of poor statistics and high ion mobility.
Source: From Statham and Pawsley, 1978.
Table15 Nominal Composition of Glass K-961
Element Wt%
Na 2.97
Mg 3.02
Al 5.82
Si 29.9
P 0.22
K 2.49
Ca 3.57
Ti 1.20
Mn 0.32
Fe 3.50
Table16 FRAME P Analysis of Fracture Surfaces
Actual
(wt%)
FRAME C (wt%)
(normalized) Rel. error
FRAME P
(wt %) Rel. error
SRM 482, 60% Au40% Cu
Location 1
Au 60.3 49.6 18 58.0 4
Cu 39.6 50.4 27 44.0 11
Location 2
Au 29.1 52 52.0 14
Cu 70.8 79 41.0 3.5
SRM 482,80% Au20%Cu
Location 1
Au 80.1 73.8 8 76.9 4
Cu 19.8 26.2 32 19.1 3.5
Location 2
Au 69.3 13 76.7 4.2
Cu 30.6 55 20.1 1.5
SRM 483, Fe3.22% Si
Location 1
Fe 96.8 97.0 0.2 100.0 3.3
Si 3.22 2.9 8.2 3.2 0.3
Location 2
Fe 96.4 0.4 97.7 0.9
Si 3.6 11 3.5 7.4
Source: From Small et al., 1979b.
Figure 67 Secondary electron image of a fracture surface of Standard Reference Material 482.
(From Small, 1979b.)
relationship between each analysis location is retained. The analyst can then manipulate
the stored data and construct an image of the sample based on its elemental composition.
One of the earliest methods of obtaining spatially resolved analysis was to deect the
analog scan of electron beam in a single direction, usually x, across the specimen surface
and simultaneously record and display the output from a WDS x-ray spectrometer on a
CRT. In this way, a line prole for the intensity of a chosen element can be overlaid on an
image of the sample. An example is shown in Figure 68.
The rst method of x-ray analysis to display elemental information in both the x and
y directions was the x-ray dot map or x-ray area scan (Cosslett and Duncumb, 1956).
Initially, this procedure, like the line scan, made use of the analog scan of the electron
beam. As the beam was scanned slowly over the sample, the x-ray intensity of a given
element as determined by a spectrometer was compared to a preselected threshold value. If
the x-ray counts are above the threshold value, then a signal is sent to the recording CRT
on the instrument, which records a full intensity spot at that location. The entire sample
area selected by the instruments magnication is scanned in this manner and the resulting
x-ray dot map is constructed. Figure 69 shows the result of such an analysis of grain-
boundary migration of Zn in a ZnCu system. In this procedure, only the presence or
absence of a given element, as determined by the preselected thereshold value can be
displayed, Minimal information is provided that reects the amount or concentration of
that element present. In addition to displaying black and white maps, the analyst could
produce color overlays of up to three dierent elements by separately photographing the
dot maps using red, green, and blue lters.
Most instruments are now equipped with digital beam control, where the electron
beam is deected such that it interrogates the sample in two-dimensional array consisting
of n6n spot analyses, where n is usually 16512 for x-ray mapping. In an instrument with
stage control, the electron beam can be static and the stage stepped in the array pattern.
Each beam or stage position in the two-dimensional array corresponds to a pixel on a map
Figure 68 Line profile of SKa x-ray intensity overlain on a target current image of a specimen
from a failed pressure vessel.
of the specimen. By storing WDS or EDS spectra at each position, the analyst can obtain a
full quantitative analysis at each pixel. Once the results from the analyses are stored in the
array, the variations in elemental compositions can be coupled to the gray-scale or color
output of a computer monitor. The completed array of pixels provides the analyst with a
spatially resolved map of the elemental composition across the specimen. In addition,
because the array is stored in the computer, the analytical information can be
postprocessed in several ways. For example, a row of pixels can be selected providing the
analysts with elemental x-ray line proles across the sample in any direction or pattern
desired. This information can be displayed as a simple line plot or can be used to construct
contour maps of a given x-ray distribution.
The uncertainty associated with a quantitative analysis obtained for compositional
mapping is essentially identical to the uncertainty associated with a conventional analysis
obtained at the same electron dose. For maps where high accuracy is required on minor
constituents, the dwell time per pixel and=or beam current must be suciently large to
provide the appropriate x-ray intensity in the peak of interest. Compositional maps under
these circumstances may require several hours to accumulate and care must be taken to
ensure instrument stability over the required time interval.
As previously mentioned, both EDS and WDS analysis systems can be used for
compositional mapping. WDS detection of x-rays, however, is superior to EDS detection
for compositional mapping, particularly for samples requiring the analysis of con-
stituents at the minor and trace levels (Marinenko et al., 1987). One of the most im-
portant advantages of WDS detection is that the pulse processing time for WDS is at
least an order of magnitude shorter than EDS. WDS detectors have a limiting count rate
Figure69 X-ray dot map of a grain-boundary migration in a ZnCu system. (From Piccone et al.,
1982.)
of about 10
5
counts per second (cps) compared with a limiting count rate of 10
4
for EDS
detectors operating at maximum resolution. In addition, the WDS systems use dirac-
tion crystals so that only a narrow energy band of x-rays are detected at any given time.
The energy is adjustable so that most of these counts are the characteristic counts from
the element of interest. This count rate compares to a limiting rate of about 10
2
10
3
cps
in the peak of interest on an EDS detector because the limiting count rate of 10
4
is
distributed over the entire energy range of the spectrum.
In addition to its higher limiting count rate, the WDS detector has a factor of 10
higher peak to background ratio than the EDS detector. Taking into account the higher
limiting count rate and peak-to-background ratio of the WDS detector, the WDS detector
has a lower detection limit of about 100 ppm compared to a lower limit of 1% or greater
for mapping on the EDS system.
One limitation of the WDS system compared to EDS systems is in the mapping of
samples which contain a large number of elements of interest. In WDS systems, the
number of elements mapped during a given digital scan is limited to the number of WDS
spectrometers. Typically, in EDS systems, all elements, with characteristic x-ray energies
above about 1 keV can be detected simultaneously.
Two important aspects that must be considered in the interpretation of composi-
tional maps are the counting statistics and resulting uncertainties associated with the
various point analyses at each pixel location. Under normal mapping conditions, it is
impractical to obtain the level of accuracy associated with conventional probe analysis
where 100 s or more are used for data accumulation.
Marinenko et al. (1987) have shown that for a 1286128 map at a magnication
below 5006, each pixel represents an area of about 2 mm in diameter on the specimen
surface. This means that the spot size of the beam can be on the order of 1 mm in diameter
and carry a current of about 1 mA. At this current density, the limiting count rate of 10
5
cps can be obtained on pure-element samples. Assuming a dwell time per pixel of 0.1 s,
a 1286128 map would require 1600 s to accumulate and have 10
4
counts per pixel. From
Poisson statistics, the 1s counting uncertainty per pixel is 1%. In the case where mulite-
lement standards are required, the dwell time per pixel must be increased to obtain the
same counting statistics, as each element is present at less than 100%. In general, dwell
times of about 0.4 s are sucient for multielement standards and require less than 2 h per
1286128 map. As in conventional analyses, the standard maps can be archived and used
indenitely, provided the instrument conditions are constant.
In the analysis of samples where one or more of the constituents are at the minor
or trace level (1% or less by weight), digital maps may require 10 h or more to ac-
cumulate. A 10-h scan on a 1286128 map translates to 2 s dwell time per pixel. If the
element of interest is at the 1% level by weight, then the x-ray intensity in the peak
would be 2000 counts, assuming a limiting count rate of 10
5
cps as stated above. The
associated counting uncertainty is 2.2% for 1s. The actual uncertainty will be larger
than this due to uctuations in the intensity of the x-ray background, which must be
taken into account for quantitative analysis. In general, it should be possible to obtain
2s condence intervals of 10% or better for constituents at the 1% weight con-
centration in an unknown sample.
The power of compositional mapping can be seen in Figure 70, which is a compo-
sitional map of the same Zn grain-boundary migration shown in Figure 69. The brighter
areas on the map correspond to a Zn concentration of 10% by weight. The faint band
extending to the left in the bottom of Figure 70 corresponds to a Zn concentration as low
as 0.2% by weight.
One of the major diculties in obtaining quantitative x-ray maps with crystal
spectrometers is the defocusing of the diraction crystal as the electron beam is moved o
the crystal axis. The magnitude of the defocusing eect is proportional to the distance the
beam is from a point centered on the optical focus of the electron probe. The defocusing is
most severe at the low magnications of 2008006 routinely used in digital x-ray maps.
Corrections for the defocusing fall into four categories, (Marinenko et al., 1987).
The rst method to avoid spectrometer defocusing is to employ, as mentioned above,
the digital movement in the microscope stage rather than the electron beam. In this si-
tuation, the electron beam position remains static at the optical focus of the diraction
crystal and the sample is moved in a raster pattern under the beam. For WDS mapping, it
is critical that the sample remains at the focus of the optical microscope during the xy
movement of the stage. This procedure has been used successfully by Mayr and Angeli
(1985). The success of this method, since it involves the mechanical movement of the stage,
is dependent on the reproducibility of the stage motion. If the reproducibility of the stage
movement is poor, then the accuracy of the quantitative maps will be poor except for
extremely low magnications. In the more modern instruments, which have optical en-
coding and a guaranteed stage positioning of 0.1 mm, the results from moving the stage will
be comparable to the other corrections methods.
The second method used to correct for spectrometer defocusing is to move or rock the
diraction crystal in synchronization with the raster of the electron beam, (Heinrich, 1981e).
By slightly rocking the crystal, the entire sample area under study will be maintained at the
focus of the x-ray crystal. The problems associated with crystal rocking are similar to those
involving stage motion. Because beamrocking requires mechanical movement of the crystal,
the results are dependent on the reproducibility of the crystal rocking mechanism. This
procedure has been described for multiple spectrometer by Swyt and Fiori (1986).
The third correction method is to collect a series of standard maps in conjunction
with the collection of a map from an unknown. If the standard and the unknown are
Figure 70 Compositional map of the same Zn grain-boundary migration shown in Figure 69.
(From Piccone et al., 1982.)
collected under the same experimental conditions, then the standard maps can be used to
construct k ratios at each pixel location, thus normalizing out the eects of spectrometer
defocusing. Although this method does not require any mechanical movement, it does
require that the instrument remain stable over the period of time necessary to collect all
the maps from the standards and unknown. This is particularly important because a
pixel-by-pixel comparison of the unknown to the standard is made which requires a
constant crystal orientation with respect to the beam raster. Unless great care is taken
during an analysis, the use of archival standard maps is not recommended because of the
possibility of introducing large errors as a result of spectrometer drift. This procedure
was used by Marinenko et al. (1987) for the analysis of the AuAg standard reference
material 481 with the results shown in Figures 71 and 72. Figure 71 presents the un-
corrected maps from the alloys and the pure-silver standard, which show the char-
acteristic banding from the defocusing of the spectrometers. Figure 72 contains the pure-
silver map and the subsequent alloy maps that have been corrected for defocusing by
normalization to the standard map. The normalized maps show very little gradation or
structure in the image gray levels indicating the artifacts from defocusing have been
removed. Table 17 contains a comparison of the average composition obtained from the
digital map and the results from a conventional point analysis. In all cases, the average
composition from each map compares quite well with the conventional point analysis as
well as with the NIST certied values (Marinenko et al., 1987).
The fourth method used is to model the spectrometer defocusing. Marinenko et al.
(1988) observed that the defocusing artifacts (i.e., banding) were equivalent to an intensity
prole from a wavelength scan across the elemental peak of interest. This is shown in
Figure 73, which compares a wavelength line scan across the CrKa
1,2
peaks to a line prole
taken from a Cr map perpendicular to the defocusing bands. The similarity of these two
traces implies that the intensity can be measured in the center band of a map and, from a
Figure 71 Elemental maps from AuAg alloys showing the effects of spectrometer defocusing
(upper left) pure Ag, (upper right) Au20Ag80, (lower left) Au60Ag40, and (lower right) Au80
Ag20. The analytical line is AgLa. (From Marinenko et al., 1987.)
model of the line prole, the intensity at any other pixel location can be calculated. This
procedure eliminates the need for measuring a standard map and greatly reduces the time
required for obtaining a quantitative x-ray map.
Figure 74 is a schematic showing the relationship between the x-rays emitted from a
defocused point on the sample and the corresponding angular deviation from the line of
focus for a vertical crystal spectrometer. The electron probe is designed such that the
maximum x-ray intensity obtained on a crystal corresponds to the point A in Figure 74,
which is centered on the electron optic axis with the aid of an optical microscope. The
distance between point A and the crystal, S
0
, is
S
0
2R sin y 119
Figure 72 Elemental maps, corresponding to those in Figure 72, corrected for spectrometer defo-
cusing by normalization to a standard map. (From Marinenko et al., 1987.)
Table17 Quantitative Analysis of GoldSilver Alloys, SRM 481
Alloy Element line Certied value Point beam analysis
a
Digital mapping
Au20Ag80 AgL 77.58 77.33 (0.4%)
b
77.63
AuM 22.43 21.93 (2.6%) 20.81
AuL 22.43 22.69 (2.3%) 22.94
Au60Ag40 AgL 39.92 39.44 (0.5%) 39.96
AuM 60.05 59.59 (2.4%) 57.59
AuL 60.05 61.26 (2.3%) 60.87
Au80Ag20 AgL 19.93 19.59 (0.6%) 19.72
AuM 80.05 80.56 (2.5%) 77.26
AuL 80.05 81.09 (2.0%) 80.30
Note: Concentration are in weight %.
a
Excitation potential 20 kV, Faraday cup current 38 nA, point beam, ve randomly selected samplings
averaged for each alloy.
b
One relative standard deviation of a single measurement is in parentheses.
where R is the spectrometer radius and y is the Bragg angle. At a defocused point, point B,
which is a distance DS from the optic axis, the angular deviation from the exact Bragg
angle is Dy. Given that Dy is small, less than about 0.01 radians, which is the case for most
mapping applications, it can be approximated as
Dy sin Dy
DS
0
S
0
120
where DS
0
DSsin C for a vertical spectrometer and C is the x-ray takeo angle for the
electron probe.
Figure 73 Comparison of a WDS line scan across the CrKa peak to a line profile taken from a Cr
map perpendicular to the defocusing bands of the spectrometer. (A) Line scan across the CrKa peak
with a LiF crystal; (B) CrKa intensity profile from the compositional map, taken along a series of
pixels perpendicular to the maximum intensity band. (From Marinenko et al., 1980.)
In calculating the background value for a given pixel in the compositional map, it is
necessary to determine DS, which is the distance of the pixel from the maximum focus line
of the spectrometer. The orientation and equation of the line of maximum focus for a
given spectrometer can be dened by the coordinates of two pixel points [i.e., (x
1
; y
1
) and
x
2
; y
2
] which lie on the line. The orientation of the line can be determined from any raw
intensity map by increasing the image theshold as shown in Figure 75. The line has the
general form Ax By C 0 and it follows that DS for any pixel point, represented by
coordinates x
3
; y
3
, in the x-ray map can calculated from
DS
Dx
3
Y
3
E
D
2
1
1=2
121
where D y
2
y
1
=x
2
x
1
and E y
1
Dx
1
.
DS is positive for points located above the line of focus and negative for points below
the line of focus. DS as dened in Eq. (120) is dened in units of pixel elements which must
be converted to centimeters in order to obtain the linear distances for the calculation of Ds.
Figure 74 Relationship between the x-rays emitted from a defocused point on the sample and the
corresponding angular deviation from the line of focus for a vertical crystal spectrometer. (From
Marinenko et al., 1988.)
Figure 75 Line of maximum x-ray intensity on a crystal spectrometer determined by increasing
the image threshold. The threshold is low in the top image and high in the bottom image. (From
Marinenko et al., 1988.)
For this purpose, the scaling factor F is used, which is dened in terms of the magnication
M, the linear dimension of the CRT display L, and the number of pixel points in the
matrix N:
F
L
MN
122
Dy can then be expressed as
Dy Ds
0
F
S
0
_ _
123
The accuracy of this procedure is demonstrated in Figure 76. Figure 76A is an experi-
mentally measured intensity prole taken perpendicular to the focal axis and Figure 76B is
the modeled prole along the same axis. The intensity proles shown together in
Figure 76C are identical within the limitations of the experiment.
The use of standard maps or modeling to characterize spectrometer defocusing is
magnication limited. At magnications of about 1506 or less the deviation in intensity
from the edge to the center of a map is about a factor of 2 and cannot be accurately
Figure 76 Comparison of experimental and modeled x-ray intensity profiles for TiKa x-ray:
(A) Experimental x-ray profile for TiKa overlain on the corresponding Ti map; (B) modeled intensity
profile; (C) profiles from (A) and (B) together. (From Marinenko et al., 1988.)
3
Figure 77 Diagram describing the CCH.
corrected by these methods. For very low-magnication maps where quantitative results
are important, stage mapping or crystal rocking are preferred.
Recently, Mott et al. (1995) have developed a form of spectral imaging that couples
the measurement, by EDS, of x-ray photons emitted from a sample with the xy position
of the electron beam. Unlike conventional mapping techniques, where the electron beam is
stepped relatively slowly from point to point and the full data collected for each point, this
mapping procedure, known as Position-Tagged spectrometry, operates under digital
beam control with the beam rastered at a rapid scan speed. The result is the real-time
Figure 78 Compositional maps for an aligned CuTi eutectic: (A) Cu map; (B) Ti map. (From
Bright et al., 1988.)
collection of elemental images from preselected energy regions of interest, a frame-aver-
aged electron image, and x-ray spectra from preselected areas (i.e., phases) of the sample
where the spectrum is a summation of the spectra from all pixels within the area. The
spectrum image is compressed and streamed in real time to disk storage. At the completion
of the Positioned-Tagged Spectrometry (PTS) run, the spectrum image consists of
complete x-ray spectra for each pixel in the digital image. This enables the analyst to
construct additional elemental maps, or spectra as needed from the stored spectrum image.
In addition, the spectra for a given image can be processed by an appropriate quantitative
routine to obtain elemental concentration maps. It is important to note that the statistical
considerations for PTS compositional mapping are the same as those mentioned pre-
viously in this section and the time requirements for high-quality compositional maps will
be similar to those mentioned above.
B. Composition^Composition Histograms
The nal aspect of electron-probe analysis that will be considered is compositioncom-
position histograms. Compositional maps provide the analyst with a visual method of
interpreting the results from the elemental analysis of some 4000 individual points on a
sample (Prutton et al., 1987, Browning, 1987, Bright et al., 1988). By associating color and
intensity, the analyst is able to spatially relate the various elements and their compositions
within the analyzed region of the sample. One problem in the interpretation of compo-
sitional maps is that it is often dicult to visualize the compositional ranges and resulting
interelement correlations from a color composite image, particularly in the case of minor
or trace constituents. An alternative method of displaying the analytical information is in
the form of a compositioncomposition histogram (CCH) (Bright et al., 1988). The CCH
provides the analyst with an image that can be used to interpret the numerical relation-
ships among the various components in the sample.
Figure 77 is a schematic diagram describing the CCH. The concentration of element
a at each pixel in the compositional map of a, is associated with the corresponding pixel
Figure 79 CCH for the CuTi aligned eutectic shown in Figure 78. (From Bright et al., 1988.)
and concentration of element b in the map of b. This is represented by the top two blocks
in Figure 77. The associated concentrations for a and b at each pixel in the compositional
image are then plotted in the CCH, bottom block, as a single point in a scatter diagram.
Associations between elements are visible in the CCH as features, such as lines or areas,
which have a detectable density of points above background. In addition, the overlapping
of multiple-image pixels at one CCH point can be coupled to the intensity of the recording
CRT and displayed in an appropriate gray-level or color scale.
Figure 80 CCH and corresponding map areas for the high-Cu region of the eutectic: (A) outline
of the high-Cu region of the CCH; (B) pixels in the compositional map that correspond to the out-
lined area of the CCH. (From Bright et al., 1988.)
An example of the type of information conveyed by the CCH is shown in Figure
78A, 78B, and 79, which are the elemental maps and the CCH for an aligned CuTi eu-
tectic alloy. The CCH (Fig. 79) shows two lobes that have a high density of pixels and
correspond to the two dierent phases of the alloy (Bright et al., 1998). In addition to the
two lobes in Figure 79, there is a distribution of points between the lobes which has a
lower pixel density compared to the density in the lobes.
Figure 81 CCH and corresponding map areas for the region of the eutectic containing both Cu
and Ti: (A) outline of the connecting pixels between the high-Cu and high-Ti lobes; (B) pixels in
the compositional map that correspond to the outlined area of the CCH. (From Bright et al., 1988.)
A useful feature of the CCH is the ability to relate a given region or feature on the
CCH to the corresponding pixels in the compositional map. An example of this back
trace capability is shown in Figure 80 where the high-Cu lobe of the CCH is outlined
in Figure 80A and the corresponding pixels in the compositional map are highlighted as
the bright areas in Figure 80B. Applying the back trace method to the points between
the lobes (Fig. 81) allows the analyst to determine readily that the connecting line
between the two lobes corresponds to the boundary regions between the Ti and Cu
phases.
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14
Sample Preparation for X-ray Fluorescence
Martina Schmeling
Loyola University Chicago, Chicago, Illinois
Rene E. Van Grieken
I. INTRODUCTION
The preparation of samples presents, for any analytical method, one of the most important
steps for a reliable analysis. It is critical with regard to errors, but better precision as well
as lower detection limits can also be achieved by suitable sample pretreatment. The X-ray
uorescence (XRF) techniques [energy-dispersive XRF (EDXRF) and wavelength dis-
persive XRF (WDXRF)] allow the analysis of almost all types of sample with usually less
eort of sample preparation. However, for some materials, the sample preparation step is
even more time-consuming than the analysis itself; therefore, suitable procedures should
be developed and introduced, leading to reliable results.
Usually, the specimens are presented to the XRF spectrometer as solids, powders,
briquettes, fusion products, liquids, or lms, and for most of them, the pretreatment can
be kept to a minimum. Especially for metallic specimen, liquids and atmospheric particles
need only small eort. If required, possible sample preparation steps may include simple
procedures like cutting, grinding, milling, and mixing, or a combination of them. The
preparation step may also involve a conversion from the present state of the sample into
another one in order to receive a homogenous sample. It is important that the treatment
must be practicable for both samples and standards.
Metals and metallic alloys often need only to be polished to obtain a suitable surface
for analysis. Liquid samples, containing high enough concentrations for a direct analysis,
can be transferred into special cups or pipetted onto a surface target and dried to obtain a
thin lm. Atmospheric particles, collected onto lters, need practically no sample pre-
treatment. However, if sample preparation is required, as for geological and/or in-
homogeneous samples, the procedure should be fast and reproducible, require small eort,
and avoid contaminations. A consultation of the literature is very important before the
application of special sample preparation procedures because usually the problem oc-
curred already earlier and some proposals or possible solutions can be found. Extensive
sample preparation should always be avoided because with each additional step, the risk
of losses and contaminations increases.
A more extensive sample preparation is necessary when the sample is very in-
homogeneous, the surface layer is not representative for the whole sample, the average
particle size or the particle size distribution varies among the samples, and the amount of
porosity or pore size varies among samples.
As a condition for a reliable analysis by XRF, a at and even surface of the specimen is
required. Particularly for the determination of light elements, the surface should be prepared
mirrorlike, as scattering eects due to a rough texture inuence the results. An appropriate
surface can be normally obtained by polishing, melting, or fusion of the samples.
If absorption-enhancement eects are severe, an internal standard or a masking
agent must be added. Sometimes, it is also necessary to dilute the sample for the reduction
of such eects. For liquid samples with a low trace element amount, preconcentration or
tracematrix separation might yield satisfying results.
A rare application is still the analysis of gaseous samples. Kno chel et al. (1983) used
synchrotron-radiation XRF (SRXRF) for the determination of nitrogen in the presence of
small amounts of xenon. Special cups were designed for this purpose and the results were
quite promising. Therefore, it is surprising that this technique is not more frequently used
for the determination of elements in gases.
In the following section, the most common techniques of sample preparation are
discussed, with emphasis on more recent applications and developments. Sample pre-
paration for special techniques, like SRXRF, total-reection XRF (TXRF), photon-in-
duced x-ray emission (PIXE), and electron-probe microanalysis (EPMA), is only briey
mentioned in some cases, because in earlier chapters of this book, extensive relevant
discussions have already been given. It should be mentioned that several classical books
about XRF include chapters about conventional sample preparation procedures (Bertin,
1970; Bertin 1798; Jenkins et al., 1981; Tertian and Claisse, 1982; Jenkins, 1988; Injuk and
Van Grieken, 2000) and, recently, an entire book was dedicated to practical sample pre-
paration in XRF and x-ray diraction (Buhrke et al., 1998).
II. SOLIDSAMPLES
X-ray uorescence is a traditional analytical method for the analysis of solid samples.
They may be presented to the spectrometer as such, as powders, as briquettes, or as
fusion products. In principle, it is possible to determine the bulk composition of solid
samples directly if the element distribution inside the solid specimen is homogeneous in
all three dimensions and the specimen shows a satisfying at surface without scratches
and striations. Often such samples need only to be polished at the surface with suitable
abrasive materials and to be cut into the appropriate size for the sample holder of the
spectrometer. If the sample is too small for the sample holder, the positioning might be
critical, and it is useful to prepare a wax mold that ts into the holder. Such a mold
permits a series of samples and standards and can be replaced reproducibly. This tech-
nique especially allows the analysis of small manufactured parts (Bertin, 1970). Often
solid samples to be analyzed show surface roughness and=or damages, which cause
problems due to absorption eects. Such specimens must be nished at the surface before
analysis in order to reduce these damages. Several dierent techniques are available for
nishing a sample surface. The most common and eective one is mechanical polishing
with special abrasives like Al
2
O
3
or SiC, or with coarse and ne abrasive paper. A nal
nish of $100 mm surface roughness for short x-ray wavelengths and down to 10 mm for
long wavelengths may be satisfactory for a reliable analysis. Other polishing techniques
are electropolishing or etching. However, these are not as universal as mechanical pol-
ishing because the sample might be destroyed or the surface composition changed.
A. Metallic Specimens
X-ray uorescence is one of the most common techniques for the analysis of samples in
the metal production and, therefore, the preparation of such a specimen should be fast,
simple, and reproducible. Usually, the metallic specimens are prepared as solid disks by
conventional methods like cutting and milling. Hard alloys can be ground and pelletized
prior to analysis. However, for most metallic samples, it is required to polish the surface
in order to avoid striations, which give rise to the so-called shielding eects (Jenkins and
Hurley, 1965; Mu ller, 1972). For a reliable analysis, the surface roughness should not
exceed the path length at which 10% absorption on the radiation will occur (Jenkins
et al. 1981). In Table 1, some 10% absorption path lengths (presented as x
90%
in the
table) for common analytical situations of metallic specimens are indicated. For mea-
surements at short wavelength, a nal nish of $100 mm might be satisfactory, which can
easily be reached with abrasive paper or diamond paste. If light elements are determined,
a 1050-mm surface roughness should be claimed and ne abrasives are required to
obtain an almost mirrorlike surface. Striations, even after polishing, cause a reduction of
the uorescence intensities, which is more serious for long wavelengths than for short
ones (Bertin, 1978; Tertian and Claisse, 1982).
Another aspect which should be taken into account is the orientation of the speci-
men inside the spectrometer. By simple rotating of the sample with 45
or 90
in the
spectrometer and repetitive measurements, the grooves decrease the uorescence intensity
more when oriented in the perpendicular direction to the incident beam than in the parallel
direction. In Figure 1, a plot of the uorescent intensity versus the groove size for Al, Fe,
Cu, Pb, and Mo is presented (Mu ller, 1972). Also, here it is obvious that the reduction of
the uorescence intensity is much more severe for elements with low Z numbers. However,
today, most spectrometers are provided with a spinning mechanism, which averages this
eect. For a spectrometer without a spinning mechanism, the sample should be placed in
such a way that the grooves appear parallel to the incident radiation in order to minimize
the eect. Several mathematical models have been developed to determine the relationship
between surface roughness and emergent analyte line intensity (Berry et al., 1969; Mu ller,
1972).
However, simple mechanical polishing is not always possible or even advisable.
Particularly, when such elements as Si, Al, or Fe are to be determined, it is sometimes
dicult to nd a suitable abrasive which does not contain one of these elements and does
not introduce contaminations into the sample. SiC and Al
2
O
3
, for instance, are very
Table1 Mass Absorption Coefcients and 90% Transmission Path Lengths for Some Elements
Measured
radiation
Matrix
composition
m-Matrix
(cm
2
=g)
r
(g=cm
3
)
x
90%
(mm)
MgKa Fe 5430 7.87 0.02
TiKa Cr 144 7.19 1.02
CuKa Al 50 2.70 7.7
CuKa U 306 18.7 0.18
ZrKa U 57 18.7 0.98
common and eective abrasives, but both contain elements of high analytical interest. In
such cases, electrolytic polishing or etching might be more useful. When the surface of the
specimen is too rough (e.g., in the case of turnings) and suitable polishing and milling is
not practicable, the samples can be prepared properly by pressing them into pellets with a
hydraulic press at several hundreds of mega Pascals. With such a procedure, most of the
turning are compacted into satisfactory smooth surfaces.
If the sample is composed of soft, malleable multiphase alloys, smearing eects of
softer components like Pb or Al cause problems. The soft elements will be enriched onto
the surface and the uorescent intensities of the softer phases increase, whereas those of
the harder ones decrease (Tertian and Claisse, 1982). In such cases, the sample should be
nished by electrolytical polishing or etching, instead of mechanical polishing.
In the case of metallic specimens with irregular shape, it is possible to embed the
piece in a special wax resin (e.g., acrylic resin and methyl acrylic resin). The resulting block
can be polished and ground to appropriate surface smoothness with abrasives like SiC and
diamond paste before analysis (Wybenga, 1979).
If the surface of the sample is not representative for the bulk composition, due to
heterogeneity, corrosion, smearing, and so forth, it is necessary to treat the sample in
dierent ways. Bronze alloys can be prepared, for example, by etching with a solution of
alcoholic ferric chloride (120 mL C
2
H
5
OH, 30 mL HCl, and 10 g FeCl
3
), and brass alloys
by a solution of aqueous ammonium persulfate [100 mL H
2
O and 10 g (NH
4
)
2
S
2
O
8
]. For
archeological objects, however, it is not recommended to treat them by etching because
many inclusions could be dissolved and lost.
Another possibility is the complete decomposition or dissolution of the sample.
However, such a radical method of sample preparation should only be carried out when
other, less aggressive preparation techniques are not suitable for obtaining satisfactory
results. It should always be taken into account that a digestion or dissolution step con-
tributes an additional source of contaminations or losses and is quite time-consuming
(Tscho pel et al., 1980). The procedure and the necessary reagents must be carefully se-
lected in order to get the highest benet. An eective and common method is the digestion
Figure1 Change in relative fluorescent intensity of massive samples as a function of groove size a
for different elements, calculated for pure elements. (From Ref. 8. Reprinted by permission of
A. Hilger, Ltd.)
of the sample with aqua regia (HCl:HNO
3
, 3:1). Most of the alloys and metals, even Pd
and Pt, can be attacked by this reagent. The strength of this combination is based on the
formation of chloro complexes during the reaction and to the catalytic eect of Cl
2
and
NOCl. The eectiveness can be improved additionally when the solution is allowed to
stand for 1020 min before heating to 60
C. So-called inverted aqua regia (HNO

3
:HCl,
3:1) is an eective combination to oxidize sulfur- and pyrite-containing samples.
Another agressive decomposition reagens is the combination of HNO
3
=HF. Here,
the complexing eect of the uoride ion is utilized and, with this combination Si, Nb, Ta,
Zr, Hf, W, Ti, NbSn alloys, FeNb, AlCr alloys, FeSi, FeZr, CuSi alloys, FeP, FeW, as
well as AlSi and CaSi alloys can be dissolved. Table 2 shows some possible combina-
tions and their applications (Bock, 1979).
For the determination of traces in Nb, Mo, W, Ti, and Ta, Eddy and Balaes (1988)
dissolved the metallic samples in HF=HNO
3
, and extracted the Ta by reversed-phase
extraction chromatography using tributyl phosphate. They pipetted the sample solution
either directly onto a lter paper or coprecipitated the trace elements with In. The de-
tection limits were between 0.05 and 0.7 mg, depending on the element to be determined.
Semiconductors as well as PbTe and GeTe can be destroyed by a combination of con-
centrated HNO
3
and 10% sodium oxalate solution (1:2) (Fano and Zanotti, 1974).
However, some elements may be lost by application of a digestion step. Especially
elements like Se, Hg, and Sn form volatile components with various kinds of acid and their
combinations. Samples treated with hot mixtures of HNO
3
=HF=HClO
4
for example, lose Se
and Cr completely, and Hg, As, Ge, Te, Re, Os, and Ru showparticular losses (To lg, 1962).
HCl alone is often not aggressive enough to attack metals and metallic alloys but
might show satisfactory results in some cases. For the determination of Cu in W alloys, the
samples are dissolved with 50% HCl, and the solution decanted from the undissolved W
powder. The undissolved W is washed with water, and both, the received solution and the
wash, are combined, diluted, and adsorbed on a piece of lter paper. Subsequently, the
dried lter is presented to the instrument (Ning and Zhao, 1995).
Sometimes, less common dissolution reagents are useful in XRF. Trace levels of Zr,
Mo, Hf, and W in Ta metal can be determined after removal of the matrix elements with
diantipyrylmethane and collection of the impurity elements onto ion-exchange paper
(Knote and Krivan, 1982). For the determination of Co in Fe, Kato (1990) dissolved the
sample with acid peroxide, mixed it with citrate, and percipitated Co from the solution of
pH 7.0 with 2-nitroso-1-naphthol.
Table 2 Some Examples of Dissolution Reagents and Their Applications
Reagents Reaction Attacked elements
Non-attacked
elements
HNO
3
Oxidation Cu, Ag, Bi, Tl, Te,
Pb, Hg, Cd, V, U, alloys
Au, Pt metals, Al, B, Cr, In,
Nb, Ta, Th, Ti, Zr, Hf
HNO
3
=HCl (1:3) Oxidation with
complexation
Au, Pt, Pd, Mo,
stainless steel, most alloys
Rh, In, Ru, Ti
HNO
3
=HF Oxidation with
complexation
Nb, Ta, Mo, W, Ti, Sn, Sb,
Si, Zr, Hf, Fe-alloy steel,
Fe alloys
HCl Solution Au, Pt metals
Other techniques are the extraction of elements from the metallic compound.
Lobanov et al. (1991) extracted Al from Cu-, Ni-, and Zn-based alloys with C
17
C
20
carboxylic acids. An almost complete extraction of Al (99%) at 6080
C was obtained.
Another, relatively new technique, is the remelting of the sample (Coedo and Dor-
ado, 1994; Coedo et al., 1994; Cobo et al., 1995). This method is particularly useful for the
determination of Cr in Mo- and Nb-ferroalloys. Such alloys are not suitable for direct
analysis by XRF, due to their inhomogenity and brittleness. With application of the re-
melting technique, the original ferroalloy is ground to grain sizes of 2 mm with a steel disk
mill, followed by a W mill, after previously crushing with a jaw beaker. Subsequently the
grained particles are mixed fairly with a portion of pure Fe (15 g FeMo alloy 25 g pure
Fe, and 12 g FeNb alloy 28 g pure Fe) and this nal mixture is melted inside an induction
furnace. Afterward, the melted metal is centrifuged and cast in an appropriate mold prior
to analysis. Calibration samples can easily be obtained in the same way.
The analysis of semiconductors is mainly carried out by TXRF or SRXRF; however,
there is also an interesting way to apply XRF for the determination of Ni in Si wafers.
Bubert et al. (1991) measured the Ni implantation of the wafers directly by XRF, but the
calibration standards were prepared in an unconventional way by spiking the gelatin-
containing Ni standard on parts of the Si wafer. The XRF analysis was performed after
drying of the sample.
B. Powdered Specimens
A common technique for geological, industrial, and biological materials is the preparation
of powders and pellets. Powdered specimens are prepared when the original sample is too
heterogeneous for a direct analysis or too brittle to form self-supporting disks or when a
suitable surface nishing is not possible.
Powders can be derived from dierent materials: solids like minerals, rocks, ores,
slags, and so forth, metal llings, metal oxides, precipitates, and residues from solutions,
ground fusion products, ion-exchange resins, and ashed or freeze-dried biological mate-
rials. Some of the materials are already available as powders, but most of them must be
pulverized by crushing, grinding, and milling. The powders are presented to the spectro-
meter directly as loose powders, packed in cells or spread out on lm materials like
Mylar
1
or other foils and as pellets or briquettes. Sometimes, fusions (see Sec. III) of the
powdered material may be a more suitable alternative, especially when particle size eects
are severe and need to be overcome. However, the preparation of a powdered sample
requires much less time than the preparation by using a fusion technique.
The analysis of a powdered specimen shows several advantages over bulk materials:
Powdered samples allow the addition of a standard and low- and high-absorption dilution.
The heterogeneity of the material will be reduced to a certain level, and standards can be
prepared easily in the same way. However, if the sample consists of elements with dierent
grinding properties, which is often the case for mineralogical and geological samples,
additives must be added to overcome such a problem. In general, 210% additive to aid in
the grinding, blending, and briquetting process is sucient for most of the materials.
To fulll the condition of a homogeneous sample surface with innite thickness, on
which most of the correction algorithms are based (see Chapter 5), the sample must be
converted into a very ne powder, otherwise particle size eects can occur and interfere
with the quantitative analysis. For very ne particles, the uorescent intensity is constant,
but it decreases with increasing particle size. This eect is more signicant for long
wavelengths than for short or intermediate ones. Furthermore, the degree of packing of
the specimen inuences the uorescence intensity additionally. However, this can be re-
duced by the preparation of pellets and by briquetting the sample; a higher pressure and a
longer pressing time for the pellets give an additional improvement.
Segregation and, hence, heterogeneity eects can arise when the particles are not of
the same size, shape, or gravity. This problem occurs particularly when the sample is
analyzed in the form of a loose powder. Claisse (Claisse, 1957; Claisse and Samson, 1972)
proposed a qualitative interpretation for the origin of such heterogeneity eects in some
publications. The eects can be a major source of errors because large variations in
uorescence intensity may occur and the inuence becomes more and more detrimental
with increasing wavelength; sometimes, errors of about 50% are possible (Berry et al.,
1969; Rhodes and Hunter, 1972; Madlem, 1976; Holynska and Markowicz, 1982). To
avoid severe errors, it is always recommended to tap the powdered sample for better
mixing of the powder prior to analysis.
Dierent mathematical methods for the correction of particle size eects have been
developed. However, with only few exceptions (see Chapter 6), they are not very useful, as
most of them require an a prior knowledge of the particle size distribution in the sample,
which is usually unknown.
1. Grinding
For the preparation of ne powders, the original sample should usually be split and milled
into smaller pieces, which are then suitable for further grinding. Splitting in smaller
subsamples can be carried out by various equipments, like jaw mills or crushers. The main
objective at this stage is to obtain a representative subsample from the original material
and to avoid sampling errors due to wrong handling or treatment. For further grinding of
the sample to appropriate small sizes, various methods and devices are available. The most
common equipments are disk mills or shatterboxes, in which samples of smaller sizes than
6 mm can be ground further.
However, both steps present a source of contaminations, as most of the grinding
tools contain elements, which might be of interest in the sample. These elements can be
introduced easily as blank values during the grinding process and, therefore, the material
of the grinding tools should be selected carefully for each particular application. Agate,
zircon, steel, alundum, and WC are the most common materials for such vessels. All of
them can introduce various blank values. Agate, for instance, introduces traces of SiO
2
,
Mg, and Ca to the specimen. This might be of less interest for geological materials, which
often contain these elements as main compounds, but for biological material, this re-
presents a major source of errors (Van Grieken et al., 1980). However, agate and zircon
equipments insert still lower blank values to the sample in comparison to other materials.
Unfortunately, agate is very expensive and brittle, and for this reason, it is mainly used for
the preparation of small sample amounts by manual grinding in a mortar. With zircon
devices, only blanks of Zr and Hf occur, which are negligible for most of the applications.
Despite its good mechanical properties, the use of WC vessels is only partially re-
commended. During the sample preparation, substantial amounts of W, Nb, Ta, and Co
can be introduced to the sample (Hergt and Sims, 1994). Especially the W contamination
can give serious problems because the L and M lines of this element interfere with the
elements of Z numbers between 28 and 35. However, despite this drawback, WC is the
most favorable material for the preparation of hard alloys due to its material properties.
Steel is also a frequently used material, and the preparation of rock samples with bakelite
phenolic resin in a steel mill showed good results (Longerich, 1995). However, a con-
tamination with Fe, Cr, Ni, and Mn is regular and can cause severe errors.
When grease and oil-forming materials are analyzed, the selection of a suitable vessel
material should be done carefully, as well. The preparation of these samples should be
carried out in vessels with smooth, nonporous surfaces, like agate. Otherwise, parts of the
sample can cling to the surface of the device and losses will occur. Sieber (1993) obtained
homogenized samples of greases by mixing them with a chemplex binder in a high-speed
rotar. The mixture was heated up during the procedure and was analyzed directly after
cooling down as a cake. Oil samples can be ground with MgO and baked afterward at a
temperature of 270
C. The received solid cake is suitable for direct analysis (Liu et al., 1992).
Reagents or additives are used during the preparation procedure for dierent rea-
sons. Fine abrasives like Al
2
O
3
or SiC are often added as grinding aids to accelerate the
process (Adler and Axelrod, 1995). The addition of wet grinding aids like ethyl or iso-
propyl alcohol leads to a better homogeneity and higher eciency. Calcination in an
airstream at 800
C and subsequent grinding to a ne power yields good results for ma-

terials like Pt or Pd (Gokhale and Wuensche, 1990; Norrish and Thompson, 1990). Ma-
terials that are dicult to treat, like rocks or ores, can be prepared much faster and more
eciently after addition of sodium stearate.
Normally, grinding is very fast and takes only a few minutes, but it should always be
taken into account that the determination of light elements requires a ne-particle size.
The eect of grinding time or particle size on the uorescent intensities of the elements Si,
S, K, Ca and Fe in coal samples prepared by the powder technique (5-g sample was
ground in WC rotary swing mill together with a 1-g boric acid binder and 100 mg sodium
stearate) is shown in Figure 2a (Wheeler, 1983). From this gure, it is clear that a grinding
time of around 6 min will reduce the particle size in a coal sample to the order of 50 mm,
but no further increase in intensity is obtained for longer grinding times.
2. Loose Powders
After grinding, the specimen can be analyzed directly as loose powder or further pressed into
a pellet. For the irradiation as a powdered specimen, the ground sample is transferred into a
special cup and covered by Mylar foil. The cup should be lled in such a way that innite
thickness is assured, which means $75% in most of the cases. The covering lm should be
made of a material with homogenous density in order to avoid scattering eects. If a sample
will be irradiated several times, as in the case of standards, such lms tend to become brittle
and may break inside the XRF unit. To avoid this, the lm should be changed regularly.
Another possibility for the analysis of a powdered specimen is the preparation of a
thin lm by dusting the powder on adhesive tape (e.g., Scotch
1
) or onto foils. This can be
carried out manually or, with higher benet, by using the so-called pu technique
(Bertin, 1978). A special device was developed for such purposes: The device is lled with
the powdered sample and subsequently the powder is dispersed into ne dust by blasting
small air volumes inside the fairly evacuated chamber of the equipment. This dust is then
deposited onto a lter or frit by further evacuation of the chamber.
A further approach is the performance of a slurry analysis. By mixing the ne-
powdered sample with a solution of 25% (w=v) nitrocellulose in 1 mg=L acetate, a
suspension is formed which can be transferred on a microscope slide or other supports
(Bertin, 1978). A simpler approach is slamming of a slurry solution with water and ne
powder and sucking this suspension through a lter (Nuclepore
1
, Mylar, etc.) with ne
pore sizes, to obtain a thin and very homogenous layer (Wybenga, 1979; Araujo et al.
1990). A major drawback of this method is the loss of water-soluble elements. To
avoid these problem, nonpolar solvents, like hexane, are sometimes used. An alternative
procedure includes mixing the samples ( $1 g) with a few milliliters of double-distilled
water and grinding to a ne suspension. From the suspension, a 0.5-mL fraction is
immediately pipetted onto Mylar foil. Careful evaporation at 80
C results in a target
containing about 2 mg=cm
2
of sample material. Microscopic photographs showed that
the sample is quite homogenous with a grain size below 10 mm (Sauer et al., 1979; Van
Grieken et al., 1979).
Figure 2 (a) Grinding time versus intensity. (b) Pelletizing pressure versus intensity. (From Ref.
30. Reprinted by permission of Plenum Press.)
3. Pelletizing
Pelletizing of the powdered samples is often required for the reduction of surface ef-
fects and to yield better precision than with loose powders. The process can be carried
out very fast and easily. The required tools are only a hydraulic press and a suitable
die set, including a die body, base, a plunger, and two polished metal disks. When the
disks are made of WC, they also allow the pressing of hard alloys and abrasive ma-
terials. For pelletizing, the powdered sample is transferred into such die and pressed
under pressures of mega Pascals for several seconds up to 1 or 2 min. For most of the
materials, this will be sucient to reach a mirrorlike surface and to smooth scratches
and turnings.
The eect of the pelletizing pressure on the uorescent intensities for a coal sample is
displayed in Figure 2b. The coal powders were pelletized with a boric acid backing at
250 MPa. With uorescence measurements, the optimum pelletizing pressure was de-
termined. The light elements such as Si and Ca show a much higher dependence on the
pressure than, for example, Fe. However, other light elements like K and S seem to have
much less dependence on pressure than Si and Ca. This might be an indication that sig-
nicant dierences in the particle size of these elements are present in the coal sample
(Wheeler, 1983).
Binders are often added to the mixture to help form stable pellets and prevent caking
of the sample at the die surface. However, in the selection of a suitable binder, some
regulations should be carefully considered. First, binders should show low contamination,
particularly for the elements of interest, have low absorption for all wavelengths of in-
terest, and be stable under air, vacuum, and x-ray irradiation. The necessary amount of
binding material must be chosen carefully as well, because binders are normally composed
of light elements or organic materials and scatterred x-rays increase the background of the
spectrum. Binders also dilute the sample, which might be a serious problem for the de-
termination of trace elements. A recommended mixture is the addition of 210% binder to
the sample. In some special cases, higher concentrations of the binder can be accepted.
Bassari and Kumru (1994), for example, used a combination of 50% soil sample and 50%
cellulose binder in their work.
Dierent types of binders are available; most of them also act as grinding aids and
can be added during the grinding procedure. Typical binders are cellulose, starch, lucite,
urea, boric acid, graphite, KCl, and so forth. (Bertin, 1978; Frechette et al., 1979; Tertian
and Claisse, 1982). Liquid binders like ethyl alcohol or diethyl ether can be mixed with the
sample manually, whereas it is recommended that binders be mixed mechanically for the
formation of a homogenous mixture.
Liquid binders have the advantage of evaporation after the mixing process. Finally,
a stable pellet is formed and only minor amounts of binding material are still present in
the specimen, which can almost be neglected. To accelerate the evaporation process,
careful heating by an infrared (IR) lamp can be performed. If the heating process is
carried out too fast, cracks may develop inside the pellet and this can weaken the whole
structure.
In the last years, several new binders, mainly polymers, have been recommended; for
example, Pb-containing pulp samples were mixed with poly(vinyl acetate) binder in order
to form a stable disk (Volodin and Uranov, 1990). Other polymers are poly(vinyl alcohol),
poly(vinyl pyrrolidone) (PVP), or methyl methacrylate (Bettinelli and Taina, 1990; Domi,
1992; Wilson et al., 1995; Watson, 1996). Watson (1996) developed a simple and fast
method for pellet preparation by mixing PVP and microcrystalline cellulose binder in a
new polyethylene bag. The obtained moist mixture is then pressed to a pellet and dried.
For the determination of traces in geochemical samples, elvacite (a copolymer of methyl
n-butyl methacrylate) was selected as the binder (Ingham and Vrebos, 1994). In one recent
application, provenance studies were performed of coastal and inland archeological pot-
tery in South Africa. Here, the ground samples were mixed with movariol as binder and
analyzed (Punyadeera et al., 1997).
For pressing a pellet, the powderbinder mixture is poured into a metal support,
which has only the analysis surface open to prevent cross-contamination and to extend
the life time of a pellet. The support is usually made of Al and painted on the sides.
The exterior paint acts as an antifriction substance in the press mold, reducing scoring
of the die. Before pressing, the container is tapped several times in order to reduce air
pockets.
Another alternative for obtaining a stable pellet is pressing after the addition of boric
acid. In this case, the powder mixture is transferred into the die and attened by a plunger.
The die has been lled earlier with a small cylinder, which acts as a spacer and prevents
backing of the powder at the rim. The used plunger is made of Plexiglas to allow the
observation of the attening process. The inset cylinder is then removed carefully, which
leaves a gap between sample and die. Boric acid crystals are poured in this gap and on top
of the sample, and the whole assembly is pressed.
In some cases, heating of the sample during the mixing procedure with binders can
occur and volatile components may evaporate. Special mixing machines with cooling
mechanisms or slower milling procedures are in use instead of ring and puck mills for
prevention of such losses (Domi, 1992).
Another procedure can be applied when only small amounts of the sample are
available. The powdered sample is placed as a thin layer on top of a backing material layer
and the pellet can be subsequently pressed in an easy way.
To check whether a specimen is innitely thick, the sample is covered by a small disk
made of Cu or other metals, depending on the elements to be analyzed, and then pressed.
The presence of Cu lines in the spectrum indicates that the sample is not innitely thick
and the pressing procedure should be repeated with more material.
For pressing of the nal pellet, some precautions need to be considered. Normally,
the used pressure is about 15 tons, which is sucient for the formation of stable pellets for
a long time. The pressure should be released carefully to avoid breaking or backing of the
pellet, and the removal of the pressed pellet from the press should be carried out with
caution for the same reason. If the pellet is too brittle, it may be broken or pulverized
again during rough handling.
However, if oily or waxy samples are pressed, they may ow under the pressure and
form coatings at the surface of the pressing tools. This can be avoided by the addition of
components, which stabilize such pellets. Sometimes, the sample structure itself might be
destroyed by unsuitable pressures or too long exposure. This is often not visible im-
mediately after pressing, but after storage of the pellet for longer times, problems might
occur. Also, conical fractures can occur inside the pressed pellet and weaken it. Un-
fortunately, such fractures are also not always visible and breaking out of the pellet inside
the instrument during the evacuation process might be the result. For the prevention of
these unwanted eects, the pellet can be exposed to vacuum in a desiccator before
transferring it into the XRF unit.
In their study, Novosel-Radovic and Malijkovic (1993) monitored the deterioration
of a pressed sample as a function of time. They found that briquets age with time,
resulting in the formation of surface cracks.
III. FUSEDSPECIMEN
In 1956, Claisse proposed preparing fused samples for analyses by XRF in order to over-
come the problems arising with powders and pellets (Claisse, 1956, 1957). This technique
has become one of the most successful methods for the preparation of specimens in x-ray
uorescence and can be applied to almost all types of samples (Feret, 1990, 1993). With a
fusion, all particle and mineralogical eects, which cause serious problems for analysis of
powdered and pelletized specimen, become negligible and the analysis shows a better ac-
curacy (Banajee and Olson, 1978; Frechette et al., 1979; Tertian and Claisse, 1982; Metz and
Davey, 1992). The basic procedure consists of heating a powdered sample together with the
ux to such high temperatures that the ux melts, dissolves the sample, and reacts with it by
the formation of a one-phase disk. Agitation during the fusion process is essential for fu-
sions with low uidity, in order to avoid the formation of bubbles and to receive a homo-
genous sample (LeHouillier and Turmel, 1974). The reaction time varies between 5 and
30 min depending on the sample composition. For a 30-mm disk 67 g material (ux and
sample) is required. For most applications, the ux=sample ratio varies between 2:1 and 10:1
(Bower and Valentine, 1986; Eastell and Willis, 1990; Kvaratskheli and Kornienko, 1992;
Ossaka et al., 1994; Spangenberg et al., 1994). In some special applications this ratio may be
dierent (Haukka and Thomas, 1977; Fink et al., 1993; Sato and Kohori, 1995).
One of the major advantages of the fusion technique is the possibility of adding a
heavy absorber for the reduction of matrix eects, especially for the determination of light
elements. Other advantages are the relatively simple preparation of synthetical standards
and the wider calibration range (Feret, 1990, 1993). The main disadvantage of this tech-
nique presents the dilution eect of the sample, which renders the determination of traces,
especially of light elements, more dicult, as their uorescence intensity is decreased.
However, in the last years, several attempts were carried out to overcome this dis-
advantage [e.g., by application of the low dilution fusion technique (LDF) (Haukka and
Thomas, 1977; Thomas and Haukka, 1978; Lee and McConchie, 1982; Eastell and Willis,
1990; Maruta et al., 1992; Yamamoto et al., 1995) or a semilow dilution technique
(Malmqvist, 1998)]. Further disadvantages include the higher costs in comparison to the
powder methods and the more complicated preparation procedure of the fusion. Some
experience is required and most of the analysts have their special tricks to obtain the
best results. Today, several automated ux preparers are commercially available with
more or less sophisticated technology (Stephenson, 1969; Schroeder et al., 1980; Kvar-
atskheli and Kornienko, 1992).
For some elements like S, however, the briquetting technique is preferred and oers
better accuracy, because high losses due to volatilization during the fusion procedure occur.
A. Fluxes and Additives
Several uxes, with dierent properties, are in use for the dissolution of the samples and
the formation of glass disks. The uxes are mainly composed of light elements, which do
not interfere strongly with the elements to be determined and form stable glass beads
(Muia and Van Grieken, 1991). Borate uxes, containing metaborate or tetraborate,
dissolve almost all materials except metallics, suldes, and organic materials. The choice
for each application is dependent on the sample composition. Common uxes are lithium
tetraborate (Li
2
B
4
O
7
), lithium metaborate (LiBO
2
), sodium tetraborate (Na
2
B
4
O
7
), and
sodium phosphate (NaPO
3
)
6
. Low-temperature uxes are potassium pyrosulfate (K
2
S
2
O
7
)
and sodium carbonate (Na
2
CO
3
).
Usually, the Li uxes are preferred to the Na ones. They produce more uid uxes
and have lower mass absorption coecients; this inuences the uorescence intensity less
and is essential for light elements. Their disadvantages are the higher reaction tem-
peratures and higher hygroscopicity. Lithium tetraborate is an eective reagent for at-
tacking basic oxides, like carbonates or Al oxide. However, its glass beads are cracking
easily and the disks should be handled with care. Lithium metaborate forms glass beads
with excellent mechanical properties and attacks specimen containing high concentra-
tions of oxidic acids (e.g., silica). Often, mixtures of the lithium uxes are used, which
can be more eective, as they combine the properties of the single components. The
addition of Li
2
CO3 or LiF increases the acidity or basicity as well as the reaction speed
and uidity.
With a mixture of sodium metaborate and sodium nitrate (NaNO
3
), samples which
are dicult to attack by lithium reagents (e.g., chrome-containing ores and refractories)
can be dissolved (Sear, 1997). NaNO
3
and boric acid react with geological materials like
casserite (SnO
2
) and chromite (FeO Cr
2
O
3
) (Couture et al., 1993). However, Na uxes
tend to wet and stick to the crucible, which makes it necessary to clean the crucibles
regularly. In Table 3, some examples for ux compositions and ux=sample ratios are
given.
Table 3 Some Examples for Flux Compositions and Typical Applications
Flux base
Flux
composition Properties Applications
LiBO
2
LiBO
2
=Li
2
B
4
O
7
4:1 Good mechanical
properties
Silica or alumina major components
(Istone et al., 1991), CaO (Alvarez, 1990)
LiBO
2
LiBO
2
=silica 22:3 Ceramics with lead zirconate (Sato and
Kohori, 1995)
LiBO
2
LiBO
2
High fluidity Coal ash, rock samples (Sweileh and
Van Peteghem, 1995)
Li
2
B
4
O
7
LiB
4
O
7
=LiBO
2
12.5:10 Aggressive Cr-containing refractories (Giles et al.,
1995)
Li
2
B
4
O
7
Bead cracks easily Metal oxides, basic oxides, basic metal
sulfides, rocks, carbonates, silicates,
zeolithes (Luke, 1963; Le Houillier and
Turmel, 1974; Eastell and Willis, 1990;
Oishi et al., 1995, Rutherford, 1995)
Li
2
B
4
O
7
Li
2
B
4
O
7
=Li
2
CO
3
Ferro-alloys, paper pigments
(LeHouillier et al., 1976; Alvarez, 1990;
Muia and Van Grieken, 1991)
Li
2
CO
3
Li
2
CO
3
=NH
4
NO
3
20:1 Feores (Sato and Kohori, 1995)
Na
2
B
4
O
7
Metal oxides, rocks
volcanic ash, MgO, chrome-containing
ores (Dow, 1981; Kvaratskheli and
Konienko, 1992)
Na
2
B
4
O
7
Na
2
B
4
O
7
=Na
2
CO
3
3:1 Slags, sinters, metal oxides (Muia and
Van Grieken, 1991)
To overcome the problem of attacking the crucible material, especially by suldes
and partially oxidized organic compounds, the sample can be preignited or an oxidant
added (Martin and Richardson, 1992). Slags from Cu-smelting processes can be analyzed
after dissolution in sodium tetraborate combined with lanthanum oxide (La
2
O
3
) as a
heavy absorber and NaNO
3
as an oxidant to prevent the attack of the crucible by Cu (Le
Houillier and Turmel, 1974). Other examples for oxidants are BaO
2
, CeO
2
, KNO
3
, and
LiNO
3
.
Sulfur-, chlorine-, and uorine-containing samples tend to stick in the crucible and
shorten their lifetimes. Preliminary roasting of the samples minimizes this problem (Dow,
1981). To avoid losses of elements, like sulfur and organic compounds, the sample can be
calcinated for several hours in a mue oven at 750800
C prior to fusion (Pella et al.,

1982; Norrish and Thompson, 1990; Muia and Van Grieken, 1991). Also, for the de-
termination of sulfur in fusion samples, the compound should be oxidized completely to
sulfate (Baker, 1982), as dierent oxidation stages show slightly dierent element lines in
the spectrum. However, if the sample contains more than 1% sulfur, the loss of volatili-
zation is too high to get reliable results. Under a highly oxidizing atmosphere during
fusion, sulfur can be retained quantitatively; for example, with ux compositions like
Na
2
B
4
O
7
=NaNO
3
(80:20) or Li
2
B
4
O
7
=LiNO
3
(80:20) (Staats and Strieder, 1993). Dicult-
to-attack sulde-bearing ores can be dissolved by a combination of NaNO
3
=NaKCO
3
and
Li
2
B
4
O
7
(Birch et al., 1995; Rao and Govil, 1995).
Sometimes, La
2
O
3
, barium peroxide (BaO
2
), barium sulfate (BaSO
4
), or cerium
oxide (CeO
2
) is added as a heavy absorber in order to minimize matrix eects, which are
particularly serious for long-wavelength x-ray lines (Pella et al., 1982; Norrish and
Thompson, 1990; Muia and Van Grieken, 1991). Barium, for example, behaves as a heavy
absorber in the analysis of rock samples for the major elements in glass beads (Bennett and
Olivier, 1976). Some of them, like barium peroxide or barium nitrate [Ba(NO
3
)
2
], also act
as oxidants. Catalysts as manganese oxide (MnO
2
) may be added to accelerate the oxi-
dation procedure as well. However, the addition of any supporting reagent should be
carefully estimated before analysis because each additional compound increases the risk of
contamination and decreases the amount of elements, which could be determined without
line interferences.
As mentioned, one of the major drawbacks of the fusion technique is the dilution
eect of the sample. This makes it often dicult or even impossible to determine trace
elements in the specimen. For this reason, the low-dilution fusion technique was developed
(Haukka and Thomas, 1977; Thomas and Haukka, 1978; Lee and McConchie, 1982;
Eastell and Willis, 1990; Maruta et al., 1992; Yamamoto et al., 1995). Here, the ux-to-
sample ratio is 2:1 (ux:sample) (i.e., lower than usual). Most often, LiBO
2
is applied as a
ux, as it is more reactive and forms uxes with higher uidity, which ensures better
homogeneity.
Especially in geological samples, relevant trace elements are often present with
concentrations of less than 10001500 ppm. These low concentrations cause problems with
the conventional fusion process because of its high dilution. On the other hand, most of
these samples are dicult to grind and pelletize. With the application of the low-dilution
fusion technique and selection of a suitable ux, these problems can be overcome.
B. Fusion Procedures
For the fusion procedure, the sample should be ground with at least 150-mesh grain sizes
to yield a fast and homogenous fusion. For samples that are dicult to fuse, like
refractories, grain sizes down to 200 mesh are recommended in order to obtain a homo-
genous fusion and accelerate the entire fusion process (Norrish and Hutton, 1969; Hutton
and Elliot, 1980). The sample is weighed out and mixed fairly. The ux, if consisting of
dierent compounds, is also mixed well and transferred into the crucible. The sample is
placed on top of the ux and both are mixed. A selection of dierent materials for
the crucible is available (Giles et al., 1995); common ones are Pt, PtAu alloys (95%:5%),
PtRhAu alloys (85%:15%:5%), zirconium grain-stabilized platinum (ZGS), and Ir or C
vessels. The latter ones act also as oxidants, but C vessels are easily attacked by suldes
and other reducing compounds. Preferable to Pt is the PtAu alloy, as it is harder and
more dicult to degrade than the pure metal. This combination is nonwetting and rela-
tively long lasting. Recently, Ir crucibles became available, which show good properties,
such as corrosion resistance to all metals, insolubility in acids, even aqua regia, and
maintenance of their properties under normal atmosphere up to 1600
C.
The fusion procedure can be carried out in high-frequency induction furnaces, gas
burners, or mue ovens. The rst two show the advantages of higher temperatures and
faster heating. The sample is previously heated until the glass-forming agent is melted;
with a further increase of the temperature to 10501100
C for $1015 min, the ux reacts

with the sample, forming a glass bead. Agitation during the fusion process is re-
commended for fusions with low uidity in order to avoid bubble inclusions (Luke, 1963;
Harvey et al., 1973; LeHouillier and Turmel, 1974; Pella et al., 1982; King and Vivit, 1988;
Norrish and Thompson 1990). The melted fusion is casted into a preheated mold, for the
formation of a disk to be analyzed, and allowed to cool down. For easier removal of the
fusion from the crucible and mold, special antiwetting agents can be added. Iodides and
bromides of light alkali and alkaline earth elements are favorable for this purpose. With
application of these agents, the crucible shows a much longer lifetime and its cleaning is
much easier. Only a few droplets of these agents are required to be added on top of the
sample=ux mixture before heating.
Sometimes, the fusion is annealed at 200
C for some minutes in order to avoid

thermal shocks (Bower and Valentine, 1986), but, usually, the mold is preheated to the
same temperature and the melt can be transferred without suering. For a reliable ana-
lysis, it may be required to clean the disk with alcohol and polish it with abrasives. The
resulting disks are stable over a long time but should be stored in a desiccator under
vacuum or in other moisture-free environments. Borates are hygroscopic and extended
exposure to ambient air may destroy the disks surface.
Various additives may be used for dierent reasons, according to the sample be-
havior during the fusion procedure. The addition of glass-forming agents like SiO
2
or
Al
2
O
3
is required to obtain a more stable disk when a higher amount of alkaline earth
elements is present in the sample. Transparency-increasing agents (e.g., LiF, NaF, or KF)
are added for higher uidity of the fusion and to assure better homogeneity.
For the fusion of organic material, preignition for several hours at 450
C is necessary
to volatize all CO
2
. Otherwise, a weight loss will occur during the fusion, which cannot be
compensated for by mathematical calculation.
Evaporation of moisture or crystal water can also introduce some weight loss. If this
loss is similar for both the sample and ux, it can be calculated using the method of
Hutton and Elliot (1980) or compensated for by the addition of SiO
2
, if less than 20%
(Harvey et al., 1973). Any additional mathematical correction procedure is then super-
uous. The losses of volatiles and=or ux usually increase with increasing temperature.
King and Vivit (1988) developed the following simple method for the prevention of losses
in geological samples: The powdered sample was dried for 2 h at 105
C and 2 g was
weighed exactly and calcinated in a mue furnace at 925
C until a constant weight was

achieved.
Cleaning of the mold can be carried out by reheating with a nonwetting agent or
inserting the crucible into a warm HNO
3
bath (Tertian and Claisse, 1982).
Sometimes, the fused disks are ground and pelletized. For the determination of Nb
and Ta in geological samples, the fused disks were pelletized with cellulose powder for a
reliable analysis (Basu Chaudhury et al., 1987). Also, for the analysis of submarine
polymetallic nodules, the samples were fused by the application of the low-dilution fusion
technique and later pelletized without binder (Cai et al., 1992).
The high-dilution technique of Tertian and Claisse (1982) was investigated for the
determination of SiO
2
in powdered plant materials. In this case, a 100-mg sample was
dissolved in 9.9 g lithium metaborate ux (Garivait et al., 1997) and satisfactory results
could be achieved.
Applications were also carried out in the eld of ceramic materials. One study dealt
with the determination of Si as SiO
2
in Si
3
N
4
. Here, the ground material was rst pyrolized
at $1500
C before fusing with LiBO

2
or a mixture of LiBO
2
and B
2
O
3
(Kaiser et al.,
1995).
When only small sample amounts are available, as in the case of air-dust samples,
microbeads might be formed with LiF and Li
2
B
4
O
7
(Moore, 1993).
IV. LIQUIDSPECIMEN
Liquid samples represent an almost ideal specimen for analysis by x-ray uorescence. They
are homogenous, particle eects are eliminated, and the obtained analytical results are
representative for the whole sample. Furthermore, normally the matrix consists of ele-
ments with low atomic numbers, where absorption eects are small and enhancement of
the analyte lines is negligible. High absolute sensitivity is observed because the penetration
depth of the primary beam is high and low absorption of the emitted secondary radiation
exists. For the analysis of liquid-specimen special cells, made of stainless steel, poly-
ethylene, or polytetrauorethylene (PTFE or Teon), are in use, into which the liquid
sample is poured. These cells are usually covered by Mylar foils with thicknesses of 3
6 mm; a lower thickness ensures less background scattering but is mechanically less stable
than the thicker ones. Sometimes, also microporous lms are used, which allow the
equalizing of pressure dierences between the liquid cell and the environment by being
permeable for air only. For the quantication of liquid samples, internal standardization
can be applied, but also calibration standards in each concentration range and blank
samples for the background evaluation are easily prepared. Solids, which are problematic
to analyze, such as powders, pellets or fusions, can be converted into liquids by dissolution
and digestion or, if trace analysis is required, the traces might be extracted with a suitable
solvent from the bulk material.
The major drawback of the analysis of liquid samples is the highly scattered back-
ground. This makes it dicult, or sometimes impossible, to determine light elements at
low concentrations and it increases the detection limits. Another disadvantage is the de-
terioration of standards with time. In contrast to standards prepared by fusion or pelle-
tizing, liquid standards change their concentration with time due to adsorption and=or
precipitation eects. Therefore, they should be prepared fresh or renewed each few days in
order to avoid systematic errors in quantitative XRF analysis. Also, the samples and the
standards may be altered by irradiation. During irradiation, the sample can be heated up
and evaporation might occur, which inuences the concentrations of the elements in the
sample. Bubbles can be formed by heating of the sample and inuencing the analyte-line
intensity. Sometimes, precipitation occurs during the irradiation process, and the pre-
cipitate can be deposited at the bottom and change the properties of the sample.
Typical detection limits for the energy-dispersive XRF analysis of liquid samples
with 30 min counting time are in the ppm range (Van Grieken et al., 1976), which is sa-
tisfactory for several applications. Chlorine and iodine were determined by Morse (1992
and 1994) directly in photographic developer and xer, respectively, with cadmium
standard solutions in polypropylene cups. Relatively high concentrations in the micro-
gram per gram level of Fe, Ni, and V in crude oils can be determined easily by using XRF
(Shay and Woodward, 1991). In the last few years, the eld of direct applications ex-
panded, particularly in the oil sector (Kendall et al., 1995; Kira et al., 1995; Lyamina et al.,
1995; Untenecker et al., 1995). It appears that XRS is an excellent technique for the
analysis of various kinds of oil from highly ranated greases (Untenecker et al., 1995) to
petroleum products and used oils (Kendall et al., 1995; Kira et al., 1995; Lyamina et al.,
1995).
However, in most cases, the elemental concentrations in liquid samples (e.g., in
environmental waters) are too low for a direct analysis of traces and the samples must be
preconcentrated prior to analysis. In general, all preconcentration techniques, which are
applied to other analytical methods, are also practicable for XRF analysis. Pre-
concentration has the additional advantage that possible matrix eects can be reduced or
even avoided (Van Grieken, 1982), and the accuracy of the results is improved. Un-
fortunately, a preconcentration step is often time-consuming, involves the risk of con-
tamination and losses, and may not always be specic for each elemental species.
Ideal for the presentation to XRF are thin-lm targets, in which the x-ray intensity is
proportional to the mass of the element on the lm. To obtain a thin-lm specimen from
suspended matter in liquid samples, the liquid sample is ltered through a membrane
lterpreferable Nuclepore or Milliporeand dried. Vanderstappen and Van Grieken
(1976) found that ltration through a Nuclepore lter leads to interference-free detection
limits of 510 ng=cm
2
for Mn, Ni, Cu, Zn, As, and Br, 1020 ng=cm
2
for Ti, V, and Cr, and
about 50 ng=cm
2
for K and Ca by using EDXRS and counting times of 2000 s. Recently,
Civici (1994) used the ltration method for the separation of suspended material from
seawater. For the internal standardization, the standard element is added before ltration
and deposited together with the suspension onto the lter surface in order to get a
homogenous distribution.
X-ray uorescence also oers an ideal technique for on-line process control in the
industry using a continuous ow of the sample through a sample chamber. Ceasy (1994)
applied this for the on-line analysis of molten metal samples with a portable EDXRF
instrument, equipped with two radioisotope sources, namely
55
Fe and
244
Cm, and a ow
cell. Another on-line application was carried out by Davidson (1994): he determined As,
Cu, and S in solutions from a lab-scale Cu electrolyte purication cell.
In fact, the XRF analysis of liquids increases from year to year. Numerous appli-
cations are cited in the review articles by Ellis et al. (1996, 1997) and Bacon et al. (1995).
A. Physical Preconcentration
Physical preconcentration methods are practicable for the analysis of rainwater, sewage,
and wastewater, and several dierent approaches have been carried out to remove the
liquid matrix in various ways. A simple and fast process of preconcentration is the
evaporation of the liquid, leaving the elements to be determined as a residue on a surface,
which can be analyzed directly. This technique shows several advantages because of its
easy handling and direct approach. The probability of contaminations is low because no
complicated and extra sample preparation steps are required. The costs are reasonable:
only suitable carrier materials are necessary and all nonvolatile compounds remain
quantitatively on the surface. Even large amounts of water can be evaporated or freeze-
dried, and the residue is later mixed with binding materials, pelletized, and analyzed.
Freeze-drying of 250 mL wastewater on 100 mg graphite followed by grinding and pelle-
tizing of the residue leads to detection limits of 5 mg=L for many elements with accuracies
around 10% with EDXRF (Smits and Van Grieken, 1997).
Several attempts have been made to deposit analyte solutions on dierent surfaces.
In general, all materials with a smooth surface texture composed of low-atomic-number
elements are suitable. Especially, Nuclepore lters and Mylar foils show low-background
and blank values for XRF analysis. However, there are also some drawbacks to this
technique. Volatile species and elements get lost during the evaporation step. In the case of
high salinity or hardness, a formation of nite crystals will occur, which introduces particle
size eects. Special background correction methods need to be applied for dierent types
of water sample. Despite these problems, evaporation is still a popular technique for the
preconcentration of various liquids. Often, the samples are pretreated or predissolved in
solvents in order to increase their capability of spotting.
For the determination of U and Ce in nuclear fuel, the sample was rst dissolved in
nitric acid solution and, subsequently, microdroplets of this solution were spotted onto a
lter. The XRF analysis of the dried lter showed an accuracy of better than 2% (Hanif
et al., 1995) for the elements of interest. Contents of less than 1 mg=g of Ca, K, S, P, Cl,
Mg, and Na could be determined in liquids, by spotting such a nitric acid solution on a
highly pure polycarbonate membrane (Go diker et al., 1990).
Mylar foil is one of the most popular substrates for the deposition of samples
(Baryshev et al., 1995). Several interesting studies were carried out by use of this medium.
Oil sample, for example, can be deposited after homogenization with an organic solvent,
leaving a thin lm glued onto the Mylar (Civici, 1995). Other substrate materials are
polypropylene and polycarbonate lms. Cations (Ca, K, Mg, Na) and anions (Cl
and
SO
2
4
) of drinking water were preconcentrated onto polypropylene foil. The addition of a
polysaccharide (GELERITE) reduced the hydrophobic eect of the foil and, thus, de-
tection limits from 0.12 mg=L for Ca to 1.78 mg=L for SO
2
4
were claimed (Warner et al.,
1995). The advantage of this technique is the possibility of a simultaneous determination
of cations and anions. In another application in this direction, the sample is transferred as
a droplet onto a polycarbonate lm, which is cemented on a 35-mm plastic photographic
slide mount. After evaporation, the resulting salt deposit is more or less circular. Detection
limits in the microgram per liter region could be reached (Meltzer and King, 1991).
Particularly, thin-lm supports (like the type A2) have recently been developed by
Process Analytics (Orem, UT). The lm can accumulate a small amount of solution in a
small spot because the lm is treated to have a hydrophilic center in a hydrophobic eld or
the lm has a dimple in its center. These lms are clean and resistant to high temperatures.
Wastewater samples with low salinity can be preconcentrated by a special vapor
ltration procedure (Luke, 1963; Rickey et al., 1977) in which the sample is deposited into
a container, with a cellophane foil bottom. The foil is permeable for water vapor, but not
for liquid water or dissolved material. Subsequent evacuation of the container leads to
deposition of the dissolved solids onto the membrane or foil, which is then presented for
analysis. In combination with particle-induced x-ray emission (PIXE), detection limits in
the range of 0.13 mg=L were claimed. However, this method shows several disadvantages:
It is time-consuming and samples with high salinity cannot be applied successfully. Crystal
formation can occur, even with very low salinity, which has to be corrected by special
matrix correction procedures (Van Grieken, 1982).
Sometimes, metal surfaces can also be used for the deposition of extracted solutions.
A thin-lm technique was applied for the determination of SO
2
4
and Cl
in small volumes
of saline samples, deposited onto suitable machined Cu disks (Dhir et al., 1995).
Other procedures are a nebulization technique (Giauque et al., 1977) and a multi-
droplet spotting technique (Camp et al., 1974), which result in a fairly homogeneous
distribution of the sample onto the surface.
The evaporation of larger samples can be carried out by impregnation of the lter
material (Whatman 41) with a sample solution. A wax ring 29 mm in diameter keeps the
spotted sample solution inside the area to be irradiated when the water is evaporated by
passing an airstream from underneath. The reported detection limits were below 50 mg=L
for 2000 s analyzing time, with optimum secondary target excitation (Giauque et al., 1977).
Water samples can be properly analyzed by TXRF without any preconcentration
step. Some microliters of the sample are pipetted directly onto a highly polished quartz
glass carrier and evaporated. The detection limits achieved with this techniques are one to
sometimes two orders of magnitude better than for conventional XRF. However, if
samples with higher salinity are analyzed, a separation step is also required.
Probably the best solution, when high precision and low detection limits are ne-
cessary, is a sample preparation involving a chemical preconcentration or separation step.
B. Chemical Preconcentration
Chemical preconcentration may be grouped into three main classes:
1. (Co)precipitation
2. Ion exchange
3. Chelation and sorption immobilization
Numerous applications to dierent water samples have been established in these
three groups (Camp et al., 1974; Rickey et al., 1977; Bruninx and Van Ebergen, 1979;
Andrew et al., 1982; Chakravorty and Van Grieken, 1982; Van Grieken, 1982; Becker
et al., 1985; Hirayama and Leyden, 1986; Shan et al., 1988) and most of them include a
nal step in which the preconcentrated sample is deposited onto a surface (lter or foil) by
sorption or ltration. This surface serves as sample carrier and is subsequently exposed to
the x-radiation.
1. (Co)precipitation Methods
Precipitation methods are quite popular for the tracematrix separation and they have
been used in analytical chemistry for a long time. They can be carried out very quickly and
with little eort. Selective precipitation of one or two species is usually the main task and
much of the time is dedicated to nding suitable reagents for this purpose. However, in the
case of XRF as a multielement technique, it is much more important to obtain a pre-
cipitate containing all elements of interest. Many attempts were carried out in this di-
rection and numerous reagents with dierent properties are practicable for this. A simple
and traditional method is the application of inorganic reagents like Fe or Al hydroxide,
which coprecipitate many elements at selected pH values. Suldes are less common,
because of the higher solubility of their precipitates. However, most of the inorganic re-
agents show an incomplete precipitation and a strong dependence on accurate pH values.
More common and eective are organic components, which form complexes of very
high stability. Often a spike element is added, acting as a carrier and an internal standard
at the same time. The most suitable organic reagents are the carbamates (Van Grieken,
1982). They form very stable and strong metal chelates. Luke (1968), for example, in-
vestigated, using his coprex technique, the coprecipitation of trace elements by sodium
diethyldithiocarbamate (NaDDTC) in the presence of a suitable metal ion spike. In a
further work, Kessler and Vincent (1972) improved the detection limits, obtained by Luke
(1968), by ltration of the received NaDDTC=hydroxide precipitate and analyzing of the
residue with a highly collimated XRF setup.
Toxic elements were successfully determined in plastic compounds for toys by ap-
plying NaDDTC. The samples were rst mineralized with molten NaOH. Then Cd, Ba,
Sb(III), Cr(III), Hg, Pb, and As(III) were coprecipitated at pH 8.5 with NaDDTC and
sodium rhodizonate and Fe
3
ions as the carrier. The results achieved by XRF were
comparable with the AAS results (Gimeno-Adelantado, 1993). When a high sample
throughput is required and all samples are of the same kind, automation might be pos-
sible. For such purposes, Tanoue et al. (1979) developed an automated device for the
preconcentration of trace metals in wastewater samples with DDTC and subsequent XRS
measurement.
Ammonium pyrrolidine dithiocarbamate (APDC) acts more eciently, especially for
concentrations below 10 mg=L at a pH of 4. APDC is the most successsful nonspecic
reagent for the preconcentration of traces at this pH in comparison to other reagents.
Quantitative recoveries are obtained for a dozen elements in water, independent of the
alkaline earth element content. Various elements can be also determined in seawater, using
APDC as reagent. A small amount of Mo as carrier ion is added to the ltered seawater
sample, then the pH is adjusted at 4, and a portion of the 1% APDC solution is added.
After 1520 min the precipitate is ltered o, dried, and analyzed. Ulrich and Hopke
(1977) achieved detection limits between 4 ng=cm
3
for Br and 80 ng=cm
3
for Ca by ap-
plication of this method. In another approach, traces of soluble metals were separated
from estuarine waters. In the rst step, the water was ltered and acidied to pH 3. Fresh
APDC solution (2%) was added and then the complexes ltered. The obtained detection
limits were between 2 and 5 m=L (Mazo-Gray et al., 1997).
Quantitative recoveries are also received by application of dibenzyl dithiocarbamate
(DBDTC) for Mn, Fe, Co, Ni, Cu, Zn, Se, Sb, Hg, Tl, Ag, Cd, and Pb with detection
limits around 1 mg=mL for 100-mL samples (Watanabe et al., 1986). The very low solu-
bility of this reagent also eliminates the need for a metal carrier (Lindner et al., 1978; Ellis
et al., 1982). A detection limit of 10 mg=L could be reached for Mo in water samples by
preconcentration with DBDTC at pH 3 (Saitoh et al., 1984).
1-(2-Pyridylazo)-2-naphthol (PAN) represents another attractive reagent for several
water samples. This organic compound is soluble in hot water and also in ethanol, but not
in cold water. This behavior can be utilized for the separation of special elements. In one
study, 2 L of water were heated to 70
C and a 20-mg portion of PAN, dissolved in ethanol,

was added. After cooling down, the precipitate was ltered o and the obtained lter
target was transferred to the XRF unit. With this procedure, about 15 cations could
successfully be preconcentrated and detection limits about 0.5 mg=L achieved (Vander-
stappen and Van Grieken, 1978).
Other organic reagents, which are less known than the carbamates, are rhodizonate
and tannin. Bauer-Wolf et al. (1993) applied these reagents for the coprecipitation of rare
earth elements (REE) in geological samples. The samples were previously decomposed and
the alkaline earth elements removed by an ion-exchange procedure. Subsequently, the
REE were precipitated at pH 13 with rhodizinate and tannin, the residue collected onto a
lter, and analyzed. Tannin, in combination with methyl violet, was used for the de-
termination of Hf, Nb, Ta, and Zr in geological samples after digestion with HCl. The
detection limits of the ltered samples were in the range of 0.10.4 mg (Zhang and Ma,
1994). Oxine or 8-hydroxychinoline is a very common reagent for the complexation of
elements in water, but its chelates are much less stable than the carbamate chelates. De-
spite this, it can be successfully applied for the preconcentration of Cu, Fe, Mn, Ni, and
Zn in sea salt. Therefore, the salt is rst dissolved in HNO
3
and ltered through a
membrane lter. After addition of Al as the carrier element, and oxine and thionalide
solutions, the sample is ltered again and subsequently analyzed. Iwatsuki et al. (1996)
achieved detection limits from 0.01 mg=g for Mn to 0.05 mg=g for Fe with this procedure.
Less ecient than the organic chelates, and therefore less popular, for the applica-
tion with XRF are inorganic reagents (e.g., Fe hydroxide and Al hydroxide). Aluminium
hydroxide might be selected for the coprecipitation of trace metals in environmental
waters. The optimum procedure involves the addition of a 1-mg Al(OH)
3
carrier to a 200-
mL water sample at pH 7.3. Quantitative recoveries are obtained for Ti(IV), Cr(II), As(V),
Pb(II), and Th(IV). The detection limits lay in the range between 0.2 and 0.8 mg=L
(Eltayab and Van Grieken, 1992). In one study, a combined technique of organic and
inorganic precipitants was used for the determination of As(III) and As(V) as well as the
total arsenic content in plant material (peach tree). The samples were rst treated by acid
digestion and then the As was separated and preconcentrated by DBDTC. Finally, the
arsenic components were precipitated Fe(OH)
3
. Detection limits lower than 0.1 mg=g and a
precision better than 5% were achieved (Pascual Brugues and Cortazar Castilla, 1995).
Sometimes, other inorganic compounds are also applied for the multielement (co)preci-
pitation and subsequent analysis by XRF; many references of earlier studies can be found
in Van Grieken (1982).
If only a few or even a single element should be separated, reagents, which form
selective complexes of low solubility with the elements of interest, are required. The main
problem, which must be solved, is the prevention of coprecipitation of other, interfering
elements; accurate chemical conditions play an important role for such selective proce-
dures. Tanaka et al. (1987) determined arsenic and antimony quantitatively after their
reduction to As(III) and Sb(III). First, the elements were treated with KBr and HCl at
80
C for 1 h. Both elements were then coprecipitated at pH 9 with a solution of ZrOCl

2
.
Detection limits of 0.3 mg=L for As and 6.1 mg=L for Sb were achieved. Sometimes, even a
speciation is possible by careful adjustment of the reaction conditions. Trace amounts of
V(V) and V(IV) can be quantitatively recovered from water at pH 1.8 and 4.0, respectively,
by reaction with NaDDTC. However, the concentration of Fe, Co, Ni, Zn, and Pb should
not exceed 100 mg=L in order to avoid interferences and receive a quantitative recovery
(Hirayama and Leyden, 1986). Microgram quantities of Cr(II) and Cr(VI) were success-
fully separated and determined by Pera niemi and Ahlgren (1995). In the rst step, Cr(VI)
is isolated from the original sample by collection onto zirconium-activated charcoal at pH
3.9 and the charcoal is ltered. The ltrate is spiked in a second step with FeCl
3
and the
pH is increased to 9. Subsequently, the formed precipitate is mixed with activated charcoal
and ltered. Detection limits better than 0.05 mg=L are reached for both species. PdCl
2
serves as the precipitation agent for the determination of iodine in urine and water samples
after digestion with chromic acid. The iodate was converted into iodite by Na
2
SO
3
and
nally precipitated as Pbl
2
(Mwaura et al., 1994).
However, it should always be kept in mind that inferences can occur by the presence of
organic material or high concentrations of alkaline elements. Most of the organic material
should be destroyed by acid treatment, but, often, stable components (e.g., humic sub-
stances) are dicult to digest and still present in the solution. Sometimes, the organic
content is so high that it is recommended to decompose the sample prior to further treat-
ment. For the separation of high alkaline earth element contents, an ion-exchange or
masking step might be useful before further precipitation. Another problem arises from
elements which are present in the sample in dierent chemical states. Some of the element
species may be incompletely enriched or even escape from the enrichment procedure. Cr
3
,
for example, is collected quantitatively by Fe hydroxide (Osaki et al., 1983; Mullins, 1984;
Ahern et al., 1985; Leyden et al., 1985), whereas Cr
6
escapes as CrO
2
4
. The Cr
3
species can
be then quantitatively collected by DBDTC or APDC in the presence of Co as the carrier
(Ahern et al., 1985; Leyden et al., 1985). This fact, however, can also be utilized for the
species analysis of Cr. In general, some drawbacks are present for each preconcentration
procedure and therefore a selection of the optimummethod requires a careful consideration.
2. Ion-Exchange Methods
The most popular techniques for the enrichment of traces from liquid samples are the
dierent ion-exchange methods. A very large number of studies dealt with various types of
ion exchangers, applied as resins packed in columns, in liquid form or impregnated onto
lters. Ion-exchange resins are available in the form of macroporous beads, membranes,
impregnates onto lters, or foamed plastics. The analyte, from which the traces should be
separated, can be taken up by dierent processes. One easy and fast solution is the batch
procedure, where the analyte solution is mixed with the ion exchanger in one container.
The whole solution is ltrated or decanted after some reaction time, and the remaining
residue is washed several times to eliminate possible impurities. The dried powder might be
briquetted for analysis or spread out onto a support material. Another common appli-
cation of ion-exchanger materials is the ltration of a liquid sample through a lter,
previously impregnated with an ion exchanger or the column technique. However, con-
ventional ion exchangers are of less interest for the enrichment of elements from liquid
samples, as they show only limited capacity and are relatively unspecic by the means of
elements. In the presence of high alkali or alkaline earth element content, for example, the
resins can easily be overloaded and most of the required elements pass either through the
column or are only partially enriched.
Despite of these drawbacks, the acid or basic resins are still quite popular for the
enrichment of traces from samples with low alkali and alkaline earth element content.
The most well-known chelating resins are Dowex A-1 and Chelex 100, containing
iminodiacetate functional groups for the complexation. Both have a wide range for the
collection of transition elements, and Co, Cu, Mn, Ni, Pb, Rb, Sr, and Zn are adsorbed
quantitatively from water samples. Chelex 100 also shows a rather high tolerance of alkali
and alkaline earth element content in natural water samples (Florkowski et al., 1976;
Clanet and Deloncle, 1980).
An anion-exchange separation of gold with Dowex 2-X10, after acid digestion of
gold containing ores, enabled the quantitative removal of the interfering elements Hg and
Zn for this application. The analysis of the dried and homogenized resin by XRF, using
the AuLa line for quantication, gave good results (Cojocaru and Spiridon, 1993).
Also, other Dowex resins (e.g. Dowex 168 with 100200-mesh grain size) are ap-
plied for the separation of rare earth elements from alkaline earth metals in geological
samples. The removal of interfering elements, after digestion of the original sample by HF,
HNO
3
, and HCl, is achieved by mixing the solvent with the anion exchanger. The rare
earth elements are retained on the ion-exchange column while the alkaline earth elements
pass through. The column is washed several times with HNO
3
and propanol-2 to remove
residuals and, nally, the rare earth elements are eluted by HCl (Bauer-Wolf et al., 1993).
Rock samples with low concentrations of REE are enriched successfully by using
bres impregnated with m-acetylchlorophophonazo. The rock sample is rst acid digested
and then a masking agent containing EDTA, CDTA and EGTA, and ascorbic acid is
added. Portions of this solutions are allowed to pass though the impregnated ber in the
form of an ion exchange column. Subsequently, the loaded ber is digested with HNO
3
and HClO
4
and, nally, the precipitate is obtained with MgCl
2
in aqueous ammonia.
Gong et al., (1995) reached detection limits of 0.050.21 mg=g with this procedure.
Speciation and preconcentration can be performed by using a mixture of Ag1-X8 (in
Cl
7
form) and AG5OW-X8 (in Na
form) and Chelex 100 beads, in order to separate

Cr(III) and Cr (VI) (Prange and Kno chel, 1985).
For a quantitative separation of transition metals from most water samples the ion-
exchange material should show less anity to alkaline and alkaline earth metals, but
should be selective for the trace metals of interest. Several attempts have been carried out
in this direction (Leyden and Luttrell, 1975; Burba and Lieser, 1977; Ducos-Frede et al.,
1995). Polyaminepolyurea resin columns, for example, were prepared from tetra-
ethyepentamine and toluene diisocyanate for the preconcentration of Ni, Cu, and Zn from
seawater at neutral pH by Leyden and Luttrell (1975). Burba and Lieser (1977) used
Cellulose hyphan eectively as the complexing agent for the enrichment of Cu and U from
seawater, freshwater, and mineral water samples. The reactive agent was received by
immobilization of 1-(2-hydroxyphenylazo)-2-naphtol on cellulose powder and by diazo-
tization of o-aminophenolcellulose and subsequent coupling with b-naphthol.
Uranium traces might be also trapped in another wayby treatment of a Dowex
168 resin with aqueous KMnO
4
solutions. In this case, amorphous manganese oxides
were generated in the reticulated structure of the resin. After elution, the sample is pre-
sented on a thin Mylar foil to the XRF unit. Furthermore, the resin has interesting
properties for the separation of inorganic micropollutants, which are frequently present in
water, without enrichment of macrocomponents (Ducos-Frede et al., 1995).
However, all preconcentration procedures based on ion-exchange columns suer
from several drawbacks. The resins or eluates obtained by the enrichment step need to be
treated further before they can be presented in a suitable form to the spectrometer. Resins
are usually ground, mixed with binder, and pelletized prior to analysis. Eluates must be
xed by ltration through a membrane or even a coprecipitation step is required. All of
these procedures prolong the time of the sample preparation and include a risk of con-
tamination and losses.
Of much higher interest are lters, which are impregnated with an ion-exchange resin
or specic agent for the enrichment of elements. The loaded lters can be then presented
directly to the spectrometer, and any further sample pretreatment is superuous. There-
fore, the risk of contaminations and losses can be kept very low and time-consuming
preparation steps are avoided.
AsO
3
3
; AsO
3
4
; CrO
2
4
; MoO
2
4
; SeO
2
3
; SeO
2
4
; VO
3
2
; and WO
2
4
from dierent water
samples were successfully preconcentrated onto cellulose lters, containing 2,2-diamino-
diethylamine as functional groups. Unfortunately, samples with high salinity cannot be
enriched quantitatively, as more than 0.01 M NaCl disturbs the enrichment capability of
the lters (Smits and Van Grieken, 1981).
Filters impregnated with ion exchangers, containing sulte and quarternary am-
monium as functional groups, were used in a study for monitoring lake water. The water
was ltered through the lter membrane and the loaded membrane was directly exposed
to the x-radiation. Such membranes might be also useful in providing general nger-
print-type information about trace element contents for river systems (Edwards et al.,
1993).
Uranium in natural water can be quantitatively separated by a simple cellulose
phosphate disk (Minkkinen, 1977). Toxic elements from water samples are collected on
sorption lters, pretreated with carboxylic acid and dithiocarbamate as complexing agents
(Tsizin et al., 1993). For the multielement determination in natural waters, an interesting
method of lter impregnation was investigated by Varshal et al. (1994). So-called DE-
TATA lters, containing conformationally exible aminocarboxylic groups as highly ef-
fective sorbents bound to cellulose matrix, were established for the preconcentration of
trace elements of natural waters. The lters were rst loaded with NH
4
for pre-
concentration and activation of the lter surface. The sample, consisting of snow, rain-
water, or even seawater of high salinity, was dissolved in HCl solution before presenting to
the lter surface. A monitoring of trace elements in underground and wastewater might be
also possible with this technique. The use of a cascade of lters under dynamic ow
conditions renders it possible to preconcentrate suspended substances and trace elements
from the solution in only one step.
Earlier studies, dealing with the enrichment of trace elements from environmental
samples onto lter surfaces, were mainly focused on ion-collecting papers (Van Grieken,
1982). However, most of these applications suer from unselectivity and low capacity for
the preconcentration of transient elements in large sample amounts, because alkaline and
alkaline earth elements are also trapped. Moreover, their capacity of enrichment for small
samples is too low to receive relevant detection limits for environmental samples.
Hyphan prepared by pelletizing of cellulose ber material as thin layers is of more
interest for large volumes. Good recoveries for trace metals are found from large volumes
of waters at pH 7. The detection limits usually lay in the range of 1 mg=L (Burba and
Lieser, 1979). Selective analysis for Co, for example, can be performed, after washing the
Hyphan-loaded lter with 3 M HCl. The washing procedure removes all other metals,
except Co. The amount of 0.4 mg=L Co can be determined, even in the presence of 1 mg=L
Fe (James and Lin, 1982; Coetzee and Leiser, 1986).
3. Chelationand Sorption Immobilization Methods
For most of the analytical methods, the extraction techniques are popular, as they supply
solutions which can be often transferred directly into the sample chamber of the instru-
ment. For XRF, however, this is normally not possible because most of the element
concentrations in the extracted solutions are still too low for a reliable analysis.
Reversed-phase extractions, in which organic chelation agents are xed to a solid
phase, are much more convenient for the measurement by XRF. For such a method, the
adsorbent and the sample solution are mixed together in a vessel. Agitation of the solution
during the reaction process ensures faster adsorption. Subsequently, the sorbent is sepa-
rated from the solution by ltration or decantation. For the removal of undesired traces,
the sorbent can be washed with appropriate solutions several times and then dried or
pelletized. The dried lter or pellet is then directly presented to the spectrometer.
Activated charcoal is well-known and often used as adsorbent. This material is a
good adsorbent for organic and colloidal materials and for the trace metal species bound
to such materials. With the addition of a chelating compound to charcoal suspensions, free
ions can be adsorbed quantitatively as well. Vanderborght and Van Grieken (1977), for
example, applied 8-quinoline as a chelating agent. The optimized preconcentration pro-
cedure consists of the addition of 10 mg 8-quinolinol per liter of water sample at pH 8 and
the application of 100 mg precleaned activated carbon to this solution. After ltration of
the suspension, quantitative recoveries were achieved for $20 ions from dierent media,
with enrichment factors near 10,000, more or less independently of the alkali and alkaline
earth element content.
Pera niemi et al. (1994) investigated zirconium-loaded activated charcoal as an ad-
sorbent for As, Se, and Hg. The activated coal was added to an aqueous solution, con-
taining these three elements; then the solution was stirred, allowed to stand, and, nally,
ltered through membranes. The lters were carefully dried at room temperature in order
to avoid losses, placed between Mylar sheets, and irradiated.
A selective determination of Se(IV) in various water samples can be carried out after
the reduction of Se(IV) with ascorbic acid to elemental Se and subsequent adsorption onto
activated carbon. After ltration, the lter is analyzed by EDXRS. Detection limits of
0.05 mg=L and a precision of 6% were found by Robberecht and Van Grieken (1980).
Foams represent another attractive extraction medium for the separation of traces
from dierent bulk materials. Carvalho et al. (1995) determined Ga from bauxite or Al-
based alloys as GaCl
4
, with polyurethane foam serving as sorption medium. The material
was rst dissolved with HFHCl, then evaporated to dryness and dissolved again in
6 mol=L HCl mixed with TiCl
3
. Finally, polyurethane foam, pretreated with HCl, was
added and the solution ltered after some minutes of reaction time. In combination with
organic chelation agents, polyurethane foam is even more ecient. Mercury was de-
termined in dierent matrices and chemical states by Braun et al. (1984) after pre-
concentration on DDTC-loaded polyurethane foam disks. The preparation of the disks
was carried out by the addition of a 4% solution DDTC in chloroform (assuring a 20%
concentration of the regent on the disk) and the addition of 0.2 mL dinonyl phthalate
plasticizer. After adjustment to pH 5, 25 mL of the sample solution were shaken with the
foam disk for 1 h to separate Hg. Extraction eciencies between 88% and 100% were
reported for 0.2 and 2 mg=L concentrations.
Gold can be extracted with tributyl phosphate as solid extractant from ore samples.
Therefore, the element is enriched from pulps after aqua regia leaching. For the de-
termination by XRF, a back-extraction with thiourea solutions at 100
C is required; to
obtain nally a thin sample, the thiourea solution can be placed inside a polyethylene
cylinder, supplied with a lter paper disk covering the bottom, and evaporated. For a 25-g
sample, the detection limits were at 10 ng=g (Dmitriev et al., 1991).
The extraction of dierent elements from coal samples is carried out in three steps,
and each step is based on the dierent solubilities of the dierent trace elements. In the
rst step, the ground coal sample was treated with deionized water 24 h, the residue re-
moved and vacuum dried. In the second step, ammonium acetate is added to the sample
and this suspension is heated to 70
C for 24 h. The resulting solution is ltered and rinsed

with water, and the obtained residue freeze-dried. In the last step, the remaining part of the
coal sample is mixed with HCL and heated again to 70
C for 24 h. After vacuum drying,

all received residues are pressed into pellets and analyzed with XRF (OKeefe and
Erickson, 1994).
Total-reection XRF has proven to be one of the most attractive techniques for the
analysis of liquid samples. Its strength is in the determination of very small sample vol-
umes with detection limits down to the ppt level (To lg and Klockenka mper, 1993). In the
last years, several applications were carried out with preconcentration of trace elements
and elution of small portions directly onto the sample carrier for analysis (Prange et al.,
1985; Barreiros et al., 1997). In one recent application, the mineral water sample was rst
preconcentrated with APDC, subsequently ltered through a Nuclepore membrane, and
dried and small portions of the powder transferred to a carrier for analysis (Kump et al.,
1997).
V. BIOLOGICAL SAMPLES
The determination of trace metals and inorganic compounds in biological materials is
more and more important in analytical chemistry, in view of its potential for diagnostics or
monitoring. Several plant materials can be used as monitoring systems for pollution and
deposition of heavy metals in the environment. The interest in clinical applications of XRS
increases from year to year as well. In vivo XRS is almost an accepted technique and
overcomes all of the diculties of laboratory treatment of the samples, like digestion,
separation, or preconcentration. The material can be analyzed in situ without any ma-
nipulations or delay. For the patient, it is much more convenient, as often painful and
protracted procedures can be avoided. Several studies dealt with the in vivo analysis, and
the main interest is focused on the determination of heavy metals in bones. Particularly,
Pb is of high interest and Rosen et al. (1993) showed that XRF represented a unique
capability for a safe, accurate, and noninvasive quantication of Pb in bones of children.
The direct determination of Pb in bone gives an indication of the ongoing accumulation,
whereas conventional blood studies only reect the recent exposures. Several studies on
the determination of Pb in tibia or other bones were carried out. They mainly dealt with the
monitoring of Pb concentrations in bones of industrial workers, under consideration of the
working conditions, duration of employment in this sector, lifestyle of the person, and so
forth. (Bleecker et al., 1995; Cake et al., 1995; Roels et al., 1995; Ryde et al., 1995). Other
heavy metals of interest were Cd and U, as studied by Bloch and Shapiro (1995) and
Nilsson et al. (1995). Further in vivo investigations dealt with the concentration of various
elements in dierent organs. Here, the main eort was in the area of kidney and lung
research (Skerng and Nilsson, 1992; Homma et al. 1995; Gerhardsson et al., 1995).
However, the sensitivity and detection limits of the in vivo applications are still rather
poor, and the treatment of the patient is not always easy. Furthermore, a highly focused
and energetic x-ray beam is required for a direct exposure of the sample and to penetrate
through the tissue material, whereas, normally, such applications were carried out using
synchrotron radiation as the excitation sources.
More conventional is the determination of traces in organic samples, like plant
materials, tissues, and so on. For such applications, it is often required to separate the
organic matrix from the traces, and several dierent separation methods were proposed
for solving this problem. They range from open digestions in the traditional way to fully
automated and expensive equipments. Sometimes, only parts of the sample were separated
and used as representative targets for the whole sample; also, separation of the sample in
dierent fractions, such as blood in various cellular and subcellular fractions, are used
(Weber et al., 1980; Mangelson and Hill, 1981). However, in most cases, the amount of a
sample available for the analysis is rather small and high sensitivity is required (Kim et al.,
1987).
Numerous articles and several reviews dealing with the sample preparation and
analysis of biological materials were published (Bacon et al., 1990; Crews et al., 1990;
Maenhaut, 1990; Mangelson and Hill, 1990; Taylor et al., 1994, 1995). In this section, the
main and most convenient preparation techniques will be presented and discussed.
A. Physical Methods of Sample Preparation
In some cases, a suitable sample preparation is possible with little or almost no eort. All
biological samples which are self-supporting and of appropriate size can be often pre-
sented in their original form to the spectrometer. Examples of such applications are bones,
hair, teeth, and nails. Also for plant samples, such as leaves, needles, tree rings, or wood,
the sample preparation is relatively simple and fast. Specimens of this category can often
be irradiated after simple procedures like cutting, grinding, or just drying. Hair samples
present good examples with little or almost no preparation eorts (Kubo, 1981; Toribara
et al., 1982; To ro k et al., 1984). The main intention of studying hair samples lays in the
deposition or enrichment of heavy elements in the whole specimen or in single segments. In
the latter case, the hairs should be cut into the required segments and the segments directly
mounted on a target frame for irradiation. Thinner samples, which do not have enough
stability to be xed directly inside the target frame, might be placed rst on a suitable
support. The main disadvantages of the direct measurement are the lack of possibility to
add an internal standard and severe matrix eects.
Direct determination in a more sophisticated way was performed by Toribara (1995).
He built a special EDXRF sample system for the determination of Hg in 1-mm hair
segments of a single hair. More conventionally, Basco and Uzonyi (1995) studied the
concentration of Ca, Cl, K, and S in hair by mounting the hair onto a sample support.
However, this method seems to suer from quantication problems. Dierences could be
reported between two types of hair, but they were considered to be negligible in com-
parison to the measured biological variability of the material.
Leaves and needles are samples which can be also analyzed almost directly. More-
over, these are samples of special interest, because they can be used as bio-indicators for
monitoring pollution of air, soil, or groundwater, and together with the determination by
XRS, an almost ideal combination is available (Kitsa et al., 1992; Marques et al., 1993;
Vincze et al., 1993; Calliari et al., 1995; Ostachowicz et al., 1995; Somogyi and Pazsit,
1995).
Pine needles are analyzed for trace elements after pulverizing and pressing into a
tablet. This tablet is placed on Mylar foil and irradiated. The detection limits vary from
70 mg=g for the light elements such as K and Ca to 0.3 mg=g for the transition metals
(Boman et al., 1996).
In an unusual way, algae material was collected directly onto a quartz carrier from
the sea. The mounted sample was washed, dried, and irradiated. However, the obtained
results were more suitable for a rst screening as for a reliable analysis, because the or-
ganic matrix caused a high background signal (Boman et al., 1993).
Sometimes, botanical samples are less stable and need to be stabilized by mixing with
binding material (Bassari and Kumru, 1994; Omote et al., 1995; Wilson et al., 1995).
Another quite common technique for xing of unstable materials is the embedding of the
sample inside a resin or wax. For the determination of S in rapeseed for example, a single
rapeseed was embedded into wax and analyzed by WDXRF (Schnug et al., 1993).
Biological liquids, like blood and serum, might be spotted directly onto a suitable
substrate without any pretreatment (Robberecht et al., 1982). Blood samples, for example,
can be pipetted in 100-mL portions onto a simple paper lter for the determination of Br in
blood (Hurst et al., 1994). Serum samples are treated almost in the same way, with the
exception that instead of a paper lter, polypropylene foil should be selected as a carrier
(Hurst, 1993). Urine samples as well as blood samples were pipetted onto Mylar foil and
dried in a refrigerator at temperatures about 24
C in order to avoid losses of volatile

components. Detection limits between 1532 mg=L Ca in urine and 6 mg=L for Sr in blood
were claimed (Viksna et al., 1995; Hong and Ha, 1996).
Several materials can be analyzed with XRF, even for trace metals, after freeze-
drying (lyophilization). For this procedure, the sample is kept under vacuum in liquid
nitrogen for at least 1 day. Then, the residue is pulverized and pressed into a pellet for
analysis. This technique has the advantage that the sample mass is reduced by a factor of
5, which results in a reduction of the spectrum background and improves the sensitivity.
Soft organic material can also be stabilized in the same way. Maenhaut et al. (1984) used
this technique for the analysis of human and animal tissue by PIXE.
Often PIXE, TXRF, or SRXRF is applied for the analysis of biological material, as
they show lower detection limits and require less eort for the sample preparation than in
the case of conventional XRF analysis. Lung tissue, for example, can be analyzed directly
by TXRF as a microtome section mounted on the sample carrier. The sample is in a frozen
state and can be cut to the required thickness for the analysis (von Bohlen et al., 1988). For
a quantitative analysis, it is sucient to determine the dry weight or the sample and add an
internal standard. Especially for very small sample amounts of a few microliters, which are
often only available for blood, serum, and plant liquid, TXRF is a very powerful tech-
nique. Blood serum can be pipetted directly onto the carrier for analysis with TXRF
without any preparation (Gu nther et al., 1992) or after dilution with water containing the
internal standard for the simultaneous determination of Br, Cu, Fe, and Zn in human
serum (Yap, 1988). Xylem sap from cucumbers was also mounted directly to the carriers
for analysis of Pb contaminations (Zaray et al., 1997). The Ni and Mo content of enzy-
matic material was determined by TXRF after dilution with 5% HNO
3
for the partial
destruction of the organic matrix (Fischer et al., 1996).
B. Chemical Methods of Sample Preparation
In most cases, the determination of trace elements at low levels by XRS is not possible
without separation of the organic matrix. Several dierent digestion, ashing, and other
separation procedures were developed for this reason; they can also be applied for the
analysis of such samples with other comparable analytical techniques, like AAS or ICP-
OES.
A sample preparation method with minimum eort is simple ashing of the material
in a mue furnace at temperatures between 400
C and 600
C. Raghavaiah et al. (1996)

determined Zn in human head hair after ashing at 600
C in an electric furnace. The hair

samples were rst cleaned with a mixture of acetone and deionized water for 30 min and,
after drying, ashed and pulverized. The powder was spread over an adhesive foil for
subsequent analysis.
For the determination of Mn, Fe, Sr, and traces of Cr, Ni, and Zn as pollution
elements in lake mussel shells, the collected shell samples were cleaned and separated into
two dierent valves before further pretreatment. Each valve was then baked in a furnace at
350
C in order to destroy the protein material. Subsequently, the material was pulverized
and pressed into a pellet, which was presented to the spectrometer (Maddox et al., 1990).
Sometimes only partial ashing is recommended. Havranek et al. (1986) performed
this for the analysis of hair. An 1-g aliquot of hair is partially ashed in a mue furnace at
200
C, the cool ash was homogenized, and a 0.3-g portion was treated with a few drops of
polystyrene solution in chloroform and pressed into a pellet. Urine samples are analyzed
as pellets as well after evaporation and partial decomposition at 220450
C (Nielson and
Kalkwarf, 1978).
However, treatment of samples at high temperatures suers from several drawbacks
and is therefore rarely employed. The major drawback is the loss of volatile components of
the sample. The addition of an ashing aid may minimize it, but the elements cannot be
retained completely (Nielson and Kalkwarf, 1978; Hang and Ha, 1996).
Another more sophisticated but even more expensive technique is the ashing of the
biological material with an oxygen plasma. For this procedure, the nely pulverized
sample is placed onto the bottom of a specially designed plasma tube made of quartz. The
tube is then connected to the plasma unit and evacuated. The sample is ashed by passing
oxygen through the tube, and continous cooling by a cooling nger assures that most of
the volatile components remain in the sample. Selenium and arsenic can be kept almost
quantitatively, but mercury shows high losses. The remaining residue is then taken up by
HNO
3
or a combination of HNO
3
and HCL. Amounts of 50100 mL of the solution are
pipetted on a foil target of Mylar or Nuclepore and dried prior to analysis. Unfortunately,
organic materials often contain high concentrations of Ca and K salts, which crystallize on
the foil and cause a high-background signal. Sometimes, it is necessary to separate such
salts by suitable extraction methods or to select an alternative way of sample preparation.
In general, ashing in an oxygen plasma is rather fast and easy to handle. However, for
complete ashing in an aordable time, the sample should be pulverized to small grain sizes
in order to obtain a suciently large surface for the reaction with the oxygen gas. Fur-
thermore, the reaction time depends on the material to be digested and might vary between
several minutes and several hours for materials that are dicult to digest (Raptis et al.,
1983; Knapp, 1984).
A traditional and relatively fast method for sample preparation is wet ashing with
HNO
3
or a mixture of HNO
3
with H
2
SO
4
, or HClO
4
. With these mixtures, most of the
organic material can be attacked (Bock, 1979). Cu, Fe, Rb, Se, and Zn in serum samples
were determined after digestion with HNO
3
. For quantication, Ga was added as an in-
ternal standard and a 20-mL aliquot was pipetted and dried onto a sample carrier for
analysis by TXRF (Raptis et al., 1983). Even more eective is a combination of HNO
3
and
HF, as it dissolves also silicates in organic materials.
A microdigestion method was developed for the trace element determination in
biological materials and human serum. For this, 500 mL of human serum were treated with
500 mL HF and dropped onto a Si-wafer chip. After drying, the chip was analyzed by XRF
(Sayama, 1995).
In general, a digestion procedure should be carried out in a closed vessel, as working
under open conditions might cause contaminations and losses which inuence the results
(Tscho pel, 1983). Using HClO
4
requires special care. This acid tends to explode when
organic material is not completely oxidized. A better and safer method is the application
of closed PTFE vessels or quartz tubes, which can also be used for the digestion under
high pressure. However, the selection of quartz tubes is highly recommended, because the
smooth surface of this material avoids adsorption eects of the elements. Moreover, it can
be cleaned easily by exposure to nitric acid fumes in order to avoid the introduction of
contaminations. PTFE or Teon might be easier to handle, but it shows higher con-
taminations and is more dicult to clean compared to quartz because of rough surface.
Zinc for example, is a well-known contaminant of Teon vessels. Another problem that
might occur with Teon is diusion from and into the walls. This is particularly serious for
volatile elements and can lead to signicant mistakes in the nal data.
For the determination of trace elements in lichen material, 200 mg of the collected
samples are digested with 3 mL HNO
3
, 0.2 mL, H
2
O
2
, and 0.05 mL HF in a PTFE vessel.
From the digested sample, targets can be prepared by pipetting 300 mL of the solution onto
a Mylar lm and drying (Calliari et al., 1995).
A very eective method for the digestion of organic materials is the high-pressure
digestion in specially designed bombs. Usually, a small amount of the pulverized sample is
placed in a quartz or Teon vessel and some milliliters of acid are added. The tube is then
placed inside a high-pressure chamber and exposed to pressures of about 200 bar under
nitrogen atmosphere, at temperatures of about 260
C. Under such high pressures, the

organic material should be completely decomposed. Several drops of the resulting solution
can be pipetted onto a foil or target, dried, and analyzed. The main drawbacks of this
procedure are the substantial eort and the requirement of a suitable instrument. Usually,
one digestion needs about 3 h and includes slow heating and cooling down of the sample
chamber. Furthermore, such instruments, working under high pressure, should be kept in
special rooms in order to avoid accidents by possible explosions (Tscho pel, 1983;
Schmeling et al., 1997).
The destruction of biological materials with reactive gases is rarely carried out, al-
though it seems to be quit ecient for some materials. In one study for example, 90% of
plant material was oxidized with HNO
3
vapor within a short time and only a simple all-
glass apparatus was used for the vapor-phase oxidation (Thomas and Smythe, 1973). The
addition of HClO
4
can accelerate the reaction and ensure complete oxidation. Almost the
same technique was applied by another group for the determination of Zn in brain tissue
by digestion in PTFE vessels under pressure (Klitenick et al., 1983).
The sample digestion by microwave plays a more and more important role (Abu-
Samra et al., 1975; Kingston and Jassie, 1986; Skelly and di Stefano, 1988), and the
available digestion systems become better equipped. Automatic ventilation to remove acid
fumes is already available in all new equipments. The interior of the oven is, in comparison
to the conventional household devices, usually acid resistant to prevent rusting and to
increase the lifetime of the device. Systems of 1000 W and greater power are in use for a
fast and complete destruction of materials that are dicult to decompose. Several metal-
free materials ensure that contaminations from the vessels are kept low. With digestion
vessels of tetrauorometoxil (TFM), the memory eects due to adsorption and diusion
are almost absent after two predigestion cycles of 30 min with concentrated HNO
3
(Noltner et al., 1990). For vessels made of peruoroalcoholoxil (PFA), a 1 day HNO
3
vapor exposure is enough to reduce the blank values under the detection limits of XRS
(Knapp, 1985).
In using microwave digestion systems, care should be taken as well, because the
pressure inside the vessels increases rapidly during the digestion procedure. Opening the
vessels too soon after nishing the procedure, without careful releasing of the inside
pressure, can create hazards. Especially when working with highly concentrated acids,
special care is required. The vessels should be smoothly cooled down and stand for a while
before removal of the sample. Usually, HNO
3
, in concentrated or diluted form, is re-
commended for the microwave digestion of organic materials. Neither mixtures of HNO
3
with H
2
SO
4
nor HNO
3
with HClO
4
are advised for use for decomposition by microwave.
H
2
SO
4
has a quite high evaporation point in comparison to HNO
3
and a substantial in-
crease of the pressure inside the vessel can occur during the digestion event, which might
lead to explosions. HClO
4
reacts explosively with incompletely reduced organic material,
which can cause dangerous injuries. In several studies, explosions were reported resulting
from overpressurizing the digestion bombs (Matthes et al., 1983; Fernando et al., 1986).
Also, the relation between acid amount and sample as well as the complete reagent
amount should be selected carefully. For safety reasons, it is better to start with small
amounts of material and acid and increase this by careful observation of their behavior. A
detailed discussion about working with microwave digestion systems can be found in the
book by Kingston and Haswell (1997).
The major advantage of the microwave technique is the short time required for a
complete reaction. By digestion with microwaves, the sample is directly attacked and the
used vessels or container do not need to be heated up. A destruction biological material
can be performed within a minimum of time compared to other technique, where con-
tainers and sample chambers are included in the heating process.
The wet digestion methods (by microwave or high-pressure ashing) are considerably
more rapid, with reaction times of about 23 h, compared to at least 8 h necessary for a
complete decomposition by dry ashing. A comparison of dierent sample preparation
methods for the analysis of organic material showed that slurry preparation needs 5 min,
microwave digestion 45 min, dry ashing 24 h, and open wet digestion 36 h (Miller-Ihli,
1988).
In combination with high pressure, the microwave digestion technique shows
quantitative recovery for elements, which would be lost by volatilization during an open
digestion. Also, traces of rare earth elements show good recoveries at the ppb level, even in
the presence of organic material that is extremely dicult to digest.
Several studies dealt with the destruction and analysis of certied biological reference
materials. Hay (V-10, IAEA) samples, for example, were digested in a microwave oven
with HNO
3
and H
2
O
2
. Five hundred milligrams of the powdered material were mixed with
4 mL concentrated HNO
3
and 1 mL H
2
O
2
and heated three times for 1 min each at 300 W.
After each heating cycle, the vessel was allowed to cool down and the pressure released.
Finally, the sample was exposed for 7 min at 300 W and 2 min at 600 W. The complete
procedure needed no more than 30 min and showed good agreement with the certied
results (Noltner et al., 1990). Very short digestion times of 1 min were found to be su-
cient for the decomposition of NIST standard material Oyster Tissue (SRM 1566a) and
Bovine Liver (SRM 1577a) in a closed PFA bomb with HNO
3
(Stripp and Bogen, 1989).
Lichen samples were studied after collection from dierent places and were proposed
as biomonitors. The collected material was rst dried and then acid-digested. For this
procedure, 200 mg of lichen material were treated with 3 mL of HNO
3
, containing the
internal standard, 0.2 mL H
2
O
2
, and 0.05 mL HF in closed Teon vessels by microwave
digestion. The nal targets were prepared by pipetting 300 mL of the decomposed sample
onto Mylar foil. The detection limits were reported between 0.1 mg=L for Cu and 10 mg=L
for S (Calliari et al., 1995).
For the determination of Cr in seed material (e.g., barley seedlings), the samples are
acid-digested using a microwave oven with 1200 W power. Then, 300400 mg of the roots
and leaves are placed into a PTFE vessel and decomposed with 34 mL HNO
3
. The sample
is then presented as a thin lm mounted on Mylar foil to the EDXRF instrument (Calliari
et al., 1993).
A special energy-dispersive miniprobe multielement analyzer (EMMA) was devel-
oped for the determination of Pb and other traces in peats. The samples can be analyzed
directly or after acid digestion in Teon bombs in a microwave oven with 3 mL H
2
O
2
,
4 mL HNO
3
, and 1 mL HF. The comparison of both methods showed satisfying results
(Cheburkin and Shotyk, 1996).
Also, for the determination of animal and plant tissue by PIXE, a microwave di-
gestion procedure might be applied. In this case, the digestion can be even performed in a
conventional household microwave oven in closed Teon vessels with high-purity HNO
3
as the reagent. A high acid concentration of 14 M should be applied in order to reduce the
dilution eect of the sample and ensure sucient sample material for the analysis of traces.
The reaction vessels are lled with vegetable oil (7.5 mL to 100 mg of the sample) to
prevent damage of the antenna. After digestion, 10 mL of the resulting solution are pi-
petted onto a 1.5-mm-thick Kimfol polycarbonate lm. The lm was previously treated
with 14 MHNO
3
and 0.05% polyvinylpyrrolydone solution to make it hydrophilic and to
achieve a small spot. The results obtained by Pinheiro et al. (1989) showed an accuracy of
better than 5% and a matrix reduction factor of 5.
In body uids with very low trace element content, it is often recommended to enrich
the traces with a preconcentration step and to separate the matrix. Cell uids and blood
serum, for example, show a relatively thick layer of a low-Z-element matrix after eva-
poration, which increases the detection limits. In principle, all preconcentration methods,
which are applicable for water analysis, are also practicable for organic uids. However, it
should be considered that the amounts of such samples are usually much smaller, and
working in microscale is often required.
Very low contents of Cr (0.3 ng=mL) in plasma can be determined after complexa-
tion with APDC and extraction with methyl isobutyl ketone. After evaporation of the
organic solvent, the residue is dissolved in acid and deposited on a thin polycorbonate foil
(Simono et al., 1985). APDC can be also applied for the analysis of hair samples. For
that, the hair samples are rst digested with a combination of HClO
4
and HNO
3
(1:5 v=v),
later distilled, and then precipitated with ADPC, whereas Y acts as the internal standard
and coprecipitation agent. The resulting precipitate is ltered through a Nuclepore
membrane, dried, and measured. The detection limits are around 0.4 mg=g for Pb and Ni
and around 2.2 mg=g for Fe (Eltayeb and Van Grieken, 1989, Eltayab and Van Grieken,
1990).
For the determination of Se in serum of patients with liver cirrhosis by PIXE, Te was
chosen as a coprecipitant and internal standard, and good results were reported (Cesaril
et al., 1989).
As for the preconcentration of traces from water samples, various kinds of ion-ex-
change resins have been proposed for biological samples as well. With the application of
cellulose-hyphan, for example, the detection limits might be reduced by about a factor of
10, by separating the trace elements (Agarwal et al., 1975). Protein material can be pre-
ferably isolated by gel electrophoresis (Szo kefalvi-Nagy et al., 1987).
C. Sample Preparation for Analysis with Spatial Resolution
For the analysis of microsamples with spatial resolution special sample preparation
methods were developed. They are well known in the eld of electron microprobe analysis
and several books dealing with this subject are available (Hayat, 1970; Hall et al., 1974;
Echlin and Galle, 1975; Reed, 1975; Erasmus, 1978; Hayat, 1980; Revel, 1984).
By application of microprobe analysis, some regulations should be strongly con-
sidered regarding collection and handling of the sample in order to avoid systematic er-
rors. For biological material, the time of sample collection is often of high importance; for
example, it should be considered that by working with tissue samples, enrichment of Na,
Cl, and Ca is taking place after the death of the cell and decreasing concentrations of
Mg and K will inuence the results also (von Zglincki et al., 1985). To avoid problems in
this direction, the time delay between sampling and analysis should be kept as short as
possible.
Furthermore, during analysis of the sample, the specimen will be transformed into
another state. Usually, a high vacuum is required for the analysis, and to avoid eva-
poration of tissue water, these must be withdrawn or immobilized by suitable procedures.
For ultrastructural studies with transmission electron microscopy, wet chemical
techniques might be applied. For such procedures, the sample is chemically xed, the
cellular processes are arrested, and the cell contents are immobilized. The tissue water can
then be removed by immersion in an organic solvent. The dehydrated specimen is then
inltrated with a suitable resin for sectioning purposes.
A more detailed discussion about such procedures can be found in Chapter 13 and in
the works of Glauert (1974), Steinbrech and Zierold (1987), and Hayat (1989).
Synchrotron-radiation XRF might be a suitable technique for microanalysis as well
(see Chapter 8). Gilfrich et al. (1991) used synchrotron-radiation XRF for the determi-
nation of elements in tree rings, which are good indicators for the geological and atmo-
spheric conditions during the growth of the tree. SRXRF oers the advantage that the
primary beam can be focused on small parts of the sample and sample preparation re-
quires only polishing of the tree slices.
The concentrations of manganese in living leaves were determined by Fukumoto
et al. (1992). In this study, the leaf was directly placed into the instrument and analyzed.
The inuence of acid rain and the exposure to severe x-ray radiation of the leave was also
monitored in the same study.
VI. ATMOSPHERIC PARTICLES
The amount of publications dealing with the analysis of atmospheric particles by x-ray
uorescence increased in the last 5 years and showed the suitability of this technique for
such samples. XRS is still the most popular technique for this kind of specimen, especially
for routine analysis, in the eld of x-ray analysis. Several studies were also carried out with
TXRF or PIXE, but easy handling of the sample and less eort make the conventional
XRF more attractive, despite its higher detection limits.
Heavy metals are nearly always present in the particulate phase of air and can be
easily separated by ltration or impaction. High enrichment factors are reached by l-
tration of large air volumes, and homogeneously loaded lters are an ideal target for XRS.
Nevertheless, there are several requirements, which should be considered carefully before
reliable results can be obtained.
The main problems which occur are bound to particle size and x-ray absorption
eects due to the lter media (lter penetration eect). If the particle size distribution of
a particular element is known, the particle size eect can rather easily be corrected.
However, in most cases, the particle size distribution is unknown or dicult to measure. If
this is the case, the particle size eect should be kept low by selection of suitable lter
materials, which collect particles on the surface like Nuclepore or Millipore lters. The
absorption of x-rays by the lter medium depends on the depth distribution of the par-
ticles, which can be calculated approximately by measuring the uorescence intensities
from the back and front sides of the loaded lter. The mass absorption coecient of the
particles can be evaluated by transmission measurements and, later, the particle at-
tenuation can be calculated (Adams and Van Grieken, 1975).
If thin membranes, like Nuclepore or Millipore, are selected for the collection, the
absorption eects in the lters are small and often negligible above 5 keV, because,
normally, all particles should stay at the lter surface. However, for light elements such as
Si, P, S, and as well as for elements having very small particle sizes, like Pb and S, the
absorption eect needs to be corrected by using a suitable correction procedure.
When choosing thick lters, for the collection of large particle amounts, an easy
and proper way to minimize serious absorption eects is the so-called sandwich geo-
metry (Van Grieken and Adams, 1975). This technique is based on simple inward
folding of the loaded lter to obtain a kind of sandwich. The heterogeneous dis-
tribution of the particles is minimized, despite the higher absorption eect for the lter
in this geometry, as it is assumed that all particles are on the surface and therefore in
the center of the sandwich, which also averages the unknown deposition depth of the
particles.
Both methods (the backfront measurement and sandwich geometry) show accurate
results when the absorption cross section of the lter is not excessively high. The particle
size distribution on the lter surface inuences the accuracy of the correction more than
the depth distribution inside the lter (Davis et al., 1977).
For the establishment of lter reference material for aerosol particles, dierent types
of lter were tested with a high-volume aerosol sampler. As conditions for the reference
material were claimed, low particle size eects, the lter thickness should not exceed
0.5 mg=cm
2
and the lateral uniformity of the lter must be within certain limits. Fiber
lters were generally excluded from this study, as they collect particles in their bulk. Only
two types of lter (polycarbonate and cellulose nitrate membranes) fullled these condi-
tions and showed an almost uniform deposition onto the surface, which was determined
by analysis of dierent spots from dierent places at the loaded surface (Wa tjen et al.,
1993).
With ltration of the atmospheric particles, usually all particle sizes present in the
aerosol down to the lter cuto recorded and particle size eects can easily occur. With
stacked-lter units, operating with dierent lters of dierent pore sizes, and dichot-
omous samplers, some kind of size fractionation can be established. With such col-
lection methods, the particle size eects can almost be overcome, as the particles are
divided into two or more fractions. For particles smaller than 2 mm, the particle size
eects are negligible in general, and, therefore, the determination of elements with a low
Z number is also possible. If impactors with several stages are applied for the aerosol
collection, the size distributions of the particles become more uniform and fulll the
requirements.
Another possibility for overcoming eects bound to dierent particle sizes and to
obtain reliable results is the analysis of lters as pressed pellets. For this, the loaded
lters are pelletized and sometimes also previously mixed with binder and analyzed
(Vigayan et al., 1997). Coal y ash, for example, was ground, mixed with poly(vinyl
alcohol) binder, and pelletized (Bettelini and Taina, 1990). In one study, it was shown
that pressing the sample into a pellet after grinding to a powder yields better reprodu-
cibility than applying the sample as a thin lm (Matherny and Balgava , 1993). The
preparation of fusions is another way to eliminate particle size eects (Pella et al., 1978;
Balcerzak, 1993). Good results were obtained by fusion of $70 mg of small dust samples
with lithium uoride and lithium tetraborate (20:80). To yield a homogenous microbead,
the sample was treated at 10501100
C for 7 min in a mue oven. Subsequently, the

fusion was poured into a specially designed mold and nally analyzed in a normal
sample holder, modied with a spacer in order to x the sample (Moore, 1993). How-
ever, it should always be considered that each additional sample preparation step might
introduce blank values to the material or dilute the sample. Especially by working in the
trace element region, which is usually the case for atmospheric particle samples, this can
cause serious problems.
One point, which should not be underestimated, is the partial or complete loss of
volatile components of the sample. Especially in the wavelength-dispersive mode, voltaile
compounds such as Cl, Br, and, in particular, S may be lost during evacuation of the
sample chamber. This eect is even more severe when working with PIXE. Hereby, the
sample is irradiated with a highly focused charged particle beam under high vacuum and
losses of about 50% of sulfur may occur. In addition to the losses of sulfur due to vo-
latilization, chemical reactions can take place and lead to signicant losses of S when
2-MeV protons or 18-MeV a-particles are used (Hansen et al., 1980).
For the collection of aerosols onto lters, a variety of lter materials is available.
Each lter material provides special properties with respect to collection eciency, me-
chanical stability, hygroscopy, and so forth and every selection is usually a compromise
among the lter properties, the collection purpose, the available costs, and the compat-
ibility with the analytical technique to be applied.
Before choosing a lter material for the collection of atmospheric particles, the blank
values of the material itself must be determined. The lter should consist of materials with
low blank values for the required elements. Furthermore, the spectral background should
be reasonably low in order to allow a reliable trace element determination. Cellulose
membrane lters, for example, especially those made of cellulose nitrate and acetate, are
unsuitable for the determination of P, S, K, and Ca, as they show high blank values of
these elements (Krivan et al., 1990). Very practicable are Nuclepore membranes because
their blank values are very low and the particles are collected only on the surface. Un-
fortunately, the price for these lters is quite high. Whatman 41 lters have a high col-
lection eciency and are mechanically stable, clean, and reasonable in price. However, the
high hygroscopicity requires a controlled humidity for weighing and handling of the lter.
They also show a much higher background signal in comparison to the Nuclepore
membranes.
The interpretation of the lter eciency is often complicated, as the test data are
usually based on unloaded or clean lters. However, during a sampling event, the lters
change their properties depending on the particle load. With increasing amounts of col-
lected particles, the eciency increases as well, despite the higher ow resistance of the
loaded lter. In general, the real eciency of the lter is higher than in the published data.
Furthermore, the collection eciency increases with higher surface velocity and larger
particle size. For the Whatman 41 lter, for example, the collection eciency is quite low
for particle sizes of 0.26 mm and surface velocities of 1.5 cm=s. With surface velocities of
100 cm=s, the collection eciency increases to 95% for both small and large particles. A
10-mm pore-size Teon lter shows collection eciencies of 6090% for low surface ve-
locities and particle sizes between 0.003 and 0.1 mm. For 0.5- and 1-mm pore-size Teon
lters, the eciency is always >99.99%, independent of surface velocity and particle size
(Lippmann, 1978).
Membranes with dierent pore sizes can be used in stacked-lter units for size-
fractionated collection or with dichotomous samplers.
Quartz-ber lters present another alternative. They show high collection eciencies
and are very clean and less hygroscopic than cellulose lters. Particles within the range of
1000.1 mm are retained on this lter. Furthermore, they are heat resistant. Haupt et al.
(1995) tested dierent techniques for the preparation of standards for the direct analysis of
quartz-ber lters. One preparation technique was based on the generation of aerosols and
their deposition onto the lter surface. The other one required spotting of a multielement
standard solution onto the lter and subsequent air-drying. The aerosol generation pro-
cedure showed much better accuracy and is, therefore, preferable for the preparation of
standards. Glass-ber lters are not recommended for trace analysis of inorganic com-
ponents in aerosols. They are much less expensive than the quartz lters, but very high and
variable blank values of diverse elements are their major drawback. However, they are
quite useful for the collection and determination of organic compounds. Sometimes, these
lters are also applied for the analysis of one single component in the aerosol sample.
Lead, for example, can be determined in total suspended air particulates, after collection
onto glass-ber lters without problems. LaFisca et al. (1991) cut disks of 32-mm diameter
from the lters and irradiated them successfully. Koutrakis et al. (1992) collected house-
hold dust onto Teon lter with a Harvard impactor. The ne-particle mass was grav-
imetrically determined and, subsequently, the concentrations of elements associated with
the ne mass determined by XRS.
In some cases, lters may also be used for the collection of reactive gases. For this
purpose, the lter is impregnated with special chemicals which retain selected components
of the gases. Hydrogen sulde, for example, can be trapped by coating the lter with ferric
ion solution. The excess Fe is removed from the lter surface by washing with appropriate
solvents, whereas the Fe sulde precipitation stays on the lter. Sulfur can be determined
directly or indirectly by measuring the Fe x-radiation. Suitable standards are available for
such measurements (Leyden et al., 1984).
Because XRF is a well-established method, which shows good reliability and easy
handling, the technique is widespread for the determination of aerosols. The use of
radioisotope sources for the excitation makes it independent of the laboratory placement
and suitable for eld application. The samples can be analyzed in situ and contaminations
and losses, which might occur during transport and handling, are avoided or kept at a
minimum (Gilfrich and Birks, 1978).
In addition to conventional XRF, TXRF is more frequently applied for the analysis
of aerosols. To utilize the low detection limits and to reduce the matrix eects originating
from the collection material, lter samples need to be digested. With this procedure, ele-
ment concentrations between 0.2 ng=m
3
for Cu and 1 ng=m
3
for Mn were determined
(Einax et al., 1994; Schmeling and Klockow, 1997). By collection with suitable impactor
systems (e.g., Battelle impactor), the aerosols are separated directly onto the polished
sample carriers required for the instrument, and detection limits of 2 ng for Cr and 15 ng
for Ca were obtained (Injuk and Van Grieken, 1995; Klockenka mper et al., 1995).
VII. SAMPLE SUPPORT MATERIALS
In addition to the specimen preparation procedure, the position of the sample inside the
spectrometer plays an important role for a reliable and precise analysis. It should be
ensured that the sample and the calibration standards are in the same form and pos-
ition for analysis, in order to avoid deviations and ensure reliable quantication.
Usually, the sample size is determined by the size of the sample holder, in which the
specimen is presented to the spectrometer. In some cases (e.g., for customized instru-
ments), the sample chamber is adapted for the nondestructive analysis of special objects
like archeological and art specimens. Usually, the sample holders of commercial in-
struments are cylindrical with a diameter of 5.1 cm and allow placing samples with a
maximum thickness of 4 cm. Smaller samples can be xed by a special mask, which is
inserted to the conventional holder. The bottom of the sample holder is normally
covered with a thin lm to prevent losses of the sample and contamination of the
spectrometer.
As ideal targets for the XRS analysis, samples prepared as thin lms are used. For
innitely thin samples all interelement and mass absorption eects are negligible. How-
ever, in practice, innitely thin means that for most x-rays, the sample thickness should be
between 10 and 200 mm, which is dicult to obtain.
Table 4 Degradation Resistance Properties of Selected Thin-Film Materials
Material Contaminants Poor degradation resistance for
Mylar P, Ca, Zn, Sb Strong, mineral acids (HCl, HNO
3
)
Polypropylene Al, Si, Ti, Cu, Fe Oxidizing, concentrated acids; aqua regia
Polyethylene Oxidizing, concentrated acids; alcohols; esters;
ketones
Polycarbonate Oxidizing, concentrated acids; alcohols; esters;
ketones; aliphatic and aromatic hydrocar-
bons; mineral, vegetable and animal oils
Polystyrene Esters; ketones; aliphatic and aromatic hydro-
carbons; mineral and vegetable oils
Kapton Strong, mineral acids; alkalines
Formvar Acids
Figure 3 Analyte line transmittance for various thin-film substances and thicknesses. (From
Ref. 182. Reprinted by permission of American Laboratory.)
With the use of thin-lm supports, special conditions for the materials are required.
The lms should be stable under measuring conditions and have low impurities, especially
for the desired elements. The lm should be thin enough to provide the highest degree of
transmittance, particularly for low concentration levels and low-energy photons. Fur-
thermore, the material should show a high resistance for degradation, which means that
the specimen is retained safely in an XRF cup during the measurement and shows che-
mical resistance against acids, organic materials, thermal softening, tearing, and stretch-
ing. For some materials these properties, are listed in Table 4.
Figure 3 illustrates the eect of thin-lm thickness on analyte-line transmittance for
some substances (Solazzi, 1985). Except Teon, almost all of the presented materials show
transmission better than 90% for photons of 3 keV or more, whereas in the low-energy
region, absorption eects are considerably higher. Teon should be used only in the
higher-energy region because its transmittance for x-rays decreases rapidly below 4 kev.
Thin Mylar lm of 2.5 mm thickness presents the best properties for irradiation and is also
acid stable within a certain level. Therefore, it is one of the most popular support materials
in XRS. However, small impurities of P, Ca, Zn, and Sb should be considered before using
this material.
Several new materials were investigated in the last few years and some of them seem
to be quite promising. Double-adhesive polyester tape, for example showed good prop-
erties for the determination of Pb in dusted samples. The powdered sample was spread
onto the tape, attached to a disk, and a thin lm obtained (Renauld and Mckee, 1995).
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Marcel Dekker, Inc. New York

) and Energies (keV)

to the electron beam in terms of dependence on wavelength

for 16.4 kV. Figure 2 illustrates the intensity of the continuous

, and although it is not zero at

is obtained. Summarizing, it appears that the intensity of the con-

relative to the incident

, Eqs. (52) and (53) reduce to

, indicating that the photon and

, second-order diraction of l 0.3 A

, third-order diraction of l 0.2 A

). The real, not formal, geometry of the

. However, for higher values of 2W, an angular dispersion widens the

in the case of lead melissate) have been synthe-

, the most important contribution in it is from the deviations of the

and beryllium and carbon for spacings above 120 A

. It probably results from

=s and must be carefully con-

=s; the covered surfaces may be quite

boron and possibly for beryllium (Nicolosi et al., 1987)

for their excellent reectivity or for their polarizing

to those with 2d 244 A

, it changes from 0.025 to 0.04 in the wavelength range 775 A

]. The relatively wide bandpass

; atomic radius of Ga 1.26 A

) and passing to the

or less and a mechanical resolution of a few thousands of

=min and slewing speeds

, with slight dierences between manufacturers. Because of the

apart. This xed angle

for the Philips scanner.

) and also in simultaneous instru-

for LiF (200) as

), the quantied dissipation of the kinetic energy of this electron in 3-eV

. A secondary collimator is placed in front

2W) CrKb DE (eV) D (

, respectively (the example is taken from EDXRF, but it is

, a spectrum that can be

, useful measurements can be made at 10.0

corresponds to 5 eV. Moreover, small tem-

, which means with poor spectral resolution. They

2y) 17152 0146 13148 8148 4150 7148

2y) 0115 8104 5118 4112 0118

2y=min) 0.0011.00 0.01? 0.00012 0.0050.1 0.0021

2y=min) 4800 600 2400 1000 1000 1200

y) 0.001 0.001 0.0025 ? 0.00001 ?

C), flow (L=min)

) ? 29, 44 29, 44 25, 39, 5 26, 24 (a)

2y=min) 0.25128 0.0676 0.0676 0.0676

2y=step) 0.0011 0.01 0.01 0.01

y=min) 4800 1000 480 480

2y) (LiF) 0.015 ? ? ?

) 0.0002 0.003 <0.01 <0.005

2y) 0115 5120

C. It is important not to exceed the maximum temperature stated

C to a maximum of perhaps 120

C, such coolers deliver working detector temperatures

C, which are suitable for Si PIN, HgI

0.8 8000 particles could be actually contributing. Assuming a Gaussian distribution,

and excitation is by a Rh tube at 60 kV. The inuence of element-

D 1SUM1 DSUM2 SUM3 25

C), the second classication 3 is