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X-Ray Spectrometry

Donald E. Leyden, Department of Chemistry, Colorado State University

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Quantitative Analysis
The most important use of EDS is the quantitative determination of the concentration or amount of elements in a variety of
materials. The qualitative information available from an x-ray spectrum is the energy or wavelength at which the x-ray
emission lines appear in the spectrum. The quantitative information is the intensity of the emitted x-radiation. This intensity
is normally expressed as the number of counts per second, I (cps), from the detector or the total number of counts, N,
obtained in a fixed period of time, such as 100 s. Because x-ray emission is an example of a random-event process, the
precision of intensity measurements can be predicted from theoretical considerations. These events follow Poisson statistics
that enable calculation of the standard deviation in the number of counts:

= (Nt)1/2

(Eq 16)

where is the standard deviation in the counts, and Nt is the number of counts collected in the time t. The relative standard
deviation (RSD) in percent is:

(Eq 17)
This result is convenient. Unlike most spectroscopic techniques, instrument precision can be adjusted to some degree by the
period of time t spent acquiring Nt counts from an x-ray line of intensity I. For example, an x-ray intensity of 100 counts
per second counted 1 s gives Nt = 100, with RSD = 10%. If the same intensity is counted 100 s, Nt = 10,000, and RSD =
1%. These statistics are for the counting process and represent only the theoretical instrumentation limit.
The electronics of most x-ray spectrometers are sufficiently stable that repetitive counting of an unmoved, stable specimen
will result in a calculated standard deviation very close to the theoretical value. However, simply removing and replacing
the sample will usually increase the standard deviation. The standard deviation obtained from replicate samples is even
larger. In fact, the total variance (square of the standard deviation) is the sum of the variances of each step in the process of
analyzing the sample:

Vtotal = Vinst + Vpos + Vprep +

Vsampling + . . .

(Eq 18)

where Vtotal is the total variance, and Vinst, Vpos, Vprep, and Vsampling are the variances resulting from instrumentation,
sample positioning, sample preparation, and sampling, respectively. Therefore, the total standard deviation in an analytical
procedure is normally larger than that predicted by counting statistics alone.
In most determinations, the instrumentation contributes the least of all the above components to the total standard deviation.
Precision for a procedure should not be suggested from the counting alone. It is more reliable to prepare replicate samples,
measure the intensities, convert these to concentrations, and calculate precision from these data.
The lower limit of detection (LLD) of an element in a sample is a parameter important to the evaluation of instrumentation
and the prediction of its applicability to certain analyses. The value of reported LLD frequently misleads because of lack of
uniformity in the criteria for the definition. Calculation of an LLD value for x-ray spectrometry is simple. The lowest
amount or concentration of an element that can be detected by the instrumentation and procedure used must be established.
The magnitude of background in the region of the peak used is important.
If a total of Nb counts are taken in the background, the standard deviation in those counts is (Nb)1/2. Assuming Gaussian
statistics, 68% of a large number of replicate measurements would give background readings of Nb (Nb)1/2 (background
one standard deviation). Therefore, if a net number of counts in excess of the background, Nn = Ni - Nb, is taken that equals
one standard deviation, that is, Nn = (Nb)1/2, these counts are expected to be greater than the background for only 68% of
the measurements.
If the net counts are twice the background standard deviation, this probability increases to 95%, and for three times, the
standard deviation increases to greater than 99% probability. The conservative definition of detection limit is often used as
the quantity or concentration that yields a net signal equal to three times the standard deviation of the background. Using
this definition, the minimum detectable concentration in a sample is:

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(Eq 19)
where CLLD is the minimum detectable concentration, Ib is the intensity of the background (cps), M is the intensity per unit
concentration of the analyte (cps/%), and t is the counting time. Such coefficients as 2 or 2 (2) 1/2 may be used. Definitive
work on the statistical basis of establishing detection limits for methods involving radiation counting is cited in Ref 15.
When comparing detection limits obtained using different spectrometers, it must be ascertained that the same method of
computation is used. The detection limit for different elements depends on the instrument and excitation conditions as well
as on the matrix composition of the sample. Criteria for establishing concentration levels required for quantitative
determinations are also ambiguous. The criterion that the concentration must exceed three times the detection limit for
quantitative measurements is often used.
Quantitative applications of x-ray spectrometry are based on the relationship between the intensity of the x-rays emitted by
an element in the sample and the concentration of that element in a thick sample or on the total amount of the element in an
infinitely thin sample. The intensities are measured using wavelength-dispersive x-ray spectrometry by setting the
goniometer at the 2 angle for the element of interest and counting x-ray pulses for a period of time to acquire sufficient
counts to satisfy the statistical requirements discussed above. The background is taken in a similar way by carefully
selecting an angle at which only background is measured.
In EDS, the intensity is normally found by fitting the spectrum to a set of computer-generated peaks or to reference spectra
of single elements previously acquired. The ratio of the area of the reference spectrum required to fit the experimental
spectrum is used as the signal proportional to the intensity of x-ray emission by the element of interest. Instrument suppliers
offer software for the fitting process.
Calibration Curves. Once the intensities of peaks in an energy-dispersive x-ray spectrum have been extracted, the data

must be processed to relate the intensity of the respective peaks to concentration. This is most easily accomplished by
plotting the x-ray counts (or counts per second) versus the concentration of the respective analyte element in standards.
Such a plot is called a working curve or calibration curve and is the most fundamental way of relating the data to
concentration. The relationship between intensity and concentration in x-ray spectrometry often depends on the total sample
composition rather than only the element of interest; this is a result of matrix effects. Such cases require simultaneous or
iterative computations of data for many elements in the sample. Use of the computer permits trying different mathematical
models for the intensity-concentration relationships.
The ideal analytical relationship is one in which the signal or intensity is linearly related to concentration:

Ii = a1Ci + a0

(Eq 20)

where I is the intensity and C is the concentration of the analyte element i. The coefficients a1 and a0 represent the slope
(sensitivity) and intercept (blank + background), respectively. Taking a set of data from standards will result in random
errors and a plot of the data scatter about a line. Therefore, a "best" line must be drawn using the data. Software using
techniques known as least squares fit (LSQ), or linear regression, calculates the a1 and a0 values for this line.
Variations in the composition of a sample may cause deviations from linearity. Measurements of the intensity of K lines of
titanium in a low atomic number matrix, such as a plastic material, represent a simple example. When the titanium
concentration is low, the mass absorption coefficient at the energy of the titanium K lines is essentially that of the plastic.
Therefore, the titanium concentration increases with the intensity of the titanium line and the mass absorption coefficient of
the sample for the titanium K lines, resulting in a negative deviation from linearity, as shown in Fig. 13. In this example, the
deviation is understood and can be corrected using mass absorption coefficients and iterative techniques. However, often it
is easier to "fit" the curve with an empirical expression rather than use fundamental information that may not be readily
available. For this purpose, polynomial regressions may be used:

I = anCn + an - 1Cn - 1 + . . .a0

(Eq 21)

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Fig. 13 A second-order polynomial fit of intensity versus concentration

If a high-degree polynomial, such as third or fourth order, is used, a good fit may be obtained. However, requiring
polynomials higher than second order indicates the presence of several interacting processes. Figure 13 shows a
second-order polynomial fit to the data. Whether a linear or polynomial regression is used, the concentration of analyte
elements can be calculated from the measured intensities of lines from samples. Regression equations for several elements
may be stored in the computer.
In many types of samples suitable for XRF, such as alloys, minerals and ores, and various composite materials, mass
absorption coefficient changes resulting from the sample composition are affected. Interelement effects may also result.
These processes are based on the physics of the absorption-emission processes. The number of simultaneous processes
occurring over a wide x-ray energy range complicates attempts to solve the corresponding mathematical relationships
exactly. This is especially true when excitation is performed with polychromatic radiation, such as a continuum from an
x-ray tube. It is often easier and more effective to use model approximations of these processes. A variety of models have
been proposed and applied to various circumstances and are described in Ref 5.
The basic processes that lead to interelement effects are absorption of x-rays emitted in a sample by another element in the
sample and the resulting enhancement of the fluorescence of the latter element, thus often called "absorption/enhancement
effects." Consider a stainless steel sample containing chromium, iron, and nickel in substantial amounts. Nickel x-rays from
the K lines are above the Kabs of chromium and iron. Therefore, nickel x-rays traveling through the sample may be
absorbed by chromium and iron as a result of the photoelectric process, thereby diminishing the nickel intensity. The
probability of this happening will increase as the chromium and/or iron concentration increases. The nickel intensity will
appear to decrease with increasing chromium and/or iron content in the sample even with constant nickel concentration.
Except for the specific photoelectric absorption of nickel x-rays by iron and chromium, the three elements would have
similar mass absorption coefficients. In the transition element series, it may be noticed that the K lines of an element with
an atomic number Z are above Kabs for the elements with atomic number Z - 2 and below. This observation is useful in
predicting absorption/enhancement possibilities.
In addition to the loss of intensity because of absorption of x-rays emitted by an element, the absorbing element may exhibit
enhanced intensity. Absorption is significant because of the photoelectric effect. In the above example, the chromium atom
with the nickel x-radiation will emit chromium x-rays. This extra mode of excitation enhances the chromium signal
proportional to an increase in the nickel concentration.
The intensity of the nickel x-radiation will be proportional to the nickel concentration, but will be decreased by an amount
proportional to the chromium concentration:

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INi = a1,NiCNi + a0,Ni + bNi,CrCCr

(Eq 22)

where bNi,Cr is the coefficient for the effect of chromium on the intensity of nickel x-rays and will have a negative value.
The corresponding relationship for chromium is:

ICr = a1,CrCCr + a0,Cr + bCr,NiCNi

(Eq 23)

where bCr,Ni is the coefficient for the effect of nickel on the intensity of the chromium x-rays and will have a positive value.
In applying such relationships as Eq 22 and 23, the b coefficients are included to reflect the qualitatively known effects of
x-ray absorption and emission. However, the degree of these effects is not easily computed from first principles. As a result,
the coefficients are determined empirically by computation from intensity data taken from standards. Assuming the data are
background corrected, the a0 terms in Eq 22 and 23 can be assumed to be negligible. Using this assumption for two
elements, there are four unknowns--a1,Ni, a1,Cr, bNi,Cr, and bCr,Ni--requiring four equations. The data for these four
equations may derive from intensities measured from four standards.
Because of experimental errors, it is preferable to use an overdetermined system in which substantially more than the
minimum required data are available. Least squares methods are used to obtain the coefficients. Obtaining reliable
coefficients requires a minimum number of standards equal to the number of analyte elements plus the number of
interactions to be considered.
Equations 21 and 22 are commonly written as:

(Eq 24)
where Ri is the measured x-ray intensity of an element in a sample relative to that of the pure element under identical
conditions; Ci is the concentration of the analyte i in the sample, aij values are termed alpha coefficients, and Cj is the
concentration of the element j interacting with the analyte element i. Equation 24 represents a binary sample. For
multicomponent cases, the relationship is:

(Eq 25)
Equation 25 has become known as the Lachance-Traill equation. Other modifications of the basic equations are the
Lucas-Tooth and Pyne model (Eq 26) and the Rasberry-Heinrich model (Eq 27):

(Eq 26)

(Eq 27)
Equation 26 is based on intensities rather than concentrations and is especially useful when the concentration of interfering
elements is not known in the standards. The basic empirical correction equations assume that an element pair exhibits only
absorption or enhancement and treat enhancement as a "negative absorption." This is not the case with many types of
samples.
Development of Eq 27 was based on analysis of chromium-iron-nickel alloy systems. The coefficients Aij, are absorption
coefficients; Bij, enhancement coefficients. Equation 27 permits independent and simultaneous consideration of absorption
and enhancement. For example, in the determination of potassium, calcium, and titanium in paint, the L lines of barium in
the paint enhance the potassium, calcium, and titanium intensity. The mass absorption coefficient of barium for the K lines
of potassium, calcium, and titanium is large. Barium must be included as an enhancer and absorber for these elements. This
increases the number of standards needed to determine the coefficients.
The algorithms proposed are based on a variety of assumptions, and none appears to work for all types of samples. Alpha
coefficients are not constant over large changes in composition (concentration) when polychromatic radiation is used for
excitation. Careful experimentation will reveal the model that provides optimum results for the sample types, analytes, and
concentration range of concern. Software is available that allows selection of various models. Many of the models are
described in Ref 6.
In using empirical corrections software, once the instrument conditions to be used are established, spectra of the standards
are obtained. The software provides least squares solutions for the values of the coefficients. A minimum of one more
standard than the number of coefficients to be calculated is required. More standards are required to use the full capability
of Eq 27. Empirical parameter software has two parts. First, coefficients are calculated from the intensity and concentration

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data of the standards. Second, the coefficients are used to compute the concentration of the analyte elements in subsequent
unknowns. The x-ray intensities of the unknowns must be measured under conditions identical to those used for the
standards. These methods are only a best fit of a function to a set of standards and should not be used for samples whose
composition falls outside the range represented by those standards.
Fundamental Parameters. The relative intensity of an x-ray spectral line excited by monochromatic radiation can be

computed for a given element, specific transition, and known spectrometer geometry:

(Eq 28)

where the terms are as defined in Table 2. However, if polychromatic excitation is used, and if the sample has many
elements to consider, Eq 28 becomes complex; such computations can be performed by computers and software is available
(Ref 16, 17).
Table 2 Definitions of symbols used in Eq 28
Symbol

Definition

IL

Analyte line intensity

I0

Intensity of the primary beam with effective wavelength

pri

Effective wavelength of the primary x-ray

Wavelength of the measured analyte line

Fluorescent yield of analyte A

gL

Fractional value of the measured analyte line L in its series

rA

Absorption-edge jump ratio of analyte A

CA

Concentration of analyte A

pri

Fractional value of the fluorescent x-ray directed toward a detector

/4
A(

pri) Mass absorption coefficient of analyte A for

pri

M(

pri) Mass absorption coefficient of the matrix for

pri

M(

L)

Mass absorption coefficient of the matrix for analyte line

Incident angle of the primary beam

Takeoff angle of fluorescent beam

In principle, this software requires no standard. The intensities are computed from Eq 28 using the geometric factors of the
instrumentation and detector efficiencies as a function of energy. However, it is more reliable if at least one standard similar
to the unknown is used for instrument calibration. The software can function with filtered tube excitation (Ref 9) and is
most useful in laboratories in which frequent quantitative or semiquantitative determinations are required on samples for
which there are no standards.
Because the computations must involve the composition of the sample matrix to determine mass absorption coefficients, the
interelement corrections are integral to the software. Fundamental parameter software will likely be improved in the future
to the extent that quantitative determinations without the need for standards often will be possible. Fundamental parameter
software written in C language for personal computers is available (Ref 18).
Special Methods. The lack of linear correlation between x-ray intensity and concentration of element in a sample matrix

is sometimes more a result of general variation in mass absorption coefficient than specific interelement
absorption/enhancement effects. These cases are especially prevalent in minerals and ores. Considerable improvement in
results will often be observed if the mass absorption coefficient for the x-ray energy (excitation and emission) used is
determined for the sample and this value used to correct the intensities for each sample. To do this rigorously would be
tedious.
One of the simplest methods to approximate and simplify this measurement frequently provides surprisingly favorable
results. The Compton scatter intensity measured for the characteristic lines of the x-ray tube increases as the mass
absorption coefficient of the sample matrix decreases, as illustrated in Fig. 14. However, all else being equal, the intensity
of emission lines of a sample increases as the mass absorption coefficient of the sample matrix decreases.

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Fig. 14 Compton scatter for rhodium tube from iron and plastic

The ratio of the x-ray emission intensity to the intensity of the Compton scatter peak from the x-ray tube characteristic lines
is often more linearly correlated to the concentration of analyte elements than the intensity alone. Figure 15(a) shows a plot
of intensity versus concentration, and Fig. 15(b) the same concentration data plotted versus the ratio of the intensity to the
Compton scatter peak of the x-ray tube. Although this procedure will not solve all problems, it can be easily tried.

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Fig. 15 Ni k intensity versus percentage of nickel in nickel ores. (a) Nickel intensity. (b) Nickel intensity
divided by scatter at 20 KeV. Symbols represent iron concentration ranging from 10 to 65%.

Before the widespread use of personal computers associated with x-ray spectrometers, sample preparation techniques were
frequently more practical for the reduction of matrix effects than application of mathematical models. Dilution of elements
in a glass matrix by fusion of the sample with a flux often minimizes absorption/enhancement effects; a constant matrix is
provided as well. Sample fusion is selected to provide accurate results. Although the mathematical manipulation of x-ray
data is performed easily, use of proper sample preparation techniques to minimize the need for such processing frequently
improves the quality of the analysis.
References cited in this section

5. E.P. Bertin, Principles and Practice of X-Ray Spectrometric Analysis, 2nd ed., Plenum Press, 1975
6. R. Tertian and F. Claisse, Principles of Quantitative X-Ray Fluorescence Analysis, Heyden and Son, 1982
9. R.A. Vane, Adv. X-Ray Anal., Vol 26, 1983, p 369
15. L.A. Currie, Anal. Chem., Vol 40, 1968, p 586
16. J.W. Criss, L.S. Birks, and J.V. Gilfrich, Anal. Chem., Vol 50, 1978, p 33
17. J.W. Criss, Adv. X-ray Anal., Vol 23, 1980, p 93
18. Tracor X-Ray Inc., Mountain View, CA
Copyright 2002 ASM International. All Rights Reserved.

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