EURO

courses
ADVANCED SCIENTIFIC TECHNIQUES
VOLUME 1

Scientific
Dating Methods

edited by
H. Y. Goksu, M. Oberhofer and D. Regulla

Kluwer Academic Publishers

for the Commission of the European Communities
Scientific Dating Methods
 EURO

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 i

Scientific Da ting Methods

Edited by

H. Y. Goksu
GSF - Forschungszentrum fOr Umwelt und Gesundheit GmbH,
Institut fOr Strahlenschutz, Neuherberg, Germany
M. Oberhofer
Commission of the European Communities,
Joint Research Centre, Radioprotection Division,
Ispra, Italy

and
D. Regulla
GSF - Forschungszentrum fOr Umwelt und Gesundheit GmbH,
Institut fQr Strahlenschutz, Neuherberg, Germany

PARI r;;r7\ ?•■•.■{', j

■CL ~" " ""'"j

k.4

KLUWER ACADEMIC PUBLISHERS

DORDRECHT / BOSTON / LONDON

Published in cooperation with NATO Scientific Affairs Division

Library of Congress Cataloging-in-Publication Data

Scientific dating methods ' edited by H . Y . Goksu, M. D b e r h o f e r , and D.

Regu i l a .
p. cm. — (Euro courses. Advanced scientific techniques ; v.
1 )
ISBN 0 - 7 9 2 3 - 1 4 6 1 - 1 <hb : a c i d - f r e e p a p e r )
1. A r c h a e o l o g i c a l d a t i n g . I . G o k s u . H. Y. I I . Dberhofer.
Martin. I I I . R e g u l l a , D. F . I V . Commission of the European
Communities. V. S e r i e s .
CC78.S35 1991
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CIP

ISBN 0-7923-1461-1

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EUR 13528
©1991 ECSC, EEC, EAEC, Brussels and Luxembourg

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C O N T E N T S

ADDRESSES vii

PREFACE ix

ACKNOWLEDGEMENTS xi

Part I : Dating Methods Based on Radioactive Decay

M.J. Aitken: Principles of Radioactive Dating 3

I.U. Olsson: Conventional Radiocarbon Dating and Some

Problems of C-14 Dating 15
R.E. Taylor: Radioisotope Dating by Accelerator Mass
Spectrometry: Archaeological and
Paleonthropological Perspectives 37
U. Haudenschild
M. Flisch: Isotope Dating 55

Z. Yegingil: Fission Track Dating and its Application 77

M. Ivanovich: Uranium Series Dating 97

PART II: Dating Methods Based on Energy Deposition in Solids

M.J. Aitken: Thermoluminescence Dating 121

M.J. Aitken: Sediment and Optical Dating 141

I.K. Bailiff: Pre-dose Dating 155

D. Stoneham: Authenticity Testing 175

PART III: Methods based on Natural Rhythmic and Chemical Changes

M.G.L. Baillie: Dendrochronology 195

D.H. Tarling: Archaeomagnetism and Paleomagnetisn

I. Principles 217
II. Magnetic Dating and other Applications 237
R. Berger
R. Protsch: Fluorine Dating 251

R. Protschr Dating of Bones in Archaeology and Anthropology 271

H.Y. Goeksu: Obsidian Hydration Dating 301

PREFACE

There is a growing need for interdisciplinary activities between

specialists in the natural and human sciences. The rapid
developments in scientific techniques and methods increases
existing gaps in communication between both scientists. There is
therefore a continuous need to transfer the current scientific
knowledge to the human scientist especially in the field of
archaeology, anthropology and geology.

In order to meet this need and to review the current state of

knowledge in scientific methods of dating the Joint Research
Centre Ispra of the Commission of the European Communities in
collaboration with the GSF Forschungszentrum fuer Umwelt und
Gesundheit Muenchen has invited internationally recognized
experts to describe and discuss the principles of different
methods, sampling, limitations, applicability, statistical
evaluation and accuracy. Some important application of each
method is presented by comparing it with other dating methods.

The subjects are covered under three main sections. Part I

contains the most frequently used methods based on radioactive
decay, i.e.,radiocarbon-, potassium-argon-, uranium series- and
fission-track-dating. In Part II methods based on energy
deposition in solids are presented by covering thermal and
optical luminescence methods. In Part III methods based on
natural rhythmic and chemical changes are described.

The publication is principally addressed to human scientists

using or intending to use dating methods in their field of
research, museum curators and natural scientists with an interest
in applied research, but also to students of history, geology and
archaeology. Certainly interested laymen may also benefit from
the presentation.

Ispra/Neuherberg

Summer 1991

H. Y. G6ksu
M. Oberhofer
D. Regulla
Editors
ACKNOWLEDGEMENTS

The editors of this publication should like to thank all the authors for
having contributed to the volume and for their effort in preparing the
texts. Thanks are also due to Mr. Pellegrini of the Euro-Courses Ispra
Organisation, who very much supported the idea to realize this publication
and to Kluwer Academic Publishers, for having accepted the material for
printing in book-form, production of the book and its distribution.

The editors
ADDRESSES

Aitken, M.J.: Research Laboratory for Archaeology and the History of Art,
Oxford University, 6 Keble Road, OXFORD 0X1 3QJ, United Kingdom.

Bailiff, I.K.: Luminescence Dating Laboratory, Department of Archaeology,

University of Durham , Woodside Building South Road, DURHAM DH1
3LE, United Kingdom.

Baillie, M.G.L.: School of Geosciences, Queen's University of Belfast, BELFAST BT7

INN, Northern Ireland.

Berger, R. : Departments of Anthropology and Geography, Institute of

Geophysics and Planetary Physics, Interdisciplinary Archaeology
Program, University of California, LOS ANGELES, CA 900Z4, United
States of America.

Flisch, M. : Abt.fuer Isotopengeologie, Univesitaet Bern, Erlachstr. 9a, CH-

3012 BERN, Switzerland.

Goeksu, H.Y. : GSF-Forschungszentrum fuer Umwelt und Gesundheit GmbH, Institut

fuer Strahlennschutz, Ingolstaedter Landstr.l, D-804Z NEUHERBERG,
Federal Republic of Germany

HaudenschiId,U. Abt. fuer Isotopengeologie, Universitaet BERN, Erlachstr. 9a, CH-

3012 BERN, Switzerland.

Ivanovich, M. : AEA Technology, Isotope Geoscience Section, Harwell Laboratory

B7, OXFORDSHIRE 0X11 ORA, United Kingdom.

Olsson, I.U. : Uppsala University, Department of Physics, Box 530, S-75121

UPPSALA, Sweden.

Protsch, R. : Anthropologisches Institut, Johann-Wolfgang-Goethe-Uni versi taet,

FRANKFURT AH MAIN, Federal Republic of Germany.

Stoneham, D. : Research Laboratory for Archaeology, Oxford University, 6 Keble

Road, OXFORD 0X1 3QJ, United Kingdom.

Tarling, D.H. Dept. Geological Sciences, Polytechnic South West, PLYMOUTH PL4
8AA, United Kingdom.

Taylor, R.E. : Radiocarbon Laboratory, Department of Anthropology, Institute of

Geophysics and Planetary Physics, University of California,
RIVERSIDE, CA 92521, United States of America.

Yegingil, Z. : Cukurova University, Art-Sciences Faculty, Physics Department,

01330 ADANA, Turkey.
PART I

Dating Methods Based on Radioactive Decay

 PRINCIPLES OF RADIOACTIVE DATING

M.J. AITKEN
Research Laboratory for Archaeology
Oxford University
6 Keble Road
Oxford 0X1 3QJ
U.K.

1. Introduction
In its broadest sense the title includes any dating method in
which there is involvement of radioactivity. There are two
categories:-
(i) Methods in which the dating clock is directly provided
by radioactive decay. This category is radioactive dating in
its strict sense: radiocarbon and uranium-series are examples
and (ii) Methods in which radioactivity plays an essential
part but in which the actual dating signal is a secondary
effect of radioactivity. Examples are luminescence dating,
ESR dating, fission track dating.
These categories will be discussed in turn, with greater
emphasis on (i). Before that the basic notions and
terminologies will be summarized. For fuller accounts of
radiometric and other dating methods, refer to Aitken (1990).

2. Radioactivity
2.1 MASS NUMBER (A) AND ATOMIC NUMBER (Z)
An atom consists of a central nucleus surrounded by orbital
electrons. In radioactivity we are concerned with the
nucleus; this consists of protons (with positive electrical
charge) and neutrons (uncharged). The mass number, A, is
equal to the total number of protons and neutrons; the atomic
number, Z, is equal to the number of protons and this is also
equal to the number of orbital electrons, thereby
characterising the chemical behaviour of an atom.
3
H. Y. Goksu et al. (eds.), Scientific Dating Methods. 3-13.
© 1991 ECSC, EEC, EAEC, Brussels and Luxembourg. Printed in the Netherlands.
Nuclei having the same Z.-value but different A are known as
isotopes. As an example, carbon has three isotopes: C-12, C-
13 and C-14. Each of these has 6 protons in the nucleus, but
6, 7 and 8 neutrons respectively. It is the 6 protons (i.e.
Z = 6) that determine the chemical identity as carbon. Thus
each chemical element has its own Z-number; on the other hand
several elements can have isotopes with the same A-value.
2.2 RADIOACTIVE DECAY
The number of neutrons in a nucleus is roughly equal to the
number of protons. Most isotopes are stable but if the number
of neutrons is increased (by some nuclear process) the
stability gets less and eventually, at a certain A-value, the
isotope is radioactive. This means that a particle is ejected
from the nucleus thereby (usually) changing its Z-number.
Continuing with the example of carbon, C-12 and C-13 are
stable but C-14 is radioactive, transmuting into a stable
isotope of nitrogen, N-14. This particular transmutation is
accomplished by conversion of a neutron into a proton (thereby
changing Z from 6 to 7), and the particle emitted is an
electron (a beta particle); emission of this negatively-
charged particle means that the charge of the nucleus
increases but there is no significant change in mass because
the mass of an electron is only about 0.05% of the mass of a
proton (or a neutron). With heavy elements (e.g. uranium)
there are also decays in which alpha particles are emitted.
An alpha particle consists of 2 protons and 2 neutrons; hence
the resultant nucleus has a Z-number which is less than that
of the parent, by 2, and an A-value which is less by 4.
2.2.1 Halflife. Radioactive decay is spontaneous and proceeds
at a rate that is totally unaffected by temperature or other
environmental conditions. Again taking carbon as an example
the probability of decay is such that for a large number of C-
14 atoms, 1% will transmute to N-14 in 83 years; this
corresponds to a halflife of 5730 years - meaning that in that
length of time the number of C-14 atoms will have halved.
Some halflives are much longer - e.g. 4500 million years for
uranium-238; some are very short - a matter of microseconds
or less.
2.2.2 Exponential decrease; lifetime. The probability of
decay is constant and immutable; hence the number that decay
in unit time is proportional to the number still present, or,
in mathematical terms,
 -(dN/dt) = aN (1)
where N is the number of atoms
t is time
and a is the decay (or disintegration) constant.
This equation determines that the number of atoms remaining
decreases exponentially, i.e.
N=N(0) exp (-at) (2)

where N(0) is the number at t=0

Alternatively equation (1) may be written
N=N(0) exp (-t/T) (3)
where T, the lifetime, equals 1/a
or, as f
N=N(0) exp (-0.693^*1) (4)
where h is the halflife; obviously T = h/0.693.
The essential characteristic of exponential decay is that
the percentage decrease per unit time is independent of how
far the decay has proceeded; thus in absolute terms the
number of atoms decaying per unit time gets less and less - as
indicated in equation (1).
2.2.3 Statistical fluctuations, standard deviation. The number
of raindrops falling per minute on a small area, in rain of
constant intensity, fluctuates about the average value; the
percentage deviation from the average becomes smaller as the
observation time is made longer. In any random process in
which n events are observed there is only a 68% probability
that the true average value lies within (1 s.d.) of n, where
the standard deviation, (s.d.), is equal to the square root of
n. For 95% probability the limits are 2 (s.d.), and for
99.7%, 3 (s.d.).
2.2.4 Radioactive decay series; equilibrium. Whereas the
'daughter product' of carbon-14 is stable, there are some
'parents' which give rise to a whole chain of successive
radioactive daughters. The naturally-occurring series are
those headed by thorium-232, uranium-235 and uranium-238; in
each case, after about 10 radioactive daughters a stable
isotope of lead is reached and this is the end of the chain.
The halflives of the daughters are longer than those of the
parents and in the equilibrium situation the amount of each
daughter adjusts itself so that its rate of decay (in absolute
terms) is equal to the rate of decay of the parent, i.e.
aA = bB = cC (5)
where a, b, c are the decay constants of parent and successive
daughters,
and A, B, C are the numbers of atoms of each.
The mechanism of adjustment can be understood by considering
the situation in which the parent nuclei have been isolated by
some process of chemical separation; then from being
initially zero, the number of first daughter nuceli builds up
until its rate of decay is exactly balanced by its rate of
production, that is, (aA)=(bB) Alternatively, if due to some
process an excess amount of daughter is present the rate of
decay will exceed the rate of production, and the amount will
decrease until the equilibrium condition (aA)=(bB) is again
reached.
The approach to equilibrium is exponential in form and,
even in the case of build-up, governed by the halflife of the
daughter concerned. This follows from the differential
equation
dN/dt = aA-bN (6)
where N is the number of daughter atoms present at time t, B
being reserved for the number present at equilibrium.
If N=0 at t=0 then the solution to equation (6) is
N=B {l-exp(-bt)} (7)
it being assumed that b>>a, so that effectively the number of
parent atoms remain constant. Since b = 0.693/h, we see that
it is the daughter halflife that determines how long it takes
for equilibrium to be reached. In uranium-series dating the
daughters used are thorium-230 (in the series headed by
uranium-238) and protactinium-231 (in the uranium-235 series);
the halflives are 75 thousand years and 33 thousand years
respectively.
In the case of a daughter that was at equilibrium but, due
to some chemical process, becomes 'unsupported' the
differential equation is
-dN/dt = bN (8)
In this case N=B at t = 0 and the form of decay is
N = B exp(-bt) (9)
3. Date Terminologies
The pre-eminent technique in archaeology, radiocarbon,
produces an age in 'radiocarbon years' and these are not quite
the same as calendar years, nor is the relationship between
the two the same for dates of different periods; conversion
of radiocarbon years to calendar years requires reference to
a calibration curve as discussed later. In general the other
techniques produce an age directly in calendar years (though
usually with error limits that encompass the difference
between radiocarbon age and calendar age).
There has been appreciable confusion as a result and with the
objective of avoiding this the 1985 International Radiocarbon
Conference at Trondheim recommended the use of cal AD, cal BC
and cal BP for calibrated dates and ages; BP means 'years
before present', the latter being defined as AD 1950.
Omission of 'cal' implies use of radiocarbon years.
While this convention may deal with the problem as far as
radiocarbon is concerned there is the difficulty for other
techniques AD, BC and BP imply calendar years, a usage
established for the two former over many centuries. This
author's preference is (i) to follow the Conference
recommendation only in respect of BP (i.e. meaning
'radiocarbon years before AD 1950') and (ii) to retain the
traditional meaning for AD and BC (i.e. calendar years with
respect to the birth of Christ), avoiding the use of AD and BC
for uncalibrated dates. In respect of BP and techniques other
than radiocarbon there is usually no problem in substituting
the simple term 'years ago' -implying calendar years before
the date of the determination. If the date of the
determination is recent enough for the latter to be relevant
then it should be quoted in terms of AD or BC.
Common terminologies for 'thousand years' are kiloyears (kyr)
and kiloans (ka), the latter being French; similarly Myr and
Ma for million years.
4. Dating by Radioactive Decay
4.1 RADIOCARBON AND OTHER COSMOGENIC RADIOISOTOPES
The interaction of cosmic-ray produced neutrons with
atmospheric and terrestrial constituents produces radioactive
nuclei. The carbon-14 produced in this way from the nitrogen-
14 of the atmosphere is one such product and this nuclei is
the basis of radiocarbon dating. Exhaustive discussion of
this method will be contained in subsequent lectures but a
brief indication of its basic principles is given below. Some
other cosmogenic radioisotopes that have possibilities for
dating are listed in Table 1 later in this subsection.
Carbon-14 is formed high up in the atmosphere, the maximum of
production being at about 15 km (50,000 feet). After
oxidation to carbon dioxide it mixes in with the non-
radioactive carbon dioxide (formed from C and C) of the
atmosphere. Entry into the biosphere is by photosynthesis
into plants and thence by ingestion into animals; entry into
the oceans, as carbonate, occurs because of an exchange
reaction that occurs at the surface of the ocean. The result
is that there is carbon-14 throughout the biosphere and oceans
(and hence it is in shells too); furthermore the ratio of
carbon-14 atoms to non-radioactive carbon atoms is
approximately the same (about one in a million million)
throughout this 'carbon exchange reservoir'. This
concentration ratio represents the equilibrium level that is
established, on a global scale, between loss by radioactive
decay and production by cosmic rays. The latter is about 7.5
kg per year and the global amount of carbon-14 is about 60
tons.
In organic matter in which the carbon is locked in and hence
no longer in exchange with the reservoir, there is loss of
carbon-14 by radioactive decay but no replenishment; this is
the case when cellulose molecules of wood are formed, for
instance. Hence from the time of formation the concentration
ratio in wood decreases at a rate determined by the 5730-year
halflife. This means that for wood which is 5730 years old
the ratio is half that for living wood, for wood which is
11460 years old the ratio is one quarter of that for living
wood, and for 17190 year old wood one eighth ... etc.
This is the basis of dating. In practice there are many
complications, the dominant one being that there have been
variations in the concentration ratio in living wood during
the past and these mean that for accurate absolute dating
calibration of the radiocarbon timescale is necessary. The
radiocarbon timescale refers to ages in 'radiocarbon years'
obtained on the assumption that the living concentration ratio
has always been constant; also, radiocarbon years are
calculated using the 'old' or 'Libby' halflife which is some
3% shorter than the subsequently determined value.
Calibration for ages back to 10,000 years is by means of
measurements on tree-rings for which the age is evaluated by
dendrochronology; further back, to about 20 ka, uranium-
series dating of coral is used. Calibration takes care of
both the concentration variations and the incorrect halflife.
The conventional method of measurement is by means of the beta
particles that are emitted when carbon-14 decays back to
nitrogen-14, the rate of emission per gram of carbon being
proportional to the concentration ratio. Since the late 1970s
direct measurement of the concentration ratio by accelerator
mass spectrometry (AMS) has been used increasingly. With the
latter the sample size can be only a few milligrams whereas
with beta counting a few grams are necessary.
Two recent texts on radiocarbon are by Taylor (1987) and by
Bowman (1990), exhaustive and succinct respectively; there is
also a useful handbook for archaeologists (Mook and Waterbolk,
1985).
4.1.1 Other cosmogenic radioisotopes. Some of these are
listed in Table 1. However, none have the same advantageous
characteristics as radiocarbon: chemical properties that
ensure distribution throughout the biosphere, production at an
approximately constant rate, feasibility of measurement and a
dating clock for which time zero corresponds to a significant
event. Of those listed, calcium-41 has been the most
thoroughly explored for archaeological purposes but practical
utilization still seems a long way off.

Table 1; Some other cosmogenic radioisotopes

(with halflives given in ka)
Aluminium-26 : 730 Chlorine-36 : 300
Beryllium-10 : 1600 Silicon-32 : c.0.1
Calcium-41 : c.100

4.2 POTASSIUM-ARGON AND OTHER TECHNIQUES FOR VOLCANIC ROCKS

In naturally occurring potassium there is a weakly radioactive
isotope, K-40, with a half life of 1250 Ma. One of the
daughter products of this decay is the gas argon-40, which is
stable. In molten volcanic products there is escape of any
10
'relict' argon and retention of newly-formed argon-40
commences on solidification; hence from that time there is
build up of argon-40 at a uniform rate and by measuring the
ratio (Ar-40/K-40) the time elapsed can be evaluated.
The long halflife of K-^40 means that the build up is very slow
- the ratio being about 0.00005 after 1 million years, 0.0001
after 2 million, 0.00015 after 3 million etc
Nevertheless by using ultra sensitive mass spectrometers it is
possible to date rocks as young as a few tens of ka given a
sufficient potassium content.
Application to archaeology is possible when human occupation
is sandwiched between two lava flows; in this way the dating
of early hominids has been possible, such as at the Olduvai
Gorge in East Africa.
There are other pairs of isotopes used in geological dating,
the next back in time being based on the formation of
strontium-87 from the decay of rubidium-87; the latter has a
halflife of 50,000 Ma.
4.3 URANIUM-SERIES DATING
Stalagmites (speleothems), coral, bone and teeth are the
principal sample types for this technique. At formation these
materials tend to incorporate uranium but no thorium - because
of its low solubility in the water from which the calcite
crystals (in the case of speleothems and corals) are
precipitated. Hence at time zero the uranium chains are in
disequilibrium; thereafer there is build-up of daughters to
equilibrium activity. The daughter principally used is
thorium-230, halflife 75 ka, in the uranium-238 series. The
initial build-up is at a uniform rate, as in the case of
argon-40, but bec&use thorium-230 is itself radioactive there
is a gradual levelling off to the equilibrium activity - when
rate of decay equals rate of formation.
Conventionally measurement is by alpha spectrometry, with an
age range of roughly 5-350 ka. Recently mass spectrometry has
been used and for coral an age range of 0.05-500 ka is
claimed.
The critical uncertainty in this technique concerns sample
integrity: (i) that the content of thorium-230 was zero at
crystal formation, and (ii) that subsequently there has not
been movement of uranium or thorium into or out of the sample.
 11
Samples fulfilling the latter condition are categorized as
'closed systems', as opposed to 'open systems' in which
movement has occurred.
Another daughter used is protactinium-231, halflife 34 ka,
occurring in the uranium-235 series. The age range for this,
using alpha spectrometry, is roughly 5-150 ka. Within that
age range it is advantageous to derive ages from both this
daughter and thorium-230. Since movement is likely to be
different in the two cases, concordance gives evidence of a
closed system.
4.3.1 Other variants. There are a variety of other ways in
which age information can be obtained from the uranium series.
One of these is ionium dating of ocean sediment, ionium being
the name for thorium-230 in earlier terminology. Because of
its low solubility thorium tends to be precipitated from sea-
water whereas the parent uranium remains dissolved. Hence in
the sediment there is thorium-230 and being unsupported it
decays according to its 75 ka halflife; thus the ratio of
thorium-230 to the long-lived thorium-232, which is also
precipitated, decreases with depth into the sediment and
allows evaluation of the time that has elapsed since
deposition. At the very recent end of the timescale, lead-
210, halflife 22 years, can be used for dating of sediments -
in the age range 1-400 years; it has also been used for the
authentication of oil paintings.
5. Energy Accumulation Techniques
These, which are category (ii) mentioned in the Introduction,
comprise fission track dating, luminescence dating and
electron spin resonance dating. In all three cases the energy
comes from the radioactivity of thorium and uranium which,
because the halflives are in excess of 1000 Ma, provide an
effectively constant source for samples not in excess of
around 100 Ma.
5.1 FISSION TRACK DATING
In the case of fission track dating the measured quantity is
the radiation damage due to spontaneous fission of the
uranium-238 nucleus; this is an alternative, but very minor,
mode of radioactive decay to emission of an alpha particle.
For uranium atoms located in a number of minerals (e.g.
(zircon) and volcanic glasses (e.g. obsidian) the fission
fragments cause substantial disruption in the structure of the
12
mineral (or glass), leaving microscopic tracks that can be
made visible (under the microscope) by prior etching with an
appropriate chemical reagent, the damaged regions being less
resistant to attack. Heating anneals the tracks and it is
such an event in antiquity that sets the dating clock to zero.

The age range that can be covered depends on the uranium

content. The minimum age routinely attainable with a sample
having 5 parts per million is about 20 ka.

5.2 LUMINESCENCE TECHNIQUES

For these the energy is stored in the form of spatial

distortion in the electron distribution in the crystals of
minerals such as quartz, feldspar, zircon and calcite. As a
result of the ionization caused by alpha, beta, gamma and
cosmic radiation electrons are trapped metastably at defect
sites in the crystal concerned. These electrons can be
released by heating and then some of them find luminescence
centres in the crystal; the resulting emission of light forms
the dating signal. The clock is set to zero in antiquity by
heating (as for instance in the firing of pottery) or by
exposure to sunlight (as for instance in windblown sediment).
The rate of accumulation of 'latent luminescence' depends on
the luminescence sensitivity of the sample and the content of
thorium, uranium and potassium-40 in the sample and the
surrounding burial soil.

The luminescence emitted on heating is termed

thermoluminescence (TL). Alternatively optically-stimulated
luminescence (OSL) can be obtained, and the process is then
termed optical dating. There is a comprehensive text by
Aitken (1985).

5.3 ELECTRON SPIN RESONANCE

This technique also utilizes the build-up of trapped electrons

but the method of measurement is different. There is no
detrapping involved; instead the sample is subjected to high
frequency electronmagnetic radiation in the presence of a
steady magnetic field. The degree of absorption of that
radiation is a measure of the trapped electron population and
hence forms the dating signal.

The technique is used in Quaternary geology and, using tooth

enamel, in the dating of early man. There is a recent review
by Grun (1989) .
 13
References
Aitken, M.J. (1985) Thermoluminescence Dating, Academic Press,
London and Orlando

Aitken, M.J. (1990) Science-based Dating in Archaeology.

Longman Archaeology Series, London and New York

Bowman, S.G.E.B. (1990) Radiocarbon Dating, British Museum

Publications, London

Grun, R. (1989) Electron Spin Resonance (ESR) Dating,

Quaternary International 1, 65-109

Mook, W.G. and Waterbolk, H.T. (1985) Handbook for

Archaeologists No. 3: Radiocarbon Dating, European Science
Foundation, 1 Quai Lezay-Marnesia, 6700 Strasbourg, France

Taylor, R.E. (1987) Radiocarbon Dating; An Archaeological

Perspective, Academic Press, Orlando, Fla 32887, USA.
 ,4
CONVENTIONAL RADIOCARBON DATING AND SOME PROBLEMS OF C DATING

I. U. OLSSON
Uppsala University
Department of Physics
Box 530
S-751 21 Uppsala
Sweden

1. Introduction

The , 4 C method was devised by Willard F. Libby in the late 1940's and his first dales appeared in
1949. He said at the 12th Nobel Symposium (Olsson, 1970) in Uppsala in 1969 that it was a 20th
anniversary. In the beginning of June 1990 there will be a 40th anniversary celebration in USA,
albeit one year too late. The proceedings will be published in Radiocarbon. Although the method
is old and well established problems remain to be solved as regards the 1 4 C-measuremenl
techniques, contamination and varying concentrations in nature. Isotopic fractionation makes a
normalization necessary. The processing of 14 C results requires a basic understanding of statistics.

2. The Principles of the Radiocarbon Dating Method

,4
C is radioactive, exists in nature in living matter to an extent of only 10"'°°o of the carbon. In
nature there are two stable carbon isotopes, 12 C and , 3 C , with abundances of 98.9 and l.lTc
respectively. The isotopes of an element exhibit similar chemical behaviour, but since the masses
are not the same they may function differently in certain reactions and physical processes, so that
the ratio between the isotopes may vary - an isotopic fractionation can be observed. The obvious
difference is, however, that isotopes may be produced which are so unstable as to decay
spontaneously. ' 4 C is produced by neutrons and nitrogen according to the formula

,4
N + n - , 4 C + />

and decays according to the formula

l4
c-l4N+/r
The neutrons are produced in the atmosphere by the cosmic rays. The half-life of radiocarbon is
almost 6000 years. Since the half-life is long and the amount of radiocarbon small the
15
H. Y. Goksu et al. (eds.). Scientific Dating Methods. 15-35.
© 1991 ECSC. EEC. EAEC. Brussels and Luxembourg. Printed in the Netherlands.
16

measurement of M C is a typical low-level measurement and interest was early focused on the
development of a technique for measuring low activities.
The radioactive carbon is oxidized to carbon dioxide and thus soon enters the carbon cycle.
This means that the carbon dioxide is assimilated by plants and reaches all living animals with
their food so an equilibrium with the atmosphere is established. When the plants and the animals
die, the direct exchange with the atmosphere ceases and the relative ' 4 C content thus decreases
with time because of the radioactivity. The M C method signifies that the decrease is measured so
that the time since the exchange ceased can be determined. In 1960 Libby was awarded the
Nobel Prize in Chemistry for this new dating method. Libby originally raised the question whether
the , 4 C activity in the atmosphere was the same throughout the world and had been the same for
thousands of years. With his technique for measurements he could not find any real variations,
but we now know that they do occur.

14
3. C M e a s u r e m e n t s by the Conventional Method

Libby (1955) started his measurement by using a Geiger counter, a detector for radioactivity,
which can be simply described as a gas-filled cylinder with a thin wire along the axis. A voltage is
applied between wall and wire to accelerate the /^-panicles towards the wire. Pulses of the same
height, independent of the energy, are obtained from a Geiger counter. The sample was in the
form of elemental carbon spread on the inner side of the cylinder wall. The carbon layer was
thick enough to absorb the ^-particles from the carbon closest to the wall. With this configuration
he was able to obtain pulses from approximately the same amount of carbon each time. It is
generally said that he used an infinitely thick layer. His counter also contained a screen inside the
cylinder. Since the material of a detector can never be wholly free from radioactivity and the
environment and the cosmic radiation also contribute some radioactivity he had to place the
detector in a heavy shield. Indeed, he used enriched methane from a sewage plant in his first
efforts to detect natural radioactivity from , 4 C . Libby's original method for , 4 C measurements
soon had to be abandoned because of radioactivity fallout from nuclear bomb tests.
Early in the 1950's an improved method for , 4 C measurement was developed. Counters filled
with carbon dioxide, made from the sample and acting simultaneously as sample gas and filling
gas, came into use. One of the advantages is that the preparation is made in a closed system, thus
eliminating the adsorption problem with elemental carbon. Another is that the detection is more
effective. The pulses are proportional to the energy and the counter is called a proportional
counter. Other gases such as methane, ethane or acetylene are also used. The pressure is
sometimes a few atmospheres although the pressure for acetylene must be limited because of the
risk of explosions. The proportional counters vary in size from a few ml to over 1 litre. With the
small counters very small samples can be measured but the uncertainty is high, although some are
filled with the gas and then left for a long period to compensate for the slow counting rate.
Scintillator counters are also used for conventional measurements. The carbon dioxide is usually
converted to benzene via catalysts. The volume will be a few ml. Good shielding is needed but the
shield can be smaller than for proportional counting. Too little attention has therefore been paid
to the existing variability, but this was recently discussed. More steps are involved in the physical
measurement so that it is difficult to achieve good results although the Belfast Laboratory is very
reliable. It is essential that all steps be observed and every uncertainly be evaluated. In
international comparisons the laboratories using scintillator counters rarely attain as good results
as those employing proportional counting. Since this is quite clear thanks to these comparisons
the situation will improve. For the same precision more samples are needed for scintillation
counting than for proportional counting.
With the introduction of proportional counters for 14 C dating the low-level counting technique
was improved. The shields were made more sophisticated to reduce the background. Mercury or
 17

PROPORTIONAL COUNTER

Fig. 1 A vertical section of the original shield for one detector perpendicular to the axis of the
proportional counter (Olsson, 1958)

very pure lead came into use, the anticoincidence shield was improved and nowadays the Geigers
are sometimes replaced by a large scintillator surrounding the main counter. The hard
component, mesons, of the cosmic rays and the gamma radiation from the environment are thus
almost eliminated, partly electronically, de Vries in Groningen (1956£> and 1957b) found that the
soft component of the cosmic radiation, producing neutrons in the shield, could effectively be
reduced by introducing paraffin with boric acid. The shield used in Uppsala is shown in Fig. 1.
When carbon dioxide is used as counting gas it must be very pure. This originally caused
problems and at three Laboratories (Groningen, Heidelberg and Lower Hutt) the problems were
solved almost simultaneously. The gas should be free from electronegative impurities, since they
have a strong tendency to combine with the electrons to ions moving far more slowly than the
electrons. The pulse will never develop enough to be delected before being cut by the electronics.
The gas is purified physically in traps and by pumping on the condensed carbon dioxide, but some
impurities have to be removed chemically. A typical chemical line based on that developed at
Groningen (de Vries and Barendsen, 1952, 1953 and 1954; Barendsen, 1955, de Vries 1956o
and 1957u) is illustrated in Fig. 2.
The pulses from the counter are so small that they must be amplified before they can be
detected. A few channels are used with different amplifications (Olsson el al., 1962). This
scheme (Fig. 3) gives the principles even for modern system based computers (Bjornfot, 1990)
with channels with different thresholds to detect /^-radiation in the one channel and a-radialion
 PLATINIZED COTRELL PLATINIZED COTRELL KMnO.
ASBESTOS FILTER ASBESTOS FILTER ­I0*C ­I0*C ­1t3"C

-: ^
H.V. H.V.
^r
/ ■ \
n
3 ­, <$>" #
X
0
PURIFIED
OXYGEN
"'-V.r,

a. T~T XJ YJ u

t ^ C;

5. *. ?•
3 B OTTLES FOR 30 B OTTLES FOR
STORAGE OF C O ; B­ 0°C ­193*C ­193°C ­193 * C STORAOF OF C O j

®T®-| ^ CrP
I$
7
sr
O
3 _«.
a ^:
vo
^
Cte
"5,

^
Z^

'n
L-i
5J
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"t

PROPORTIONAL COUNTER

^
J o T^
THE CHEMICAL APPARATUS FOR COMB USTION
IX
•s. AND PURIFICATION OF C 0 2 FOR A PROPOR­
3 3- TIONAL COUNTER.

Tl
>- CARBON-14 D ATING LABORATORY
-*]
5
UPPSALA
.? P
 19

CAJR - W s O N S ^ , , , .

AM PL. AMPL. UNIVIBR ANT1-OONC| I CATR 2. -

SO" 5-10- 58pt ,— TRAP FOLL P\G

ATTEH UNIVIBR.
1-0.1" 50)ii TOLLK " ^ ( M E S O N S V 1 2 G

PROPORTIONAL CATR AMPL ATTEN. UNIVIBR. ANTKOMC CATH.

FOLL. C 50" i-ai« 50p» TRAP FOLL. 'PX

CATR o(MESONS»/5) 3( .
FOLL.

CATR AMPL. UNIVIBR. ANTVCOINC CATH. _B

42pl '/"IN
FOLL. 50-2500'

CATH.
o(MESONS*£) 1 N
FOLL

QUENCHING UNMBR. MIXER

AMPL. DELAY
125 M I

J
CIRCUIT E2*il

CATH.
FOLL

Fig. 3 Block diagram of the electronic system as used until 1989 (Olsson el al., 1962).
in another after anticoincidence (a.-c.) with the Geiger. The total number of pulses before the
a.-c. is also registered (mesons plus /^-particles in one channel).
Since another chapter is devoted to 14C measurements with accelerators it suffices to say that
the problems in nature discussed below apply to the H C dating method per se. Accelerators can
be used for small samples and thus also offer possibilities for improved prelreatmenls.

4. Statistics

The ,4 C results are given as a result ± the statistical uncertainty of the physical measurement. The
radioactive decay occurs spontaneously and there is a statistical spread around a mean value
(Fig. 4). For example we may choose a time of t minutes when 100 decays are registered as a
mean. During one period of t minutes we may obtain 90 decays, during another 1 10, during a
third 105 but sometimes 80 or even less, or 120 or slightly more. This means that a sample 3000
M
C years old will sometimes be dated as 2900 or 3100 years if the statistical uncertainty is ±100
years; in 2pc of the cases, however, it will be dated at 2800 years or even younger and in 2% at
3200 years or even older. Two dates 2850± 100 and 3 150± 100 years may thus dale the same
object. It is indeed often difficult to judge whether or not two dates refer to the same event.
When a mean value is required it should be calculated as weighted, if the single values indicate,
or can be regarded as part of, a statistical spread. If they are independent measurements given as
7', ± (7,, T2 ± <72. T, ± in
20

T-ad T+atf

Fig. 4 Statistical distribution around a mean value. There is a 687c probability that the age is
between (T-o) and (T+a) and a 957c probability that it is between (T-2a) and (T+2a),
(Olsson, 1983).
the weighted mean value will be

T=
+ + +
w w w
with the statistical uncertainty

The statistical uncertainty of a sum or difference is

a=± v W + fe)2
When N decays are registered the uncertainly is ± JN . Thus 10,000 decays yield an uncertainty
of ±100 equivalent to 1%. Moreover a prolongation of the counting time with a factor 4 yields
half the uncertainly expressed as a percentage. For 14C measurements an uncertainty of 1 ^ in the
activity is equivalent to ±80 years in the ,4 C age.
According to the author all uncertainties in the physical measurement should be included in
the statistical uncertainty of a ,4 C age. For conventional dating with gas-filled detectors this
means the uncertainty due to the measurement of the filling pressure, the choice of voltage, the
background instability - partly dependent of the barometric pressure and other factors (Olsson
el al., 1962; Olsson, 1988) - but also the isotopic fractionation as explained below. Some
laboratories have only used the statistical decay. Since this is the dominant factor in normal
conventional laboratories it is usually of little significance, but for high-precision work the decay
rate is determined with a small statistical uncertainty and the other contributions to the final
uncertainty will be more important calculated as a percentage.
It has been revealed that unfortunately many laboratories have underestimated the statistical
uncertainties in the measurements (see Nature, (1982) vol. 298, p. 619-623, and Radiocarbon,
 21

cpm

OXALIC ACID PR1

10.50
OECEMBER 1965-JANUARY 1967

10.00
n i
r+
9.50
12/12 31/1 22/3 11/5 30/6 19/8 8/10 27/n DAY

Fig. 5 The oxalic-acid values for proportional counter from December 1965 to January 1967,
plotted with error bars (+ l a ) .
(1990) vol. 32 no. 3 in press). By repeated measurements of the standard and background
samples it is possible to check the reproducibility, and calculate whether or not the statistical
uncertainties are realistically estimated. A simple plot (Fig. 5) yields good information. If many
results are available it is advantageous to plot the actual values as a histogram together with the
received and the expected distribution (Stuiver, 1982). In this connection (Fig. 6) the ratio
between the received and the expected sigma values, the A"-value or c/?/a Exp , should be
calculated. This value should be about 1.0, if all uncertainties are considered in the physical
measurement and the apparatus has a long-term stability. The recently installed data acquisition
system using computers in the conventional radiocarbon laboratory (Bjornfot, 1990)
automatically calculates the A"-values for the nocturnal subvalues (e.g. 100-min. periods) for
each channel. The K-value for the /7-channel of one of the two detectors was between 0.84 and

BACKGROUND PR4
FEB.-AUG. 198 6
CTR/O^O.91

Fig. 6 The ratios between the real and expected o-values and the distribution curves for
background determinations from February to August 1986.
22

Table 1. The half-life of C 1 4 , according to the four latest measurements.

Laboratory First Mass- Revised Mass- Normalized

publication spectrometer value spectrometer value to
determination determinatior Aldermaston
used in first used for revi: mass-
publication value spectrometer

N.B.S., 5760 ± 50* N.B.S. 5745 ± 50* N.B.S. 5715

Washington D.C., 1 and 2 1, 2 and 3
U.S.A.

Aldermaston, 5780 ± 65° Aldermaston 5780

England

Dept. of Physics, 5680 ± 40* Harwell 5685 ± 35* Harwell 5695

Uppsala, +
Sweden Aldermaston

Dept. of Physics, 5660 ± 30 c Pisa

a Statistical error calculated by the investigators.

b Probable error calculated by the investigators.

1.22 and for the other between 0.63 and 1.36 for the latest 15 periods, mostly one night but in
some cases over the weekend. Seven A'-values were > 1.0 in the first counter and 10 were so in
the second.

5. The Half-Life of Radiocarbon

When Libby devised the l 4 C method very little was known about the half-life (Olsson ei «/.,
1962), but fairly accurate measurements were available early in the 1950's. Libby (1955)
calculated a new mean value, 5 5 6 8 ± 3 0 years, which would be used for several years although
doubt had been raised. A longer half-life seemed to fit better to the results of some samples with
known age. In 1961 and 1962 three physical measurements were released - all indicating a longer
half-life. The mean value was calculated as 5 7 3 0 ± 4 0 years (Table 1) and this is still accepted as
the physical half-life. All three Laboratories discovered independently that a very thin layer of
the carbon dioxide adheres to glass walls and concluded that earlier investigators were unaware of
this potential source of a systematic error. Since very 1 4 C-rich gas has to be diluted at the half-life
measurements, there is a risk of memory effects unless precautions are taken.
When the new values were published it had already been known for some years that the
relative , 4 C content in the atmosphere varied, and that there was a need for calibration of the l 4 C
lime scale. In consequence of this fact together with conjecture that still more new measurements
could be completed the l 4 C community in 1962 decided to go on calculating ' 4 C ages with the
Libby half-life (5568 or 5570 years). Another reason was also adduced. It was thought that a
change to a new half-life would cause confusion and questions whether a specific result was
 23

calculated with the new of the old half-life. Indeed, confusion ensued notwithstanding, since for
some years many published results were, after recalculation, based on the new half-life.
Unfortunately some authors did not even know which half-life was used for their own results.

6. Isotopic Fractionation

The translation, rotation and vibration energies are proportional to the masses of the isotopes if
the other conditions are the same. This is the basic cause of isotopic fractionation. The heavy
isotopes are enriched in some processes and depleted in others. These are, however, minor
effects and in nature of importance only for rather light elements. The percentage change in mass
between the carbon isotopes amounts to almost lO^o and the isotopic fractionation must be
considered.
The degree of fractionation is usually expressed as the deviation, 6 , in per mille from a normal
value - that for a chosen standard. For U C work the PDB standard is chosen. It is a belemnile - a
carbonate from the mollusk Belimnilella americana from the Peedee Formation in South
Carolina.

<J' 3 C = (y? J i i m p | e //? s l andard- 1) X 1000

where R is the ratio between the contents of the , 3 C and the , 2 C in the sample or the standard
respectively.
When a plant assimilates carbon dioxide, a kinetic process, the heavier isotope is depleted;
when the carbon dioxide is dissolved in water the heavier isotope is enriched. Craig (1954) wrote
that the enrichment of , 4 C should be almost exactly twice that for , 3 C . Early in the 1950's few
scientist had considered the consequences of the fractionation for M C dating, but nowadays
normalization is regarded as a necessary routine procedure.
The (5 , 3 C value for the carbon dioxide of the air was -7%o until recently and for our normal
plants -25%o. Because of the burning of fossil fuels and deforestation the value for air has
assumed a more negative sign. The thermodynamic laws imply that the fractionation is
temperature dependent. Furthermore the spread of 6 , 3 C values can be expected. About two
decades ago there was a breakthrough in the knowledge of the pholosynthetic processes. Our
normal trees, flowers and grass assimilate according to the Calvin cycle (C 3 -plants), but some
plants such as Zea mays and Desmostachya bipinnata according to the Hatch-Stack cycle
(C 4 -plants). The 6 , 3 C values are around -25%o and -13%o respectively for these two groups. A
greatly simplified picture is given in Fig. 7. Succulents constitute a third group among the
terrestrial plants having both C 3 and C 4 assimilation (CAM plants). Submerged plants lake their
carbon from the bicarbonate, the dissolved CO z or even from the C 0 2 released from the
sediments. The bicarbonate may in fresh water have a wide range of 6 , 3 C values since the
dissolved bicarbonate can exchange with carbon dioxide derived from decaying organic matter in
the ground. Some investigators prefer to write the equation for this in one step. Old carbonate
ma> be dissolved by the action of carbon dioxide in the ground where the partial pressure can
reach verv high values, close to 1 atmosphere. Normal air contains 0.035"c> carbon dioxide. The
contribution from the atmospheric carbon dioxide dissolved in rain water is very small. In areas
with little vegetation it might be delectable and yield a b , 3 C value between that for carbonate and
that for air. The soil carbon dioxide may also contribute to rock erosion, so that the bicarbonate
formed at silicate-rock erosion will exhibit a 5 l 3 C value close to -15%o, which is also small.
Carbonate can also be dissolved by influence of humic acid, with a <5 , 3 C value typical for the
limestone. This will be of importance in areas with peat bogs. Oxidation of organic matter such as
peat yields bicarbonate, which can dissolve carbonate, and the 6 , 3 C value will be between that for
24

sc , ;
POB
-40
CO, C0 2 SUBMERGEO CO, C4 COj CAM
PLANTS AIR PLANTS AIR ASSIMI-
AIR PLANTS SOIL
MARINE FRESH- LATION
WATER

MARINE FRESH WATER

HC0 3 " CaC0 3 HCO3" HCO3" C0CO3

Fig. 7 General picture of the isotopic fractionation of atmospheric carbon dioxide when dis-
solved by water and assimilated by plants. The boundaries are approximate (Olsson and
Osadebe, 1974).
the two contributions, or about -12 %o. In the two cases of sulphate reduction of methane and
volcanic carbon dioxide predictions are very difficult by reason of the varying 13C content of the
sources.
Because of the fractionation all 14C results must be normalized. Since this was not realized in
the early days, when the 14C was very new and wood was frequently used as standard for the age
determinations, it was decided to normalize all samples for age determinations to -25 %» - the
normal value for wood. The normalization is visualized in Fig. 8, which shows that the correction
can amount to a few centuries. For marine carbonate it is about 400 years. When the ,3C content
is higher than the chosen normal value, as for carbonate, equivalent to a negative value closer to
zero than -25 %o or a positive 6 13C value, the MC content is also too high and must be reduced at
the normalization. This means that the sample will be assigned an older age than without this
normalization.
Typical values of the <5 13C distribution are given by Lerman (1973), Olsson and Osadebe
(1974), Stuiver and Polach (1977), Deines (1980), Gulliksen (1980), and Olsson (1986). From
such distributions it is possible to obtain approximate values for later corrections to be executed if
no ,3 C determinations were made, when the sample was dated.

7. Contamination

A contamination with 1% "infinitely old" carbon will make the sample appear 80 years too old at
the dating. By "infinitely old" carbon we mean carbon old enough to contain no detectable ,4 C.
Since the activity has decreased with a factor 2e (=64), thus to about 1.5°i, in six half-lives or
33,000 years "infinitely old", in radiocarbon work, may be about 100,000 years old or older.
Sediments are often easily contaminated with older material by erosion and reworking. The
contaminants may be slightly or much older than the real sample. Archaeological samples are
 25

—I r—
2x(.5) = .10
~ B 0 years
younger

2x(-6) = -12
^rn^ ~100 years
older

2x(-25) = - 5 0
•25 ~ 4 1 0 years
older

2x(-11)=-22
~180 y e a r s
older

Wood Origin
Standard

.30 -25 -20 -15 -10 Ajr -5 0 *5 613C(PDP)%«.

Fig. 8 The d^C normalization to - 2 5 % in PDB (Olsson, 1980).

oflen contaminated with younger material. This may be rootlets but very often humic acid
penetrating the sample. Olsson published (1972, 1974r>, 1980, 1986, 1987, and 1989) two sets of
curves indicating the error when the contaminant is older or younger, respectively, than the
sample. The curves are given for certain percentages, between 1 and iO^o. of the contaminant
and can yield information down to one thousand years age difference. In Fig. 9 the error is given
by a set of curves for contaminants up to 1500 years younger than the sample and amounting to
between I and 5Qec. In Fig. 10 a set of curves indicates the apparent age when infinitely old
samples are contaminated with "modern" contaminants having an activity equal to that of the
radiocarbon standard for age measurements.
An archaeologist or earth scientist must always raise the question whether a sample really can
dale what should be dated even if rootlets, humic acid or other materials contaminating the
sample are removed physically or chemically. Wooden tools may have been used for a long lime
and dating the remains does not give the date when the tools were discarded but the date when
the corresponding tree rings were laid down in the living tree. Similarly the wood may be re-used,
collected as drift-wood or taken from a long dead, dry tree. Charcoal may be displaced by the
action of worms or simply fall down in cavities. Poles are driven into the ground. In Iceland and
other volcanic areas vegetation may be burned by the ash at volcanic eruptions and a root
penetrating from the surface down into another ash layer can be burned and the charcoal
26

(Tift = 5570)

500 1000 1500

AGE DIFFERENCE BETWEEN SAMPLE AND CONTAMINAT

Fig. 9 The influence of contamination with younger material, when this is up to 1500 years
younger and the degree of contamination 509c at maximum (Olsson. 1983).
misinterpreted as belonging to the deeper layer. Erosion as a consequence of water level changes
may disclose old charcoal and this may be redeposiled. In some areas glaciers or normal ice may
force sediments to be redeposiled elsewhere. Shell banks are natural deposits of redeposiled shell
and may consist of shells from thousands of years, but shell mounds may have been created by
man in a rather short lime. Birds may fly long distances carrying small animals and drop these far
 27

£0000

30000 -

10000 2X00 30000 40000 50000

YEARS
AGE OF SAMPLE

Fig. 10 Apparent ages as a function of the ages of samples when contaminated with various
amounts of recent material, between 0.2 and 20% (Olsson and Eriksson, 1972).

away from the site of capture. There are examples of shells in sorted circles lifted to the surface
by the frost action in areas with permafrost. Sediments in lakes and rivers mostly contain
minerogenic material washed thither from the environment or freed by erosion, and some
carbonaceous material easily follows. If this is graphite it is an "infinitely old" contaminant often
giving rise to serious errors, when the organic-carbon content is low. Winds may transport foreign
panicles from distant places. The list may be much longer but here ends with disturbed
stratigraphy because of ploughing or even mixed samples in museums or during collection. The
person collecting samples must be aware of the risks, consider the context and inform the
laboratory about the situation.
Carbonate samples - especially forams, thin shells and shell fragments - can easily be
contaminated by atmospheric carbon dioxide which penetrates the shell structure and is absorbed
on inner surfaces. As was staled in the paragraph on the half-life thin layers of carbon dioxide
may adhere to a surface. This is difficult to remove by flushing the sample with an inert gas,
pumping the sample in a container to high vacuum, or heating the sample gently to avoid breaking
the carbonate into calcium oxide and carbon dioxide. Small shell fragments and old shells in
particular should be stored dry and sealed from the atmospheric carbon dioxide. The samples can
be sealed into a evacuated glass tube and stored there until it is time to date them.
28

SAMPLE
ROOTS ETC. REMO VED

| TREATMENT WITH HC1 lQQ'c I

| WASHINGS (liquid rejected)!

| EXTRACTIO N WITH NoO H 8 0 ' C ~ | - -t.IQUID ~|

y m HLIQUID I
| TWO WASHINGS |
t
|WASHINGS (I. r.) |
S*
[EXTRACTION WITH NoO H 8 0 ' C |-
V
| TWO WASHINGS ( 1 . r.Tl >—ILIQUID"

■ T
IWASHINGSl IMIXTURE
y
|HC1 ADDED UNTIL p H ; c . 3| |PRECIPITATION WITH H C l | |PRECIPITATI
O N WITH HC1
t t T ~^E~
PRECIPITATE LIQUID PRECIPITATE LIQUID
WASHED REJECTED WASHED REJECTED
y
jDRYINGl PRYING I
y
INSOLUBLE FRACTIO N SOLUBLE FRACTIO N 2 SOLUBLE FRACT ION 1
INS SOL 2 SOL 1

SUGGESTED T REAT MENT FOR CHARCOAL ET C.

THE NUMBER OF EXT RACT IONS WIT H NoOH MAY BE INCREASED IF NECESSARY

Fig. 11 Suggested treatment for charcoal and other samp les (Olsson, 1979).

8. Pretreatment

II is obvious thai careful pretreatment can remove many types of contaminant and that a good
description of the context may help the scientists in the dating laboratory to choose a suitable
procedure. All treatments start with physical cleaning such as removal of roots, rootlets and outer
layers of wood etc., if the sample is large. Most samples such as wood, charcoal, other well
preserved plant remains, peat and sediments are usually treated with dilute hot HC1 at least
overnight to dissolve carbonate. Some samples consume so much acid that more must be added
repeatedly until the liquid stays acid for at least one day. The Ca**-ions are removed by repealed
washings until the liquid is almost neutral. The next step is lo remove humic acids (Fig. I 1) by
treatments with diluie NaOH at +80CC at least overnight. Such long treaiments are recommended
to allow the liquid lo penetrate the interior of the sample lo extract humic acid and e.g. resins and
olher compounds in wood. The treatment with sodium hydroxide is sometimes repealed. The
sample is washed again until almost neutral. Then the insoluble fraction (INS) is acidified to
remove any absorbed atmospheric carbon dioxide. E xtracted substances (SOL) from the
hydroxide are precipitated either with HC1 or with Ca2*-ions. As a rule ihe SOL fraction is the
best fraction for organic sediments and the INS fraction for wood, charcoal and peat. Sometimes
cellulose is made from plant samples. It is very difficult to determine how much material is
removed at a treatment like that just described. Charcoal and wood samples in good condition
normally lose half iheir weight, but there are records of charcoal samples losing much less but also
about 9 0 ^ of the weight. It is sometimes necessary to make two or more extractions with
hydroxide. It has happened (Olsson, 1983) that the soluble fraction was about 23^t> of the
insoluble and dated about 1000 years younger. Figure 9 shows that the error would have been
 29

ACTIVITY
CONTAMINATION OF SHELLS IN AIR
% OF INTERNATIONAL » Total sample
STANDARD . Q u t e r f r a c t i o n

10 ° Inner fraction
•

­ i ­
i i

} 1< : h:
■

*75JJ » 75p <75p >75u SMALL ONE WHOLE

<250p <250u PIECES VALVE
VERY MO 1ST AIR NORMAL MOISTURE IN AIR

Fig. 12 The co ntaminatio n o f shell samples o f different size fractions after sto rage in the air in
the Labo rato ry after being sto red fo r several years in a museum (Oisso n el al.).

more than 200 years if the two fractions were mixed and dated as one sample, as if no hydroxide
treatment was applied. It should indeed be mentioned that the Groningen Laboratory very soon
(de Vries and Barendsen, 1954; de Vries et al., 1958; and de Vries and Waterbolk, 1958)
realized the importance of a good pretreatment including a step with hydroxide.
The outside of shell samples was early removed with acid in Groningen at their pretreatment
since these parts were regarded as more easily contaminated than the interiors. In Uppsala we
started early to leach the samples by acid not only to remove the outside but also to peel off at
least another layer and compare the ages of the different layers. The first results after
introduction of this type of fractionation were presented at the ,4 C conference in 1959 in
Groningen. ,4 C measurements of different layers allows assessment of the risk of contamination
(Fig. 12). It was also discovered that shell samples should be washed with deionized or distilled
water which had been boiled or acidified to remove any dissolved carbon dioxide (Oisson and
Eriksson, 1965).
Recrystallization can involve contamination and may be detected by X-rays although such an
investigation cannot reveal contamination by atmospheric carbon dioxide.
Bones are often abundant at archaeological sites and should be good dating material.
Unfortunately loo few experiments on the pretreatment were made in early days so that many
erroneous dates have been released. Hydrochloric acid has mostly been used and the product has
been called collagen although this is a misleading description. The pretreatment used should
always be given together with a result, but for bones it is essential for any judgements of the
reliability. Sometimes a treatment with NaOH is included to remove humic acid. In Uppsala
systematic investigations have been performed, mostly on bones from Svalbard. D ifferent schemes
for HC1- and ED TA-lrealments have been tested (Oisson et al., 1974; El-D aoushy et al.,
1978). The final ED TA-method always worked and is the only method the author would use for
conventional dating under three conditions: a) the treatment concludes with a HC1 treatment and
dissolution of the collagen-derived product in water, b) all treatments are done slowly with
extractions lasting about three days so that the liquid can penetrate the sample; the extractions
30

should be repealed several limes, c) the extract is carefully removed from the sample by suction
with a water pump. It is essential to remove the organic EDTA-salt to avoid contamination, but
this is no problem with the recommended procedure. It should be mentioned that the
EDTA-solution is slightly basic so the humic acid will be dissolved. Special amino acids can be
extracted for accelerator measurements, since smaller samples can be used. Taylor (1980)
published a survey of various methods employed in the different conventional laboratories.
Soot layers can at least theoretically be dated even if it is difficult to concentrate the soot.
Contaminating rootlets can be extracted by making cellulose, leaving the soot intact for removal.
Problems may arise because of transport of the soot and small charcoal fragments in the ground.
In Uppsala we failed with soot in sand.
Mortar dating offers special problems. A survey of the literature is given by Olsson (1987).
CaO, quicklime, is obtained by heating carbonate. Water is added to the oxide to yield
hydroxide. This is used as the mortar, after water and sand has been added, and is hardened by
access of atmospheric carbon dioxide to carbonate. At the treatment it is essential that any
carbonate added with the sand be removed. Other sources of error have been detected, such as
unfired carbonate (old or contemporaneous with a reservoir age) left in the quicklime, incomplete
hardening, or the hardening took centuries rather than weeks, and the mortar was still alkaline
after hundreds of years so that the carbon dioxide was not contemporaneous with the building.
Usually several fractions are recovered by adding acid; the first should be the most reliable, since
the C 0 2 is more easily removed from the mortar than from the aggregate. Extrapolation to a very
small first fraction is feasible. Checks on the 6 13 C should be made. Pains must be taken with
every sample since mortar dating is not yet fully understood and more research on the treatment
is needed.
Since sediments are mixtures of different materials it does not suffice in reality to apply a
standard treatment with acid and base. Lipids can be extracted chemically and terrestrial material
separated from the submerged material. Still it is very difficult to execute a very good
preireaiment of sediments. Laboratories using accelerators have a chance to work on extractions
in order to achieve a good fraction. In Uppsala we have made some lipid extractions with good
results. But these cannot serve as a test of the general suitability. Organic solvents are used so it is
essential to remove them carefully.

9. Global Variations of the Relative Radiocarbon Concentration

The burning of fossil fuels has caused the M C / ' 2 C ratio to diminish. This is called the industrial
effect or the Suess effect, since it was first demonstrated and discussed by Suess. The decrease
during this century was about 2% until an increase was perceived because of tests of nuclear
weapons. The industrial effect is not the same over the whole globe. The nuclear-bomb effect
originally varied much more. At mid-latitudes in the northern hemisphere an excess of lOO^c
over the standard was reached in 1963-1964. A latitudinal effect was seen so the excess was less
to the south and still smaller in the southern hemisphere. This excess has now decreased to about
15"o and is almost the same everywhere on land. Part of the extra radiocarbon has gone into the
sea. The maximum for the surface water was reached a few years later than for the atmosphere
and is far from distinct. Already earlier there was a few per cent less radiocarbon in the surface
layer than in the atmosphere.
The natural variations can be studied on material which is dendrochronologically dated. This
means that the tree rings are counted and checked for missing or double rings. By using several
logs, partly overlapping in time, and checking them for characteristic patterns in tree rings it is
possible gradually to go thousands of years back in time, de Vries in Groningen (1958) was the
first to try to explain the detected variations. One year earlier Munnich in Heidelberg (1957) had
 31

4000
REAL AGE BP

Fig. 13a Comparison between the calibration tables presented by Suess (1970); Damon el al.
and Michael and Ralph at the New Zealand Conference (Olsson, 1974a).

published several dales really indicating such variations. The effect is called the de Vries effect.
The variations exhibit a long-term variation, usually ascribed to geomagnetic variations and a
short-time variation correlated with variations in solar activity. When the charged particles from
the cosmic rays enter the earth's magnetic field they are diverted, so if the intensity increases the
production of radiocarbon will decrease because of the shielding effect. The solar radiation has a
similar effect but since radiocarbon is also emitted the correlation is less straightforward. Finally
the climate must have some influence, with changing amounts of water available for dissolution of
carbon dioxide, decreasing solubility at increasing temperature and varying size of the biosphere.
The changing atmospheric carbon-dioxide concentration and the changing circulation of the
oceanic water masses also must have an impact.
The variations of the relative content of radiocarbon have been discussed through the years. In
1969 the Twelfth Nobel Symposium was devoted to this theme. The first high-precision dales
were published by Stuiver (1978). Some laboratories have since issued more results, but the
majority were published by Stuiver in Seattle and Pearson in Belfast working the C02-filled
proportional counters and scintillator counters respectively. Their results have been
recommended by the MC community for use as calibration curves and are published in
Radiocarbon, (1986) vol. 28, 2B. Values from other laboratories are included provided they have
passed the critical evaluation by the authors themselves. The reader is therefore referred to lhat
volume. Curves made after the New Zealand symposium in Lower Hutt in 1972 are presented
here (Fig. I3a,b; Olsson, 19746) to give an idea of the general trend and the different
interpretations of the then existing measurements.
32

DAMON tl al |
THE WIDTH INDICATES
THE STATISTICAL UNCERTAINTY

7000
REAL AGE B P

Fig. 13b Comparison between the calibration tables presented by Suess (1970); Damon el al.,
and Michael and Ralph at the New Zealand Conference (Olsson, 1974a).
It should be mentioned that radiocarbon results can be calibrated with the help of a computer
and either a diskette bought from Seattle or a diskette from some other Laboratory such as
Gliwice, Granada or Groningen. It should also be recalled that certain problems may arise at the
calibration. Some problems concerning reservoir age and regional variations will be discussed
below. If a sample has a certain age of its own as a segment of a peat core or charcoal from
several years this can be taken into account al the computer calibration. The reservoir age of the
oceanic surface water can also be considered, although that section must surely be reviewed in the
light of new results on the reservoir effect in certain areas.
If a sample is contaminated the apparent age cannot be used for calibration. This emerges from
the following example. If a sample consists to 50% of actual sample and 50% of graphite without
any 14 C activity it will be dated one half-life too old. It is advisable to use the calibration curve for
the radiocarbon age of the real sample and proceed from there, but this is difficult if the degree of
contamination is not known. Similarly the , 3 C normalization should be based on the ' 3 C content
of the real sample. If samples from the southern hemisphere, or areas where the radiocarbon
level generally is different from the normal global activity, are to be calibrated, the activity
difference expressed in years must be subtracted if the level is lower than the global activity.

10. Regional Activities

At the Twelfth Nobel Symposium Lerman et al. (1970) presented results indicating a few per
mille lower activity in the southern hemisphere than in the northern; this was ascribed to the
exchange rate between the atmosphere and the surface water. In certain areas there may be some
 33

dilution of the activity because of volcanic action and this has to be considered. The author and
others have had problems with samples from Iceland. Many samples have been regarded as dated
too old. A long record of the activity at Svalbard and at Abisko in northern Sweden indicate a
rather steady difference in the relative radiocarbon activities. The nuclear-bomb excess activity
on Svalbard is lower despite the general smoothing between the northern and southern
hemispheres. Similar results are obtained from measurements on plants and atmospheric carbon
dioxide from Iceland and on plants from islands in the Arctic.

11. Reservoir Effect

It has long been known that the relative 14 C activity in the oceans is lower than in the atmosphere
and most 14 C workers now accept that the same applies for lakes. This is called the reservoir
effect. It should be stressed that the values discussed in this paper are normalized for 6 , 3 C
deviations from - 2 5 %o.
A simple model for the oceans is a 2-box model . There the surface water down to about 80 m
is regarded as one well mixed reservoir and the deep water as another, although much larger.
There is some resistance to exchange over the boundary and thus the percentage of carbon going
down from the upper to the lower is much higher than the percentage of the lower going upwards.
This means that some of the radiocarbon in the lower reservoir has time to decay before the
exchange, so the relative activity will be smaller. Since this carbon with low activity rises into the
upper reservoir the supply of low-activity carbon makes the carbon in the upper reservoir appear
old. The exchange between the surface water and the atmosphere also meets some resistance.
The effect for large areas is about 5 ^ , equivalent to about 400 years. At some coasts with
upwelling water the deficiency is larger. In the southern hemisphere the effect is also larger as a
rule.
There is a reservoir effect too in lakes. It was long thought that this was due to dissolution of
old carbonate and most hard-water lakes have an appreciable reservoir age. Mook (1980)
discusses the groundwater and this dissolution. See the heading Isotopic Fractionation. It would
seem that the exchange over the surface plays an unimportant role for the reservoir age of lakes.
There may also be a contribution by aged groundwater, water which has had no contact with the
atmosphere for years. Decaying plants also release some carbon dioxide should also detract from
the activity.

12. Acknowledgement

The author expresses her gratitude to the Swedish Natural Science Research Council for
supporting Iter work in the conventional Radiocarbon Laboratory since the planning started 35
years ago.

References

Barendsen, G.W., 1955. Ouderdomsbepaling met radioactieve koolstof. Thesis, Groningen.

Bjornfot, L., 1990. A Computer Based Data Acquisition System for C-14 Measurements.
Uppsala University Department of Physics Report 1221, 60 pp.
Craig, H., 1954. Carbon 13 in plants and the relationships between carbon 13 and carbon 14
variations in nature. J. Geol., 62, p. 115-149.
34

Deines, P., 1980. The isotopic composition of reduced organic carbon. In Handbook of
Environmental Isotope Geochemistry. (Fritz, P., and Fontes, J.Ch. eds.) vol. I, The
Terrestrial Environment A, p. 239-406.
El-Daoushy, M.F.A.F., Olsson, I.U., and Oro, F.H., 1978. The EDTA and HC1 methods of
pre-lreating bones. Geol. Foren. Stockholm Forh., 100, p. 213-219.
Gullikscn, S., 1980. Isotopic fractionation of Norwegian materials for radiocarbon dating.
Radiocarbon, 22, p. 980-986.
Lerman, J.C., 1973. Carbon 14 dating: Origin and correction of isotopic fractionation errors in
terrestrial living matter. In Proc. 8th Int. Conf. on Radiocarbon Dating, Lower Hull, Oct.
18-25, 1972. Royal Soc. of New Zealand, p. 612-624.
Lerman, J.C., Mook, W.G., and Vogel, J.C., 1970. C14 in tree rings from different localities. In
Radiocarbon Variations and Absolute Chronology, Nobel Symposium 12 (Olsson, I.U., ed.)
p. 275-301. Almqvist & Wiksell, Stockholm and J.Wiley & Sons, New York, London and
Sydney.
Libby, W.F., 1955. Radiocarbon Dating. Univ. Chicago Press.
Mook, W.G., 1980. Carbon-14 in hydrogeological studies. In Handbook of Environmental
Isotope Geochemistry (Fritz, P. and Fontes, J.Ch., eds.) vol. 1. The Terrestrial Environment
A. p. 49-74.
Munnich, K.O., 1957. Heidelberg natural radiocarbon measurements. In Science, 126,
p. 194-199.
Olsson, I., 1958. A C' 4 dating station using the C0 2 proportional counting method. Arkiv Fysik,
13, p. 37-60.
Olsson, l.U. (ed.), 1970. Radiocarbon Variations and Absolute Chronology. Nobel Symposium
12, Uppsala, Aug. 11-15, 1969. Almqvist & Wiksell, Stockholm and J. Wiley &. Sons, New
York, London and Sydney.
Olsson, I.U., 1972. The pretreatment of samples and the interpretation of the results of 14C
determinations. In Climatic Changes In Arctic Areas During The Last Ten-thousand Years,
Symposium in Oulanka and Kevo, Finland, Oct. 4-10, 1971. Acta Univ. Oul. A3, Geol. 1,
p. 9-37.
Olsson, I.U., 1974a. The eighth international conference on radiocarbon dating, Geol. Foren.
Stockholm Forh., 96, p. 37-44.
Olsson, I.U., 1974£>. Some problems in connection with the evaluation of C14 dales. Geol. Foren.
Stockholm Forh., 96, p. 311-320.
Olsson, I.U., 1979. The importance of the pretreatment of wood and charcoal samples.
Radiocarbon Dating. Proc. 9th Int. Conf., Los Angeles and La Jolla, 1976 (Berger, R. and
Suess, H.E., eds.) p. 135-146.
Olsson, I.U., 1980. Progress in radiocarbon dating, promising techniques and trends in the
research. Fizika, 12 S2, p. 37-68.
Olsson, I.U., 1983. ,4 C-datering - popular genomgang av laboratoriearbetet och syn pa felkallor.
In Bua Vastergard - en 8000 ar gammal kustboplals (Andersson, S., Kaelas, L., and
Wigforss, J., ed.) Arkeologi i Vastsverige, 1. GAM, p. 203-221.
Olsson, I.U., 1986. Radiometric dating. In Handbook of Holocene Palaeoecology and
Palaeohydrology (Berglund, B., ed.) p. 273-312. J. Wiley & Sons.
Olsson, I.U., 1987. Carbon-14 dating and interpretation of the validity of some dates from the
Bronze Age in the Aegean. In High, Middle or Low? Acts of an International Colloquium on
Absolute Chronology Held in Gothenburg 20lh-22nd August 1978. Part 2 (Astrom, P., ed.),
p. 4-38.
Olsson, I.U., 1988. Low-level counting using gas-filled counters as applied to MC dating with
emphasis on reliability. In Low-level measurements and their applications to environmental
 35

radioactivity (Garcia-Leon, M. and Madurga, G., eds.) p. 171-223. World Scientific,

Singapore, New Jersey and Hong Kong.
Olsson, I.U., 1989. The , 4 C Method. Its possibilities and some pitfalls. An Introduction, PACT,
24, P. 161-177.
Olsson, I.U., El-Daoushy, M . F . A . F . , A b d - E l - M a g e e d , A., and Klasson, M., 1974. Ceol.
Foren. Stockholm Forh, 96, p. 171-181.
Olsson, I.U. and Eriksson, K.G., 1965. Remarks on C' 4 dating of shell material in sea sediments.
In Progress in Oceanography, 3, p. 253-266.
Olsson, l.U. and Eriksson, K.G., 1972. Fractionation studies of the shells of Foraminifera.
Etudes sur le Quaternaire dans le Monde, Proc. VIIT Congres 1NQUA, Paris 1969,
p. 9 2 1 - 9 2 3 .
Olsson, I.U., Goksu, Y., and Stenberg, A., 1968. Further investigations of storing and treatment
of Foraminifera and mollusks for 14 C dating. Geol. Foren. Stockholm Forh, 90, p. 417-426.
Olsson, l.U., Karlen, 1., Turnbull, A.H., and Prosser, N.J.D., 1962. A determination of the
half-life of C M with a proportional counter. Arkiv Fysik, 22, p. 2 3 7 - 2 5 5 .
Olsson, I.U. and Osadebe, F.A.N., 1974. Carbon isotope variations and fractionation corrections
in , 4 C dating. Boreas, 3, p. 139-146.
Stuiver, M., 1978. Radiocarbon timescale tested against magnetic and other dating methods.
Nature, 273, p. 271-274.
Stuiver, M., 1982. A high-precision calibration of the AD radiocarbon lime scale. Radiocarbon,
24, p. 1-26.
Stuiver, M. and Polach, H.A., 1977. Reporting of , 4 C data. Radiocarbon, 19, p. 355-363.
Suess, H.E., 1970. Bristle-pine calibration of the radiocarbon time-scale 5200 B.C. to the
present. In Radiocarbon Variations and Absolute Chronology, Twelfth Nobel Symposium,
Uppsala, 11-15 Aug. 1969 (Olsson, I.U., e d . ) . Almqvist & Wiksell, Stockholm and J. Wiley
& Sons, New York, p. 3 0 3 - 3 1 1 .
Taylor, R.E., 1980. Radiocarbon dating of Pleistocene bone: Toward criteria for the selection of
samples. Radiocarbon, 22, p . 9 6 9 - 9 7 9 .
de Vries, HI., 1956a. Purification of CO z for use in a proportional counter for l 4 C age
measurements. Appl. Sci. Res., Sect. B, 5, p. 387-400.
de Vries, HI., 1956£>. The contribution of neutrons to the background of counters used for , 4 C
age measurements. Nuclear Physics, 1, p. 4 7 7 - 4 7 9 .
de Vries, HI., 1957a. The removal of radon from C 0 2 for use in 14 C measurements. Appl. Sci.
Res., Sect. B, 6, p. 4 6 1 - 4 7 0 .
de Vries, HI., 1957£>. Further analysis of the neutron component of the background of counters
used for , 4 C age measurements. Nuclear Physics, 3, p. 6 5 - 6 8 .
de Vries, HI., 1958. Variation in concentration of radiocarbon with time and location on Earth.
Proc. Koninkl. Nederl. Akademie van Wetenschappen - Amsterdam, Ser. B, 6 1 , No. 2,
p. 9 4 - 1 0 2 .
de Vries, HI. and Barendsen, G.W., 1952. A new technique for the measurement of age by
radiocarbon. Physica, 18, p. 652.
de Vries, HI. and Barendsen, G.W., 1953. Radiocarbon dating by a proportional counter filled
with carbondioxide. Physica, 19, p. 9 8 7 - 1 0 0 3 .
de Vries, HI. and Barendsen, G.W., 1954. Measurements of age by the carbon-14 technique.
Nature, 174, p. 1138-1141.
de Vries, HI. and Barendsen, G.W., and Waterbolk, H.T., 1958. Groningen radiocarbon dales
II. Science, ill, p. 129-137.
de Vries, HI. and Waterbolk, H.T., 1958. Groningen radiocarbon dates III. Science, 128,
p. 1550-1556.
RADIOISOTOPE DATING BY ACCELERATOR MASS SPECTROMETRY:
ARCHAEOLOGICAL AND PALEOANTHROPOLOGICAL PERSPECTIVES

R. E. Taylor
Radiocarbon Laboratory
Department of Anthropology
Institute of Geophysics and Planetary Physics
University of California, Riverside
Riverside, California 92521 USA

1. Introduction

Over the last decade, accelerator (or atomic) mass spectrometry has been applied to the direct or ion
counting measurements of a number of cosmogenic isotopes including 10Be, 14C, MA1, 32Si, '"CI, 4'Ca,
and IMI. The great advantage of ion counting is the order-of-magnitude increase in detection efficiency
for rare isotopes from that possible with decay counting. This greatly enhanced capability of AMS
technology led initially to the expectation in isotope dating applications of significant reduction in
sample sizes along with major reductions in counting times for existing isotopic dating methods as well
as the ability to explore the potential of methods previously proposed but not amenable to studies to
determine practical feasibility. In addition, in the case of the 14C method, AMS methods had the
potential to provide a means of significantly increasing the useful dating time frame out to as much
as 100,000 years.
Several of the initial expectations of early AMS researchers—specifically major reductions in sample
sizes and the speed with which samples could be analyzed—have now been fully realized and
demonstrated. The general availability of AMS technology has allowed innovative approaches for the
examination of a wide range of issues and problems in a series of disciplines including archaeology
and paleoanthropology, paleobotanical and environmental studies, as well as in geology, geophysics,
geochemistry, biogeochemistry, hydrology, and space sciences, and, most recently, in the biomedical
sciences.
Initial descriptions of the experiments demonstrating the feasibility of AMS-based isotopic
measurements first appeared in 1977 [1-3]. There was a rapid expansion in interest in AMS
applications as research groups with extensive previous expertise in the operation of heavy ion particle
accelerators turned their attention to modifications of their general purpose instruments previously
used for nuclear structure and ion implantation studies, to function also as AMS systems. Other
groups developed special purpose, dedicated AMS systems designed specifically for isotopic
measurements. Advances in AMS research with regard to accelerator hardware technology, special
sample prctrcatmcnt and preparative techniques, and disciplinary and interdisciplinary applications
have been periodically summarized in a series of AMS conferences (Table 1).
This review will focus primarily on developments in AMS technology as reflected in recent advances
in the most widely used Quaternary dating method used in archaeology and
paleoanthropology—radiocarbon (l4C). This discussion will also summarize an example of recent
research made feasible by the advent of AMS technology. This involved the exploration of the
practical usefulness of using radiocalcium 4lCa to infer ages for calcium-containing samples such as
bone. The basis the HC method is widely-known and needs no general discussion [10]. The 4lCa
technique is a method that holds the promise of extending the age range for the dating of terrestrial
bone samples to as much as 0.8 to 1.0 x 10* years under a set of tightly constrained circumstances [11].
The basis of the method and current problems with the 41Ca method will be more fully discussed in
section 6.
37
H. Y. Goksu et al. (eds.). Scientific Dating Methods, 37-54.
© 1991 ECSC, EEC. EAEC, Brussels and Luxembourg. Printed in the Netherlands.
38

Table 1. Major Symposia on Accelerator Mass Spectrometry

Location Dates Publication

Reference

1st Rochester, New York, USA April 20-21, 1978 [4]

2nd Argonne, Illinois, USA May 11-13, 1981 [5]

3rd Zurich, Switzerland April 10-13, 1984 [6]

- Oxford, England June 30-JuIy 1, 1986 [7]

4th Niagara-on-the Lake April 27-30, 1987 [8]

Ontario, Canada

5th Paris, France April 23-27, 1990 [9]

2. Historical Background
Until the early 1980s, isotopic age determinations were based on measurements obtained by various
types of decay counting technologies and conventional or low energy mass spectrometers. As the term
denotes, decay counting infers isotopic concentrations by counting decay events in some type of
ionization or scintillation detector and comparing the count rate observed in an unknown age sample
to that which is exhibited in appropriate standards under a common set of experimental conditions.
For the "C method, this involves the counting of beta particle emissions from the decay of MC. In
conventional mass spectrometry, a portion of a sample is ionized and accelerated through a magnetic
and/or electrostatic field. Mass separation and characterization is based on differences in ions
imparted energies of a few thousand electron volts. Determination of stable isotope ratios (e.g., «'3C,
515N) employ conventional mass spectrometers.
Accelerator mass spectrometry links particle accelerator and mass spectrometry technologies. The
basic concept behind AMS as an analytical technique was briefly explored during experiments
conducted just before World War II by Luis Alvarez using the 60-inch Berkeley cyclotron [12].
However, until the late 1970's, no further experiments with particle accelerators were carried out. At
that time, several investigators recognized that significantly higher efficiencies of atom-by-atom
detection such as that employed in conventional mass spectrometers would permit the use of sample
sizes several orders of magnitude below that which is typically possible with decay counting [13].

3. Elements of AMS Analysis

Mass spectrometers take advantage of the differences in mass of different isotopes to detect and
measure their concentrations. The process of measurement requires that the sample atoms to ionized
by stripping off or adding to the electrons on the outer "shells" of the atoms. The atom in the form
of an ion can then be influenced by magnetic fields. This property of ions permits them to be
accelerated in a vacuum. When such acceleration occurs, the trajectories of these particles can be
deflected when they are passed through a magnetic field of appropriate strength. The degree of
deflection of the pathway of a monoenergetic ionized beam largely depends on the difference in mass
of the different isotopes comprising it.
 39

ION
SOURCE

Figure 1. Simplified representation of conventional mass spectrometry instrumentation.

Figure 1 illustrates, in a highly simplified form, the essential components of a conventional mass
spectrometer. These include an ion source where the sample either in the form of a solid or gas is
ionized and accelerated, a high vacuum pathway, an analyzing magnet, and a detector. The ions of
the isotope selected for analysis reach the collector in greatest concentration. Ions of greater mass
are insufficiently deflected (because of their greater inertia) for a given magnetic field strength and
particle velocity, whereas ions of lesser mass are excessively deflected. These ions collide with the
walls of the accelerator tube, lose energy, and are removed from the spectrometer by pumping. By
varying the strength of the magnet or the energy imparted to the ions, relative concentrations of
different isotopes can be measured. Using an isotope of known concentration as a standard,
quantitative measurements of isotope ratios can be obtained. If the amount of a given isotope is
sufficient and the differences in mass are large enough, the isotopic composition of a sample can be
obtained.
Despite sustained studies, particularly at the Stanford Research Institute in the early 1970s, attempts
to make direct counting measurements of MC using modified conventional mass spectrometers were
frustrated because of the extremely low natural MC concentrations (14C/'2C = ca. 10"12) and because
14
N and stable molecular ions with similar charge-to-mass ratios as HC—e.g., I3CH or l2CH2—could not
be sufficiently eliminated from the mass spectra. Because of this, relatively high backgrounds could
not be suppressed [14, 15].
In the late 1970s, successful direct counting of '*C was accomplished by accelerating sample atoms
in the form of ions to much higher energies than was employed in conventional mass spectrometers.
40

r
HIGH ENERGY ION SOURCE
MASS SPEC.
ACCELERATOR / MOLECULAR
DISSOCIATOR

C" ' C
7 MV LOW ENERGY
MASS SPEC.

14
DETECTOR

Figure 2. Simplified representation of TAMS-type AMS system at the University of

California, Lawrence Livermore National Laboratory (LLNL), Van de Graaff
Tandem-Accelerator Laboratory. J. C. Davis and J. C. Vogel, personal
communication.

As simply illustrated in Figure 2, this was accomplished by inserting some type of particle accelerator
between the ion source and the analyzing magnet(s). To obtain AMS-based isotopic measurements,
initial investigators employed both a cyclotron [1] and tandem electrostatic particle accelerators [2, 3].
At first, the term high-energy mass spectrometry (HEMS) was used to designate this approach.
Accelerator (or atomic) mass spectrometry (AMS) is now more commonly used, while tandem
accelerator mass spectrometry (TAMS) refers to the use of a tandem accelerator for AMS
measurements.
The term "tandem" refers to the fact that particle acceleration in electrostatic systems is
accomplished in a two-step "pull-push" process. Negative ions are accelerated through a voltage to
a positive terminal ("pull") and then "stripped" to produce a positive ion which is accelerated away
from the terminal ("push"). Although the first AMS HC measurement on an archaeologically-related
sample was conducted on a cyclotron [16] and research on the use of a cyclotron for AMS
measurement continues [17,18], at the present time, all operational AMS systems employ TAMS-type
instruments. The great advantage of TAMS instruments is that 14N does not form negative ions or
does not form negative ions that live long enough to pass through the accelerator to the detector. In
addition, the stripping that takes place in a tandem accelerator system insures that no molecules
survive in their transit through the accelerator. These two factors account for a significant portion of
the sources of background experienced in the initial conventional mass spectrometry experiments with
l4
C.
Figure 2, which is a highly simplified schematic of the AMS system operating at the University of
California/Lawrence Livermore National Laboratory (UC/LLNL), illustrates the basic components
of an TAMS-type AMS system. The actual configuration of currently operating AMS instruments are
highly varied depending on the type of particle accelerator employed including whether the system is
dedicated to AMS or is part of a much larger accelerator laboratory. Since the LLNL accelerator can
provide high energy particle beams of various types, the UC/LLNL AMS system is only one of several
experiments being conducted using LLNL tandem.
In this system—which is one of more than twenty TAMS instruments now being used to obtain AMS
H
C and other cosmogenic isotopic measurements—the ion source produces ions by cesium
bombardment on the surface of a graphite target prepared from C0 2 obtained from sample
combustion or acidification. The ions are analyzed at the low energy end of the accelerator which acts
 41

Figure 3. AMS instrumentation at LLNL facility represented in Figure 2. Beam proceeds

from left to right. Source: J. C. Davis and J. C. Vogel.

both as a conventional mass spectrometer and as an injection magnet directing the ions into the
accelerator as C. The accelerator functions not only to accelerate the negative ions to several million
electron volts but also to dissociate all molecular species. On exiting the accelerator the carbon beam
is in the C4* charge state. The less abundant stable carbon isotope, l3C, is measured using a detector
mounted in the beam line following the first high energy analyzing magnet. After analyses in a second
magnet, the l4C is measured in an ionization chamber and solid state detector. Measurements are
obtained as ratios of | : C/"C and/or "C/ U C and known standards are used for normalization.
Technical features of the various types of AMS systems have been discussed in a number of review
papers [19].
To gain an appreciation of the physical scale of one type of AMS facility, Figure 3 provides an
photographic overview of the UC/LLNL AMS system showing the accelerator tank in the upper left
and first high energy analyzing magnet in the foreground. Not visible in this view is the low energy
mass spectrometer located at the opposite end of the accelerator tank. Figure 4 is a photograph of
the ion source at the low energy end of the system. Samples in the form of graphite are pressed into
metal sample holders which are inserted into a wheel housing shown in the photograph slightly right
of center. The top of the sample holder wheel can be seen. Figure 5 is a photograph of the detector
assembly (at the top center of the photograph) which houses the ionization chamber and solid state
detector. Below the detector assembly are electronic components for the detector and controls for
maintaining constant gas pressure in the ionization chamber.
42

Figure 4. Sample wheel and ion source for the LLNL AMS system. The cesium beam is
located between the two large insulator rings in the center of the photograph.
The wheel containing 60 samples is located to the right of the insulator rings
while the high-vacuum turbo-pump and the initial ion beam transport elements
are to the left of the cesium source. Source: J. C. Davis and J. C. Vogel.

4. AMS Advantages

Three advantages of AMS technology in the measurement of cosmogenic isotopes were initially
anticipated as a result of the greatly enhanced detection efficiency for cosmogenic isotopes such as l4C.
These were (i) major reductions in sample sizes-from gram amounts of carbon to 1-5 milligrams and,
with additional efforts, to the level of a few hundred micrograms; (ii) major reductions in counting
times-to achieve + 1% counting statistics, reductions from several days for conventional systems and
even weeks and months with micro- and mini-counting systems [20] to minutes and hours for AMS
systems; and finally, for existing dating techniques such as MC; (iii) significant increase in the
applicable dating time frame—for 14C, from the currently routine 40,000/50,000 years out to as much
as 100,000 years [1,11]. For l4C, the projected extension of the time frame using AMS technology was
anticipated due to a consideration of the data summarized in Table 2.
In a gram of modern carbon there is approximately 5.9 x 1010 atoms of MC. However, on the average,
over a one-minute period, less than 14 of these atoms will decay and be available for detection. In
a sample 100,000 years old, the decay rate of 14C will have dropped to a level far below the detection
limit of any decay counting instrument. However, in one gram such a sample, there are still over 105
atoms of ,4C available for detection. It has been suggested that the ultimate upper limit for ,4C using
AMS technology would be a function of neutron flux in soils into which samples are deposited. Very
 43

Figure 5. Radioisotope detection chamber for the LLNL AMS system. Tank at top of
photograph is 6-anode transverse ionization detector. Signal amplifier and data
collection electronics are in the near rack while the other rack contains the
equipment needed to kept the ionization gas at a constant density. Source: J. C.
Davis and J. C. Vogel.

Table 2. Comparison of HC decay counting and direct counting.

I4 M
C Decay Counting C Direct Counting

modern 13.5 dpm/gm carbon 5.9 x 10'° atoms ' C/gm carbon

50,000 0.03 dpm/gm carbon 1.4 x 108 atoms "C/gm carbon

100,000 0.00007 dpm/gm carbon 3.2 x 103 atoms l4C/gm carbon

 44

400 r io 4

■ 111, i I'M h i l t i f i f rl? 11

i|^y WIC'ROSAMPLE' i
DECAY COUNTING!

40 L ,o3U : r i r M n f.-:-»ir I-IT!-:-.TMT:- , <t Trunin urn*'.

Q .{EXTENDED RANGE'
O COUNTING!
Q: 2­3%]J
UJ
Q. , ­ i t DECAY COUNTING: #,'•*
I­ I02 .,<.,.,­:­!» " t i f f :ff[t 0 . 2 ­ 0 . 5 % ] # £ • '
O r­1111II i 111 Tt±±:: r:i|l!l!ll|!H­T'­r
rdtiSTANDARD:::
HHSTANDARD irttc:­­:­:­'­'* 7 ' *'
). DECAY COUNT iNGrrr­
3
13:[±Q5­i5%)­}r'
o
o
*" | o
10
<
o
Q.
>-
1.0
1 _ DIRECT _
COUNTING::­:

"- 0.1
1 [t M 0 % ] " v

£_ _L _L
10 I02 I0 3 io 4 io 5

(milligrams of carbon)
L _L _L
0.001 0.01 0.1 I 10 100
(grams of carbon)
TYPICAL SAMPLE SIZE
Figure 6. Relationship between sample size and typical counting periods for differnt types
of conventional decay counting sytsetms as compared with direct counting by AMS
technology. Source: Figure 3.4 in Taylor [10].

low levels of l4C would be produced in situ. However, additional studies are necessary to determine
the degree to which, this effect could be detected even in samples approaching 10s years in age [21].
As noted previously, the first two of the three anticipated benefits of AMS technology-major
reductions in sample size and counting times-have been fully realized over the last decade [22, 23].
Figure 6 illustrates the impact of direct counting technology on typical counting periods as well as
sample sizes when compared against several types of decay counting approaches. For both sample
sizes and counting times, order-of-magnitude reductions have been made possible on a routine basis.
However, the projected third advance has been frustrated due to general inability at present to exclude
microcontamination of samples primarily with modern carbon introduced during sample preparation.
The source of a significant portion of this contamination results from the current requirement that
samples must be converted to graphite for use in the ion source of an AMS system. Parts per million
 45

Table 3. Comparison of procedures for decay and direct counting

technologies in radiocarbon measurements

Decay Counting Direct Counting

Pretreatment: Isolation of in situ fraction of sample

Preparation: conversion of sample Preparation: conversion of sample

to form required by method of to form required by method of
measurement (gas/LS) measurement (solid/gas [projected])

Production of ions from sample

Acceleration of ions

Separation of l4C from all other

isotopes and molecules

Count decay events of l4C Count individual 14C ions

Infer 14C concentration by Infer l4C concentration by

comparison with standards comparison with standards

of modern carbon contamination translates into background levels which generally limit the maximum
ages that can be resolved to between 40,000 and 50,000 years.
In an excellent study of this problem carried out by the University of Washington AMS group, an
AMS l4C measurement of 69,030 + 1,700 years was obtained on a specially prepared sample of
geological graphite. However, graphite prepared from CO : obtained from a sample of marble—which,
like geologic graphite, should exhibit no 14C activity due to its great geologic age—yielded an apparent
age of 47,960 + 670 years [24]. Currently under development is a C0 2 gas source for use on AMS
systems [25]. Such a source would eliminate the requirement that samples be converted to graphite.

5. Applications of AMS Technology

The development of AMS technology has now provided the technical means by which very low organic
carbon content sample types, such as organic extracts from bone and ceramics along with microsample
materials such as single seeds, can be effectively and efficiently dated by l4C. It should be emphasized
that AMS-based l4C age determinations are not inherently more-or less—accurate than decay
counting. There simply now exists the routine capability to obtain suites of l4C measurements on
samples containing milligram amounts of carbon—and with additional efforts, samples containing as
little as 100 micrograms of carbon. Table 3 summarizes the differences in the procedures to obtain
l4
C determinations using decay as opposed to direct counting. Antecedent to the use of either
technologies to infer age is the fundamental requirement for physical and chemical pretreatment of
a sample to eliminate contamination and to isolate an jn situ or indigenous fraction.

5.1. RADIOCARBON DATING OF BONE

One of the most dramatic illustrations of the impact of AMS technology on processes for establishing
temporal controls for archaeological and palcoanthropological materials has been the great expansion
46

Table 4. Definition of confidence levels denoting reliability of association of sample materials with
archaeological/human skeletal feature. Taken from Taylor [10].

Confidence level Definition Example

Essential certainty age estimate on object for
which temporal placement
sought
High probability age estimate on material
in direct functional
relationship with
object/event for which
temporal placement
sought
Reasonable age estimate on
possibility enclosing deposits
of assumed similar
age to the object/
event for which
temporal placement
sought
Possibility age estimate on
component of deposit
correlated with
deposits containing
object/event for which
temporal placement
sought
l4
C analysis on human bone
to obtain age estimate on
human burial
l4
C analysis of textile
used to wrap burial to
obtain age estimate on
burial
l4
C analysis of charcoal
in sediments adjacent to
burial to obtain age
estimate on burial
14
C analysis of charcoal
in sediments associated
stratigraphically/
geomorphologically or
cross-dated on the basis
of some cultural feature
with the burial to obtain
age estimate on burial

in the direct MC dating of bone—and particularly human bone samples. The interest in obtaining
well-documented age estimates directly on human bone derives from the recognition that the most
frequent cause of anomalous age estimates using 14C values is a misassociation of sample material used
for the actual age determination with the archaeological and/or geological context for which temporal
assignment is required. The basic issue was framed in simple and straightforward terms more than
two decades ago by Frederick Johnson [26] when he declared that a l4C age estimate".. .does not date
a site . . . or a grave or a level. The date is that of the sample and it is the task of the archaeologist
to discover the true relationship between the sample and the area or place it came from."
An accurate 14C age estimate directly on human bone totally obviates the need to infer age for
hominid skeletal sample on the basis of some presumably "associated" organic such as charcoal. Table
4 contrasts the "essential certainty" of association of sample with archaeological context accomplished
by the use of human bone in contrast to lower levels of confidence of other sample materials. When
14
C age determinations are obtained directly on a bone sample clearly identified on widely-accepted
morphological criteria as being genus Homo, any question of human involvement or human agency
is, by definition, rendered moot and one can evaluate the accuracy of a l4C on physiochemical grounds
alone.
 47

5.1.1. Background and Context. Historically, bone has been widely regarded as an unreliable and
problematical material for '4C analysis. The initial experience of the Chicago laboratory yielded a
hierarchy of reliable sample materials which began with charcoal and wood, followed by grasses, cloth
and peat, well-reserved antler, and, at the bottom of the list, well-preserved shell. (Surprisingly,
"heavily burned bone" was listed along with charcoal at the top of this list. However, the organic
material was not the bone itself but carbonized skin, hair and other residual fatty tissue.) Bone itself
was excluded from the Libby listing. The initial view was that bone would be a "very poor prospect"
because of its relatively low, largely inorganic, carbon content, its very porous structure and the
"potential for alteration"—i.e., isotopic exchange of the carbonates in the bone with ground water and
soil carbonates [27].
Other laboratories, however, did undertake the measurement of bone samples and quickly
confirmed lobby's impression that bone yielded inconsistent results when compared with the results
from other sample types. The problem with bone was quickly traced to the fact that the l4C
measurements were being carried out on the total or whole-bone matrix which is composed largely
of inorganic constituents. Inorganic carbonates in a bone which has been buried in an active soil
profile can be derived from either primary carbonates associated with the indigenous apatite structure
(calcium carbonate incorporated in calcium phosphate crystals and other amorphous,
carbon-containing inorganic materials) or secondary or diagenetic carbonates which had been
transported into the bone matrix from the groundwater and soil environment by chemical exchange
and/or through dissolution and reprecipitation processes. Unfortunately, it has been determined that
"C values obtained on a total carbonate fraction can be significantly older, essentially the same age,
or younger than an organic fraction from the same bone [28]. Studies whose aims is to isolate the in
situ apatite fraction in bone has been pursued [29]. However, difficulties in accomplishing this on a
consistent basis has led the majority of researchers to focus their attention on the isolation of one or
more organic fractions.

5.1.2. Biogeochemistry of Bone. Between 60%-70% of the organics contained in fresh, fat-free
mammalian bone is composed of the protein collagen. In vivo mammalian collagen can be
distinguished by a number of biogeochemical indices, e.g., a distinctive nitrogen/carbon ratio, a
characteristic pattern in the relative concentrations of the approximately 20 amino acids which make
up the collagen, as well as a relatively high concentration (ca. 10%) of hydroxyproline, one the amino
acids found almost exclusively in collagen. In principle, collagen MC values should yield as valid a l4C
age estimate as that obtained from, for example, wood. Unfortunately, the physical and chemical
structure of bone and woody plant materials are significantly different. The cellulose and lignin
structures in woody plants are, from a biochemical perspective, relatively stable. Because the organic
structure of these materials is strongly-bonded chemically, absorbed inorganic and organic compounds
can usually be effectively removed with acid and base extractions. In contrast, subfossil bones
recovered from archaeological and/or paleontological contexts in most temperate and tropical
environments have generally been effected by one or more types of biogeochemical diagenetic
processes which results in the hydrolysis and denaturation of the collagen structure. Generally
speaking, without the use of chromatographic methods, it can be sometimes difficult in
diagcnctically-affectcd bone to distinguish denaturization products of the indigenous organic
compounds from, for example, the various types of humic and fulvic compounds present in almost all
temperate-latitude soils.
In MC studies on bone, a wide spectrum of organic substances have been extracted and labeled with
a variety of terms-including collagen, gelatin, purified proteins, acid soluble, acid insoluble, base
soluble, base insoluble, total amino acids, and one or more amino acids. In some reports, "collagen"
has been used as simply a generic label to designate the organic residue of a bone which remains
following the destruction of all carbonates by treatment with an acid. Depending on the diagenetic
history of the bone, this designation may or may not correctly characterize the physical nature of the
organic product. In the absence of specific biochemical data (e.g., amino acid composition), a more
accurate reference for such an organic fraction would be "total acid insoluble (and/or soluble) organic
fraction."
48

5.1.3. Analytical Strategies. Two related strategies have been employed in working with bone samples
undergoing 14C analysis. The goal of the first approach is to develop a technique which can be
generally applied to all bones which will exclude contaminants and yield a product composed
exclusively of organics indigenous to the sample bone. A widely employed method of bone
pretreatment in this tradition is based in whole or in part on a technique first described by Longin in
the early 1970s. Following the elimination of the inorganic carbonates by acid treatment, this
approach extracts the insoluble residue with water at 90°C at a controlled pH to produce a gelatinous
residue. In the original study, it was assumed that only collagen would be present in the insoluble
gelatin product because the impurities would be removed in the liquid fraction [30]. The second
strategy utilizes similar preparative techniques but focuses on the isolation and separate i4C analysis
of different organic fractions from the same bone. This approach evaluates the accuracy of the ,4C
values on the basis of the degree of concordance among the organic fractions [31].
In the vast majority of bone samples where the collagen structure remains intact, it appears that
with proper chemical pretreatment, the 14C activity of most organic fractions can be used to infer an
accurate age. However, a major problem in the examination of validity of l4C determinations on bone
where the yields of organic product is very low. With conventional l4C decay counting technology,
these low yields raised difficulties in that it sometimes required adjustments in the pretreatment
procedures. The requirement of sample size sometimes impeded an intensive investigation of the
biogeochemistry of a bone sample to insure that indigenous bone fractions were identified and
extracted. As we have noted, the advent of accelerator mass spectrometry has permitted meaningful
analysis to be obtained on sample sizes several orders of magnitude below that possible with
conventional decay counting with as a result over the last decade, a large corpus of bone 14C values
have been obtained.
5.1.4. Contributions. An excellent example of the great potential of AMS technology to examine
multiple l4C fractions in bone was recently reported by Stafford .et _aj. [32]. Using a well-preserved
mammoth (Mammuthus sp) bone—i.e., a bone exhibiting a collagen amino acid profile—associated with
a wood sample dated by 14C at 11,490 + 450 l4C years (AA-823), these researchers dated fifteen
separate organic fractions prepared by a variety of preparative methods including the chromatographic
separation of individual amino acids. As summarized in Figure 7, all of the organic extracts exhibit
l4
C ages younger than the wood sample. However, nine of the fractions yielded 14C ages which were
within two sigma of the wood value, while five fractions exhibited still younger ages. With the
exception of one organic fraction which may have been contaminated with an organic solvent, the
youngest organic fraction was about 2,000 ( + 500) years younger than the presumed actual age of the
bone. The principal contaminant in the bone was identified as humics (fulvic acids), which yielded
14
C ages of about 5,000 l4C years.
One of the major contribution of AMS MC analysis over the last decade has been to revise the age
estimates assigned to human skeletal materials from localities in the Western Hemisphere. In the
1970s, a group of human bone samples from sites in the New World had been assigned ages ranging
from 17,000 to 70,000 years based on data obtained from decay counting l4C values, uranium series
and amino acid raccmization-inferred ages [33, 34]. As a consequence of AMS-based [4C
determinations which are summarized in Table 5, all of the previous age assignments were reduced
to less than 7,000 14C years.

6. Radiocalcium Dating
The development of AMS technology has led not only to advances in existing isotopic dating methods
but also has made it possible to investigate the potential of new methods some of which had been
previously suggested but had not been practical to pursue until the advent of AMS techniques. An
example of such a method is that based on an isotope of calcium-4'Ca . The possible use of 4lCa as
a means of dating calcium-containing sample materials such as bone was first suggested by Yamaguchi
in the early 1960s [35]. However, due to the difficulty of measuring 41Ca with decay counting, it was
not until the introduction of AMS technology is the late 1970s that the potential of using 4lCa was
again raised.
 49

■ WOO
D | ca. 2100 years —
• XA
D PURIFIED
▲ HCL-INSOLUBLE I A 1
♦ HCL-SOLUBLE I ♦—I
I • 1
I A 1
X =FULVIC ACID S , A ,
I—•—I
I A |
I • 1
\ I • 1
X I • 1
DOMEBO MAMMOTH i—•—i
i—• 1
i—■ 1
i i i I i i i I i i i I i i i I i i i I i i i I i i i I

5000 6000 7000 8000 9000 10000 11000 12000

14
C YEARS B.P.
Figure 7. D istribution of U C values on wood associated with D omebo Mammoth and
various organic extracts from D omebo Mammoth bone. D ata taken from Stafford
ct al. [32]

6 . 1 . B ASIS OF THE METHOD

Raisbcck and Yiou [36] provided the first detailed outline of a dating model for the radiocalcium
method. Figure 8 summarizes the basis of the method. Like l4 C, 41Ca is produced by cosmic-ray
neutron secondaries. However, the bulk of the isotope is not produced in the atmosphere as is the
case with l4 C. Rather, it is produced primarily in the upper meter of the soil profile by neutron
capture on 40Ca. The cosmic-ray produced 4l Ca is mixed with the other naturally occurring calcium
isotopes into the surface soils and is taken up into the plant tissue where it then would be
incorporated into bone mineral through ingestion of plant materials. A 4 l Ca/Ca equilibrium ratio
would be maintained in living organisms by exchange and metabolic processes.
In contrast to 14C dating, where the death of an animal or plant and the isolation of a sample from
one of the carbon reservoirs constitutes the t = 0 event, zero B. P. in the 4l Ca method would occur
when a sample is permanently shielded from the effect of the cosmic-ray produced neutron irradiation.
This could be accomplished either through burial or placement in a cave/rock shelter environment
to a sufficient depth. The required depth would vary as a function of the surrounding soil or rock
media. Age inferences would be based on the measurement of the residual 4l Ca with respect to the
stable isotopes of Ca. The decay of 4l Ca to 4IK takes place by electron capture and the emission of
a neutrino. With a half-life of about 103 years, 41Ca could potentially be employed to infer age for
calcium-containing samples over about the last 106 years.

6 . 2 . ASSUMPTIONS

To be able to employ directly changes in 41 Ca/Ca ratios to infer an age for calcium-containing samples
with some degree of accuracy, a scries of conditions would need to hold. They include (i) that the
50

Table 5. Revisions in age estimates on bone from purported New World late
Pleistocene contexts based on AMS UC determinations. Except for
the Old Crow sample, all bones were identified as human skeletal
material. Data taken from Taylor et al. [35]

Skeleton/ Original Estimate Revised Estimate

14
Artifact Basis Age C Age Laboratories

Sunnyvale AAR 70,000 3600-4850 UCR/Arizona

AMS

U-series 8300/9000 63001 UCSD(Scripps)/

Oxford AMS

Del Mar AAR 41,000-48,000 49001 UCSD(Scripps)/

U-series 11,000/11,300 Oxford AMS
14
Los Angeles C> 23,000 3560 UCR/Arizona
AAR 26,000 AMS

Taber geologic 22,000-60,000 3550 Chalk River

AMS

Yuha 14C
22.0002 1650-3850 Arizona AMS
AAR 23,000
U-series 5800

Old Crow5 ,4
C 23,000 1350 Simon Frazer/
McMaster AMS
14
Laguna C 14,000-17,150 5100' UCSD(Scripps)/
Oxford AMS

'Amino acid fraction.

2
Diagenetic carbonates.
3
Artifact fabricated from bone.

initial concentration of cosmogenic 4lCa in samples has remained essentially constant over the
projected 4lCa time scale (or appropriate corrections can be made for documented variations); (ii) that
the 41Ca/Ca ratio in a sample has not been altered except by 41Ca decay since the sample was shielded
from the effects of neutron irradiation, e.g., no postdepositional exchange/contamination of the in situ
4l
Ca as occurred; (iii) that mixing of cosmogenic 41Ca in the source of calcium for a sample has
occurred over a relatively short period of time as compared to the 41Ca half-life; (iv) that the half-life
of 4lCa is accurately known; and (v), that natural levels of 4lCa can be measured within reasonable
levels of uncertainty [37, 38].
It should be emphasized that the projected 41Ca method carries with it potentially serious deficits
that could easily put quite rigid constraints on the types of dcpositional environments that can be
expected to give straightforward results. The fact that lithospheric rather than atmospheric production
 4l
Co(e,i/)4lK

t|/2 = ca. 1 0 0 , 0 0 0 YEARS

Figure 8. Basis of radiocalcium method: production, distribution and deacy of ''Ca. Taken
from Taylor [11].

predominates raises the strong possibility that localized mixing and erosional effects may cause
significant variations in initial 4lCa/Ca ratios in many environments. In addition, since samples which
have not been buried deeply enough will continue to be subject to <[Ca formation from the cosmic-ray
generated neutron secondaries, the burial histories of samples may affect 41Ca concentrations.
Localized variations in uranium concentrations would also perturb 41Ca levels particularly in bone
which can concentrate uranium over time as would "Ca produced through neutrons generated by
natural radioactivity (uranium and thorium) in the burial environment. Also, one might reasonably
52

expect post-depositional exchange of calcium isotopes in some samples through various effects. These
and other factors suggest that samples from each site or locality might exhibit unique initial "Ca
concentrations. An additional complicating issue is that the current precision with which the half-life
of 41Ca is known is estimated to be on the order of + 30%.
To develop a practical method of employing 41Ca concentrations in calcium-containing samples to
infer age and to determine the degree of general applicability, a series of studies must be undertaken
that, in broad outline, would parallel the initial set of experiments which established the utility and
accuracy of the 14C method. All of the experiments which would be needed to demonstrate the
general usefulness of the 41Ca method would require the existence of a practical and effective means
of measuring natural 4lCa values in terrestrial samples.

6 . 3 . STUDIES TO DATE

Since 1980, several groups have examined various approaches to the measurement of 4lCa at natural
concentrations. Initial experiments have been summarized in Taylor .et .a!. [37]. The first direct
measurement of the 4'Ca terrestrial concentration in natural samples was accomplished at the Argonne
National Laboratory using the Argonne Tandem Linac Accelerator System (ATLAS) following the
pre-enrichment of the 4'Ca employing a Calutron isotope separator at the Oak Ridge National
Laboratory [39]. These experiments indicated that 41Ca/Ca concentrations down to about 6xl0"14 can
be unambiguously measured with this AMS system. Using pre-enriched samples with more than 2
orders of magnitude enrichment, 4lCa concentrations below this value could be inferred down to
about 5 x 10''6.
Pre-enriched bone, surface and deeply-buried limestone samples exhibited 41Ca/Ca ratios well above
the limit observed with the background sample. The inferred 4l Ca/Ca ratio measured in modern bone
was 2.0( + 0.5) x 10"'\ This is somewhat higher than the secular equilibrium value of 8 x 10"13
estimated by Raisbeck and Yiou [36]. There was the initial expectation that the surface limestone
would exhibit about the same 4 'Ca/Ca ratio as the modern bone sample and the 11-meter limestone
several orders of magnitude below this. However, both limestone samples, within error, showed about
a factor of 2-3 lower 4lCa concentrations. There are a number of possible explanations that would
account for these results. For example, the high 41Ca/Ca ratio in contemporary bone may indicate
a contribution of anthropogenic 4'Ca originating from the nuclear weapons test era prior to 1963,
similar to the effects observed for MC1 [40, 41].
The ability to provide an independent temporal scale for the Middle and early Late Pleistocene
comparable to that established for the Early Pleistocene by K/Ar values and for terminal Pleistocene
with 14C data, would clearly be of major significance in providing critical data that would impinge on
several important debates currently underway among archaeologists and paleoanthropologists. Over
the next half-decade, experiments now underway should determine the general feasibility and
practicality of utilizing 4'Ca to provide a chronometric scale for this time period.

References

[1] Muller, R. A. (1977) Science 196, 489-494.

[2] Nelson, D. E., Korteling, R. G. and Scott W. F. (1977) Science 198, 507-508.
[3] Bennett, C. L., Beukens, R. P., Clover, M. R., Gove, H. E., Liebert, R. B., Litherland, A. E.,
Purser K. K., and Sondleim W. E. (1977) Science 198, 508-509.
[4] Gove, H. E. (ed.) (1978) First Conference on Radiocarbon Dating with Accelerators,
University of Rochester, Rochester, New York.
[5] Henning, W., Kutschera W., Smither, R. K. and Yntema, J. L. (eds.) (1981) Symposium on
Accelerator Mass Spectrometry (ANL/PHY-81-1), Argonne National Laboratory, Argonne,
Illinois.
[6] Wolfli, W., Polach, H. A. and Anderson, H. H. (eds.) (1984), Proceedings of the Third
International Symposium on Accelerator Mass Spectrometry, Nuclear Instruments and
Methods in Physics Research B5, 91-448.
 53

[7] Hedges, R. E. M. and Hall, E. T. (eds.) (1986), Workshop on Techniques in Accelerator

Mass Spectrometry, Oxford Radiocarbon Accelerator Unit, Research Laboratory for
Archaeology, Oxford University.
[8) Gove, H. E., Litherland A. E., and Elmore, D. (eds.) (1987) Accelerator Mass Spectrometry,
North-Holland Physics Publishing, Amsterdam.
[9] Yiou, F. and Raisbeck, G. (eds.) (1990), Proceedings of the Fifth International Symposium
on Accelerator Mass Spectrometry, Nuclear Instruments and Methods in Physics Research,
in press.
[10] Taylor, R. E. (1987) Radiocarbon Dating, An Archaeological Perspective, Academic Press,
Orlando.
[11] Taylor, R. E. (1987) Analytical Chemistry 59, 317A-333A.
[12] Alvarez, W. (1981) in Symposium on Accelerator Mass Spectrometry (ANL/PHY-81-1), W.
Henning, W. Kutschera, R. K. Smither, and J. L. Yntema, (eds.), pp. 1-15. Argonne National
Laboratory, Argonne.
[13] Oeschger, H., Houtermans, J., Loosli, H. and Wahlen M. (1970) in Radiocarbon Variations
and Absolute Chronololgy, I.U. Olsson, (ed.), pp. 471-4%, Almqvist & Wiksell, Stockholm.
[14] Anbar, M. (1978) in First Conference on Radiocarbon Dating with Accelerators, H. E. Gove,
Ed., pp. 1-15, University of Rochester, Rochester, New York.
[15] Wilson, H. W. (1979) in Radiocarbon Dating, R. Berger and H. E. Suess, (eds.), pp. 238-245.
University of California Press, Berkeley
[16] Muller, R. A., Stephenson, E. J. and Mast, T. S. (1978) Science 201,347-348.
[17] Bertsche, K. J., Friedman, P. G., Morris, D. E., Muller, R. A., and Welch, J. J. (1987) in
Accelerator Mass Spectrometry, H. E. Gove, A. E. Litherland, and D. Elmore, (eds.), pp.
105-109. North-Holland Physics Publishing, Amsterdam.
[18] Bertsche, K. J. (1989), unpublished doctoral dissertation, University of California, Berkeley.
[19] See the references in Table 1. One of the more recent general reviews is Wolfli, W. (1987)
in Accelerator Mass Spectrometry, H. E. Gove, A. E. Litherland, and D. Elmore, (eds)., pp.
1-13. North-Holland Physics Publishing, Amsterdam.
[20] Harbottle, G., Sayre, E. V. and Stoenner, R. W. (1979) Science 206, 683-685.
[21] Wand, J. O. (1981) unpublished doctoral dissertation, Oxford University, pp. 254-270.
[22] Taylor, R. E., Donahue, D. J., Zabel, T. H., Damon, P. E. and Jull, A. T. J. (1984) in
Archaeological Chemistry III, J. B. Lambert, (ed.), pp. 333-356. American Chemical Society,
Washington, D. C.
[23] Hedges, R. E. M. and Gowlett, J. A. J. (1986) Scientific American 254, 100-107.
[24 Schmidt, F. H., Balsley, D. R. and Leach, D. D. (1987) Nuclear Instruments and Methods in
Physics Research B29.97-99.
[25] Bronk, C. R., and Hedges, R. E. M. (1987) in Accelerator Mass Spectrometry, H. E. Gove,
A. E. Litherland, and D. Elmore, (eds.) pp. 45-50, North-Holland Physics Publishing,
Amsterdam.
[26] Johnson, F. (1965) in Proceedings of the Sixth International Conference Radiocarbon and
Tritium Dating, R. M. Chatters and E. A. Olson, (compilers) pp. 762-780, Clearinghouse for
Federal Scientific and Technical Information, Springfield, Virginia.
[27] Libby, W. F. (1952) Radiocarbon Dating, p. 45, University of Chicago Press, Chicago.
[28] Taylor, R. E. (1982) in Nuclear and Chemical Dating Techniques: Interpreting the
Environmental Record, L. A. Currie (ed.), pp. 453-473, American Chemical Society,
Washington, D. C.
[29] Haas, H. and Banewics, J. J. (1980) Radiocarbon 22, 537-544.
[30] Longin, R. (1971) Nature 230, 241-242.
[31] Taylor, R. E. (1987) Nuclear Instruments and Methods in Physics Research B29, 159-163.
[32] Stafford, T. W., Jr., Jull, A. J. T., Brendel, K., Duhamel, R. C. and Donahue, D. (1987)
Radiocarbon 29, 24-44.
[33] Taylor, R. E. (1990) in The Peopling of the Americas, Dillehay, T. and Meltzer, D. (eds.),
Telford Press, Caldwell, New Jersey.
54

[34] Taylor, R. E., Payer., L A., Prior, C. A., Slota, P. J., Gillespie, R., Gowlett, J. A. J., Hedges,
R. E. B., Ml, A. J. T., Zabel, t. H., Donahue, D. J. and Berger, R. (1985) American
Antiquity 50, 136-140.
[35] Yamaguchi, Y. (1963) Progress of Theoretical Physics 29, 567.
[36] Raisbeck, G. M. and Yiou, F. (1979) Nature 277, 42-44.
[37] Taylor, R. E., Slota, PJ., Jr., Henning, Kutschera, W. and Paul, M. (1989) In Archaeological
Chemistry IV, R. O. Allen (ed), pp. 321-336,American Chemical Society, Washington, D.C.
[38] Taylor, R. E., Slota, PJ., Jr., Henning, Kutschera, W. and Paul, M. (1989) in Proceedings of
the 26th Archaeometry Symposium, R.M. Farguhar, R. G.V. Hancock, and L. A. Pavish (ed),
pp. 58-61, University of Toronto, Toronto.
[39] Henning, W., Bell, W A , Billquist, P. J., Glagola, B., Kutschera, W., Liu, Z., Lucas, H. F.,
Paul, M., Rehm, K. E. and Yntema, J. L. (1987) Science 236,725-727.
[40] Elmore, D., L. E. Tubbs, D. Newman, X. Z. Ma, R. Finkel, K. Nishiizumi, J. Beer, H.
Oeschger, and M. Andree (1982) Nature 300, 735-737.
[41] Bentley, H. W., F. M. Phillips, S. N. Davis, S. Gifford, D. Elmore, L. E. Tubbs, and H. E.
Gove (1982) Nature 300, 737-740.
ISOTOPE DATING

U. HAUDENSCHILD
M. FLISCH
Abteilung fur Isotopengeologie
Universitat Bern
Erlachstr. 9a
CH - 3012 Beme
Switzerland

1. Introduction

Isotope dating means evaluating the age of geological events through the rate of decay of
radioactive isotopes.
During the 18th and 19th centuries the pioneers of geology established stratigraphic
relations by which they could define the relative age of different geological units and
estimate their position within the evolutionary history of our planet.
With the discovery of radioactivity, for which Henri Becquerel and the Curies won
the Nobel Prize in 1903, another instrument for dating fossil materials was developed. In
1907 Bertram Boltwood dated three uraninite. samples using their U/Pb ratio (Faure 1977).
In the late fifties a number of laboratories in Europe and the USA started developing
methods for routine dating of geological material, an ongoing process which leads to even
greater precision and faster data handling, and provides information not only about large
scale sample material but also about different parts of the crystal lattice of one single
mineral specimen thanks to the use of modern laser technique and computer supported
mass-spectrometers.
In the light of this development it is obvious that the lower age limits for dating
decrease and samples of only a few tenthousanths of years can be dated using classical
methods such as K-Ar or 40 Ar- 39 Ar.

2. Fundamentals

Whichever radiometric system we use, we can state that the number of isotopes (dN) that
decay during a certain time (dt) is proportional to the total number of radioactive isotopes
(N):

dN/dt = -ANor (1)

dN/N = -At, where A. is the decay constant (A = In 2/t\p) (2)

The time integral of Eq. (2) is

In N = -At + C (3)
55
H. Y. Goksu et al. (eds.). Scientific Dating Methods, 55-75.
© 1991 ECSC, EEC. EAEC. Brussels and Luxembourg. Printed in the Netherlands.
56

Knowing t to be zero at the beginning of the radioactive decay the number of radioactive
isotopes at to is assumed to be No and therefore

In N = -At + In No or (4)

In N/No= -At which leads us to the age formula (5)

t = 1/A In No/N (6)

Therefore to establish the age of any sample we would have to know the actual number of
radioactive isotopes (N) and the number of isotopes at the beginning of decay (No). N can
be directly measured, it is called the parent isotope (M). No can be calculated by adding the
number of daughter isotopes (D) generated by radioactive decay of the parent isotope (M)
to M, e.g. No = M + D

therefore t = 1/A In (1 + D/M) (7)

The accuracy of the dating method is dependent on accurate measurement of D and M and a
proper knowledge of A. Interlaboratory comparison of results is possible only if identical
values for A are used. Constants for U-Pb, K-Ar and Rb-Sr dating, which are
internaltionally accepted today were proposed 1977 by the IUGS Subcommision on
Geochronology (Steiger & Jager 1977). For K-Ar they are:
Potassium
40 K ex. 40An A(40Ke) = 0.581 x 10"10/yr
40 K £. 40Ca: A(40Kp) = 4.962 x 10-10/yr
A(40K) = A(40Ke) + A(40Kfs) = 5.543 x KHtyyr
39
isotopic abundances K = 93.2581 atom%
40
K = 0.01167 atom%
41
K = 6.7302 atom%
Argon
atomic ratio 40Ar/36Ar atmospheric = 295.5
(for explanations see below).
All results anaylzed before to this date should be recalculated if other constants were used.

3. Analytical Procedure

Within this lecture explanations will be limited to the application of radiometric dating
methods on archeaological problems.
Archeological samples can be dated only if they are deposited in a sedimentary pile
intercalated with volcanic material e.g. tuff horizons or lava flows, since no mineral phase
of the detritic sediment would yield the sedimentation age. Tuffitic rocks can rarely be
reliably treated as whole-rock samples. Preferably several mineral phases of each sample
should be analyzed. Concordancy between different mineral ages is an indication of a
meaningful result. Discordant ages can result from alterations of several minerals
 57

(feldspars may be coated with clay minerals), or excess argon (especially in olivine,
pyroxene or amphibole) incorporated in the crystal lattice during crystallisation.
Lava flows may be dated as whole-rocks provided they are fresh and free of xenolithes. If
xenolithes are present, these have to be separated. A crystallisation age can be determined
from the remaining matrix. To check for the reliability of whole-rock ages at least two
samples from different localities should be dated. Still better is the separation and analysis
of different phenocrysts and the matrix alone of at least one of the samples taken. With the
K-Ar method the following minerals can be dated: micas, sanidin, hornblende. Excess
argon may be recognized by analyzing pyroxene or olivine crystals etc.

3.1. SAMPLING AND MINERAL SEPARATION

Before taking samples for isotopic analysis hand-size specimens should be taken for
microscopic investigation. Each sample should be checked to be fresh and have a suitable
composition (amount and size of phenocrysts). The use of a V-spectrometer to briefly
evaluate the samples with the highest potassium content in the field may be useful.
For mineral separation samples of 5-30kg are taken (depending on the mineral
needed). The material, with the exception of one hand specimen which is stored separately,
is crushed in a rock crusher to a grain size of about 2mm, milled between two rotating
metal discs and sieved to varying grain size fractions. Each fraction is then treated
individually. Accessory minerals such as zircon, apatite, sphene or monazite needed for
fission-track dating are separated out of the smallest grain-size fraction on a Wilfley
shaking-table (see chapter "Fission Track Dating" in this volume). Minerals such as micas,
feldspars or amphiboles can be separated according to their magnetic properties on
magnetic separators, according to their density using heavy liquids such as bromoform,
methyleniodide or cleici-solution and according their shape on dry-shaking tables. The
different methods of mineral separation often have to be repeatedly used in order to obtain
a pure mineral concentrate.
For whole-rock dating of lava flows a suitable grain-size fraction is sieved out of
the crushed material. After sieving the sample is washed in distilled water to remove dust.
After drying the sample aliquots for the different analytical procedure are separated using a
Jones splitter (see below).

3.2. CHEMISTRY

For potassium analysis the samples are dissolved in hydrofluoric-perchloric acid mixture.
Excess acid is evaporated and a sample solution is prepared in hydrochloric acid which can
then be analyzed by various analytical methods. For the argon analysis the pure sample can
be introduced into the extraction system directly.

3.3. MASS SPECTROMETRY

For highly precise isotope analysis the mass-spectrometric isotope-dilution (ID) method is
necessary. A known quantity of a certain isotope ( 38 Ar, 4 0 K), the spike, of the element
under investigation is therefore added to the sample. The ratios of the intensity measured
for each isotope and the intensity measured for the spike enable us to calculate the absolute
quantities of each isotope.
58

The mass-spectrometer consists of three main units, 1) an ion source, 2) an

analyzer, 3) a collector/amplifier system usually connected to the computer. Figure 1
shows a mass-spectrometer schematically. The sample can be inserted into the ion source
either in the form of a purified gas a sample solution (see above) evaporated onto a filament
wire which can be heated to emit the sample in the form of ions (called thermal ionisazion).
The gaseous sample is usually ionized by electron bombardment. The ions are accelerated
and focussed through a number of charged plates to form an ion-beam. Within the analyzer
the isotopes are separated in a magnetic or electric field according to their mass/charge ratio
and collected in Faraday cups. The signal registered on the collector is intensified by an
amplifier, digitized and processed on the computer.

Co

Fig. 1. Schematical graph of the mass-spectrometer

Main components:
IS : ion source F : Faraday collectors
Sp : sample holder A : amplifier
PI : focussing plates A/C : analog-digital converter
M : analyzer (magnet) C : computer
 59

4. K-Ar Dating

The K-Ar dating method depends upon the radioactive decay of 4 0 K to 40 Ar and 40 Ca by
electron capture and (3 -emission respectively. With a total half-life of 1.25 x 109 years
10.5% of the 4 0 K decays to 4 0 Ar, 89.5% to 4 0 Ca. The isotopes formed through
radioactive decay are termed 4 0 Ar radiogenic ( 40 Ar*) and 4 0 Ca radiogenic ( 40 Ca*).
According to equation (7) the K-Ar age equation is:

t = 1/A(40K) • l n ( 1 + *(4°K) • 4 °Ar*/A (4 o Ke) • 40K) (8)

Geological samples do contain not only 40 Ar* but also atmospheric argon adsorbed on the
sample surface and in the mineral lattice. According to the 40 Ar/ 36 Ar ratio of 295.5 of the
atmospheric argon, the contribution of air-argon to the 40 Ar* can be corrected with:

40 Ar * = 4 0 A r m c a s u r c d . 295.5 X36ArmCasured (9)

4.1. REQUIREMENTS

According to the above comments, the requirements for the K-Ar age determination are the
following:

At the time of the closure of the argon system in the sample, only atmospheric argon was
incorporated.
This requirement leads to the problem of the "excess" argon. Rocks which rapidly
crystallised at the earth's surface or crystallized under high pressure (great depth or impact)
may incorporate so-called "excess" argon with a 4 0 Ar/ 3 6 Ar ratio differing that of the
atmospheric argon. For Quaternary samples, where the 40 Ar* component is very small,
this problem becomes particularly serious. Volcanic extrusives are very important for
Quaternary dating. Their initial isotopic ratios depend on the history of the developement of
their parent magma. Recent MORB show very high 4 0 Ar/ 3 6 Ar ratios of up to 26,000
(Allegre et al. 1983; Marty et al. 1983; Sarda et al. 1985, Jambon et al. 1985). Initial
40
Ar/ 3 6 ratios in volcanic lavas may therefore be considerably different from the
atmospheric ratio. Owing to incomplete degassing of rapidly cooled rocks excess 40 Ar may
be found in lava flows and their phenocrysts.
Excess 36 Ar is found less frequently than excess 40 Ar. Samples with high porosity
and a high content of crystallised glass have been found to have varying amounts of excess
36
Ar. These observations indicate that extreme care must be taken when dating young
volcanic rocks. As mentioned above, the best approach in dating Quaternary samples is to
analyze several minerals of each sample individually or use two different age determination
methods on the same sample. Further possibilities for detecting disturbances of the argon
system will be given below.
Once the mineral or whole-rock system is closed neither parent nor daughter isotopes
should be incorporated or lost.
The accomplishment of this requirement may cause severe problems in areas
affected by metamorphism. Owing to their fast cooling, Quaternary volcanic samples rarely
lead to the problems of isotope gain while weathering, recrystallisation, decomposition of
60

minerals or hydrothermal alteration may cause loss of potassium and especially argon. As
mentioned above, each sample should therefore be carefully examined under the
microscope before any age determination work is started.

The composition of the atmospheric argon has remained constant since the closure of the
mineral or whole-rock sample Under analysis.
The argon composition of the modem atmosphere is the result of past degassing of
the earth. According to studies of noble gas systematics in the atmosphere and the earth-
mantle (Allegre et al. 1983, Sarda et al. 1985) the present day 40 Ar/ 36 Ar atmospheric ratio
can be considered as having been caused mainly by a intensive degassing of the mantle at
about 4.4 Ga followed by a slow continuous degassing up to the present day. Because of
the initial catastrophic outgassing the atmospheric 40 Ar/ 36 Ar ratio may be considered as
having been constant since about 2 Ga.
Isotopic measurements on cherts of the Gunflint formation with ages of 2.1 Ga
(Turner et al. 1983) yielded a 4 0 Ar/ 3 6 Ar ratio identical to today's atmospheric values.
Samples with ages in the order of 10 Ma or more contain a 40 Ar* fraction of more than
90% of the total argon content. Any small error introduced by assuming the 40 Ar/ 36 Ar ratio
to be constant will have an insignificant effect on the age measurement. For Quaternary
samples the 40 Ar/ 36 Ar ratio may be assumed to be constant.
Following the above requirements analysis of two or more independent mineral
systems should yield identical results. Because microscopic observation cannot distinguish
between independent minerals and minerals which form a composite system, the ideal
approach would be to separate and analyse each mineral individually.

4.2. POTASSIUM ANALYSIS

The potassium content of the sample can be analyzed using various methods such as:

- atomic adsorption spectrophotometry

- flame photometry
- X - ray fluorescence
- isotope dilution mass-spectrometry.
Flame photometry is the easiest and most cost-effective method for potassium analysis.
Sample solutions prepared in 0.1N HC1 are analyzed on the flame-photometer using
lithium as an internal standard. The error on a single determination in Berne is less than
1%. Between October 1984 and June 1985 the standard B4B was analyzed 47 times giving
a mean value of 7.896 ± 0.022 %K - an error on the reproducibility of 0.29%. The
interlaboatory value for B4B is 7.910 ± 0.083 %K - an error on the reproducibility of
1.1%.
Very small K contents (< 0.5%) are analyzed by isotope dilution. The sample
solution is therefore spiked with a 4 0 K spike (35.927 % 4 0 K) and analyzed on a solid
source mass-spectrometer with thermal ionisation (see above).
The 40 K (mol/g) content can be calculated according to the isotopic abundances of
potassium given in section 2.
 61

4.3. ARGON ANALYSIS

In addition to the above explanation of mass-spectrometry the argon extraction system as

used in Beme will be described in detail.
The most widely used method for quantifying the volume of 40 Ar* in a sample is
the isotope dilution method described by Kirsten (1966) and Dalrymple & Lanphere
(1969). The gas is extracted by heating from a sample of known weight, and an exactly
known volume of very pure (>99.9996 %) 38 Ar (Schumacher 1975) is added as a spike
( 38 Ar is the least abundant isotope of argon in the atmosphere). The 40 Ar* content of the
sample can be calculated according to the intensities of the different isotopes found by the
mass spectrometer.
In 50,000 years a sanidine feldspar will accumulate about 1.9 x 10-8 ccSTP/g of
40
Ar*. Thus to measure lg of sample in this age range with an error of less than 5% at 1<J,
a high precision mass-spectrometer and a good working extraction system are essential.
In April 1983 a new argon extraction and purification system was constructed in the
KAW isotope laboratory in Beme (Flisch 1986). The system described by Flisch (1982)
was optimized for routine K-Ar age determination of terrestrial samples, and fulfil, the
following requirements:
- high precision
- good reproducibility of results
- low blank
- flexibility in sample size
- regulation of extraction temperature from low to high
- a routine measuing procedure capable of measuring samples from Quaternary to
Precambrian age

Furthermore low construction and running costs were necessary together with simple
servicing and high sample throughout.
To fulfil these requirements, a Pyrex line was coupled to an RF generator for
sample outgassing, and with a MM 1200 static vacuum mass spectrometer from VG
Isotopes, U.K., using the isotope dilution technique.

4.3.1. Argon System. Figure 2 shows schematically the arrangement of the KAW
extraction apparatus.
Extraction Furnace: The extraction furnace consists of an upper Pyrex "Christmas Tree"
and a lower, double-walled, water-cooled quartz/Pyrex part.
Up to 16 samples in the form of aluminum spheres may be stored in the branches
of the Christmas tree. Each sample is placed in front of a small cylindrical metal piece
which can be moved with the help of two magnets. The sample can be dropped through a
quartz glass chimney into a molybdenum crucible. Two cylindrical metal pieces are
connected by a chain, the upper one lying in a longer branch of the Christmas tree. The
chain can be moved by moving the upper metal cylinder with a cylindrical electro-magnet.
Samples sticking in the chimney (e.g. by static electricity) may be freed by moving down
the lower metal piece. During the extraction the chimney can be closed by a coin which is
inserted on top of the lower metal cylinder.
Through induction from the coils of an RF generator the Mo crucible may be heated
to a maximum temperature of 2,050°C. The double-walled lower part of the tree allows the
glass system to be cooled during extraction. The heating is limited to the crucible. After
sixteen extractions the tree has to be disconnected from the system and cut between the
62

C II Ti n i Ti IV

Fig. 2. Extraction and purification system

CI-II charcoal fingers PV pneumatic valve

CT cold trap R reservoirs (air/spike)
EF extraction furnace RP rotary pump
IG ion gauge SS sample storage
IP ion pump Til-IV Ti-getters
MS molecular sieve TMP turbomolecular pump
P 1-4 thermo-coupled vacuum gauges Vl-10 high vacuum valves
PAI pipette air inlet W ventilation valve
PSI pipette spike inlet W cooling water

sample part and the chimney. The glass parts are washed in pure HNO3 to dissolve the
mirror formed during the extraction. The crucible is placed in concentrated HF while the
metal parts are cleaned in an ultrasonic bath in ethanole. All parts of the system can be
reused.
 63

Purification System: A U-cooling-trap, four Ti getters and a SORB-AC Zr-Al-getter (AP

10 GP from SAES Milan, Italy) are used for purification of the extracted gas.The cooling-
trap is inserted into a dry-ice/acetone mixture to freeze out water vapor. The Ti-getters are
used to getter the hydrocarbons and oxygen while hydrogen and remaining hydrocarbons
are bound by the SORB-AC getter. The vacuum in the purification system is controlled by
three vacuum gauges. Each part of the system can be pumped via a single valve.

Spike and Air Shot System: Reproducible spike and air shots stored in reservoirs with
known volumes of about 1,000ml can be introduced into the argon line through pipettes.
Each pipette is constructed from two membrane valves enclosed in a robust stainless steel
housing, and each has a well calibrated volume of about 0.1ml. A second spike reservoir
with an argon volume of about one tenth of the original one will be installed in the near
future to facilitate the precise measurement of lower 40 Ar* content.

Mass Spectrometer and Data Handling: The argon isotope intensity is measured on a MM
1200 mass spectrometer with a magnetic sector of 12 cm radius and a deflection of 60°.
The Farraday collector can be connected either to a CARY 401 or to a KEITHLEY 642
amplifier. The digital-voltmeter readings are transferred to a MAKROTEK personal
computer. Automatic measurements are run on a Keithley (ASYST) program recently
adapted by our group.

Vacuum System: In the bakeable part of the extraction system we use B ALZERS UVD-8H
high vacuum valves, which have a small dead-volume, a low leak-rate and high durability.
One disadvantage is the low flow-rate of about 0.5 1/sec.
The main pumping system comprises a LEYBOLD TURBOVAC 150
turbomolecular pump backed by a two-stage oil rotation pump fitted with a molecular
sieve. An argon-free high vacuum is maintained in the inner part of the purification system
using a 25 T/sec ion pump. The pressure in the extraction and purification system is
controlled by four HASTINGS DV-18 thermocouple gauges with an optimum working
range of 10"1 to 10"3 torr. A high vacuum ionisation gauge is positioned between the line
and the turbo molecular pump (TMP).
Line and pumping system are separated by a pressure-sensitive relay circuit which
controls a pneumatic valve. In the event of a power failure the valve closes, preserving a
static vacuum in the line and preventing back flow from the pumps. Should a leak occur in
the line, the valve again closes, minimizing the atmospheric contamination of the pumps.

4.3.2. Sample-Preparation. Samples are weighed into small cups formed from aluminum
household foil. Depending upon the size of the sample, between 6 to 12 cm 2 of foil is
used. The sample weight depends on age and potassium content and ranges from a few mg
to lg. Ideal sample weights for micas of 15 to 300 Ma are 0.1 to 0.0 lg. With these
weights and the used spike volume the ratio 38 Ar spike to 40 Ar total is approximately one
to one. For samples of Quaternary age a sample weight of 0.8 to 1.2 g is required.
Before measuring is started, the glass part of the purification system is baked out at
180°C for a minimum of 18 hours. Lower temperatures of 100 to 120°C are used for
preheating clay minerals because of their lower rate of retention of argon.
4.3.3. Analytical Procedure. Before the first extraction in a new furnace the Mo crucible is
preheated for 30 minutes to a temperature of 2,000°C to minimize any contamination of
the sample by atmospheric argon degassed from the crucible. Four argon analyses can be
64

made a day. The analytical procedure is precisely timetabled, which is important for the
blank correction. The time taken for the gas extraction is exactly 30 minutes with gradual
heating to 1750°C over 25 minutes. Complete degassing of high-temperature feldspars
(sanidine, anorthoclase) requires an extraction temperature of 1900°C maintained for 15
minutes because of the high viscosity of the melt. In this case the blank correction would
be calibrated for an extraction time of 40 minutes. Gasses extracted from the first and third
sample each day are pumped by charcoal finger CI surrounded by liquid nitrogen, the
gasses from extraction two and four by charcoalfinger C2. The spike inlet occurs 10
minutes before the end of the extraction. The extracted gas is purified in the U-tube and
frozen out at the charcoal finger. After separating the purification from the extraction side
by valves two and six respectively the charcoal finger is defrosted and the Ti-getters cooled
down from an operation temperature of 800-820°C to 300°C. Finally the remaining gas is
purified at the SORB-AC getter and introduced into the ion source of the mass
spectrometer by a direct connection between the line and the MS. Masses 35.5 - 40 - 35.5 -
38 - 35.5 - 36 - 35.5 are measured six times in sequence by the automized measuring
program, masses 40 and 38 and the corresponding baselines are measured for 10 seconds
each, mass 36 and the corresponding two baselines during 15 seconds each because of
their low intensity. The results are processed in a computer. Errors are calculated according
to the error propagation of the Gaussian law, combining the error of the isotope ratios with
the uncertainities from the spike calibration, sample weight and potassium analysis.

4.3.4. Blank and MS Data: For the entire extraction, purification and measuring procedure
(including outgassing an aluminum foil cup) the 40 Ar blank lies between 3 and 7 x 10"9
ccSTP. Less precise measurement of 3(>Ar results in a spread of the 40 Ar/3 6 Ar blank ratio
from 275 to 320. The mass discrimination of the mass spectrometer combined with the
non-linearity of the CARY 401 amplifier can be quantified by the measurement of air shots
of different volume. Unfortunately on most mass spectrometers the 40 Ar/ 36 Ar atmospheric
ratio cannot be measured as 295.5 because of a mass discrimination dependence upon the
mass number of the isotope and the total gas pressure in the analyzer. The actual 40 Ar/ 36 Ar
atmospheric ratios measured in Berne are 302.6 ± 0.3 (1<?) for 40 Ar amounts of >2.1 x
10"6 ccSTP and 303.3 ± 0.5 (lo) for 4 0Ar amounts of <2.1 x 10"6 ccSTP, showing a
discrimination towards isotopes of lower mass numbers.

4.3.5. Spike and Spike Calibration: The isotope dilution method (Dalrymple & Lanphere
1969) is used with an exactly known amount of the 99.9997 % enriched 3 8 Ar spike
(Schumacher 1975) added to each measurement.Recent measurements have shown that ten
years after the initial filling of the spike reservoir, the spike still has a purity of 99.987 %
38
Ar. The impurity is corrected as air argon. The spike has been calibrated against age
standards B4Mu, B4Bi, LP-6 and GLO and against calibrated air shots (Flisch 1982).
Table 1 shows routine analysis of standards and air shots.
The spike calibration contributes an uncertanity factor of 0.5% to the final error of
the age value measured.
A method of spikeless Ar measurement which shows a remarkable degree of
reproducaibility (a few per cent) on determination of very young samples (< 100,000
years) has been reported by Cassignol & Gillot (1982). This method needs considerable
calibration, is extremly time consuming and its advantage over the isotope dilution method
is limited to the determination of Neoquatemary ages.
A measure of the reliability is the table of results for the standards GLO and LP-6
(Table 1). Another indication for the reproducibility are the results presented by Jiiger et al.
 65

(1985) on their Quaternary standard BB-6 which has an age of 450,000 years, lg aliquots
were analyzed from each of 16 splits. The 40 Ar* content gave a value of 2.884 ± 0.076 x
10-8 ccSTP with an error on the reproducability of 2.6% (ltf). This demonstrates both the
usefulness of the the BB-6 volcanite as a standard and the suitability of the extraction and
measuring routine for samples of Quaternary age.
Sanidine from the Quaternary Bishop Tuff, California, measured immediately after
an LP-6 biotite standard (129 Ma) gave an age of 0.731 ± 0.02 Ma, corresponding well to
the age of 0.74 Ma proposed by Izett (1982) and clearly demonstrating the absence of a
detectable memory effect.
Time interval between September 1st 1983 and August 30ih 1984 (manual measurement)

Sample number of analysis value measured value published

(Odin 1982)
(x 10-6 ccSTP 40Ar rad/g ± 1<7)

GLO 19 24.74 ± 0.19 (± 0.77%) 24.85 ± 0.24

LP-6 10 43.16 ±0.31 (±0.72%) 43.26 ± 0.44

Air 12 5.014 ±0.018 (± 0.36%) 5.016 ± 0.05

Time interval between April lOlh and April 12lh 1990 (automyzed measurement, one Christmas tree)

LP-6 6 43.25 ±0.31 (±0.72%) see above

Table 1. Mean values of standards and air shots

4.4. AGE LIMITS OF THE K-Ar METHOD

Because of the physical and technical requirements of the K-Ar method, the technique has
a wide range of applications for samples of a high age. In age determination of
Precambrian samples, diffusive argon-loss can occur indicating ages which are too low. In
the Quaternary range, the lower limit can be as young as a few thousand years (Cassignol
& Gillot 1982).
The limitation is a relatively small quantity of 40 Ar* combined with a high air argon
fraction. The two factors which have the greatest influence on the overall error of an age
determination are:
-the error on the 36Ar measurement, which can be relatively high owing to the low
amount of 36 Ar extracted from a sample compared with the amount of other isotopes; this
necesssitates measurements in a highly sensitive range of the amplifier, and
66

- the error on the discrimination correction.

The error on Quaternary age measurements can be reduced if the precision of the 36 Ar
measurement can be increased, if the error of the discrimination correction can be reduced,
or if the sensitivity of the measuring system can be increased. A consequence of higher
sensitivity is more precise determination of the 36 Ar, but the range of application is
restricted to very young samples because of the limitations of the amplifier. In addition,
two different amplifier settigs would require two different system calibrations - especially
for the discrimination correction - as well as two separate spikes. Nevertheless, age
determination of sanidine feldspar with 10% K and an age of 7,500 years is still possible
with a 1<3 error of 10%. Because of the problems outlined in section 3, K-Ar determination
in such a young age range is very difficult and a combination with other age determination
methods e.g. 14 C are strongly recommanded.
For routine determinations in Berne the ( 40 Ar/ 36 Ar)atm ratio is measured as 303.3
± 0.5, the amplifier input resistor is 1010Ohm and the spike volume is calibrated to 1.2 x
10"6 ± 6 x 10"9 ccSTP 38 Ar. A 1<? error for samples with >5% 40 Ar*, 1% potassium and
an age > 275,000a is less than 10%. Similarly sanidine with 10% potassium and an age of
27,500 years will give an error of about 10%. The amplifier resistor may be set to 10 11
Ohm, and the installation of a spike with a ten times smaller volume (1.2 x 10~7 ± 6 x 10 -10
ccSTP 38 Ar) is planned for the near future. According to these settings the determinaton of
a minimum age of about 7,500 years should still be possible.

4.5. DIAGRAMS FOR PRESENTATION OF K-Ar DATA

For the K-Ar age determination the 40 Ar* concentration in a sample must be very precisely
determined. As already pointed out, this may be quite difficult, because the total 4 0 Ar
content of a sample consists not only of 4^Ar* but also of a 4 0 Ar contribution from the
spike, the blank, the atmosphere and possibly from excess argon. The 40 Ar spike fraction
and the 4 0 Ar blank fraction can be precisely determined by reliable spike and blank
measurements, whereby the 40 Ar spike fraction is normally negligible. The atmospheric
40
Ar component is adsorbed onto the sample surface or incorporated into the crystal lattice.
The (40Ar/36Ar)atm is constant, and the 40 Ar atm fraction can therefore be defined easly.
The 4 ^Ar excess is due to the incorporation of a certain amount of Ar which has a
40
Ar/ 3 6 Ar ratio higher than 295.5 at the time of the closure of the system. 4 0 Ar loss is
generated by diffusion under high temperatures. The only way to check for excess or loss
of 40 Ar is to measure several samples of the same geological unit or to measure different
minerals of the same sample and plot the results on the graphs discussed below.

4.5.1. K versus 40Ar"rad" Diagram. This diagram discussed in detail by Harper (1970),
therefore also called the "Harper diagram", compares the data from different samples of the
same formation (e.g. whole-rocks, clay minerals etc.) in order to determine whether an
excess of 4 0 Ar* is present or if 4 0 Ar was lost. In the diagram the total potassium
concentration in % or the 4 0 K concentration in mol/g is plotted against the blank, spike and
air corrected 40 Ar concentration in mol/g or ccSTP/g. If the individual sample points are
linear (Fig.3) the intercept of the line drawn through the data-points with the 40 Ar rad-axis
quantifies the 40 Ar excess or loss. Such 40 Ar loss or 40 Ar excess amount may be used as a
 67

correction to obtain the real 40 Ar radiogenic concentration when calculating the individual
sample ages. The slope (tan «) of the line calculated through the individual sample points is
proportional to the excess or loss corrected age of the sample, provided both the 40 Ar* and
the 4 0 K concentrations are plotted in mol/g. This line is called an isochron (Harper 1970).
For each sample the slope of the dot-dashed lines (Fig. 3) are proportional to the
uncorrected K-Ar model ages. The regression line calculated through the sample points of
an undisturbed system intercepts at the origin. Intersections below or above the origin may
indicate argon loss or gain.

Himmt/wi or XK KCmal/g) Or

Fig. 3. K versus 40\r "rad" isochron diagram.

(For explanation see text)

4.5.2. 40K/36Ar versus 40Ar/36Ar Diagram. This diagram is often used to show the
analytical data after spike and blank correction. It has created many errors in interpreting
analytical data. Figure 4 shows an "isochron" drawn through four different data points
obtained for the same sample. Different aluminum foils for wrapping the samples have
been used which obviously contain different amounts of contaminating air argon. The
spread on the isochron is solely a function of this air argon and the line thus represents a
mixture of sample and air argon and does not reveal the presence of any excess argon. The
point of interception of the air mixture line at 295.05 illustrates the accuracy of the air and
discrimination corrections. If the 40 Ar excess or loss is small compared to the amount of
atmospheric argon (as is normally found in young samples) this diagram is not sufficiently
precise to reveal the 40 Ar excess or loss. Even a small amount of excess 40 Ar or ^ A r loss,
however, can seriously affect the determination of the age of the sample, especially for
young rocks. The K versus 40 Ar rad diagram discussed above is much more precise.
An isochron in the 40 K/ 36 Ar versus 40 Ar/ 36 Ar diagram will give a reliable result,
provided the individual data points are not linear in a l/36Ar versus 40 Ar/3 6 Ar diagram. In
this case the pattern of the data points on the isochron is due not only to the different 36 Ar
68

values but also to the different K content of the sample. In this case the 40 K/ 36 Ar versus
40
Ar/ 3 6 Ar diagram has no advantage over the K versus 4 0 Ar* plot and the latter is
preferable. The 4 0 K/ 3 6 Ar versus 4 0 Ar/ 3 6 Ar diagram may have an advantage over the
"Harper" diagram if several samples of the same rock (e.g. pluton, lava flow, metamorphic
unit) have the same potassium content but incorporate different amounts of initial argon.
This causes a spread of the sample points on the isochron. The isochron must be very well
defined with a correlation of ±1. This indicates that the 4 0 Ar/ 3 6 Ar ratio of the initially
incorporated argon must have been the same for each sample as must the amount of
diffusive argon loss. The point of interception of the isochron with the y-axis must show a
significant difference from the 40 Ar/ 36 Ar ratio of the atmosphere, otherwise it cannot be
distinguished from an air mixture line. Here the data points should be linear array in the
l/ 3 6 Ar versus 4 0 Ar/ 3 6 Ar diagram, and the intercept of the regression line with the
40
Ar/ 3 6 Ar axis must be the same as in the 4 0 K/ 3 6 Ar versus 40 Ar/ 36 Ar diagram. If these
requirements are fulfilled the combination of initial 40 Ar excess and later diffusive argon
loss may also give accurate isochron-ages.

(10/3B)Ar

300 ..

2 x10s

Fig. 4. 4 0 K / 3 6 A r versus 4 0 A r / 3 6 A r diagram: four measurements on the

same Quaternary sample defining an air mixture line.
 69
40
5. The Ar/ 3 9 Ar Method

The 40Ar/39Ar method offers the possibility of determining the isotope ratios of potassium
and argon simultaneously instead of analysing K and Ar concentrations on two aliquots.
Absolute isotope concentrations are not required, therefore no spiking is necessary. Very
small samples which cannot be split (e.g. single crystals) can still be analyzed. Another
advantage over the conventional K-Ar method is that under certain circumstances excess
argon and argon loss may be recognized.
Before mass-spectrometric analysis the sample is irradiated with fast neutrons in a
nuclear reactor to transform 3 9 K to 39 Ar. To determine the precise amount of 3 9 K
transformed to 39 Ar, the irradiation conditions (e.g. irradiation time, neutron flux density)
have to be known. Therefore standards of known age are irradiated together with the
samples. The 3 9 K/ 3 9 Ar ratio of the samples can be determined according to the
proportionality to the ratio measured on the standards. In practice the proportionality factor
J is determined by

J = ?^/A e . 39K/40K AT/<}>(€)<?(€) d€ (10)

(where A. is the total decay constant of 40 K, A.e is the decay constant of 40 K to 40 Ar, AT is
the irradiation time, <j>(e) is the neutron flux density at energy €, and 0(e) is the capture
cross section 39 K for neutrons having energy € and the integration is carried out over the
entire energy spectrum of the neutrons) on the standards according to

j = eMm . 1/(40Ar*/39Ar)> (11)

and inserted into the age equation as

t = 1/A ln(l + J 40Ar*/39Ar). (12)

Corrections have to be made for interfering isotopes because 40 Ar, 36 Ar and 39 Ar

are produced in the reactor from 40 K, 40 Ca and 43 Ca respectively. 37 Ar produced during
irradiation can be used for the correction of 36 Ar and 39 Ar according to the (36Ar/37Ar)Ca
and ( 39 Ar/ 37 Ar)Ca ratios, which have to be determined empirically by irradiating K-free
materials (Ca-salts) under similar conditions as the samples. The quantity of 40 Ar produced
during irradiation is fortunately so small that it may usually be ignored for the calculation.
A correction possibility is given by the ( 40 Ar/ 39 Ar)K ratio determined by analysis of
irradiated K-salts (Dallmeyer 1979).
As shown above an age can be calculated on the basis of the measured 40 Ar*/ 39 Ar
ratio of the sample. If the sample has been degassed in one step (total degassing age), the
age result should correspond to the age obtained by K-Ar dating. Instead of degassing a
sample totally in one step only the 40 Ar/ 39 Ar method offers the possibility of degassing the
sample stepwise at different temperatures and calculating an age for each temperature
interval separately. If the sample has lost or gained neither argon nor potassium since the
time of its initial cooling the calculated ages should be identical for all temperature steps. If
the sample lost argon partially owing to a metamorphic event age results of the different
temperature intervals will reveal discordant data. The same applies to excess argon
incorporated in the crystal lattice.
70

2.0
1.8
1.6
■ E
1.4
1.2
■

1.0
0.8
0.6 J 1 «
< ' -
0.4 ■

■
0.2 39Ar release (%)
i . i
20 40 60

Fig. 5. Hypothetic time versus 39 Ar release diagrams for an undisturbed

sample (above) and a sample containing excess-argon bearing minerals,
which melt at high temperature (below).

The results are plotted in an age vs. %-39Ar-release diagram (Fig. 5). An
undisturbed sample should yield a straight line in the plot (plateau), all temperature steps
should show identical results. Argon loss due to a thermal overprint may be recognized by
lower ages at low temperature than at high temperature while excess argon in fluid
inclusions may yield too high ages at low temperature. Whole-rock samples containing
minerals bearing excess-argon, such as pyroxen or olivine, may give extremely high age
 71

results at high temperature (high degassing temperature for pyroxene and olivine compared
to a possible feldspar-bearing groundmass).
In addition a 4 0 Ar/ 3 6 Ar vs. 3 9 Ar/ 3 6 Ar diagram may be drawn according to the
diagram discussed in section 4.5.2. Argon loss or gain may be detected in the initial
40
Ar/3 6 Ar ratio of the isochron which can be calculated through the ratios given for each
temperature step.

5.1. ARGON LASER EXTRACTION

The advantage of the 4 0 Ar/ 3 9 Ar method is that no sample-splitting for potassium and
argon-determination is necessary. The system may be improved by using a laser-beam
instead of an RF-generator for the fusion of the sample. The fusing energy is concentrated
on a spot of a few tens to a few hundred jum in diameter. The extraction system and
therefore the blank may be minimized.
The use of a continous argon-ion laser for dating single crystal-grains was
described by York et al. (1981). A laser beam of about 600jum in diameter focused
through a pyrex sample-holder onto a chip of slate allowed the sample to be degassed in
several stages by gradually increasing the power of the laser. Laser extraction and
conventional RF stepwise heating yielded identical age spectra. By reducing the diameter
of an Nd-YAG-laser to 80-120jmm 75 spots on the surface of a single phlogopite grain
could be separately analyzed (Phillips & Onstott 1988). Age distributions between margin
and core of single grains may be mapped, excess argon trapped in the core of a grain or
diffusional argon loss along the crystal rims may be observed directly.

6. Application of Radiometric Dating Methods to Quaternary Samples

The K-Ar and 40Ar/39Ar-methods have gained wide popularity in dating young volcanic
provinces such as the Neapolitan area (Italy) (Gasparini & Adams 1969), Iceland (Everts
& Schwarzbach 1972) and Hawaii (Gramlich et al. 1971, McDougall & Swanson 1972,
Stearns 1973).

6.1. BB-6 QUATERNARY STANDARD

Between 1983 and 1985 samples from the Huabei area, China, were dated in our
laboratory as part of a UN-CCOP Swiss-Chinese cooperation project. Basalt samples from
the Da Tong volcanic area yielded Quaternary ages around 0.383 ± 0.028Ma while
samples from Zhang Jia Khou, Wu An and Da Hei Shan Isaland were of Neogene (3.52 to
8.08Ma) age (Chen et al. 1984). A positive correlation between grain size and potasssium
content and a negative correlation between grain size and Ar* were concluded to have been
caused by a decreasing plagioclase content with decreasing grain size and an increasing
amount of air argon adsorbed on an increasing surface area respectively. The measurement
of different grain-size fractions yielded an average age of 0.383 ± 0.056Ma (2cf).
An alcali-olivine basalt sample from Hoa Tian Si (Da Tong area) was considered to
be suitable (reproducible age, low content of atmospheric argon) for the production of a
quaternary standard. 25 kg of unaltered, holocrystalline rock were crushed, milled and
sieved. According to the correlations between grains-size, potassium-content and %Ar rad
mentioned above a grain-size of 60-80 mesh was selected as offering the best compromise
72

between sample homogeneity and the amount of air argon adsorbed. Repeated analysis of
various amounts (0.3g, 0.5g, l.Og) indicated that lg was suitable for homogenous
samples.
K-Ar analysis of 16 aliquots made by splitting the sample into 32 equal portions of
lOOg yielded a mean age of 0.441 ±0.013Ma (2<?). Olivine phenocrysts separated from
the sample yielded an age of 2.93 ± 2.73Ma while the matrix had an age of 0.426 ±
0.030Ma (Jager et al. 1985). Improper handling of the sample (simply removing sample
material instead of splitting to obtain the lg samples needed for analysis) may therefore
result in separation of olivine from the matrix and a continuously changing composition of
the remaining standard material.

6.2. QUATERNARY VOLCANISM IN THE EIFEL, WEST GERMANY

Dating Quaternary volcanic rocks from the Eifel not only reveals the age of different phases
of eruption but also allows a subdivision of the Rhine-terrace deposits according to their
tuffitic intercalations, time correlations between volcanic activity and climatic conditions
e.g. glacial-interglacial periods within the Quaternary of Central Europe, and the (indirect)
dating of hominid artefacts.
Fuhrmann & Lippolt (1985) dated nosean, sanidin, the heavy-mineral fraction,
groundmass and the whole-rock of a phonolite from Schellkopf separately. They could
show that the sanidin and the groundmass sample yielded 40 Ar/3 9 Ar plateau ages (0.373 ±
0.013Ma and 0.387 ± 0.014Ma respectively) close to the total degassing age (0.400 ±
0.016Ma for groundmass) while nosean revealed a step-like age distribution increasing
from 1 to 60Ma with increasing degassing temperature. Nosean, identified as the main
carrier of excess argon therefore imprints its degassing behavior on the whole-rock sample
where low temperature degassing-steps revealed ages around 0.4Ma increasing with
increasing temperature up to 2.4Ma. Similar observations were described in the Central
West Eifel (Fuhrman & Lippolt 1987) where mafic phenocrysts (pyroxene, olivine)
introduced excess argon to the whole-rock sample while most groundmass separates
showed comparable plateau and total degassing age-results.
By dating single grains of about lmg sample weight with a laser extraction system
van den Boogard & Schmincke (1987) found sanidin grains in the Rieden phonolite lapilli
with 40Ar/39Ar ages which seemed to be too high, indicating the possibility of the presence
of an inherited component incorporated into the magma during its eruption. They could
prove at least four main phases of eruption within the past 700 000 years, correlating
paleosol horizons around a 0.22Ma and a 0.44 to 0.45 volcanic layer with interglacial
climatic conditions. Hominid artefacts found above the 0.44Ma tuff-horizon were assigned
to homo erectus, artefacts above the 0.22Ma layer possibly to homo sapiens
neandertalensis.

6.3. THE HOMINID FOSSILS OF THE AFRICAN RIFT

One of the most fascinating problems of Quaternary dating with wide public interest is the
age of our human ancestors. Since the fifties a large number of hominid fossils have been
excavated at different locations, mainly in the African Rift, in Ethiopia, Kenya, Tanzania
and South Africa (Johanson & Shreeve 1989). Proper dating of the fossil bones is one of
the major conditions for determining a human genealogy. Argon dating depends on the
presence of suitable volcanic material at the excavation site. Hominid material is often
 73

found far from datable horizons. Often the fossils are not even resting in their original
stratigraphic position but have been washed out of the sediment. Proper stratigraphic
profiles therefore have to be established and extrapolated to areas featuring datable volcanic
rocks. Age determinations can then be correlated with the stratigraphic profile and the
fossil-bearing horizon can be fitted into the local stratigraphy.
The problems involved in dating fossil hominids can be demonstrated by the variety
of data given for the Hadar Formation in Ethiopia. The Kada Hadar tuffitic horizon (KHT-
2) overlying a variety of fossil hominides (Johanson & Taieb 1976) has been dated by
Aronson et al. (1977) with the K-Ar and the fission-track method with 2.6Ma. Three
million years were measured on the Sidi Hakoma tuff (SHT) which underlies the fossils.
Using another profile (Ounda Hadar) Walter & York (1981) could show a correlation
between K-Ar age and the alteration of the basalt stratigraphically situated above the SHT.
On aphanitic noncrystalline material the basalt horizon could be dated by the 40 Ar/ 39 Ar
. method with 3.6-3.7Ma. A detailed revision of the analysis using new constants (see
section 1), another constant for the 38 Ar pipette and additional samples from Ounda Hadar
yielded K-Ar ages of BKT-2 around 2.9Ma (Walter et al. 1982). Hominid fossils found
within the Kada Hadar horizon (KHT) can therefore be put at 2.9Ma - 3.6Ma.
Similar ages have been described for fossil hominid finds at Laetoli, Tanzania
(Leakey et al. 1976). Biotite separated from several tuff horizons yielded identical results
using the K-Ar and the 39 Ar/ 40 Ar method. Direct K-Ar age determination was possible on
hominid footprints left in a tuff horizon in Laetoli (Hay & Leakey 1982). Underlying
samples were dated to 3.8Ma while samples from the footprint tuff itself could be dated
with 3.5Ma proving the existence of upright walking human ancestors 3.5Ma ago.
Another fossil-bearing area is situated around Lake Turkana, Kenya. Tuff horizons
intercalated in the Pliocene sediments were used not only for dating purposes but also for
correlating stratigraphic profiles of several sites west of Lake Turkana (Walker et al.
1986). A cranium identified as belonging to australopithecus boisei was found 3.8m below
a tuff horizon dated with K-Ar to 2.52 ± 0.05Ma. Assuming a constant sedimentation rate
for the overlying sediments, the cranium woul have an age of 2.55Ma. On the basis of
palaeomagnetic polarity boundaries used for geological dating the age would be about
2.45Ma. A slight difference between the two dating methods is evident. An age of 2.50 ±
0.07Ma was considered reliable.
The Okote Tuff Complex, East Lake Turkana, was dated to 1.64 ± 0.03Ma
(McDougall et al. 1985). In connection with other strata dated at Koobi Fora, the age of
homo erectus fossils found at Nariokotome (Brown & Feibel 1985; Brown et al. 1985)
could be estimated at 1.60 ± 0.05Ma. Eight of ten anorthoclase concentrates yielded K-Ar
ages between 1.60 and 1.70Ma (McDougall et al. 1985). Two samples revealed ages of
1.94Ma and 2.47Ma. The anomalously high ages might be caused by contamination of the
anothoclase separates with detrital feldspar. In this case contamination can not be totally
avoided despite careful selection of the sample material. Only the analysis of a large
quantity of samples guarantees the indentification of inappropriate material.
The examples selected should show the possibilites and problems of archeological
isotope dating. In addition to all analytical work proper evaluation of the sample material,
accurate sample separation and careful interpretation of the results are all essential.
74

Acknowledgements

The authors wish to thank Prof. E.Jager for critical reading of the manuscript. Help from
other members of the Berne Isotope Geology Laboratory was appreciated. Isotope studies
in Berne are supported by the Swiss National Science Foundation.

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Walker, A., Leakey, R.E., Harris, J.M. and Brown, F.H. (1986) Nature 322, 517-522.

Walter, R.C, York, D. and Aronson, J.L. (1982) The Geological Society of America,
94th annual meeting, Abstracts with Programs 13, 7, p 575.

York, D., Hall, CM., Yanase, Y., Hanes, J.A. and Kenyon, W.J. (198) Geophysical
Research Letters 8, 11, 1136-1138.
FISSION TRACK DATING AND ITS APPLICATION

Z. YEGINGIL
Cukurova University
Art-Sciences Faculty
Physics Department
01330 Adana
Turkey

1. General Facts of Fission

1.1. EARLY RESEARCH ON FISSION

In 1938, Hahn and Strassman found that an isotope of barium (Z= 56) was
produced by bombarding uranium with neutrons. It was the key. In the
same year Meitner and Frisch (1) accepting the conclusions of Hahn and
Strassman, proposed that the uranium nucleus, on absorption of a slow
neutron, could assume a shape sufficiently deformed to promote its rapid
division into two approximately equal masses; the name fission was
suggested for this process. The energy released in such a transformation
could be estimated simply from the semi-empirical mass formula and the
appearance of two heavy fragments, with kinetic energies of the order of
75 MeV, was predicted for each process. Ionization pulses corresponding
to this energy were observed in a uranium- lined chamber irradiated by
neutrons. News of the fission hypothesis was brought by Neils Bohr early
in 1939, to a meeting of the American Physical Society, and in the
outburst of experimental activity which immediately ensured the main
characteristics of nuclear fission were established in many laboratories
through the world. These experiments were mainly brief; they established
the following facts (2):

(a) The fission of uranium leads to a wide variety of nuclear fragments,

which are produced in pairs such as the following

U + n > Te + Zr
92 52 40

or > Ba + Kr
56 36

(b) The fission fragments recoil in opposite directions and have a range
77
H. Y. Goksu et al. (eds.). Scientific Dating Methods, 77-96.
© 1991 ECSC, EEC. EAEC, Brussels and Luxembourg. Printed in the Netherlands.
78

of about 3 cm of air which is reasonable for particles of energy = 75

MeV.

(c) The fission fragments are unstable against 0-emission as they have
excess neutrons in comparison with their charge. Successive fi particles
appear in a fission chain, e.g.

40., /3~ 140_ (3~ ^ 140 D P" 140. |3~ 140_ , ,

Xe —!—> Cs —-—> Ba —-—> La -—> Ce (stable)
54 55 56 57 58

leading to a stable nucleus.

(d) A few fast neutrons are produced simultaneously with the fission
fragments.

1.2. ENERGY RELEASED IN FISSION

By direct heat measurements, and other methods, the average energy

released in fission is about as follows:
MeV
Kinetic energy of fragments 159
Kinetic energy of neutrons 7
Beta rays from fission fragments 11
Gamma rays from fission products 23

Total 200

We see that a significant fraction of the release occurs by delayed

radioactive processes. A check on the total energy may be obtained by
striking a suitable average of calculations like the following, which
refers to one mode of fission, yielding stable zirconium and
praseodymium.

Masses of Reactants Masses of Products

235 92
U 235.124 Zr 91.942
141
1 neutron 1.009 Pr 140.959
3 neutrons 3.027
236.133 235.928
The difference 0.205 mass units, corresponds to energy release of 190
MeV (3).

1.3. LIQUID DROP MODEL EXPLANATION OF NUCLEAR FISSION

The original theory of the fission process was developed by Bohr and
Weeler (4) on the basis of the liquid drop model. The process is now
envisaged to occur as shown in Fig. 1. The binding energy of the
captured neutron sets the compound nucleus into violent vibrations.
During elongation the volume of the drop remains approximately constant,
but the total surface area increases thus the volume energy does not
change appreciably, but the surface energy increases. Also during
elongation the mean distance of separation between nucleons increases,
 79

(S
NEUTRON

CO
+c=o

DISPLACEMENT OF FISSION
PRODUCT

Fig. 1. The binding energy of the captured neutron sets the

compound nucleus into violent vibrations which break up the
nucleus. Some fission fragments are formed in excited s t a t e s
which decay by gamma radiation with typical lifetimes of
10 to 10 sec, after which most fission fragments decay
by negative beta decay towards the stability line (3).

Fig. 2. Fission Barrier: Potential energy diagram. A certain

amount of activation energy has to be furnished to produce
fission. The approximate shape of the system is given above
the diagram (3).

so that the electrostatic energy produced by the charge distribution

decreases. For small deformation the surface energy increase is g r e a t e r
than the electrostatic energy decrease, hence there is an increase in
the total potential energy of the system, as seen in Fig. 2. There is,
though, a limit to increase in the surface energy for, with increased
elongation, the drop forms a dumpbell shape, after which further
separation of the two halves does not greatly increase the surface area.
However, as the two parts of the dumpbell expand, the electrostatic
energy continues to decrease. This results in a net reduction in the
potential energy of the system as the distance of separation has become
greater than the range of the short-range nuclear forces. The
electrostatic force is still effective. Potential energy continues to be
transformed into kinetic energy as the distance of separation between
the two fission products increases.
80

2. Passage of charged particle through crystals

2.1. ION-EXPLOSION-SPIKE MODEL

In the late 1950's fission tracks were discovered by Young (4a) , E.C.H.
Silk and R.S.Barnes. They had exposed samples of the crystalline mineral
mica to ions produced by the fission of heavy elements. The ions were
slowed and finally stopped by a series of interactions with the atoms in
the crystal lattice of the mineral. As they did so they left thin linear
t r a c k s t h a t were visible at extremely high magnification. In 1959, Silk
and Barnes published electron micrograph of some of those tracks, thus
establishing a new field of investigation (5).

Fig. 3. Ion-explosion-spike model: (A, B) The passage of a

heavily-ionizing particle leaves in its wake a narrow region
containing a high concentration of positive ions. (C) Mutual
repulsion can drive these ions into interstitial positions..
(D) Subsequent processes include neutralization of the
positive ions and relaxation of the surrounding lattice into
the disrupted region (12).

In 1965, Fleischer, Price and Walker Proposed a semi quantitative

model for track formation which is embodied in what they call "the
ion-explosion-spike model" (Fig. 3) (6). According to this model the
fission fragments, moving at high speed and having a strong electric
charge, ionizes the atoms along its path in the target material by
stripping them of some of their electrons. If the target material is a
conducting solid, as metals and certain minerals are, the stripped
electrons are immediately replaced by free electrons and the crystal
lattice remains undamaged. If on the other hand, the material is an
 81

insulating solid, as most rock forming minerals are, the stripped

electrons are not replaced, and the atoms are left with a net positive
charge. Their mutual electric repulsion pushes them apart, damaging the
crystal.
An insulating solid can record a fission track even if it is not a
crystal. Amorphous solids such as volcanic glasses, man made glasses and
plastics are also damaged by fission fragments. The process of track
formation in these substances involves the breaking of chemical bonds
rather than the disruption of a crystal lattice but the net result is
the same : a narrow region along the path of the fission fragment is
made less resistant to chemical attack than the surrounding material.

2.2. TRACK ETCHING GEOMETRY

Although it is possible, under some circumstances, to directly observe

tracks of charged particles with the electron microscope, this technique
has a number of severe limitations. A much more versatile and sensitive
technique is available for track delineation. The method consists of
immersing the irradiated samples in a suitable chemical reagent. The
reagent must be capable of slightly etching the bulk material, while at
the same time preferentially attacking the particle damage trails. Thus
immersion in a solvent causes enlargement of damage trails, where they
intersect the surface, from their initial diameters (less than 100 A )
resulting in etch-pits of diameters in the order of the wave length of
visible light. These then, act as strong scattering centers, appearing
dark in normal bright field illumination where they become visible under
an ordinary light microscope (as shown in Fig.4). This makes possible

/
' > * •
%

N 4 .<- V ***'
t
Tig. 4. Examples of the two different geometry of fission
track etch pits in different materials. (a) typical
cylindrical pits in zircon (b) conical pics in obsidian.
 82

the observation of relatively light particles over large track ranges.

Large track densities are not needed, and observations can be made in
virtually any sample thickness (7,8).
The etching process can be affected in a complex way by large
number of variables including the exact composition and history of
sample and type, concentration and temperature of the
etchant.Orientation of the surface, agitation of the etchant, as well as
the presence of impurities in trace quantities may alter the etching
behaviour.
For track development r a t e of chemical attack of the particle
damage trail, r , must be greater than that of the bulk material,
j- , i.e. |- / r >1 (Fig. 5). We call the quantity r /r the etch ratio.

ORIGINAL SURFACE
V
- 1/ ■I.
ETCHED SURFACE
\
i
Fig. 5. Track registration geometry. Because of the large
free-energy associated with a disordered structure, the
radiation damage trails are far more chemically reactive than
normal material. Thus immersion in a solvent causes
enlargement of damage trails, resulting in etch-pits of
diameters in the order of the wave-length of visible light.
The etch pit shape is determined by the bulk r a t e of attack,
P and the rate, |- , along a fission fragment damage trail.

Under ideal etching conditions the etched tracks are conical in

shape, with sharp terminal ends. The quantity, 9 one half of the cone
angle is given by

6 Sin TEAT

As etching proceeds, the vertex of the cone remains sharp until it

reaches the point where the particle comes to rest, further etching
causes the apex to become rounded.
Not all the particle damage tracks (latent tracks) which intersect
the sample surface can be developed through the chemical etching
technique. In order to produce a latent, etchable track, a charged
particle must have a r a t e of ionization above a certain critical value,
characteristic of that material. The quantity p / p is a function of the
rate of ionization of the charged particle, increasing as the rate of
 83

ionization rises. There is also a geometric restriction: latent tracks

making an angle less than

5 = Sin r /r
c 'B 'T

with the surface will not be seen because the surface dissolves more
rapidly than the tracks can deeper. Thus it is desirable to have the
etch ratio as large as possible.
The chemical etch development of the particle damage t r a i l s
produces permanent, three dimensional cavities or tracks. The dimensions
of tracks may vary from a fraction of a micron to several hundred
microns. The observation and measurement of tracks require the use of an
optical microscope.

3. Fission Track Dating Technique

3.1. FISSION AND URANIUM

Most of the naturally occurring objects contains trace quantities of

uranium. During the long history of these materials the uranium has
undergone a very slow spontaneous process of decay which consists in
part of the nuclear fission of individual atoms of the U isotope. U
undergoes spontaneous fission with an estimated decay constant 6.9x10 ,
Spontaneous fission decay rate of U is about a million times slower
than the r a t e of alpha particle emission, so only one decay in a million
is by fission. We know that the rates of radioactive decays are very
slow. The half life of U is 0.713x10 years and that of U is
4.51x10 years. Thus uranium decays by a and (3-radiation, so slowly t h a t
it can be considered stable and its quantity constant in the nature.
In spontaneous fission process, U nuclei split into two fragments
without any external stimulus. U fissions spontaneously with a half
life of about 8x10 years. The half life for spontaneous fission of
U is even higher by a factor of about 20, so that its contribution by
the spontaneous fission can be neglected in our conditions. Spontaneous
type of fission is not to be confused with the neutron induced fission
,235,.
of U.
235
In induced fission process, adding a neutron to U converts it
23 6 2T8 239
into nucleus U,whereas adding a neutron to " U converts it to U.
The excitation energy is higher in the former case than in the latter,
and this difference is enough to cause U formed in this way to decay
by fission, whereas U decays by gamma ray emission. As a consequence,
only U, a 0.7 percent abundant isotope, undergoes fission under
bombardment with low energy neutrons. If the maximum of the potential
for fission of U, which is about 170 MeV high, were lower by even 1
MeV, the 99.3 percent abundant isotope U would also be fissionable
with slow neutrons (2).
The fission induced by nuclear reactions we have been discussing
here is the induced fission of U atom with thermal (slow) neutrons.
3.2. PRINCIPLE OF FISSION TRACK DATING TECHNIQUE

The principle of dating of fission track analysis is quite simple.

Provided that fission fragments produce tracks that are permanent, a
84

AGE OF EARTH ^ J j .
lOOOmy
s'
/'
.'"'MINERALS
UJ
< I «iy

IOOO
100
MAN-MADE
GLASSES
10

I 10 100 IOOO I my IOOO my

FISSION TRACK AGE
(YEARS BEFORE PRESENT)

Fig. 6. Comparison of fission track ages with those 'Known'

by other methods. In the case of natural minerals, dates
measured by means of radiometric dating methods (12).

simple count of the track density together with a measure of the uranium
content allows the age of the sample to be measured. This assumes that
235
no other sources leave tracks which might be mistaken for U
spontaneous fission tracks. It has been applied to a wide range of
materials, and, as Fig. 6 shows, has yielded ages that are in agreement
with 'known' ages over a wide time span, extending from man-made objects
as little as 20 years old to natural crystals formed more than 1000
million years ago. Below = 2 x 10 yr, concordant ages are the rule,
while for greater ages, frequent discordancies are observed (6,9).
The experimental procedures used in fission track dating are
extremely simple. After determining the density p of spontaneous
(fossil) tracks, the sample is sent to a nuclear reactor and exposed to
a flux of thermal neutrons. These produce a density p of new tracks by
inducing uranium fission. The age T, of the sample is then determined
from the ratio of new and old track densities by means of the following
equation:

p / pr [exp (A T)-l] (A /A ) (I / <r <f>)

's i r
D f D
where A and A are the total decay and spontaneous fission decay
235
constants, cr is the thermal neutron fission cross section of U. <p is
 85

the time integrated flux of thermal neutrons. The quantity I is the

fraction of uranium atoms fissioned during the irradiation (10).
The materials chosen for dating are of course, not selected at
random; in order to be datable they must satisfy certain conditions of
track permanence and track density.
Tracks will fade in any material that is heated to a sufficiently
high temperature. Fig. 7 shows that this fading temperature varies
widely from substance to substance. In some, it is so low that tracks
would fade in geological times even at ambient temperatures; one such
mineral is calcite. In others, by laboratory experiments it was concluded
that tracks should last for much longer than the age of the solar
system at 300 K and hence are effectively permanent.

o
Id
w O
CO
< (0 CO
3 w
<
_i
at
(9
CO Ft HS IS Id
.01
a UjO gui CC
_i
ui £=< E * <
53 SI I- COOT N U O

800 1000 IKDO

TRACK FADING AFTER 1 HOUR ANNEAL

Fig. 7. Track fading conditions. The fission track density

relative to that at room temperature is shown as a function
of the annealing temperature for various minerals. In each
case, the heating is for one hour period (12).

In any material, the age measured is the time since the sample was
at a high enough temperature to remove previously formed tracks. In
principle, dating a suite of minerals from the same site allows a
thermal history to be constructed.
There must be a sufficiently high track density to allow the
compiling of adequate statistics. In large homogeneous samples, as few
as 5 tracks/cm can be adequate, while in small samples 10 cm on a
86

|YOUN0E3T AQE
Y0UN0E3TA0E URANIUM
MEASURED CONCENTRATION M E A S U R E D BY ACCESSIBLE AOE
EASILY BY W E I O H T C O N S I D E R A B L E IN VARIOUS MATERIALS
LABOUR
A
SMIUJONyr - — 1/IOppM — — PO.OOOyr HORNBLENDE

3 0 0 , 0 0 0 yr - 1 p p - - — SOOOyr A
NATURAL
—
A 8LASS
30,000yr — 10 P P M — — SOO yr
AMTITB

8 0 0 0 yr — — 1 0 0 p p M — — SO y r
1 1)
SOOyr — —i/toon** — - • yr ZIRCON
A
3 0 yr — - i % -— 10 M O N T H * MAN-MAOE
•LASS
B
3 , r - — io%- - 1 MONTH

4 MONTHS — j — 1 0 0 % —— 3 0AY3

Fig. 8. Uranium concentration required for dating as a

function of the age of the sample. For a determination by
"considerable labour" nearly 40 hours of such work are
assumed. For an "easy" measured age, it is assumed that the
observer will spend one hour at the microscope counting
fission track etch pits. On the right are indicated the
lowest ages which should be measurable in various minerals on
the basis of typical uranium contents (12).

side 100,000 tracks/cm may be needed. It follows that it is not

possible to set precise, general criteria on the required density. Fig.
8 shows the uranium content needed in a material of a given age to allow
an age determination. It also includes some examples of specific
materials t h a t are potentially appropriate for measuring different ages.
Although there are many rocks and minerals for which the
geochronological applications of the fission track method is successful
(12), so far only a few of these materials are of interest for
archaeology. This limitation is essentially caused by the small number
of tracks which accumulate in a specimen during man's relatively short
presence on Earth. In order to establish a precise age, hundreds or
preferably thousands of tracks have to be counted; consequently the
fission track method has to be applied to materials if it is
possible, with sufficiently high uranium contents.
The most useful material for archaeological applications of the
fission track method is natural glass. Among the natural glasses,
obsidian is of particular interest. Because of its remarkable hardness,
obsidian was highly valued for making sharp tools and weapons in
prehistoric times. Obsidian contains uranium up to 20 ppm, thus ages as
young as a few thousand years can be measured. Glass
shards from tuff layers and pumice can also be used for dating (10a,
10b).
 87

3.3. THE FISSION TRACK AGE EQUATION

If the fossil tracks counted are only tracks from spontaneous fission of
uranium and the same etching and track counting methods are used
in counting fossil and induced tracks in the same sample the age T of a
mineral is given by the equation (11)

T= In [l + p / pr A r<4 <r I/A 1 1/A

[ s i D fj D

The number of spontaneous tracks on a square centimeter of

material, p (through an internal surface) is given by the following
expression
2 3 8 2 3 8 2 3 8
>T"L ^ /ivt ,- D 1
p = (TA ) (N C R i) )
8 f V
where
N = number of atoms per unit volume of material
V
238 238
C = fraction of those atoms that are U
238 23 8
R = range of U fission fragments
238 23 8
T) = etching efficiency of U tracks.
The product of first two terms, TA gives the fraction of U-238
238 238 238
atoms that fission in the time T. The product, N C R i) is the
V

number of U-238 atoms per unit area that are within a range R of the
etched surface and can lead to etchable tracks at that surface.
The induced track density p is measured on a freshly cut internal
surface after neutron irradiation with <p thermal neutrons per unit
area. It is given by
I ^ r», ,~235 D 235 235.
p = (o- 0) (N C R T) )
1 v
235
where the first parenthesis defines the fraction of U caused to
235
fission and the second parenthesis gives the U atoms per unit area
that can lead to etchable tracks at the etched surface.
If we assume that the range R and etching efficiency T) for
spontaneous and induced fission tracks are the same, the above equations
can be combined to give the age in terms of the two track densities and
natural constants (12).
-8 —8 —2

The ratio IoVA has a value = 6 x 10 or 5 x 10 (y cm ),

depending on whether we use A s 7 x 10 y~ (13) or 8.4 x 10~ y~
_22 2
(14,15) respectively, with o- s 5.8 x 10 cm for thermal neutron
fission. This yields the simple relation
T = 6 (or 5) x 10 (p / p ) <p years
g
The last equation in the case of young samples of ages « 4.5 xlO
years is then the basic fission track age equation, and involves
88

essentially the measurable quantities p , p and thermal neutron dose <j>.

To measure the neutron dose <p we include with each group of samples
to be neutron irradiated a piece of neutron dosimeter (10)(a
dosimeter glass) of fixed uranium content. The density of fission
induced in this glass will be a measure of the neutron dose.

4. Procedure for Studying Tracks

4.1. SAMPLE PREPARATION

In order to achieve reliable ages in the region of a few million years,

the minerals examined should have uranium contents of the order of at
least 1 ppm. Apatite, zircon and sphene usually contain relatively high
U concentrations. These are common constituents of many rocks. Different
standard mineralogical techniques may be applied to isolate such
minerals out of rock sample. Mostly used are the heavy liquid
and magnetic separation. In these techniques, rock is crushed down to
grain sizes that correspond roughly to the dimensions of typical
mineral crystals within the rock (usually s 200 >x). By these ways one
type of mineral grains are segregated into different p a r t s according
to their density and (or) magnetic characteristics.
In order to isolate apatite and zircon from quartz and feldspar and
to separate them from each other, one first uses bromoform (density
:2.69 g cm ). The bulk minerals will float in this liquid while apatite
and zircon will both sink in it. One then tips latter into a container
of pure di-iodo-methana (density : 3.325 g cm ). Apatite floats and
zircon sinks; the two can thus be separated.
Using conventional epoxy resins, the apatite crystals may be
mounted on glass slides, in batches of several tens or hundreds of
grains. Since zircon requires a highly caustic etchant zircon grains are
usually mounted in a Teflon wafer (16). A glass slide is placed on a
hotplate maintained at about 290 C. Zircon crystals are sprinkled onto
the slide and a Teflon wafer placed on top of them. A second glass
slide, preheated to about 290 C, is then placed on top of the assembly
and, upon applying a slight pressure, the Teflon flows around the
grains. The mount is then removed from the hotplate and, on cooling, the
two glass slides may be easily detached from the Teflon.
After the mounting process, both apatites and zircons are ground to
produce flat crystal surface. This is carried out either by using
corborundum powder spread on a glass plate and lubricated with water, or
by using "wet and dry" emery paper. The next step is the preliminary
polishing of the crystals, achieved by using diamond paste spread on
polishing pads, with a suitable lubricant. Polishing preferably s t a r t s
with "6 fi diamond polishing compound" (or 1 (i Al 0 powder) and ends
with " 1 n or 1/4 fx diamond polishing compound" (or 0.03 (i Al 0
powder).
Polished crystals are now ready for etching. Apatites are treated
with dilute nitric acid at room temperature. A typical etching treatment
might be 1 minute in 57. aqueous solution of HNO at 23 C (17).
Zircon crystals mounted in Teflon are etched in the mixture of 11.5
p a r t s KOH and 8 parts NaOH. Wafers containing the polished zircons are
 89

then floated onto this mixture at a temperature of about 220 C (18).

Etching is performed in platinum crucibles and the etching time will
vary depending upon the track density. Those with a high track density
(>10 tracks/cm ) will etch in 4-6 hours. Etching times of 18-24 hours
are required for most zircons of average track density
(10 -10 tracks/cm ). Zircons with < 10 tracks/cm will require much
longer times.
The etching treatment is followed by thorough washing of the
samples, possibly in an ultrasonic cleaning bath, and by an equally
thorough drying. It is important to ensure that no caustic traces remain
whose fumes could attach the microscope objective lens and cause sever
corrosion. This is particularly important in the case of etching with HF
acid for glasses.
Finally, the etched tracks may be counted under an optical
microscope using an overall magnification of ~ 400-1000 x.
After describing the basic procedures it is necessary to consider
several different routes by which a fission track age may be obtained.

4.2. THE POPULATION METHOD

In this method (19) the mineral grains are divided into two groups. The
first group is mounted in epoxy and polished. These grains are used to
determine the fossil track density. The second group of mineral
grains is heated in a furnace to temperature high enough to cause
complete annealing of the fossil tracks and then irradiated. Following
the irradiations they are mounted, polished and etched along with the
unannealed set. The induced track density is then determined from the
grains in irradiated group. This method can be used only if the uranium
concentration of all the grains is uniform and required minimum of
several hundred grains. Apatite usually can be dated by this method.

4.3. THE EXTERNAL DETECTOR METHOD

To apply this method (20) some grains are mounted in epoxy (or teflon)
polished and etched to reveal the fossil tracks. The mount is then
covered with a piece of muscovite or Lexan (a polycarbonate plastic),
which has the uranium content lower than those of the mineral grains.
The grain mount then irradiated with thermal neutrons. The induced
fission tracks emanating from the crystals are then recorded in the
detector; and, upon etching the detector sheet, the induced track
density due to each mineral grain can be measured. The advantage of the
external detector method is that in this method the fossil tracks are
counted on the grain and the induced tracks are counted on the image of
the grain in the muscovite detector; therefore, variations in uranium
concentration can be dealt with. It is possible but not recommended, to
date only one grain using this method; normally five or more grains
would be dated. This method is used for the most minerals other than
apatite. The etching efficiencies for the mineral and the muscovite are
not usually similar, then the proper correctoin is needed.
Although other approaches are possible, the population and external
detector methods are the most widely adopted schemes in routine fission
track dating. For example, a third method is primarily used for dating
glasses by Fleischer and Price (21), involves mounting, polishing and
90

etching a sample prior to irradiation. Before the irradiation the fossil

track density is determined. The sample is then irradiated. After the
irradiation it is repolished (to remove about 20-30 fi), etched and
counted again. The second count contains both the fossil and induced
tracks. The induced track density is obtained by subtracting the fossil
track density from the combined track density.

5. Neutron Dose Measurements

The neutron dose, a sample is subjected, must be determined as

accurately as possible in fission track dating technique. The best way
to determine the neutron dose is to place a standard in the irradiation
package. The standard should have a uniform uranium concentration and
should produce an easily counted track density. Then it might be
possible to count about 100 tracks with a minimum amount of effort and
time. If the uranium concentration is too low it might be necessary to
scan several square centimeters to get enough tracks. The standards are
counted at = 400-500 magnification. At this magnification there are
about 4000 fields of view per square centimeter. On the other hand, too
much uranium in the standard could produce too many tracks which also
makes counting difficult. A standard containing uranium concentration
between 0.3 and 30 ppm will be useful as a monitor for most geological
material.
The glass standards suitable for neutron dose measurements are
available from the U. S. National Institute of Standards and Technology
(NIST). There are two glasses available and they contain the following
uranium concentrations: 37.4 ppm U and 0.82 ppm U. These
two glasses are the ideal glasses in dating geological
materials.
In order to have an accurate determination of the neutron dose the
standards must be calibrated. One of the ways to calibrate a standard is
the comparison of the track density in the standard, with the track
density in another piece of the same glass which has been irradiated
under known conditions. Then the neutron dose, the standard receives,
can be calculated as follows:

<Pu = p u / p k ( <t>k )
where
0 = unknown neutron dose
u
d> = known neutron dose
*k
p = unknown track density
u
p = known track densityJ
'k

6. Track Fading Experiments

At room temperature, fission tracks are essentially stable in most

materials. As the temperature is raised however, there comes a point
when electrons and ions in the material rearrange themselves and the
t r a c k s begin to disappear. After a certain time at that temperature all
t r a c k s will be erased. The process is called annealing. Different
 91

materials require different temperatures to erase the tracks in the same

length of time as shown in Fig. 7.
In a typical track fading experiment, the sample is first heated
sufficiently to remove all fossil tracks. Then the sample is irradiated
with thermal neutrons in order to induce fresh fission tracks. The
sample is then divided into many pieces which are annealed at various
temperatures for various durations. After that, using precisely the same
etching conditions, the pieces are etched and fission tracks are
studied.

1.8 2.0
[lO3/ K]

Fig. 9. "Arrhenius plot for Libyan Desert Glass" All points

with identical track density reduction lie on a straight line
in such a diagram, resulting in typical "track retention
fans" (etching time : 120 s in 487. HF at 23 °C) (22).

The results of numerous track fading experiments can be summarized

as follows:

1) With increasing annealing duration and annealing temperature the

track density decreases in a characteristic way ("Arrhenius plot") (Fig.
9) 2) Fission tracks do not disappear abruptly when the temperature is
increased. The fading process is gradual. 3) Different materials have
different retention properties. For instance, fission tracks are more
stable in zircon than in apatite and are more stable in acidic natural
glasses than in basic ones. 4) During the fading process there is also a
track size reduction. It means that partially annealed tracks are
smaller than unannealed tracks (Fig. 10) (22)
92

DENSITY OF TRACKS (in V.)

Fig. 10. Etch pit length vs. track density for apatite. The
mean track diameter in an annealed sample is plotted against
the track density for that sample; the data are normalized to
the mean diameter and track density for an unannealed sample
(etching time: 15 s in 657. HN0_ at room temperature) (22).
There exists a relationship between track density and track size
for the various materials. Therefore, by track size studies it is
possible from the correction curves to determine the degree of track
fading and calculate the preannealing track density.

6.1. ANNEALING CORRECTION TECHNIQUES

In deriving the age equation, it was assumed that the spontaneous and
induced fission tracks both had the same etchable range. If, however,
the fossil tracks have been shortened by some heating event in nature,
then the apparent fission track age is lower than the true age. Apatites
and glasses commonly show the effects of fossil track fading whereas
zircons and sphenes generally do not.
Suppose that a rock is subjected for a certain length of time, to
some constant, rather high temperature at which a moderate amount of
track shortening takes place. If tracks are shortened by an amount AR,
yielding a track density reduction Ap, this track density reduction will
in turn, lead to a reduction AT in the measured fission track age. The
important point is that this apparent age T-AT, does not correspond
to the true formation time of the rocks. This case is completely
different than severe annealing events in which all tracks are
eliminated so that the fission track "clock" is thereby reset (17).
Several methods have been devised to allow for partial annealing.

6.1.1 The Track Size Correction Technique. This technique uses the
smaller sizes of partially faded tracks compared to freshly induced
 93

tracks (23). From the degree of track size reduction, the original
pre-fading track density can be recalculated by using the experimentally
established correlation between track density and track size reduction
due to partial fading. This technique is very time consuming because it
needs a lot of size measurements and correction curves for each sample.
This correction technique has been applied to tektites (23,24), volcanic
glasses (25),mika (27) and apatite (23).

6.1.2 The Plateau Correction Technique.This technique uses the higher

thermal stability of partially faded tracks compared to fresh induced
tracks (26). In the laboratory, fossil and induced tracks a r e annealed
together in several steps under controlled conditions. The r a t i o of
fossil to induced track density is plotted as a function of the
temperature of continued annealing. For a sample with partial loss of
fossil tracks, the ratio increases and reaches finally a plateau value.
The age calculated from this value is corrected for the original,
partial track loss. With this technique fission track ages of tektites,
obsidian and apatites were corrected (28,28a).
For the interpretation of the corrected fission track ages it must
be kept in mind that only the partial track fading is corrected.
Therefore the corrected fission track age dates the time when the sample
crossed last from the temperature zone of track instability to partial
track stability. This may be either a formation age or a cooling age.

7. S t a t i s t i c a l E r r o r s in Fission Track Dating Technique

In fissin track dating technique, the track density p can be calculated

by the equation

/ A
i-l

for the tracks which have been measured in n crystals ( o r in different

types of materials).In the given equation, N is the number of tracks
counted in the total area A of the crystal.The subscript i r e f e r s the
value of the relevant parameter in the ith crystal.The basic assumption
in fission track counting statistics is that the fission track
count is part of a Poisson distribution.So that, the e r r o r e(p) , in
the track density is given by
1/2

e(p) =
l«, / A

Usually,the fission track counts do not obey the Poisson

distribution because of the different uranium contents of a group of
crystals.Thus the error of a track density can be calculated by the
standard e r r o r (s.e.) of the counts:
1/2
£ ( N -N ) 2 / n(n-l) / A

where N = Y N /n is the mean of the counts.

** l
1=1
94

The relative e r r o r cri

p /p ) of the ratio p /p in the age
s i s i
equation
is calculated by the e r r o r propagation standard law
, s 1/2

Cr(P (Tip ) + <r(p )

s/Pl) =
s 1

where <r(p ) and cr(p ) are the relative errors of spontaneous and
s i
induced track densities respectively.For a Poisson distribution <r(p )

1/2
(or crip ) ) has to be taken as 1 / N .Otherwise cr(p ) (or
E
i■ ="l
i '

<r[p )) is calculated by using the standard error equation.

For E DM (E xternal Detector Method) the Poisson e r r o r s a r e used to
calculate the e r r o r in the spontaneous to induced track density ratio.
The track counting e r r o r s are combined with e r r o r s assigned to
other measurements,such as the neutron fluence 0 in order to arrive
at the uncertainty in the fission track age.The statistical aspects of
fission track counting have been discussed in detail in several papers
(29,30,31,32,33).

8.Conclusion

During the last decades,significant improvments were brought to the

fission track dating technique.The further came from a better
understanding of the latent fission track stability in geological
environments. The heating experiments offered the possibility of
indirect control of the closing temperature or of its variability within
a given mineral species. For instance for apatites , the linearly
extrapolated temperature of total annealing (for one hour heating)
varies due to their chemical compositions.The variations of this formal
temperature between various samples of a given mineral, reflects
variations of the geological closing temparatures and is taken into
account for an interpretation of the corresponding cooling history of
the related rock samples (22).

ACKNOWLEDGEMENTS

I wish to thank Dr.G.Bigazzi who critically read the manuscript and made
useful comments. I also extend my thanks to Dr. H.A.Khan for his kind
helps.
 95

References

I. Meitner, L. and Frisch, O.R. (1939) Nature 143, 239.

2 . Burcham, W.E. (1973) Nuclear Physics: an Introduction Longman Group
Limited, Great Britain.

3. Cook, C.S. (1961) Modern Atomic and Nuclear Physics, D. Van

Nostrand Company Inc., New York.

4. Bohr, N. and Wheeler, J.A. (1939) Phys. Rev. 56,426.

Silk, E.C.H. and Barnes, R.S. (1959) Phil. Mag. 4,970-971

4a. Young,D.A.(1958) Nature 182,375-377.

5. Silk,E.C.H. and Barnes,R.S. (1959) Phil.Mag. 4,970-971..

6. Fleischer, R. L., Price, P.B. and Walker, R.M. (1965a) Jour. Appl.
Phys. 36,3645-3652.

7. Fleischer, R.L., Price, P.B. and Woods, R.T. (1969) Phys.. Rev. 88,
563-567.

8. Henke, R.P. and Benton, E.V. (1971) Nucl. Instrum. Meth. 97,
483-489.

9. Fleischer, R.L., Price, P.B. and Walker, R.M. (1965b) Annual

Reviews of Nuclear Science 15, Academic Press, New York.

10. Fleischer, R.L., Price, P.B. and Walker, R.M. (1965c) J. Nucl. Sci.
Engr. 22, 153.

10a. Wagner, G.A. (1977) Nucl. Track Detect. 2, 51-64.

10b. Bigazzi, G., Bonadonna, F.P., Belluomini, G. and Malpieri.L. (1971)

Boll. Sec. Geol. Ital. 90, 469-480.

II. Price, P.B. and Walker, R.M. (1963) J. Geophys. Res. 68, 4847.

12. Fleischer, R.L., Price, P.B. and Walker, R.M. (1975) Nuclear Tracks
in Solids: Principles and Applications, University of California
Press, Berkeley.

13. Hurford, A.J. and Gleadow, A.J. (1977) Nucl. Track Detection 1,
41-48.

14. Spadavecchia, A. and Hahn, B. (1967) Helv. Phys. Acta.

40,1063-1079.

15. Storzer, D. (1970) Ph.D. Thesis, University of Heidelberg.

16. Hurford, A.J. (1976) The Birkbeck Laboratory Manual on Fission

Track Dating, Birkbeck College, University of London.
96

17. Durrrani, S.A. and Bull, R.K. (1987) Solid State Nuclear Track
Detection: Principles, Methods and Applications, Pergamon Press,
UK.

18. Gleadow, A.J.W., Hurford, A.J., and Quaife, R.D. (1976) Earth
Planet. Sci. Lett. 33, 273-276.

19. Naeser, C.W. (1967) Bull. Geol. Soc. Am. 78, 1523-1526.
20. Green, P.F. and Durrani, S.A. (1978) Nucl. Track Detection 2,
207-213.

21. Fleischer, R.L. and Price, P.B. (1963) Jour. Appl. Phys. 34,
2903-2904.

22. Wagner, G.A. (1979) In:Lectures in Isotope Geology Springer-Verlag,

Germany, 170-177.

23. Storzer, D. and Wagner, G.A. (1969) Earth Planet. Sci. Lett. 5,
463-468.

24. Durrani, S.A. and Khan, H.A. (1970) Earth Planet. Sci. Lett. 9,

431-445.

25. Storzer, D. (1970) Earth Planet. Sci. Lett., 8, 55-60.

26. Storzer, D. and Poupeau, G. (1973) C.R. Acad. Sci. Paris 276, Serie

D., 137-139.

27. Bigazzi, G. (1967) Earth Planet. Sci. Lett. 3, 434-438.

28. Arais, C., Bigazzi, G. and Bonadonna, F.P. (1981) Nucl. Tracks 5,
129-136.
28a. Burchart,R.,Dakowski,M. and Galazka,J.(1973) Geochronology
Conference "ECOG II" Oxford.

29. Green, P.F. (1981) Nucl. Tracks 5, 77-86.

30. Galbraith.R.F. (1990) Nucl.Tracks Rad. Meas. 17,207-214.

31. Galbraith, R.F. (1981) Math. Geol. 13, 471-478.

32. Galbraith, R .F. and Larlett.G.M. (1985) Nucl.Tracks Rad.
Meas. 10,361-363.

33. McGee.V.E. , Johnson.N.M. and Naeser.C.W. (1985)

Nucl.Tracks.Rad.Meas. 10,365-379.
URANIUM SERIES DATING

M. IVANOVICH
AEA Environment & Energy
Isotope Geoscience Section
Harwell Laboratory, B7
Oxon 0X11 ORA
United Kingdom

1. Introduction

The principal aim of geochronology is to classify the earth's history in

terms of a sequence of events of known duration. The main available matrix
of evidence is contained within the terrestrial rocks. Precise physical
measurements, however, capable of providing an estimate of the absolute age
of specific rocks and minerals become possible only with the discovery of
radioactive decay. Virtually all quantitative determinations of geologic age
are based on the phenomenon of radioactivity. Thus, determination of
absolute age is based on the fact that a given radionuclide decays at a known
rate, and forms a geologic clock. In principle, any radionuclide can be used
as a radioactive clock provided its half-life, which determines its decay
rate, is of chronologically useful duration.
Mass spectrometric techniques have been instrumental in an early
development of dating with the ancestral radionuclides of the decay series:
11S 133
as'U, U and Th. However, because of the long half-lives of these
radionuclides, their applicable range is for samples older than a million
years. Thus, radiometric dating of Quaternary deposits remained an
under-explored endeavour until relatively recently. During the last 35 years
much effort has been made to develop the shorter-term U-series methods for
the application to the fields of archaeology, Quaternary geology, and
geomorphology. By dating deep sea deposits, ice cores, estuarine and
lacustrine sediments, recent volcanic events, fossil organic remains, and
combining these with paleoclimatic inferences,' a detailed picture of the
timing and intensity of late Pleistocene climatic events (ice ages) have been
97
H. Y. Goksu et at. (eds.). Scientific Dating Methods, 97-117.
© 1991 ECSC, EEC, EAEC, Brussels and Luxembourg. Printed in the Netherlands.
98

constructed. However, very few radiometric techniques are as yet capable of

dating events in the 300,000 to 1,000,000 years period.
The uranium series disequilibrium dating methods encompass a spectrum of
techniques involving many different nuclides [1]. These methods can be
divided into two distinct groups: (i) methods based on accumulation of decay
products of U (or daughter deficiency methods); and (ii) methods based on the
decay of unsupported intermediate radionuclides in the series (or
daughter-excess methods). In the first case, a present radionuclide may be
deposited free of its daughters or a daughter deficiency of known extent may
be established, so that at some subsequent time, the age of the deposit can
be determined from the extent of growth of the daughter(s) into secular
equilibrium with its (their) parent(s). Examples of this group of dating
J30
methods are the Th/ 23 *U and 23
iPa/ 235 U dating of carbonates. In the case
of the second group, the daughter nuclide is initially present in excess of
its parent, and the sample is dated by measuring the decay or this excess
230
since the formation of the sample. Examples of this group are the Th~ and
231
Pa~ excess dating of deep sea sediments [1-3].
The three naturally occurring radioactive decay series are illustrated
in Fig 1 where only the longest-lived radionuclides are depicted. Each
radionuclide is characterised uniquely by its own decay constant, \ (the
probability of decay per unit time) which is related to its half-life tw (the
time required for exactly one half of the originally present nuclei to decay)
by X = ln2/ti,. As can be seen in Fig 1, the daughter nuclide half-lives
relevant to radiometric dating range from several years to several hundred
thousand years. In contrast the parent nuclide (23,U, 232
Th and 235
U)
half-lives are all of the order of thousand million years.
In any naturally occurring material which contains uranium and which has
remained undisturbed for several million years, a state of secular
equilibrium between the parent and the daughter radionuclides in a decay
series will have been established. By definition, the state of secular
radioactive equilibrium implies that the activity of the parent radionuclide
is equal to that of the daughter radionuclide i.e. the ratio of the parent to
daughter activities is unity. However, when a sedimentary deposit such as a
calcite deposit is formed various geochemical processes conspire to cause
isotopic or elemental fractionation initiating a state of disequilibrium
between parent and daughter radionuclides [4]. If no diagenetic changes or
 99
238 232 235
U SERIES Th SERIES l i SERIES

"«u "'a » 5 U.
H 47.10'y) l2-tS.I0 5 yl I7 0i-10*yl

a. n' P o a
I liamnl cu: • ICTyl

»'Th
4 "°Th 2
"Th ,n
Th
yf
"'Th ° ='Th
(2t1dayl (752»10'y> (139.10°yl e I191yl (25 6hl I18 2aayl

I"
««RQ
I^l613hl
228pG
I
^'Rc
I21-6yl r
\
'»Ra
M602y) (6 7 y l I3 5iday] |1U3dcyl
i 1
i i

i i
"'Pb M7
Pb
1
»« P b ISIaolel (Stable!
IStaUel

Fig. 1 A shortened list of the longer-lived member-radionuclides

of the three naturally occurring radioactive decay series.
100

other migrating mechanisms occur after the initial formation of the deposit
in that state of disequilibrium, it is possible, in principle, to determine
the time of the original event by measuring the extent to which the
radionuclide system has returned to the state of secular radioactive
equilibrium.
All the dating equations relevant to this discussion derive from the law
of radioactivity. However, details of the derivations are beyond the scope
of this chapter and the interested reader is referred to Ref [5].

2. Dating methods based on accumulation of decay products of uranium

2.1 The 2 3 °Th/ 2 3 *U dating method

230
If a sample contains no T h (see Fig 1) at the time of formation, then at
230 23
any later time, the Th/ * U activity ratio is given by the relationship

1 " e"Xl3ot / 1 \ X„c

23
°Th/ 2 3 *U = + 1

I -y _ g (^330 ^3 3 *)t |
(1)

230 23 238
where symbols Th, *U, U represent concentrations of each of the three
radionuclides in the sample being dated in units of specific activity
(disintegrations per minute per gram), X j 3 0 and X j J 4 are decay constants of
230
T h and 2 3 *U in inverse units of time (year" 1 ), and t is age in years.
Fig 2 is an isochron plot showing a graphical solution of equation (1). It
illustrates the relationship between J3<>Th/23*U and 2 3 *U/ 2 3 «U activity ratios
for closed systems of varying initial (23*U/23*U) activity ratio. In
practice, the dating range of this method is considered to be about 350 ka.
It can be seen from Fig 2 that in the range of less than 30 ka, the
relationship between the 2 3 C Th/ 2 3 *U activity ratio and age is virtually
independent of the 2 3 * U / 2 3 8 U activity ratio in the sample.

The criteria for 2 3 °Th/ 2 3 *U dating can be summarised as follows: (1) the
sample must contain uranium above the minimum threshold of 0.05 parts per
million by weight; (2) there must be no thorium precipitated with uranium in
the sample during deposition; (3) all 2 3 0 T h and 2 3 *U must be derived from the
 101

■; 30

n 1 1——r
0 4 o « 0 1
" ° T l l / n i U a c l i . i l y ratio

23
Fig. 2 Graphical solution of the °Th/23,,u" dating equation:
23
plot of "U/ 23 "U activity ratio against 2J0
Th/ 23,, U
activity ratio for closed systems of varying initial
( 23 *U/ 23 *U) 0 activity ratio.
102

carbonate portion of the sample; (4) the system being dated must remain
closed to migration or addition of radionuclides after formation; and (5)
sequential stratigraphic ordering of ages along the growth axis of a
carbonate deposit should be observed.

2J1
2.2 The P a / J 3 5 U dating method
23S 231
The »3ipa/i3 5u dating method is based on the decay of U to Pa. The
231 23S
relation between P a and its grandparent U is simple because the
231
half-life of the intermediate nuclide T h (tw = 25.6 h) is short enough to
consider it always in secular equilibrium with its parent. Thus, the age
relationship is:

_x
jsipa/usu = i _ e 23it^ (2)

J35
The U activity is usually calculated from the ' 3 »U activity because the
3
335u/» «u activity ratio in nature is considered to be constant at 1/21.7.
l31
The P a / 2 3 5 U method has a range of up to 200 ka.
If, however, equations (1) and (2) are combined to calculate the
231
P a / 2 3 0 T h activity ratio the following expression is obtained:

23ipa/JJ0Th = (3)

I _ e"^J3lt

21.7 [(1 - e " X 2 3 o t ) + ( " . U / J J . U _ D li!!_ (1 _ e"(Xj3° " Xj!l)t

)]
^J 30 ~ ^llt

Fig 3 presents a graphical solution of equation (3) , clearly demonstrating

that the age range of the age equation written in this form extends to about
300 ka.
The criteria for this dating method are the same as listed in section
2S0
2.1 for the Th/ 2 3 *U dating method. The usefulness of this method is in
providing an independent concordance test between the two daughter ingrowth
2J
dating methods. However, because of the low specific activity of ipa (due
235 2J
to low abundance of its grandparent U ) the measurement of ipa (directly
 103

001 0 03 0 03 004 0 05 0 06 0 07 0 OS 0 09 0 10
no
' Pal Th Oct i v i t y ratio

F i g . 3 Variation of " " u / 2 3 ' and 2,I

Pa/230Th activity ratios
with time. The solid lines are isochrons representing
different ages, as indicated in thousand of years, and
the broken l i n e s represent the change of the a c t i v i t y
23
r a t i o s with time for three different I n i t i a l "U/ 2 3 'U
a c t i v i t y r a t i o s as indicated.
104

or indirectly via 22 'Th) is not practicable for samples containing less than
some 3 ppm uranium.

3. Dating methods based on the decay of excess of uranium daughters

Natural fractionation of U-series daughter nuclides from their parents in the

hydrological cycle leads to insoluble daughter-nuclide excesses in the bottom
sediments [6]. This excess decays with time at a rate determined by the
decay constant of the particular nuclide, providing a useful dating method if
the initial amount of excess is known. Thus, the age or accumulation rate of
a deposit can be determined by a general decay equation of the form:

C = C0e~Xt (4)

where X is the decay constant of the unsupported daughter nuclide, C 0 the

initial excess of the time of deposition, and C, the excess measured at time,
t. Equation (A) is valid provided the parent nuclide activity is regarded as
constant (this is quite a reasonable assumption because the parent half-lives
are nearly always much longer than those of their daughters in excess).
Clearly the unknown quantity in equation (A) is the value of C 0 , the
knowledge of which depends on the particular environment of the sample.

3.1 The JJ*u7 J3 «U dating method

23 23<
The decay of excess *U towards the secular equilibrium with U is derived
from the law of radioactivity:

(J3»U/"«U) - 1 (J3*U/ J 5 > U) 0 - 1 e XlJ4t

(5)

where ( 23 *U/ 23e U) and ( 2 3 *U/ 2 3 *U) 0 are the present and initial activity
ratios, respectively. It should be noted that equation (5) can be derived
23
from equation (4) if the present and initial *U-excess are set equal to C
and C 0 in equation (4), respectively. In principle, this method should date
6
Pleistocene samples up to at least 10 y. The main problem of this dating
method is the inherent difficulty associated with establishing the value of
23
the initial *U-excess ( C 0 ) . This is not surprising considering the
 105

23
variability of the *U/ 2 3 'U activity ratio in terrestrial waters. In
23
general, no reliable a priori assumption about the initial »U/23,U
activity ratio can be made, thus limiting the applicability of the method
[7-12]. Some notable exceptions do exist both in terrestrial and in marine
environments. In the former case, fresh water carbonate formed in caves
(speleothem) can, in some very favourable conditions, be dated once the
constancy of ( 2 3 * U / 2 3 , U ) 0 ratio is established for a group of samples over
the length of a specimen. Winograd et al. [13] obtained concordant
23
* U / 2 3 , U and 230
Th/ 2 3 *U dates on vein calcites deposited from groundwater.
2J
On the other hand, Harmon et al. [14] have observed that *U/23,U
ratios often change after interruptions in the growth of the speleothem. The
situation appears to be somewhat more favourable in the marine environment
23
where the » U / J 3 1 U activity ratio is uniform in seawater [15]. Thus,
unaltered fossil corals and Mn nodules have been dated successfully using the
u * U / 2 3 » U dating method [16-18].

Chalov et al. [10,19-21] estimated the age of some major

Kazakhstan lakes by a residence-time analysis, having observed that the
23
*U/ 2 3 'U activity ratios in the lake waters were lower than in the incoming
23
rivers. These authors attributed the difference to the decay of excess *U
during the U residence in the 'no-outflow' lakes. Thus, by treating the
river water activity ratios as the ( 2 3 * U / 2 3 , U ) 0 values, these authors
23
calculated the ages of the lakes from the present * U / 2 3 a U ratios of the
lake water using the following equation:

X23
(23»U/23'U) - 1 (JJ4U/J3.U),, _ i J L i _e »t AJJtt (6)

23
As Ku [22] observes, the underlying assumption of constant *U/ 2 3 "U activity
ratios in the feedwaters has had to be extrapolated over 2 x 10 5 y
introducing an element of risk in such application, although the ages
obtained by Chalov et al. [10] were in agreement with those derived
from chloride accumulation and other geological considerations.
106
230 231
3.2 The Th- and Pa-excess dating methods
23
The °Th-excess dating method was first used by Piggot and Urry [23,24] who
226 230
measured Ra in sediments as an index of Th. The sedimentation rate, s
(cm/unit time) at a depth in a core, x (cm) may be related to the age, t of
the sediment by s = x/t. Then, substituting this expression for t in
equation (4) yields:

in C = inC0 - (X230/s)x . (7)

For a constant C„ and s, a plot of in C against x yields a straight-line.

Such a relation validates the assumption of constant C0 and s, while the
slope of such a straight-line is the measure of sedimentation rate, s. To
230 23
obtain C in equation (7) (i.e. the Th-excess) the measured *U activity
23 23 23
is substracted from the measured °Th activity (i.e. °Th-excess = °Th -
23
*U). Ku [25] justifies the 'correction' on the grounds that U in a typical
pelagic sediment is associated mostly with detrital clays in which only
I30
U-supported Th is present. This correction becomes particularly
230
significant in deeper strata where Th-excess is low. However, Ku [22]
quotes many instances of non-linear plots yielded by equation (7), and
230
suggests that this could be caused by possible variation in initial Th
concentration due to the change in bulk sediment settling rate. The
23
°Th/232Th and 231
Pa/23°Th dating methods discussed later in this chapter
230 231
are modifications to the Th-excess and Pa-excess methods designed to
cope with this problem in the marine environment.
231
The Pa-excess dating method is also based on the decay of unsupported
231
Pa in sediment cores and Mn nodules. The method may be useful as a
230
complementary technique to the Th method, although both methods are
subject to the same limitations.
Sackett [25] and Sackett et al. [26] used a different approach in
231 231
interpreting the Pa data. This author assumed that the Pa deposition
rate was constant for a given area of the ocean floor. Then, by measuring
231
the total Pa-excess in the core, and the amount below some depth in the
core, the age of that level can be calculated by a modified version of
equation (7):

£n (n/n t )A, sl
(8)
 107

23
where n is 'Pa-excess below the depth of age t, and n is the total
23
•Pa-excess in the core. The method depends on the validity of the
231
assumption that the P a deposition rate is constant thus, yielding ages
independent of variations in the bulk sedimentation rate. A similar approach
230
was applied to Th-excess dating method in the measurement of deep sea
sediment accumulation rates [27] , and by Ku et al. [28] and Ku and
Knauss [29] in the measurement of Mn nodule growth rates.

23
3.3 The °Th/ 2 3 2 Th dating method
230
In an effort to minimise the limitations associated with the Th-excess
dating method, Picciotto and Wilgain [30] suggested that use of the
230
T h / 2 3 2 T h activity ratio for C and C 0 in equation 4 instead of
230
Th-excess per total sediment. The reason for this substitution is that
232 230
the T h activity should provide the measure of initial T h activity in a
sediment because of the chemical identity of these nuclides. However, the
23 232
method has been criticised on the grounds that although °Th and T h are
chemically similar, their geochemical histories in the marine environment
differ a great deal [22]. The former is produced in the ocean, whereas the
latter is mostly an integral part of continental detritus carried to the
230
ocean floor. Indeed, the depth profiles of T h / 2 3 2 T h are similar to those
230 130
of T h per non-carbonate. Both methods fail to improve the T h per total
sediment approach and, in fact, both appear to be vulnerable to fluctuations
in carbonate content. However, Ku [22] concludes that with cautious data
230
interpretation, the T h / 2 3 2 T h derived results should be usable.

Isotopic fractionation also occurs between actinides during magmatic

23
processes such that in unweathered Quaternary igneous rocks the »U/ 2 3 'U
23, 235
ratio is often unity while U and U are in disequilibrium with their
230 231 22 21
daughters Th, Pa, «Ra and °Pb [31-35]. These rocks have been dated
23
using the oxh/ 2 3 , U disequilibrium relationship ( 230 Th may be either
23
depleted or in excess with respect to *U). The basic assumption in this
approach is that various mineralogical phases of solidifying magma inherit
230
different Th/U ratios (hence Th/ 2 3 »U) but identical 230
T h / 2 J 2 T h and
u » U / 2 3 , U activity ratios. Therefore, if a mineral has acted as a closed
230
system for a time t following crystallization, its T h / 2 3 2 T h activity ratio
should be given by the following expression:
108

23
°Th/ 2 3 2 Th = ( 2 3 °Th 0 / 2 3 2 Th)e~ X j 3 ( | t + ( 23 »U/ 232 Th)(1 - e " X j 3 o t ) (9)

230 J30
where T h 0 is the initial T h activity at the time of crystallization
from magma. The two unknowns in equation (9), 2 3 0 T h 0 / 2 3 2 T h and t can be
determined uniquely for two or more minerals of common origin. This can be
expressed analytically for two minerals A and B belonging to the same rock as
follows:

(10)

A,join (1 - [ ( 2 3 « T h / 2 3 2 T h ) A - ( 2 3 °Th/ 2 3 2 Th) B ]/[( 2 3 «U/ 2 3 2 Th) A - ( 23 »U/ 232 Th) B ]}

Thus, the accuracy of the age measurement depends on the U/Th fractionation
between the two minerals. An example of a graphic solution of equation (10)
is given in Fig 4. Minerals of the same formation age in a rock form a
J 3 o t 230
straight-line (isochron) with the slope (1 - e ), and the Th/232Th
230 232 23ot
axis-intercept ( Th 0 / Th)e~ . Those not plotted on a defined
isochron are products of a different crystallization time and melt
( , 3 0 Th/ 2 3 2 Th) composition domain. (For further discussion of the application
of this dating method to volcanic rocks see ref [36].)

23
3.A The *Th dating method
23
The *Th is formed in sea and groundwaters by decay of its immediate parent
23
*U. In common with other Th isotopes, this nuclide is adsorbed rapidly on
23
particulate matter after the >U decay [37]. In the shallow marine
23
environment *Th is found in excess in sediments in spite of its short
half-life. Rather rapid sedimentation rates encountered in shallow water
regimes can be obtained through the application of equation (7) after
23
substituting the *Th decay constant for X 2 3 0 in that equation. The
importance of this nuclide has been established in the studies of particle
reworkings and diagenesis in shallow water regimes.
 109

/ ^ 2 0 0 ky

50 k v ^
o / s i
o
' / i

(Th),
/ ' « Oky
o
o
^ b c

\
<l //
(Th)t A ^

238
U/232Th activity ratio

Fig. 4
Th c VhVrxxyp.'hl'Yh - 238jj/232Th isocliron diagram showing the schematic evoluion
of an initially isotopically homogeneous crystallizing magma. At 0 y the system crystallized dree
phases n, b and c, then erupted, and became isotopically closed. All of the crystals had the sane
230
Tri/ 232 Th activity ratios initially - designated (Th)). With time, 23f)Th grows or decays
238
towards radioactive equilibrium with U, and the isocliron will rotate about the point (Th)0 on
the equilinc - a line of slope 45°. Isochrons are shown for 50 and 200ky. At any time >350ky,
then 230Th~238Tj and the points a,b and c will lie along the equiline.
110
22
3.5 The «Th/ 2 3 2 Th dating method
22,
The T h / 2 3 2 T h activity ratio varies between 5 and 30 (averaging about 15)
in surface and deep waters of the ocean [22]. Thus, only a small
22 232
proportion of the measured *Th in these waters derives from T h in water,
22
and confirms that the rest must derive from the *Ra input to the water from
the bottom sediments [38,39]. The existence of disequilibrium between the
two nuclides observed in lacustrine environment [40] suggests the possibility
of dating modern sediment using equation (4). Because of a relatively short
228
T h half-life of only 1.9 y, the range of the method only extends to
22,
approximately 10 y. However, because of the relative mobility of Ra,
22,
T h has often been found to be deficient, instead of in excess, with
232
respect to T h [41], rendering the method of very limited use.

3.6 The 2 i°Pb dating method

210
The Pb dating method has been applied to the measurement of
sedimentation rates in lakes, estuaries, and coastal marine sediments. The
210 222
isolation of P b (tv = 22.3 y) is ascribed to its precursor R n which
222
escapes from the earth's surface into the atmosphere. Most of R n remains
210
in the troposphere where it decays to P b through a series of short-lived
210
intermediaries. The P b residence time in the troposphere is estimated to
range from days to a month before it is removed by precipitation and dry
210
fallout [42,43]. This atmospheric flux of unsupported Pb is presumed to
have remained constant at a given locality, and so Goldberg [44] first
21
proposed to date permanent snow fields by the measured °Pb activity

The age of different horizons in a sediment core can be calculated using

21
equation (4) from the unsupported °Pb activity (210Pb-excess = 210
Pb -
226 210 222
Ra) assuming that P b and R n are immobile in the core. Two different
age calculations can be carried out depending on the choice of two
assumptions: (1) constant initial concentration, or (2) constant rate of
supply.
210
The first method assumes that the Pb-excess remains constant with
time at a particular location. Then, the difference in age between the
surface sediment and sediment at depth, n is given by:

t = in [(21°Pb-excess)„/2i°Pb-excess) ]X, 1 0 (11)

n ° n
where (210Pb-excess) and (2 l0Pb-excess) are excess activities of 210 Pb at
o n
the two positions in the core in units of dpra/g of dry matter, and X J I 0 is
210
the Pb decay constant (0.03114 y" 1 ). When the accumulation rate is
constant in time, then equation (7) applies:

in(21°Pb) = 2n(21°Pb) - (XJ10/R)M (12)

n o

where M is mass depth in (g/cra2) dry matter, and R is the accumulation rate
of sediment in (g/cm2)y_1 dry matter.
210
The second method assumes that the flux of Pb-excess supply to the
sediment is constant with time at a particular location. Thus, similar to
equation (8), the age (t) for a horizon at depth n is calculated from:

Xjlot
I ('"Pb-excess) = nt(l-e ) (13)
n t

where I (210Pb-excess) is the total excess activity of 210

Pb from surface to
2 210
depth n in units of (dpm/cm ), and n is the total Pb-excess in the core
down to a deposition horizon much older than 100 y.
The more commonly used approach is the one based on the constant initial
concentration [45-48]. Obviously, when sedimentation rate is constant the
two methods should yield identical results.

4. Criteria for dating suitability

In principle, all radiometric dating methods must be based on a set of

assumptions, and criteria for their validity must be formulated. In the case
of U-series disequilibria dating methods, the choice of basic assumptions
and criteria depends on the kind of sample being dated and the environment
from which the samples are derived. There are, however, certain general
criteria which apply to U-series dating methods and they are: (1) There must
be a measurable quantity of U in the sample (for practical reasons the
minimum U content required for alpha spectrometry technique is 0.05 ppra or an
equivalent activity of a daughter nuclide and a. factor of 10 less for mass
spectrometry). (2) In the case of dating methods based on accumulation of U
daughter products, no daughter nuclide can be present in the sample at the
112

time of deposition of the parent nuclide nor introduced into the sample
during the lifetime, fossilization or diagenesis; otherwise appropriate
corrections should be implemented to correct for the original presence of the
daughter nuclides in the sample. Similarly, in the case of the dating
methods based on the decay of daughter excess, the initial nuclide content
must be known reliably. (3) The dated sample must be a closed system to
post-depositional migration or addition of any radionuclides used for dating.
This means radioactive decay and growth must be the only processes
responsible for changes in isotopic abundances since formation of the
system.
The criteria for ascertaining the extent to which the closed system
assumption applies vary for different types of samples, and are discussed in
detail for different materials: calcite cave deposits [49], corals and
shells [50], coral [16], travertines[51], and many other authors (see ref
[36] for example). These criteria are listed below.
(1) The samples should be impermeable to sea or groundwaters because the
flow of water through the system may cause alteration in U or Th
content.
(2) There should be no evidence of weathering in the sample.
(3) Deposits known to have been initially composed of aragonite (for
example, coral) should show no conversion to calcite, since U or its
daughters may have been mobilized during the conversion and
recrystallization.
(4) Samples partially replaced by secondary materials should not be dated.
(5) In the case of carbonate samples, there should be little (or no) HN0 3 -
insoluble residue.
23l
(6) In the case of terrestrial carbonate, there should be no or little Th
present in the sample as this nuclide is usually indicative of the
presence of detrital material in the sample.
(7) Apparent radiometric ages must be in agreement with stratigraphic
sequence.
(8) Agreement should be obtained for ages determined by several independent
J3
methods such as °Th/ J 3 'U, J31
Pa/J35U, J31
P a / I 3 0 T h , He/U and 14
C.
 113

5. Summary

The Quaternary period of the geological record is characterised by episodic

fluctuations in global climate. Its timescala is such that no single
physical dating method provides a sufficient range to cover the entire
period. Uranium series dating methods encompass a spectrum of dating
techniques involving daughter nuclides of varying half-lives and therefore,
they provide absolute dates for a period between 350 ka and the present. In
this chapter various uranium series dating methods have been outlined and
criteria for datability listed.

Acknowledgements. The author thanks Mrs. Brenda Boardman for producing

this manuscript.

References

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[31] Anestad-Fruth, E. (1963). Uranium Series Disequilibrium in Recent

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23
(1966). Disequilibrium of the "U series in basalt. Earth planet.
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Pollution history of Narragansett Bay as recorded in its sediments.
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22, 3-24.
PART II

Dating Methods Based on Energy

Deposition in Solids
THERMOLUMINESCENCE DATING

M.J. AITKEN
Research Laboratory for Archaeology
Oxford University
6 Keble Road
Oxford 0X1 3QJ
U.K.

1. Introduction
Thermoluminescence dating is applicable to quite a number of
sample types: pottery, bricks, burnt stones, burnt flint and
stalagmitic calcite being some of them. Unburnt sediment that
has been deposited by wind (e.g. loess, sand dunes), and in
some circumstances by water, can also be dated. This aspect
is the subject of this presentation, which will also deal with
the alternative measurement technique of optical dating based
on optically-stimulated luminescence (OSL).
Thermoluminescence (TL) and optical dating together comprise
what is conveniently described by the term luminescence dating
(LD).

Thermoluminescence dating was developed from the late 1960s

onwards in the first place for pottery and other forms of
baked clay. The TL signal comes from quartz, feldspar, zircon
and a few other minerals; all these are present in the clay
itself in fine grain form or as larger grains which have been
added by the potter as 'grog' in order to improve the
refractory properties. An early application was to art
ceramics; this had a very powerful impact in museums and art
auction rooms, an impact which continues to-day - 'TL test
report' is a phrase of common currency among dealers and
collectors. During the 1970s application to archaeological
pottery developed, with an increasing understanding of the
technical problems involved. Towards the end of that decade
extension to stalagmitic calcite (unburnt) and burnt flint
took the technique back beyond the 50,000 year limit of
radiocarbon and there is now an important contribution being
made in the dating of early man, and in particular the
relationship between anatomically modern man (Homo sapiens
sapiens) and Neanderthal Man.

Although luminescence dating has developed only during the

last three decades, study of luminescence has been going on
121
H. Y. Goksu et at. (eds.). Scientific Dating Methods. 121-140.
© 1991 ECSC, EEC. EAEC. Brussels and Luxembourg. Printed in the Netherlands.
122
for more than three centuries, an early observation being by
Sir Robert Boyle (1664). Use in mineral identification began
in the nineteenth century and later, more or less in parallel
with TL dating, there was development of thermoluminescence
dosimetry (TLD), using highly-sensitive natural and artificial
minerals, for assessment of exposure to nuclear radiation as
an alternative to film badge dosimetry.
There is an introductory test for new practitioners of TL
dating (Aitken 1985) as well as an account more suitable for
archaeologists and other users (Aitken 1990).
2. The Essential Basics
The observed TL in a sample - the 'natural TL' results from
the effect on the minerals concerned of continued exposure to
a weak flux of nuclear radiation from uranium and other
radioactive impurities in the sample itself and in its
surroundings. The essential basis of dating can be expressed
by the equation
'natural TL'
age = (1)
(TL sensitivity) x (annual dose of radiation)
where TL sensitivity is measured after exposing a portion of
the sample to a known dose of radiation from an artificial
radioisotope, and annual dose is determined from radioactivity
measurements - the natural radioisotopes providing the annual
dose have very long halflives and annual dose is presumed to
be constant.
2.1 THERMOLUMINESCENCE
In broad terms the overall effect can be described as a
cumulative distortion in the distribution of electrons in the
crystal lattice concerned; when the distortion is released
there is emission of light and this is the dating signal which
is measured. One way of releasing the distortion is by
raising the temperature - hence thermoluminescence. Thus heat
is the agency by which the stored signal (the latent TL) is
observed; it is also the agency by which the latent TL is set
to zero in antiquity - during firing by ancient man in the
case of pottery. This zero-setting event, which may be
achieved in other ways too, is the event which is dated.
 123
2.1.1 The traps and centre model. Although reality is much
more complex, it is convenient to use the simple model of
figure 1 for discussion. The electron traps and luminescence
centres are formed by defects in the crystal lattice of the
mineral concerned, for example by a missing atom, by an atom
out of position, by the presence of an impurity atom. As far
as the build up of latent TL is concerned, these defects are
taken to be part of the constant scenario of the crystal and
it is the movement of electrons between them which is the
basis of dating. Heating by ancient man empties traps of the
electrons that had accumulated during geological time, this
emptying being due to the enhanced thermal vibration of the
crystal lattice at elevated temperature. Following this,
traps once again begin to fill up with electrons - due to the
effect of nuclear radiation. Electrons are detached from
centres and other stable positions in which they had taken up
residence after the heating, and for a very brief time they
diffuse around the crystal. In the course of this diffusion
a few get caught in traps, the remainder returning to stable
positions. The longer the exposure to nuclear radiation the
greater the number of electrons that are trapped.
For measurement the sample is heated, thereby emptying the
traps, and the faint emission of light resulting from the
acceptance of some of the released electrons into luminescence
centres is detected by means of a sufficiently sensitive
photomultiplier. This TL has an intensity which is
proportional to the number of electrons that were trapped;
hence the years that have elapsed since firing can be
determined as indicated by equation (1).
2.1.2 Stability: the plateau test. The foregoing assumes
that electrons caught in traps stay there indefinitely. In
fact, the lifetime of an electron in a trap is not infinite
and has a value which depends on the type of trap. An
associated characteristic is the temperature at which the TL
is emitted during heating up for measurement. 'Shallow' traps
with short lifetimes are emptied early whereas 'deeper' traps
stay immune to the lattice vibrations until a higher
temperature is reached; thus in quartz the TL peak close to
100 degrees C is associated with a trap having a lifetime of
a few hours at room temperature whereas the lifetimes of the
trap types responsible for the TL peaks in the region of 350
degrees C are upwards of a million years.
Figure 2 shows TL glow-curves for a sample in which there
is a mixture of unknown minerals. In the natural glow-curve
there is no emission of TL until a temperature of 200 degrees
C is exceeded - because the electron lifetimes in the shallow
124

wmwmw///,
^wConduction band^^

Shallow traps Deep traps

Luminescence
centres

Fig. 1: The basic trap and centre model. The effect of

nuclear radiation is to populate the traps with electrons.
Electrons are easily evicted from shallow traps by vibrations
in the crystal lattice but for those in deeper traps there is
negligible leakage over millions of years - unless the
temperature of the crystal is raised thereby intensifying the
vibrations. Some of the evicted electrons reach luminescence
centres and there is then emission- of light, of a wavelength
characteristic of the centre. Eviction from traps can also be
caused by subjecting the sample to a beam of light.
The depth of a trap is defined by the energy, E, necessary
to detach its electron and allow it to diffuse briefly around
the crystal unit until it is captured by a luminescence centre
or at another stable location; while diffusing it is
described as being 'in the conduction band'. In some minerals
there is also a 'sub conduction band' mode of escape whereby
the electron reaches a nearby centre by a localized
transition; the energy required for this is substantially
less than E.
~° 20,000 -
o
o
CD
in
L~
CD
a.

c
O
u
CD
o 10,000
c
CD
u
tn
CD

c
E
o
E
i_
CD

100 200 300 400 500

Temperature (°C)

Fig. 2: The plateau test. Curve N is the natural glow-curve

from one portion of the sample and curve 'N+beta' is the
'natural + artificial' glow-curve obtained from another
portion to which an artificial dose of beta radiation has been
administered; the red-hot glow from the heater plate is also
shown. The dashed line represents the ratio between the two
glow-curves.
126
traps corresponding to lower temperatures are too short for
any significant accumulation of electrons to occur. The ratio
of natural TL to the TL from another portion of the sample
sample to which a dose of nuclear radiation from a
radioisotope source has been administered gradually increases
from zero at around 200 degrees C to a steady plateau level
for temperatures above 300 degrees C. This plateau indicates
that the TL in that temperature region is associated with trap
lifetimes that are much longer than the period over which the
natural TL has been accumulating - that is, there has been
negligible leakage from the traps concerned. A level plateau
has other significances too; one of these is that the heating
in antiquity was sufficient to empty all traps. Another is
that the TL observed is true radiation-induced TL rather than
spurious TL arising from parasitic surface effects: these are
poorly understood but are usually suppressed by filling the
glow-oven with an inert gas such as nitrogen, argon or helium;
prior-washing of the grains in acid also helps.
Although a necessary condition for a sample to be considered
as reliable, for some varieties of mineral a good plateau is
not a sufficient condition: despite a good plateau being
observed there may have been anomalous fading (see later).

2.2 SENSITIVITY TO RADIATION

As indicated in equation (1), an essential component of age
determination is measurement of the sample's sensitivity -
that is, the latent luminescence acquired from a given dosage
of nuclear radiation. The primary step in this is to expose
a portion of the sample to beta or gamma radiation from a
calibrated radioisotope source (strontium-90/yttrium-90 being
used for beta'; cobalt-60 or caesium-137 for gamma); the
latent luminescence acquired is then measured. The
calibration needs to be in terms of the energy absorbed per
unit weight of sample and the unit is now the gray (1 J/kg);
until recently the rad (1 erg/g) was in use; 1 gray = 100
rad.

The luminescence acquired per gray of beta radiation is the

same as per gray of gamma radiation. However, the nuclear
radiation emitted by naturally-occurring radioisotopes also
includes alpha particles; the luminescence per gray for this
type of radiation is substantially less than for the other two
types - by a factor of between 3 and 15, depending on the
minerals concerned. Again a calibrated radioisotope source is
used (usually americium-241 or curium-244). The alpha
particle effectiveness relative to beta or gamma radiation is
 127
expressed as t h e a-, b- or k- value.
In m e a s u r i n g sensitivity the dose-rate is necessarily higher
than that t o w h i c h t h e sample w a s naturally exposed b y many
orders of m a g n i t u d e . H o w e v e r , although some dose-rate
dependence has been reported for particular t r a p s , there does
not seem to b e a n y significant dependence in general - as
evidenced b y agreement of luminescence ages w i t h those of
other t e c h n i q u e s .

2.2.1 Growth curves; equivalent dose and paleodose. Although

in general the sensitivity is independent of dose-rate, there
is some dependence of total dose, as illustrated in figure 3;
it is evident that a series of measurements spanning different
dose levels is necessary. For young samples a correction for
supralinearity is important whereas for old ones approaching
saturation attention is focused on exponential curve fitting.
In the additive dose technique a number of portions of sample
with the natural signal still intact are given different
additional laboratory doses; in the regeneration or 'second-
glow' method the natural signal is first removed by heating
(in the case of pottery) or by bleaching (in the case of
unburnt sediment).
From figure 3 it follows that the concept of sensitivity is
too simplistic. Instead the equivalent dose (ED or Q) is
determined, this being an evaluation, based on the growth
curve, of the dose that the sample must have received during
antiquity in order to have acquired the observed natural
signal. Equation (1) is replaced by
ED
age = (2)
annual dose
Some authors reserve ED for an evaluation based on the
assumption of linearity, using paleodose (P) when correction
is made for non-linearity. Other terminologies in use are
accrued dose, accumulated dose, archaeodose and total dose,
abbreviations AD and TD being used.
2.3 RADIOACTIVITY AND ANNUAL DOSE
The naturally-occurring radioactive impurities in clay, soil
and rocks are principally uranium, thorium and potassium-40.
These contribute to the annual dose in roughly equal
proportions; in addition there are minor contributions from
rubidium-87 and cosmic rays. The nuclear radiations emitted
128

-
Sublinear
-
/ -.— Saturation
s^^
-

Linear /
-

- Supralinear /

i i 1 1 i

Dose

Fig. 3: Thermoluminescence growth curve showing supralinear,

linear and sublinear regions.
 129

by the radioactive impurities comprise alpha particles, beta

particles and gamma radiation. These have ranges of the order
of 0.02 mm, 2 mm and 20 cm respectively; hence for a sample
thicker than about 10 mm the annual dose consists of an
internal component, which is predominantly alpha and beta
particles, and an external component, which is gamma rays
originating in the surrounding 20-30 cm of burial soil or
rock, and cosmic rays. The relative size of the external
component, and hence the importance of its accurate
assessment, depends on circumstances; for pottery it may be
as low as 20% of the whole whereas for varieties of burnt
flint weak in radioactivity it may be as high as 80%.

2.3.1 Measurement. One approach to evaluation of annual dose

is to determine the content, for both sample and soil, of
uranium and thorium (for typical pottery: 3 and 10 parts per
million respectively) by neutron activation, and the content
of potassium (typically a few per cent, of which 1 part in
10,000 is potassium-40) and rubidium by some chemical
technique such as atomic absorption or flame photometry; once
the radioactive contents are known the contributions to the
annual dose are obtained by reference to nuclear data tables;
the cosmic ray contribution is obtained by calculation based
on thickness of overburden. Another approach uses particle
counting techniques; thick-source alpha counting, beta
counting and gamma spectrometry. A third approach uses highly
sensitive thermoluminescence dosimetry phosphors developed
primarily for nuclear hazard monitoring. This is the 'set a
thief to catch a thief approach and beta-TLD and gamma-TLD
have proved very effective; for the latter, capsules of
phosphor are buried on-site, usually for about a year in order
to average out seasonal variation in water content (see
below). On-site measurements may also be made with a portable
gamma spectrometer.
The preferred approach depends on site circumstances as well
as on the expertise and facilities of the laboratory
concerned; all approaches have their drawbacks and use of two
in parallel is desirable for reliability. Even when two
approaches give the same answer there are residual
uncertainties which are the ultimate barrier to smaller error
limits in the age than about plus or minus 5%. The most
obvious of these uncertainties arises from the influence of
moisture, both in sample and in burial soil. Water absorbs
part of the nuclear radiation emitted by the radioisotopes and
for a given 'dry' measurement in the laboratory the actual
annual dose is lower by a factor dependent on the water
content. Although this factor can be determined for the water
130
content as found in sample and soil on excavation there may
have been variation in the past - due to man-made change in
the water table or due to climatic change - and it is the
average water content over the burial period that is relevant.
In 'typical' circumstances the effect of water is to cause a
reduction of the order of 10-20% in the annual dose and so,
unless the variation in the past has been dramatic, the
uncertainty introduced is quite small - but it is the ultimate
barrier to better accuracy, as mentioned above. Of course for
a site which has always been dry this does not apply.
2.4 PRESENTATION FOR TL MEASUREMENT
In pottery there are commonly inclusions of quartz and
feldspar, with zircon being present to a much lesser extent;
quartz and feldspar usually contain negligible amounts of
uranium and thorium, certainly an order of magnitude less than
the baked clay matrix in which they are embedded. Because
alpha particles have such a short range (around 0.02 mm) the
centre of an inclusion greater than about 0.04 mm is shielded
from them; hence the larger the grain the lower the average
annual dose it receives. Thus measurement of the grains as a
whole is liable to give an erroneous age because the
appropriate annual dose for insertion in the age equation
depends on the number of inclusions and their size
distribution. This dependence is avoided by one of several
approaches to preparation of the sample for measurement.
In the fine-grain technique polymineral grains of less than
0.01 mm are separated out by sedimentation and deposited on
aluminium or stainless steel discs (usually 1 cm diameter)
ready for luminescence measurements; such grains are fully
penetrated by alpha particles. In the quartz inclusion
technique grains in the size range 0.09-0.125 mm are obtained
using magnetic and heavy liquid techniques of separation
together with sieving. By etching with concentrated
hydrofluoric acid the alpha-irradiated skin is removed and the
residual cores carry only the annual dose from beta, gamma and
cosmic radiation (except when there are slight traces of
uranium and thorium in the quartz itself). In the alkali
feldspar inclusion method somewhat larger grains are used and
there is separation into sodium and potassium feldspars; the
latter carry an enhanced annual dose because of the intragrain
contribution from the potassium-40 beta particles.
Plagioclase feldspars may also be used.
2.4.1 Zircon dating. Although rare in most types of pottery,
 131
in some types it is necessary to eliminate grains of this
mineral when employing either of the inclusion techniques;
this is done by density separation using heavy liquids,
removal is necessary because of the exceptionally high uranium
and thorium content of zircons, which results in these grains
having a very much higher ED than those of quartz and
feldspar.
However in zircon dating this high radioactive content is
exploited. The ED of a grain is dominated by the internal
alpha dose and hence there is no interference by water content
- zircon is a hard, compact mineral impervious to water.
Furthermore the high degree of independence of soil gamma
radiation allows application to already-excavated pottery in
museums.
Unfortunately the technical difficulties of dating zircon
are great and although it has been demonstrated as feasible it
is not yet routinely available. The favoured approach is the
autoreqeneration method in which, after measurement (and hence
also elimination) of the natural TL of, say, 50 grains (in the
size range 0.1-0.2 mm) they are stored for some months; at
conclusion of the storage period there will have been
reaccumulation of TL due to the internal radioactivity.
Essentially the age is obtained by simple proportions:
(natural TL)
age = ' x (storage time) (3)
(autoregenerated TL)
A small correction is made in respect of environmental
radiation.
2.5 ANOMALOUS FADING
It is possible to predict the lifetimes of electrons in
various types of trap by laboratory study of kinetic
behaviour, for example by measuring the rapidity with which
the traps concerned lose electrons during storage at a
succession of elevated temperatures. Such prediction is on
the basis of the trap and centre model; there is also the
assumption that for eviction from a trap an electron needs to
be given enough energy (E in figure 1) to get well clear of
the trap so that it can diffuse around the crystal until
captured by a centre or another trap. For traps in quartz,
feldspar and zircon which are associated with TL emitted in
the glow-curve region about 30 degrees C the predicted
lifetimes are upwards of several million years. Yet there are
some samples of feldspar and zircon for which, following
132
irradiation, there is appreciable loss of electrons from deep
traps in a matter of days, let alone thousands of years;
also, some such samples pass the plateau test. This failure
to live up to stability expectations is termed anomalous
fading; this is in contradistinction to thermal fading - loss
of electrons in accordance with kinetic predictions such as
happens from shallow traps at room temperature or from deep
traps at elevated temperature).

Two mechanisms have been put forward to explain anomalous

fading. Both postulate localised transitions from traps to
nearby centres, the energy required being less than that for
diffusion around the crystal. Whereas that suggested by
Visocekas (1979) is pessimistic, that of Templer (1986) is
optimistic - in the sense of predicting that reliable ages can
be obtained from samples exhibiting anomalous fading as long
as appropriate thermal or optical pre-treatment is given;
thermal pre-treatment is now routinely applied whenever
stability is in doubt.

The above refers primarily to samples for which anomalous

fading can be detected in laboratory storage tests over days,
weeks or months. A limitation that may or may not be related
is the so-called '100,000-year barrier' in sediment dating
when using polymineral fine grains (Debenham 1985); breaching
of this barrier is in progress.

3. Applications

It is not possible in the space available to give a definitive

assessment of the role of TL dating in archaeology and
Quaternary geology but illustrative indications of some types
of application are now given. Dating of unburnt sediment is
excluded here since it is the subject of another chapter,
likewise pre-dose dating.

3.1 BAKED CLAY

3.1.1 Pottery. For a reliable date of good accuracy, say plus

or minus 5-10% of the age, about half-a-dozen pottery
fragments each of 10 grams or more are needed from each
context; a variety of fabrics is preferred. Ideally the
pottery should have had a homogeneous soil surround to a
distance of 30 cm or more; the burial depth should have been
at least 30 cm for at least two-thirds of the burial period.
As has been indicated, samples of burial soil are needed for
radioactive analysis in the laboratory; preferably, on-site
radioactivity measurements are made.
 133
3.1.2 Authenticity testing. For art ceramics on the shelves
of museums or in the hands of collectors and art dealers the
external gamma irradiation received from the soil or other
storage environment cannot usually be determined.
Nevertheless, because the gamma component is not the major
part of the annual dose, in most cases it is possible to
determine a TL age to an accuracy of around plus or minus 20%;
this level of accuracy is usually adequate to give a clear-
cut distinction between ancient and modern, which is the usual
requirement.
Quite a small sample is used, about 0.1 gram of powder being
obtained by drilling a small hole, 4 mm across by 4 mm deep,
in an unobtrusive location. Porcelain poses problems because
of its hardness but a satisfactory procedure has been
developed (Stoneham 1983); for this a 3 mm cylinder is
extracted and cut into thin slices for measurement using the
pre-dose technique.
3.1.3 Retrodiction of radiation levels at Hiroshima and
Nagasaki. The apparent TL ages of bricks and roof tiles from
buildings erected prior to the atomic bomb explosions in 1945
are in excess of the true ages due to the high levels of
radiation during and immediately after the events. Using
bricks and tiles for which the dates of manufacture are known
the bomb dosages can be evaluated. For buildings sufficiently
distant from the epicentre for human survival this is relevant
data in relating incidence of subsequent cancer to radiation
dose.
Electron spin resonance has also been used in this context
through measurement on teeth and pearl buttons; this gives a
more direct evaluation of the actual dose received by the
individual concerned.
3.2 OTHER HEATED MATERIALS
These can be dated essentially on the same basis as pottery,
though there tend to be differences in emphasis in respect of
dosimetry measurements for annual dose.
3.2.1 Burnt stones. In pre-pottery cultures it was common
practice to use 'pot-boilers' for cooking. Stones, or balls
or clay if stones were not plentiful, were heated in a fire
and then placed in the food container, which might be a skin
bag or a stone trough. Because the stones tended to shatter
when placed in the water reuse was not convenient;
consequently burnt fragments are plentiful on such sites and
often there are large mounds of them, for instance, on sites
134
of the first millennium BC in the Orkney Islands (TL dates by
Huxtable et al 1976). A particularly intriguing application
has been to the vitrified forts of Scotland (Sanderson et al.
1988; Strickertsson et al. 1988). These hilltop ramparts
were evidently fired to surprisingly high temperatures,
presumably by enemy action, and had formerly been assumed to
be of the first millennium BC; however, the spread in TL ages
is from 2000 BC to AD 1000, thus stimulating substantial
reappraisal of the archaeological evidence.
In burnt stones there are a variety of minerals that may be
encountered and hence a corresponding variation in TL
characteristics. Large grains are more likely than in pottery
and hence problems of radioactive inhomogeneity are
accentuated. However, in some cases this can be put to good
use as is illustrated in the dating of granite stones from
Scandinavian sites (Mejdahl 1983); large grains of alkali
feldspar have an annual dose that is dominated by potassioum
within the grain thereby weakening dependence on external
radioactivity and wetness.
3.2.2 Burnt flint. Being a form of quartz, similar TL
properties are to be expected; in fact these are usually
superior and it is an excellent material for dating. However
it has two serious limitations. First, the external gamma
contribution to the annual dose is usually dominant, thereby
accentuating dependence on environment. Secondly, on Middle
and Lower Paleolithic sites there is usually a paucity of
flints that are sufficiently well burnt and not too small.
Flint implements (blades, scrapers, arrowheads, etc.) were
in widespread use by Palaeolithic man, and in addition to the
implements themselves, there remain some of the flakes, chips
and cores associated with manufacture. Some of these
artefacts were heated accidentally by falling into the fire,
some were heated deliberately in order to improve the
'knapping' properties.
It is essential that the heating was sufficient to set the
TL clock to zero by erasure of the geological TL. Depending
on the duration of heating a temperature in the range 300-400
degrees C is required, the higher the better though excessive
heating is liable to produce flint which shatters into small
pieces when processing begins. The critical test for
sufficiency of heating is through measurement of the TL
plateau and as this is intrinsic to the dating procedure there
is no point in considering ancillary techniques. It seems
that visual appearance (reddening, vitreous lustre, potlids,
crackling, etc.) is not always a reliable guide to adequacy of
heating, and in collecting for dating the policy should be to
 135
collect too many rather than too few and hope that on trial in
the laboratory enough will be found satisfactory; upwards of
half a dozen are desirable though some dating indication can
be obtained from one or two if necessary.
As indeed is also the case with pottery and burnt stones, it
is important to saw off and discard the outer 2 m m of the
sample on commencement of processing for TL measurement. This
is for two reasons. First to eliminate the 'beta transition
layer' where the annual beta dose corresponds partly to the
radioactivity of the flint and partly to that of the burial
soil; this is particularly important with flint because its
radioactivity is usually much lower than for soil; hence
inclusion of the layer would tend to give an age that is
erroneously too old. Secondly, flint is translucent and if
there has been significant exposure to light since extraction
from the soil (such exposure should be minimised by putting
into a black plastic bag as soon as possible) there is risk of
appreciable reduction of TL in the surface layer due to
'bleaching' . After this sawing it is necessary that a disc of
not less than 5 mm thick and 30 m m across remains for
measurement. This requirement of being big enough conflicts
with the requirement of sufficiency of heating, for the bigger
the flint the longer must have been the duration of heating in
order to reach the necessary temperature.
The age range for which burnt flint is useful is very
roughly 5000-500,000 years; the lower limit is set by the
intensity of the TL being too weak and the upper limit by the
onset of saturation. Both are highly dependent of the TL
sensitivity of the samples concerned and on the level of
radioactivity.
Published results at present extend from flints burnt only
2000 years ago at the Alice Boer site in Brazil (Beltrao el
al. 1982) to flints burned about 250,000 years ago at the
Lower Palaeolithic site of Belvedere in The Netherlands
(Huxtable and Aitken 1986; Aitken et al. 1986).
As an illustration of the importance of the technique in
Palaeolithic studies, Figure 4 shows the results obtained at
two cave sites in Israel (Valladas el al. 1987; Valladas et
al. 1988); these are directly relevant to the question of
whether in south-west Asia anatomically modern humans ('proto-
Cro-Magnons') were well installed, c.100,000 years ago, long
before the arrival of the Neanderthals (Homo sapiens
neanderthalensis) or whether the former evolved from a
Neanderthal population c.40,000-50,000 years ago. At Kebara,
Unit XII contained the skeleton of an adult Neanderthal and at
Qafzeh, layers XVII-XXVIII contained a number of proto-Cro-
Magnon skeletons. The dating of the latter layers, to 92,000
136

KEBARA QAFZEH
Unit Layer
VI

XVII

VII
XVIII

VIII

XIX

IX

XXI

X
XXII
XI
XXIII

XII

50 100
Age (thousands of years)

Fig. 4: Burnt flint dates for two caves in Israel. A

Neanderthal skeleton was recently found in Unit XII of Kebara
Cave and 'Proto-Cro-Magnon' remains have been found at Qafzeh
throughout the layers shown. (Derived from Valladas et al.
1987, 1988).
 137

plus or minus 5,000 years ago, indicated that these early

modern humans were already present in the area during oxygen
isotope Stage 5; together with the Kebara dating of about
60,000 years these results give strong support to the prior
arrival of the modern humans. Electron spin resonance dating
of animal tooth enamel from the relevant layer of Qafzeh is in
agreement.

3.2.3 Volcanic products. Lava from the Chaine des Puys,

France, has been successfully dated using plagioclase feldspar
extracted from it; they suggest that the useful age range for
this mineral is 3000-30,000 years. Quartz is not present in
most lava but has been used for dating other volcanic
products; also, quartz pebbles trapped in lava have been
used. Dating of airborne volcanic ash samples in the age
range 450-13,000 years has been achieved using the glass
component. An indirect way of dating volcanic eruptions is by
means of the soil or rock over which the molten lava has
flowed and solidified; for soil, standing pottery techniques
can be used.

3.2.4 Metallurgical slag; glass. Although slag is of prime

importance in archaeometallurgy, successful dating has not yet
been achieved, the microdosimetry being extremely complex.
Glass from ancient windows and vessels has so far resisted
attempts at dating also, one difficulty being very low TL
sensitivity.

3.3 UNBURNT MATERIALS: CALCITE, SHELL, BONE AND TEETH

Of these, only the first (in stalagmitic form in palaeolithic

caves, i.e. speleothems) is suitable because for the others
decomposition occurs when the sample is heated for
measurement; the technique of a later chapter, ESR, is
applicable and for calcite too, with advantages over TL. For
either technique one critical question in respect of any
unheated material is whether at crystal formation the latent
signal was zero. For both techniques it is certainly low
enough to be unimportant in the age range of applicability;
for TL it is essential to interpose the correct colour filter
in front of the photomultiplier in order to reject light from
specks of limestone, carrying geological TL, which are
presumed to have been incorporated in the calcite during
formation.

The age range for dating calcite is roughly 5,000-500,000

years, the latter limit being imposed by signal instability.
138
A difficulty with old samples is interference by
recrystallisation when effectively the TL clock gets reset;
to some extent this can be recognised in visual inspection;
this effect also upsets the other techniques for dating
calcite - uranium series and ESR, though with the latter a
signal indicative of recrystallisation may sometimes be
apparent.
With either TL or ESR there is considerable difficulty in
making a reliable evaluation of the annual dose. This arises
from non-uniformity of the radioactivity within a cave. The
calcite is usually much weaker than the sediment present and
although dosimetry capsules may be left in drilled holes close
to the prospective samples it is likely that there has been
dose-rate variation during the past due to movement of
sediment and growth of further stalagmites. A secure
circumstance in this respect is when a fragment of calcite is
well buried in sediment and there is evidence that that has
been the case for the lifetime of the calcite. Another
advantage of this situation is that the annual dose is likely
to be dominated by the gamma component, hence making
irrelevant the possibility of zoning effects which are
observed in some calcite samples; if the annual dose is
predominantly internal, there is risk that zoning will cause
the apparent age to be erroneously too recent.
4. Concluding Remarks
The early prospects for archaeology in respect of pottery
dating are only now beginning to be realised, a number of
factors contributing to this delay. The complexities that
have gradually revealed themselves are severe, reliable dating
being both labour intensive and needful of close specialist
supervision; hence it is expensive, more so than a
radiocarbon date. With the advent of automated measurement
equipment and computerised data handling the situation is
changing - as evidenced by the output of Scandinavian
archaeological dates by the Nordic Laboratory for
Thermoluminescence Dating, based in Denmark. Another factor
has been the early tendency to think of TL as a cheap
alternative to radiocarbon; it is not cheap, as just noted,
nor is it an alternative - in general the precision attainable
being not so good. Now that it is seen as complementing
radiocarbon, in the sense of applicability to sites and
regions where suitable samples for radiocarbon are not
available and to periods in which radiocarbon accuracy becomes
poor because of timescale distortion, the technique will have
 139
increasing o p p o r t u n i t y t o d e m o n s t r a t e its c a p a b i l i t y . In
a p p l i c a t i o n t o testing t h e a u t h e n t i c i t y o f a r t ceramics t h e
impact h a s been powerful n o w for n e a r l y t w o decades and
t h e r m o l u m i n e s c e n c e is a commonplace w o r d i n r e l e v a n t museums
and a u c t i o n h o u s e s , as well as among d e a l e r s a n d private
collectors.

It is beyond t h e 50,000-year range o f r a d i o c a r b o n that

luminescence d a t i n g is m a k i n g its strongest archaeological
c o n t r i b u t i o n , b o t h t h r o u g h a p p l i c a t i o n t o u n b u r n t sediment and
t h r o u g h T L dating of stalagmitic c a l c i t e a n d b u r n t flint. A
n o t a b l e e x a m p l e o f t h e latter is t h e a p p l i c a t i o n referred to
in 3.2.2 - w h i c h established (with c o n f i r m a t i o n b y E S R ) that
a n a t o m i c a l l y m o d e r n humans w e r e installed i n s o u t h - w e s t Asia
some 100,000 y e a r s a g o t h e r e b y u p s e t t i n g the e s t a b l i s h e d idea
of e v o l u t i o n from Neanderthals s u b s t a n t i a l l y later o n . Burnt
flint h a s a far greater significance f o r m o d e r n man's
u n d e r s t a n d i n g o f ancient m a n than the latter suspected w h e n h e
a c c i d e n t a l l y fall into t h e f i r e !

References
A i t k e n , M.J. (1985) T h e r m o l u m i n e s c e n c e D a t i n g , A c a d e m i c P r e s s ,
and Florida

A i t k e n , M . J . (1990) Science-based D a t i n g i n A r c h a e o l o g y ,
Longman Archaeology Series, London and N e w York

A i t k e n , M . J . , H u x t a b l e , J. a n d D e b e n h a m , N . C . (1986)
T h e r m o l u m i n e s c e n c e dating i n t h e p a l a e o l i t h i c : b u r n e d flint,
stalagmitic calcite and sediment, Assoc. Fr. Etude Quat. Bull.
26, 7-14

Beltrao, M.C., Danon, J., Enriquez, C.R., Poupeau, G. and

Zuleta, E. (1982) Datations par thermoluminescence des silex
brules du site archeologique Alice Boer (Bresil), C.R. Acad.
Sci. Paris 295, 629-32

Boyle, R. 1694, Experiments and considerations upon colours

with observations on a diamond that shines in the dark,
published by Henry Herringham, London

Huxtable, J., Aitken, M.J. Hedges, J.W. and Renfrew, A.C.

(1976) Dating a settlement pattern by thermoluminescence:
the burnt mounds of Orkney, Archaeometry 18, 5-17
140
Huxtable, J. and Aitken, M.J. (1985) TL dating results for the
palaeolithic site Maastricht-Belevedere, Mededelingen Rikjks
Geologische Dienst 39, 41-44
Sanderson, D.C.W., Placido, F. and Tate, J.O. (1988) Scottish
vitrified forts: TL results from six study sites, Nuclear
Tracks and Radiation Measurements 14, 307-16
Stoneham, D. 1983, Porcelain dating, PACT, 9, 227-39
Strickertsson, K. , Placido, F. and Tate, J.O. (1988)
Thermoluminescence dating of Scottish vitrified forts, Nucl.
Tracks and Radiation Measurements 14, 317-20
Templer, R.H. 1986, The localized transition model of
anomalous fading, Radiation Protection Dosimetry, 1, 493-7
Valladas, H., Joron, J.L., Valladas, G., Arensburg, B., Bar-
Yosef, O., Belfer-Cohen, A., Goldberg, P., Laville, H.,
Meignen, L. and Rak, Y (1987) Thermoluminescence dates for the
Neanderthal burial site at Kebara in Israel, Nature 330, 159-
60
Valladas, H., Reyss, J.L., Joron, J.L., Valladas, G., Bar-
Yosef, 0. and Vandermeersch, B. (1988) Thermoluminescence
dating of Mousterian 'Proto-Cro-Magnon' remains from Israel
and the origin of modern man, Nature 331, 614-16
Visocekas, R., 1979, Miscellaneous aspects of artificial TL of
calcite: emission spectra, athermal detrapping and anomalous
fading, PACT, 3, 258-65
SEDIMENT AND OPTICAL DATING

M.J. AITKEN
Research Laboratory for Archaeology
Oxford University
6 Keble Road
Oxford 0X1 3QJ
U.K.

1. Introduction
This chapter follows on from the preceding one on dating by
thermoluminescence (TL) and it uses the terminology and basic
concepts developed there. It deals first with the dating of
unburnt sediment by TL, and secondly it gives an outline of
the use for this purpose of the optical technique, in which
optically-stimulated luminescence (OSL) is the dating signal.
A recent review of sediment dating is contained within an
article on luminescence dating in its application to
Quaternary geology by Berger (1988); a less specialist
account is included in Aitken (1990).
1.1 THE BASIS OF SEDIMENT DATING BY TL
In Figure 1 glow-curves are shown for windblown (aeolian)
sediment from a paleolithic site of NW Europe; curve (a) is
the natural thermoluminescence, curve (b) is the same except
that this portion had been put out in the February sunlight
for an hour, and in the case of curve (c) there had been 24 hr
illumination with a sunlight simulator. Besides illustrating
why thermoluminescence work has to be done in subdued red
light, these glow curves show the most likely basis for being
able to use thermoluminescence to obtain the deposition date
of unheated sediment; exposure to sunlight prior to
deposition causes 'bleaching' to near zero of previously
acquired thermoluminescence and when the sunlight is cut off
by later sediment being deposited on top the
thermoluminescence re-accumulates in the same way as in
pottery after firing.
The sediment illustrated was from a deposit of loess, the name
given to layers, sometimes several meters thick, of silt-sized
sediment (2-60 m) which extend from NW Europe across northern
141
H. Y. Goksu et al. (eds.). Scientific Dating Methods, 141-153.
© 1991 ECSC. EEC, EAEC. Brussels and Luxembourg. Printed in the Netherlands.
142

200 300 400

Temperature (°C)

Figure 1 - 'Bleaching' of TL due to exposure to light. Curve

(a) is the natural TL; curve (b) after exposure to sunlight
for 1 hour; curve (c) after exposure to simulated sunlight
for 2 4 hours

Electronics

luminescence

sample
green light
from laser

Figure 2 - Measurement of OSL for optical dating. The colour

filters give severe discrimination against the green laser
light and enable a rather weak blue-violet luminescence signal
from the sample to be detected by the photomultiplier
 143
Asia to China as well as occurring in the Americas and many
other parts of the world. According to the majority of
geologists it originates from the grinding action of glaciers
but in dry windy conditions it may have been carried up to
several hundred kilometers from its source. During this
transportation, perhaps high up in the atmosphere, there is
ample opportunity for thermoluminescence to be bleached quite
apart from the time it lay on the surface before being blown
by the wind or after deposition prior to being covered. The
involvement of glacial action suggests there may be
correlation with climate and for this reason its dating is of
considerable interest in Quaternary research; equally it is
important in the dating of paleolithic sites either when
remains of human occupation are found in the loess itself or
in establishing the chronology of a stratigraphic sequence.

Sunlight is not the only agent that has b e e n suggested for

erasure of previously-acquired thermoluminescence. Dating of
loess was initiated in the USSR around 1965 at the Kiev
Institute of Geology and in this work weathering and glacial
grinding are put forward as additional possibilities. However
it is currently taken for granted in nearly all laboratories
that the effect of sunlight is at any rate dominant.

Dating now extends to many other types of sediment, for

example, 'desert loess', sand d u n e s , ocean sediment, sediment
in lakes filled by melting glaciers, and even the dust
incorporated in the ice of a glacier itself. This explosion
of interest was triggered by work on ocean sediment in Canada
at Simon Fraser University in the late 1970s; this research
led to the realisation that solar resetting was the mechanism
that explained the observed increase w i t h depth of paleodose
in the ocean cores being studied and that it might be relevant
in many other situations. In hindsight, given the insistence
in thermoluminescence laboratories on the need for subdued red
light, it is surprising that this widespread extension of
thermoluminescence dating was so long delayed.

1.2 THE BASIS OF OPTICAL DATING

As will be discussed shortly, although the bleaching of TL is

substantial it is not always complete; this is particularly
the case for marine and lacustrine sediments on account of the
absorption of short wavelengths by water. The need for
assessment of the zero-age residual introduces uncertainty as
well as complication and this led Huntley et al (1985) to
pioneer the optical dating technique in which the luminescence
144
signal is obtained by the direct action of light (in evicting
electrons from traps) rather than by the action of heat. This
is the logical way to obtain the signal for dating unburnt
sediment since there is automatic selection of those traps
which are light-sensitive, i.e. easily set to zero by exposure
to daylight. The experimental arrangement commonly used
follows that of Huntley et al (1985) and is similar to that
indicated in Fig. 2; a critical feature is the colour filters
in front of the photomultiplier which must discriminate
against the green laser light used for excitation by many
orders of magnitude while allowing through the blue-violet
light which constitutes the luminescence signal. Subsequently
it has been shown that longer wavelengths can be used for
excitation, even infrared in the case of feldspars, and that
a high-power xenon arc lamp can be substituted for the laser.
Use of a longer wavelength makes it easier to separate the
wanted signal from the unwanted excitation light.

Suitable signals can be obtained from various minerals,

including quartz, feldspar and zircon. Exposure to sunlight
reduces the signal to a minute percentage of its initial value
in a matter of minutes rather than the hours that are required
in the case of the TL signal. Hence it is to be expected that
in most circumstances of sediment deposition there will be no
residual to worry about and that quite short pre-depositional
exposures will be acceptable. However, it seems that although
the signal level may be zero at deposition there is a tendency
for it to recuperate subsequently, this recuperation not being
due to exposure to radiation; the effect is not strong but in
some circumstances it may be the limiting factor in reaching
ages of less than 1000 years; otherwise the limitation is due
to the weakness of the signal. As regards the upper limit to
the age range the same considerations apply as for TL dating
of sediment.

Because of the rapidity of bleaching of the OSL signal

meticulous precautions against exposure to light have to be
taken in sampling and during mineral separation. Otherwise
procedures are somewhat similar to those of TL dating, though
a disadvantage of the technique is the need, following
artificial irradiation, to remove unstable components of the
signal; this is done by means of a 'pre-heat' before
measurement, e.g. 1 hour at 160 C.

In principle this technique can be used on burnt materials

too, though it has yet to be seen whether it is advantageous
in this respect. The elimination of the need to heat the
 145

sample to at least 400 C as required for TL suggests the

possibility of application to biogenic materials such as bone,
teeth and shell.

2. Evaluation of Paleodose using TL

Evaluation of paleodose is complicated by the need to allow

for the fact that the natural thermoluminescence is composed
of two components: the thermoluminescence acquired since
deposition and the zero-age thermoluminescence that the sample
had w h e n it was deposited. If this latter is substantial, as
is often the case, failure to make allowance for it will lead
to a thermoluminescence age that is much too old. Although
weathering and glacial grinding may play a part in resetting
the thermoluminescence, because of the difficulty of making
laboratory studies of those effects the methodology evolved is
based on the presumption that sunlight is the agent. From the
success achieved it seems that this is a satisfactory working
hypothesis.

2.1 ZERO-AGE THERMOLUMINESCENCE: THE UNBLEACHABLE RESIDUAL

For a sample exposed to the sun there is a certain probability

per incident photon that an electron will be evicted from its
trap and so the rate of eviction will be proportional both to
this probability and to the number of trapped electrons, as
well as to the intensity of the light. This simple model
leads to the expectation that the number of electrons
remaining trapped at time t will be exponentially dependent on
t, similar to the case of radioactive decay. However
experiment indicates that this is not the case (see Figure 3)
and that as the 'bleaching' proceeds the probability of
eviction decreases. Thus w e have the concept of the 'easy-
to-bleach' thermoluminescence being removed first followed in
turn by thermoluminescence which is harder and harder to
bleach until eventually an unbleachable residual component is
left.

The time required to remove all but this latter depends of

course on the intensity and spectrum of the bleaching
illumination, as well as the susceptibility to bleaching of
the minerals present in the sample. The practical question in
evaluating paleodose is whether, at deposition, the bleaching
has been sufficient to remove all but this residual component
and it is only the third method outlined below, the partial
bleach method, that satisfactorily deals with a sample that,
at deposition, had retained some of its bleachable
 200

c
O
u

CD
100
c

a
E

I J_
100 200 300 /.00 500
Bleaching time (min)

Figure 3 - Thermoluminescence remaining after bleaching for

various times. Data are for the level of natural TL (at a
glow-curve temperature of 280 C) of fine grains of loess from
the Palaeolithic site at Biache, France. Bleaching was by
means of a 300 W solar simulator set at half-power, giving an
irradiance that was approximately half that of natural
sunlight. The unbleached level, not shown, was about four
times the TL remaining after 5 minutes of bleaching (the
highest point shown).
 147

thermoluminescence. However the two methods described first

are simpler and are applicable where the presumed
circumstances of deposition were such as to ensure full
removal of the bleachable component; the more the
thermoluminescence is dominated by feldspar, the more is this
likely to be the case.

2.2 THE ADDITIVE DOSE METHOD

The additional dose method is basically the same procedure as

used for pottery except that instead of reading off the
equivalent dose from the intercept on the dose axis it is read
off from the intercept on a horizonal line the level of
thermoluminescence remaining after a long laboratory
bleaching. Although it can be established that the laboratory
bleaching is long enough for only the unbleachable component
to remain, there is the risk, as just discussed, that the
exposure to sunlight prior to deposition was not sufficient to
reach this level. A check of this is given by the plateau
test in which the paleodose is plotted against glow-curve
temperature; the degree of bleaching is dependent on glow-
curve temperature and if the bleachable component had not been
fully removed at deposition there will not be a plateau.

2.3 THE REGENERATION METHOD

Except for measurement of natural thermoluminescence all

portions are subjected to long bleaching and then artificial
irradiations (beta or gamma) are administered, thereby
regenerating the thermoluminescence growth characteristic; of
course a new portion must be used for each data point. The
paleodose is read off from a horizontal line drawn at the
level of the natural thermoluminescence. An advantage is that
if there is no alpha contribution to the thermoluminescence,
separate evaluation of any correction for non-linear growth is
unnecessary; if there is an alpha contribution then as in
other methods allowances need to be made for the fact that the
alpha growth characteristic is likely to reach sublinearity at
a higher dose level than the beta/gamma characteristic.

2.4 THE PARTIAL BLEACH METHOD

In this method the glow-curves of some portions are measured

after artificial irradiation as in the additive dose procedure
while for another set of portions a short bleach is
administered between irradiation and measurement, giving a
partially-bleached growth line. On the basis that the amount
148
of thermoluminescence removed by the bleach is a given
fraction of the bleachable thermoluminescence, the intercept
of the two lines indicates the equivalent dose.
Alternatively, this can be seen by regarding the difference
between the pair of points at each irradiation level as the
response to dose of the easily bleached component of the
thermoluminescence; this includes the difference for zero
laboratory dose, that is, the difference between (N) and (N +
Bleach). If these differences are plotted against dose then
the equivalent dose is given by the intercept on the
horizontal axis in the usual way.

It does not matter if the bleaching prior to deposition was

incomplete as long as it was more complete than that effected
by the short laboratory bleach. If it was less complete, then
the short laboratory bleach will be able to reach components
of the natural thermoluminescence that were acquired prior to
deposition thence causing the evaluated equivalent dose to be
overestimated. Indication as to whether the laboratory bleach
was too long can be obtained by recreating the bleached line
using different bleaching times; as long as the completeness
of the bleaching does not exceed that of the bleaching prior
to deposition, the same equivalent dose should be obtained
irrespective of bleaching time. If the laboratory bleaching
is too strong, an erroneously large equivalent dose will be
obtained.

Of the three methods this is the only one that accommodates

partial resetting. On the other hand, because it is a subtle
method dependent on the concept that some parts of the
thermoluminescence are more easily bleachable than others, it
is unlikely that it would be applicable to a partially reset
sample for which glacial grinding or weathering had been
dominant.

2.5 USE OF PHOTOTRANSFER

Phototransferred TL (PTTL) refers to the TL obtained from

shallow traps following exposure of the sample to a light
source. The exposure to light causes eviction of electrons
from deep traps and some of these are re-trapped in shallow
traps; being shallow these are initially empty in the natural
sample and in the case of an artificially-irradiated sample
they can be emptied by an appropriate pre-heat. Hence the TL
from the shallow traps is a measure of the electron population
in those types of deep trap that are light-sensitive. Thus in
respect of low residual this technique should have the same
 149
advantage as optical dating, though procedurally it is more
time consuming.

3. TL Dating of Sediment: Some Other Aspects

3.1 AGE RANGE

Uncertainty about the residual signal is the limitation at the
most recent end of the range; in round terms the limit can be
taken as 5000-10,000 years, less for feldspar than for quartz.
The furthest age that can be reached with quartz is limited by
the onset of saturation; as with pottery dating this depends
on the quartz concerned and on the annual dose, in round terms
the limit should be put at about 50,000 y e a r s , more if the
annual dose is low as pertains in quartz-rich sand-dunes for
instance. Otherwise the limitation is the stability of the
signal. There may be a limit of around 100,000 years for
fine-grain polymineral samples but substantial extension
beyond this may be possible if appropriate thermal pre-
treatment is used for coarse-grain alkali feldspar extension
to around 500,000 years seems to be feasible.

Sampling
Strict precautions against exposure to light need to be taken
during sampling. If the sediment is consolidated the sample
can be obtained as a lump and then in the subdued lighting of
the laboratory the exposed surfaces can be scraped away.
Alternatively, the sample can be obtained by forcing a
cylinder into an exposed section of sediment, having first
scraped off the surface layer and then kept light on it to a
minimum while the cylinder is being put in position.

In sediment dating sample and soil are one and the same, and
if on-site radioactivity measurements are made with a gamma
spectrometer these can be used to determine the alpha and beta
components of the annual dose in addition to the gamma
component. However, if radon escape is occurring this is not
a reliable procedure and laboratory measurements in addition
are advisable. Most other aspects - technique of measurement
(fine-grain, inclusion, etc.) and wetness correction - are as
for pottery.

In sampling for optical dating, because the traps utilised are

so much more light-sensitive precautions against bleaching
during collection and sample preparation have to be ultra
stringent.
150

4. Optical Dating

4.1 PRE-HEAT PROCEDURES

Whereas in TL the light resulting from electrons stored
(following artificial irradiation) in shallow traps is emitted
in the early part of the glow-curve, below 300 C, with OSL
there is no such intrinsic separation of the 'unstable' signal
away from the wanted stable signal from deep traps. Instead
it is necessary to administer a 'pre-heat' before measurement
is made; if this is too mild then some unstable signal will
remain; if too strong then there will be some reduction of
the stable signal. In practice the severity of pre-heat is
chosen so that there is some small reduction of the latter;
by applying the same pre-heat to the natural samples the
(natural/artificial) ratio is valid as far as stable signal is
concerned. Considerations with respect to pre-heat are
simpler for quartz than for feldspar or polymineral samples.

4.1.1 Quartz. With this mineral there is the fortunate

circumstance that the OSL signal is dominated by light
associated with ejection from the traps responsible for the
325 C peak in the TL glow-curve. This is certainly the case
when green light (the 514 ran line from an argon ion laser) is
used for stimulation and even if a shorter wavelength was used
there is likely to be the same domination because irrespective
of wavelength these traps are the most easily bleachable.
Thus TL measurements can be used to establish a pre-heat that
slightly attenuates the 325 C peak and once established it can
be used for all quartz samples. The consequent OSL signal
then has the same stability as this 325 C peak - which has an
electron storage lifetime of upwards of 10 millions years.
One convenient pre-heat is 5 minutes at 220 C; another is 8
hours at 160 C.

The statement above that the traps associated with the 325 C
peak are the most easily bleachable needs further comment. It
might be expected that shallow traps would be more easily
bleachable than deep ones; this is emphatically not the case.
Likewise there does not seem to be any correlation between
stability of OSL signal and wavelength of stimulating light.

Besides TL evidence with regard to adequacy of pre-heat,

direct OSL evidence can also be obtained. The EDs obtained
using different severities of pre-heat are plotted - either
versus duration for a fixed temperature or versus temperature
for a fixed duration; for all pre-heats of adequate severity
 151
the EDs will be the same, thereby giving a plateau in the plot
of ED versus duration or temperature. For pre-heats of
inadequate severity the EDs will be lower than the plateau
value because of unstable components in the artificial OSL.
4.1.2 Feldspar, zircon and polymineral finegrains. Whereas
optical dating using quartz is now well-established,
utilization of these minerals is still in the investigatory
phase. Unlike quartz there is no dominant contribution from
any single trap type, the whole TL glowcurve showing a
decrease on exposure to light - as illustrated in Fig.l.
Hence there is not the same simplicity in establishing what
degree of severity constitutes an adequate pre-heat. At
present it is usual practice to obtain, for each sediment
dated, EDs for several degrees of severity; in general it
seems that 1 hour at 160 C is usually sufficient. Of course
if quartz is present in the polymineral grains then this is
inadequate; however although a sediment may be rich in quartz
its OSL (and TL) is likely to be dominated by feldspar because
by comparison with most varieties of that mineral, quartz is
rather dim.
4.2 INFORMATION FROM SHAPE OF SHINE-DOWN CURVE
Although the 'shine-curve' does not give indication of
stability its shape is nevertheless of interest. Initially,
for a power at the sample of about 5 mV/cm , it decreases by
around 5%/sec whether quartz or feldspar, but after about 10
seconds the decrease is slightly slower, i.e. it does not
correspond to the single exponential that would be expected if
the OSL was due to a trap type of unique bleachability
exhibiting first-order kinetics. For quartz, non-first-order
kinetics due to retrapping is part of the explanation; there
is also contribution from traps of lower bleachability. For
feldspar or polymineral fine-grains the effect of a range of
trap bleachabilities is likely to dominate the shape of the
shine-curve though retrapping effects may also be present.
4.2.1 The 'shine plateau'. By calculating the ED for each
point of the shine-curve a quantitative comparison of shapes
can be obtained. If the shapes obtained from artificially-
dosed and pre-heated portions are the same as from the
'natural' portion, then the ED will be independent of shine
time, i.e. there is a plateau. If the pre-heat is inadequate
but leaves electrons in trap types that are empty in the
'natural' then the plateau is likely to be upset. Also, in
the case of polymineral fine grains, if there has been
152
inadvertent exposure to light during collection or sample
preparation, then there will be a relatively lower
contribution in the 'natural' (compared to the 'artificials')
from easy-to-bleach traps and the ED obtained will be at
shorter shine times than at longer ones. The same effect will
occur if there has been inadequate bleaching during deposition
in antiquity - because the 'relict' OSL will contain an
excessive contribution from hard-to-bleach traps.

Thus for a variety of reasons a good shine plateau is a

necessary condition for accepting a result as reliable.

4.3 USE OF INFRARED DIODES

In utilization of infrared diodes (wavelength 880nm) for

stimulation it has been found that for polymineral fine grains
the same ED is obtained as when using stimulation by green
light. On the other hand no signal is obtained from quartz or
zircon using 880 nm. Hence use of the infrared diodes allows
a feldspar-only ED to be obtained without the need for mineral
separation; subsequently after elimination of the feldspar
signal with infrared it is possible to obtain a quartz-only ED
using green light. Another use of the infrared diodes is in
checking quartz separates for freedom from feldspar.

5. Summing-Up

Where there is assurance of adequacy of bleaching during

sediment deposition in antiquity TL is a satisfactory
technique to use, and indeed is widely used and well-tried.
TL has the advantage over OSL that in the glow-curve 'stable'
light is separated out from 'unstable' light.

Of course the demand of 'adequacy' is more severe in young

samples than in old, and for young samples OSL is likely to
become the preferred technique, likewise for sediments
deposited in circumstances where exposure to light was rather
brief (say, less than 10 hours) or where due to the deposition
being under water there was serious attenuation of that part
of the daylight spectrum which is most effective in bleaching
- the short wavelength end from blue to ultraviolet.
 153
References
Aitken, M.J. (1990) Science-Based Dating in Archaeology,
Longman Archaeology Series, London and New York
Berger, G.W. (1988) Dating Quaternary events by Luminescence.
Geological Society of America Special Paper No. 227
Huntley, D.J., Godfrey-Smith, D.I. and Thewalt, M.L.W. (1985).
Optical dating of sediments, Nature 313, 105-107
 PRE-DOSE DATING
I.K. BAILIFF
Luminescence Dating Laboratory,
Department of Archaeology.
University of Durham,
South Road, Durham Dili 3LE, England.

1. Introduction

The capability of the thermoluminescence (TL) method to provide absolute dates for pottery and
other fired materials has made available an important dating tool in archaeology. The specific
association between the TL date and the date of firing pottery, combined with the value of pottery
artefacts as chronological markers, offer significant advantages over other dating techniques in
certain cultural or chronological periods. The range of the pre-dose technique - roughly 2000
years - limits its archaeological application compared with other dating methods (and
luminescence techniques), but it has high utility for certain types of dating problem. The errors
associated with age determinations, while within the general limits associated with the TL
method (ie +5 - +10% of the age for single dates), are attractive in calendrical terms (±50 in
1000 years at best) within the range. In many regions in Europe where chronologies are often
presumed to be well established, there are suprisingly persistent problems of forming
chronological frameworks for coarse-ware pottery. In the Medieval period, for example, the
problem is exacerbated by the lack of excavated kiln sites and often sparse documentary evidence
to provide chronological markers.
The pre-dose technique is one of several TL techniques (Aitken, this volume) available to
determine the dose accrued since the xeroing event (eg firing)which is required to evaluate the
TL age equation. In its simplest form, this equation is:
^ _ Accrued dose
Age
~ Dose-rate

where the dose rate is the annual dose delivered to the TL minerals arising from the decay of
naturally occurring radioisotopes (uranium, thorium and potassium) within the sample and the
surrounding burial medium.
The aim of this paper is to bring together the most recent interpretations of the application of
pre-dose technique to dating natural samples and to put them into the context of experimental
procedures which may be used in a dating laboratory. Before embarking upon that task, there are
other applications of the technique which should be mentioned here. At an early stage the
potential for the technique to offer a method of accident dosimetry was realised (Fleming and
Thompson, 1970) and has since been successfully developed for accident dosimetry in populated
areas based on the use of bricks and other ceramics for the measurement of fall-out from the
Nevada Test Site (Haskell et al, 1981, 1985, 1988; Bailiff and Haskell, 1984) and bomb dose at
Hiroshima (Haskell ct al, 1984; Maruyama et al, 1987). This work is not only making a notable
contribution to environmental dosimetry but is providing an important stimulus for pre-dose
research relevant to dating studies (eg low-dose behaviour). The use of the pre-dose effect for
the determination of firing temepcrature has also been suggested (Sunta and David, 1982;
Watson and Aitken , 1985; Goksu et al, 1989).
155
H. Y. Goksu et al. (eds.), Scientific Dating Methods, 155-173.
© 1991 ECSC, EEC. EAEC. Brussels and Luxembourg. Printed in the Netherlands.
156

2. Observing the pre-dose effect

Quartz grains of about 0.1 mm diameter within coarse ware pottery will typically absorb a dose
of ~ 2 Gy per millennium. The administration of a dose of 2 Gy would be expected to give rise to
very intense TL emission from a phosphor used for personnel dosimetry such as lithium fluoride.
However, the TL emitted from an aliquot (eg 2 mg) of quartz grains extracted from a
millennium-old sherd of such pottery, is likely to be very weak and, above 300 °C, barely
detectable above the supressed thermal radiation from the heater plate. This is one reason why
the high temperature TL emission from quartz is often not suitable for dating relatively young
archaeological samples. However, if following the first glow curve measurement, a dose of
ionizing radiation (eg of several Gy) is administered to the above aliquot at room temperature,
the glow curve subsequently obtained (without delay) will reveal additional strong TL peaks at
-100 and -230 °C, in addition to weak emissions at higher temperatures. Repetition of this
procedure will show that the intensity of the 100 and 230 °C TL peaks increases with each cycle
performed and also that the emission is sufficiently bright to enable a well resolved 110 °C TL
peak using much lower doses (-10 mGy). While the 110 CC peak would not be expected to be
used for dosimetry measurements because its mcanlife at ambient temperatures is only several
hours (Fleming, 1979), the substantial change in sensitivity which occurs with dose and heating
to elevated temperatures is the key to a means of comparatively sensitive dosimetry which may
be used over recent archaeological limcscalcs. The effect of sensitization observed is referred to
as the pre-dose effect in quartz and was first reported by Fleming (1969) who later developed the
pre-dose technique (Fleming, 1973). During the intervening period a phcnomcnological model
for the effect was proposed after a detailed study by Zimmerman (1971b) which has since
provided a framework within which much of the discussion concerning empirical behaviour has
been conducted.

3. The Pre-dose technique

3.1 MEASUREMENT OF SENSITIZATION

The basis of the technique is the measurement of the change in sensitivity of the 110 °CTL peak
with previous radiation exposure followed by heating to ca 500 °C and the experimental steps
required to measure changes in sensitivity are illustrated in figure 3.1 (see Appendix for further
details of sample and measurement conditions). The change in the sensitivity due to activation of
the unknown naturally accrued dose (usually referred to as the accrued dose, AD) is given by
ASN=S N -S Q

Similarly for the thermal activation of the calibrating dose, (5,

ASIX+B= s N + B - s N
Consequently an estimate for the AD is obtained from the expression,

AD={B.-^L-BTD1 3.1

where BID = s u m of activated test doses.

 157

o
u
o
I-
o

75 100 125 50
TEMPERATURE CO

Figure 3.1 Sensitization of 110 °C TL peak of quartz

An aliquot which has previously received an unknown radiation dose by natural exposure is used
for the following measurements.
Step 1. The sensitivity of the 110 °C TL peak is measured by administration of a small test
dose (-10 mGy) to an aliquot held at a controlled storage temperature (eg 20 °C);
immediately afterwards the aliquot is rapidly heated (eg 10 °/s) to -150 °C and then
allowed to cool (usually taking less than 1 minute); during heating the TL emission is
recorded.
During the first sensitivity measurement, the initial sensitivity, S 0 , is recorded. The
height of the peak (or area under the glow curve) is denoted S x , where the subscript
denotes the history of thermally activated dose for the aliquot (following previous
convention: o, N, N+6, N+2J3, etc).
Step 2. To activate the sensitization effect, the aliquot is rapidly heated (10 7s) to a selected
temperature, T, and then allowed to cool to the storage temperature. This is referred to
as thermal activation. T = 500 °C in this example.
Step 3. Measurement of the sensitivity, SN', A superscript can be used to denote the maximum
temperature of activation T; Sx.
Step 4. A laboratory calibrating dose, B, is administered and the aliquot heated to •150°Cto
remove (and record if required) the 110 °C TL peak.
Step 5. Measurement of the radiation quenched sensitivity, ST..
Step 6. Thermal activation to selected temperature T.
Step 7. Measurement of the sensitivity, SN+B-

The experimental conditions (eg optical filters, heating rate etc) for the measurement of
sensitivity should remain unaltered throughout an experiment.
158

In deriving expression 3.1 the following assumptions have been made:

a) The maximum temperature of thermal activation is appropriate.
b) The sensitization is linear with 'prc-dosc'.
c) The initial sensitivity measured in the laboratory is the correct baseline for measurement
of subsequent sensitivity changes.
d) The sensitivity change per unit dose the natural dose and the calibrating dose arc the
same.
Somewhat to the inconvenience to the experimentalist, experience has shown that one or more of
the above assumptions usually need careful examination. Although this was recognized by
Fleming in his primary work on the technique, experimental data gathered from a wider range of
types of sample and the identification of further aspects of the prc-dosc mechanism have revealed
the need to establish the detailed characteristics of each sample. Much of the discussion of such
characteristics is couched in the terms of Zimmerman's model and before embarking upon an
examination of the procedures in current use it will be helpful to present the basic elements of the
model.

3.2 ROLE OF THE PRE-DOSE MODEL

One of the important findings of Zimmerman's research was establishing that the change in
sensitivity of the 110 °C TL peak was the result of an enhancement in luminescence
recombination probability rather than a change in electron trapping probability. The model
devised to explain this effect is illustrated with the aid of a simplified energy band diagram in
figure 3.2. Under the action of ionizing radiation (eg natural or laboratory), free electrons and
holes are trapped at the four trapping sites; L and R compete for holes and, in freshly fired
quartz, the probability of capture at L is much lower than at R. Immediately following the
administration of a dose, B, rapid thermal stimulation (eg 10 °/s) will cause electrons in T to be
liberated into the conduction band and recombine at activated L centres giving rise to blue/uv
emission associated with the 110 °C TL peak - for freshly fired quartz the TL sensitivity is at a
'low' level, reflecting a relatively small population of activated L centres. At higher temperatures
(eg >300 °C) electrons in the valence band are thermally excited into the R traps, providing free
holes which are captured at L sites and increase the population of activated luminescencent
centres; between 500 and 600 °C the transfer process is complete. The TL emission measured
following a further radiation dose of the same size is greater because of the higher population of
activated L centres. The change in the TL emission is a function of the net increase in the
population of activated L centres which in turn is related to the hole population in R traps. Thus
the TL sensitivity will be proportional to dose where the filling of R traps and the activation of L
centres is linear. Further cycles of dose/heating cause continued increase in the population of
activated luminescence centres since the process of sensitization is cumulative.
There have been several clarifications of pre-dose behaviour based on experimental data and
theoretical considerations. Chen (1979) pointed out that a competing electon trap during heating
is needed in the model since the TL emission is proportional to both the sensitization and the
dose; whereas T 2 was originally required for charge balance it is likely to have a role of the type
suggested by Chen and further developed in subsequent work (Chen ct al, 1988). Aitkcn and
Murray (1976) made the observation that a reduction in L centre population following the
measurement of the 100 °C TL peak may, if the radiation dose is sufficiently large, reduce the
population of activated L centres by a significant amount. The effect, although noted in earlier
 159

work but not taken into account, is referred to as radiation quenching and has important
implications for the use of the technique.

CONDUCTION BAND

Figure 3.2 The Pre-dose Model

The model requires two hole (L and R) and two electron (T\ and T2) traps; Ti and L are
associated with the 110 °C TL peak; T 2 is sufficiently deep to be a 'thermally disconnected' trap.
In order to participate as a luminescence centre L needs to be activated by hole capture. R
participates as a non-luminescence reservoir for holes.
Details of the placement of some of these trapping levels in the forbidden gap are available. The
thermal depth of Ti has been measured for a number of types of quartz and is ~ 1 eV (see
Aitkcn, 1985, p272). The emission spectrum of the 110 °C TL peak has a dominant band with
peak wavelength 360 - 380 nm (Zimmerman, 1971b; Bailiff, 1979; Akber and Prescott, 1988)
which places L at a depth of -3.3 - 3.4 eV; other bands not associated with sensitization may also
be present (sec text). Zimmerman was able to show that by the application of uv radiation (-240
nm; 5.2 eV) the prc-dose effect could be reversed with high efficiency, which was interpreted as
a transfer holes from L to R. The sum of these two values (-8.6 eV) is not inconsistent with
recent evaluations of the band gap of quartz. Evaluations (albeit few; see text) of the activation
energy of hole transfer place R at 1.3 - 1.6 eV above the valence band and indicate more than
one level. These levels may vary according to sample and thermal treatments; for example, David
(1981) reports considerably lower values for pink quartz. The depth of T2 has yet to be
established.
Significant progress has been made in the identification of participating defects and there is good
evidence to link Ti and L with (GCO4)" and (H3O4) ° centres respectively and the transfer of
charge between R and L may be effected by the movement of hydrogen (Yang and McKcevcr,
1988; Yang and McKcevcr, 1990).
160

>-
>

4 6
CUMULATIVE DOSE

Figure 3.3 Sensitization and Radiation Quenching

Changes in sensitivity as a result of successsive dose/ activation cycles using a single aliquot and
a fixed dose. The arrows indicate the effect of radiation quenching; the upper and lower open
circles represent the activated sensitivity values and the radiation quenched sensitivity values
respectively.

3.3 THE EFFECT OF RADIATION QUENCHING

If the procedure outlined in fig. 3.1 is continued so that a series of S values are obtained
following repeated dose/activation cycles, the changes of sensitivity typical of an archaeological
sample are shown in figure 3.3. Clearly, because of the effects of quenching, the growth of
sensitivity with dose cannot be represented by a single function. If quenching is not taken into
account, the growth of sensitivity with dose is sub-linear (upper open circles) whereas the change
in sensitivity is similar for a number of activations. Aitken and Murray (1976; also Aitken, 1978)
sought to reconstruct the growth curve in the absence of radiation quenching; previously the
quenched values of S had not been determined. The method proposed achieves this correction by
adding a cumulative quenching correction, Qi; to the sensitivity value after the ith activation
cycle, Sj, where
Q = Z Qi ; qL = S; - Stx (i; o, N, N+B, N+2B, etc)
i
In making these corrections it must be assumed that the growth of activated L centres is linear;
however, this may belie the true nature of the form of such growth. Two interpretations of the
action of radiation quenching within the framework of the model are that it reflects a reduction in
population of either a) L centres (which can be activated) or b) activated L centres. While the
former is more likely to arise from thermal deactivation, experimental evidence gathered so far
tends to support the latter since linearity in sensitization (AS) is frequently found where the
 161

degree of radiation quenching measured is significant (eg 10-50% of SN). Assuming radiation
quenching depletes the population of activated L centres we will assume that the growth in their
number, as reflected in the sensitivity, can be illustrated graphically using a simple development
of fig 3.3 where a saturating exponential of the form
S = S„(l-e-D/B) 3.2
(where, B = constant; S„= saturation value of S in the absence of quenching) is used to
describe the growth of activated L centres with dose (after Chen,1978).

a)
Figure 3.4 The effect of quenching

a) Modelling sensitivity change. ■ 1 ^ p ->l

b) Growth characteristics. °y<T©

Growth characteristics calculated
using equation 3.3 (B=17.3; S„ = 65) Or
where no quenching occurs (1). The z
UJ
predicted growth characteristic using in . Q6-
quenching data obtained with an
archaeological sample is shown by / i<­ P ->i
curve 2 (quench = 40% SN). Curve 3
represents curve 2 corrected for /
quenching using Aitkcn and Murray's
procedure. DOSE

b)

100

>-
1­ 80
>
1—
ir> 60
zLU
in
40

20

5 10
CUMULATIVE D OSE
162
By choosing a point (1) on the curve defined by eqn 3.2 (see Tig. 3.4a) to represent SN at dose
value 1. After administration of a laboratory dose G, the action of radiation quenching results (2)
in the reduced sensitivity value SN, where the corresponding value of the abscissa is given by,

Dq = -Bln(l-S^/S„)

After thermal activation, the increase (from (2) to (3)) in the population of activated L centres, as
monitored ly measurement of the sensitivity, is detrmined by :

3
N+B-
S„(l-e-(Dq+6)/B)

and the abscissa value plotted (4) is 2B dose units following the normal experimental procedure.
Repeated use of this equation generates a set of sensitivity values, as measured experimentally.
The sensitization is given by:

AS = S„ (1 - S7S„) (1 - e -B/B) 3.3

In using the above expression to describe the change in S as a function of dose, growth curves
(curve 2, fig. 3.4b) may be derived using selected degrees of radiation quenching (NB a function
of dose). The general effect of radiation quenching is to reduce the asymptotic value of S
approached after a series of dose/activation cycles. A further factor can be introduced in
equation 3.3 to account the effects of non linear filling of R. Curve (3) obtained when curve (2)
is corrected for quenching using Aitkcn and Murray's method illustrates the problem which arises
when the filling of L centres is sub-linear. For a series of measured S values - as shown in fig. 3.3
for example - the parameter B is expected to be the same and this offers a means of constructing
the curve which describes the filling of L centres with dose (for a fixed increment B). Following
Chen's graphical technique, an estimate for B may be obtained by using an interative procedure
where different values are selected for S„.
To simplify the task of analysis and to avoid the potential masking effects of correcting for
quenching following Aitkcn and Murray's procedure, the analysis is currently performed in terms
of sensitivity change in each activation cycle, as described in the following sections.

3.4 DIAGNOSTIC APPROACH TO TESTING

Dealing with the complexities of prc-dose behaviour is a task which often appears daunting to
those unfamiliar with the technique. Although the use of the technique requires considerable
experimental effort, an approach incorporating diagnostic elements has evolved which aims to
simplify the evaluation of accrued dose and detect at an early stage samples which have
unreliable properties.
Assessment and evaluation comprise the following stages:
Stage 1. Measurement of the thermal activation characteristic (TAC)
Stage 2. Investigation of the initial sensitivity
Stage 3. Characterization of the change in sensitivity with laboratory dose.
 163

3.5 CHARACTERISTICS OF THERMAL ACTIVATION

The testing of a large body of archaeological ceramics and modem bricks (covering a wide range
of dose acquisition and thermal treatments used in manufacture) has revealed the importance of
establishing the characteristics of each sample. Strong dependence of sensitivity change with
activation temperature in the region of maximum sensitization and changes in the characteristics
of activation on first heating have been observed which require careful choice of thermal
activation procedure. The thermal activation characteristic (TAC) is obtained by measuring the
sensitivity as a function of activation temperature (from ca 200 °C to 500 -700 °C at suitable
intervals, eg 50 °C). TAC measurements can be performed in two ways:
a) Using a single aliquot, the sensitivity is measured after each thermal activation to
selected temperatures and thus the aliquot undergoes multiple thermal activations.
b) As a) except that a new aliquot is used for each sensitivity measurement and the results
arc normalised by S0. Each aliquot is thus thermally activated only once.
A qualitative assessment of the behaviour of a sample is usually obtained from two types of TAC
measured using procedure a) with different aliquots (requiring considerably less experimental
effort):
#1: Activation [0 -> N] of the naturally accrued dose, followed by activation [Nl -» N+B]
of an administered laboratory dose of size B, estimated to correspond to the accrued
dose.
#2: Activation [0 -> (N+B)] of the natural plus additional laboratory dose B, followed by
activation [(N+B)i -> (N+B)+B] of an administered laboratory dose B, of size estimated
to correspond to the accrued plus additional dose.
The term additive dose is used to indicate that a dose was administered before the first
activation (#2); where two or more thermal activations are performed with the same aliquot (#1
and #2) the term multiple activation is used to describe the procedure.
The TACs are examined to establish:
1. The temperatures at which onset of sensitization and maximum sensitization occur.
2. The onset of thermal deactivation beyond ca 550 °C.
3. The level of initial sensitivity.
4. The sensitization (AS) obtained after activation of the accrued and laboratory doses.
Examples of TACs obtained using aliquot #1 are shown in fig. 3.5. For a well fired ceramic the
onset of sensitization occurs above ca 300 °C and maximum sensitization is usually obtained
between 500 and 600 °C; for this sample there is no evidence of the effects of significant thermal
deactivation following activation to high temperatures. The effects of radiation quenching can be
seen by a substantial reduction in sensitivity after administration of the dose, B. The initial
sensitivity, S0, for an 'ideal' sample is expected to be several percent of SN; in fig. 3.2, SQ/SN is
roughly 20% and further investigation would be required (discussed below) to establish whether
this represents the correct sensitivity baseline.
Presentation of the TAC data in terms of relative sensitivity vs temperature (fig. 3.6) provides a
means of detecting of changes in the activation characteristic. The assumptions of the originally
devised technique require that the TACs are of similar shape, but it is not uncommon to
encounter alterations following first activation. At an empirical level the choice of activation
procedure will be affected by the existence of peaks in the TAC (due to the action of thermal
dcacalivation). The TACs arc often sharply peaked for high-fired materials because they require
164

higher temperatures to achieve maximum sensitization (see Fleming and Thompson, 1970;
Bailiff and Haskell, 1984). In terms of the model a shift in the onset of sensitization to lower
temperatures indicates the introduction of R traps closer to the valence band after thermal
activation. This could be due to:
a) ambient activation of the accrued dose
b) redistribution of the same quantity of trapped charge within the R traps
c) an increase in the population of R traps.
Where ambient activation has not occurred the TACs [0 -> N] and [0 -»(N+6)] are expected to
be similar, in fig. 3.6 this condition is met indicating that the TAC alteration between first and second
activation cycles is not due to ambient activation. The possibility of whether either b) or c) can be
identified is discussed in section 3.7.
As a precursor to more detailed measurements, estimates for the accrued dose may be obtained
using expression 3.1 based on the results from aliquot #1 and using the following expression
with the additive dose results from aliquot #2 (the two evaluations may not agree, as discussed
below).
AS(N+e)
(AD +6) = <R: •ftID 3.4
AS (N+B)+B

N-D

> ■

j-
>

cr>
LU
to

50 150 250 350 450 550

TEMPERATURE CO

Figure 3.5
TACs obtained with one aliquot. The sensitivity, S x , is measured after rapid heating to
temperature T (as indicated) and cooled to room temperature. The temperature increments
selected may differ according to the characteristics of the sample, but should be similar where
TACs arc to be compared. Activation of the naturally accrued dose changes the sensitivity from
S o to S N (TAC [0-» N]), and activation of the administered laboratory dose 6 changes the
sensitivity from S|\ to SN+g (TAC [N4. -» N+B]). Data from tests on quartz extracted from late
Iron Age pottery.
 165

>-
1-

co

Q
LU
CO
_l

<
ex
o

0.0 i i i IUI | rT | i i | i i | i i

50 150 250 350 450 550 650

TEMPERATURE C O

Figure 3.6
Normalised TACs: the sensitivity is expressed as a fraction of the maximum sensitivity change
obtained during the TAC measurement. A change in TAC shape is revealed between the thermal
activation of the first dose (1), followed by activation of an administered laboratory 6 dose (2).
Similar alterations were obtained between first ([0 -> N] and [0 -»(N+B)]) and second ([NX -»
N+B] and [(N+B)± -> (N+B)+B]) TACs using separate aliquots. Data from tests with quartz
extracted from medieval pottery.

3.6 THE INITIAL SENSITIVITY

Based on studies of fired quartz (eg Fleming and Thompson, 1970), the value of S0 is expected to
decrease to a small but finite value with increasing firing temperature. Although S0 is usually
expressed as a fraction of SN, the dose equivalence of S0 is a more useful parameter for
comparisons between samples. The dose equivalent value of S0, denoted AD0 , may range widely
in well fired pottery; for example of 30 samples extracted from British medieval pottery
manufactured locally, the majority of AD0 values were less than several hundred mGy, but in a
few cases, in excess of 1 Gy. Where the values of AD0 are only a small fraction of the AD, any
uncertainty in the determination of S0 will not have a significant effect of the calculation of age;
in such cases it is assumed that S0 has remained at the same level since firing during burial.
From the model, holes may be transferred from L to R at ambient temperatures if the they are
located in R traps sufficiently close to the valence band, as reflected in the TAC. While
determinations of the activation energies are sparse, depths in the range 1.3 - 1.6 eV were
obtained by Fleming (1979) which, using a range of possible values of the frequency factor, give
mean lifetimes at ambient temperatures of between -150 years to >107 years assuming
monomolccular kinetics. The accurate determination of R trap depth clearly needs more detailed
166

study. However, holes lost from R traps due to ambient activation are expected to be trapped at L
centres, increasing the initial sensitivity measured in the laboratory. The experimental evidence
gathered so far from archaeological samples indicates that there is no systematic increase in
initial sensitivity with age of sample within the range of the technique. There are a number of
empirical tests which may be applied to test whether ambient activation has occurred. The results
of such tests rely on the assumption that the L centres once activated by hole transfer remain
unaltered during the timescales under consideration unless the sample is subject to treatments at
elevated temperatures (eg by secondary burning due to a fire). Before such tests arc applied there
are potential contributors to the emission recorded in the measurement of S0 which should be
accounted for if present. These include:
a) TL emission from other minerals.
b) Spurious luminescence (eg from the surface underlying the measurement aliquot and
grain fastening agents such as silicone oil).
Minerals other than quartz are known to emit TL within the region of emission of the 110 °C TL
peak and also to exhibit sensitization (Bailiff, 1987). For granular samples (eg 90 - 150 u.m),
belter precision can be obtained by removing feldspar components, but for slices (eg in the case
of porcelain) mineral separation cannot be applied. Evidence gathered so far in this laboratory
suggests that the spectral emissions from quartz and feldspar are sufficiently similar to prevent
optical discrimination with absorption filters; consequently the senstivitics measured will reflect
the combined properties of the mineral fractions of the sample,.
If S0 is a small fraction of SN, measurements to determine the AD can proceed; otherwise it is
prudent to determine the extent of any uncertainty in the level of S 0 .

3.6.1 Further Tests for High S0 samples Part of the experimental evidence used to support
Zimmerman's model for the pre-dose effect was the reduction of sensitivity by irradiation with
UV (~ 240 nm) and subsequent recovery without substantial loss by thermal activation. This was
referred to as UV reversal and was interpreted as the transfer of holes from L centres to R traps
initiated by the photo-excitation of electrons from the valence band into the L centres.
Consequently UV irradiation provides the basis for distinguishing contributions to the measured
sensitivity which are not associated with the pre-dose mechanism.

Procedure: UV reversal.
1. Measure S (usually S0)
2. Irradiate with uv (-240 nm) for 15 min.
3. Heat sample to -150 °C to remove phototransfcrrcd TL (see eg Aitkcn, 1985)
4. Measure sensitivity, S'"
5. Repeat steps 2-4 until no further reduction obtained
Notes.
240 nm radiation may be obtained from a medium pressure Hg lamp. The required irradiation
times are nominal and will vary according to strength of the lamp and the properties of the
sample, in particular the opacity of the grain surfaces.
The residual component of the initial sensitivity, 5^, may not be negligible and in such cases it
has been found (Bailiff, 1979) that the emission spectrum is slightly altered. For two
archaeological samples tested, the peak wavelength of the emission shifted to shorter
wavelengths (< 340 ±15 nm) and for a sample of annealed geological a-quartz there was a bias
 167
towards longer wavelengths. Although little improvement in discrimination against emissions
not connected with the pre-dose effect was obtained using commercially available colour filters,
the spectral data support the use of S^" as the sensitivity baseline. Establishing the cause of the
residual pre-dose sensitivity, (S£" - S^, is a more complex problem to unravel. Two possible
causes include: a)the residual represents the sensitivity that would have been measured after
firing and b) the residual is the result of ambient activation. In principle, the former can be
investigated by testing the resetting characteristics of the sample after refiring.
Based on simple considerations of proportional activation, it can be shown that for a given (and
stable) form of TAC partial activation of the accrued dose will cause a change in the position and
slope of the TAC [0 -> N] compared with the TAC [NJ. -> N+B]. A procedure for calculating the
degree of activation based on changes in the TAC has been proposed by Sutton and Kommeir
(1985). For this type of analysis to be valid at least two R trap levels are required since, for a
single R trap where the hole transfer process can be described by monomolecular kinetics, the
forms of the (normalised) TACs are expected to be similar. As discussed above, the currently
preferred procedure is to compare the TACs [0 -> N] and the additive dose TAC [0 -> (N+B)]
since any changes due to heating are expected to be similar in both cases and the TAC[0 ->
(N+B)] will reflect the filling of any R traps emptied by ambient activation. It can be appreciated
that a detailed investigation of high initial sensitivity presents a considerable additional
experimental burden and uncertainties may still remain after use of these procedures. For dating
applications it may therefore be prudent to reject samples diagnosed to fall into this category and
test alternative fabrics from the context.

3.7 EXPLORATION OF GROWTH CHARACTERISTICS

The next step to perform is to establish the detailed behaviour of sensitivity change with dose.
The choice of procedure for thermal activation is based on the TACs and it is normally sufficient
to obtain adequate verification that maximum sensitization has been obtained (ie emptying the
charge held in R traps). The activation procedures for samples which exhibit a peak in the TAC
arc inevitably a compromise between the competing effects of sensitization and thermal
deactivation. A procedure of three thermal activations to increasing temperatures can be used to
provide values of S verifying the TAC peak (eg in fig 3.6, at 500, 550 and 575 °C), the
temperatures chosen depending on the structure of TAC. It can be seen that with large changes in
S in the vicinity of the TAC peak, a high degree of reproducibility in activation procedure is
essential. Recent work (Haskell and Bailiff, 1990) has shown that a further activation step
(equalization anneal) may be required at the end of each cycle if the positions of the TAC peak
change after first activation; the aliquot is heated to a temperature which is equal or greater than
the highest temperature reached in cither cycle.
The filling of R traps and the activation of L centres with dose is explored using multiple
activation and additive dose procedures.

3.7.1 Multiple Activation Procedure In terms of the model the multiple activation (MA)
procedure provides a means of characterization of the filling of L and R. A series of activations
using the same laboratory beta dose, B, is designed to test the linearity in the acquisition of holes
at the L centres. As illustrated in fig. 3.7(and with reference to fig. 3.3), the use of afixeddose B
and measurement of change in sensitivity with repeated dose/activation cycles permits the growth
of activated L centres with dose to be established. Where the activation of L centres is linear, the
168
value of ASN/ASN+B remains constant with reapeatcd activation cycles. By varying the value of B
with separate aliquots (aliquots #2 and #3 in see fig. 3.7), the filling of the R traps is examined
(for such analysis it is convenient to only evaluate ASN and ASN+B ); the range of doses should be
selected such as to test linearity to at least twice the 1st estimates of the accrued dose. When B is
equivalent to the accrued dose, as is the case for aliquot #1, ASN = ASN+B (NB based on a
preferred value of S0). The R characteristic is obtained by plotting the 1st data points for each
aliquot; where the filling of R is linear, as shown by the broken line, the characttcristic should be
linear and pass through the origin.
The results for different aliquots can be conveniently normalised by ASN ar>d the MA procedure
evaluation of the accrued dose can be obtained using equation 3.1.

2.0 -A Al iquot *2

AS

ASN
- □ Al iquot ■

o o—e—e—e—e—e—e—e—e—o Al iquot *3

0.0
2 4 6
CUMULATIVE DOSE (ACTIVATED)

Figure 3.7. MA Sensitization Characteristic

The following measurements are performed on a single aliquot.
Step 1. Record luminescence emissions to 150 °C; measure initial sensitivity S0.
Step 2. Thermally activate the naturally accrued dose, including the equalization anneal if
required; measure sensitivities SN.
Step 3. Administer dose B equal to the 1st estimate for accrued dose; record sensitivity SB
Step 4. Measure radiation quenched sensitivity, S .
Step 5. Thermally activate laboratory dose; measure sensitivities SN+B.
Repeat steps 3-5 to obtain measurements of S: and SN+2B etc.
N+B
From the sensitivity measurements,
S 0 - ^N- ^ J ' SN+B- S N + B ' ^N+2B' ctc>

the changes in sensitivity from quenched to activated S values are given by

ASN, ASN+B . ASN+2B - etc, for each completed activation cycle.
 169
3.7.2 Non-linear Filling of L centres and R traps It is frequently the case for archaeological
samples that the filling of R traps is sub-linear within the dose region of interest (eg 2-5 Gy); the
onset of saturation of the growth of activated L centres will will appear to be delayed because of
the beneficial effects of radiation quenching.
Where non-linear filling of R traps is evident, evaluations of the AD using eqn 3.1 will be
overestimates of the AD which increase with size of B used. However, providing that L centre
linearity prevails, the correct AD may be evaluated by finding the dose B for which ASN =
ASN +B . Previous results (Bailiff, 1979b) have indicated that an exponential function (Chen,
1979) similar to expression 3.2 can be used to describe the R characteristic; it is important to
verify that saturation filling of the R traps was not obtained during the acquistion of the natural
dose, otherwise only a minimum age can be calculated.
Where the growth of activated L centres is indicated by the reduction of AS values with
cumulative dose, use of eqn 3.1 will also provide overestimates of the AD; in such cases it is
likely that the filling of R traps will also be non-linear. It is to be noted, however, that a similar
reduction in AS values may result from the effects of strong thermal deactivation, and this
indicated by finding a linear R characteristic within the same dose region (where fewer thermal
activation cycles have been applied). In Chen's comprehensive discussion of the graphical
methods for dealing with the different types of saturation, he found certain cases where both
corrected (using Ailken and Murray's procedure) and uncorrected sensitivity values could be used
to obtain satisfactory dose evaluations Since the method described above for obtaining the 'true'
growth characteristic for the filling of L centres is not expected to provide satisfactory precision,
the use of uncorrected sensitivity values may provide a means of extracting the correct AD.
Clearly the procedures required are not straightforward and it may be more expedient to derive an
AD of higher uncertainty from for example.the R characteristic and include an allowance for
ovcrcstimation of the AD based on the characteristics of the sample.

IT)
o
Q

<
_ J
<
>
UJ

*' A D D I T I V E DOSE
Figure 3.8. Modified Additive Dose Characteristic
Of four aliquots, additive doses are administered to three and the dose received before first activation is
evaluated using the MA procedure. The intercept of the extrapolated curve with the dose axis represents the
correct AD.
170

3.7.3 Additive Dose Procedures Results obtained using the MA procedure have a precision
which can be deceptive since there is empirical evidence (Bailiff, 1983) to show that a change in
pre-dosc characteristics occur in some samples during the first thermal activation (in the model it
is assumed that the characteristics remain unchanged). Additive dose procedures are used to
detect such changes. Two procedures are available where, after administration of the additional
laboratory dose B, a) aliquots are activated only once and normalization of sensitivity values is
achieved by weight or S0 and b) the MA procedure is used. The former is referred to as the
additive dose procedure (used by Fleming to test for saturation effects) and the latter,
representing a subsequent development, as the modified additive dose (Bailiff, 1985) and the
spike (Haskell and Bailiff, 1985) procedures.
Whereas high precision can be obtained using the MA procedure because of normalization by
ASjsi, normalization by S0 or weight is frequently poor unless aliquot size is large (eg 20 mg)
which is unrealistic for most archaeological samples where only 50 mg may be available. The
additive dose characteristic ( S vs dose) is not affected by radiation quenching but it is likely that
the growth curve will be sub-linear reflecting combined saturation effects in the filling of L and
R. The AD estimate is obtained by extrapolation of the fitted curve to the dose axis (S = 0) and
subtracting the estimate for AD0, the dose equivalence of the initial sensitivity (S = S 0 ).
The problem of poor precision obtained using the additive dose procedure is avoided by
applying the MA procedure to evaluate the accrued plus additive dose, (N+B). The modified
additive dose and spike procedures are similar, differing only in methods of data analysis. Using
a range of additive doses, the estimates for (N+B) are obtained using the methods described for
the MA procedure. The estimates for (N+B) are expected to be a linear function of additive dose
B, as shown in figure 3.8, if the sensitization per unit dose is altered by a factor which is
independent of dose; recent experimental evidence provided by Haskell and Bailiff (1990)
supports this interpretation. The initial experimental evidence for this effect suggested that it was
associated with changes in the TAC, but tests with further ceramics (Bailiff, 1985) has shown
that the effect may also be found in samples where no TAC alteration is detected. While the
causes of the effect have yet to be determined, the need to check all MA estimates of the AD
using an additive dose procedure is essential.

4. Application to dating

In evaluating the TL age equation, the assessment of the annual dose is similar to that required
for the quartz inclusion technique (Fleming, 1970). As discussed in the Appendix, the dose
contribution from alpha radiation can be considered to be negligible and the sources of annual
dose are beta, gamma and cosmic radiation. Appropriate techniques for the measurement of these
contributors arc beta-TLD (Bailiff and Aitken, 1980), and gamma-TLD or gamma spectrometry
(eg Aitken, 1985). One advantage of testing ceramics of the last two millennia is the general
improvement of manufacturing technology which results in finer and less porous fabrics. Since
the annual dose varies according to water uptake within the sample and burial media
(Zimmerman, 1971a), lower porosity contributes to a lower uncertainty in the age.

It will be no suprisc to the reader to lcam that much of the effort in recent years concerning the
use of the technique has been devoted to obtaining a better understanding of the pre-dose effect
rather than producing dates. As part of such research, archaeological samples provide a valuable
 171

resource since they possess what cannot be easily simulated in the laboratory - the effects of time.
Nonetheless, following Fleming's initial test programme with archaeological pottery and
subsequent use of the technique for authentication (see Stoneham, this volume), the results of a
small number of dating programmes have been published (Wright, 1979; Bailiff, 1982, 1985,
1987; Robertson and Prcscolt, 1988). These programmes have been chiefly concerned with the
dating of ceramics of the last 1500 years, a range which is limited more by saturation effects than
the occurrence of ambient activation (there is one exception; Bowman and Demetsopoullos,
1980, reported on feasibility tests with burnt flint from a palaeolithic site). Although only a
modest number of prc-dose entries (two) have been published so far in the Ancient TL Date List
(1988), it is anticipated that their number will increase in future lists.

5. Summary

The prc-dose technique is, and has been, capable of yielding reliable and accurate dates. The
recent developments have provided the means for correction of certain types of behaviour which
would otherwise have provided inconclusive results. They also offer a sound basis for the
termination of tests on samples which have unsuitable properties and which, using earlier
procedures, may have gone undetected and resulted in anomalous dates, thus affecting the
perceived accuracy of the method. The prevention of the the production of dates by such
screening is of key importance in developing a reliable technique. Althougth the technique is
complex ana the procedures time consuming, its routine use is now a more feasible proposition
with the advent of semi-automated TL readers. Exciting developments have been made in the
characterization of the physical mechanisms associated with the pre-dose effect and when
complete will provide the first detailed physical description of TL in natural materials used for
dating.

Acknowledgements
The author currently holds a Science and Engineering Research Council Advanced Fellowship
and is pleased to acknowledge supporting grants from the SERC and the University of Durham.

References
Ailkcn M.J. (1979) PACT 3, 319-324.
Aitkcn, M.J. (1985) Thermolumincscence Dating, Academic Press, London.
Ailkcn, M.J. and Murray, A.S. (1976) The 1976 Symposium on Archaeometry and Archaeological
Prospccuon, Edinburgh, (cd H. McKcrrcll). HMSO, London.
Akbcr, R.A., Robertson, G.B., and Prcscolt, J. R. (1988). Nucl. Tracks, and Radiat. Mcasls. 14 (1/2), 21-26.
Ancient TL Date List. (1988) (cd I.K. Bailiff) Supplement to Ancient TL. ISSN 07035-1348.
Bailiff, I. K. (1981) PACT 6, 468-472.
Bailiff, I. K. (1982) PACT 6,468-472.
Bailiff, I. K. (1983a) PACT 9, 345-355.
Bailiff, I. K. (1983b) PACT 9, 208-214.
Bailiff, I.K. (1985) Nucl. Tracks and Radiat. Measts. 10, 771-777.
Bailiff, I. K. (1987) Appendix 4-7. In The dosimetry of the atomic bombs at Hiroshima and
Nagasaki, Vols I and II (Wm. C. Rocsch, Ed). Radiation Research Foundation, Hiroshima.
Bailiff, I.K. and Aitkcn, M. J. (1980) Nucl. Instrum. and Methods 175, 224-226.
172

Bailiff, I.K. and Haskell, E.H. (1984) Radiat. Protect. Dosim. 6, 245-248.
Bowman, S.G.E., and Demetsopoullos, I.C. (1980) Nucl. Instrum. and Methods 175, 219-221.
Chen, R. (1979) PACT 2, 325-335 .
Chen, R., Yang, X.H., and McKeever, S.W.S. (1988) J. Phys. D: Appl. Phys. 21, 1452-7.
David, M. (1981) Ind. J. Pure and Appl. Phys., 19, 1048-1053.
Fleming, S.J. (1969) Unpublished D.Phil thesis, Oxford University.
Fleming, S.J. (1970) Archaeometry 12(2), 133-145.
Fleming, S.J. (1973) Archaeometry 15(1), 13-30.
Fleming, S.J. (1979) Thermoluminescen.ee techniques in archaeology, Clarendon Press, Oxford.
Fleming, S.J., and Thompson J. (1970) Health Physics 18, 567-568.
Gcksu, H.Y., Weiser, A., and Regulla, D.F.. (1989) Ancient TL 7(1), 15-17.
Haskell E.H., and Bailiff, I.K. (1985) Nucl. Tracks and Radiat. Measts.10, 503-508.
Haskell E.H., and Bailiff, I.K. (1990) Radiat. Protect. Dosim., in press.
Haskell, E.H., P.L. Kaipa and M.E. Wrenn. (1981) Ancient TL 12, 9-11.
Haskell, E.H., Kaipa P.L., and Wrenn M.E. (1984) Proc. 2nd US-Japan Joint Workshop for
Reassessment of Atomic Bomb Radiation Dosimetry in Hiroshima and Nagasaki., 32-44
Haskell, E.H., Kaipa P.L., and M.E. Wrenn. (1985) Nucl. Tracks and Radiat. Meas. 10(4-6),
513-516.
Haskell, E.H., Kaipa, P.L., and M.E. Wrenn. (1988) Nucl. Tracks and Radiat. Meas. 14(1-2),
114-120.
Maruyama, T, Yoshikazu Kumamoto, Yoneta Ichikawa, Tsuneto Nagatomo, Masaharu Hoshi,
Edwin Haskell and Prasad Kaipa. (1987) W. Roesch (Ed.) U.S. Japan Joint Reassessment of
Atomic Bomb Radiation Dosimetry In Hiroshima and Nagasaki, Final Report Vol I .
McKeever, S.W.S., Chen, C.Y., and Halliburton, L.E. (1985) Nucl.Tracks and Radn. Measts.
10(4-6), 484-495.
Robertson, G.B., and Prcscott, J.R. (1988) Nucl. Tracks Radiat. Meas., 14(1/2), 299-305
Sloncham, D. (1983) PACT 9, 227-239.
Sunta, CM., and David, M. (1982) PACT 6,460-467.
Sutton, S.R., and Kornmcicr, C M . (1985) Ancient TL 3(3), 1-5.
Watson, I.A., and Ailkcn, M.J. (1985) Nucl. Tracks Radiat. Meas., 10(4-6), 517-520.
Wright, D.A. (1979) PACT 3, 336-344.
Yang, X.H., and McKeever, S.W.S. (1985) Nucl. Tracks Radiat. Meas., 14, 75-79.
Yang, X.H., and McKeever, S.W.S. (1990) J. Phys. D: Appl. Phys 23, 237-244.
Zimmerman, D.W. (1971a) Archaeometry 13, 29-52.
Zimmerman, J. (1971b) J. Physics C: Solid State Physics 4, 3277-3291.

Appendix: Experimental Notes

1. Samples The association of the pre-dose effect with the quartz 110 °C TL peak initially led to
the use of quartz inclusions (90 - 150 u.m), although polymincralic fine-grain (1-8 |im) samples
were (Fleming, 1973b) and since have been successfully employed (but limited in maximum
activation temperatures where aluminium sample discs are used) in the authentication of ceramic
works of art. For both types of sample it was presumed that the emission was dominated by
quartz, although it was recognised that the -130 °C TL peak of potassic feldspar could also
contribute to the TL emission as indicated by a high temperature shoulder in the glow curve.
Where inclusions were extracted, the practise in earlier procedures was to use sample purified
only by magnetic separation. HF acid etching treatments employed in the inclusion technique
 173

(Fleming, 1970) to remove the outer layer of quartz grains penetrated by alpha radiation from the
surrounding sample medium and to further isolate the quartz fraction were not used. Since the
efficiency of alpha radiation in producing trapped charge which contributes to pre-dose
sensitization is one or two orders of magnitude lower than that for high temperature TL the need
to assess the alpha dose contribution has not been considered to be necessary (Fleming, 1973).
Despite problems reported by Fleming, no firm evidence has subsequently emerged to indicate
that HF acid etching, if used, has a significant effect on the pre-dose effect in quartz, although
changes in properties of a sample may result by the removal of other contributing luminescent
minerals (Bailiff, 1987). There has been considerable success with the use of semi vitreous
ceramics (Stoncham, 1983; Robertson and Prcscott, 1988) such as porcelain for authentication
studies and thin slices are prepared for measurement (see also Stoncham, this volume).

2. Measurement system The requirements for a TL reader for pre-dose measurements are
somewhat higher than for other types of TL measurements (eg Aitkcn, 1985); the oven should be
capable of heating to ca 700 °C at a linear rate (2-20 °C/s) and water cooling of the heater plate
assembly is recommended to provide reproducible temperatures during the administration of test
doses because of the short half life of the 110 °CTLpcak. A high degree of reproducibility in the
control of the heating of the sample is also required because of the rapid changes in degree of
sensitization with activation temperature. Radiation sources capable of delivering test doses of
ca 10 mGy/min and calibrating doses of ca 1 Gy/min arc recommended for dating work and
because of the need to minimize the time between irradiation and measurement; Sr90/Y90
radiation sources which can be installed in the vicinity of the TL reader are often used (Bailiff,
1981) which permit in situ irradiation of aliquots.
Although the absence of black body radiation in the temperature region required to measure the
110 °C TL peak simplifies the specification of the detection system, a high gain photomultiplicr
(eg EMI 9635Q) with a quartz window and low dark noise is recommended to permit the
reduction in size of the test dose necessary to obtain measurable signals. Although fastening
agents such as silicone oil can be used satisfactorily where activation temperatures below 600 °C
arc used, the placement of loose grains on the heater plate (Haskell et al, 1988) is to be preferred
and consequently an oven plate free from vibration is essential. It has been found that where
silicone oil is used, an optical filter may be required to isolate the 360 nm band emission from
quartz (using a Corning 7-51 or Schott UG 11) and suppress longer wavelength spurious
emission from the oil.
AUTHENTICITY TESTING

DOREEN STONEHAM
Research Laboratory for Archaeology
Oxford University
6 Keble Rd
Oxford OX1 3QJ
UK

1. Introduction
Thermoluminescence (TL) authenticity testing of ancient ceramics has been in
operation for over 20 years. The main TL analytical technique is a modification of
the fine-grain dating technique first developed by Zimmerman (1971). Occasionally
other specialist techniques are adapted when there is sufficient sample but generally
sample size limits the number of measurements which can be made. The full range
of object types which can be tested covers pottery and terracotta from all cultures,
porcelain and stoneware and the casting cores from bronzes. The criteria are first
that the material should have been fired to 500°C or more and secondly that there
should be no overlap between the period of manufacture of the genuine article and
any later copies. As a general rule, the time span between the two should be a
factor of two.
Thermoluminescence is the light which is emitted when a sample of pottery is
heated, which is separate from the red hot glow observed when materials are fired
to above 400°C. The phenomenon is described in more detail by Aitken (1992). The
intensity of the TL signal is proportional to the time which has elapsed since the
object was last fired, normally this is in the kiln although there may be exceptions.
Heating the pottery to above 500°C in the kiln releases any thermoluminescence
which has accumulated during the geological lifetime of the clay and sets the dating
clock to zero. If a piece of pottery was sampled and tested just after leaving the
kiln, there would be no TL signal. However, if a period of centuries elapses between
the kiln firing and the laboratory testing, a measurable signal is observed.
The important constituents in the pot giving rise to the TL signal are quartz and
felspars which are exposed to the radiation from radioactive isotopes occuring
naturally in the clay body and also from the burial environment and cosmic rays.
Values obtained from a series of measurements of TL sensitivity and radioisotope
concentration can be used to calculate the approximate date of firing.
2. Sampling
2.1 EXAMINATION
The choice of sampling site is critical as many objects subjected to authenticity
testing have been restored or are a composite of many different pieces belonging to
more than one object. Pastiches consisting of a genuine section married to a
completely modern part are a frequent occurrence. The object should be observed
critically in a good light and all parts which could be assumed to have suffered some
sort of damage during burial should be examined for joins. If these sections appear
to be whole, they should be noted for sampling later, as it is possible that parts such
175
H. Y. Goksu el al. (eds.). Scientific Dating Methods, 175-192.
© 1991 ECSC, EEC, EAEC, Brussels and Luxembourg. Printed in the Netherlands.
176
as horses' legs, manes and bases could be completely new additions. Chinese
equestrian groups from the Six Dynasties and Tang periods in particular are
frequently composed from a genuine horse with a modern rider as an equestrian group
will often fetch a better price than the horse alone. Elaborate saddles on such
objects should be suspected, as well as particularly fresh painting on any type of
object. It is not easy to examine pigments in every case and it should be noted that
an authenticity test will only guarantee the sample of powder which is tested and this
is not necessarily representative of the whole object.
Another aspect to note is any obvious change in pottery colour or join between a
head and body. Both sections should be tested to see if they both give the same age
and the glow-curves should be compared to confirm that they are both similar in
shape. A gross difference in glow-curve shape indicates that a different clay has
been used for different parts of the piece, even though the same age may be
obtained. Some Mexican anthropomorphic vases have been "created" when two
objects were neatly sawn in half and tops and bottoms changed. After glueing and
skilful painting over the join, the two pieces then sold for far higher prices than they
would have in their original state.
The lesson to be learned is that anything which is described as "unique" or "unusual"
should be regarded with grave suspicion and the features that make it rare or unusual
should be tested. Having examined the piece and selected one or more suitable
sampling sites, the object should be taken to a dark room illuminated with a red light
similar to that used for photography, for the drilling.
2.2 EXAMINATION AND EQUIPMENT
As the TL signal is easily bleached by white light, all sampling must be carried out
under dim red light and the sample stored in a light-proof packet. Before drilling, all
loose dirt should be removed from around the sample site: in addition, any vents
should be blocked with tissue and sealed with tape. It is surprising how easily soil is
shaken loose from a surface and falls onto the sample. The sample is then useless as
the geological TL component from the unfired soil is added to the archaeological TL
component resulting in a TL age which is too high. The drilling site should be easily
accessible and not restricted by another part of the piece. It should be completely
visible and situated so that the powder falls down onto the paper - an obvious point
but surprisingly often overlooked.
The most useful drill to use is a small powered hand-held drill of the type used for
handicraft work, either run from a 12 volt battery or from the mains via a DC
transformer. The speed should be variable up to 16,000 rpm with a maximum power
of 80 watts and a current of 0.6amps. The best drill bits are those used for dental
work on the root canal of the tooth, with a straight side and sharp point. One such
make is obtainable from Wright Dental Sales, 2 Commerce Rd, Brentford, Middlesex
TW8 8LE, UK. The reference is Komet drill, H219-104-023. If a substitute is sought,
please note that twist drills are highly unsuitable.
2.3 DRILLING THE SAMPLE
Before collecting the powder for the TL sample the surface area must be cleaned by
passing the edge of the drill over it and the outer 2mm must be removed as this will
have received only a reduced radiation exposure from radioisotopes inside the pot.
In addition the TL has probably been bleached by exposure to light and it may also
have been contaminated with dirt. This portion of powder is discarded. The TL
sample is collected on shiny weighing paper so that all the grains can be decanted
 177

into the sample bcttle leaving none of the fine grains behind. The powder is drilled
by moving the drill at an angle to surface so that a conical, rather than a cylindrical
hole results. At least 100 mgm of powder should be collected and placed in a small,
smooth sided container which is immediately placed in a light proof envelope and
labelled. Any further samples should be collected in the same way. The samples
should be catalogued on a card with details of the object and sampling sites. Finally
the object should be photographed so that a record can be retained by the test
laboratory.
The question of overheating the sample by drilling is sometimes raised. Fleming
(1971) conducted a series of experiments on a Persian bowl and consluded that the
localised drilling temperature lies between 160°C and 240°C.
3. Preparation
3.1 STANDARD FINE-GRAIN METHOD
This method is described in Zimmerman (1971). It is modified for authenticity work
as there is less sample available. The procedure described below is routinely used in
Oxford. The requirements are: 2-3 test tubes and rack, 6x flat-bottomed glass tubes,
6 cms in height and 1 cm diameter with rack, 6x1 cm diameter aluminium discs,
Analar grade acetone.
1. Put powder into test tube and add acetone to a depth of 8 cms.
2. Shake well and leave to settle for 2 minutes. After this period there will be a
deposit of large grains (>10 \im diameter) at the bottom of the tube. Above is a
suspension of grains of diameter 10 um or less.
3. Decant into another test tube, leaving the heavy deposit behind. Pour steadily
and without tilting the test tube backwards as this will cause turbulence.
4. Put test tube of heavy grains in oven to dry. These will be used for alpha
counting and potassium analysis. Leave the suspension for 20 minutes.
5. After 20 minutes there will be a deposit at the bottom of the test tube. This
contains grains 4-10 um in diameter. The suspension contains the ultra fine grains
(<4 urn).
6. The suspension should be poured off - either into a sink or into a third test tube
if you wish to retain it in case of mishap (advisable).
7. Add acetone to the deposit, shake and leave for 20 minutes. Stages 6 and 7 should
be repeated as often as necessary until the suspension is crystal clear. This is
generally by the third washing.
8. To deposit the sample. Decant the final washing and add fresh acetone slowly.
The right dilution is reached when the suspension just begins to become translucent.
This can be checked by holding it up to the (red) light with a finger behind. The
outline of the finger should just be faintly visible. If diluted too far, the discs will
be too thinly covered and have poor reproducibility, if the covering is too thick, it
will flake and fall off the disc when dry.
3.2 PRE-TREATMENT OF THE ALUMINIUM DISCS
Aluminium sheet of thickness 450 um is cut into discs of 1 cm diameter. Before
cutting the discs the surface of the sheet should be roughenend with a sanding
machine to produce a fine network of scratches which serve to stabilise the fine-
grains and produce an even deposition. After cutting, the discs should be cleaned
with solvents to remove dirt and grease and then in acetone to remove the fine
178
particles of metal. After drying, they should be annealed at 500 °C for 2 minutes to
prevent a spurious signal from the aluminium during measurement. After annealing
they can be stored For 3-4 days before use. After that time they should be re-
annealed.
3.3 DEPOSITION
1. The flat-bottomed tubes should be cleaned and stood in the rack.
2. Place one disc into each tube and cover with 1 cm of acetone. Ensure that there
are no bubbles of air trapped underneath.
3. Shake the suspension and pipette 1 cc onto each disc taking care to shake the
suspension between depositions. Leave the discs a drying oven at 50 °C for at least
10 hours and do not open the door or shake the sample before they are completely
dry.
3.4 NOTES ON THE DIFFERENT TYPES OF SAMPLE
Some samples are more difficult to deposit than others - probably it is connected
with the grain shape. Some samples will contain a high proportion of ultra-fine
grains giving a poor yield of fine grains for deposition. In general, samples from well
made pottery with fine homogeneous bodies and fired to around 7-900°C will make
the best discs. Examples of this are Greek and South Italian pottery (5th-3rd century
BC) and most Chinese pottery from the Han dynasty (206BC-220AD) to the present
day. High fired samples (porcelain and stoneware), should be drilled with a diamond
drill and not with a tungsten carbide drill as this overheats and all that will be
obtained is a low yield of mainly ultra-fine grains. This type of pottery will be
discussed in another section. Coarse pottery and low-fired pottery is difficult to drill
as a large hole results from drilling and the yield of fine grains is small. The large
grains can be crushed before preparation although there will be some inaccuracies
due to the dosimetry. Examples of the latter kind of pottery are most African
pottery and glazed Islamic fritware.

3.5 SPECIAL TREATMENT

Acid washing. Spurious TL is a common problem in fine-grain dating. It is often
caused by the presence of carbonates in the sample and these can be easily removed
using a 5% solution of acetic acid in distilled water. Since authenticity samples are
so small, it is necessary to alpha-count the sample before treatment so that the true
count is obtained (alpha counting is described in a later section). Acid washing
removes a portion of the sample and the count is altered as a result of this. In
addition, a few milligrams can be removed for potassium analysis if there is enough
sample and this is augmented as described in stage 1 of the procedure.
1. After alpha-counting the sample retain a few milligrams for potassium analysis
if possible, add the remaining powder to acetone in a test tube and leave for 20
minutes. Decant and dry the residue in the oven. This portion is to be acid washed.
The suspension contains ultra-fine grains and these can be left for several hours to
allow as much to settle as possible, this residue can then be added to the portion
reserved for potassium analysis.
2. The acetic acid solution should be added to the dried sample and shaken in a test
tube. Leave for as many hours as possible, shaking occasionally.
3. Use the centrifuge to draw all sample to the bottom of the test tube and discard
 179

the acid. Wash the sample in distilled water using the centrifuge, at least four times
so that all traces of acid are removed.
4. Wash the sample in acetone, in the centrifuge, three more times.
5. The sample is now ready for the standard fine-grain preparation. If there are
problem with coagulation, this is because the sample has not been properly washed
and the distilled water washing in the centrifuge should be repeated.
Type of sample to be acid washed. Ideally all samples should be given the acid pre-
treatment before the standard preparation but this is time consuming. It should
always be used on white or very pale samples, Greek and Italian antiquities, all
European ceramics including Italian Renaissance pieces, majolica and all British
pottery. Any pottery contained white inclusions which are not quartz, such as shell
temper, should be treated.
4. Thermoluminescence measurements.
4.1 THE TL OVEN
The TL oven to be used for measurement must be fitted with a vacuum pump and
attached to a source of pure nitrogen (Aitken et.al. 1968). If any part of this system
is omitted, most of the samples will give a spurious signal due to the presence of
oxides. Even flowing nitrogen through the system is useless if air is not evacuated
from the equipment first. Many of the problems encountered in authenticity testing
can be traced to this omission.
There are several versions of TL oven on the market from single sample manual or
semi-automated sets made by Littlemore Scientific Engineering, Railway
Lane,Littlemore, Oxford 0X4 4PZ, UK or by Daybreak Nuclear and Medical Systems
Inc., 50 Denison Drive, Guildford, CT 06437, USA. A fully automated, multi-sample
reader is made by the Riso National Laboratory, Denmark, enquiries from L. B0tter-
Jensen. The oven should be fitted with a low background (less than 40Hz)
photomultiplier tube, (such as is obtainable from Thorn EMI, Bury St, Ruislip,
Middlesex HA4 7TA, UK.) fitted with a Corning 7-59 filter and a Chance-Pilkington
HA3 heat rejecting filter.
4.2 IRRADIATION AND MEASUREMENT
At least six discs should be prepared for each sample. The procedure is similar to
that used for fine-grain dating except that the number of measurements are
restricted. Two discs are used to determine the natural TL signal and second glow
measurements, two discs are used for N+B measurements and two discs are used for
N+a measurements. The B-doses chosen for both the second glow and the N+B values
should be approximately equal to the ED and 2xED values, if the object is assumed
to be genuine. The approximate value for the ED is five times the age, expressed in
mGy. The corresponding oc-doses should be ten times higher as alpha particles are
around one tenth as efficient at producing thermoluminescence as beta irradiation
(Zimmerman, 1972). Strontium-90 is the most commonly used radioisotope for beta
irradiation although most of the irradiation comes from the daughter product,
Yttrium-90 (Aitken 1985). The most convenient radioisotope for alpha irradiation is
americium-241. The maximum recommended heating rate is 5°/sec. Glow-curves
from a genuine Tang dynasty horse (Fig.l) and a modern copy (Fig. 2) are shown and
the difference in the natural TL between the two samples is clearly seen.
When all the glow-curves have been recorded, they should be subjected to plateau
180

tests both for N/N+P and N/N+a. Generally plateaux begin at 250-300°C and should
extend for 150°. Plateaux which begin at a much lower temperature than 200°C
should be treated with some caution as it is possible that the object has been
subjected to clandestine irradiation to increase the TL age artificially. This is
unlikely despite all the literature on the subject but the possibility remains. The
glow-curve should be examined for any evidence of TL at low temperature peaks
which would not normally be stable after the archaeological life-time. Conversely,
a plateau which starts much after 325°C could be due to refiring of the object to a
lower temperature than the original firing. This can happen during restoration.
Often the alpha plateau is poorer than the beta plateau, most probably because a high
proportion of the natural dose arose from internal beta irradiation. The a-value
changes across the glow-curves depending on which traps are alpha sensitive.
Analysis to evaluate the equivalent dose should be carried out in a region for which
there is a mutual alpha and beta plateau. The only exceptions to this rule are when
there is a very clearly defined peak above 325°C: in this case the TL should be
integrated over the peak. The most obvious case is when analysing pottery from the
Lower Niger region (Mali etc).
4.3 ALPHA COUNTING.
The aim with authenticity testing is to produce an approximate date if possible.
Once the ED has been calculated the result is often fairly obvious for older objects
but it is still essential to complete the analysis. Thick source alpha-counting on a
full ring is usually not possible so the method is modified. Instead of 42 mm rings,
a perspex holder of 16 mm diameter is used. 16 mm discs of zinc sulphide are cut
to fit into the base of the holder and a stainless steel plug sits on top of the sample.
Before measurement the holder and screen with stainless steel plug in place are left
to count for 24 hours to measure the background and to check that the screen is not
contaminated. A background of approximately 0.03 counts per kilosecond is
acceptable. The grains which are larger than 10 \im diameter (in the test tube,
drying in the oven) are used for alpha counting. If there are some large mineral
inclusions in this sample, they should be crushed so that they pass through a 20 u.m
sieve. As a precaution, before use, the sample should be weighed. If the weight is
greater than 10 mgs, it should be possible to cover the surface. If this is not the
case, an adjustment has to be made, based on a weight calibration, further details of
which are given below.
The sample should be counted for 100 counts which normally takes around 24 hours.
The longer it can be left to count, the more reliable are the statistics. However it
should be noted that, particularly with a coarse material, the count may not be
representative of the rest of the body as it is such a small sample. The count,
expressed as counts/kilosecond is normalised to a 42 mm ring by multiplying the
reduced count by the appropriate normalisation factor which is the square of the
ratio of diameter of the reduced ring to 42 mm: a factor of seven in the case of a
16 mm ring. This normalised value is the one to use in the age equation.
It is important to note that if the alpha-count approaches zero (check that the
screen has been correctly located in the holder and is the right way up), this is a sign
that the sample is not pottery but some form of plaster and that the sample has been
taken in a restored area.
Weight Normalisation. An approximate weight normalisation factor can be measured
as follows.
1. Select a fragment of pottery which is made form fine particles and appears to be
 181

homogenous.
2. Crush and sieve through a 20 |im sieve.
3. Alpha count on a 42 mm screen ensuring that the zinc sulphide is completely
covered.
4. Alpha count on the reduced size screen, enduring complete coverage.
5. Repeat the a-counting measurements on the reduced size screen with a selection
of different weights from 1 mgm upwards. For very small weights of powder spread
the sample as evenly as possible over the screen to cover the maximum surface.
6. Plot the count-rate of the sample divided by the count-rate of the 42 mm ring
versus the weight. The form of the graph is a curve reaching an asymptopic value.
Although an unsophisticated method of normalisation, it is very useful to have this
graph when alpha-counting small samples.
4.4 POTASSIUM ANALYSIS
Ideally a potassium analysis should be performed for every sample but sometimes this
is not possible. Sufficient powder should always be drilled for this purpose in the
case of young material such as Italian Renaissance sculpture which have the added
problem that copies were made in the 19 century. Potassium analysis is also
essential when the alpha count is abnormally low as potassium-40 then makes a
significant contribution to the dose-rate. Potassium-40 is often a major contributor
to the dose-rate of Chinese porcelains when it can rise to 6% and above in some
cases as opposed to the average value of 1-2% for pottery. Another occasion when
it is important to carry out this analysis is in the situation when the TL age is either
much higher than expected or much lower - but not so low that the object is a fake.
Sometimes pieces are misattributed, sometimes the sample is contaminated with soil
or restoration material and sometimes wrong assumptions are made regarding
unknown dosimetry values.
There are several analytical techniques for determining potassium content. Flame
photometry is one such technique and although should normally be carried out on 100
mgm of sample, it can be used (although with larger errors than the 5% standard
error) on sample as low as a 6 mgm. A straightforward weight normalisation factor
is applied after measurement. Most pottery has a potassium-40 content between 1
and 2% but values from 0.2 to 6% have been recorded during authenticity work.
4.5 CALCULATION.
The data should be taken from the alpha and beta plateau regions and the ED and a-
value can be calculated, albeit with fewer measurement points. Reasonable linearity
should be obtained with the four alpha and four beta data points, some scatter is to
be expected if light levels are low due to either low sensitivity or because the
sample is young.
The intercept correction has to be calculated from two points only, in many cases,
which is of dubious value; however, it can be used as an indicator. If the correction
is zero or very small, it can be assumed that there has not been any sensitivity
change. If the correction is of the same order of magnitude as the ED, it is unwise
to proceed with the analysis without further investigation as it is often a sign of
unfired or poorly fired material.
The standard age equation (Zimmerman, 1971) is used to obtain an approximate age
for the object with assumptions regarding the environmental contribution to the dose-
rate being inserted into the appropriate place. No water content correction is
applied -samples are presumed to have been buried in a totally dry environment,
182

which is normally impossible, so there will be a systematic error in the TL age which
will be underestimated by a few percent. The other unknown is the environmental
contribution to the dose-rate and this effect could be very important. An arbitrary
value of 1 mGy/yr is assumed which is probably an underestimate of the true value.
The result is a systematic error in the TL age which is likely to be overestimated.
The net effect of these two unknown values hopefully minimises the error in the TL
age. If the TL age differs by more than 25% the reason should be investigated; it
could be due to bad disc deposition or loss of a portion of the sample during
measurement. Timing of automated systems should be checked as well as the shutter
mechanism for any malfunction. Sometimes the object has been misattributed or, in
the case of a lack of proper chronology, the age is estimated by the owner, or an
archaeologist has hazarded a guess when he published his report. Almost without
exception, if this is the case, the pseudo-archaeological age is greater (sometimes
by a factor of two) than the TL age. In this case the possibility of anomalous fading
should be investigated.

4.6 FADING CORRECTION.

Anomalous fading was first observed by Wintle et al. (1971) and later attributed by
Templer (1986) to the presence of an unstable TL component which can be removed
by storing laboratory irradiated discs at around 100 C for several days prior to
measurement. This is not always practical and Stoneham et al. (1988) described an
alternative technique, based on that described by Templer (1985) which can be used
on authenticity samples. After the TL measurements have been completed, used
discs are given an arbitrary alpha irradiation, sufficient to give light levels
comparable with previous measurements, and stored in an oven for 2 weeks. The TL
signal is then measured and compared with the TL signal obtained immediately after
an identical alpha irradiation. The difference in TL between the two signals is due
to the removal of the unstable component by heating and storage for two weeks and
the ED should be corrected accordingly. Alpha irradiations are used as sensitivity
changes between consecutive measurements are minimal.

4.7 LIMITS OF PRECISION

Even though results may be perfectly reproducible, growth linear and the intercept
correction is zero, realistic error limits should be quoted if any form of date is given
for the test object. 100 mgm samples represent only between 10" and 10 of the
total weight of the object in many case and is not necessarily representative of the
clay as a whole. With such small samples it would be surprising if they were. In
addition the number of measurements is limited by the sample size. Both alpha-
counting and potassium analysis are carried out on samples which are at least an
order of magnitude lower than the recommended sample size. In addition the
environmental contribution is unknown as is the water content. When all these
factors are taken into consideration it is surprising that an authenticity date is able
to do much more than distinguish between fake and genuine for anything less than
2,000 years old.
Aitken et al. (1972) give the calculations for an archaeological context. The error
limit for a context is 6% (1 SD) and for a single sherd, 9%, providing that all the
measurements can be carried out on an archaeological site and the samples are
surrounded by a homogeneous environment for at least 1 metre in any direction. If
the authenticity testing is carried out exactly as described and every measurement
 183
is rigorously carried out, a high proportion of TL authenticity ages fall within 25%
of the archaeological age - or prove indisputably to be modern copies. For those that
fall outside this limit the reason should be sought.
For objects manufactured even as recently as the 18th century, there should be no
problem distinguishing the real thing Jirom a copy - so long as that copy is made in
themid-late 20th century, however 18 century objects cannot be distinguished from
19 century copies - a problem with many French ceramics. The rule that the age
between the genuine article and later copies should be at least a factor of two should
be born in mind. Should the natural sample contain any spurious component it may
be impossible to determine anything regarding authenticity. Italian Renaissance
objects were made in the 1 4 - 1 6 centuries with copies made in the 19 century
which makes their identification more complicated as such copies have a TL signal,
whereas 20th century copies have a negligible signal which makes their identification
easier.
An added complication in the case of Italian Renaissance sculptures is the history
of copies which were made almost continuously from the artist's lifetime during the
following centuries. Such pieces are described as "in the school of" and could nave
been made in many cases during a period of 300 years after the artist's death, being
used as practice pieces for young artists to emulate. When dating such objects this
fact should be born in mind. The same problem is encountered with the French artist
Palissy.
5. Pre-dose analysis.
In some cases it is not possible to use the standard fine-grain technique as a spurious
signal is obtained despite all precautions. This is particularly true with many so
called "white-bodied" clays from the Tang dynasty of China (Fleming, 1973). The
type of object encountered are tomb goods depicting horses, camels, courtiers,
matrons, musicians - in fact figures which would have been familiar to the deceased
during his lifetime and figures of which were placed in his tomb to give reassurance
after death. Many of these pieces are lead glazed - usually horses or camels - and
it is these which have a very light coloured body - rarely completely white but a
range of off-white shades of beige, pink and pale yellow. Among the unglazed
examples, female musicians and dancers and the type of court lady referred to as a
"princess are nearly always have light coloured bodies, rather than brick red.
These Chinese examples contain a high quartz content and so instead of high
temperature analysis, changes in sensitivity of the 110°C peak, or pre-dose peak can
be utilised (Zimmerman, J. 1971). It is more usual, when carrying out pre-dose
dating, to extract the quartz inclusions for this work but with the small, drilled
authenticity sample at one's disposal, this is not possible. Instead, the powder is
prepared in the usual way and deposited onto rhodium covered copper discs for the
analysis. The effect is often enhanced if the sample is first acid-washed. The copper
discs must be coated otherwise a spurious signal is obtained from oxidation. The
coating of rhodium, few microns thick, is done commercially and not only prevents
physical changes to the copper but is an excellent heat conductor. It is also very
good for suppressing spurious TL particularly when very low light levels are
encountered as in zircon dating (Templer 1988).
The first stage in pre-dose analysis is measuring the Thermal Activation
Characteristic (TAC). The TAC monitors the growth of the pre-dose peak to
determine the temperature of maximum activation (Haskell et al., 1975). Heating
the sample above this temperature causes deactivation and an overestimate of the
ED. Only one disc is required for this procedure and, as a modification of the
184

multiple activation method is used as described by Aitken (1979), the pre-dose peak
is monitored twice for each temperature interval to check that it does not deactivate
when heated twice to the same temperature.
It must be born in mind that the lifetime of this peak is 146 minutes and all
measurements must be made immediately after irradiation to minimise loss of signal.
The maximum recommended heating rate is 5°/sec. for measurement and 2°/sec for
the high temperature heating, although this is sometimes difficult to achieve.
5.1 MEASURING THE TAC.
1. Give disc a 10 mGy exposure (called a test dose), heat immediately to 150°C. The
small peak which appears at 110 C is SQ.
2. Heat to 250°C, cool, apply test dose, heat immediately to 150°C to record pre-
dose peak. Repeat this sequence.
3. Repeat stage 2 but heat to 275°C twice.
Continue monitoring the growth of the 110CC peak, increasing the activation
temperature in regular steps, preferably every 25-30 degrees. A plot of TL intensity
of the 110°C versus the activating temperature, otherwise known as the TAC should
gradually increase to a maximum value which may be anywhere between 300°C and
650°C or more. It is important to have a TL oven which is capable of reaching 650°C
or more as 500°C is often too low an activating temperature. The activation
temperature to use should be just below the maximum, and at the selected
temperature, the second reading should be greater than the first.
5.2 MEASUREMENT
A minimum of three discs are used for the actual pre-dose measurements. The
following sequence of measurements is used for each of the three discs.
1. Apply test dose of 10 mGy using a beta or gamma source. Heat immediately to a
temperature of 150°C to record SQ.
2. Heat the sample to the activating temperature determined from the TAC.
3. Cool to room temperature. Apply test dose (10 mGy) and heat immediately to
150°C to record S N .
4. Cool. Give the sample an irradiation dose of 1.5, (2.5) or (3.5) Grays with a beta
or gamma source to monitor the sensitivity change in the pre-dose peak. Heat to
150 C. Each of the three discs is given a different radiation dose at this stage. The
TL reading does not have to be recorded.
5. Cool. Apply test dose, heat immediately to 150°C to record S' N .
6. Heat to the activating temperature.
7. Cool to room temperature, apply test dose and heat to 150°C to record S N + e .
5.3 CALCULATION
The difference (S N - SQ) is related to the archaeological dose and the value (SN+B -
S' N ) is related to the monitor dose (either 1.5, 2.5 or 3.5 grays) plus twice the test
dose, which will be called D in the equation below. The ED is given by the equation
below where the archaeological dose is equal to ED - test dose.
 185

ED= ^—5_xD

The dose should be the same for all three discs indicating linearity; however there
is probably a systematic error in the measurements (experimental work indicates that
this is probably of the order of around 20%) so the agreement can sometimes be
misleading.
The a-value approaches zero for the pre-dose technique and is assumed to be zero
in calculations. The error limits using this method should be taken to be larger than
with the fine-grain technique and +/-30% is not unreasonable. This is quite sufficient
to establish authenticity without any shadow of doubt for Tang objects, where the
maximum age of copies is 80 years (in 1991) as opposed to a genuine age of 1200
years.
5.4 OBSERVATIONS.
This method is not so straightforward as the fine-grain method. In the first place
two separate TL analyses are required, both of which are time consuming and require
a certain skill in interpretation. Secondly, the TL growth is not linear although it
may appear so over small dose intervals; in fact for low doses it is possible to
overestimate the age and for higher doses, the age can be underestimated. An added
complication is that saturation effects appear to set in at EDs of a few grays, which
is manifest by gross non-linearity and an overestimation of the age. The signs of
saturation are:
1. Little change of sensitivity between S*[ and S'^
2. Increasing EDs with increasing value or the monitor dose.
3. EDs are grossly excessive.
The approach to saturation is hypothesised to be exponential (Chen, 1979). It has
never been established whether the form of the sensitivity growth over the whole
dose range is truly linear at any stage, or whether it can be represented by a single,
non-linear equation, possibly exponential.
The risk of underestimation of the age is particularly associated with those samples
where it is not possible to establish the maximum activation temperature from the
TAC because the TL oven is not able to heat to a sufficiently high temperature.
However it is possible to get some indication of authenticity as it will be obvious that
the object is within 30-40% of the true age and is definitely not modern - or vice
versa.
Another source of uncertainty is whether the value of SQ, in the case of a high SQ,
is the true value or whether there has been any ambient activation (Bailiff, 1979). An
important cause of high SQ sherds is incomplete firing and this is particularly
noticable in the case of African terracottas and bronze cores where the S ^ / S Q ratio
is unity. This is caused by incomplete annealing of the geological signal - the firing
temperatures being probably in the range of 400-450°C.
Before proceeding with dating, the value of S n should be noted. Ideally this should
be as close to zero as possible and for a genuine object S N / S Q should be 10 or more.
However in practice it is rare to find that SQ is so low and it is more usual to have
a value of S N /S 0 equal to 5. For modern copies the ratio will often approach unity
186

as Sxj is low but it should be obvious that the piece is modern, as SM + « should be very
mucn greater than S N . To be completely sure that the sample is modern, the
calculation should be made assuming that Sg is zero and if the TL age is then far
younger than it should be, the piece can be confidently assumed to be modern.
The Tang effect The outstanding virtue of this method is that it enables the
authentication of objects exhibiting the Tang effect which would otherwise be
undatable. Such objects, always from the Tang dynasty of China and having a light
coloured clay body, have a clean glow-curve leading to an excessive TL age. This is
most likely due to some mineral such as zircon in the clay but as yet this has not
been identified. The problem is that such clays are not confined to genuine pieces
but when they occur in a modern copy, it is easy to be misled by this effect and
believe that the object is genuine as the apparent dose is not so excessive that
unfired material is suspected.
6. Other types of fired clay.
6.1 INTRODUCTION.
Although we have dealt in detail with pottery - by which we mean any form of clay
which has been fired between 500 and 900°C, two other types of fired clay can be TL
tested. These are the casting cores of bronzes which are the clay moulds over which
the molten bronze is poured, and stoneware and porcelain, which are, in effect,
pottery fired between 1200 and 1400°C so that the body is partly vitrified,. The
principle of TL dating is the same although sample collection and preparation
techniqes are different.
6.2 BRONZE CORES
In many cases the clay casting core of a bronze is trapped inside parts of the body.
This is particularly true of all types of Chinese bronzes, South East Asian bronzes
such as Indian or Thai, and is often, although not invariably true for Roman bronzes.
It is rarely true for Renaissance and European bronzes where the lost wax method
was used and often little or no trace remains of the original core. Examples of bronze
core testing are given in Fleming (1974).
Sampling Traces of the casting core may be seen in the base of objects and if the
base is open, it should be possible to see if there is more core trapped inside the
object. South East Asian bronzes are almost always completely enclosed and a hole,
about 5mm in diameter, has to be drilled in the back to gain access. Chinese bronzes
with handles normally have a "seam" line where the handles are not completely
closed and it is then possible to extract core material. It is not desirable to use
material from the base as it is frequently contaminated but if this is unavoidable, the
remanent core should be sufficiently thick that at least 2 mm can be scraped from
the outside before taking the TL sample. Core from inside an enclosed body is
fortunately protected and apart from the risk of wax or corrosion products in the
sample, it should be uncontaminated. Cracks in the body through which soil or ground
water could seep should be regarded with caution.
Before taking any samples the object should be minutely examined for signs of
welded areas where damage has been repaired. Welding raises the temperature of
the metal to several hundred degrees and the core just beneath will almost certainly
have been thermally drained. Although bronze is a good conductor of heat, pottery
 187

is a poor one, so it is likely that a sample of core at a site remote from the
renovation will not have suffered adverse effects. It is very important to examine
joints such as the neck of figures to see if there is a tell-tale line indicating that the
head has been missing at some stage in the history of the piece. There is a good
chance that an unrelated head has been substituted so if there is any suspicion it is
strongly advisable to take a sample from the head as well as the body.
The core should be sufficiently soft that it can be removed with the drill or a metal
probe or scoop. A bicycle spoke bent at the end makes an excellent probe for
reaching in small holes and up into bodies. Since extracting core material does not
damage the object in the same way as it does for pottery (apart from the hole which
may have to be drilled for access), as much sample as possible should be taken as
long is there is no risk of contamination. This ensures that a 42 mm ring alpha count
can be made as well as there being 100 mgm of sample available for potassium
analysis. In addition, if there is any question about the fine grain result, the piece
can be dated by the quartz inclusion method (Fleming 1978).
Quartz inclusion dating If there is any doubt about the purity of the sample it is
possible to use the quartz inclusion method to authenticate the piece as there is
usually a high proportion of large grains in most bronze cores. Occasionally ground
water carrying fine particles of soil will permeate any exposed core, such as in the
base for example, and these will be deposited in the core material itself and since
the particles are very fine, they will tend to mix with the fine grains during sample
preparation and be deposited on the discs. 100 u.m quartz grains are used in inclusion
dating and these samples should be free from contamination by fine soil grains.
The sample for testing should be crushed and sieved and grains between 90 and 150
u.m diameter collected. Since there is likely to be relatively little sample available,
it is advisable to crush gently and for short periods only, to maximise this fraction.
When all the sample has passed through the 150 u.m sieve, the coarse fraction should
be sieved again through the 90 jim sieve to remove as many fine grains as possible.
The coarse fraction should then be washed in acetone to remove the rest of the fine
particles clinging to individual grains. After drying, the sample should be suspended
in dilute HC1 to remove carbonates. It is now ready for the etching process.
The sample is etched for 40 minutes in concentrated HF, stirring every 5 minutes
to ensure that all the grains are in complete contact with the acid. After this time
the acid is poured away and the sample washed 6 times in distilled water using the
centrifuge to ensure that no grains are lost in the process. An alternative methods,
after the acid has been discarded and after the first water washing, is to wash the
grains thoroughly through a 60 jim mesh sieve. This is followed by washing three
times in acetone using the centrifuge as before. The grains are then dried. The
grains should roll in the test tube when they are dry if the washing has been
sufficiently thorough.
No other reagents should be needed as their use only masks the basic problem that
some acid remains. The water washing should be repeated if the grains appear
"sticky" or if the acetone goes cloudy as this is an indicator of incomplete washing
and proceeding with the analysis even after the use of other reagents will result in
residues being deposited in the glow oven and the appearance of spurious peaks in the
glow-curve.
Finally the grains should be sieved using a 90 jim sieve and any which pass through
the sieve should not be used for inclusion dating as the dosimetry will be affected.
However if very little sample remains after this treatment, they may be included as
it is imperative to get a result even if a small error is introduced into the final
calculation as this is unlikely to be more than 5%.
Heavy liquid separation. It is advisable to remove any zircon or heavy minerals
which may contain radioisotopes as their inclusion in the sample can result in an
overestimate of the ED. Sodium polytungstate solution with a density of 2.8 is
sufficient and the sample should be placed first into the test tube and the solution
slowly added. Centrifuge at the slowest speed for 1 minute. At the end of this time
the quartz should be at the top of the tube and it may not be possible to see anything
at the bottom. The bottom of the tube should be frozen in a flask of liquid nitrogen
and the remaining liquid quickly tipped into a beaker. The sides of the tube should
be washed in water to remove all the light (quartz) grains.
The grains should be washed into a 60 jim sieve and repeatedly rinsed in water. If
the water is slightly warm it will help to remove the polytungstate more efficiently.
No trace of polytungstate should remain as it gives a spurious TL signal. After
washing the grains should be dried.
Ideally more than 6 mgm of quartz grains should be spread in a monolayer on each
disc using a minimal amount of oil (either Viscosil or Silkospray). However this might
not be possible with authenticity samples as the yield may be too small so the
scatter will be high. Around 10% scatter can be expected among 20 discs each
carrying about 6 mgm of sample. Weight normalisation is of no value as the TL comes
principally from around 3% (Zimmerman, 1971) of the grains and if there are too few
grains the statistics are poor. However it should be possible to confirm whether the
piece is authentic from a few measurements. No alpha measurements need be
carried out as the a-value approaches zero with 100 u.m inclusions. It should be
remembered that the source calibration for quartz inclusions is 17% higher than for
fine grains.

6.3 Porcelain and stoneware.

The technique for testing porcelain is described by Stoneham (1986). Both porcelain
and stoneware have clay bodies which are sufficiently high fired to be partly
vitrified. This has a two-fold effect. As the bodies are so hard, normal drilling
techniques are ineffective and the sample becomes overheated - to the extent that
on some occasions sparks are produced from the burning particles. In addition there
is no crystalline structure to the body which consists of particles of quartz whose
edges have fused into a sea of glass produced by a quartz and feldspar interaction.
This affects the TL signal which is often weak and unrelated the archaeological age
and in addition has gross fading properties as well as sensitivity changes.
Triboluminescence is also a problem although it has been reported that washing any
grains for a short period in concentrated HF removes this effect.
Drilling. Diamond and sapphire are both harder than porcelain so either can be used
although diamond is the easiest to obtain. A hollow core drill should be used of 5 mm
external diameter with a wall of 1 mm embedded with diamond. The diamonds should
be as small as possible and there should be diamond on the cutting edge of the drill.
It is advisable to have some kind of frame to support the drill to hold it steady as this
can be very difficult when the drill is hand held; and also when the drilling procedure
is started the drill has a tendency to skate over the glazed surface. For this reason
the sampling site should be at least 1 cm thick and if the site is a base rim this
should be 1 cm wide to avoid the risk of damage to the edges, either before the drill
starts to cut or when removing the core.
All drilling must be carried out under running water which should flow over the
cutting edge at all time, otherwise the sample overheats and diamonds can be
stripped from the drill. The water supply can be either from the tap or alternatively
 189

can flow through the centre of the drill. The motor should be powerful enough to
sustain the cutting action, more power is required than when drilling pottery. The
speed of the drill should be adjusted so that it is the minimum to sustain the cutting
action without jamming the drill and burning out the motor. If the speed is too fast,
a lot of sample is lost from the side of the core. The core should be about 5 mm long
and when drilling has finished it will usually still be attached to the body of the pot
at its lower end. To remove the core, a small hollow tube with a small segment cut
out of the lower rim, should be placed completely over the core and moved from side
to side. This should snap the core away from the body and it can then be withdrawn.
The tube will have to be manufactured in the laboratory to the worker's own
specification.
The core has to be cut into slices 200 jim thick. This can be done with a diamond
impregnated annular blade, with the sample fixed in place with dental wax. Water
must Flow over the sample while it is being cut. Alternatively the sample can be
attached to aluminium probes 15 mm long with Superglue. These probes have the
virtue that the sample can be cut down to the last 200 um. The two outer slices
should be discarded as as they have been exposed to light. However the light will not
have penetrated below this depth. About 6 slices can be cut from one core. All
discarded fragments should be retained for alpha counting and potassium analysis.
Measurements Only pre-dose analysis is suitable for porcelain testing as the high
firing affects the high temperature signal. The matrix contains partly vitrified
quartz grains which retain their crystalline nature in the centre and this gives rise
to a pre-dose signal.
One slice is used to determine the form of the TAC using a platignum cup to
support the grain if an automatic TL system is used. Otherwise the slice can be place
directly on the plate. No oil is needed. The heating rate should be as low as possible
as porcelain is a heat insulator and as the signal comes mainly from the upper
surface, there will be a considerable temperature lag. In most cases the activation
temperature will be between 600 and 700 °C. The second stage of measurement is
carried out exactly as described for the discs. The sources should be calibrated for
both grey and white porcelain (these values are different) and the beta dose delivered
can be 30-40% higher than to fine-grains on aluminium if a plaque type source is
used. The values are different again for ceramic sources.
The criteria for accepting the values and the dose-rate calculations are the same
as for pre-dose dating with grains. High fired materials are waterproof and so it can
be assumed that they have been completely dry throughout their lifetime so that one
source of systematic error has been removed. However the error limits should still
be assumed to be 25-30% as for more conventional pre-dose authenticity testing.
7. Clandestine Irradiation
Although this is a popular topic for academic discussion, there are probably easier
ways of passing an object off as a fake, as discussed in the section SAMPLING,
Examination. In priciple the TL age can be increased by exposing the object to a
form of penetrating ionising radiation such as from a cobalt or caesium gamma
source, as this has the same effect as the beta irradiation from the radioactive
inclusions inside the pottery body. However if all the measurements are carried out
systematically and any suspect glow-curves are discarded, it would be very difficult
for an irradiated object to pass the test although in the hands of a skilled TL worker
it would not be impossible. If there is any suspicion of irradiation, it is necessary to
examine any zircons in the pottery, if they can be extracted. Zircon grains have a
190
high concentration of uranium inclusions and most of the dose carried by zircons is
from these radioactive inclusions. A description of the technique is given in the paper
by Zimmerman et al. (1974) which describes the authentication of core material from
a bronze horse. It is possible that bronze cores are the only material which can be
extracted in sufficient quantities for this type of analysis as far more material is
required than for fine-grain dating.
8.Glozel
No article on authenticity testing would be complete without reference to the site
of Glozel in France, and a resume of the facts can be be found in the catalogue of
the exhibition at the British Museum, "Fake? The art of deception" (Stoneham, 1990)
Several thousand objects have been recovered from this site since its discovery by
Emil Fradin in 1924, and controversy over the finds raged for several years until,
after two court cases, interest waned. However the controversy flared up again after
the publication by McKerrell et al. (1974) of TL dates from several objects from the
site showing that they were ancient. Acrimonious debate followed this and currently
there is a research project investigating these claims, publication of which is
expected in 1992. In effect, the whole reputation of thermoluminescence
authenticity testing hangs in the balance - is Glozel the limit to which the method
can be applied?

100 200 300 100 200 300 400 50(

Temperature ('C) Temperature fC)

Fig.l. Glow-curves from a genuine Fig.2. Glow-curves from a modern

Tang dynasty horse. Curve A is the
natural, N and curve B is N+P where
? is a laboratory irradiation of 5 Gy.
he ED is 5.8 Gy.
copy of a Tang dynasty horse. A is the
natural TL, N and B is N+P where 6 is
a laboratory irradiation of 5 Gy. The
ED is 0.4 Gy.
 191

REFERENCES
Aitken M.J., Fleming, S.J., Reld, J., Tite, M.S., (1968) Elimination of spurious
thermoluminescence, Thermoluminescence of Geological Materials (ed. by D.J.
McDougall, Academic Press), 133-142
Aitken M.J., Alldred, J.C.,(1972) The assessment of error limits in
thermoluminescence dating, Archaeometry, 14, 257-267
Aitken, M.J, (1979) Pre-dose dating: predictions from the model, PACT 3, 319-324
Aitken, M.J. (1985) Thermoluminescence Dating, Academic Press (London).
Bailiff I.K., (1979) Pre-dose dating: high S 0 sherds. PACT 345-355.
Chen, R., (1979), Saturation of sensitization of the 110°C TL peak in quartz and its
potential application in the pre-dose technique.
Fleming, S.J. (1971) Thermoluminescent authenticity testing of ancient ceramics: the
effects of sampling by drilling.
Fleming, S.J. (1973) Thermoluminescence and glaze studies of a group of Tang
dynasty ceramics, Archaeometry, 15, 31-52
Fleming, S.J. (1974) Thermoluminescence dating of ancient ceramics and bronzes,
Medicine, Science and law, 14, 11-14
Fleming, S.J. (1975) Authenticity in Art. The Institute of Physics, London and Bristol.
Fleming, S.J. (1978) The quartz inclusion method, Pact,2, 315-318
Haskell E.H., Bailiff, I.K., (1985) Diagnostic and corrective procedures for TL
analysis using the pre-dose technique, Nucl. Tracks 10, 503-508
McKerrell, H., Mejdahl.V., Francois, H., Portal, G. (1974), Thermoluminescence and
Glozel, Antiquity, 48, 265-272.
Stoneham, D. (1986) Porcelain dating using thermoluminescence, Scientific and
Technological Insights on Ancient Chinese Pottery and Porcelain, 339-343
Stoneham, D. and Winter, M.B. (1988) The removal of anomalous fading in
authenticity samples, Nuclear Tracks and Radiation Measurements, 14, 127-130.
Stoneham, D. (1990), The mysterious discoveries at Glozel, article in Fake? The art
of deception, ed. M. Jones, British Museum Publications Ltd, London.
Templer, R.H., (1985) The removal of anomalous fading in zircons, Nuclear Tracks
and Radiation Measurements, 10, 531-537.
Templer, R.H., (1986) The localised transition model of anomalous fading, Radiation
Protection Dosimetry, 17, 493-497
192

Wintle, A.G., Aitken, M.J., Huxtable, J, (1971) Abnormal thermoluminescence fading

characteristics, Proc. 3rd. Int. Conf. Lumin. Dosim., Riso, Denmark, 105-131
Zimmerman, D.W. (1971) Thermoluminescent dating using fine grains from pottery,
Archaeometry, 13, 29-52
Zimmerman, D.W., (1972) Relative thermoluminescence effects of alpha-and-beta-
radiation, Rad. Eff., 14, 81-92
Zimmerman, D.W.,Yuhas, M.P., Meyers, P. (1974) Thermoluminescence authenticity
measurements on core material from the Bronze Horse of the New York Metropolitan
Museum of Art, Archaeometry, 16, 19-30.
Zimmerman, J., (1971) The radiation-induced increase of the 110°C
thermoluminescence sensitivity of fired quartz, J. Phys. C : Solid State Physics., 4,
3265-32
PART III

Methods based on Natural Rhythmic,

and Chemical Changes
DENDROCHRONOLGY

M.G.L.Baillie
School of Geosciences
Queen's University, Belfast
Northern Ireland

The origins of the method

As a dating technique, dendrochronology makes use of the annual nature

of tree-growth. The regular year-on-year production of tree-rings

represents a natural clock linked precisely to solar years. At its

simplest, an ancient tree stump, in a forest, can be dated by

comparing Its pattern of wide and narrow growth rings with the ring

pattern of a nearby living tree of the same species.

In the United States, 1n the early 20th century, Douglass observed

that such procedures actually worked for drought stressed pines. He

then used the same logic to extend the overall tree-ring pattern far

back in time by overlapping patterns from living trees to older

historic and archaeological timbers. A tree-ring master pattern 1s

therefore a year-by-year record of average ring width extending back

for hundreds or thousands of years. With such a long master

chronology, for a particular species and for a restricted geographical

area, it becomes possible to date samples of ancient wood, of that

species and from that area, by comparing the sample pattern with the

master pattern, see Figure 1.

The only limitations on the method relate to the length of the

available master chronology and the number of growth rings 1n the

sample. This latter point 1s particularly Important because, as with

fingerprinting, there must be sufficient "pattern" to ensure a unique

"match" between the sample and the master pattern. So

dendrochronology, 1n any area and for any species, 1s dependent on the

existence of a long master chronology and on long-lived samples. By

195
H. Y. Goksu el at. (eds.), Scientific Dating Methods. 195-215.
C 1991 ECSC, EEC, EAEC, Brussels and Luxembourg. Printed in the Netherlands.
 SAMPLE RING PATTERN

SEARCH MATCH f
DATE

11 1
1
1 I
1
Y MATCH

1 SITE MASTER
▼ t
DATE

Fig.1 Schematic r e p r e s e n t a t i o n of the dating process for e i t h e r

s i n g l e samples or s i t e chronologies
 197

1929 Douglass had constructed a pine chronology for the American

south-west which ran back to AD 701. He was therefore able to supply

precise felling dates for timbers from prehistoric Amerindian sites

simply by matching their ring patterns against the master chronology.

This new level of chronological refinement was revolutionary in

archaeology (Bannister and Robinson 1975).

It is important to realise the debt that dendrochronology owes to

Douglass. He addressed most of the major problems associated with the

method and demonstrated that it could be made to work successfully and

repeatably. Moreover, right from the start there was more to the

method than simply dating ruins for archaeologists. Douglass

recognised that the annual variations 1n ring width must be a response

by the trees to alterations in the climatic or environmental factors

affecting their growth. In the semi-arid Southwest his chronology

represented a proxy record of past rainfall modulated by longer term

changes 1n solar output - the factor which particularly interested

Douglass.

Thus, in addition to dating information, it 1s now generally

recognised that tree-ring chronologies represent stores of past

environmental Information. Douglass's work undoubtedly set the scene

for all that was to follow. There are two main issues, namely dating

and environmental reconstruction, with many sub-Issues relating to

specific areas and specific research topics. The main developments 1n

the last six decades have been as follows:

First, and still 1n north America, there was the construction of the

very long brlstlecone pine chronology - spanning some eight millennia

(Ferguson 1969). Although this work had no direct dating applications

for archaeologists, 1t did allow the isolation of precisely dated

samples for calibration of the radiocarbon timescale. By 1970 that

work had allowed the comparison of tree-ring dates and radiocarbon

dates back to 5200 BC with consequent correction tables for the

conversion of radiocarbon date ranges to calendar date ranges (Suess

198

1970). That work in itself was one of the most important applications

of dendrochronology co the refinement of chronology. Again, workers

were quick to exploit the environmental potential of these long

records.

The second major development was the spread of the method into Europe

and, as importantly, into the study of deciduous oak. The European

beginnings were a direct result of the success of Douglass's efforts

but they were necessarily rather slow - it was the 1960s before the

first oak chronologies, covering the last millennium, were published.

The reasons for this are obvious. Compared with the long-lived and

highly sensitive American pines European oak is relatively short-lived

and less responsive to single climatic parameters. Thus

cross-matching the ring patterns of oak was more "difficult" and to

builrl a long chronology more successive cross-matches were necessary.

In retrospect, it is now clear that the flowering of European

dendrochronology was intimately connected with, indeed was dependent

upon, the availability of computers. With access to powerful

computers, from the late 1960s, it became possible to use

"statistical" matching programs to aid in the cross-dating process.

So, in both Ireland and Germany the 1970s saw the construction of oak

chronologies comparable in length to the bristlecone pine.

These European efforts, although effectively independent, had many

aspects in common. For the prehistoric period, both relied on the

preservation of large numbers of sub-fossil oaks from the later

Holocene in either bog or river gravel deposits; both saw as a goal

the duplication and checking of the Suess/Ferguson radiocarbon

calibration, using European - Old World - wood samples; both would

Inevitably provide precise calendar dates for some wood-bearing

archaeological sites; both envisaged the eventual production of useful

environmental information. In the discussion which follows, the '

species under consideration is European oak

 199
Applications of dendrochronology

Living trees

In each new area the construction of a basic master chronology tends

to follow the same course. Studies on trees with known felling dates,

or on cores from living trees, allow the testing of methodologies for

cross-dating. Site masters are constructed and compared to ascertain

the distance over which reliable cross-dating can be achieved.

Additional studies - replication between chronologies and comparison

with historical records - allow the exact calendrical nature of the

method to be proven; it is obviously important to demonstrate that the

species being studied does not miss or duplicate growth rings.

With a reliable methodology established the chronologies are then

extended by overlapping with site chronologies constructed using

timbers from historic buildings.

Dating buildings

Once a chronology from an historic building has been firmly

cross-matched with the living-tree chronology, 1t is immediately

possible to supply felling dates for those historic timbers.

Similarly, with the new extended chronology the dendrochronologlst can

begin to date samples from buildings of known or unknown date. In the

former case, dating timbers from buildings with historical

documentation, 1t 1s possible to check for factors such as timber

storage, seasoning, re-use and refurbishment. Hollsteln (1980) was

able to demonstrate that in a large number of German cases felling was

between one and three years before the recorded building dates. This

evidence 1s of course extremely useful as it suggests that the felling

dates of timbers do supply a very good guide to the actual dates of

construction.

One limiting aspect of dendrochronology quickly becomes apparent

when dating medieval buildings. This relates to the question of

200

sample completeness. The dendrochronologist may be adept at measuring

the ring pattern of a sample and dating that ring pattern against a

master chronology: the result being a precise date for the last

existing growth ring on the sample. However, it is soon apparent that

not all samples are complete out to the underbark surface - the

felling year. So there can be a difference between the date of the

last ring on the sample and the felling date of the tree from which

the sample came. Such considerations are obviously extremely

important when dealing with samples from an historical context. It is

at this stage that questions relating to the number of sapwood rings

(the outer zone of growth rings immediately beneath the bark -

fortunately easily recognisable in oak) are resolved and allowances

for missing or damaged sapwood are produced. To reinforce the fact

that dendrochronology relates on a biological system, it has been

observed that the number of sapwood rings in a mature oak varies

geographically. For example, sapwood in Irish oaks represents 32+/-9

rings whereas in the eastern Baltic the figure is 14+/-3 (Bail lie et

aj., 1985). So as well as constructing regional chronologies it is

also important to produce regional sapwood estimates.

Replication

The construction of chronologies back into the medieval period also

highlights the internal consistency of the tree-ring method. It

becomes apparent that the method can be checked internally at three

levels. The first level relates to the construction of site

chronologies. By averaging the Information from a number of ring

patterns, themselves in precise chronological synchronization, it is

possible to iron out a lot of the "noise" in the individual tree-ring

patterns and produce a site master which has a stronger and more

stable "signal". Consistent cross-matching between a number of •

individual ring patterns is called primary replication. Other site

 201

chronologies serve to confirm existing chronologies and links between

chronologies - this is secondary replication. Finally there is the

ability to compare whole chronologies, constructed by independent

workers. T his allows for overall chronological synchronization -

tertiary replication. It is replication which makes dendrochronology

the robust discipline it is. In the case of the German oak

chronologies it could be demonstrated that four independent workers

had all produced chronologies back to AD 1000 which were in exact

synchronization. T he Irish medieval chronology was proven to be 1n

exact synchronization with the German chronologies by step-wise

correlations via English chronologies (Baillie 1982).

These exercises made it apparent that, for oak, the matching

"signal" extended over very considerable geographical distances, in

northern Europe, and suggested that the dating method was 1n fact very

stable. Any new, internally replicated, chronology section - of

reasonable length - will tend to cross-date with neighbouring

chronologies over distances up to hundreds of kilometres.

Trade

The latter points open up some Interesting lines of enquiry. T he

matching signal is very widespread but does have a strong geographical

component. For example, although strong cross-dating can be

demonstrated between Irish and English chronologies or between north

and south German chronologies, individual ring patterns will tend to

match better against more local chronologies. T his suggests that,

once a widespread grid of chronologies is available - as is the case

for oak 1n northern Europe - it should be possible to source timbers.

Indeed this turns out to be the case. Recent examples show that oaks

used in England and T he Netherlands in the later middle ages were

imports from the Baltic (Baillie et al.. 1985), while Eckstein has

traced timbers from dark age Dorestad to their source area some 350 Km

up the Rhine (Eckstein et al.■ 1984). Even more exotic 1s the recent

attribution of one of the "Danish" Roskilde boats to an original

202

source in Ireland (Bonde pers com).

Other information from tree-rings

It has also become apparent, from various difficulties in acquiring a

continuum of samples from all periods, that reflections of

socio-economic activity could be deduced from the depletions and

re-generations of medieval trees. For example, there is a clearcut

building hiatus in the mid-fourteenth century which highlights the

effects of the Black Death on the building activities of humans across

Europe, from Ireland to Greece.

Dating archaeological sites

As the application of dendrochronology is pushed progressively back

into the 1st millennium AD, and beyond, there is increasing

involvement with archaeological timbers. Archaeological applications

differ from the experiences with building timbers principally in the

condition of the timbers and in the greater difficulties experienced

in putting together a master chronology. Compared with medieval

chronology construction, where buildings of a particular century can

be targeted for suitable samples, archaeological sites are often

poorly dated in advance. Chronology construction depends, to a large

extent, on the availability of museum specimens and samples from

ongoing excavations. As regards condition, archaeological samples are

normally uncovered wet and with sapwood which has deteriorated during

burial. Thus the dendrochronologlst has to alter measurement and

storage practises to cater for the more difficult wet samples.

The eventual reward, once a suitable master chronology has been

linked together, is the production of precise dates for archaeological

timbers and, normally, a rapid firming up of the chronological

framework of periods which were previously only loosely dated.

Simple, single phase, archaeological sites can often be precisely

dated to the year of construction. More complex sites can be

Investigated for evidence of multiple felling episodes and for

 203

synchronization of activity 1n different areas. While the individual

dates are of obvious interest to the archaeologists concerned, the

accumulation of dates from wide spreads of sites soon begins to show

up phases of activity on larger scales. In Ireland it became apparent

that the construction of sites, where oak timbers were utilized in

waterlogged contexts, was far from uniform in the first millennium AD

(Baillie 1988), see Figure 2. The distribution may well be of more

interest to historians than to archaeologists as one of the phases is

bracketed by two well recorded outbreaks of plague in the AD 540s and

the AD 660s. Interestingly both Becker (1974) and Hollstein (1980),

following a post-Roman lull, found an upturn in the number of dated

oak coffins in Germany beginning within a decade of the mid-sixth

century.

This sort of information, providing a context for the individual

sites and for the human activity represented by site construction, 1s

of wider Interest, and probably of greater importance, than the simple

dating of sites and objects.

Prehistoric chronologies

It 1s probably fair to say that it 1s the prehistoric period in

northern Europe which stands to benefit most from the application of

dendrochronology. Moreover, in the BC era, there is a clearer balance

between environmental and archaeological information. As noted above,

the long oak chronologies, going far back Into prehistory, were

originally envisaged as tools for refining the radiocarbon dating

method and for unravelling aspects of Holocene bog and river gravel

development. The vast majority of the timbers used in the prehistoric

chronologies had survived in purely natural conditions. The eventual

precise dating of some prehistoric timber structures could be regarded

purely as fallout from more inherently environmental projects.

In retrospect, given the length of the tlmescale Involved, the •

construction of the major oak chronologies in both Ireland and Germany

 2

MAJOR PLAGUES

544 664
■7

5
IRISH ARCHAEOLOGICAL SITES
3

nr
DATED BY DENDROCHRONOLOGY

fl a QL 1

AD 100 200 300 400 500 600 700 800 900 1000

Fig.2 The numbers of Irish archaeological sites, for each

quarter century of the 1st millenium AD, which have
been dated by dendrochronolgy.
 205

was extremely rapid. This was partly a result of the large numbers of

sub-fossil timbers available and partly a result of the character of

individual "site" assemblages. Whereas archaeological sites

inherently tend to represent defined episodes of activity, natural

groves of oaks tend to be part of regenerating systems. Groups of

trees found in peat deposits, or in river gravels, tend to show a

spread through time. Thus sub-fossil site chronologies tend to

represent many hundreds (sometimes thousands) of years of chronology.

These long chronological building blocks meant that the overall

Irish and German oak chronologies were pieced together very rapidly,

between 1970 and 1984 (Pilcher et al 1984; Leuschner and Delorme

1984). Moreover, independent work meant that the whole system could

be checked by tertiary replication. With the basic chronologies

complete, Becker (1982) could publish his definitive survey of the

development of German river valleys during the later Holocene.

Similarly two parallel high-precision radiocarbon calibration curves

were completed by the mid-1980s (Pearson et al., 1986; Stuiver and

Becker 1986); prehistoric chronology had come of age.

Prehistoric dating

With completed chronologies available, to beyond 5000 BC, it was

immediately possible to provide precise calendar dates for some oak

bearing archaeological sites back as far as the Neolithic, from

Switzerland (Becker et al.. 1985) to England (Hlllam et al.. 1990).

Such datings demonstrate nicely that there is no fall off in precision

with Increasing age. The major Corlea 1 track in central Ireland was

constructed using timbers felled either late in 148 BC or early in 147

BC (Raftery 1990) whereas the English Sweet Track timbers were felled

either late in 3807 BC or early in 3806 BC. With samples complete to

the underbark surface, it is possible to supply dates to such

resolution wherever master chronologies and suitable long-lived

samples exist. While such precise archaeological datings are

impressive achievements in themselves, as yet, too few sites have been

206

dated to allow the tracing of cultures or typologies over wide

geographical areas; such possibilities will come with time.

At present, much effort is going into environmental reconstruction.

With many hundreds (indeed thousands) of ring patterns tied down

precisely in time it is possible to investigate phases of growth

initiation and phases of die-off both within deposits and between

deposits (Leuschner and Delorme 1988). Ultimately phases can be

checked on independent bog systems in Ireland, England and north

Germany. These in turn can be checked against phases of river erosion

in central Europe (Becker 1982) as well as against accumulating

evidence for human activity.

One surprising revelation from this type of work has been the

recognition that the environmentally sensitive Irish bog oaks appear

to have been recording the effects of major prehistoric dust veils.

Coincidences between the dates of significant acidity layers in the

Greenland 1ce-cap (Hammer et al 1980) and episodes of widespread

occurrence of narrowest growth rings 1n Irish oaks has led to the

identification of a series of dates which may prove to have

significance for prehistoric populations. The dates are 4370 BC, 3195

BC, 1628 BC, 1159 BC, 208 BC and AD 536 (Baillie and Munro 1988). It

1s already apparent that the last two of these dates are Intimately

connected with known trauma for human populations, while 1159 BC and

1628 BC could easily prove, in due course, to be archaeological marker

horizons (Baillie 1991).

The serious application of dendrochronology is bound to

revolutionize archaeological studies. Rigid chronological frameworks

will allow the tracing of change through time. The identification of

environmental events, whether catastrophic or advantageous may help

with the interpretation of such changes in the archaeological record.

The great advantage being that both dates and environmental

Information derived from tree-rings are on exactly the same tlmescale;

real-time comparisons will become possible. For example, we now know

 207

that there was a significant volcanic dust-veil event which started in

208 BC. Its effects were felt dramatically in China, where large

numbers of people died due to famine (Wiseburd 1985). There are

indications of a synchronous downturn in Irish, German and American

trees - in 207 BC, 208-204 BC and 206 BC respectively. Recent

evidence shows that in ancient Rome, around 205 BC, there were

"unusual atmospheric apparitions, epidemics and a disruption of the

food supply" (Forsyth 1990). Such dating resolution in itself supplies

pressure for general chronological refinement. It becomes important

to know that a major phase of river gravel deposition began in central

Germany immediately after the 208-204 BC event rather than before. If

the event was the cause of real change in the archaeological record

this will only become apparent when the archaeological record is dated

to equivalent precision.

Inevitably the success of dendrochronological application will

encourage the construction of more and more chronologies. One

principal aim has to be the application of the method in the Aegean

and the Near East. Kuniholm and Striker (1987) have made a dramatic

start and already has sections of chronology totalling some thousands

of years. This holds out hope for the ultimate resolution of specific

dating questions relating to Egypt, Mycenae, Switzerland and Wessex,

amongst others.

Practicalities

As noted above, the dating of long-lived oak samples is now routine in

many areas of northern Europe, particularly within a broad triangle

bounded by Ireland, Sweden and Switzerland. Within that area a series

of long master chronologies are already 1n existence. Moreover, the

chronologies form part of a well replicated system. So, for northern

Europe the first major criterion of dendrochronology has been

fulfilled.

The other main criteria relate to the length of sample ring

208

patterns and to sample completeness. It 1s in these areas that

control slips away from the dendrochronologist. However, it is in

these areas that the consumer - the archaeologist or geomorphologist

or building historian - can help to maximize dating potential. There

are several simple rules.

1) Wherever possible multiple samples should be taken. Experience

everywhere shows that dating success increases considerably if a site

chronology can be constructed. A mean chronology of even four or five

trees will stand a much better chance of being dated than a single

ring pattern.

2) Where multiple samples are available, selection should be for

a) samples from different trees,

b) long ring patterns and

c) the presence of sapwood, ideally complete sapwood.

3) Wherever possible involve an experienced dendrochronologist before

sampling.

Such rules have certain repercussions for excavation and post

excavation practise. For example, if substantial oak posts with

sapwood are uncovered early in an excavation it becomes important to

immediately safeguard the all important sapwood. Frequently samples

have been left exposed during excavation with resultant sapwood loss -

the sapwood being much less robust than heartwood after burial. While

the timbers have still been datable, the critical information - the

exact felling dates - have been lost. In many contexts, for example,

those relating to historical events or relating to other

dendrochronologically dated sites or events, the absence of a felling

date may severely limit the usefulness of the tree-ring dates.

The dating process and its limitations

Assuming that suitable timbers are provided by the consumer, the task

of the dendrochronologist is to measure the sample ring patterns'and

cross-date them. It is at this point that geographical location, the

 500 1000 1500 AD 2000
— I — 1

• t IRELAND 11 t

t = 6.5 4.2 6.6 8.1

\ SOUTHWARK MERSEA REF6 ENG-WALES

8.0 4.9 7.5 5.8

J
i i GERMANY ii •
^

Fig.3 Consistent tertiary replication in the datas of sections

of English chronolgy against Irish and German master chrono-
logies.
210

length of ring pattern and the number of available samples become

critical.

The geographical factor comes into play when the sample(s) are from

an area at some distance from the nearest master chronology. In such

cases long-lived samples will always stand a better chance of dating

than short samples and site chronologies, composed of a number of ring

patterns, will always tend to have greater likelihood of unique dating

than individual samples. Fortunately, as time goes on, more and more

local chronologies become available and many regions, for example

Germany, become effectively "saturated" from the point of view of

chronological coverage.

The question of the length of ring pattern needed for successful

dating is a more vexed one. Where patterns of hundreds of years are

involved absolutely unique dating is virtually certain. Ring patterns

or site master chronologies can be compared with local master

chronologies using statistical computer programs such as CROS (Baillie

and Pilcher 1973) or CR0SS84 (Munro 1984). It is important to

remember that the dendrochronologlst is not really using the

correlation program to date the sample - obviously no level of

statistical correlation would confer absolute certainty - rather the

dendrochronologist is using the computer to Indicate where the true

matching position is likely to be. Practised human judgment and

back-up correlations against both other chronologies and individual

ring patterns either confirm or reject any particular matching

position. It is in this way that several levels of replication can be

built into the decision making process. Figure 3 shows examples of

tertiary level replication, where sections of English chronology can

be dated against two independent chronologies.

These last statements go some way towards explaining why the length

of sample ring patterns is the critical factor. If the ring pattern

1s "short" it can be "matched" 1n more than one, position - possibly

many positions. It then becomes Impossible for the dendrochronologist

to achieve a unique dating. The question, of course, is the minimum

 211

useful length of ring pattern. Here experience is important.

Individual ring patterns should be very long - where possible hundreds

of years. Replicated site chronologies can, because of their enhanced

signal, afford to be shorter - down to perhaps 100 years. With

samples or site chronologies spanning less than 100 years, dating can

still be possible, especially within a restricted area or where the

samples are otherwise in very tight control. However, it will often

be the case that with such short sequences, qualifications may have to

be written into any report on the dating exercise. Indeed, there

comes a point where, although interesting information may be obtained

by comparing very short lived material, that information is no longer

dendrochronological. For example, if ten roundwood posts from a

single structure each contain only 40 growth rings, it may be possible

to demonstrate that all belong to the same phase (or are not

inconsistent with a single phase). While such an observation may be

of interest, it is completely different from absolute dating. Such

exercises should logically be called tree-ring studies to

differentiate them from dendrochronology. Dendrochronology as a term

implies Involvement with absolute dating.

It is evident from these last points that there has to be a grey

area between dendrochronology and tree-ring studies, and that grey

area falls somewhere between the absolutely certain dating frequently

achieved with long ring patterns and the non-dating of very

short-lived sequences. As a guide, a useful cut-off is around 100

rings. For anyone concerned about this issue, the following

observation may be of assistance. The methodology used with such

success in constructing the long European oak chronologies was devised

and tested on the matching of long-lived trees - long ring patterns.

With ring patterns longer than 100 years, that same methodology is

known to hold with a high level of success. Straight application of

the "long-lived oak" methodology to short ring patterns will, on the

basis of even the most preliminary tests, show that there will be
212

frequent errors (Pilcher and Baillie 1987). So, if a consumer wishes

to have short-lived samples "dated" that customer must ask the

dendrochronologist to prove that such dating is reliable i.e. a new

short sample methodology, must be justified.

Conclusion

Dendrochronology is of limited applicability in terms of species,

geographical area and sample length. However, where it is applicable,

its results are second to none in terms of calendrical precision.

Thus sites with dendrochronological dates tend to become intrinsically

more important than other sites in any review situation. Precisely

dated sites can be fitted immediately into the developing scheme of

environmental change; more poorly dated sites must inevitably take

second place.
 213

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Baillie, M.G.L. (1982) Tree-Ring Dating and Archaeology. Croom-Heim

London

Baillie, M.G.L. (1988) Marker dates - T u r n i n g P r e h i s t o r y into History

Archaeology I r e l a n d 2, No.4, 154-155

Baillie, M.G.L. (1991) Marking i n Marker Dates: towards an archaeology

with h i s t o r i c a l p r e c i s i o n . World Archaeology 23, No.2, 233-243

Baillie, M.G.L. and Munro, M.A.R. (1988) I r i s h t r e e - r i n g s , Santorini

and v o l c a n i c dust v e i l s . Nature 332, 344-346.

Baillie, M.G.L. and P i l c h e r . J . R . (1973) A Simple C r o s s - d a t i n g Program

f o r Tree-Ring Research Tree-Ring B u i l e t i n 33, 7-14.

B a i l l i e , M.G.L., H i l l a m , J . , B r i f f a , K. and Brown, D.M. (1985)

Re-Dating the E n g l i s h A r t - H i s t o r i c a l Tree-Ring Chronologies Nature

315, 317-319

B a n n i s t e r , B. and R o b i n s o n , V . J . ( 1 9 7 5 ) T r e e - r i n g d a t i n g and a r c h a e o l o g y
World Archaeology 7 , No.2, 210-225.

Becker,B. 1974 Eine E i c h e n c h r o n o l o g i e der Alamannischen Totenbaume

und Grabkammerbretter von H u f i n g e n , O b e r f l a c h t und Zobingen

F u n d b e r i c h t e aus Baden-Wurttemberg. 1 , 545-564.

Becker, B. (1982) Dendrochronologie und P a l a o o k o l o g i e Subfossiler

Baumstamme uas Flussablagerungen e i n b e i t a g zur Nacheiszeitlichen

Avenentwicklung im S u d l i c h e n M i t t e l e u r o p a A u s t r i a n Academy o f

Sciences.

Becker,B. (1985) Die A b s o l u t e C h r o n o l o g i e der P f a h l b a u t e n N o r d l i c h der

Alpen im J a h r r i n g k a l e n d e r M i t t e l e u r o p a s , in Becker,B. et al (eds)

Dendrochronologie i n der U r - u n d - F r u h g e s c h i c h t e . Schweizerische

Gesellschaft f u r Ur-und-Fruhgeschichte, Basel.

214

Eckstein, D., Baillie, M.G.L. and Egger, H. (1984).

Dendrochronological Dating, Handbook for Archaeologists No j, European

Science Foundation.

Ferguson, C.W. (1969) A 7104-Year Annual Tree-Ring Chronciogy for

Bnstlecone Pine, Pinus Anstata. from the White Mountains,

California. Tree-Ring Bulletin 29, 2-29.

Forsyth, P.Y. (1990) Call for Cybele The Ancient History Bulletin

4.4, 75-78

Hammer,C.U., Clausen, H.B. and Dansgaard, W. (1980) Greenland Ice

Sheet Evidence of Post-Glacial Volcanism and its Climatic Impact.

Nature 288, 230-235.

Hi 11am, J., Groves, C M . , Brown, D.M., Baillie, M.G.L., Coles, J.M.

and Coles, B.J. (1990) Dendrochronology of the English Neolithic.

Antiauity64, 210-220

Hollstein, E. (1980) MittelEuropaische Eichenchronologie Phillip Von

Zabern, Mainz am Rhein

Kuniholm.P.I. and Striker, C.L. (1987) Dendrochronological

Investigations in the Aegean and Neighbouring Regions, 1983-1986.

Journal of Field Archaeology 14, 385-398.

Leuschner, von H.H. and Delorme, A. (1984) Verlangerung der Gottingen

Eichenjahrringchronologien fur Nord- und Suddeutschland bis zum Jahr

4008 v. Chr. Forstarchiv 55, 1-4.

Leuschner, von H.H. and Delorme, A. (1988) Tree-Ring Work in Gottingen

 215

- Absolute Oak Chronologies Back to 6255 BC Pact II.5 Wood and

Archaeology 123-132

Munro, M.A.R. (1984) An Improved Algorithm for CrossDating Tree-Ring

Series Tree-Ring Bulletin 44, 17-27.

Pearson, G.W., Pilcher, J.R., Baillie, M.G.L., Corbett, D.M. and Qua,

F. (1986) Hign-Precision 14-C Measurement of Irish Oaks to Show the

Natural 14-C Variations from AD 1840 to 5210 BC. Radiocarbon 28,

911-934.

Pilcher, J.R. and Baillie, M.G.L. (1987) The Belfast CROS Program:

some observations. British Archaeological Reports (International

Series) 333, 157-163.

Pilcher, J.R., Baillie, M.G.L., Schmidt, B. and Becker, B. (1984) A

7272-Year Tree-Ring Chronology for Western Europe. Nature 312,

150-152.

Raftery, B. (1990) Trackways Through Time: Archaeological

Investigations on Irish Bog Roads 1985-89. Headline, Dublin.

Stuiver, M. and Becker, B. (1986) High-Precision Decadal calibration

of the Radiocarbon Time Scale, AD 1950-2500 BC. Radiocarbon 28,

863-910

Suess.H.E. (1970) Bristlecone Pine Calibration of the Radiocarbon

Timescale from 5200 BC to the Present. In: Radiocarbon Variations and

Absolute Chronology ed I.U. Olsson, John Wiley and Sons, New York,

303-309.

Weisburd.S. (1985) Excavating Words: A Geological Tool Science News

127, 91-96
ARCHAEOMAGNETISM AND PALAEOMAGNETISM

/. PRINCIPLES

D. H. TARLING
Dept. Geological Sciences
Polytechnic South West
Plymouth PL4 8AA
England

1.1 Introduction

The basic principles of archaeomagnetism and palaeomagnetism are identical. Both methods
depend on the fact that most geological and archaeological materials can acquire a magnetization in
the Earth's magnetic field at a particular time and that this record of the geomagnetic intensity and
direction can be preserved and eventually measured in the laboratory. As the Earth's magnetic
field changes in time and space, it is possible to relate the preserved magnetic properties, determined
from samples of archaeological or geological materials, to past changes of the Earth's magnetic field
at that locality. Where the actual date of specific geomagnetic characteristics are known, then
such a comparison can be used for absolute dating, i.e. to assign a specific calendar date for the time
that the magnetization was acquired. However, when the date for the geomagnetic parameters is not
known, the magnetic properties of materials from different localities within the same region can still
be compared for relative dating purposes, i.e. determining whether the magnetization at the two (or
more) localities had been acquired at the same time or not. This information can then be used to
improve our knowledge of geomagnetic field behaviour and so to gradual improve the precision and
range of magnetic dating. The difference between archaeomagnetism and palaeomagnetism is almost
entirely dependent on the age range involved. Archaeomagnetism is concerned with archaeological
time scales and palaeomagnetism with geological time scales, but clearly these overlap. In practice, the
two terms are usually used in the context of the problem being investigated, i.e. whether it is
primarily archaeological or geological. Alternately, as adopted here, archaeomagnetic studies are
217
H. Y. Goksu et al. (eds.). Scientific Dating Methods, 217-236.
© 1991 ECSC, EEC, EAEC, Brussels and Luxembourg. Printed in the Netherlands.
218

those based on short-term changes of the geomagnetic field, i.e. time-scales of a few years to few
millennia, while palaeomagnetism is based on much longer time-scale changes, i.e. some 100,000
years or more. The processes by which magnetizations are acquired by archaeological and geological
materials will be described first, followed by an outline of the physical basis for such processes. In
order to understand which components of the Earth's magnetic field are likely to be recorded, the
time-scale of the acquisition of remanences in archaeological contexts is then considered, prior to
the methods of sampling, collection and measurement. As more than one form of magnetization is
usually present, the methods by which the different components are isolated is described next. The
general features of the Earth's magnetic field are considered in the final section, with consideration
of how such properties can be used as an assistance to archaeologists described in the following
chapter, including dating but many other less well known applications for such properties.

1.2 The Physical Processes

1.2.1 TYPES OF MAGNETIZATION

If a magnetic substance is placed in a weak magnetic field (c.0.1 mT) then it becomes magnetized in
the same direction as the applied field and the intensity acquired is proportional to the strength
of the applied field (the constant of proportionality is known as the magnetic susceptibility).
This magnetization is termed an induced magnetization as it is induced by the applied field and
disappears on its removal. All magnetic objects lying in the Earth's magnetic field show such an induced
magnetization and it is the basis for the location of buried archaeological objects by means of field
magnetometer surveys (Aitken, 1974). This form of magnetization is not remanent as it does not
remain after the removal of the magnetizing field, but if stronger magnetic fields are applied ( >1 mT),
then not all of the magnetization disappears after the removal of the inducing field, i.e. there is a
remanent magnetization or, simply, a magnetic remanence. Remanences can be acquired in a variety
of ways. This particular type is termed an isothermal remanent magnetization as it ithe
magnetization remaining after applying a strong magnetic field at room temperature. Its intensity is
proportional to the strength of the applied field and also on the composition and grain size the
material. (This form of magnetization is the basis for most industrial iron or steel magnets.)
The intensity of the remanence of a magnetized object gradually decreases if it is left in zero
magnetic field. The rate of decay is logarithmically dependent on the tota time that it is left in zero
magnetic field. Conversely, if the same object is demagnetized and then placed within a magnetic
field, it will gradually acquire a remanent magnetization in the direction of the ambient field, the
 219

intensity of the remanence increases as an exponential function of the duration of the applied field.
Such remanent magnetization is termed viscous or time-dependent magnetization.
If a grain of magnetic mineral, such as magnetite, is heated to a temperature of 700°C and then
cooled to room temperature (20°C) while in a weak magnetic field (c.0.5 mT), it acquires an
increasingly strong magnetic remanence as it cools. The direction of the remanence is the same as that
of the applied field and it has an intensity, for any given material, that is proportional to the
strength of the magnetizing field (for fields less than c.l mT). This form of remanence is termed
thermal remanent magnetization and is lost if the same grain is reheated to high temperatures. In the
case of magnetite, >570°C. The minimum temperature at which all remanences are destroyed on
heating is specific to the mineralogical composition and is termed the Curie temperature. (For
most archaeological and geological objects, the two main magnetic minerals are magnetite and
haematite which have Curie temperatures of 570°C and 675°C respectively.)

Figure 1.1. Deposition Remanence

Detriial grains, as they are deposited, can be magnetically aligned by the Earth's magnetic field.
Particular sized particles are intergranular, after deposition, and can still be aligned by the field. This
direction becomes locked in asthe sediment compacts and the water content reduces.

Another form of magnetic remanence arises when a minute magnetic grain, < 0.001 um, grows
within a weak magnetic field. As its size increases, it acquires a magnetization in the same direction as
the applied field. This magnetization is termed a chemical remanent magnetization, sometimes also
known as crystal remanence, and has very similar characteristics to thermal remanence.
Finally, there is another form of natural remanence associated with sediments. This arises as a
result of the alignment of already magnetized particles by the Earth's magnetic field as they are
deposited (Figure 1.1). This is in exactly the same way as magnetic compass needles are aligned by
220

the geomagnetic field. Very small magnetic grains ( <0.1 pm) are rapidly aligned by the Earth's field,
but Brownian forces readily randomize such alignments. Conversely, large grains (>30-50
um)) are virtually unaffected by the weak aligning force of the geomagneticfield and their
orientation is almost entirely controlled by the gravitational and hydrodynamic forces operating durin
deposition. After deposition, such large particles tend to be flat lying and cannot be aligned by the
geomagnetic field as they are physically locked by other large grains. However, small grains,
around 1 um diameter, are oriented by the geomagnetic field during deposition in water or air. Some
of this alignment is lost during the actual process of deposition, usually causing some flattening of these
grains. Shortly after deposition, such small grains usually occur in intergranular spaces and are still
surrounded by water. This allows the weak aligning force of the geomagnetic field to physically rotate
these grains so that their magnetizations become parallel to the field. As the sediment compacts and
water content is reduced, such grains become locked withinthe sediment and hence retain the alignment
imposed by thegeomagnetic field at that time. This form of remanence is sometimes termed
depositional remanent magnetization although it is more precisely termed detrital remanent
magnetization as the remanence is carried by the oriented detrital grains. Most of the magnetic
properties of the detrital grains are controlled by their original processes by which they were
magnetized, but the intensity of magnetization of a sediment also depends of the degree of alignment of
the individual grains and this, in turn, is partially dependent on the strength of the geomagnetic field
at that time.

1.2.2 PHYSICAL EXPLANATION OF MAGNETIC REMANENCE

While a full understanding of the physical cause remanence in archaeological or geological

materials is not essential in the interpretation of archaeomagnetic or palaeomagnetic
measurements, it is important to outline the physical bases for the processes of magnetization and
demagnetization upon which such magnetic methods depend. As the nuclei of all atoms are surrounded
by electrons, allatoms are magnetic as magnetism arises from the motion of an electrically charged
particles. However, such magnetizations (diamagnetism and paramagnetism - see below) are
extremely weak when compared with the normal understanding of magnetization. However, in
very specific atomic structures, the electron motions are shared between adjacent atomic nuclei and
become closely coupled to each other. Such substances are termed ferromagnetic and are those
which, in every-day life, are called magnetic. However, all substances are magnetic at an atomic level
and all atoms fall into one of only two categories - diamagnetic or paramagnetic. Substances in
which an applied field results in an induced magnetization opposite to that of the applied field are
 221

termed diamagnetic, while those which have an induced magnetization parallel to the inducing
field are termed paramagnetic. Both diamagnetic and paramagnetic magnetizations are lost as
soon as the induced field is removed. However, ferromagnetic substances have the ability to be
much more strongly magnetized and also to retain a memory of the inducing field, i.e. they are
capable of acquiring a remanent magnetization.
The physical explanation of remanence is based on two fundamental concepts - that of magnetic
domains and that of magnetic relaxation times. As the electron spins in a ferromagnetic substance
are coupled together, the individual electrons are shared between neighbouring atoms. In some
substances, such as iron, nickel and chrome, the electron spin orbits are directly linked to each
other and the quantum-mechanical force responsible for this is termed an exchange force. In more
complex structures, such as their oxides, the electron spins are shared between the metallic ions by
means of the electron orbits of an intermediate anion and the quantum-mechanical forces are termed
superexchange forces. The exchange force causes the electrons to align in the same direction and this
direction is determined by the actual shape of the crystal lattice of the material. In the oxides, the
electrons are coupled in anti-parallel arrangements, the orientation of which is also dependent on
the shape of the crystal lattice. However, the antiparallel coupling means that such materials can be
conceived as comprising two magnetic lattices, oriented in opposite directions to each other. In
some substances, these two magnetic lattices are of the same magnitude and their magnetizations

1111 t It 1 t ♦ t♦
t t t! ! i t1 f ♦ t ♦
! t !1 t I t1 t ♦ t ♦
(a) lb) Id

Figure 1.2. The three forms of ferromagnetism

(a) Ferromagnetism (s.s.), with one one lattice and a very strong external field, (b) Antiferromagnetism,
in which both antiparallel magnetic lattices cancel to result in zero external field, and (c)
Ferrimagnetism, with a medium external field due to an imbalance between the two antiparallel magnetic
lattices.
222

therefore cancel each other when viewed from the outside of the substance. These are termed
antiferromagnetic, but in ferrimagnetic substances, one lattice is stronger than the other so that the
substance does have an external magnetic field. There are thus three categories of ferromagnetic (sensu
law) behaviour (Figure 1.2):
(i) ferromagnetic (sensu stricto) with a single magnetic lattice and consequently very strong
magnetization
(ii) antiferromagnetic with two equal and oppositely magnetized lattices and hence no external
magnetization
(iii) ferrimagnetic with two oppositely magnetized lattices, but with one predominating to give an
external magnetic field, but much weaker than for ferromagnetic (s.s.) substances although much
stronger than for paramagnetic materials.
Materials which contain ferromagnetic (s.l.) particles will thus have ferromagnetic properties. If iron
or steel is involved, then this will have ferromagnetic (s.s.) properties. More commonly, in
archaeological and palaeomagnetic environments, it is the presence of iron oxides that account for most
of the properties. Of these, magnetite (Fefi^ and haematite (Fe2Oj) are by far the most significant,
although hydroxides, such as goethite (FeO.OH), can be important in sediments or weathered materials.
Goethite, however, is chemically unstable and is usually destroyed on heating to some 110-130°C.
Magnetite is a ferrimagnetic substance with a strong magnetization, while haematite is a distorted
antiferromagnetic material, i.e. the two magnetic lattices are not quite antiparallel and so there is a net
magnetization perpendicular to the lattices. Haematite is therefore much weaker than magnetite, but is
very stable chemically and hence is stable to heating, while magnetite can be affected by heating,
depending on the redox conditions.
Spherical magnetite grains can be magnetized by almost the same amount in all directions, i.e. it has
low crystalline anisotropy, but haematite can virtually only be magnetized within the basal plane of its
crystal lattice, i.e. it has very high crystalline anisotropy. If the magnetite grain is non-spherical, then it
is most readily magnetized along the long axes of its shape, i.e. it has strong shape anisotropy, while the
crystalline anisotropy of haematite is much more important than its shape, although the cleavage
planes of haematite mean that most flakes of haematite will effectively have a shape anisotropy as the
two coincide. If elongated grains of magnetite have a net direction, then an applied field will be
deflected towards the net shape anisotropy. Similarly, if the crystalline axes of haematite are aligned,
then an applied field will be deflected towards the basal planes. In both cases, the material itself can be
regarded as magnetically anisotropic and the direction of remanence observed will therefore not
correspond exactly with the direction of the field in which it was acquired. However, the anisotropy
must exceed 1% for a deflection of 1° and most materials in archaeological environments show
 223

anisotropics of less than 2%.

If the magnetic grains are unevenly distributed within the material, then clearly the magnetization
itself will be inhomogeneous. Critical to this is the sample size as inhomogeneity effects on a scale
smaller than a sample will tend to be averaged out during the measurement of the sample, but larger
scale inhomogeneity can lead to differences in intensity, in particular.

1.2.2.1 Magnetic Domains. The internal quantum-mechanical forces attempt to align the spins of all
shared electrons so that they all have the same orientation. However, this results in a strong
magnctostatic magnetization caused by the north and south magnetic poles at opposite ends of the
magnetic material. These magnetic poles attract each other, resulting in a magnetostatic force which
tries to break up the internal magnetic. As a consequence of these competing forces, small volume
elements form within ferromagnetic crystals, magnetic domains, within which all the magnetic spin
alignments are along the same crystallographic axis (Figure 1.3). The magnetostatic forces are then
largely compensated by the domains having different orientations within the crystal so that their north
and south poles are close to each other. Thus a balance is achieved as, within each domain, the aligning
forces are satisfied and the magnetostatic forces are largely satisfied by the domain arrangements. In
the absence of an external magnetic field, this balance usually results in the formation of closure
domains (Figure 1.3).

N N

tttt tt I I t
ttt t tt I I XX i
(*) rw oo

Figure 1.3. The formation of magnetic domains.

(a) Although the internal crystalline forces are all satisfied, they result in the formation of strong poles
on opposite ends of the grain. This magnetostatic force results in the formation of two volumes (b)
within which the super-exchange forces are satisfied and the magnetostatic forces are reduced, (c) The
ideal situation is where the internal and external forces are evenly balanced so that there is no external
magnetic field to the grain.

The individual domain sizes are somewhat variable, depending on the shape of the crystal, the presence
of lattice defects, and the like. In most archaeological and geological materials, such domains are of the
224

order of 1 urn in diameter, but can be as large as 3-5 urn, while there is no limit on how small they may
be. Crystal grains that are larger than some 8-10 urn normally form two or more domains and their
magnetic behaviour is then termed multi-do main, while grains of the size of a domain, or smaller, can
only contain one domain and their magnetic behaviour is single-domain and can differ drastically from
that of multidomain particles (Figure 1.4). When an external magnetic field is applied to a multidomain
grain, then the domains in alignment with the applied field increase in volume at the expense of the
non-aligned domains by means of the do main wall (between bordering domains) unroll to increase
the total number of aligned electron spins. However, grains of single domain size have no domain
walls and their direction of magnetization within the crystal lattice remain unchanged until very large
field are applied, when the entire alignment within the domain flips into a new alignment with the
applied field.

(«■■) Go
Figure 1.4. Single domain and multi-domain behaviour.
When a strong field is applied to (a) multidomain grain, the magnetization changes gradually, to
eventually become saturated in strong fields. However, the magnetization of (Wsingle domain grain
does not change until the external field suddenly reverses the entire direction of magnetization.
 225

1.2.2.2 Relaxation Times The second fundamental concept is that each individual magnetic grain within
an object has a characteristic relaxation time (t), that is to say that it takes a specific lime for a

magnetization in one direction to change to the directly of a newly applied field (Neel, 1955). Some
grains will have very short relaxation times and will thus rapidly loose any original viscous
rcmancnce and the same grains will also rapidly acquire a remancnce when left in a new magnetic
field. However, other grains will have very long relaxation times, i.e. they will loose their
original remanence so slowly that it is imperceptible even over millions of years and similarly,
any original magnetization will take an indefinitely long time to relax into the direction of a newly
applied field direction.

10000 SOOO JOOO WOO 900 eco

Cram aiamrt*r ( A )

Figure 1.5. The relaxation time spectrum for magnetite.

The time for a magnetic remanence to relax from one direction of an external field to that of another is
the relaxation time. This is exponentially dependent on time, grain size and temperature for single
domain particles, but is always short for multidomain particles.

On the basis of the above concepts, it is possible to explain the processes of remanence acquisition
in either natural or laboratory conditions. The Curie temperature is the temperature at which the
vibration of the individual electrons exceeds the coupling imposed by the super-exchange forces, so
that ferromagnetic materials behave as paramagnetic substances above this temperature. On
cooling through the Curie temperature, the magnetocrystalline forces couple the electron spins, resulting
in ferromagnetic (s.l.) behaviour. At temperatures slightly below the Curie temperature, the
226

magtization of all grains can readily relax into alignment with an applied field. However, as the
temperature decreases, the relaxation time of all grains increases exponentially (Figure 1.5).
However, very small grains will still have very short relaxation times, as will multidomain grains.
However, a range of grain sizes will have relaxation times that are now long relative to the
duration of the experiment, c.20 minutes. These will therefore remain in their original alignment
even if the direction of the applied field changes. This means that grains with relaxation times
equal or greater than the duration of the experiment will have their directions of magnetization
blocked in. The temperature at which which each individual grain has its remanence blocked in for
some 20 minutes is therefore known as its blocking temperature. As further cooling occurs, even
more grains acquire relaxation times that are longer than the duration of the experiment and the
intensity of the thermal remanence and its stability increases. By room temperature, most grains
between 600 A and 1 urn have relaxation times greater than that of the laboratory experiment, while
those between 800 A and c.l pm have relaxation times of millions of years, i.e. their magnetic
directions will not relax into that of any new geomagnetic field direction and will thus preserve the
direction original acquired during cooling throughout archaeological and even geological
times.substance has a low relaxation time, but on further cooling, difference in relaxation time of
the individual grains means that some will still relax into a new direction, while others retain the
alignment already acquired. It can also be seen that the total remanence at 20°C comprises the
sum of the magnetizations acquired at all higher temperatures over which the external field was
applied.
In an identical way, grain that are increasing in size have, initially, very short relaxation times,
but their relaxation time increases as they increase their volume. At a critical volume, known as the
blocking volume, the remanence becomes blocked in for the duration of the experiment. Further
growth results in even greater increases in the relaxation time until the grain become large enough that
two or more domains can form, when its relation time drops drastically as domain wall motions
become operative.

L3 TIME SCALES OF REMANENCE ACQUISITION IN ARCHAEOLOGICAL

ENVIRONMENTS

There are thus four main forms of natural remanent magnetization that commonly occur in
a range of archaeological environments (Figure 1.6), i.e. magnetic remanences :
(i) thermal, acquired by cooling in a magnetic field
 227

(ii) chemical, acquired by crystal growth in a magnetic field

(iii) detriial, acquired be sediments during and shortly after their deposition.
(iv) viscous, acquired by lying for a prolonged time in an magnetic field

Puddling clays
(chemical/deposifional) Bricks (thermal)

Morrar (chemical or
deposiNonal)

Piaster (chemical or
Porsherds (Thermal)
deposirional)
\
Cemenr tchemical or
deposihonal)

Ditch infil
{deposihonal]

Figure 1.6. Examples of remanence in an archaeological site

Many areas of an archaeological site may exhibit remanence dating back to some specific event at the
site.

Thermal remanence is acquired at a particular identifiable time, e.g. the time when a kiln cools down
or a pot cool down within a kiln, usually 1 to 2 days. This means thatshorter-term geomagnetic
fluctuations are likely to be averaged out during the cooling process. Chemical remanence can
sometimes be associated with a particular event, such as a manufacturing process, but is more likely to
be associated with weathering and decompositional processes which may well be prolonged, resulting in
a possibly stable magnetization associated with the average geomagnetic field direction over several
hundred years. Detriial remanence is clearly associated with the time of deposition, but the fact that
it can also occur after deposition must raise some question about its time of acquisition which could
well be some decades (or even longer) in a quiet sedimentary environment However, some cases are
known, such as Iron Age hill fort ditches, in which the archaeological context clearly indicates
that the remanence was acquired almost immediately after the initial sediment infill of the ditch.
Clearly viscous remanences are acquired over prolonged times and thus do not usually relate to a
particular event.
Other forms of remanence can be acquired by various laboratory processes, either deliberately or
228

inadvertently, which can affect the magnetization of samples, but are only relevant here in terms of
their effect on the purity of the recorded magnetization. However, isothermal remanence can also
occur naturally, such as if the site has been struck by lightning. While such an invent is brief and
probably well marked, it rarely has archaeological significance and it is not, in any case, possible to
magnetically date this remanence as the geomagnetic field is completely swamped by the complex
magnetic fields associated with lightning (Tarling, 1983).

1.4 COLLECTION AND SAMPLING

Most archaeological materials of interest have been fired and hence tend to be hard, often brittle.
For studies involving only intensity studies, such materials can be sampled by simply breaking
appropriately sized pieces from the structure or object. For directional studies, such materials can
often be sampled by standard palaeomagnetic methods, i.e. either by drilling, using portable rock
drills, or by orienting a flat surface and then taking this surface as part of a hand sample (Figure 1.7). In
general, drilling is often not desirable because of the water coolant, noise and fumes associated with
drilling, particularly in restricted or enclosed areas. The noise and fumes can be reduced using
electrically powered drills, but all forms of drilling tend to leave obviously holes than can be difficult
to cover if the site is to be preserved. Generally hand sampling is more desirable within an
archaeological site, but this raises difficulties in finding a flat orientable surface and thus tends to reduce

(b)
(Q)

Figure 1.7. Hand samples

Flat surfaces can be oriented directly and hand samples of appropriate dimensions removed.
Alternately, non-magnetic disks can be attached, the upper surface of which can be oriented before
removing it, with some of the material.
 229

the accuracy with which the sample can be oriented. The optimum method, developed specifically for
sampling archaeological materials (Tarling, 1983; Clark et al., 1988) is the disk method in which plastic
or wooden disks are glued to the object to be sampled. The flat surface of the disk is then oriented
and the disk then removed with a piece of the object attached to it. This sample can then be used
directly in some magnetometers or can be shaped afterwards.
Orientation requires two measurements - the direction of true North (or other known direction in the
horizontal plane) and the angle of a flat surface relative to horizontal. If the disk method is used, a
horizontal arrow is marked on the surface of the disk. The direction of this arrow is then determined
using a sun compass whenever possible. The dip of the surface of the disk, which is perpendicular to
the horizontal arrow, can then be measured relative to horizontal. Where a sun compass cannot
be used, then a gyrocompass can be used, or the orientation of the arrow relative to objects in
known orientations or locations (e.g. church spires, landmarks, etc., or a known North/South line at the
site itself) can be determined by conventional surveying methods. (For further details see Tarling,
1983)

1.5 MEASUREMENT AND ANALYSIS OF VECTORS

A wide variety of magnetometers are available for the measurement of the direction and intensity
of remanence. Most of these have been designed primarily for geological purposes and for use with
standard size samples, mostly 2.1 cm high cylinders of 2.5 cm diameter, or cubes of 2.1 cm side.
Such instruments will not be described in detail as such information is readily available elsewhere
(Collinson, 1983). The most sensitive and fastest are cryogenic magnetometers, but most
archaeological materials can be readily measured using standard instrumentation - spinner or astatic
magnetometers. In some instances, wide aperture spinner magnetometers and most astatic
instruments allow the measurement of irregularly shaped samples, otherwise it is necessary to shape
the samples to the standard sizes. This is, in any case, generally necessary for subsequent
demagnetization procedures described below.
The measurement of remanence of a sample can usually be undertaken with a precision around ±1-
2° in direction and ±2-3% in intensity (Tarling, 1983), with a further reduction in the error of
measurement in direction being associated with orientation, rendering the total average error per
sample to some ±2-3°, although the repeatability of a measurement is commonly better than ±1°.
However, the observed remanence is a summation of all the remanences within the sample and it
is necessary to dissect this remanence and particularly to remove the effects of viscous remanences
230

that are rarely of archaeological or geological interest Conveniently, viscous remanences must
be associated with grains of low relaxation lime and these are mostly readily removed by partial
demagnetization methods. These are of two main types, using either thermal or alternating
magnetic fields. In both cases, the temperature or field strength applied is increased in steps and the
remaining remanence measured. The results can then be either tabulated or illustrated, usually by means
of cartesian plots (Figure 1.8). Computer and visual analysis of these data can then be used to
determine linear segments of the demagnetization vector.

// V
// "/
//
/ /
( |
/

(a) (b) (c)

Figure 1.8. Examples of Cartesian plots
(a) An example of single component remanence, i.e there is no difference between the directions
at all demagnetization level, although the intensity decreases, (b) An example of two components. The
lower coercivity component is associated with viscous remanence acquired in the present Earth's
magnetic field, while the higher coercivity is the original thermal component (c) An example of
three components. The low coercivity component is of viscous origin, the intermediate is associated
with a reheating event when the sample had been heated to 350 C which is superimposed on an
earlier thermal remanence acquired while cooling from 700 C.

Normally the viscous component is removed first If large, then this component may be seen as a
single low blocking temperature or low coercivity vector, but commonly the initial
demagnetization steps reveal a curving vector due to an overlap in the blocking temperature or
coercivity spectra of both the viscous and original components. In most instances, a linear vector is
then defined which is directed towards zero on the cartesian plot The definition of the linearity of this
vector can then be used as a measure of its precision.
In some cases, this simple pattern is not found. Weathering or decomposition of the original
materials can mean that there is an additional chemical component of remanence, which, if
 231

protracted, will mirror the viscous component in direction, but will have much higher stability to
demagnetization. Similarly, chemical components can be generated by the thermal demagnetization
process itself if this induced chemical changes. No chemical changes are associated with
alternating magnetic field demagnetization, but this is a complex process and laboratory induced
components, such as anhysteretic remanences and gyroremanences. These extraneous
magnetizations usually increase in importance with an increase in the applied field, thus preventing the
original vector continuing towards zero as demagnetization proceeds so that a vector intermediate
between the viscous and high coercivity vectors can usually be defined as the characteristic
magnetization for that sample.
The art of analysis is then to determine the true origin of the characteristic vectors. Clearly,
within any one structure or object, the magnetization acquired when it was originally fired should be
essentially uniform and so all samples should show similar directions of remanence. In some cases,
however, there may have been differential motion between different areas of the sites after the
original firing or some areas may have been reheated at some later time. In this later instance, the
reheated magnetization may be merely superimposed on the original thermal remanence, in which case
both components can be separately identified (and the temperature of the later heating determined -
see Applications), or it may completely overprint the previous magnetization. Clearly the hardest
interpretation is one where chemical changes have occurred over a range of times, in which case both
the blocking temperature and coercivity spectra are both drastically altered. The simplest
"solution" is not to collect weathered or altered materials! However, generally a sensible
interpretation can be undertaken if combined with discussions with the archaeologists familiar
with the site.
When the vector has been defined, then it has both an intensity and a direction. The direction can
then be rclatedireclly with the Master Curve (next chapter) of declinationand inclination for that locality
in order to obtain an archaeomagnetic date based on the directional properties.
The intensity of the vector can also be used to estimate the ancient field strength in which the
magnetization took place. This relationship is simple as the intensity of remanence (M^) acquired in a
past field ( F ^ should be exactly proportional to the intensity acquired (M,^ in a known field (F^,
i.e.:
M F
a nc rt ri c
I F
1 ab 1 a ti

Unfortunately the problem of giving a laboratory thermal remanence without affected the magnetic
mineralogy and also defining the comparable component of the natural remanence ismuch more
232

difficult than indicated by the simplicity of this formula (Figure 1.9). On the other hand,
palaeointensity determinations can be made on unoriented materials, such as pot shards. Until recendy
palaeointensity determinations have been slow and tedious as they require repeated heating and
cooling. Such prolonged thermal cycling also tended to increase the probability of thermally
induced chemical changes that can prevent further analysis of the original magnetic components.
More recent techniques (for example Aitken etal., 1981,1985; AUsop et al., 1984; Rogers & Boyd,
1984; Boyd, 1985) use very small samples, c. 3 mm dimensions, with all heating and cooling steps
completed in 20 to 60 minutes. This speed tends to reduce thermally induced chemical changes and
the techniques now have in-built methods of determining when such changes have occurred. The
remaining physical problems are thus the effects of differences in cooling rates between the
natural and laboratory conditions (Fox & Aitken, 1980; McClelland Brown, 1984), inhomogeneity of
remanence (particularly with small specimens) and magnetic refraction in large structures (Aitken et
al., 1981; Hammo-Yassi & Tarling, 1984; Tarling, et al.,1986). Nonetheless, while current studies are
improving our understanding of such difficulty, the fundamental problem is still the precision of
measurement relative to the rate of change of the ancient field. At the moment, there are inadequate
observations for the construction of reliable reference curves.

Anci«nr fi«M ■ 0­65

Figure 1.9. An example of a palaeointensity determination

A plot of the intensities of the original natural remanent magnetization (NRM) against the laboratory
induced thermal remanent magnetization (TRM) at different temperatures allowsan evaluation of the
ancient geomagnetic field strength in which the original natural remanence was acquired by cooling
in the ancient geomagnetic field.
 233

1.6 GEOMAGNETIC ASPECTS

Our direct knowledge of the Earth's magnetic field dates back to the late 16th century, since when
geomagnetic observatories have recorded changes in direction, while its changes in intensity have only
been monitored since 1835. Such observatory data, supplemented by field measurements, show that
most of the Earth's magnetic field (c.80%) can be modelled as if there is a simple bar magnet at the
Earth's centre, but aligned at an angle of 11.3° to the Earth's axis of rotation (Figure 1.10). This
component of the field is known as the geomagnetic dipole field while the remaining 20% of the field
is termed the non-dipole field and can be simulated by 12 magnetic dipoles, in different
orientations, at the core/mantle boundary. The fields of these dipoles, as observed at the Earth's surface,
have dimensions similar to that of the European continent, i.e. a few thousand kilometres in
extent, over which the nature of the geomagnetic properties are similar (Figure 1.11).

Figure 1.10. Geomagnetic model

Some 80% of the geomagnetic field can be simulated by a single dipole at the Earth's centre and
aligned at 11.3 from the Earth's axis of rotation. The remaining field can be simulated by small
dipoles near the core/mantle interface.

Even the earliest observations revealed that the direction of the geomagnetic field gradually changed
direction with time (Figure II. 1, next chapter) and the global intensity of the field has been decreasing
since it was first determined (Figure 1.12). It is now known that the geomagnetic field varies on
virtually all time-scales, from nanoseconds to millennia in addition to irregular fluctuations,
particularly magnetic storms. Most of the short time scale regular variations, i.e. less than 1 year,
are of little significance in archaeomagnetic studies as their magnitude is low ( <0.1% of the total field)
and their effects are usually averaged out during the acquisition of the remanence (Section 1.3).
234

Magnetic storms, which occur irregularly, can last for several days and can have amplitudes that are
some 1% of the normal field with directions changes that are less than 1° in medium to low latitudes,
but could be important in high geomagnetic latitudes. As such events are related to sun-spot
activity, the frequency and intensity of magnetic storms show an 11 year cyclicity reflected the solar
sun-spot cycle. However, at the present stage of technology, the determination of the past direction
and intensity of the field using archaeomagnetic and palaeomagnetic methods are not yet sufficiently
precise to allow the detection of ancient magnetic storm activity.

Figure 1.11. The non-dipole field

This is a simplified map of vertical component of the Earth's non-dipole magnetic field showing the
regional nature of this field.
Archaeomagnetic dating is therefore based on the average behaviour of the geomagnetic field over a
few hours or days and the dating of archaeological materials is entirely based on the long term ( >1
year) changes in direction and intensity of the geomagnetic field, secular variations.
Unfortunately, such secular variations have only been monitored in specific localities sincel600 and
ourcurrent knowledge of the geomagnetic field behaviour is unable to predict past or future geomagnetic
trends. Indeed, one of the major reasons foran interest in archaeomagnetic and palaeomagnetic studies is
to actually define the geomagnetic field behaviour over longer time-scales than are available from
direct observations. Nonetheless, it is know that, during this century at least, the non-dipole field has
tended to drift westwards, as has the rate of secular variation, at a rate of some 0.2° longitude/year.
Theactual position is complicated as some of the regional dipole features are increasing while others
decrease. It is also unclear whether there are stationary parts of the non-dipole field in addition to the
westward drift. It is also disputed whether westward drift is a temporary or persistent feature of the
geomagnetic field.
 235

tnso un LIOO tnoi in

Figure 1.12. The changing intensity of the geomagnetic field

Based on observations made near London between 1860 and 1955 - with the intensity shown in nano
tesla (nT).
236

REFERENCES

Aitken, M. J. (1974) Physics and Archaeology Clarendon Press, Oxford.

Aitken, M.J., Alcock, P.A., Bussell, G.D. and Shaw, C.J. (1981) Archaeometry 23, 53-64.
Allsop, A l . , Griffiths.V. and Aitken, M.J. (1984) Geophys. J. R. astr. Soc, 77, 307.
Boyd, M. (1985) Geophys. J. R. astr. Soc, 81, 322.
Clark, A. J., Tarling, D. H., and Noel, M (1988) /. Archaeo. Sci., 15,645-667.
Collinson D. W. (1983) Methods in Rock Magnetism and Palaeomagnetism, Chapman & Hall,
London.
Fox J. M. W., and Aitken M. J. (1980) Nature 283,462-463.
Hammo-Yassi, N. and Tarling, D.H. (1984) Geophys. J. R. astr. Soc, 77, 309.
McClelland-Brown E. (1984) Geophys. Res. Utters 11,205-208.
Neel, L. (1955) Adv. Phys. 4,191-243.
Rogers, J. and Boyd, M. (1984) Geophys. J. R. astr. Soc, 77, 308.
Tarling D. H. (1983) Palaeomagnetism, Chapman & Hall, London
Tarling, D.H., Hammo, N.B., and Downey, W.S., (1986) Geophys., 51,634-639.
ARCHAEOMAGNETISM AND PALAEOMAGNETISM

//. MAGNETIC DATING AND OTHER APPLICATIONS

D. H. TARLING
Dept. Geological Sciences
Polytechnic South West
Plymouth PL4 8AA
England

II.1. Introduction

The previous chapter described the physical basis of archaeomagnetism and palaeomagnetism
and also the general features of the geomagnetic field as derived from direct observations. In
this chapter, the determination and dating of much earlier geomagnetic changes is described,
mainly based on the construction of "Master curves" for Britain. This is followed by a
consideration in the errors of directional dating and then using determinations of the past intensity
the geomagnetic field. This will then be followed by an outline of those very long term features
of the geomagnetic field behaviour that can be utilized for dating purposes. However, magnetic
measurements can be used for a surprising variety of archaeological purposes, of which dating is
the best known. Less well-known uses include the restoration of the original shape of the
objects or structures, the sourcing of artefacts, determination of past heating temperatures,
evaluation of different manufacturing technologies, evaluation of the local environment, etc.
These are discussed in the final sections. Where examples are unreferenced, they are from
unpublished reports by the author, commonly in conjugation with post-graduate students.

II.2 Secular Variation Reference Data

II.2.1 DIRECTIONAL SECULAR VARIATION

As the behaviour of the geomagnetic field before 1600 AD is essentially unknown from direct
evidence, archaeomagnelic observations are invaluable in attempting to build up region patterns of
changes in direction and intensity. Unfortunately, archaeological sites with available materials of
precisely known age are not abundant and occur over wide regions. In order to construct a
regional pattern, therefore, it is necessary to construct a "master curve" for a specific locality in
which the values determined at more distant sites are corrected to those predicted at the central
point. Such corrections necessarily involve a model of the probable geomagnetic field behaviour
within a subcontinental scale region, i.e. some lf/km 2 . Until recently, the only correction
237
H. Y. Goksu et al. (eds.). Scientific Dating Methods, 237-250.
© 1991 ECSC. EEC. EAEC. Brussels and Luxembourg. Printed in the Netherlands.
238

undertaken was 10 assume that the geomagnetic field can be simulated by an axial geocentric
dipole, i.e. the field closely corresponds to that of a single dipole at the centre of the Earth and
aligned along the Earth's axis of rotation. On this basis, the only correction undertaken was for the
difference in inclination (dtincl.) as a function of the difference in latitude (8 lat.), i.e.
2 tan (8 lat.) = tan (8 incl.)

between the reference point and the archaeological site itself. Such a correction is probably
adequate for sites within some 100 km distance of each other, but can lead to problems due to the
spatial variation of declination in particular - for example, comparing results from northern and
southern France (Thellier, 1981). A more effective correction is the "regional inclined
geocentric dipole correction" (RIGDC) in which it is assumed that the regional properties of the
geomagnetic field can be represented by assuming the field is due to a geocentric dipole that is
inclined relative to the Earth's axis of rotation. The location of the geomagnetic pole,
based on the archaeomagnetic observation, is then used to assess thedirection of the geomagnetic
field at the reference location. Tests of this model against the present day observed geomagnetic
field over a region of lCkm 2 , i.e. from localities within 550 km of the reference location, shows an
average agreement with the observed field of 0.88±0.32° which can be considered less than the
precision in most observations. Similar considerations will also apply to determinations of the
intensity of the past geomagnetic field, but the imprecision of current techniques mean that any
difference between an axial and an inclined dipole correction is well within the current
measurement error.

II.2.2 AN EXAMPLE: THE BRITISH DIRECTIONAL MASTER CURVE

Archaeomagnetic studies commenced very early as Boyle (1691) was the first person to
determine that bricks, as they cooled, acquired a thermal remanence. However, the first substantive
archaeomagnetic work in Britain was by Cook & Belshd (1958), following earlier studies in France
(Thellier & Thellier, 1942). The work in Britain was continued by Aitken and his colleagues and
summarized by Aitken <4 Weaver(1962), Aitken & Hawley (1971) and Aitken (1974).
(Thellier's pioneering work in France was summarized by Thellier, 1981. Other secular variation
curves have been constructed for other areas - notably Bulgaria (Kovacheva, 1982), and the
southwestern United Slates (DuBois, 1975; Sternberg, 1987).) Subsequent British
archaeomagnetic directional studies have been summarized by Clark et al. (1988) in a review
which gave more emphasis to the reliability of the archaeological age than had previous summaries.
However, Clark et al. included an automatic correction has been made for magnetic "refraction"
(Harold, 1960). It is not considered, at this stage, that the universal occurrence of such an
effect is adequately substantiated (Tarling et al., 1986) and, if present, should only applied to
specific sites for which adequate physical observations have been made.
 239

Figure II. 1 Direction Secular Variation for Britain

The variation in declination and inclination is known since 1600 by direct observations. The
information on the preceding 2,000 years is based on some 172 site determinations, but remains
poorly defined for pre-Roman times (shown dashed).

If there is a sufficiently large, precisely defined data base (172 sites, although many more less
well dated sites also exist). In theory, the curve should "draw itself", i.e. the mean directions,
corrected to the reference location, should all lie on the same curve. While such a curve is
becoming evident (Figure II. 1), its definition is not as precise as would be indicated by the
expected errors in the determination of the mean direction. This could indicate that the
geomagnetic secular variation has been, historically, more variable than it appears to have
been since 1600 AD, but it is much likely to reflect unrecognized errors in the archaeomagnetic
determination. Nonetheless, it is also clear that there issufficient agreement that a "Master curve" is
adequately defined, although need more refinement, particularly for the "Dark Ages" between
c.350 A.D. and 800 A.D. and for pre-Roman times. Both periods reflect the general absence of
well-dated archaeological sites of these ages - the latter largely reflecting the inaccuracies in 14C
dating. It is also evident that while there are many apparently well defined archaeomagnetic
directions, there are significant inconsistencies between directions defined for any given time.
Such inconsistencies may be caused by archaeomagnetic, archaeological, or geomagnetic factors.
240

II.3. ERROR ASSESSMENT BASED ON THE BRITISH OBSERVATIONS

11.3.1 ARCHAEOMAGNETIC ERRORS

The errors in orientation are likely to be largely averaged out where more than 5 or 6 separately
oriented samples have been obtained from the same site, particularly if sun compass orientations
have been used. Similarly, measurement errors are likely to have been small and averaged out
in the determination of the mean direction. In general the influence of such errors on the
determination of the mean direction is likely to be much less than 2° (Tarling, 1983a). Most
observations of large structures show deviations that are greater than the likely orientation and
measurement errors, of which "magnetic refraction" (Harold, 1960) appears to be the most serious.
While the physical explanation of this phenomenon is still under consideration (Tarling et al
1986), it seems unlikely to account for errors of more than 2-3°, and probably less if any given
structure is sampled systematically - although this is frequently inhibited by the nature of the site
itself. Nonetheless, it seems likely that most observations for the sites of the same age should be
similar within some 2-3°, yet larger discrepancies are clearly present.
It is clear that major deviations could be attributed to the presence of strongly magnetized
materials nearby (Hoye, 1982), for which there may no longer be archaeological evidence, but
most studies of large archaeological structures (Tarling et al . 1986) have not shown clear evidence
for such deviations.

11.3.2 ARCHAEOLOGICAL "ERRORS"

Probably the largest source of error in determining any secular variation curve is the paucity of
well-dated archaeological material. This absence largely reflects the fact that archaeomagnetic
dating -s commonly not attempted unless other methods of dating have failed. It is not uncommon
for an archaeological site to be assigned a specific age, with the actual uncertainly in the age only
becoming evidence if the archaeomagnetic data are inconsistent with the proposed age. It is
probable that the age estimates used in the classification are, in fact, much less certain than stated
in the literature. In addition, a site is usually regarded as being in situ by an archaeologist if it has
not actually been moved by human agencies. However, differential compaction commonly means
that previously horizontal hearths are now tilting at angles of a few degrees which may either be
not observed or, more commonly, the archaeomagnetic investigator is not informed of such
disturbance (Gentles & Tarling, 1988).

11.3.3 GEOMAGNETIC "ERRORS"

The construction of a secular variation curve from dispersed localities requires some correction, as
discussed earlier, but the RIGDC seems unlikely to introduce errors greater than the orientation and
 241

measurement errors, i.e. <2°. Magnetic storms during the cooling of an archaeological structure,
usually one or two days, are similarly unlikely to cause significant deviation of the ambient field
direction.

II.4 ARCHAEOMAGNETIC DIRECTIONAL DATING POTENTIAL

If the British data are accepted as reasonably typical, then it is possible to determine the annual
rales of change of the geomagnetic field during the last 2,000 years (Tarling, 1988, 1989). These are
0.08±0.06° for declination, 0.04±0.03° for inclination and 0.06±0.03° for the solid angular
change. If it is assumed that theaverageerror for determination of the direction of remanence at a
site is 1-2°, and that there are no systematic errors involved, then this would suggest and average
dating accuracy at a single site of 15-30 years.
The potential for this form of dating is therefore very high. There are, however, two main
problems. The main problem is the lack of definition of the available Master reference curves.
This tends to reflect the lack of well dated archaeological sites from which samples have been
examined as archaeologists, in general, would not consult with those working in
archaeomagnetism is they already knew the date of the site. However, as more data of imprecise
age become available, then the observations should increasingly lie on a secular variation curve
which need then only be dated for a few "golden spike" sites in order to provide this degree of
age resolution. The second problem is the reliability of the magnetic data itself. In general, the
most serious errors appear to arise from two sources, (i) site disturbance so that there has, for
example, been differential settling within the site, and (ii) the effects of differential cooling,
inhomogeneity and possible refraction effects. The former can only be assessed by adequate
archaeological knowledge of the site itself and its immediate vicinity, while the latter are likely to
become less significant as the understanding of the processes of remanence acquisition improves.
At this stage, the precision is more realistically assessed as lying between ±25 and ±50 years.

US ABSOLUTE DATING USING PALAEOINTENSITY DETERMINATIONS

Since 1860 A.D., the Earth's magnetic field has been decreasing at an average annual rate of
some 0.05% (Tarling, 1983a). If this change were global, then it could be a very useful tool for
both dating and correlation on a global scale. However, while most of this decrease appears to
be related to the decay of the main dipole field of the Earth, the change in the non-dipole field -
which accounts for some 20% of the total field - locally obscure this change and therefore
effectively destroys this method for intercontinental correlation purposes. Unfortunately, the
present stage of technology also inhibits this method for dating purposes based on geomagnetic
secular change. However, there have been significant improvements in the repeatability of some
242

determinations, giving grounds for considering that the past intensity of the field may now be
determinable to ±2-3%. Once this technological problem has been reduced, then it is clear that this
method will be of major importance as the reference master curve can be based on well dated
ceramics and the technique can then be applied to plentiful, unoriented materials. There is
certainly indications that, with very careful work, references curve may soon be available for
certain areas (Ailken et al., 1989a,b)., such as Greece (Figure II.2).

Figure II.2 Geomagnetic field intensity changes in Greece

(After Aitken et al., 1989a)

II.6 RELATIVE DATING USING DIRECTIONAL METHODS

Relative dating can sometimes be as archaeological (or geologically) as valuable as absolute
dating. In the case of the Late Minoan destruction levels on Crete (Figure II.3), for example, the
main Interest is whether such destructions were contemporaneous and whether they were
synchronous with the eruption of the Thira (Santorini) volcano some 120 km to the north. Magnetic
studies (Downey, 1983) of the fired destruction levels indicated two phases of burning while
studies of the Thira volcanic ashes indicated an eruption which corresponded with the destructions
on Central Crete (Downey and Tarling, 1984). Current research in Egypt, to establish an Egyptian
"master" curve, may eventually allow correlation between the Minoan and Egyptian chronologies,
but the extant relative dating in Greece still provides a major constraint on speculations on the
significance of such events.
As indicated above (Section 4), the establishment of synchroneity can be established within
some 15-30 years if there are adequate data, but 30-50 years may bea more realistic estimate.
 243

II.7 GEOMAGNETIC REVERSALS AND EVENTS

While most dating in archaeology is based on directional secular variation of the the geomagnetic
field. The Earth's magnetic field shows drastic changes on much longer time-scales that provide
convenient time-markers foranthropological studies, in particular, and provide a major link between
true archaeological studies and those of geological interest. One of the most significant features of
the long term behaviour of the field is its capability tochange polarity, i.e. for the north and south
magnetic pole to be interchanged. The last reversal of the field was some 720,000 years ago (Figure
II.4), but there has been, during the last 40 million years or so, an averageof three reversals of
polarity per million years, most of which have now been dated by radioactive methods. The record
of these polaritychanges have been used extensively in China for dating hominid remains, while in
Britain.cave sediments in Westbury, Somerset, have been found to have reversed magnetization
immediately below remains of what is thought to be the earliest occupation by Man in Britain, thus
suggesting an age between 500,000 and 720,000 years for this occupancy. The actual duration of
polarity reversal is now thought to be of the order of 9-10,000 years, which is quite precise for
intercontinental correlation purposes, when compared with most other techniques.

Figure 11.3. Relative Dating in Crete

The directions of remanence in Late Minoan I(B?) sites in central Crete are identical, but differ
from those of Eastern Crete LMI(B?) sites, suggesting an age difference for these fire destruction
levels. Both of these directions differ those from an LMIA hearth at Akrotiri on the volcanic
island of Thira some 120 km north.
244

Slorno Ic 31008 P I
uuaanvlcUOOOBPI
Mens lc.2t U M B P I

__ll'. 8loh# i B r o o le IO BO O 0BPI

,■_ — Biwa I IcIBO O O O BPI

Biwa n lc29S O O 0BPI

Figure II.4. Geomagnetic Reversals and Events during the last 2,500,00 years.

There is some evidence that the geomagnetic field attempts to reverse polarity for short intervals,
a few hundred years, but it has not yet been established that all such "excursions"are real and,
when real, whether they are global or local. At the moment, some "excursions" appear to be both
real and global, but all of these are still poorly defined and uncertain.

n.8 OTHER APPLICATIONS FOR THE MAGNETIC PROPERTIES OF

ARCHAEOLOGICAL MATERIALS
II.8.1 DATING BUILDINGS ON THEIR ORIE NTATION

A special case of archaeomagnetic dating that has still been little used is to date parts of, or entire
buildings by measuring their present orientation relative to true North (Searle, 1974). For periods
when it was considered that magnetic compasses pointed to the "Pole of the Universe", religious
buildings, in particular, were constructed on the assumption that true east-west and north-south
orientations were given by the magnetic compass. Comparison of their actual orientation
therefore provides a reading of the direction of the E arth's magnetic field at the time of their
construction. In western E urope, it was only after 1600 that it was realized that the compass
bearings were changing annually. This method has been successfully applied in Denmark by
 245

Abrahamsen (1985) to the dating of Romanesque churches and also revealing interesting
geographical differences.

11.8.2 FIRING TEMPERATURES

The two commonest magnetic minerals are magnetite and haematite, although goethite is
common within sediments. These essentially mark different degrees of oxidation, with goethite at
one extremeand magnetite the least oxidized. These three minerals are usually present in moderately
pure forms and so have different, but specific, temperatures above which their magnetic properties
are destroyed (the Curie temperature). These are 675°C. for haematite and 570°C. for magnetite.
Goethite commonly forms during weathering but it is chemically unstableand usually decomposes at
temperatures near 200°C. If goethite is present, then the material has not been reheated
significantly since the goethite formed.
Any archaeological materials that have been heated over 675 C C, will have had all previous
magnetic remanenccs destroyed so magnetic methods cannot distinguish between heatings to
higher temperatures, although strong heating often results in the oxidation of magnetite to
haematite. If the heating or reheating is to temperatures below 675°C, then the materials will only
record the direction of the geomagnetic field as they cool from their heating temperature.
If samples of these materials are then incrementally reheated in the laboratory and their
direction of remanence measured, the cooling remanence will be seen up to, but not above, the
laboratory temperature corresponding to the archaeological heating temperature. Naturally, there
are some complications in such temperature estimates as the duration of the peak heating is also
important, but this rarely gives rise to errors of more than 10-20°C.
This method is now being increasingly used in geological contexts to determine the
temperature of emplacement of volcanic ashes, some of which are of direct archaeological
interest such as those overlying Pompeii and Herculaneum, Italy (Kent et al., 1981) and the Minoan
city of Akrotiri, Greece (Downey, 1983). So far, this method has not been used in studies of
technological processes, possibly because many of these are at temperatures in excess of 675°C.
Nonetheless, several technological problems depend on assessment of temperatures below this limit.

11.8.3 BUILDING AND OBJECT RECONSTRUCTION

As individual objects, ranging from pots to entire structures, are heated then cool, they become
uniformly magnetized in the direction of the geomagnetic field at that time. The determination of
this direction can then be used to place individual samples into either their absolute or relative
positions which they had when they originally cooled.
246

H.8.3.1 Relative positioning When (he absolute direction of the field is not known, or irrelevant,
such as in the case of broken pots, then individual sherds can be placed in positions whereby their
magnetic directions are all parallel (Figure II.5a). This means that each individual shard can be
positioned in its position relative to all other sherds from the same pot - thereby allowing the pot to
be reconstructed (Bumham & Tarling, 1975). This is probably not a practicable proposition
when sherds from several potsare present, but may well have considerable value in determining the
shape of the original pot when only a few non-contiguous sherds are available (Figure II.5b).
Similar considerations apply to other fired objects or the structures (Figure II.5c,d) within which
the firing took place. In the case of smelters, for example, the purpose of specific objects is not
always known (Tarling, 1983b). However, if these can be placed in their position within the
structure, their purpose may well be clear. Thus such reconstructions can be of considerable
advantage in determining the technology in past times.

(«.> a?

Gv Oil
Figure II.5. Pot and Building Reconstructions
When either buildings orobjects are fired, they acquire a uniform magnetization in the Earth's
magnetic field as they cool. This enables the previous orientation of now dispersed parts of, for
example, (a) a kiln or (b) pot, to be placed into their firing position. Similarly cast objects such as
(c) statues or (d) coins can be estimated, e.g. bronze Roman coins are usually magnetized close to
vertically if the coin is placed horizontally with the Emperor's head downwards, while hot-
silvered coins of similar age are magnetized within the plane of the coin.

II.8.3.2 Absolute positioning If the direction of the geomagnetic field at any one place is known
for a specific time, then any object heated at that place at that time can be repositioned into its
previous position of firing by rotating the object until its magnetic remanence correspond with the
known direction. This can obviously be undertaken within only 1-2° if the previous field direction
 247

is known, but an approximate orientation can still be undertaken as, for most of archaeological
lime, the average direction of the geomagnetic field is northerly and its local inclination from
horizontal varies from zero, near the equator, to vertical at the geographic poles. It is thus possible to
approximately re-orient samples on this basis. For example, the orientation of statues when cast
can be determined fromeilher the material of the statue or its baked core (FigureII.5c). The
magnetic evidence from the Indian Sultanganj Buddha, for example, indicates that it was cast in an
inverted position, facing due East
Coins also illustrate some of the potential of this type of study. The position in which Roman
bronze coins were struck can, for example, be determined from theirdirection of remanence (Figure
II.5d). Preliminary studies (Tarling, 1982) suggest that most such bronze and copper coins were
cooled when they were struck and their direction of remanenceshowed that the Emperor's head was
downwards at that lime (Figure 4d). In contrast, some hot-silvered coins appear to have been
magnetized while in a vertical position (Figure 4d). Similar analyses could be of interest to
distinguish, for example, coins cooled in centrifuge from those cooled in other systems.
The distinguishing of site disturbance can, in itself, be of interest although this clearly
prevents directional dating. In the case of one long barrow, for example, the remains of a fire
within the barrow showed such strongly dispersed directions of remanence that the ashes must
have been raked and deliberately moved prior to the insertion of human bones. In this case, the
archaeological evidence forsuch disturbance was moderately clear, but it is often difficult to
determine such movement. Differential settlement at a fired site can be determined by comparison
of the remanent directions from different parts of the site as these must have had a uniform direction
at the original time of cooling. It is also of interest to determine the degree to which pots, bricks,
tiles, etc., were stacked during firing as this also has implications for the technology at the time of
firing.

II.8.8.4 PROVENANCING (SOURCING)

The determination of the source of archaeological materials is frequently of major importance in

determining past trade routes and cultural contacts. It is often possible to undertake such
sourcing by visual characteristics, but there are several cases where such "finger-printing" is
only possible by expensive methods. In the case of obsidian artefacts, for example, the most
effective method has been by minor and rare element analyses using neutron activation.
Study of the magnetic properties of such artefacts, from both geological and archaeological
contexts, shows that three simply measured magnetic properties - initial remanence, low field
susceptibility and high field remanence - are characteristic for most geological sources at about
0.1% of the cost of neutron activation. In some instances, the magnetic technique has detected
new sources prior to neutron activation analysis (Figure II.6). In some cases they can be more
sensitive than rare earths or minor element ratios (McDougalletal., 1983). While no
248

so
• *)
100 1000
Solu-olion Rmcntnii (Am'kg-')

Figure II.6. Obsidian Sourcing

In this example, Sardinian obsidians can be seen to come from four four sources, as identified by
ihcir magnetic properties prior to the confirmation from chemical studies.

magnetic studies have yet been made of Central American obsidians in this context, mere would
certainly appear to be considerable potential in obtaining magnelic "finger-printing" of the known
source localities. The cheap cost also opens the possibility of quantitative study of the magnitude of
tradeat different times.

11.8.5 ENVIRONMENTAL STUDIES

The composition and quantity of magnetic minerals within lakes, ponds, post holes, etc., is
influenced by the nature of the environment, in particular whether the area nearby has been
subjected to accidental or deliberate firing (Tile & Mullins, 1971). It is the concentration of the
minerals from such surface events into ditches, etc., that enables magnetic surveying to provide plans
of subsurface features in addition to that of magnetic objects (e.g. Clark 1986). The mineralogy
and concentration is now providing significant new evidence on the degree of burning in the region,
the rale of erosion (indicative of land clearance orclimatic effects - Tite & Lininglon, 1975), and so
forth. As these aspects are particularly well described by Thompson & Oldfield (1986), they will
not be discussed further.

11.8.6 FORGERIES, TECHNOLOGIES, etc

Any forgeries involving heat will normally mean that the object became magnetized when it was
cooling. It is unlikely that the strength of the geomagnetic field at the time of the forgery was
identical to that of the original event. Similarly, the amount of viscous remanence acquired will
be much greater if the object has only been buried for a short period than if it has been in the same
 249

position for considerable periods of time. At this stage, the understanding of viscous remanence
would prevent the distinction between the real heating event and a forgery made during
Antiquity, but it is normally possible to identify 20th century forgeries involving healing, e.g.
the manufacture of "ancient" brass coins. Similarly, ancient coins tend to have more impurities
than modern ones, including gold and silver, and the presence of iron or iron oxide impurities can
be distinguished using non-destructive magnetic methods.
Similarly, the fact that certain technologies involving cooling with the objects in specific
orientation, as used for building or object reconstruction, means that the authenticity of the
manufacturing process can be evaluated by determining the present magnetic properties.

II.9 CONCLUSIONS

A wide variety of archaeological problems are capable of solution, or at least limitation, by

study of magnetic properties. Some of magnetic analyses are well established, such as
archaeomagnetic dating, but there are very many other applications - particularly where it is
important to re-locate objects in their original position when fired. However, even the simple
measurement of the intensity of remanence, the low field susceptibility and saturation
magnetization can provide information of considerable interest. It is thus surprising that these
techniques are not more widely used, particularly as they are extremely cheap and fast.
Furthermore the samples are often essentially unaffected, other than in their magnetic properties,
allowing other investigations to be made on precisely the same samples. It would appear,
therefore, that there is a considerable potential, largely untapped, for the application of the study of
the magnetic properties of materials found within archaeological sites.

REFERENCES

Abrahamscn N. (1985) Geol. Inst. Aarhus. Geoskifter 23, 1-61.

Ailken M. J. (1974) Physics and Archaeology. Clarendon Press, Oxford.
Aitkcn M. J., and Weaver G. H. (1962) Archaeometry 5, 4-22.
Aitken M. J., and Hawley H. N. (1971) Archaeometry 3,83-85.
Ailken, M.J., Allsop, A.L., Bussell, G.D. and Winter, M.B. (1989a) Physics Earth Planet. Ints.,
56,49-58.
Aitkcn, M.J., Allsop, A.L., Bussell, G.D., Liritizis, Y., and Winter, M.B. (1989b) Archaeometry,
31.77-87.
Boyle R. (1691) Chpt 1 in Experimenta & Observations Physiquae. Chymico magnetical
experiments and observations. London,.
Burnham R. J. P., and Tarling D. H. (1975) Studies in Conservation 20,152-158.
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Clark, A.J. (1986) Geophysics 51,1404-1413.

Clark A. J., Tarling D. H., and Noel M. (1988) J. Archaeo. Sci., 15, 645-667.
Downey W. S. (1983) Ph.D. thesis Univ. Newcastle upon Tyne, 1-717.
Downey W. S., and Tarling D. H. (1984) Nature 209, 519-523.
DuBois R. L. (1975) in: Magnetic Fields: Past and Present, Fisher R. M., and el al., Eds., New
York, Goddard Space Center, 133-144.
Gentles D. S., and Tarling D. H. (1988) in: Science in Archaeology - Glasgow 1987, Slater E.
A., and Tate J. O., Eds.,, Council for British Archaeology, 647-667.
Harold, M.R. (1960) Archaeometry 3,45-47.
Hoye G. S. (1982) Archaeometry 24, 80-84.
Kent, D.V., Ninkovitch, D., Pescatore, T. and Sparks, S.R.J. (1981) Nature 290,393-396.
KovachevaM. (1982) Phil.Trans. Roy. Soc. Lond. A303, 79-86.
McDougall J. M., Tarling D. H., and Warren S. E. (1983) J. Archaeo. Sci. 10, 441-452.
Searle S. (1974) New Scientist 61, 10-13.
Sternberg R. S. (1987) Geophysics 52,368-371.
Tarling D. H. (1982) Archaeometry 24, 76-79.
Tarling D. H. (1983a) Palaeomagnetism. Chapman & Hall, London
Tarling D. H. (1983b)J. Archaeo. Sci. 10,41^2.
Tarling D. H. (1988) in: Secular Solar and Geomagnetic Variations in the last 10,000 years,
Stephenson F.R., and Wolfendale A.W., Eds., Dordrecht, Kluwer Acad. Publ., 349-365.
Tarling D. H. (1989) in: Geomagnetism and Palaeomagnetism, Lowes F. J., Collinson D. W.,
Parry J. H., Runcorn S. K., Tozer D. C , and Soward A., Eds., Dordrecht, Kluwer Acad. Publ.,
55-62.
Tarling, D.H., Hammo, N.B. and Downey, W.S. (1986) Geophysics 51,634-639.
Thellier E. (1981) Phys. Earth Planet. Ints. 24, 89-132.
Thellier E., and Thelher O. (1942) C R . A c a d . Paris 214,382-384.
Thompson R., and Oldfield F. (1986) Environmental Magnetism. Allen & Unwin, London.
Tile M. S., and Mullins C. (1971) Archaeometry 13,229-236.
Tile M. S., and Linington R. E. (1975) Nature 265, 565-566.
FLUORINE DATING

RAINER BERGER
Departments of Anthropology and Geography
Institute of Geophysics and Planetary Physics
Interdisciplinary Archaeology Program
University Of California
Los Angeles,CA 90024 USA
REINER PROTSCH
Anthropologisches Institut,Johann-Wolfgang-Goethe Universitat,
Frankfurt-am-Main
Deutschland
INTRODUCTION
Fluorine is the most reactive chemical element in the Periodic
Table. It was discovered in 1771 by Scheele and isolated in 1886
by Moissan.In nature it occurs mainly as fluorspar, CaF_, and
cryolite, Na^AlF,, but seems widely distributed in groundwater
everywhere in ppm-quantities. Virtually all fluorine is composed
19
of stable F, whereas its radioactive isotopes of mass 17,18,20
and 21 decay quickly with half-lives from a few seconds to less
than 2 hours. Fluorocompounds are the basis of air-conditioning
and are responsible to a large extent for the"ozone hole".Other
applications are in glass etching,as a catalyst in gasoline pro-
duction and in exotic high energy fuels. Fluoridation of drinking
water below 2 ppm has been used to increase the dental health of
human populations.
Inasmuch as bones and teeth are the hardest tissues in mammals
or the human body, they tend to last the longest in the archae-
ological record. Therefore the dating of bones has become a primary
focus of archaeological and physical-anthropological exploration.
The direct dating of especially human bones is one of the most
convincing approaches to demonstrate the existance of man in a
particular time-frame. It is here that fluorine dating has found
its application since the element is invariably found in hard
tissue. The earliest application of fluorine dating is that by
Carnot (189 3) which led Cook and Heizer to apply it to North
American Indians in 1947.Perhaps the most celebrated use of this
techniques was the exposure of the Piltdown Hoax by Oakley (194 8).
251
H. Y. Goksu et at. (eds.). Scientific Dating Methods. 251-270.
© 1991 ECSC, EEC. EAEC. Brussels and Luxembourg. Printed in the Netherlands.
252

Generally, fluorine assay has been used in conjunction with

tests for the presence of uranium and nitrogen as described
in Oakley (1963,1969,1970). Experience has shown that ground-
water exposes bones to ppm-amounts of fluorine and uranium
which both increase in concentration in bones of progessing
age. On the other hand nitrogen decreases with age as the
bone organic compounds such as collagen loose their amino-
acids to the attack of saprophytes and groundwater. The com-
bined assay of fluorine,uranium and nitrogen has been called
the F-U-N Method which as a chemical technique is temperature
and environmentally dependent in contrast to nuclear-based
methods such as radiocarbon or potassium/argon dating which
do not suffer from temperature effects. However, there are not
always available nuclear methods which allow the direct dating
of bones of a given age.
Radiocarbon dating by the measurement of radioactive decay or
direct mass analysis ranges back to about 40-70000 years.
Potassium/argon dating of volcanic tuff deposits in which bones
or teeth may be preserved begins usually in the few-100000 years
range although more recent dates are possible with enrichment
techniques. However, despite the advent of aminoacid racemization
and uranium series dating, there has remained somewhat of a gap
in the several 10000's to 100000's of years range in which hominid
fossils are found. It is here that fluorine dating offers some
possibilities augmenting other techniques for constructing a
temporal framework.

FLUORINE DEPOSITION

World-wide water-soluable fluorides are found in trace quantities

(ppm-range) in almost any ground water. In the case of bone or
teeth, fluoride ions replace the hydroxyl-group of hydroxy-apatite
and become locked in place in the mineral matrix of these tissues
principally composed of calcium hydroxyapatite.

Ca 5 (PO.) _ (OH) + fluorine ion —>• Ca 5 (P0 4 ) 2 F

 253

Due to the extreme reactivity of fluorine with any other

molecular entity, it is very firmly bound in the fluor-
apatite and not exchanged for hydoxyl-ion again. Thus it
accumulates in time up to a theoretical limit of 3.8% of
bone tissue. The rate of accumulation varies with the availa-
bility of fluorine in ground water, the ambient temperature
and other factors such as catalytic processes. Consequently
bones exposed to the same groundwater and general environment
will absord similar amounts of this halogen whereas bones
with a more recent depositional history will contain less,
or older ones more as the case may be. This then is the basis
for the fluorine dating method which for obvious reasons provides
relative ages, in other words it permits the chronological
seriation of bones from the same or very similar environments
(Middleton 1844,Carnot 1883).
It remained for decades to pass before this methodology was
put to a convincing test in distinguishing the antiquity of
the Galley Hill skeleton from that of the Swanscombe skull
(Oakley and Montagu 1949).Both were found in river terrace
gravels near Swanscombe: the Galley Hill skeleton at a depth
of about 2.5m and the Swanscombe skull at roughly 7.3m. In
general context were Lower Palaeolithic handaxes and remains
of extinct animals. After chemical analysis for fluorine and
nitrogen (Oakley 1963,1969,1970) the following results were
obtained which show that Galley Hill and the Swanscombe skull
pertain to entirely different times periods.

Galley Hill skeleton 0.5% F and 1.6% N

Swanscombe skull 1.7% F and traces of N
Fossil mammals from 1.5% F and traces of N
Swanscombe gravels

In fact the radiocarbon laboratory of the British Museum

determined the radiocarbon age of Galley Hill to 3310 + 150
years since sufficient organic tissue was left in the bone
254
for direct dating (Barker and Mackey 1961).

THE PILTDOWN HOAX

In 1911 Charles Dawson found in the Piltdown gravels of England
fragments of a fossilized human skull and other vertebrate bone
specimen which greatly excited Sir Arthur Smith Woodward of the
British Museum of Natural History and led him to join Dawson's
excavation. Over the next several years more finds were made.
However the star discovery was a fragmentary human skull consis-
ting of a virtually anatomically modern cranial portion coupled
with a decidedly ape-like jaw including a prominent canine (Fig.l),
Since a number of distinguished scientists believed in the au-
thenticity of the Piltdown skull it was accepted by many even
though others rejected it as a strange association of incompatible
bone pieces. In 1948 Oakley proposed that the bone fragments in
question be dated by the fluorine method. Besides the human
cranial fragment, the mandible, canine tooth another 17 bone
specimens were tested. As Oakley describes it, all these pieces
were thought to belong two two distinct time series: an older
group belonging to the early Pleistocene including the grinding
teeth of a rare species of elephant and a much more recent group
consisting of remains of beaver, red deer and even hippopotamus
dating to a time just before the last glaciation. Fluorine tests
showed the older group to contain from 2-3% of this halogen,
whereas the human bone fragments ranged only between 0.1-0.4%.
At this point the seemingly insignificant difference in fluorine
contents did not alarm the investigators of the human bones. How-
ever Weiner's hypothesis that the association was bogus was tested
in 19 53 when a more sensitive procedure for determining fluorine
became available (Fryd 1955). As a result the mandible was found
to contain no more fluorine than modern bones or teeth while the
cranial fragments indicated an ancient origin.
In addition nitrogen and uranium tests were made which together
with the fluorine assays prove the Piltdown skull assembly to
be a hoax perceived by some as the work of Sir Arthur Conan Doyle.
 255

Fig.l.
The Piltdown skull,Eoanthropus Dawsoni.
After a photograph from the original in
the British Museum,Natural History,London.
:56

i comparison of the F,U and N data is found below adapted from

)akley (1970) which prove the point.

Piltdown cranium 0 . 1 %F 1 ppm U 1.4% N

Piltdown mandible 0 .03 " 0 3.9 "
Modern bone 0 .. 0 3 " 0 4.0 "

PALAEONTOLOGICAL APPLICATIONS

Just as human bones can be subjected to F-U-N analyses, animal

bones can be tested equally well. As Oakley (1970) points out
these tests can establish the relative ages of different types of
vertebrate bones from the same or nearby sites or trace the origin
of specimens from several possible sources. Examples of this
type of research involve saber-tooth"tigers" (Epimachairodus)
and an extinct elephant found at Piltdown (Elphas cf.planifrons).
Often known age animal remains can serve as chronological guide
fossils in comparative studies involving hominid remains. A case
study involves gigantopithecus teeth of the type found by von
Koenigswald in Chinese drug stores. Non-destructive testing for
uranium showed that these teeth agreed well in age with bones
belonging to Middle Pleistocene animals thus placing them into
a far more well established time-slot than was possible before.

GEOMORPHOLOGICAL APPLICATIONS

Just as the focus of research may be on either hominid or animal

remains, their presence often can date the sedimentary strata in
which they are buried. Care must be taken to avoid either intrusive
burials or natural redeposition from other sources of origin.How-
ever careful stratigraphic inspection can often alleviate concerns
over unusual circumstances of burial. Just as archaeologists are
often dismayed at the lack of suitable dating methods in the periods
preceeding the last glaciation, so are geomorphologists whose
dating repertoire is equally handicapped in many cases as well.
Applications of F-U-N dating in geomorphology are very rare, be-
cause academic training usually does not combine archaeology or
physical anthropology with geomorphology or sedimentology.
 257

MODERN FLUORINE DATING

Experience with fluorine measurements in bone and teeth so

far has shown that the density of the specimen in question
affects its fluorine content. Dense tissue will tend to ab-
sorb the halogen slower than spongy portions. Therefore it
is necessary to normalize the fluorine content to the actual
absorbing molecule concentration, in other words to relate
the fluorine content to the phosphate content of the bone
rather than to the entire weight of material which may contain
fine-grained soil particles. In this manner the density
character of the host substance is eliminated as a variable
(Fleming 1976). Consequently the ratio 100x%F/%P 2 O 5 is
determined. As pointed out earlier complete substitution of
the hydroxy-group in calcium hydroxyapatite allows a maximum
introduction of 3.8% fluorine into bone which in its fresh
state contains 42% of phosphate (P20,-) . In terms of the ratio
100x%F/%P2O,- complete fluoridation is equivalent to the value 9
Occasionally this number has been exceeded. It is nor clear
if this is due to the measurement technique used for the deter-
mination of fluorine by X-ray diffraction (Fleming 1976) or because
fluorine has begun to be substituted for oxygen atoms in the
phosphate group of apatite.
Fluorine can be detected quantitatively by a number of methods
such as distillation (Singer and Armstrong 1959).diffusion (Hall
1960),ion exchange (Talvitie and Brewer 1960),X-ray diffraction
(Niggli,Overweel and van der Vlerk 1953),photon activation analysis
(Meyers 1968), photon and neutron activation analysis (Bratter et
al.1977) and by ion probe.
Experimentally it has been found that the fluorine concentration
versus age can vary significantly so that a world-wide calibration
curve is not possible similar for example to those used in radio-
carbon dating. Samples a few thousand years old may possess the
same fluorine content as those tens of millions of years old. In
contrast specimen older than 10000 years hardly ever have a low
100x%F/%P 2 O 5 ratio on the order of 0.1 or less (Fig.2).
 258

10
t-
. . :: •:: . • .­ • . * . * ; •
AJ! •• • : " *
.­ « • • . •.
*:
1.0 > •• •

100%F
%P2O5
• •• •
•­• . •* •
0.1

_] I I I I 1 I 1 I LLJ_ _! I ■ t I I I I I I I t I I I I I I I I I I I

10 10 10 10 10

YEARS

Fig.2.
Variation of fluorine/phospate ratio in time.
After Fleming (1976).
 259

URANIUM IN HARD TISSUE

Similar to fluorine uranium is absorbed in bones and teeth from

the groundwater. The rate of uptake is dependent on concentration
of the element in g r o u n d w a t e r , temperature and environmental fac-
tors such as pH and catalysts which play a r o l e . Generally the
concentration of uranium varies significantly w i t h the geological
environment: granitic parent rock and volcanic rocks tend to
generate high ppm-levels in groundwater whereas sediments usually
are considerably lower if they were derived from sedimentary rocks
themselves. In contrast to fluorine which is chemically bound as
fluorapatite,uranium appears to displace calcium atoms in the
mineral matrix of bone or teeth and become part of the crystal
arrangement of the apatite.
Uranium can be detected in a non-destructive manner in specimens
by radioactive counting methods which leave the original sample
intact. This is in contrast to fluorine assay where small samples
need to be removed for testing which sometimes may be difficult
due to curatorial aspects if the piece in question is a single
tooth. A case in point is the chemical dating analysis of G i g a n t o -
pithecus teeth (Oakley 1970) alluded to earlier under p a l a e o n t o -
logical applications. Since only non-destructive testing seemed
warranted at the time, a variety of fossils w e r e tested for their
uranium content expressed as ppm of U , 0 R .

Lower Pliocene
Hipparion dentine 130
90
Lower Pleistocene
Equus sanamensis 30
Middle Pleistocene
Ailuropoda dentine <1
Gigantopithecus <1-10
Liucheng Cave fauna <1-10

On the basis of matching uranium concentrations the Gigantopithecus

type specimens belong into the M i d d l e P l e i s t o c e n e .
260

NITROGEN IN BONE

Nitrogen occurs in bone and teeth in the amino-group of the

amino-acids which make collagen and dentine, the hard-tissue
proteins which bind together the mineral constituents and that in
turn provide these tissues with their mechanical strength.
Fresh bone typically contains 4 to 5 % of nitrogen. Thus this
element is an indicator for the amount of protein left in archaeo-
logical samples. Typically the remaining nitrogen is analyzed
by a micro-Kjeldahl method. The rate of degradation of bone
proteins is heavily dependent on environmental conditions such
as temperature and moisture which also control the micro-
organisms effective in destroying bone proteins. Some of these
proteins seem to possess greater resiliency to destruction such
as osteocalcin which due to its chemical nature lasts the longest.
While frozen arctic conditions may preserve mammalian tissue
virtually intact as some frozen Siberean mammoths have shown,
very dry conditions in caves or artifical environments may lead
to mummification which also preserve tissue. Another medium is
found in peat bogs where anaerobic and mildly acidic conditions
prevail which inhibit decay. In contrast moist and warm tropical
regions permit very rapid destruction of tissues by a variety
of competing processes so that mammalian tissue there is virtually
completely destroyed within a few centuries or even much less.
Hence the ambient environmental conditions greatly control the
level of remaining aminoacids or nitrogen making this type of
analysis dependent on site or analogous ecosystem. It should be
remembered that within a given site there may exist different
conditions of preservation caused by such factors as variations
in permeability. While one end of a skeleton may be deposited
in sand another may be highly preserved in a dense clay matrix
which preserved the organic components of bone. Last not least
there occur special depositional situations such as in tar pits
where bones many tens of thousands of years old are compositionall}
identical with modern bone (Ho,Marcus and Berger 1969). Yet in
an intra-site comparison nitrogen analysis permits the sorting
of bones into contemporaneous groupings or differentiation most
 261

of the time as shown for the Galley Hill/Swanscombe case or

the Piltdown Hoax.

THE F-U-N METHOD TODAY

Depending on the time range and the questions asked the

parallel analysis of these three elements has proven to be quite
successful as shown at length by Fleming (1976). However,
there are so many environmental factors involved that it is
difficult to make sweeping generalizations. Instead, a variety
of examples will show the potential and the limitation of this
dating approach. One must bear in mind at this juncture that
there exists a gap in direct dating methods between some 40-70000
years ago and techniques suitable for the several hundred thousand
and million-year-plus range. This explains why F-U-N has been
used in this interval where quantitative methods are scarce
and where its greatest potential lies.
The classical examples of the Piltdown Hoax and the Galley Hill/
Swanscombe case have already been explained. Other studies in
Europe include an attempt to construct a calibration curve for the
interglacials of the Pleistocene in Germany based on fluorine
(Richter 1958). In France certain human bone material was found
in the Quaternary deposits at La Denise near Puy-en-Velay in
context with faunal remains. However, analyses of both types of
bones showed a marked difference. The human skull fragment versus
animal bone showed a fluorine content of 0.19 to 4.89 and a
nitrogen assay of 1.6 8 as opposed to 0.74. Clearly these bone
specimen were not coeval in time with the human being more recent
(Heinz and Oakley 1969) .
At Steinheim,Germany were found hominid remains of a transitional
form between Homo erectus and Homo sapiens neanderthalensis in
an open air site composed of calcareous deposit. Amino acid
racemization dating places this find in the 240000 - 250000 year
range ( Czarnetzki and Protsch, in preparation ).F-U-N analyses
of the os frontale give 3.02 % F, 203 ppm U and 0.32 % N.
In Greece the Petralona skull has been recognized as another
transition of the same type: between Homo erectus and Homo sapiens
neanderthalensis. The find was made in a cave where the skull had
262

been covered and preserved in calcareous dripstone. An ESR-date

( electron spin resonance ) placed the skull 203000 years B.P.
while amino acid racemization gave 210000 - 230000 years. The
F-U-N data are 4.11 % F, 309 ppm U and 0.36 % N also from the
os frontale ( Protsch , in preparation ) .
Recently three Homo sapiens sapiens were analysed from Bruhl and
Kelsterbach, both in Germanv. These finds were associated with
Mammonteus primigenius. The analytical data are as follows:

Bruhl F-U-N

Hominid I, Os frontale 2.63 % F 173 ppm U 1.96 % N

Hominid II, " 2.60 182 1.90
M. primigenius, Tibia 2.68 165 2.13

Radiocarbon and Amino acid Racemization Dates

14
Hominid I, Cs frontale c 31000 + 2780 (Fra-123)
6.3m
A-A 30000 (Fra-A-35a)
14
Hominid II, Os frontale c 25500 + 1500 (Fra-132)
6 .0m
A-A 26000 (Fra-A-35b)
14
M. primig. Tibia C 25450 + 1450 (Fra-132a)
6 .0m
A-A 26500 (Fra-A-35c)

Kelsterbach - F-U-N
Hominid (H.s.s.),Os occ. 2.98 % F 13 8 ppm U 1.20
M. primigenius, Bone 2.80 109 2.00
M. primigenius. Bone 2.93 130 1.55

Radiocarbon Date
Hominid, Calotte 14,
C:. 29000 + 530 (UCLA-2361)
4 . 6m
(Protsch and Semmel 1978,Protsch 1986)
These data show first of all that the m a t e r i a l in each site fits
stratigraphically and the general context is assured. M o r e o v e r ,
the F-U-N data provide by their similarity an indication what
kind of data can be expected from these German Upper Pleistocene
environments. In other w o r d s , these sites are of an archaeological
integrity which Galley Hill/Swanscombe,Piltdown or La Denise w e r e
not.
 263

In Africa the prehistoric site with perhaps the greatest visi-

bility is Olduvai Gorge for which Hay (1971) evaluated the strati-
graphy in terms of the regional geology. Those levels suitable
for radiocarbon dating were also assayed for their F-U-N character-
istics with the following results:

Hominid I Middle Naisiusiu Level 2.2 %F 3 ppm U 0.45 %N

Hominid II " 2.3 3 0.43
Fauna I " 2.8 3.5 0.64
Fauna II Upper Naisiusiu Level - 2.5 1.21

Radiocarbon Dates
Hominid I, bone fragments:16920 + 920 (UCLA-1740)
Fauna I, " " :17550 + 1000 (UCLA-1695)
Fauna II, " " : 10100 + 600 (UCLA-1321) (Berger and
Libby 19 69)
These analyses provided the first quantitative chronological
framework for some of the upper stratigraphic levels at the gorge
using direct dating of bones in sealed context.
A similar analytical approach was used at Fish Hoek in southern
Africa to assess the hominid finds uncovered there:

Hominid Uncertain provenience - %F ppm U 0.60 %N

(Oakley)
Fauna Howieson's Poort Layer - - 0.60
Hominid " " " 0.40 - 0.60
Fauna " " " 0.20 - 0.60
Hominid Upper Stillbay - - 0.58
Fauna " " - 17 0.52
Fauna " - - 0.46

Radiocarbon Dates
StilLbay Layer by charcoal, 183 cm: 35600 (Gx-267)
Stillbay hearth by charcoal, 244 cm:36000 + 2400 (UCLA-1235)
(Berger and Libby 1968)
Bone, Equus capensis,Upper Stillbay 260 cm: 35,630 + 2500
(UCLA-1744) (Berger
and Protsch 19 89)
264

For Florisbad the F-U-N and radiocarbon data can be summarized

via a more comprehensive table (Protsch 1974) :

Homo sapiens I Peat I 2.6 %F 24 ppm U 0 . 1 6 %N

Homo sapiens II " 2.0 25 0.21
Homo sapiens III " 1.10 24 1.70
Homo sapiens IV " 1.60 24 0.40
Unknown bones " 2.10 - 0
Unknown bones Spring 2.80 - 0.60
Hippo.amph.bones Peat I 2.0 23 0.20
Hippo.amph.teeth " 2.6 23 0.09
Hippo.amph.teeth " 2.5 23 0.08

Radiocarbon Dates
Hippo.amph.bones: 38680 + 2000 (UCLA-1745E)(Berger and Protsch
1989) ; associated wood: 38250 + 3800 (UCLA-1745C) (Bada et al.
1974)
Both the Fish Hoek and Florisbad finds have been discussed in
terms of their human evolutionary significance by Protsch (1973).
While Fish Hoek's placement morphologically was never seriously
in question as a form of anatomically modern man,Florisbad was
considered by some as more of the Neanderthal-type-Sut the present
dates point more to a Homo sapiens capensis or near anatomically
modern man.
Regarding Homo sapiens neanderthalensis, the earliest type discovered
at Rabat,Morocco appears to date from about 180000 to 190000 years
ago. This specimen was found in very dry, sandy deposit and showed
a F-U-N composition of 1.83% F, 98 ppm U and 0.96% N which is
quite different from the Petralona skull with 4.11% F, 309 ppm U
and 0.36% N out of a cave environment of similar latitude.
In the Americas, F-U-N Dating was tried very early by Cook and
Heizer (1947) who found Carnot's (1893) fluorine measurements so
promising that they decided to analyze various human fossils
uncovered in North America. However, their data do not show a
very decisive separation in fluorine values to base very distinc-
tive dates on as can be seen in the next table:
 265

Limestone Cave,Calaveras Co,

California, 4-Cal-10,human bone 0.01 %F 3.62 %N
Same location,horse bone 0.26 4.19

Open air site,Tranquillity,

California,4-Fre-48,human bone 0.16 2.26
Same location,mammal bone 0.20 1.73

Dry stream bed,Los Angeles Man,

4-LAn-172, human bone 0.08 3.61
Nearby location, mammoth bone 0.12 4.35

Open air site,Melbourne,Florida,

Brevard Co, 9-Br-44, human bone 0 ,. 1 0 5.50
Same location, horse bones 0 ,. 1 2 6 .20
Same location, mammoth bones 0 .. 1 2 3.45

Cook and Heizer's report list more measurements than are reported
here which are averages and thus do not reflect some internal
variation. They concluded that man was present in America prior to
the final extinction of some elements of the Pleistocene fauna.This
agrees with the view that man was responsible to a large extent for
the demise of the megafaune in the Americas as summarized by Martin
and Klein (1984) .
Over the years interest in the first arrival of man in the Americas
has sparked interest in early fossil human material. Included here
are a list of radiocarbon dates and fluorine assays to provide an
indication of the nature of the analytical data.

Bishop's Cap Cavern ,NM.5320 + 120 BP 0.47 %F

(UCLA-1432; Berger and Protsch 1989)

Haverty Man or 4050 - 7900 BP*

Angeles Mesa, Calif. 10080 + 810 BP** 0.04
(*Taylor 1983; ** Berger and Protsch 1989)

Laguna,California 17150 + 1470 BP* 0.30

>14800 BP* 0.34
5100 BP**
(* Berger and Libby 1969; ** Bada et al. 1984; also
Taylor et al. 1985)
266

Los Angeles Man,Calif. >23600 BP* 0.11 %F

3560 BP**
( * UCLA-1430, Eerger et al.1971, Berger 1975;
** Taylor et al. 1985)

Lovelock Cave, Nevada 3380 + 60 BP 0.11 %F

(UCLA-1459C, Berger and Protsch 1989)

Mostin Site, California 10470 + 490 BP 0.30 %F

(UCLA-2171,Kaufman 1980; Berger and Protsch 1989)

Stanford Han or 3600-4850 BP*

Sunnyvale, California 4350 + 130 BP** 0.27 %F
5130 + 70 BP**
(* Taylor et al. 1983, Taylor et al.1985:
** UCLA-1425B and -1861,Berger and Protsch 1989)

Tranquillity Fan,Calif. 2550 + 60 BP 0.12 %F

(UCLA-1623, Berger and Protsch 1989)

Truckhaven, California >500 BP 0.07 %F

(UCLA-1712, Berger and Protsch 1989)

None of these North American specimen have substantial fluorine

concentrations when compared to other continents. Some of the
differences in age determinations need to be resolved by further
unambiguous radiocarbon tests made directly on the original samples.
For South America the list of direct dating and fluorine com-
parisons follows below:
l4
Cochabamba,Bolivia, by C~ 13050 + 250 BP 1.60-1.73 %F
(Fra-102), by AA 13200 (Fra-A-7).
14
Punin,Ecuador by C 10700 + 200 BP 1.48 %F
(Fra-101), by AA 10600 (Fra-A-5)

Sacaba,Bolivia by AA 18000 BP 2.08 %F

(Fra-A-10)
As one would expect the South American dates echo the North Ameri-
can finds given the understanding that both were settled via the
Beringian connection.
A recent intra-site study is that of Moundville,Alabama (Haddy and
Hanson 1982) which illustrates the use of nitrogen and fluorine.
 267

SUMMARY
Fluorine dating has shown its value as a seriation technique
for intra-site chronological analysis as well as inter-site
comparisons when environmental conditions are similar. More-
over the method can be very helpful in detecting unrelated
hard tissue samples as in the case of say Piltdown or Galley
Hill/Swanscombe. Thus it can assist in recognizing unusual
deposition or intrusion. When samples of different time periods
are heavily mixed as in some caves, fluorine dating can un-
scramble the most likely chronological sequence.
On a world-wide basis Old World hominid samples have shown the
highest fluorine absorption values, while the lowest are found in
the New World which was settled much later.
The fluorine dating methodology coupled with uranium and nitrogen
testing as the F-U-N Method is also applicable to palaeontological
and geomorphological research for evaluating problems pertinent to
either age or stratigraphy. While F-U-N by itself cannot provide
dates in years, it certainly can establish order where formerly
there was none especially in those time ranges where neither
radiocarbon or potassium/argon dating is applicable and where
other methods do not provide convincing evidence by themselves.
This discussion of fluorine dating was prepared for the 100 year
anniversary of the initial publication by A.Carnot: Recherche
du fluor dans les os modernes et des os fossiles published in
Acad.Sci.Comptes Rendus 114. 1189-1192 (1892).
268

REFERENCES

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ceedings National Academy of Sciences U.S. 71, 914­917.

Barker,H. and Mackey, J. (1961) Radiocarbon 3_, 39­45.

Berger,R. (1975) World Archaeology 7,174­186.

Berger,R. and Libby,W.F. (1968) Radiocarbon 10,402­416■

Berger,R. and Libby,W.F. (1969) Radiocarbon 11,194­209.

Berger,R. and Protsch,R. (1989) Radiocarbon 31,55­67.

Berger,R. Protsch,R., Reynolds,R.,Rozaire,C.and Sackett.J.R.

(1971) Contrib.Univ.Calif.Archaeological Research Facility,
Berkeley 12, 43­49.

Brätter,P.,Gawlik,D.,Jost,P.,Möller,J. and Reimers P. (1977)

Zeit.Anal.Chemie 283, 121­127.

Carnot,A. (1893) Annales des Mines ,Memoires ,Ser . 9 , 3_, 155­195.

Cook,S.F. and Heizer,R.F. (1947) American Jour.Physical Anthro­

pology 5_, 201­220.

Fleming,S. (1976) Dating in Archaeology,St.Martin's Press,

New York.

Fryd,C.F.M (1955) Bull.Brit.Mus.(Nat.Hist.)Geol.2(6),266­267.

Haddy,A. and Hanson,A. (1982) Archaeometry 24,1,37­44.
Hall,R.J. (1960) Analyst 83,560.

Hay,R.L. (1971) in M.D.Leakey,01duvai Gorge I I I ,Cambridge Univ

Press,Cambridge ,pp.9­18 .
 269

Heintz,N. and Oakley,K.P. (1969) Comptes Rendus 268,2873.

Ho,T.Y.,Marcus,L.F. and Berger.R. (1969) Science 164,1051-1052.

Kaufman,T.S. (1980) Early Prehistory of the Clear Lake Area,

Lake County,California. PhD Dissertation,University of California,
Los Angeles.
Martin, P.S. and Klein,R.G.(1984) Quaternary Extinctions,Arizona,Tucso
Meyers,P. (1968) Some Applications of Non-Destructive Activation
Analysis, PhD Dissertation,University of Amsterdam.

Middleton,J. (1844) Proceedings of Geological Society 4^, 43.

Niggli,E., Overweel,C.J. and van der Vlerk,I.M. (1953) Pro-

ceedings Koninklijke Akademie Wetenschapen B56, 416-420.

Oakley,K.P. (1948) Advancement of Science 16_, 336-337.

Oakley,K.P. (1963) in D.Borthwell and E.Higgs (eds.) Science

in Archaeology,Basic Books or Thames and Hudson,London.

Oakley,K.P. (1969) in D.Brothwell and E.Higgs (eds.) Science

in Archaeology,Praeger,New York.

Oakley,K.P. (1970) in D.Brothwell and E.Higgs (eds.) Science

in Archaeology,Praeger,New York,pp.33-45.

Oakley,K.P. and Montagu,M.F.A. (1949) Bull. Brit. Mus. (Nat.

Hist.) Geol. 1,25-48.

Protsch,R. (1973) The Dating of Upper Pleistocene Subsaharan

Fossil Hominids and Their Place in Human Evolution: With Morpho-
logical and Archaeological Implications. PhD Dissertation,
University of California,Los Angeles.

Protsch,R. (1974) Homo 25,No.2,68-78.

270

Protsch,R. (1986) in M.R.Zimmerman and J.L.Angel (eds.)

Dating and Age Determination of Biological Materials, Croom
and Helm,London, pp.3-38.

Protsch,R. and Semmel,A. (1978) Eiszeitalter und Gegenwart 28,

200-210.

Richter,K. (1958) Eiszeitalter und Gegenwart 9_, 18-27.

Singer, L. and Armstrong,W.N. (1959) Analytical Chemistry 31,105-

109.

Talvitie,N.A. and Brewer,L.W. (1960) American Industrial Hygiene

Association Journal 2^, 287-293.

Taylor,R.E.,Payen,L.A.,Gerow,B.,Donahue,D.J.,Zabel,T.H.,Jull,
A.J.T. and Damon,P.E. (1983) Science 220,1271-1273.

Taylor,R.E.,Payen,L.A.,Prior,C.A.,Slota,P.J.,Gillespie,R.,
Gowlett,J.A.J.,Hedges,R.E.M.,Jull,A.J.T.,Zabel,T.H.,Donahue,
D.J., and Berger,R. (1985) American Antiquity 50 (1),136-140.
DATING OF BONES IN ARCHAEOLOGY AND ANTHROPOLOGY
REINER PROTSCH
Institute of Anthropology and Human Genetics
J.W. Goethe University Frankfurt
Germany

Introduction

For several hundred years only the morphology of fossilized bones of

homlnlds found in archaeological sites was used to determine their
possible age. A find of a homlnld was judged by its "primitive " or
"advanced" morphology and dated either recent or old. Such "relative"
dating was called by K.P. Oakley (1964) R 4 -dating and is still used
largely today by most anthropologists. Since it was found, however, that
many groups of fossil hominlds did live sympatrically, that is at the
same time in the same area, and also that the same group would display
the same morphology for sometime, more than 1 0 0 , 0 0 0 years a more
accurate type of age determination had to be found. Two "absolute"
dating techniques are presently supplying more accurate age
determination on bones than do relative techniques s u c h as
morphological dating. These are radiocarbon and amino-acid-datlng.
The application of these techniques to osteologlcal material of fossil
homlnlds can verify or negate evolutionary theories such as the origin of
"anatomically modern man". A large series of absolute dates of fossil
hominlds from Africa, Europe, and other continents showed clearly that
"anatomically modern man" was present in Africa at least 1 0 0 , 0 0 0
years B.P. and possibly up to 2 0 0 , 0 0 0 years B.P. It clearly proves that
the old theory of evolution of "anatomically modern man" as a transition
from Neanderthal in Europe around 3 2 , 0 0 0 to 3 0 , 0 0 0 years B.P. is
not possible anymore. The absolute dating of bones by the above
mentioned two techniques can also solve other problems In archaeology
and anthropology, like for example, the question of the origin and
geographical locality of domestication of animals. Depending on
mlcroenvironmental conditions, bones are often the only material
preserved in archaeological or anthropological sites. In time periods
before two million years B.P., before the advent of cultural materials,
bones and teeth provide the only indication of habitation of early
homlnlds. Whereas until recently the archaeologist eliminated most
osteologlcal material and only preserved archaeological remnants we
now know that even smallest pieces of bones and teeth can provide a
wide range of information concerning the past and life habits of our
ancestors. Information as to the age of an Individual, palaeoecological
conditions, sexual dimorphism, and paleopathology are only a few
interesting aspects which can be obtained from studying bones, besides
that important question of the time period in which the bones
271
H. Y. Goksu el al. feds.). Scientific Dating Methods. 271-300.
© 1991 ECSC, EEC. EAEC. Brussels and Luxembourg. Primed in the Netherlands.
272

originated. The direct dating of bones can solve Important

anthropological questions. Bones can be dated by various methods and
pinpoint a precise period of time to which a fossil or cultural remnant
belongs. Often a said period covers, as is the case of "anatomically
modern man", a time span ranging from 30,000 years up to the possibly
2 0 0 , 0 0 0 years. The Neanderthals are also known to date anywhere
from 28,OOO up to possibly 2 0 0 , 0 0 0 years. Designating a hominid as
an early or very late representative of anyone hominid group could be
crucial in solving an evolutionary controversy in paleoanthropology.
Problems related to more recent time periods like Mesolithic, Neolithic,
Bronze Age, Iron Age, or even historic times can also be answered.
Accurate absolute dating is often the only means by which an
archaeological interpretation is possible, especially when archaeological
materials are not associated with burials. Whereas in time periods older
t h a n 1 0 0 , 0 0 0 years B.P. amino-acid dating is the only technique
which can be applied to bones, it also provides from 1 0 , 0 0 0 to
5 0 , 0 0 0 years B.P. a reliable tool to cross-check C ^ - d a t i n g . Amino-
acid-dating, however, can hardly be used in time periods below 1 0 , 0 0 0
years B.P. Within this crucial period radiocarbon dating presents the
only physico-chemical means of absolute time placement. It is important
to note that C* ^-dating provides often the sole means for solving
anthropological and archaeological questions. Unfortunately many
archaeologists and some anthropologists view absolute dating as simply
additional information. If the dates do not coincide with their relative,
purely archaeological and anthropological estimation, absolute dates are
often totally disregarded. Under certain environmental conditions bones
provide the only dateable material. An example of this were several sites
in which bones were found and dated in order to solve the question of
the earliest appearance of "anatomically modern man" in Europe and in
Africa (Glowatzky and Protsch, 1973; Henke and Protsch, 1978; Protsch,
1974, 1975, 1976; Protsch and De Villiers, 1974; Protsch and
Glowatzki, 1974; Protsch and Semmel, 1978), the arrival and
appearance of Man in the Americas (Berger et al, 1971; Bischoff et al,
1976; McNeish et al., 1970; Protsch, 1978 b), and the question of
earliest animal domestication in the Near East and south-eastern
Europe (Berger and Protsch, 1974; Protsch and Berger, 1974).
By dating bones from different geological environments, using both the
inorganic and organic portions, it was found that the organic portion
quite often supplies the only accurate dates. With very few exceptions,
which were probably due to secondary induced contamination, dates on
the organic portion collagen agreed favorably to historical time periods
in question. Comparative historical dates ranged from late Middle Age
dates, early Middle Age dates, Roman times, the Bronze Age, as well as
from a number of different Egyptian dynasties. When, however, other
organics like wood and charcoal were found in association with
osteological materials, absolute dating was applied to both.
Archaeologists and anthropologists argue quite often that radiocarbon
 273

dates dating to earlier than historical times, that Is earlier than 5 , 0 0 0

years B.P., could be wrong. Then again why should a contamination
factor exist only in older materials? In this case relative geological,
palaeontologlcal, or archaeological association correlating with absolute
radiocarbon dates can be used to support the accuracy of an absolute
dating technique. If one compares the overall accuracy on dates on all
organic materials commonly used for radiocarbon dating, we come to
the conclusion that collagen-radlocarbon-dating proves to be as exact as
other dates processed on different materials like wood, charcoal, and
other non-osteologlcal organlcs.
There is, however, a severe shortcoming in collagen-radiocarbon-dating.
In a large percentage of samples processed, often nearly all osteological
material available is needed for dating. On the other hand, in many
instances only small amounts of osteological material are needed. It is
directly related to conditions of preservation. Samples stemming from
extremely dry and hot environments can show excellent preservation. In
most such cases only a few grams of bone are needed for absolute
radiocarbon dating. The same is true for preservation conditions in
extremely cold environments such as permafrost. In a number of cases
pertaining to osteological materials found in arctic locations a few grams
of bone were sufficient for dating. The La Brea Tar Pits bones from a site
in California are an excellent example of an another preservation which
provided superb conditions for the yield of large amounts of collagen In
bones. In all three above described situations the amount collagen in
bone is comparable to that of fresh bone - that is anywhere between 23
% and 27 % depending on the age of individual and type of species.
On the other hand, quite often the inorganic portion of bones, this was
the case in some Egyptian samples, has been leached out of osteological
materials in situ conditions. In these cases sometimes a total of only
twenty grams of bones contained as much as sixteen to seventeen grams
of collagen. One quarter of the sample was thus sufficient for
radiocarbon dating. Organic components of other osteological materials,
which are found in and completely covered by calcareous deposits such
as loess and travertine, are also most often exceptionally well preserved.
In such cases relatively small amounts of material are needed for
collagen-radlocarbon-dating.
Each environmental situation is thus quite different and it is t h u s
necessary for the above mentioned reasons that the dating specialist
collects detailed geologic and geomorphologic Information for the
particular site before accepting osteological material for dating. If
possible, he should collect the material personally, especially If a large
series of dates and the application of different methods is planned.
If bones stem from an environment which dissolves either organic or
inorganic portions quickly, such as jungle or other humid or hot
environments in tropical or subtropical areas, and if then the bones are
preserved at all, they are usually preserved poorly. An alkaline type of
environment such as limestone caves generally preserves only the
274

Inorganic portion of the bone, rapidly dissolving the collagen portion. In

such cases only a minimal amount of organlcs is still preserved. A date
for such samples can subsequently only be obtained by processing large
quantities, quite often many pounds of bone. Bones, preserved under
such conditions, might yield a date but the complete skull or skeleton
would have to be sacrificed to obtain a date. It is on the other hand
possible for the dating specialist to estimate with fair accuracy the
amount of osteological material needed for radiocarbon-collagen-dating.
J u s t as there are many reasons causing contamination when dating
organic materials such as wood and charcoal (rootlots, humic acids,
etc.) the specialist dealing with the dating of bone samples faces the
same and many additional problems. This is the reason why the dating
of bones was thought to be complicated by many archaeologists. An
absolute date which did not comply with the "relative" estimation of the
archaeologist or anthropologist was often put aside and the laboratory
which processed the sample blamed for the noncompliance with the
estimation. Careful reexamination of a large series of samples which had
yieled such "erroneous" dates revealed quite often that the errors
occurred during selection, excavation, and handling prior to submission
to the laboratory and not in the dating facility itself. False marking and
faulty collection procedures by the archaeologist often falcify results.
This includes the handling of bones with fatty or oily hands, packing of
bones in other organic materials like cotton or paper, or marking a
stratigraphic position and origin incorrectly. Whenever possible,
samples should thus be collected by the dating specialist himself. He
should also keep his own collection notes, pack bones in cellophane,
aluminum foil, or similar nonorganic packing materials and record in
detail the stratigraphic and geomorphologlc conditions of the
stratigraphic horizon. This is not meant to suggest that all
archaeologists have insufficient knowledge of the dating procedures
which follow the collection of bones.
The following main points are described below In some detail

1. Micromorphological analysis by thin-section-polarisation

microscopy
2. Principles of radiocarbon dating
3. Calculation of bone sample amounts needed
(by mlcroanalysis-N)
4. Dating of the inorganic portion of bone, the apatite
5. Dating of bones by accelerators
6. Dating of the organic content of bones - the collagen
7. Kelsterbach - a case study in C ^-collagen-dating and
amino-acid-dating

The below mentioned steps should be followed when processing bones

by absolute dating techniques such as radiocarbon and amino-acid-
dating.(Fig. 1)
 275

BONE SAMPLE
i
thin section analysis
F,U,N-analysis
visual contaminant removal,
i
sand removal by doubly-dist. H_0
1mm com pacta (shellac etc.) removal
i
aceton/2-ethoxyethanol reflux
47o HCl-20min-periosteal/shellac border treatment
I
hydrolysis by HCl
collagen strands. tropocollagen

renewal of solution l-UO solution-weak HCl

i
NaOH humic acid treatment humic acid removal by NaOH
i i
repeated doubly-dist. H-0 washing repeated doubly dist. H~Owashing
neutralization with HCl
I HCl treatment-slight acidity
washing in h^O
gelatine conversion
collagen strand drying l
6N HCl-24hr treatment
combustion of collagen
liquid chromatography
amino - acid collection
amino- acid drying
(collagen/gelatine/amino-acid)
^sample combustion
"~~ i
CO.
CO2 analysis for C
<rC12/<rC13 analysis
1
CO9 cleaning by hot CuO
*■ 1

Fig.1 Steps to be followed KMnO^ and AgNC^ treatment

when processing bones by ab­ C02thermal circulation (CuO/Ag)
solute dating techniques
sample count in 21 proportional counter
( 2600 min. minimum)
276
1. Micromorphologlcal analysis by thin-section
polarisation microscopy

Bones can also be examined visually and will give good information
pertaining to secondary In situ contamination due to microorganisms.
The technique of thin-section-polarisation-microscopy has only been
recently applied to osteological samples from cave and open-air sites.
Microorganisms such as algae, fungi, and bacteria do not feed only on
the organic content of fresh bone, the collagen, which is used for such
dating techniques like radiocarbon and amino-acid dating. Older bones
which had been buried in limestone caves often still show an amazing
high content of the organic portion of bone. It was found that even bones
several hundred thousand years old (Petralona and Reillngen) contain
some ancient organics which are due to Infiltration of bone by the above
mentioned microorganism which feed on the collagen. The polarisation-
technique can, however, determine quite accurately whether
contamination is recent or ancient and we can thus differentiate visually
between these and the collagen of bones. If fungi feed on the collagen of
recently buried bones contamination in radiocarbon dating is not
important since fungi don't photosynthesize and do not carry recent C 1 4
into the organics of bones. Most algae and bacteria could, however,
cause contamination In old bones by carrying in recent radiocarbon. All
of these microorganisms show up as black deposits in the interstitial
spaces of bones, in the lacunae, matrix, and all parts of the traversian
system. We can actually determine which types of microorganisms are
present, be it bacteria or fungi with specific diagnosis as to species by
using scanning-electron-microscopy. Rarely do these microorganisms
Infiltrate Into the more denser parts of the compacta. As a precaution,
especially if some parts of the primary apatite are leached out, all of our
bone samples which are chosen for radiocarbon or amino-acid dating
are subjected to the polarisation technique and, if microorganisms are
present, also to SEM. Whereas contamination due to the presence of
fungi cause no problem in radiocarbon dating they can cause serious
contamination, if they are of recent origin, in amino-acid dating.
Postcranial compacta is rarely affected by such secondary infiltration
and subsequent contamination whereas the dlploe of cranial parts are
quite often massively contaminated.

2. Principles of Radiocarbon Dating

Radiocarbon measurements have been used for a wide variety of

purposes b u t only a small fraction of these involve age determination
useful In paleoanthropology and archaeology. Materials used for dating
are wood, charcoal, peat, leather, paper, and other organic materials,
 277

some inorganic materials like shell, mortar, the organic portion of Iron,
teeth, and bones. Teeth and bones are most often used in an
anthropological context. Of these one should only use the organic
portion for absolute dating, as will be described later. Before we go into
detail on the dating of the organic portion of bones and teeth it is
necessary to comment on some of the basic principles of radiocarbon
dating. The same theoretical principles which pertain to the dating of
the above listed materials are also applicable to the dating of the organic
portions of teeth and bones. These principles were originally described
by Libby (1952, 1955) and were covered thoroughly subsequently In the
literature. A few corrections were added concerning the exact half-life in
the computation of dates and conversion and application of the absolute
C 1 4 ages to historical times. The following is a brief review. Three
isotopes of carbon are present In the total carbon reservoir of the earth
(atmosphere, biosphere and ocean). They are C , C 1 3 , the stable
isotopes, and the radioactive Isotope c l 4 . There is, however, a difference
In the relationship of these three isotopes to each other depending on
whether they occur in the biosphere, the atmosphere, or the oceans. All
of these contain for the most part inorganic carbon. Irregardless of these
differences, the mean ratio between C , c l 3 , and C i 4 is approximately
100:1:0,01. Of the three isotopes, the stable isotopes C 1 2 and C 1 3 are
not subject to physical changes with the exeption of C , the radioactive
Isotope. It undergoes radioactive decay at a constant rate of about one
percent per eighty years. At the same time, the supply of C ^ 4 is
continually replenished in the upper atmosphere by nuclear reactions
associated with cosmic radiation. Highly energetic cosmic rays infuse
into the upper atmosphere and interact with atmospheric nuclei to
produce free secondary neutrons. They collide again with nitrogen
atoms, specifically those of the isotope N* 4 and from C .

N 7 1 4 + 1101=0614 + ^ 1

The c l 4 produced In this reaction has a half-life of

5,730 +/- 30 years (Mann, Marlow, and Hughes 1961) which Is the
most recent calculation. However, in the radiocarbon date list reports
the "Libby half-life" value of 5,568 +/- 30 years is still used. The
chemical properties of the radiocarbon atoms produced do not differ
from the stable Isotopes c l 2 and c l 3 . The c l 4 atoms are oxidized by
atmospheric oxygen and form radioactive carbon monoxide molecules.
They are again oxidized mostly again with atmospheric oxygen and to a
lesser extent through the action of bacteria in the biosphere (Pandow,
Mac Kay, and Wolfgang 1960; Mac Kay, Pandow, Wolfgang 1963). We
thus have a continuous supply of radioactive carbon dioxide entering
the total carbon reservoir of the earth.
The three Individual reservoirs obtain radioactive carbon dioxide
through its entry into the atmosphere where it becomes a radioactive
part of all atmospheric carbon dioxide. It Is in the biosphere that carbon
278
dioxide, and with It radioactive carbon dioxide with the Isotope C * 4 is
Incorporated into plants by way of photosynthesis. Herbivorous fauna
accumulate the same amount of C 1 4 when they eat plants. The same
applies to carnivorous fauna which prey upon other animals.
Omnivorous animals like man ingest both and subsequently show the
same activity of radiocarbon in all of their soft and hard skeletal
components as do plants, herbivorous fauna, and carnivorous fauna.
The mean life of the c a r b o n 1 4 atom Is about 8 , 0 0 0 years. When it
deslntegrates, the products of decay are again a nitrogen atom and an
electron, In this case a beta particle. The equation would look as follows

C614 = N214 + 6-l.

It is estimated that the production of C 1 4 in the atmosphere is in a

state of equilibrium with its radioactive decay in the total carbon
reservoir of the earth. J u s t as the equilibrium is maintained in the total
reservoir it is also maintained in every living organism. A living organism
exchanges carbon with the atmosphere constantly in such a way that its
specific radiocarbon activity is identical to that of the atmosphere. Since
a dead organism, be it plant or animal, is unable to obtain newly
produced radiocarbon its C * 4 activity decreases through radioactive
decay at the time of death. The measurement of the C * 4 activity of the
organism at any one time enables us to calculate that moment In time at
which the organism discontinued the exchange of carbon. Since the rate
of decay is known we are able to calculate the total time period which
has passed since the death of an organism. Averaging its present
activity and comparing it to any organic sample with modern activity
(oxalic acid) we can calculate its age.
It was originally assumed that the radiocarbon activity in the carbon
reservoir was constant over time as well as that the half-life of C 1 4 was
accurate. New corrections in radiocarbon dating made it possible to use
this technique with a high degree of accuracy when compared to other
absolute direct dating techniques which are presently available. A
number of specialists supplied additional corrections (Suess, 1965;
Damon, Long and Grey 1966). The technique has become increasingly
refined due to the above.
The following assumptions are crucial for accurate age calculations
using radiocarbon dating. It is crucial to observe the assumption of an
accurate half-life calculation (Libby, 1955, p. 36) (convert the old Libby
half-life of 5,568 +/- 3 0 to the new half-life of 5,730 +/- 3 0 by
multiplying the former by 1,03). The knowledge and detection of all
factors causing variations in the production of carbon-14 and making a
detection possible is important (de Vries 1958; Willis, Tauber and
Munnich, I 9 6 0 ; Ralph and Stuckenrath I960; Stuiver 1961 and 1965;
Elsasser, Ney and Winkler 1956; Kigoshi and Hasegawa 1965). It Is also
important to know the carbon reservoir exchange rates (Suess 1965)
 279
14
and finally that an Interference of c a r b o n distribution and activity Is
also caused by man. The small variation In atmospheric c a r b o n 1 4
concentration which can deviate up to 2 % over a few thousand years
was adequately corrected by the research of Stulver (1961, 1965) and
Suess (1965 Stulver and Suess, 1966).

3. Calculation of bone sample-amounts needed

(microanalysis-N)

If one assumes that the organic portion of bone is the only material that
can be dated by radiocarbon with accuracy the question of the amount
of bone needed for dating must first be discussed. This question can be
easily solved contrary to what most anthropologists and archaeologists
believe.
Microanalysis, or N - Dating (a relative dating technique, or actually R4-
datlng) can be used for such computation (Oakley, 1968).
FUN-Datlng (Fluorine, Uranium, and Nitrogen) was already used In the
last century for dating (Mlddleton, 1844) and again in the 1950's by K.P.
Oakley. With the application to osteologlcal materials we are able to
obtain some idea of the relative time periods involved after the burial of
osteologlcal materials. Fluorine can be found in the mineral portion of
bone fluorapatlte which forms as a result of conversion from
hydroxyapatlte (calclum-hydroxyphospate). It occurs to some extent in
living bone material and to a much larger degree in buried osteologlcal
materials. The amount of fluorine found in adult human individuals is
about 2 0 g. Of that 95 % is contained In the skeletal system as
fluorapatlte(see also R. Berger). Of this, the dentition contains IO to 7 0
mg F / l O O g dry substance. A healthy organism ingesting a dally
minimum of fluorine accumulates 1 mg/liter drinking water mainly In
this teeth. It is a natural preventative-measure against caries. The
fluorine balance is at equilibrium up to a dally uptake of ca. IO mg (6
mg F-/1 water). Larger amounts are normally eliminated through the
kidney. Deviations in the accumulation of fluoride do, however, occur. In
some cases, extreme accumulation during dental development (8 to IO
years) obstructs the development of the enamel (dentalfluorosis). An
extreme uptake in bones could also lead to certain pathological
conditions. Such a case Is the femur of Homo erectus erectus
(Pithecanthropus erectus) dating to about 4 8 0 , 0 0 0 years B.P. which
was found In 1881 by Dubois in Java. It was thought that
Homo erectus erectus drank water In this locality with an unusually
high content of fluorine. Bones displaying such an unusual premortal
history cannot be used as a relative dating tool. Under normal
circumstances it is the Irreversible substitution of fluorine and also
uranium in bones which makes them suitable as a relative dating tool.
With the passing of time both elements accumulate in ever greater
amounts. Thus, when bones are buried In different levels at the same
280
location, bones positioned In lower levels show greater amounts of
fluorine and uranium than do those positioned above them and are thus
older. The accumulation of both elements Is dependent on time as well
as on the water-content present at that location. The presence of
uranium In bones on the other hand could, Immediately after
combustion of a sample for radiocarbon dating, somewhat Interfer with
the countrate of the sample Itself. This interference Is due to the fact
that after combustion uranium Is converted to Radon ( R n 2 2 2 ) . One
could t h u s theoretically calculate the total original amount of uranium
present right after combustion. As a matter of fact. In order to avoid
counting interference with C ^ , it is necessary to store the CO2 for a few
weeks until the Radon decayed to sufficiently low amounts.(Rn 2 2 2 half-
life is 3,825 days).
Like F and U nitrogen can be also a useful tool and in several ways. The
amount of nitrogen, contrary to F and U, decreases in time. It Is directly
related to the total amount of collagen and therefore also to the total
carbon of the organic portion. Nitrogen diminishes with increasing bone
age as protein is removed from the bones. With it all amino acids
containing that element are removed as well. In order to compute the
total amount of a bone sample needed for radiocarbon dating one simply
applies micro-N-analysis. Studies on modern bones have shown that the
amount of collagen, and therefore of nitrogen, differs only insignificantly
in different bones of the same individuals, in different age groups, and
in one and the same species. Comparative readings on bones In the
same and In different strata of the same location of a site, however,
supply a fairly accurate estimation of their time association relative to
each other. Since collagen constitutes 2 0 - 25 % of the total weight of
modern bone, which again contains roughly 5 0 % carbon, one can
easily calculate the total amount of bone needed for radiocarbon-
collagen dating. Nitrogen estimates in modern bone range from 4.70 %
(Berger et al.,1964) to 5.36 % (Eastoe and Courst, 1963) and 4.63 % to
5.41 % in a series of own experiments using young to very old sheep
bones. Any bones submitted for radiocarbon dating, from whatever
locality or environmental surroundings they originate, should be first
subjected to a nitrogen microanalysis. The result of the latter is then
multiplied by 3,0 +/- 0,5. Unless bones stem from a very old geological
and t h u s unfavorable environmental location, In which nitrogen h a s
decreased to unusually low amounts indicating the near absence of
collagen and thus also carbon, bones can usually be used for dating.
The total weight of samples used for radlocarbon-collagen-dating were
sometimes as small as 8 g and quite often as large as 6 kg.
The nitrogen content of bones can be determined by two different
methods - Dumas or Kjerdahl.
Even counters with volumes under 1 1 for which little collagenous
material and carbon Is needed, it is not recommended to process bone
samples with mlcroanalytical-N readings below O.IO %. Even though,
theoretically, a counter could still be filled to capacity using several
 281

pounds of bone with extreme low nitrogen readings. Some of the organic
material Is destroyed during the process of HCl-treatment in which, no
matter how weak that solution, much of the tropocollagen and free
amino acids are usually hydrolized. In this case decalcification with the
sole purpose collecting the organic materials can no longer be
controlled. In the last twenty years about a third of all samples (about
2 0 0 0 ) submitted to us, which dated relatively to between 2 0 , 0 0 0 and
5 0 , 0 0 0 years and which originated from temperate environments, had
readings below O.IO %. They were therefore unsuitable for conventional
radiocarbon dating. Such samples could then, providing the history of
the palaeotemperature was known, only be used for amino acid dating.
A great number of such samples from well-known archaeological sites
with great anthropological significance did stem from Africa. They were,
for example, from Klasies river, Otjiseva, Cave of Hearth, Tulnplaas and
Cape Flats, Just to mention a few examples. All of these were bone
samples of the geographical subspecies of Homo sapiens afer,
"anatomically modern man" in Africa, as distinguished from fossil m a n
groups such as Homo sapiens neanderthalensis, Homo erectus, and
others. Such small samples can now be dated by radiocarbon-
accelerator dating which can be used for effectively dating even
extremely small bone samples.
But even in the case of extremely low nitrogen readings a radiocarbon
date on a hominid skull could still be obtained by conventional dating.
In such cases one would use, unfortunately, all of the osteological
material present. But there is a solution to the problem. If there is direct
association of a hominid to abundant fauna, with the same or very
similar overall microanalytical readings, they are obviously
contemporaneous. If this is the case the usually abundant associated
faunal material can be used for radiocarbon dating. That absolute
radiocarbon date could then in turn also be applied to the hominid.
Such a procedure was called A2 -dating by Oakley. Examples of
"indirect" dating are other absolute dating methods such as K/Ar-dating
or Uranium series dating. A 2 -dating could then become in connection
with relative microanalytical dating a reliable dating tool. It might
actually be more accurate to term this type of bone/bone association Aj
- A2 dating, since It is neither direct absolute dating (Aj) nor dating of
associated materials (A2). Examples of such dating (Aj - A 2 ) were In
Africa sites like Florisbad, Saldanha, Naivasha, Lukenya Hill (Grm-22),
Fish Hoek, Border Cave, and Bushman Rock Shelter (Protsch, 1974 a,
Protsch. 1974 b; Protsch, 1974 c; Protsch, 1976 a; Protsch, 1976 b;
Protsch, 1978). Several hominids from these sites could be dated
directly by radiocarbon along with their associated fauna. They yielded
in nearly all cases the same or at least closely comparable results. This
type of dating procedure was used in Florisbad (Aj- A 2 date, 38,680 +/-
2 0 0 0 , UCLA 1745B, on fauna; A 2 on charcoal/wood 38,550 +/- 3 8 0 0 ,
UCLA 1745C). Unfortunately even In more recent articles (Rightmire,
1979) older C** dates using mimic acid contaminated peat are still
282
referred to as "accurate" dates. Florisbad is a typical example of a site
where only bone dating, be it by radiocarbon or amlno-acids, can be
applied. The associated fauna at Florisbad, mainly
Hippopotamus amphlbius. Illustrates that a C ^ 4 - date can be
successfully obtained on associated materials rather than on the
homlnld itself. In this case we had to use large amounts of bone (746
grams) because of a low collagen and nitrogen content.

4. Dating of the inorganic portion of bone - the apatite

Until a few years ago most radiocarbon specialists and archaeologists

claimed that radiocarbon dating of both bone materials (organic and
inorganic) was unreliable. This caused specialists to r u n a series of
dates on the same samples, using both the inorganic apatite portion as
well as the organic portion. Haynes (1968) obtained different results
using osteologlcal materials recovered from one and the same horizon at
the Lehner Site. The archaeological age of the bone was estimated
relatively to the archaeological Clovis age. Using the apatite from
mammoth bone he obtained an age of 9,980 +/- 2 2 0 years B.P. (A-
874C) (Haynes, 1968) whereas the organic portion yielded a much more
recent date of 5,610 +/- 3 5 0 years B.P. (A-8O6A). The apatite of the
mammoth dental material again yielded a different age of 7,780 +/- 150
years B.P. (A-876C). The dates, which should have been the same
showed a discrepancy of as much as 2 , 0 0 0 years. The various
inorganic fractions had obviously suffered from different exchange
phenomena during burial at the site under changing geochemical and
hydrologlcal conditions. The exchange of C within the two inorganic
portions cannot be compared to that of the organic materials. There is
also a large microanalytical difference in the makeup of bone apatite and
that of the enamel of teeth. Even though they are chemically essentially
the same their crystalline makeup differs substantially. That of bone
(compacta) shows much greater interstitial space when compared to that
of the enamelic structure of teeth.
The collagen structure undergoes completely different exchange
phenomena. If bones are pretreated correctly in the laboratory the
collagen can never yield ages older than their true age. Any
contamination can only result in more recent dates. Apatite on the other
hand can be contaminated either way. The resulting ages are either too
old or too young.
The two-phase system of bone consists of a bone mineral, besides minor
components of other elements, which surrounds the organic structure
(Mc Lean and Urist, 1968). It is described by Protsch (1985) in detail
elsewhere.
Electron-microscopic and thin section studies, using different crystals,
made it possible to distinguish a variation In porosity, crystallinity,
formation of secondary apatite, as well as fossil algae and fungi in the
 283

osteonic and osteocytlc structure throughout the compacta. There are

many possible sources of error when the inorganic portion of bone is
dated. Some of these are, for example, secondary apatite from alkali
phospate solutions, carbonate substitution in bone apatite, and carbon
isotopic exchange.
In order to determine possible contaminants and their origins
investigators analyzed the carbon isotopic composition of fresh bone to
fossil bone and found their various fractions to be practically identical to
the presentday carbon isotopic composition. There are hardly any
significant variations in the isotopic carbon composition of bones of
animals of different age, sex, different parts of the same animal, or
species.
When a series of fossil bones of mammoth (Mammuthus primigenlus)
and cave bear (Ursus spelaeus) were analysed they showed a great
variation in chemical composition. The finds originated from different
palaeoenvironments, namely from open-air sites as opposed to cave
sites. Even bones from the same location, but from different layers of
that location, showed a great variation in chemical makeup. This is why
microanalytical studies on different layers in the same location are of
such great value. Bones of different species, but in close proximity to
one another in the same layer of one site, showed on the other h a n d
quite similar results. Since there is carbonate substitution in the apatite
structure researchers tried to remove the substituted carbonate by
fractional hydrolysis. All results using different techniques described by
Protsch (1986) proved to be unreliable when compared to ages of known
historical radiocarbon-collagen ages.
Secondary formation of apatite can also be detected by electron-
microscopy and luminescence studies. However, it cannot be removed
from the primary apatite by any presently known technique, including
fractional hydrolysis. Radiocarbon dating of the apatite portion of fossil
bone yields unreliable results and thus only the organic portion of bone
can be used for dating.

5. Dating of bones by accelerators

Conventional radiocarbon dating measures the 6-decay of radiocarbon.

Depending on the size of the gas counters used, sample sizes vary quite
drastically. In laboratories using very large counters, based on the gas
protortional CO2 or on liquid scintillation equipment, some smaller
samples can never be processed. This led to a continous improvement of
the dating equipment, electronics and counters, with a specific
tendency to reduce the volume of the latter. Some conventional CO2
laboratories use today counters as small as 2 0 0 ml. Regardless of how
small a conventional counter is, it still requires a relatively large sample
to start with and thus many grams of osteological material have to be
sacrificed to obtain an accurate date.
284
A second shortcoming in the conventional method of dating is the time
involved In the actual dating process. This is because a long time period
is required to gain a statistically adequate number of disintegrations of
atoms or counts for dating. These are at least 1 0 , 0 0 0 and more for
older dates. Usually the smaller the counter, the larger the time required
to obtain a date. The time requirements range anywhere from an
overnight count to several days or even weeks. Generally it can be said
that large counters need larger samples but shorter counting periods
and small counters need small samples but longer counting periods.
Most laboratories utilize several counters with different sizes.
Depending on the equipment the dating range of most conventional
dating laboratories Is anywhere between 4 0 , 0 0 0 and possibly 5 0 , 0 0 0
years. Some isotopic enrichment equipment can increase the range of
u p to 7 5 , 0 0 0 years (Grootes, 1978; Stuiver et al., 1978). The total cost
of a standard conventional radiocarbon laboratory is anywhere between
3 5 , 0 0 0 to 1 2 0 , 0 0 0 U.S. dollars.
A new method - accelerator or cyclotron-radiocarbon-daring was
announced in 1977 (Muller, 1977) with the specific Idea of dating
minimal amounts of material, much less than needed in conventional
radiocarbon dating, and an increase of the time range with a shorter
counting time. A known age sample, dated by the conventional
radiocarbon method by R. Berger (1979), was used to calibrate one of
the first accelerator dates (Muller, Stephenson and Mast, 1978).
There are, as Is usually the case In any new method, some
shortcomings concerning accelerator dating. It is mainly the cost of the
equipment which is at least IO to 2 0 times above that of conventional
equipment. Refinement has to proceed in such a way that statistical
errors of cyclotron measurements exceed those presently achieved by
conventional radiocarbon by at least one order of magnitude. Berger
(1979, p.102) points out that large high energy cyclotrons probably
contain some contaminant radiocarbon which might inadvertently be
produced by physical experiments. He also mentions other shortcomings
of accelerators. There is also the question of mixture of radiocarbon from
the Inorganic portion of the bone which as well as mixture of the
inorganic portion with the organic. A clear separation of these is
presently hard to achieve. These contamination factors might render
most cyclotron dating useless and favor again conventional dating. It is
t h u s suggested that whenever enough osteologlcal material Is available,
a sample relatively estimated to date below 5 0 , 0 0 0 years, and N-
microanalysis suggests a fairly high carbon/ collagen content In the
sample, that conventional dating be applied.
Accelerator dating extends conventional dates from 5 0 , 0 0 0 to 7 0 , 0 0 0
or even u p to 1 0 0 , 0 0 0 years. This would double the age range of
conventional counters. It could also provide a means to date rare and
precious samples of fossil hominids - for example
Homo sapiens neanderthalensis, Homo sapiens rhodeslensis, and
Homo sapiens soloensls which existed sympatrically and allopatiically
 285

In a crucial time period In human evolution together with "anatomically

modern man". Most of these hominids cannot be dated by A2-
technlques like K/Ar, Fission Track, or Uranium series dating since they
usually are not associated with materials suitable for such dating
methods. The only other method left to supply relative/absolute dates
would than be amlno-acld-dating. Its few shortcomings could be cross-
checked by the application of accelerator-dating. Both techniques
require only minimal amounts of bone material and the shortcomings of
each method could be controlled by using the same sample materials.
Berger (1979) pointed out that accelerator dating Is subject to sample
contamination. A sample dating to 1 0 0 , 0 0 0 years, and contaminated
by only IO ppm of modern carbon could be off by as much as IO %,
thus actually dating to only 9 0 , 0 0 0 years. Presently, in a strict sense,
accelerator radiocarbon dating on bones is only a "relative" dating
technique. "Absolute" dating applies to those methods which have less
than a 5 % dating error .Those techniques with errors of more than 5 %
are considered relative techniques. Many famous hominid samples
which could be available for accelerator dating have not only undergone
natural contamination but were in addition to this subject to man-made
contamination caused by preservatives.

6. The processing and dating of the organic portion of bone

(collagen)

Considering the aforementioned it is obvious, that the Inorganic portion

of bones, the apatite, can hardly ever be used for radiocarbon dating.
The organic portion of bone (collagen) does hardly ever suffer under
exchange phenomena. Only under very rare circumstances occurs
Infiltration of non-osteological organics Into bone. These organics
originate, as was mentioned above, from algae, fungi, and saprophytes
most of which actually feed on the organic portion of fresh or even
ancient bone. If they intruded the bone at some ancient time they
become also fossilized. J u s t as the collagen they are then of an age
which is, if not identical, at least fairly close to that of the original burial
date of the bone. 90 % of these microorganisms infiltrate and feed on the
collagen when the bone is still fresh and on the surface of a site. The
only other possible source of contamination could result from the entry
of excessive humlc acids from the surrounding layers. This is usually
due to plants, or even a bog deposit, at the location. This contamination
can, however, be easily eliminated by laboratory procedures.
A second contaminant, though quite rare, could result from deposits
such as tar. Berger, Horney and Libby (1964) have shown that these
contaminants can be quite easily eliminated by using liquid
chromatography. Bone is composed of an interstitial substance which
h a s a fibrillar structure similar to that of all other connective tissue.
The fibres consist mainly of collagen as well as of some reticular fibres.
286

Collagen is characterized by its content of mucopolysaccharides. Inside

this elementary substance, also called the organic matrix, a complex
mineral substance is deposited consisting chiefly of calcium, phosphate,
carbonate, and citrate. Depending on the age of the individual there are
some small percentage differences in collagen content among species.
Anywhere from 25 % to as much as 35 % of the dry, fat free weight of all
bone is made up of collagen. Because younger individuals are still in a
developmental stage in which chondral ossification is in progress they
show a greater percentage of the organic portion. Older individuals
possess smaller amounts of collagen which could also be due to a
pathological condition. The trained bone-dating specialist can easily
distinguish differences between bones of very young individuals, species
differences, and also pathological conditions by using thin-section-
microscopy which was described above. Since this is a new technique
most dating specialists are not yet experienced in this particular
technique and often neglect to apply it as a preliminary step in bone
processing. It is certainly also an important aid in calculating the weight
of bones for dating, besides N-microanalysis. The organic matrix is
usually visible as a blueish or yellowish deposit in the thin-section-
polarisation-micrographs. The interstitial substance (collagen or organic
matrix) h a s two chief components, the collagenous fibres and the
ground substance. Bone collagen yields glue of gelatine when boiled. It
constitutes as much as 9 0 - 96 % of the dry, fat free weight of the
organic fraction of bone. Intact collagen occurs in fibrils with a double
cross-banding at intervals averaging 6 4 0 A and gives a characteristic X-
ray diffraction pattern. It is chemically characterized by a high content
of pyrolidine and glycine and a low content of aromatic amino acids.
Hydroxyproline is an index for a quantitative estimation of mature
collagen, as is hexosamine for the ground substance. Individual collagen
fibrils of fresh bone and fossil bone which were found in locations
suffering from minimal environmental influences are typically 0 , 3 - 0,5
in diameter and arranged in small bundles 3 - 5 in thickness. In fossil
bone quite a large amount of collagen or tropocollagen must be present
to allow extraction of enough organic substance for radiocarbon dating.
Contrary to that only small amounts of amino acids, which are nearly
always present, are necessary for amino-acid-dating.
A high content of organic material is usually found in the compacta of
long bones and the lamina externa or lamina interna of the
neurocranium. Spongiosa or diploe render themselves less suitable for
collagen extraction since they are quite often intruded by rootlets. In
addition to this they are frequently, due to their fragile and spongy
nature, the first areas to be invaded by water, algae, fungi, and
saprophytes. Compact bone, on the other hand, is ideal for the
extraction of collagen. The dense outside mineral structure of compacta
shields its central portion from infiltration of both foreign substances
and water. Studies of organics in different locations in one and the same
bone have shown that the organic portion of compacta, when it is
 287

compared to the organic portion of the sponglosa, can differ by a

magnitude of three. When dating teeth of macrofauna the selection of
cement and dentine over enamel should be preferred. It Is because the
total organic portion of enamel Is much smaller than that of the
compacta of bones and also that of cement and dentine somewhat
smaller than that of the sponglosa. Preservation of organlcs In enamel,
cement, and dentine Is better over long time periods due to their denser
mlneraloglc structure. A fully developed crown enamel consists of only 3
% organlcs (glucoprotein) the rest consists entirely of calcium salts in
the form of densely packed apatite crystals.
Dentine on the other hand, which constitutes the largest portion of a
tooth, depending again on type of tooth and species, is a fibrillar,
calcified, collagenous matrix traversed by odontoblastic processes which
are composed of a proteinlike elastin. Dentine is still much denser and
harder than compacta but resembles bone in its structure, chemical
nature, and development. Dentine is similar to bone in that it contains
about 25 - 28 % organic and about 7 0 - 72 % inorganic fractions.
Dentine is formed throughout the life of an individual with a somewhat
greater activity in old age when the pulp cavity also becomes reduced in
size.
Large teeth, as for example those of mammoth, hippopotamus, and
other macrofauna are quite suitable for radiocarbon-collagen-dating.
Here the extreme dense inorganic structure of the enamel and the
cement overlying the dentine provide an excellent shield against
environment and microorganisms. The enamel on the surface is thick
enough to provide this shielding effect but constitutes only 6 to 8 % of
the total dental weight. It is wrong to assume that the low organic
content of teeth makes them unsuitable for dating. This assumption is
based on the misconception that it is the enamel which is being dated.
In reality it is the dentine which provides in teeth the greater amount of
dateable material. If we look at the three components of teeth we find
that the organlcs in the cement are much greater than those of the
enamel and only minimally smaller than in the compacta of bone.
Processing of bone and dental material usually starts with the removal
of possible contaminants. If bones are carefully and tediously
examinated absolute dates should be ultimately as correct as those
obtained from other organic materials. The first step should be the
above mentioned thin section analysis.With this method man-made
substances like shellac or other preservatives, as well as tar, can also be
easily detected. Contamination due to these substances is equally
possible in charcoal, wood, or other organic materials which are usually
considered more suitable for radiocarbon dating. This has been pointed
out by Sellstedt, Engstrand, and Gejvall (1966). Due to its dense nature
bone is actually less prone to contamination than most other materials.
The second step in the preliminary analysis to bone dating is the
calculation of total bone material needed for radiocarbon collagen
dating. A few milligrams of compacta make it possible to calculate the
288
total bone material needed. In the case of dental material only dentine
should be used.
Our experience is that in about half of the samples processed rootlets
are present. Neglecting to inspect the samples with a microscope prior to
further processing is often responsible for a more recent date. This type
of visual inspection and removal of foreign objects by hand often
constitutes the greater part of the total processing time of a sample.
Rootlets infiltrate more easily the spongiosa, often necessitating its total
removal. Sand and rootlets often infiltrate Haversian canals and
trabeculae in the central part of a long bone and the spongiosa has to be
scraped off totally. Insects of more recent time periods are quite often
mixed-in with sand and are again a cause of contamination. The
removal of sandy materials in their final stage should be done with
doubly distilled water. The bones should be dried after this since they
can be better inspected visually. About one mm of the compacta should
then be removed by scraping off the periosteal surface. This procedure
removes still adhering extraneous natural contaminants which possibly
infiltrated the more porous periosteal surface of the compacta. It also
removes man-made contaminants and preservatives like shellac. To
make absolutely certain that no contaminants remain bones should be
broken up into smaller pieces and then treated on reflux for several days
in a solution of acetone and 2-ethoxy-ethanol. Many bones from
museum collections were covered several times with preservatives and
will often require a much more extensive reflux treatment. Treatment
could last for weeks. After drying the bones mild HCl-treatment should
follow. Most preservatives like shellac are visually detectable after the
acetone reflux treatment. They emerge as hardened whitish deposits
which can easily be pealed off the bone surface. In cases where several
coats were applied a short immersion In a 4 % HC1 solution for 2 0
minutes creates a space between the periosteal-compacta surface and
the coat of preservatives above. Even the most persistent preservatives
can ultimately be pealed off after this procedure. After repeated washing
in doubly distilled H 2 0 the sample should be dried again. Frequently
another type of contamination could be present which can ultimately
affect samples used for amino-acid-dating. The author, as well as Siddle
(1967), Woleman, and Miller (1971), conducted a number of experiments
and found considerable amino acid contamination in commercially
available analytical grade hydrochloric acid (37 %). Such contamination
could also be present in ammonium hydroxide used during the liquid
chromatography stage. HC1 can contain up to 8 , 3 0 0 nmol
contamination and ammonium hydroxide could contain five to ten times
as much. This can cause serious errors in very old samples. All HC1
used for processing of bone samples should thus be doubly distilled and
ammonium hydroxide should be made from distilled ammonia gas on a
vacuum line.

All bone pieces should be treated in a HC1 solution until only the
collagen strands are visible. As an alternative bones could also be
 289
pulverized and then treated In a weaker solution of HC1 and doubly
distilled water. In the first case the Investigator Is able to see how well
the collagen Is preserved but has to renew the solution constantly,
possibly over a period of several days and up to one week. The
concentration of the solution is always dependent on the reaction of the
apatite portion of bones. An extremely concentrated solution could also
easily hydrolize a larger part of the collagen. The second processing
method, that of pulverizing the bone, is certainly more expedient and
might take only a few hours but it involves the risk of hydrolysis of the
tropocollagen.
After the apatite portion of the bone is completely dissolved the
insoluable organic portion is separated with a Biichner funnel. Only
glassfilter paper should be used. The remaining organic portion is then
washed several times with doubly distilled H 2 0 . It is then treated with a
1 % solution of sodium hydroxide for removal of humid acids, washed
again repeatedly In distilled water, neutralized with HC1, and washed
again until neutral. It is usually at this stage that smaller rootlets
which had remained in the compacta can be easily detected on the filter
paper.
The collagen and tropocollagen is then converted to gelatine by heating
in doubly distilled water (pH = 3) at about 90°C using a heater with a
stirring magnet for 4 to 6 hours. Usually after 2 to 3 hours some
gelatine can already be detected and the non-gelatinous preservative
substances, if still present, would harden and show up. They can be
easily removed by hand. Other remaining impurities can be removed by
centrifugatlon. The final product will solely contain bone-organlcs.
The gelatine is then placed in a flask containing 6 N HC1, refluxed for
twenty-four hours, and filtered. The clear solution is then concentrated
to a volume of about lOO ml. It is at this point that either one of two
different processes for further analysis can selected. If no petroleum (tar)
products are suspected in the sample it can be neutralized, dried,
combusted, and converted to CO2 in a pure oxygen atmosphere .
If, however, contamination is still suspected the following procedure
should be applied. A column (5 cm diameter) containing Dowex 50-WX8
resin charged with 4 N HC1 is used to collect pure amino acids by liquid
chromatography. The filtered hydrolysate is then passed through a
column at a rate of 3 0 m l / h (Ho, Marcus and Berger, 1969). The resin is
then washed repeatedly with distilled water to remove all contaminants.
The column is then eluted with an excess of 5 N ammonium hydroxide
at a flow rate of 3 0 to 6 0 m l / h in order to liberate the amino acids. One
liter of yellowish-brown affluent is thus collected per sample run. This
affluent containing the amino acids is then evaporated to dryness. It h a s
a distinctive odor and is dark-brown in color.
In both cases the procedures by which the collagen, or dried amino
acids, are converted to carbon dioxide In a stream of oxygen are
identical. A two step combustion procedure involves the burning of the
sample in an inner-tube and passing of nitrogen through that tube while
290

oxygen Is passed through the outer tube. Complete combustion is

achieved by a second process whereby the oxygen is again passed
through the inner tube and the sample thus burned in a pure oxygen
atmosphere. The nitrogen gas simply works as a pushing device.
Further purification on the processing line is achieved by passing the
CO2. the product of the combusted carbon and the oxygen, through five
traps containing O.l N silver nitrate, chromic acid, potassium
permanganate, hot copper oxide (5OO0C), hot copper/silver at 450°C,
and dry-ice /acetone water traps. Final purification is by thermal
circulation over hot copper (600°C) and silver wool in a 5 1 glass
container with an external quartz convection tube. Prior to this, and
each counter filling, the C 0 2 is routinely passed over hot Cu/Ag (450°C),
at least 6 times in a separate system and vacuum distilled at - 78°C. The
C02-gas quality after this procedure was found to be excellent.
Counting procedures at the Frankfurt radiocarbon laboratory are
described elsewhere in detail (Protsch, 1987).

7. Kelsterbach - a case study in C-14-collagen and amino-

acid-datlng

In spring of 1952, during bulldozing operations in the north-west corner

of the Willersinn gravel pit, south-west of Frankfurt near Kelsterbach, a
fossilized homlnld calotte was discovered. The "Kelsterbach Homlnld" is
a female about forty years of age.(Fig. 2)
The original site of discovery has remained undisturbed until today
because further digging was continued solely in northerly and easterly
directions. These circumstances made it possible for geologists to
determine the precise stratigraphic relationship of different finds in that
location 2 0 years later. It was possible, on the basis of the still
undisturbed stratigraphic sequence and the graphs and drawings made
at the time of discovery of the calotte, to make a reliable and accurate
estimation of the geological situation of the hominld and faunal remains
in question (Protsch and Semmel, 1978) as well as apply relative
geologic dating.
The calotte belongs to a layer at a depth of 4,60 m. The analysis of
some sandy remains extracted from the left auditory meatus supported
the accuracy of the observation that all materials originated from that
stratigraphic layer. The hominld layer belongs to the lower part of a 5 m
thick gravel-bed which was formed by Intermittent sand-gravel layers
located at the "Obere Niederterrasse", the so called t/gj terrace (Becker,
1965, 1967; Semmel, 1969, 1972, 1974). It was deposited by the Main-
river during the Upper Pleistocene. A mixture of clayey flood-plain
deposits and quicksand was covered by remains of sediments called the
"Laacher pumice tuff'.
The layer in which the fossils were found is the second youngest terrace
of the Main-river. Its chronological origin has been a point of frequent
Fig.2 :<elsr«rb.-.-ch fossil: z«d. honinid calotte
292
discussions (Becker, 1965,1967; Semmel, 1969, 1972, 1974; Semmel
and Protsch, 1978). Other faunal remains were also discovered within
the terrace, but in a much higher layer. One of these, a mammoth
molar, was dated by radiocarbon at the laboratory in Hannover in 1960
and yielded a date of 15,810 +/- 4 1 0 years B.P. (Hv-1961). Since the
mammoth fragments were recovered from a level substantially above
those of the hominid it was reasonable to assume that the hominid
dated relatively older. However, since the above date is based on the
dating of the apatite portion of the bone it is probably contaminated with
either recent or ancient radiocarbon. On the other hand it can be
assumed that the mineralogical makeup of the bed makes such
contamination improbable. It was void of any calcareous deposits and
any leakage through the layers from above can be practically ruled out.
Perculating water with high solution of calcium carbonate and calcium
phosphate could cause secondary apatite accumulation in bone making
C*4 dates either too old or too recent. Geomorphological analysis of the
stratigraphy of the upper layer, as well as results of pollen analysis of its
clays, assign the terrace quite reliably "relatively" within the late phase
of the Wurm-Glacial (Upper Pleistocene).
In order of obtain a more accurate and absolute date for the calotte a
small bone sample was removed from its occipital. Enough organic
material could be extracted from it for radiocarbon-collagen as well as
amino-acid-dating. The process of extraction and absolute dating for the
Kelsterbach Hominid is described in detail elsewhere (Protsch and
Semmel 1978). According to radiocarbon results the calotte dates
absolutely to 31,230 +/- 1580 years (Fra-5). Amino-acid-dating of the
same sample yielded an age of approximately 3 2 , 0 0 0 years B.P.
(Protsch and Semmel, 1978). The amino-acid-date can be viewed as
either a relative or absolute date. This is due to the difficult
reconstruction of the palaeotemperature history which is necessary in
amino-acid-dating. The radiocarbon results can be considered as quite
accurate and therefore as an absolute date. Since in this case the
results of both dating methods coincide, it can be assumed, that amino-
acid-dating and paleotemperature calculation was accurate. Generally
one can assume that a date of at least 3 1 , 0 0 0 years B.P. is acceptable
for the calotte. Dates on teeth and bones of the mammoth which was
found positioned somewhat above the hominid and dates on the
hominid itself were also processed at UCLA. The dates were somewhat
younger (23,675 +/- 8 6 0 ; UCLA-2359 and 2 9 . 0 0 0 +/- 1525; UCLA-
2361). The mammoth fragments were found in layers below that
stratum which was dated by the Hannover laboratory to 15,810 +/- 4 1 0
years (Hv-1961).
 293
neutralized. Both the homlnld and the faunal sample showed nearly
perfectly preserved collagen strands.
The collagen samples were then subjected to hydrolysis in order to
dissolve the peptide bonds. The resulting clear fluid was evaporated and
the residue dissolved In distilled water and desalted on resin. The amino
acids were eluted and the solution reduced with the help of a rotary
evaporator.
The actual amino-acid analysis was performed using a automatic-
amlno-acid-analyser (Beckman Multichrome B 4255).
The excellent preservation of the organic substance of both samples
could be observed on the chromatograms. Even those amino acids
which normally disintegrate rapidly, namely threonine, serine, and
hydroxyproline, were still present. Even the diastereomere type of L-
hydroxyproline could be shown. Unfortunately no constants of this
amino acid are available yet which presently makes dating by this amino
acid impossible.
The temperature during burial of the fossils (hominid and mammoth)
was taken as 8.8°C (Protsch and Semmel, 1978) and resulting date for
M. primlgenius came to 3 0 , 1 0 0 years B.P.
Using the same palaeotemperature as above for the
M. primigenlus the age for the hominid was calculated as 3 2 , 0 0 0 years
B.P. Since the mammoth was stratigraphically positioned slightly above
the hominid it was be expected to be more recent than the hominid.
As can easily be seen in the case of Kelsterbach a series of radiocarbon-
collagen-dates can be supported and verified by amino-acid-dates (Fig.
3). If in addition to these further relative chronological evaluation is
applied by using microanalysis, faunal-, and geomorphological- or
stratigraphic analysis, a reasonable chronological placement for any
fossil hominid in question is possible.
Kelsterbach is thus the first individual of "anatomically modern man" in
Europe which appeared after the extinction of the Neanderthal
(Homo sapiens neanderthalensls). It is also the first absolutely dated
specimen of the subspecies Homo sapiens sapiens in Europe. Members
of this population are known as Cro-Magnon.
Radiocarbon-collagen-dating and amino-acid-dating are the only two
reliable direct absolute dating techniques presently available to date
bones and teeth. The two techniques have solved important
archaelogical and anthropological questions. In archaelogy an important
question, the beginning and the area of origin of domestication of
animals, was solved by the application of C 1 4 -dating. A series of bone
samples from different sites in the Near East and South-eastern Europe,
using the bones of different species of wild and domesticated animals,
were dated and compared to each other. It was found that the old
theory, that everything started in the Near East, cannot be supported
anymore. Some species, like the pig ,were actually domesticated earlier
in southeastern Europe.
294

Microanalysis of Kelsterbach

Species Material Location F% U ppm N %

M. primigenius bone, 420 m 2.80 109 2.00
femur
M. primigenius bone, 450 m 2.93 130 1.55
femur
H.s.sapiens bone, 460 m 2.98 138 1.20
Os occipitale

The nitrogen content of the Kelsterbach Hominid was

1.2 % N. 7 0 grams of bone yielded about 6 grams of collagen and 2.60
grams of pure carbon which again yielded about
4.5 1 CO2. This was more than enough for a total counter filling. Actually
only 3 0 to 35 grams of bone would have sufficed for C 1 4 -dating
purposes. The sample was processed in 1978 several years after the
radiocarbon measurements on mammoth teeth and shells were
processed at the Hannover laboratory. The yield of CO2 from the
collagen sample of the Kelsterbach Hominid was between 92 - 95 %. The
Hominid sample was counted 36 hours (2160 minutes), three times (two
sigma-standard deviations), and dated to 31,OO +/- I6OO years
(Protsch and Semmel, 1978).
The microstructure of bone of Mammonteus primigenius indicated
that little material was needed for radiocarbon dating. The sample was
stratigraphically positioned slightly above the hominid. Microanalysis of
the faunal material was 1.55 % N, a slightly higher reading than in the
stratigraphically older hominid. 150 grams of bone yielded 13.4 grams
of collagen, half of which (ca. 6.8 grams) was carbon. This was more
than enough for two counter fillings. The results of the mammoth bones
were 3 0 , 3 0 0 +/- 1 9 0 0 (Fra-5a) and 23,675 +/- 86O (UCLA-2359) years
B.P.
Bada, Protsch, and Schroeder showed in 1974 that comparative dating
by C * 4 and amino-acid-dating can supply absolute dates for hominids
which could not be dated by other methods. The site of Kelsterbach was
ideal in that it provided different sample materials (bone, teeth and
molluscs) which could be dated by different methods.
The hominid cranial and postcranial faunal material was processed by
the isoleucine-epimerization-method. Five grams of compact bone used
for each sample. Small pieces of bone were removed from the calotte of
the hominid, specifically from Os ocipitale close to the lambdoid suture,
and from a femur of M. primigenius. The outer surface was
mechanically abraded and cleaned with a dental abrading machine
until about one millimeter of surface material had been removed.
Samples were subsequently treated in doubly-distilled water and
ultrasonification. The pretreated bone material was then submerged in
2n HC1 and the nearly totally preserved collagen strands removed and
 295

STRATIGRAPHY OF K E I S T E
B R A C H

C BS O+40 » ■— " ch»'CO»l l«v»'

yallow gravai

TT7 Ituff]

light gray loam

/ / /
rad graval

'"CLA?3i9) C '*30.30O±?000 / / / / / / / / / / / / / / / / / / / / / / / / V/'

A-m 30100 / MAMMONTEUS PRIMIGENIUS POSTCRANIAL B ONES'

(*"­*"­"■> W/////////////
CU 2 9 0 0 0 ±1525 C 14 3123O­
M 580 / / / / / / / S/J
(UCLA ­2361) (Fra­5)
—— A ­■ 2aooo
(Fra ­ A­10)

• O * o °­
light yallow graval

H» = Radiocarbon Laboratory Hinnovir

Fra = Radiocarbon Laboratory Frankfurt / Man
UCL A Radiocarbon Laboratory Lot Angelas

Fig.3
StratiariTihv of K«lsterbach
296
The application of a combination of radiocarbon- and amlno-acld-dating
to remains of earliest "anatomically modern man" remains from Europe
and Africa supplied the basis for a new evolutionary theory In
anthropology. The old theory that "anatomically modern man" evolved
directly from Neanderthal in Europe around 3 2 , 0 0 0 to 3 0 , 0 0 0 years
B.P. was proven to be wrong. Both dating techniques dated material of
"anatomically modern man" up to 8 0 , 0 0 0 and up to 2 0 0 , 0 0 0 years
B.P. in Africa. The new dates support the new theory, that "anatomically
modern man" evolved in Africa around 2 0 0 , 0 0 0 years ago and
migrated to Europe around 3 0 , 0 0 0 years B.P. were he replaced
Neanderthal (Protsch, 1974; Genet-Varcln, 1979)
 297
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Suess, H.E. (1965) Secular Variations of the Cosmic-ray-produces

Carbon-14 in the Atmosphere and Their Interpretations, Journal of
Geomorphological Research 7 0 , 5937-52.

Stuiver, M. (1961) Variations in Radiocarbon Concentration and

Sunspot Activita, Journal of Geophysical Research 66, 273-6.

Stuiver, M. (1965) Carbon-14 content of 18th and 19th Century Wood:

Variations Correlated with Sunspot Activity, Science 149, 533-5.

Stuiver, M., Heusser, C. J. and Yang, T.C. (1978) North American glacial
history extended to 75.OOO years, Science 2 0 0 , 16-21.

Stuiver, M. and Suess, H. E. (1966) On the Relationship Between

Radiocarbon Dates and True Sample Age, Radiocarbon 8, 534-40.

Wolman, A. and Miller, S.L. (1971) Amino Acid Contamination of

Aqueous Hydrochlorid Acid, Nature 234, 548-9.
OBSIDIAN HYDRATION DATING

H.Y. GOKSU
GSF - Forschungszentrum fur Umwelt- und Gesundheit
Institut fiir Stahlenschutz
Ingolstadter Landstr. 1
D-8042 Neuherberg
Federal Republic of Germany

1. Introduction

The method of dating obsidian artifacts is based on the measurement of

hydration rim developed on the surface. When a fresh surface of obsi-
dian is exposed to the atmosphere, it absorbs water. The absorbed wa-
ter at the surface diffuses at a constant rate into the obsidian and
causes a hydrated layer. The thickness of this hydrated layer depends
on the time of the exposure, the chemical composition of the obsidians
and the effective burial temperature.
In order to evaluate the age from hydration thickness into age, the
rate of hydration must be assesed. This is achieved by two general
methods. One involves the direct calibration of the hydration thick-
ness with known radiocarbon, potassium-argon ages or cultural dates on
materials associated with the obsidian. The second method involves an
experimental determination of the hydration rate. In recent years re-
finement of the method is achieved by experimental determination of
hydration rate constant at room temperature with resonance nuclear
methods or at accelerated laboratory conditions or hypothetically on
the bases of composition (Lanford et al, 1976; Leach, 1977; Friedman
and Long, 1976; Michaels, 1967; Michaels et al, 1983).
Obsidian hydration dating was originally developed to date archaeolo-
gical artifacts and slowly adapted to date geological events and depo-
sits, covering time span from 200 years to 1/2 million years.
301
H. Y. Goksu et al. (eds.). Scientific Dating Methods, 301-317.
© 1991 ECSC, EEC, EAEC, Brussels and Luxembourg. Printed in the Netherlands.
302

2. General Principle

2.1 THE NATURE OF OBSIDIAN

Magmas of granitic composition frequently are erupted on the earth's

surface as viscous fluids. High viscosity is characteristic of lavas
rich in silica and potassium, therefore, most glassy rocks are rhyoli-
tic. The interiors of these flows cool slowly while the exterior cools
rapidly and has not enough time to crystallize. The volcanic glass
formed this way often called obsidian and can be as much as 10 or 20
meters thick. Obsidian occurs in almost all lava flows of rhyolite
composition, and its distribution is therefore associated with the
volcanic activities around the earth.

Obsidian varies in appearance from clear colourless to grey-green,

brown, red, and black. It is usually transparent in thin pieces but
may appear opaque due to the presence of microscopic crystals of vari-
ous minerals that scatter the transmitted light. Its usefulness as a
tool-making material derives from its conchoidal fracture. Obsidian
can be readily flaked by percussion and pressure techniques similar to
those used for flint knapping.
Obsidians formed in volcanic eruptions usually had not enough time to
become crystallized when they were suddenly exposed to air. Since they
had no time to complete their natural geological formations through
time, they went through various alterations. One of those is the ab-
sorbtion of water (hydration) from the environment and it is this par-
ticular alteration that allows the age determination.

2.2 HYDRATION PROCESS AND RATE EQUATION

Laursen and Lanford (1978), studied the hydration phenomenon by mea-

suring hydrogen concentration profiles using the N resonance nu-
clear reaction method. It appears that the hydration involves the
inter-diffusion of hydronium ions (H.,0 ) with mobile alkali ions
in the glassy phase of the obsidian. This ionic inter-diffusion model
 303
also explains the drastic changes in alkali contents of natural glas-
ses because in obsidian the only major mobile charge carriers are the
monovalent alkali ions like Na and K . The exchange of these al-
kali ions with positive hydronium (H.JD )ions proceeds according to
the following equation:

2 H 2 0 + Na + (glass) H 3 0 + (glass) + NaOH. (3)

Only some of the alkali ions take part in this reaction, however, pos-
sibly because of incipient crystallization or devitrification that is
not detectable by optical methods. Tsong et al., (1978) studying che-
mical variation in altered surfaces of obsidian by sputter-induced op-
tical emission, showed constant concentrations for network-forming
cations such as Si and Al along depth profiles buth strongly varying
concentrations for network modifying elements (K, Na, Li, Mg). The
deepest penetration was noted for H, indicating that alteration is
initiated by hydration which causes an increase in density and refrac-
tive index and in addition causing the hydrated layer to become mecha-
nically strained.
Ross and Smith (1955), first noted that the hydrated layers formed on
weathered obsidians set the bases of hydration dating.
When obisidian is formed, it contains about 0.1 to 0.3 % water by
weight. The hydrated layer contains ten times more water than the rest
of the obsidians. Subsequently, considerable density difference occurs
between the hydrated and unhydrated layers, and this produces differ-
ence in refraction index which can be observed under a microscope. On-
ce the water is absorbed at the surface, the hydration continues at an
essentially constant rate and the thickness of the hydrated layer pro-
vides a measure of the time that has elapsed since the production of
the tool.
Friedman and Smith (1960) showed that the rate of penetration (diffu-
sion) of the water can be expressed by using the standard diffusion
equations. By solving these equations for suitable boundary condi-
tions, the thickness of the hydration layer (D) is expressed by the
following equations.
304

D 2 = kt

. . -E/RT
k = A e '

where:

t is the time since the surface of the obsidian is ex

posed to the air,

D is the hydration thickness

k is the hydration rate constant which is a function of

temperature of the environment and of the chemical
composition of the obsidian

E is the activation energy expressed in calories per mole

R is the universal gas constant expressed in calories per

degree per mole

T is the effective hydration temperature in degrees Kelvin.

A is a constant depending on the chemical composition of the

obsidian

Obsidian as a natural glass has a complex structure as a result of its

formation. It is assumed that all rhyolitic obidians behave similarly
in terms of the hydration process. Over the years, some of these con-
clusions have been challenged; experimental determinations began by
Friedman and Long (1976) and continued by Michels (1981,1983). Besides
the general diffusion equation suggested by Friedman and Smith (1960),
other researchers suggested various empirically derived hydration egua
tions.
 305

Clark (1961, 1964) found that the expression X = Dt 1//2 did not sa-
tisfactorily describe the relationship between hydration and time. He
3/4
suggested a central California hydration equation X = Dt , based
on the hydration dating of obsidian artifacts and radiocarbon dates.
Katsui and Kondo (1965) presented an obsidian hydration rate for
Hokkaido, Japan, based on data from six radiocarbon dated levels with
obsidian artifacts ranging from 1000 to 15,000 years. The rate was
2 3 2 3
1.6-2.0 microns /10 years and 0.82 microns /10 years
established for "Temperature Zone 2" and the "sub-Arctic Zone", re-
spectively.
Meighan et al. (1968) suggested a linear hydration equation for West
Mexico, X = Dt, where D = 3.85 microns/10 years based on the rela-
tionship of 16 radiocarbon dates and 115 obsidian hydration measure-
ment of artefacts. Johnson (1969) presented an obsidian hydration rate
for the Klamath Basin of California and Oregon based on the correla-
tion between 10 radiocarbon-dated levels and 107 obsidian artifacts,
2 3
suggested that the rate of 3.54 microns /10 should be used for
this region.
Morgenstein and Riley (1975) used a linear hydration rate for
Hawaiian basaltic glasses based on X = Dt where D = 11.77 microns/10
years. Furthermore, it was proposed that the reaction of water with
glass does not slow down with increasing depth of hydration but re-
mains rather constant which accounts for the linear rate.
Kimberlin (1976) using the hydration results of a group of chemically
related obsidian artifacts from the Morret site, Colima, Mexico sug-
gested another hydration equation which is expressed as; X = Dt as
well as illlustrating the influence of the initial concentration of
water on the rate of hydration.
Various possible reasons were considered to explain the differences.
Kimberlin (1976) suggested that invesigators mentioned above might
have used obsidian of varying compositions which hydrated at differing
rates. Others have cited stratigraphic mixing of excavated obsidian
artifacts as obvious causes of distorted rate formulas. Friedman et
al, (1976, 1978) and Meighan (1976) conseived the problem as lying in
306

the rather short spans of archaeological time usually involved in ac-

tual studies, which would cause the depth to age conversion to appear
to be linear, wherease on a much longer time scale the true curve form
of the relationship would show up clearly. Furthermore, they have not
considered the radiocarbon dating correction curves in establishing
their empirically-derived hydration equations.
A further likely source of data distortion in rate calculation may
come from stratified archaeological deposits. The mean annual soil
temperature just beneath the surface may be higher than that of either
the air above or the deeper soil levels . Thus chemically identical
obsidian flakes in the deposit will have hydrated at different rates
while the strata built up with time. Thermal history of the flakes may
be further altered by the effect of human presence in especially, in a
cold climate where fire was used for heating. Shallowly buried obsi-
dian under these floors would have been subject to accelerated hydra-
tion causing 10 % increase for every 1° C change in the effective hy-
dration temperature. In general, to correct for this kind of varia-
tions due to increased temperatures, one should subtract some con-
stant amount from the observed hydration thickness of the pieces from
all levels before the age is converted.

On the basis of the experimental evidence from several investi gators

(Friedman and Long, 1976; Michels, 1978) as well as com parisons of
hydration thickness with radiocarbon and K-Ar dated events covering a
long time span, including Shanidar Cave (Friedman and Smith, 1960),
rhyolite flows (Friedman and Obradvich, 1981), Mummy Cave (Friedman
and Trembour, 1978), and Government Mountain-Sitgraves Peak (Findlow,
1977), is commonly accepted to day that the hydration thickness
increases with the square root of time.

2.3 PHYSICAL AND CHEMICAL PARAMETERS IN OBSIDIAN HYDRATION

The intrinsic parameters like the alumina and alkali concentrations,

the initial water content, the specific volume, the silicon-oxygen
ratio are important factors which influence the hydration processes.
 307
Haider and Roberts (1970) showed the dependency of the diffusion
coefficient on the Al20-./Na2 ratio. This shown by assuming that
the chemical structure of rhyolitic obsidians may approximate the
chemical structure of relatively simple glasses and their inter rela-
tionships to "water" bond formation and the hydration phenomena.
Erikson et al (1976) considering the variables like alumina, alkali
concentrations and the initial water concentration, the specific volu-
me, the silicon-oxygen ratios, concluded that the structure of obsi-
dian influences the diffusion kinetics of water in the hydration pro-
cess. Consequently, it will be necessary to determine the individual
hydration rate for each obsidian extrusion and to determine the source
of each obisidian sample prior to dating.
Friedman and Long (1976) hydrating obsidians of different chemical
composition in laboratory at elevated temperatures to speed up the hy-
dration, showed that the hydration rate is controlled mainly by the
amounts of Si, Ca, Mg, and H 2 0.
It is observed that increased SiO_ contenten increases the hydration
rate, but increased CaO and MgO reduces the rate. Additionally it was
observed that A_0^, FeO, Na„0 and K„0 contentent of obsidians
have a little effect on the hydration rate (Figure 1 ) . It is further
shown that, If the chemical composition of the obsidian is not known,
the refractive index, which is a more easily determined property, mea-
surable under the microscope and be used as a substitute (Figure 2 ) .

2.3.1 Methods for the Determination of Chemical Composition

Chemical composition of the obsidians are commonly measured by neutron

activation analysis, atomic absortion spectroscopy or X-ray floures-
cence. However, the influence of chemical composition on the hydration
rate in obsidian is more difficult to quantify. It has been shown that
obsidians can be grouped according to their sensitivity and saturation
dose which can further be used to correlate with hydration rate (Goksu
and Tiaretken, 1979).
308

S i O , - 43(CoO<MgO) - 2 0 ( H 2 0 )
0 10 20 50 40 43

/
/ , /

t\
/ / ,
/ *Ts"^

77
in —f—i
/
to
u
UJ
K
O

ffl /
A

< /

"in
ffl
Q.
' /y

tfr
s
1-
// / 1

/
/ /
.JL / 20 24
HYDRATION RATE - ( / t m ) V l 0 3 TEARS
28 K 36 40

t
0 10 45 4

//I .
20 10 40

/
12

10

lit
1 /
3 /
-J
UJ
/
in / /
s /
o
UJ
/ .
o |
^ 4t //
4 I
a
UJ
a.
2
!
K
/
/

W,
0 1
\ ' t

I 1
-2 !

te
HYORATION RATE - < ^ m ) V l 0 3 YEARS

Figure 1: Generalized curves of hydration rate as a function of tem-

perature. The Si02-45 (CaO+MgO)-20 (H20+) index is
given for each curve from Friedman and Long (1976)
 309

z
.490
I

HYDRATION RATE AT I O * C - ( / i m ) 2 / I 0 3 YRS

Figure 2. Hydration rate at 110 °C as a function of refractive index

N(3 for the 12 obsidian samples from Friedman and Long
(1976)

The difference in composition of rhyolithic and trachtic obsidian,

causes a major change in the hydration rate. However, the effect of
minor differences in composition, such as can exist among rhyolithics
obsidian outcrops within a specific geographical region, is not yet
understood. More ideal conditions may be achieved by measuring the
individual hydration rate of each individual sample by one of the ad-
vance methods like tritiumexchange or N resonance nuclear methods.

2.4. EFFECT OF ENVIRONMENTAL TEMPERATURE ON HYDRATION RATE

As with all diffusion processes, the rate of hydration is temperature

dependent and follows the Arrhenius equation. It has been shown that
the rate of hydration for obsidians buried in equatorial region (30°C)
310
is more than ten times the rate for obsidians buried in arctic regions
(1°C). Obsidian hydration rate increases roughly 10% for each 1°C in
crease in temperature.
When the obsidian hydration technique was first developed, tempera­
tures based on the gross thermal subdivisions provided by the earth's
climatic zones were used as in Figure 3. It has been soon realized
that a better definitions of temperature is needed to resolve the ob­
14
served inconsistencies between the obsidian hydration and C dates.
The effective hydration temperature (EHT) is defined in order to take
into consideration the fluctuating temperature conditions.

Estimated " e f f e c f i v Hydration rate

temperature ­ °C m i c r o n s 2 per 1000 years
A -Coastal Ecuador 30 II
CM
w 80 B -Egypt 28 8.1
c
o C­ Temperate no. 1 25 6.5
o 70 D­ Temperate no. 2 20 4.5
E E­ Sub Arctic 5 0.9
60
F­ A r c t i c 1 0.4
o
■D
0>

■o
>>

0)
c
o
2000 4000 6000 8000 10.000

AGE ­ years
Figure 3: Relation step of hydration thickness and age for six tem­
perature zones from Friedman et al., (1966)
 311
Additional refinements have been applied to estimate the mean annual
air temperature to compensate for site altidude, findspot depth, sea-
sonal snow cover, geothermal effects etc. While this approach remains
the best feasible way to cope with the temperature factor in many in-
stances, the obvious alternative of making present day on site mea-
surements at points of interest has been gaining support in recent
years. For this purpose various low cost self contained, non mainten-
ance field censors developed to integrate temperature over a long
period of time.
Trembour et al, (1986) discussed the applications of water diffusion
cells, first described by Ambrose, 1976.
The temperature is integrated by the diffusion of water through a
plastic wall driven by the difference in the activity of water between
the two sides of the plastic. Because the water activity on each side
is maintained constant, the rate of diffusion of water is only a func-
tion of temperature. In the original model described by Ambrose, the
plastic sphere was filled with a desiccant that maintained the inter-
nal water activity at a value close to zero, whereas the outside of
the cell was placed in pure water with a constant activity of one. As
the cell was exposed to a fluctuating temperature, during periods of
high temperature the rate of water transmission would be high, while
during low temperature the water transmission rate would decrease.
Thus, the weight gain of the cell would reflect the integrated water-
transmission rate and therefore an intergrated temperature for the
period of cell exposure. Two weighings, one before and one after expo-
sure and the length of exposure time can provide the data for this
integrated measurement.
The authors also described the use of cells to measure the relative
humidity of the environmental air. In this case a pair of cells was
used. One cell had a constant water on one side, desiccant on the
other. The second cell was exposed to a varying activity gradient by
allowing the outside of the cell to be exposed to the ambient air. The
first cell gained or lost water only as a function of temperature,
whereas the second (adjacent) cell was affected by both varying tem-
perature and varying humidity (water activity). The ratio of the
weight changes of the two cells was found to be a function of the
relative humidity.
312

3. Experimental Procedures

The experimental set-up for this method is rather simple and requires
only equipment for cutting and polishing and a polarizing microscope.
In order to measure the thickness of the hydration layer a thin slice
3
(4 x 4 x 2 mm ) is cut from the obsidian artefact perpendicular to
the surface to be examined. The slice is mounted on a glass slide,
grounded down to a thickness of about 50 micron, then examined under
an optical microscope. Since the hydrated layer of the obsidian has a
higher refractive index than the non hydrated obsidian, the division
between the two regions is seen under the microscope as a relatively
sharp line. The thickness of the hydration layer can vary between
1 micron to 50 microns. By using the image splitting eye piece and
crosspolarized light, the thickness of the hydration can be determined
with an accuracy of + 0.1 micron.

There are other methods developed to mesure the hydration thickness.

Gibon and Michels (1967) used electron microscopy.
Laursen and Lanford (1978) used narrow isolated resonance in the
following reaction:
15 4 14 4
N+^H — C+ He+ gamma-ray

The hydrogen profiles is measured by converting the gamma yield curve

to hydrogen concentration. The method provides measurement of
hydration thickness as low as few Angstroms allowing hydration rate
determinations at room temperature. It may also be used for individual
calibration by mea- suring the the hydration rate of individual
artefact (Leach, 1977; Lanford et al, 1976)
Lowe et al, (1984) proposed to use the tritium exchange method for
hydration rim measurement. The method is based on the measurement of
the water that has diffused through the obsidian surface by exchanging
the hydrated water with tritiated water. The amount of exchanged tri-
tium activity in the sample is measured by beta emission from the
surface of the obsidian.
 313

4. Conplicating factors in age determination

When selecting obsidian artefacts for age determination studies, it is

essential to avoid artefacts whose hydration layer has been altered by
either physical or chemical processes. For example, an artefact which
has been exposed to running water or wind-blown sand for any length of
time may have lost part or all of its hydration layer through abra-
sion. Similary, certain chemical environments, such as those in the
vicinity of hot springs, can effectively disolve outer part of the hy-
dration layer. In addition, since the mechanical strain increases as
the hydration layer becomes thicker, it is possible that with very old
artefacts, an initial hydration layer has fallen off in certain pla-
ces. On the new surface created this way a new hydration layer starts
to grow again. Although artefacts suffering from the above faults can
normally be rejected on the basis of careful microscopic examination,
it is advisable whenever possible to make measurements on various sur-
faces and at least six different artefacts from the archaeological
context under consideration.

A piece of obsidian exposed to the sun will hydrate much more rapidly
than buried obsidians. Therefore such surface materials should be
avoided.
Obsidians found in burned layers should not be collected for hydra-
tion measurement. It is shown that light fire on the site may not af-
fect the hydration rate but, prolonged fires may increase the hydra-
tion rate. Further complication may arrise if the vegitation which
covers the site is removed by fire, the samples would be exposed to
solar heating.
Another effect that can create problems in dating stratified deposits
is the vertical movement of artifacts caused by disturbance of the de-
posit by man and animals as well as by the natural movement of large
objects in the soil caused by alternate wetting and drying. This ef-
fect will be especially important in deposits where the rate of accu-
mulation with time is slow or variable and a shift of a few centime-
ters in strati graphic position may represent a thousand years or
more. The other problem in dating obsidians by hydration method stems
314
from the re-use of the artefacts, therefore it is necessary to measure
hydration thickness in various surfaces (Michels, 1969). The possible
re-use can be detected by careful microscopic analysis (Figure 4 ) .

RE-USED PART

Figure 4. Hydration rim of a re-used obsidian artifact collected from

the fifth river terrace, Shirataki. Note hydration procee-
ding from cracks as well as surface (From Katsui and Kondo
(1976))

5. Conclusion

Obsidian hydration dating, despite its known difficulties is shown to be

a very versatile tool for relative and chronometric age determination.
The technique has advantages over the others because it provides the
 315
date of production of the artefact. By proper selection of the samples
and careful observation of the hydration thickness, 10 % accuracy can be
obtained. The method is simple and quick and does not require very com-
plicated instrumentation. It can therefore provide a very rapid survey
of the artifacts even during the excavation. However, like other dating
methods, it must be used with caution and with an appreciation of its
limitations. It is also capable of giving valuable information with a
minimum of effort and expense, particularly for young volcanic events,
where it is difficult to apply thermoluminescnce or potasiumargon dating
methods.
316

References

Ambrose, W. (1976) in R.E. Taylor (ed.) Advances in obsidian Glass stu-

dies, Noyes Press, Park Ridge, New Jersey pp. 81-106

Clark, D.L. (1961) Current Anthropology 2, 111

Clark, D.L. (1964) Archaeological Survey Annual Report UCLA 4, 141

Clark, D.L. (1984) Arctic 37, 91-109

Ericson, J.E. and Berger, R. (1976) in R.E. Taylor (ed.) Advances in

obsidian Glass studies, Noyes Press, Park Ridge, New Jersey, pp. 46-62

Ericson, J.E., Mackenzie, J.D and Berger, R. (1976) in R.E. Taylor (ed.)
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Evans, C. and Meggers, B.J. (1960) American Antiquity 25, 523-537

Findlow, F.J. (1977) The Kira 43, 27-28

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Katsui, Y. and Kondo, Y. (1965) Japanese Journal of Geology and

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Studies, Noyes Press, Park Ridge, New Jersey, pp. 63-81
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Lanford, W.A., Trawetter, H.P. Ziegler, J.F and Keller, J. (1976)

Applied Physics Letters 28, 566-568

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Leach, B.F. (1977): New Zealand Journal of Science 20, 123-138

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Studies, Noyes Press, Park Ridge, New Jersey, pp. 106-120

Michels, J.W. (1967) Science 158, 211-214

Michels, J.W. (1969), American Antiquity 34, 15-22

Michels, J.W. (1971) in Brill (ed.) Science and Archaeology, pp.

498-546, MIT Press, Cambridge

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Tsong, I.S.T. (1978), Science 201, 339-341

SCIENTIFIC DATING METHODS

There is a growing need for an interdisciplinary interaction between

specialists in the natural and human sciences. The rapid developments in
scientific techniques and methods increase already existing gaps in
communication between both types of scientists, especially in the fields of
archaeology, anthropology and geology.
In order to meet this need and to review the current state of knowledge in
scientific methods of dating the Joint Research Centre Ispra of the
Commission of the European Communities in collaboration with the GSF
Forschungszentrum fur Umwelt und Gesundheit, Munich, has invited
internationally recognised experts to describe and discuss the principles
of different methods, sampling, limitations, applicability, statistical evalua-
tion and accuracy. A major application of each method is presented by
comparing it with other dating methods.
The subjects are covered under three main sections. Part I contains the
most frequently used methods based on radioactive decay, i.e.
radiocarbon, potassium-argon, uranium series and fission-track dating. In
Part II methods based on energy deposition of solids are presented by
covering thermal and optical luminescence methods. Part III describes
methods based on natural rhythmic and chemical changes.
The publication is principally addressed to human scientists using or
intending to use dating methods in their field of research, museum
curators and natural scientists with an interest in applied research, as well
as to students of history, geology and archaeology. Interested laymen
may also benefit from the presentation.

KLUWER ACADEMIC PUBLISHERS EUAS1 ISBN 0-7923-1461-1