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ADVANCED SCIENTIFIC TECHNIQUES
VOLUME 1
Scientific
Dating Methods
edited by
H. Y. Goksu, M. Oberhofer and D. Regulla
COURSES
A series devoted to the publication of courses and educational seminars
organized by the Joint Research Centre Ispra, as part of its education and
training program.
Published for the Commission of the European Communities, Directorate-
General Telecommunications, Information Industries and Innovation,
Scientific and Technical Communications Service.
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
ISBN 0-7923-1461-1
Publication arrangements by
Commission of the European Communities
Directorate-General Telecommunications, Information Industries and Innovation,
Scientific and Technical Communication Unit, Luxembourg
EUR 13528
©1991 ECSC, EEC, EAEC, Brussels and Luxembourg
LEGAL NOTICE
Neither the Commission of the European Communities nor any person acting on behalf of the
Commission is responsible for the use which might be made of the following information.
ADDRESSES vii
PREFACE ix
ACKNOWLEDGEMENTS xi
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.
Tarling, D.H. Dept. Geological Sciences, Polytechnic South West, PLYMOUTH PL4
8AA, United Kingdom.
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)
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.
,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 + />
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.
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THE CHEMICAL APPARATUS FOR COMB USTION
IX
•s. AND PURIFICATION OF C 0 2 FOR A PROPOR
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>- CARBON-14 D ATING LABORATORY
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UPPSALA
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19
CAJR - W s O N S ^ , , , .
ATTEH UNIVIBR.
1-0.1" 50)ii TOLLK " ^ ( M E S O N S V 1 2 G
CATR o(MESONS»/5) 3( .
FOLL.
CATH.
o(MESONS*£) 1 N
FOLL
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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
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
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
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.
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.
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
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
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)
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 -
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
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
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:
■
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.
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.
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.
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
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
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
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].
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 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
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
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.
I4 M
C Decay Counting C Direct Counting
modern 13.5 dpm/gm carbon 5.9 x 10'° atoms ' C/gm carbon
400 r io 4
"- 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
Acceleration of ions
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.
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].
l4
Essential certainty age estimate on object for C analysis on human bone
which temporal placement to obtain age estimate on
sought human burial
l4
High probability age estimate on material C analysis of textile
in direct functional used to wrap burial to
relationship with obtain age estimate on
object/event for which burial
temporal placement
sought
l4
Reasonable age estimate on C analysis of charcoal
possibility enclosing deposits in sediments adjacent to
of assumed similar burial to obtain age
age to the object/ estimate on burial
event for which
temporal placement
sought
14
Possibility age estimate on C analysis of charcoal
component of deposit in sediments associated
correlated with stratigraphically/
deposits containing geomorphologically or
object/event for which cross-dated on the basis
temporal placement of some cultural feature
sought 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
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]
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
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
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
[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):
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)
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
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.
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.
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
Co
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:
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:
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.
The potassium content of the sample can be analyzed using various methods such as:
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
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
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)
Time interval between April lOlh and April 12lh 1990 (automyzed measurement, one Christmas tree)
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
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
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
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
(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
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
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.
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.
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).
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.
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.
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.
References
Allegre, C.J., Staudacher, T., Sarda, P. and Kurz, M. (1983) Nature 303, 762-766.
Aronson, J.L., Schmitt, T.J., Walter, R.C., Taib, M., Tiercelin, J.J., Johanson, D.C.,
Naeser, C.W. and Narin, A.E.M. (1977) Nature 267, 232-327.
Dallmeyer, R.D. (1979) in E. Jager and J.C. Hunziker (eds.) Lectures in Isotope
Geology, Springer Verlag, Berlin, Heidelberg, New York, pp.77-104.
Dalrymple, G.B. and Lanphere, M.A. (1969) Potassium-Argon Dating, W.H. Freeman,
San Francisco
Everts, P., Koerfer, L.E. and Schwarzbach, M. (1972) Neues Jahrbuch Geol. Palaont.
Monatshefte 1, 280-284.
Faure, G. (1977) Principles of Isotope Geology, John Wiley & Sons Inc., New York
Flisch, M. (1986) in A.J. Hurford, E.Jager and J.A.M.Ten Cate (eds.) Dating Young
Sediments, CCOP Technical Secretariat, Bangkok, pp. 299-323.
Fuhrmann, U. and Lippolt, H. J. (1987) Neues Jahrbuch Geol. Palaont. Mitteilungen (4),
213-236.
Gasparini, P. and Adams, A.S. (1969) Earth and Planetary Science Letters 6, 225-230.
Gramlich, J.W., Lewis, V.A. and Naughton, J.J. (1971) Geological Society of America,
Bulletin 82, 1399-1400.
Hay, R.L. and Leakey, M.D. (1982) Scientific American, February 1982, 38-45.
75
Izett, G.A. (1982) U.S. Geological Survey Open File Report, No 82-582, 44p.
Jager, E., Chen Wen Ji, Hurford, A.J., Liu Ruo Xin and Hunziker, J.C. (1985) Chemical
Geology (Isotope Geoscience Section) 52, 275-279.
Jambon, A,. Weber, H.W. and Begemann, F. (1985) Earth and Planetary Science Letters
73, 255-267.
Johanson, D.C. and Shreeve, J. (1989) Lucy's Child - The Discovery of a Human
Ancestor, William Morrow, New York.
Kirsten, T. (1966) in O.A. Schaeffer and J. Zahringer (eds.) Potassium Argon Dating,
Springer Verlag, Heidelberg, pp. 7-39.
Leakey, M.D., Hay, R.L., Curtis, G.H., Drake, E.R. and Jackes, M.K. (1976) Nature
262, 460-466.
McDougall, I. and Swanson, D.A. (1972) Geological Society of America, Bulletin 83,
3731-3738.
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(eds.) Conference on planetary volatiles. LPI, Technical Report No. 83-01, p. 188.
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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
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):
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
(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.
(d) A few fast neutrons are produced simultaneously with the fission
fragments.
Total 200
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
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).
/
' > * •
%
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
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.
6 Sin TEAT
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.
AGE OF EARTH ^ J j .
lOOOmy
s'
/'
.'"'MINERALS
UJ
< I «iy
IOOO
100
MAN-MADE
GLASSES
10
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:
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
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
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)
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
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.
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
<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
1.8 2.0
[lO3/ K]
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.
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).
/ A
i-l
e(p) =
l«, / A
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 '
8.Conclusion
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
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.
10. Fleischer, R.L., Price, P.B. and Walker, R.M. (1965c) J. Nucl. Sci.
Engr. 22, 153.
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.
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.
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.
26. Storzer, D. and Poupeau, G. (1973) C.R. Acad. Sci. Paris 276, Serie
D., 137-139.
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.
M. IVANOVICH
AEA Environment & Energy
Isotope Geoscience Section
Harwell Laboratory, B7
Oxon 0X11 ORA
United Kingdom
1. Introduction
"«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
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].
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
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
or indirectly via 22 'Th) is not practicable for samples containing less than
some 3 ppm uranium.
C = C0e~Xt (4)
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].
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:
£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.
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)
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.
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
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
References
[7] Cherdyntsev, V.V. (with F.I. Chalov et al.) (1955). Uranium series
disequilibrium dating. Trans, of the 3rd Session of the Commiss. for
Determining the Absolute Age of Geol. Formations, Izd. Akad. Nauk
SSSR, 175-182.
[8] Cherdyntsev, V.V., Kazachevskii, I.V., and Kuzmina, E.A. (1963).
Isotopic composition of uranium and thorium in supergene zone.
Geochem. Int. 3, 271-283.
[9] Thurber, D.L. (1963). Anomalous t"U/"*U and an investigation of
the potential of "*U for Pleistocene chronology, PhD Thesis,
Columbia University, New York.
[10] Cherdyntsev, V.V., Tuzova, T.V., and Musin, Ye.A. (1964). The isotope
l3 23a
ratio *U/ U in natural waters and use of it in the nuclear
geochronology. Geokhimiya 5, 404-413.
[11] Thompson, P., Ford, D.C., and Schwarcz, H.P. (1975). »3*U/J3»U ratios
in limestone cave seepage waters and speleothems from West Virginia.
Geochim. Cosmochim. Acta 39, 661-669
[12] Osmond, J.K., and Cowart, J.B. (1976). Theory and uses of natural
uranium isotopic variations in hydrology. Atomic Energy Rev.
144, 621-679.
[13] Winograd, I.J., Szabo, B.J., Coplan, T.B., and Riggs, A.C. (1988). A
250,000 year climatic record from Great Basin vein calcite: Implications
for Milankovitch theory. Science 242, 1275-1280.
[14] Harmon, R.S., Thompson, P., Schwarcz, H.P., and Ford, D.C. (1978). Late
Pleistocene paleoclimates of North America as inferred from stable
isotope studies of speleothem. Quat. Res. 9, 54-70.
[15] Ku, T.-L., Knauss, K.G., and Mathieu, G.G. (1974). Uranium in open
ocean: concentration and isotopic composition. EOS Trans. Am.
Geophys. Union 55, 314.
[16] Thurber, D.L., Broecker, W.S., Blanchard, R.L., and Potratz, H.A.
(1965). Uranium-series ages of coral from Pacific atolls.
Science 149, 55-58.
[17] Veeh, H.H. (1966). '3°Th/23»U and J3*u/'3SU ages of Pleistocene high
sea level stand. J. Geophys. Res. 71, 3379-3386.
[18] Ku, T.-L., Broecker, W.S. (1967). Uranium, thorium and protactinium
in a manganese nodule. Earth planet. Sci. Lett. 2, 317-320.
115
[19] Chalov, P.I., Merkulova, K.I., and Tuzova, T.V. (1966). Absolute age of
the Aral Sea determined from unbalanced uranium. Dokl. Akad. Nauk
SSSR 169, 89-91.
[20] Chalov, P.I., Svetlichnaya, N.A., and Tuzova, T.V. (1970). Results of
determinig the absolute age of lake Balkhash based on nonequilibrium
uranium. Dokl. Akad. Nauk SSSR 195, 190-192.
[21] Chalov, P.I., Svetlichnaya, N.A., and Tuzova, T.V. (1970). Isotopic
composition of uranium (23*U, 23,
U) in waters and bottom sediments of
Balkhash lake and the age of the basin. Geokhimiya 7,
848-854.
[22] Ku, T.-L. (1976). The uranium-series methods of age determination.
Ann. Rev. Earth planet Sci. 4, 347-380.
[23] Piggot, G.S., and Urry, H.D. (1939). Radium content of an ocean-bottom
core. J. Wash. Acad. Sci. 29, 405-410.
[24] Piggot, G.S., and Urry, H.D. (1942). Time relations in ocean sediments.
Bull. Geol. Soc. Am. 53, 1187-1210.
[25] Sackett, W.M. (1965). Deposition rates by the protactinium method.
In: Symp. on Marine Geochemistry, eds. D.R. Schink and J.T.
Corless, University Rhode Island, 29-40.
[26] Sackett, W.M., Broecker, W.S., and Thurber, D.L. (1965). The
131
geochemistry of Pa and the dating of pelagic sediments. Ann. Rep.
AEC Contract AT (30-1).
[27] Korainz, M.A., Heath, G.R., Ku, T.-L., and Pisias, N.G. (1979). Brunhes
timescales and the interpretation of climatic change. Earth planet.
Sci. Lett. 45, 394-410.
[28] Ku, T.-L., Omura, A., and Chen, P.S. (1979). Beryllium-10 and
uranium-series isotopes in manganese modules from the Central North
Pacific. In: Marine Geology and Oceanography of the Pacific
Manganese Nodule Province eds. J.L. Bischoff and D.Z. Piper.
Marine Science 9, Plenum Press NY, 791-814.
[29] Ku, T.-L., Knauss, K.G. (1979). Radioactive disequilibrium in
fissure-filling material and the implication in dating of manganese
nodules. In: La genese des nodules de manganese ed. C. Lalou,
CNRS Paris, 289-293.
[30] Picciotto, E., and Wilgain, S. (1954). Thorium determination in
deep-sea sediments. Nature 173, 632-633.
116
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).
wmwmw///,
^wConduction band^^
Luminescence
centres
c
O
u
CD
o 10,000
c
CD
u
tn
CD
c
E
o
E
i_
CD
-
Sublinear
-
/ -.— Saturation
s^^
-
Linear /
-
- Supralinear /
i i 1 1 i
Dose
3. Applications
KEBARA QAFZEH
Unit Layer
VI
XVII
VII
XVIII
VIII
XIX
IX
XXI
X
XXII
XI
XXIII
XII
50 100
Age (thousands of years)
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
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
Electronics
luminescence
sample
green light
from laser
c
O
u
CD
100
c
a
E
I J_
100 200 300 /.00 500
Bleaching time (min)
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.
4. Optical Dating
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.
5. Summing-Up
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
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.
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
AD={B.-^L-BTD1 3.1
o
u
o
I-
o
75 100 125 50
TEMPERATURE CO
The experimental conditions (eg optical filters, heating rate etc) for the measurement of
sensitivity should remain unaltered throughout an experiment.
158
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
>-
>
4 6
CUMULATIVE DOSE
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
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:
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.
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
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
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
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.
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.
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)
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.
(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.
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.
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.
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?
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
M.G.L.Baillie
School of Geosciences
Queen's University, Belfast
Northern Ireland
comparing Its pattern of wide and narrow growth rings with the ring
then used the same logic to extend the overall tree-ring pattern far
species and from that area, by comparing the sample pattern with the
SEARCH MATCH f
DATE
11 1
1
1 I
1
Y MATCH
1 SITE MASTER
▼ t
DATE
repeatably. Moreover, right from the start there was more to the
Douglass.
for all that was to follow. There are two main issues, namely dating
First, and still 1n north America, there was the construction of the
1970). That work in itself was one of the most important applications
records.
The second major development was the spread of the method into Europe
but they were necessarily rather slow - it was the 1960s before the
The reasons for this are obvious. Compared with the long-lived and
So, in both Ireland and Germany the 1970s saw the construction of oak
Living trees
to follow the same course. Studies on trees with known felling dates,
Dating buildings
between one and three years before the recorded building dates. This
construction.
the ring pattern of a sample and dating that ring pattern against a
master chronology: the result being a precise date for the last
not all samples are complete out to the underbark surface - the
last ring on the sample and the felling date of the tree from which
rings whereas in the eastern Baltic the figure is 14+/-3 (Bail lie et
Replication
patterns and produce a site master which has a stronger and more
northern Europe, and suggested that the dating method was 1n fact very
Trade
Indeed this turns out to be the case. Recent examples show that oaks
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
normally uncovered wet and with sapwood which has deteriorated during
century.
Prehistoric chronologies
the long oak chronologies, going far back Into prehistory, were
method and for unravelling aspects of Holocene bog and river gravel
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
was extremely rapid. This was partly a result of the large numbers of
Irish and German oak chronologies were pieced together very rapidly,
1984). Moreover, independent work meant that the whole system could
Prehistoric dating
with Increasing age. The major Corlea 1 track in central Ireland was
BC (Raftery 1990) whereas the English Sweet Track timbers were felled
One surprising revelation from this type of work has been the
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
208 BC. Its effects were felt dramatically in China, where large
evidence shows that in ancient Rome, around 205 BC, there were
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.
and the Near East. Kuniholm and Striker (1987) have made a dramatic
of years. This holds out hope for the ultimate resolution of specific
amongst others.
Practicalities
fulfilled.
trees will stand a much better chance of being dated than a single
ring pattern.
sampling.
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,
Assuming that suitable timbers are provided by the consumer, the task
• t IRELAND 11 t
J
i i GERMANY ii •
^
The geographical factor comes into play when the sample(s) are from
than individual samples. Fortunately, as time goes on, more and more
chronological coverage.
These last statements go some way towards explaining why the length
samples or site chronologies spanning less than 100 years, dating can
be the case that with such short sequences, qualifications may have to
to demonstrate that all belong to the same phase (or are not
With ring patterns longer than 100 years, that same methodology is
basis of even the most preliminary tests, show that there will be
212
Conclusion
second place.
213
REFERENCES
Baillie, M.G.L. (1982) Tree-Ring Dating and Archaeology. Croom-Heim
London
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.
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.
Science Foundation.
Forsyth, P.Y. (1990) Call for Cybele The Ancient History Bulletin
4.4, 75-78
Antiauity64, 210-220
Archaeology 123-132
Pearson, G.W., Pilcher, J.R., Baillie, M.G.L., Corbett, D.M. and Qua,
911-934.
Pilcher, J.R. and Baillie, M.G.L. (1987) The Belfast CROS Program:
150-152.
863-910
Absolute Chronology ed I.U. Olsson, John Wiley and Sons, New York,
303-309.
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.
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.)
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.
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
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
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
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.
Cram aiamrt*r ( A )
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.
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
Puddling clays
(chemical/deposifional) Bricks (thermal)
Morrar (chemical or
deposiNonal)
Piaster (chemical or
Porsherds (Thermal)
deposirional)
\
Cemenr tchemical or
deposihonal)
Ditch infil
{deposihonal]
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).
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)
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)
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
// "/
//
/ /
( |
/
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.
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).
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.
REFERENCES
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.
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.
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
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
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.
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).
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.
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.
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).
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.
Slorno Ic 31008 P I
uuaanvlcUOOOBPI
Mens lc.2t U M B P I
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.
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.
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.
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.
so
• *)
100 1000
Solu-olion Rmcntnii (Am'kg-')
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.
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.
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
REFERENCES
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
FLUORINE DEPOSITION
Fig.l.
The Piltdown skull,Eoanthropus Dawsoni.
After a photograph from the original in
the British Museum,Natural History,London.
:56
PALAEONTOLOGICAL APPLICATIONS
GEOMORPHOLOGICAL APPLICATIONS
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
Lower Pliocene
Hipparion dentine 130
90
Lower Pleistocene
Equus sanamensis 30
Middle Pleistocene
Ailuropoda dentine <1
Gigantopithecus <1-10
Liucheng Cave fauna <1-10
NITROGEN IN BONE
Bruhl F-U-N
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
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:
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
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
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.
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
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
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
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.
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
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.
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
Microanalysis of Kelsterbach
STRATIGRAPHY OF K E I S T E
B R A C H
yallow gravai
TT7 Ituff]
/ / /
rad graval
(*"*""■> 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
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
References
Berger, R., Homey, A.G.. and Llbby, W.F. (1964) Radiocarbon Dating of
Bone and Shell From Their Organic Components, Science 144, 9 0 0 -
lOOl.
Berger, R., Protsch, R., Rozaire, C. et al. (1971) New Radiocarbon Dates
Based on Bone Collagen of California Palaeo-Indians, Contributions of
the University of California, Archaeological Research Facility, UC-
Berkeley 12, 43-7.
Mann, W.B., Marlow, W.F. and Hughes, E.E. (1961) The Half-life of
Carbon-14, International Journal of Applied Radiation and Isotopes
11,.57-67.
Muller, R.A., Stevenson, E.J. and Mast. T.S. (1978) Radioisotope Dating
with an Accelerator: A Blind Measurement, Science 2 0 1 , 347-8
Nelson, D.E., Korteling, R.G. and Scott, W.F. (1977) Carbon-14: Direct
Detection at Natural Concentrations. Science 198, 507-8.
Oakley, K.P. (1968) Frameworks for Dating fossil Man. Aldlne Publishing
Company, Chicago
299
Pandow, M., MacKay, C. and Wolfgang, R. (I960) The Reaction of
Atomic Carbon with Oxygen: Significance for the Natural Radiocarbon
Cycle, Journal of Inorganic Nuclear Chemistry 14, 153-8.
Protsch, R. (1976a) The Naivasha Homlnid and its Confirmed Late Upper
Pleistocene Age, Anthropologlscher Anzeiger 35, 2 / 3 , 97-102.
Semmel, A. (1969) guartar. In: Erl. geol. Kt. Hessen 1:25.OOO, Bl. 5916
Hochhelm, Kummerle und Semmel eds, Wiesbaden 3, 51-99.
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.
H.Y. GOKSU
GSF - Forschungszentrum fur Umwelt- und Gesundheit
Institut fiir Stahlenschutz
Ingolstadter Landstr. 1
D-8042 Neuherberg
Federal Republic of Germany
1. Introduction
2. General Principle
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:
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
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
z
.490
I
■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.
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
5. Conclusion
References
Ericson, J.E., Mackenzie, J.D and Berger, R. (1976) in R.E. Taylor (ed.)
Advances in obsidian Glass studies, Noyes Press, Park Ridge, New Jersey,
pp. 25-45
Friedman, I., Smith, R.L. and Long, W.D. (1966), Bulletin of the
Geological Society of America 77, 323-330
Michels, J.W., Tsong, 1ST and Smith, G.A. (1983) Archaeometry 25 (2),
107-117
Ross, C.S. and Smith, R.L. (1955): American Mineralogists 40, 1071-1089
Trembour, F.W., Friedman, I., Jurceka, F.J., Smith, F.L. (1986) Journal
of Atmospheric and Oceanic Technology 3, 186-190