Radiation Measurements 46 (2011) 749e753

Contents lists available at ScienceDirect

Radiation Measurements
journal homepage: www.elsevier.com/locate/radmeas

Current topics in ESR dating

Anne R. Skinner
Williams College, Williamstown, MA, USA

a r t i c l e i n f o a b s t r a c t

Article history: After over 25 years, the use of electron spin resonance (ESR) is well-established in dating sites of
Received 22 November 2010 geological, paleontological and archaeological interest. Like any scientic technique, there have been
Accepted 3 January 2011 changes in understanding and in methodology. Improvements have not, however, changed the obser-
vation that external dose calculations are still a signicant source of uncertainty in ages.
Keywords: Examples from Europe, Africa and the Americans illustrate this point. For Pradayrol Cave (France), the
ESR
occupation age, 330 ka, is unchallenged, making this the oldest known Neanderthal site in France. For
Dating
Roc de Marsal, also in France, on the other hand, discrepancies between TL and sedimentary dose rates
Archaeology
Paleoanthropology
imply substantial differences in interpretation. In the Western Egyptian Desert, where artifacts and
Geology datable material are not well-correlated, the dating results show consistency with expectations based on
global climate change, even in deated sites. Climate change is also the question in geological studies in
the Bahamas where, despite concerns about cosmic dose history, ESR dates conrm other evidence for
sea level changes. We show that an uncertain age is not the same as an impossible one.
2011 Published by Elsevier Ltd.

1. Introduction
Electron spin resonance (ESR) has by now a quite respectable
history, particularly when one considers the series of symposia of
which this is the ninth. Almost exactly 25 years ago to the day, Dr.
Motoji Ikeya convened the rst ESR Dating and Dosimetry
symposium in Ube, Japan. At that meeting, virtually all the papers
were on dating (some 90% of those in the proceedings). At this
meeting, the contribution of dating is much smaller, not because
the technique is less useful, but because other applications dealing
with modern radiation exposures have become more signicant,
thanks to international instability.
Currently almost every site of archaeological and paleontolog-
ical interest that exceeds the radiocarbon limit relies at least in part
on ESR dating, except those conveniently associated with volcanic
deposits. Atapuerca, in Spain, currently the oldest known habita-
tion in Western Europe, is one example (Falgures et al., 1999). ESR
has been used to settle dating problems. At Mezmaiskaya Cave in
Russia, radiocarbon dates suggested that the Neanderthal infant
might be only 29 ka old, a remarkable survival for that area. ESR
dates, in contrast, were a more plausible 55 ka, suggesting that the
tested bones had been contaminated with modern carbon (Skinner
et al., 2005). An even more dramatic example comes from Obi-
Rakhmat Cave, Uzbekistan. Radiocarbon dates were scattered, with
no coordination with depth. U-series dates, on the other hand, were
E-mail address: Anne.R.Skinner@williams.edu.
essentially uniform over multiple strata. The ESR dates, however,
showed the expected correlation with depth (Fig. 1). Again,
contamination had spoiled the radiocarbon results, and closer
examination of the U-series samples showed that they came from
a single draped owstone (Skinner et al., 2007).
Lest one assume that ESR always provides the nal word on ages,
one should note a current controversy in Brazil. Northeastern Brazil
has a rich display of rock art, some of which is overlain by calcite
deposits. Radiocarbon analyses of the overlay at Toca do Serrote da
Bastiana suggest an age of w2500 years BP while ESR ages appear to
be 38 ka (Rowe, 2010). Here the ESR ages are implausible given the
current thinking on the peopling of the Americas. The conict is not
yet resolved; if evidence is found of occupation of the area, the ESR
dates may yet be accepted. If not, it would be important to establish
why the ESR dates are apparently so old.
In recent times there have been signicant advances in both
theory and practice of ESR dating. Perhaps the most important
change in protocols has been the development of coupled ESR/U-
series dates on tooth enamel (e.g., Grn and McDermott, 1994).
Although many other materials can be used, tooth enamel is the
most important, especially in older sites, because of the signal
stability. Initially, however, ESR dates were totally dependent on the
model used for U-uptake, and the general practice was to quote three
dates, Early Uptake (EU), Linear Uptake (LU) and Recent Uptake (RU).
The decision as to the most plausible then depended on some
outside factor. And, of course, it was clear that combinations of these
models were possible (Blackwell et al., 2001a). Being able to report

1350-4487/$ e see front matter 2011 Published by Elsevier Ltd.

doi:10.1016/j.radmeas.2011.01.003
750 A.R. Skinner / Radiation Measurements 46 (2011) 749e753

Fig. 1. Summary of dating results for Obi-Rakhmat Cave, Uzbekistan, showing that ESR ages correlate with stratigraphy.

a single age increases the authority of and condence in results. The
method is not always needed; some results are model-independent.
Not all teeth can yield U-series results, although instrumental
improvements are assisting here, so one can still see some EU/LU/RU
results. Still, this development amounts to a revolution.
Other researchers have studied the ESR spectra with a view to
understanding basic theory. They have used spectral deconvolution
to show details of radiation sensitivity (Rudko et al., 2010) and
investigated whether the articial irradiation of samples truly
mimics natural (Joannes-Boyaun et al., 2010).
While these developments have improved our ability to analyze
our data, one major limitation remains. Like all members of the
trapped charge dating family (OSL, TL, IRSL as well as ESR), ESR
dates are dependent on a knowledge of sample environment. All
components within a range of 30 cm must be evaluated, as well as
cosmic doses. When the sample environment is reasonably
homogeneous, evaluation can be straightforward. Unfortunately
most sites are lumpy e they contain multiple sedimentary layers
and within the layers are a variety of mineralogical elements such
as bones, stone tools, and boulis.
The ways to measure that environment have not changed
signicantly in the last 25 years. The three alternatives remain:
Often there is reasonable condence in the measurement of the
modern dose rate, but then we must remember that this may not be
the time-averaged dose rate. The environment, even in a cave site,
may change considerably over time. The existence of bones and
teeth in the sediment poses a particular issue. These elements take
up uranium from ground water, and so their contribution to the
sedimentary dose rate changes with time (Blackwell and Blickstein,
2000). Bones may also lose uranium! The importance of some of
these variabilities can be shown by gures that diagram the effect
of changes in (e.g.) water concentration on the calculated age
(Fig. 2). Even the overall effect of assumptions on external dose can
be shown (Fig. 3), letting the reader evaluate the extent to which
dose rate uncertainty translates into uncertainties in conclusions
drawn from the calculated ages.
Additionally, the isochron technique (Blackwell et al., 2001b) for
teeth can provide insight into this. The AD (accumulated dose) for
a sample can be expressed as the sum of external and internal
contributions:
AD ADext ADint ADext Dint t (1)

a TL dosimetry
b Gamma spectroscopy
c Geochemical analysis of sediments

There have been improvements in instrumentation for all of

these, but nothing that relieves their limitations. TL dosimetry
yields a time-averaged dose rate over a period of months, but the
need to leave the dosimeter in place means that it cannot be put
exactly where the sample was found. If by chance it could, by the
time a sample is discovered half of its sedimentary cover has been
removed. Gamma spectroscopy can measure dose at the precise
site of the sample in approximately an hour, but suffers again
from the removal of much of the material contributing to the
dose. Also it is not practical to bring gamma spectroscopes to
many sites and in addition, there may be calibration issues.
Chemical analysis in principle can consider all sedimentary
elements. However, completely precise evaluation of a lumpy site
would require considering every single lump. With the devel-
opment of laser-based Total Station measurements, the locations
of such elements can be determined but the time required for
calculation becomes unrealistic. At best, a reasonably average Fig. 2. Example of the effect of sedimentary water assumptions on sample age.
distribution can be used. As a result, dose rates from different Changing the assumption from moderately damp (20%) to totally saturated (40%) does
methods can easily differ. not change the calculated age within 1s error.
 A.R. Skinner / Radiation Measurements 46 (2011) 749e753
Fig. 3. Example of the effect of total external dose rate assumptions on sample age.
Here, unless the assumed external dose rate is very much smaller than calculated, the
effect is less than that due to U-uptake modeling.
where Dint is the internal dose rate. If the tooth has multiple
subsamples, plotting the internal dose rate against the AD for each
subsample yields a line whose slope is the sample age and whose
intercept is the time-averaged total external dose, ADext. Dividing
ADext by t yields the time-averaged external dose rate, which can
then be compared to the modern value. As this method establishes
age without reference to a particular external dose rate, whereas
standard methods explicitly include such a dose rate, isochron ages
are independent of standard values.
Finally we must be concerned about reworking e is this sample
in its initial position? Customarily we date at least three samples
from a site, or from a layer within the site, and if the ages agree,
reworking is unlikely. However, frequently three samples are not
available from a layer, or, indeed, from the entire site.
2. Case studies
Let us look at some case studies that consider some of these
issues.
2.1. Pradayrol Cave
In 1998, at Pradayrol, Lot, France, a Homo cf. neanderthalensis
incisor fragment was found associated with extinct Middle Pleis-
tocene fauna at Pradayrol. The site also yielded a Middle Pleistocene
tool assemblage. The fauna suggest a steppe grassland with warm
Mediterranean climate at the time of occupation. 230Th/234U dating
on the stalagmites failed to give ages, due to diagenetic alteration
(Sronie-Vivien and Tillier, 2002). Standard and isochron ESR was
used to date four teeth from Layer 2A, which housed the incisor
fragment. Burrows and potential debris ows made a test for
stratigraphic integrity essential. Looking for possible stratigraphic
mixing, 17 more fragmentary teeth from Layer 4B were also dated
by ESR. In both layers the lumpy cave sediments are lumpy
contains boulis and bones. The standard external dose rate was
therefore determined by volumetric averaging of sedimentary
components.
For teeth in this time range, LU model ages have proved most
reliable (Blackwell et al., 2005). The average LU age for the teeth
751
from layer 2A was 330.2  5.4 ka, making this the earliest known
Neanderthal site. In addition to standard methods, an isochron was
calculated for one tooth, FT18, which had 6 subsamples. The LU
isochron agreed both with the standard age (344.0 ka) and with the
modern dose rate (0.754 mGy/y). Isochrons can also suggest details
of sample history; in this case there may have been minor diffu-
sional remobilization of uranium within this tooth. The average age
correlates with Oxygen Isotope Stage (OIS) 9, an interglacial period
whose climate would agree well with that suggested by the faunal
material.
The ages of the teeth from Layer 4B showed much greater vari-
ability. As noted, they were fragmentary, and in some cases lacked
attached dentine, making calculations problematic. Although one
tooth dated to 883  100 ka, and was clearly reworked, ages for the
others averaged 421 14 ka (LU). This age, which correlates with OIS
11, indicates that the layers are in stratigraphic succession.
Reworking appears to be minimal, restricted to Layer 4B.
The Pradayrol site thus represents a classic example of ESR
dating. From a multiplicity of samples, some in poor condition, we
can extract a consistent picture of the site, both in time and in
space.
2.2. Roc de Marsal
Roc de Marsal is a cave site in the Dordogne region of France. A
complete and articulated Neanderthal infant skeleton was found
there in 1953 (Dibble et al., 2009). Mousterian tools, faunal remains
and hearths occur in 12 of the 13 layers within the cave. Systematic
ESR dating of 24 teeth from nine layers, using volumetrically
averaged sedimentary components from 65 samples, has yielded an
age range of 72e91 ka, increasing with depth. The upper layers
appear to correlate with OIS 4 and the lower with OIS 5, consistent
with faunal remains (Fig. 4.) However, TL dosimeters were also
placed in the cave, as part of a project to use TL to date heated int
from the hearths. These yielded a much higher dose rate for the
lower layers, suggesting the entire site dates to OIS 4. The site is
extremely lumpy and thus a classic example of the difculties of
sedimentary analysis. In this case we have Total Station information
on the concentration of bones and the larger boulis. Where these
elements are bones, we have considered the increase in dose rate
with time as the bones concentrate uranium. Even with these
renements to sedimentary analysis, the dose rates do not match
the TL values. It may well be that, since the dosimeters were
emplaced well away from the ESR samples, the dose rates derived
from them do not reect local dose rates around our samples. Given
the stratigraphic coherence of the ESR dates and their agreement
Fig. 4. ESR dating results for Roc de Marsal, showing correlations with OIS 4 and OIS 5.
752 A.R. Skinner / Radiation Measurements 46 (2011) 749e753
with fauna, at present we see no need to change our conclusions,
but quite possibly this is not the nal result for this site. Ideally we
would look for a third method not dependent on environment, but
the site is clearly too old for radiocarbon and no materials for
U-series dating are available. In any case, our experience with
Obi-Rahkmat, noted above, suggests that even a third dating
method might not resolve the disagreement.
2.3. Egyptian oasis sites
The expansion of hominin occupation out of East and South
Africa implicitly must involve settlements in northern Africa.
Although today the Sahara desert presents a substantial barrier to
hunter-gatherers, there is both geological and anthropological
evidence that at many times during the Quaternary the region had
sufcient water to support human and animal life (Churcher et al.,
1999). When rainfall was higher during pluvial events that may or
may not correlate with global climate events, tufas were deposited
by springs, and these springs in turn fed small lakes large enough to
support freshwater molluscs. Understanding the timing of these
events would clarify the relationships between local and global
climate change. In addition, establishing dates for these events
would indicate time periods when hominins could have migrated
from Africa to Eurasia.
Fig. 5. A. Sedimentary layers as deposited during the Pleistocene. B. Mixing of fauna and artifacts as a result of deation.
In addition to faunal remains, tools of every major Paleolithic
tradition have been found in the Western Desert of Egypt, at
Dakhleh and Kharga oases. Unfortunately, the dominant feature of
a desert environment is the reworking of sediments by wind
ablation. Thus during the dry periods that punctuated the possible
settlements, the materials have been reworked into deated
aggregates.
As the Pleistocene sediments erode, deation drops their fossils
and large sediment grains onto the surface as a mixed lag (Fig. 5).
Since all have been displaced and look similar, deation often
thwarts attempts to trace tools and teeth back to their original layer.
At Site D006, Dakhleh, the tooth fragments that appear pristine and
young when collected within a few centimeters of each other, gave
ages that differed by up to 100e150 ka, and thus probably derived
from several different layers. The challenge, therefore, at these sites
is to reconstruct at least a portion of the paleoenvironment in order
to establish some external dose rate. Additionally, we must model
the cosmic dose rate as a function of time.
Teeth, the favored ESR dating material, are scarce in these oases.
To date, they have only been found at Dakhleh and are usually
fragmented and lacking dentine. In calculating ages, we modeled
cosmic dose rates, using minimum and maximum sediment depts.,
namely total exposure for their whole history versus total cover for
the same time. The models show that geologically plausible
 A.R. Skinner / Radiation Measurements 46 (2011) 749e753
assumptions do not signicantly change the calculated ages, sug-
gesting that the models are relatively robust and not so much of
a concern as feared. The fragment ages group in three time ranges:
50 ka, at the boundary of OIS3 and 4; 100e130 ka, during OIS
5ce5e; and around 160 ka, during OIS6. These ages agree well with
U-series ages on spring mounds around the area. Of course it is not
possible to correlate these with the MSA assemblages found. But
the dates suggest probable occupation times at which both food
and water would be available.
At Medauwara, near Kharga Oasis, no teeth have been found but
there are abundant deposits of snails, found in stratied lake
sediments. A single species, Melanoides tuberculata, has proven to
have strong signal stability and is sufciently wide-spread to allow
direct comparisons between different regions. Conceivably a single
deposit could represent mixing of several time periods as the snails
are light and blow easily. Measuring ve grab samples from a single
stratied deposit showed no variation within experimental
uncertainty, so reworking is not likely. Artifact assemblages here
include ESA as well as MSA tools, in deated sites. Most sites within
the oasis show signs of multiple occupations, represented by
different strata. Ages at Medauwara fall at 19 ka (OIS 2), 72 ka (OIS
4), 90 ka (OIS 5), 187e229 ka (OIS 7) and nally 2 Ma. Again the
presence of fauna at these time periods does not guarantee occu-
pation by hominins, merely the possibility of their presence.
2.4. San Salvador
As detailed in Deely et al. (this volume), ESR dating has been
used to look at events related to changes in sea level that correlate
with signicant climate change. Here, as with the Egyptian oases,
the external dose problem is related to changing cosmic dose rates
as the sample is periodically covered and uncovered, both by water
and by sediment. The approach of shows good agreement with
other measures of high sea stands and could thus be extended to
other regions.
3. Conclusions
Advances in understanding the science underlying ESR dating
are important, and thus studies on spectra need to be encouraged.
So far, however, for archaeological research the concerns raised by
spectral variability do not meet the level of uncertainty presented
by the external dose. It may never be possible to ascertain external
dose rates with the level of detail that results in uncertainties
comparable to the limits quoted, for example, by radiocarbon
researchers. Those involved with ESR dating should be straight-
forward in acknowledging this. Publishing graphs such as Figs. 2
and 3 might well become standard parts of papers. The exis-
tences of limits on a technique do not discredit its basic value. ESR
dating remains an essential tool for researchers of human antiquity,
antiquity of other fauna and of processes shaping the earth.
753
Acknowledgments
Thanks are due to many collaborators whose samples are dis-
cussed in this report. I must also acknowledge the students at Wil-
liams College and in the RFK Science Research Institute, headed by
Dr. Bonnie Blackwell and Dr. Joel Blickstein, who prepared and
analyzed many of the samples. Financial support came from the NSF,
Williams College, the RFK Science Research Institute, McMaster
Nuclear Reactor, and grants awarded to collaborators. Dr. Blackwell
prepared most of the gures herein and provided useful comments
on the text.
References
Blackwell, B.A.B., Blickstein, J.I.B., 2000. Considering sedimentary U uptake in
external dose rate determinations for ESR and luminescent dating. Quaternary
International 68-71, 329e343.
Blackwell, B.A.B., Skinner, A.R., Blickstein, J.I.B., Lebel, S., Leung, H.Y.M., 2001a. ESR
isochron analyses at Bau de lAubesier, Provence: Clues to U uptake in fossil
teeth. Geoarchaeology 16, 719e761.
Blackwell, B.A.B., Skinner, A.R., Blickstein, J.I.B., 2001b. ESR isochron exercises:
how accurately do modern dose rate measurements reect paleodose
rates? Quaternary Science Reviews (Quaternary Geochronology) 20,
1031e1039.
Blackwell, Bonnie, A.B., Liang, Sisi, Golovanova, Lubov, V., Doronichev, Vladimir, B.,
Skinner, Anne, R., Blickstein, Joel, I.B., 2005. ESR at Treugolnaya Cave, Northern
Caucasus Mt., Russia: Dating Russias Oldest Archaeological Site and Paleo-
climatic Change in Oxygen Isotope Stage 11. Applied Radiation and Isotopes 62,
237e245.
Churcher, C.S., Kleindienst, M.R., Schwarcz, H.P., 1999. Faunal remains from a Middle
Pleistocene lacustrine marl in Dakhleh Oasis, Egypt: paleoenvironmental
reconstructions. Palaeogeography, Palaeoclimatology, Palaeoecology 154,
301e312.
Dibble H.L., Goldberg P., McPherron S.P., Sandgathe D., Turq A. ROC DE MARSAL
(Campagne du Bugue, Dordogne): Rapport dopration pour lanne, 2009.
Falgures, C., Bahain, J.J., Yokoyama, Y., Arsuaga, J.L., Bermudez de Castro, J.M.,
Carbonell, E., Bischoff, J.L., Dolo, J.M., 1999. Earliest humans in Europe: the age
of TD6 Gran Dolina, Atapuerca, Spain. Journal of Human Evolution 37,
343e352.
Grn, R., McDermott, F., 1994. Open system modeling for U-series and ESR dating of
teeth. Quaternary Science Reviews 13, 121e125.
Joannes-Boyaun, Renaud, Grun, Rainer, Bodin, Thomas, 2010. Decomposition of the
laboratory gamma irradiation component of angular ESR spectra of fossil tooth
enamel fragments. Applied Radiation and Isotopes 68, 1798e1808.
Rowe, M.W., September 2010. Dating of Rock Paintings in the Americas: a Word of
Caution. IFRAO Congress. Symposium: Pleistocene art of the Americas
(Pre-Acts).
Rudko, V.V., Vorona, I.P., Baran, N.P., Ishchenko, S.S., Zatovsky, I.V., Chumakova, L.S.,
2010. Physically-based parameters: the mechanism of CO2- radical formation in
biological and synthetic apatites. Health Physics 98, 322e326.
Sronie-Vivien, M.R., Tillier, A.M., 2002. La dent humaine de Paradyrol (Caniac-du-
Causse, Lot) dans son contexte stratigraphique et palontologique. Palo 14,
257e264.
Skinner, A.R., Blackwell, B.A.B., Martin, S.A., Ortega, A.J., Blickstein, J.I.B.,
Golovanova, L.V., Doronichev, V.B., 2005. ESR dating at Mezmaiskaya Cave,
Russia. Applied Radiation and Isotopes 62, 219e224.
Skinner, A.R., Blackwell, B.A.B., Wrinn, Patrick J., Main, Abubakar, Baboumian, Shaunte,
Blickstein, J.I.B., Krivoshapakin, A.I., Derevianko, A.P., Lundburg, J.A., 2007. ESR
analyses on tooth enamel from Paleolithic layers of the Obi-Rakhmat hominid site,
Uzbekistan: tackling a dating controversy. Radiation Measurements 42,
1237e1242.