2918 Radiocarbon Dating /sources of Error

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2918 RADIOCARBON DATING/Sources of Error

Kutschera, W. (2005). Progress in isotope analysis at ultra-trace This uncertainty, or , is estimated in the error (stan-
level by AMS. International Journal of Mass Spectrometry. dard deviation or ) that is reported with a measured
242, 145–160.
McGeehin, J., Burr, G. S., Jull, A. J. T., Reines, D., Gosse, J.,
(estimated) 14C age. It is typically based on counting
Davis, P. T., and Muhs, D. (2001). Comparison of sediment statistics, but may also include components due to
dating techniques. Radiocarbon 43, 687–690. other laboratory corrections (e.g., error on fractiona-
McNichol, A. P., Jull, A. J. T., and Burr, G. S. (2001). Converting tion correction). In recent years, there have been
AMS data to radiocarbon values: considerations and conven- several publications where the use of a laboratory
tions. Radiocarbon 43, 313–320.
Purser, K. H., Liebert, R. B., and Russo, C. J. (1980). MACS – an
error multiplier has been introduced. Such an error
accelerator radioisotope measuring system. Radiocarbon 22, multiplier captures sources of variation in the esti-
794–806. mated 14C age that are not accounted for in the
Schroeder, J. B., Hauser, T. M., Klody, G. M., and Norton, G. A. quoted error.
(2004). Initial results with low energy single stage AMS. The interpretation of a single measured 14C age
Radiocarbon 46, 1–4.
Southon, J., Santos, G., Druffel-Rodriguez, K., Druffel, K.,
and its associated error, is as follows: we assume
Trumbore, S., Xu, X., Griffin, S., Ali, S., and Mazon, M. that the measured 14C age (an age estimate) is a
(2004). The Keck Carbon Cycle AMS Laboratory, University realization of a random Gaussian process with a
of California, Irvine: initial operation and a background sur- ‘true but unknown 14C age’ and  equal to the quoted
prise. Radiocarbon 46, 41–49. error. The best estimate of the true 14C age is the
Suter, M., Jacob, St, and Synal, H.-A. (1997). AMS of 14C at
low energies. Nuclear Instrum. Methods Phys. Res. B 123,
measured 14C age, but the true value is highly (95%)
148–152. likely to lie in the range:
Suter, M., Jacob, S. W. A., and Synal, H. A. (2000). Tandem AMS
at sub-MeV energies. Nuclear Instrum. Methods Phys. Res. B estimated radiocarbon age  2  quoted error:
172, 144–151.
Synal H-A, Stocker M, and Suter M (2005) MICADAS: A new
compact radiocarbon AMS system. Abstracts, 10th Traceability
International Conference on Accelerator Mass Spectrometry,
Berkeley, CA.
It is often important to be able to compare results
Tuniz, C., Bird, J. R., Fink, D., and Herzog, G. F. (1998). from different laboratories or from the same labora-
Accelerator Mass Spectrometry: Ultrasensitive Analysis for tory at different times. This is, in many cases,
Global Science. CRC Press, Bocan Raton. achieved by establishing a chain of calibrations to
primary, national, or international standards.
Traceability may be demonstrated through compar-
ison of measurement results on a certified reference
Sources of Error material, or through using an accepted procedure.
E M Scott, University of Glasgow, Glasgow, UK Frequently, numerous measurements are needed to
define reference materials. This can be achieved as
ª 2007 Elsevier B.V. All rights reserved.
one result of proficiency trials for laboratories or
laboratory round-robin/intercomparisons. For 14C
dating, the primary standard is 1890 wood, but the
Errors and Uncertainties in Radiocarbon reference material most closely associated (and often
Dating called the primary standard) is oxalic acid (NBS OxI
Since an estimated carbon-14 (14C) age, X, can be and NIST OxII). Additional secondary standards
considered as a realization of a random process (due have also been developed, including IAEA C1–C6.
to the nature of radioactive decay), we can consider a Such secondary standards (and further in-house
conceptual model which states that there is a true but reference materials) are measured on a routine
unknown14C age (often in statistical terminology called basis, providing in-house quality assurance.
a parameter, written as m), and that our estimated 14C We can now investigate the basis for this concep-
age can be modeled as a realization of a random vari- tual model more carefully and also some of common
able with expected value equal to the true age and measurement terms and descriptors that are used.
variance (or uncertainty) represented by a further
unknown parameter, 2. The commonly used probabil-
The Nature of Measurement
ity model for the 14C-dating process is the Gaussian or
normal model, defined by the mean which equals the and Uncertainty
true but unknown 14C age and the standard deviation All measurement is subject to uncertainty, which can
or measure of uncertainty. This is frequently written as: be considered to have two components, one resulting
from the analytical procedure and the other arising
X,Nðm; 2 Þ from the sample selection process. Every time an
RADIOCARBON DATING/Sources of Error 2919

analytical measurement is made we get a different Accuracy and Precision


result. Typically we cannot analyze the entire sample,
Measurements are routinely described as being accu-
it must be selected from the environment it is found
rate and/or precise.
in, it may not be fully representative (there may be
Accuracy is the closeness of agreement between a
some heterogeneity, i.e., slightly different 14C com-
measurement and the true or reference value. If we
position), so these sources of variation represent the
imagine a series of measurements, each with the same
uncertainty due to sampling. Often the emphasis in
true value, then if the average of the measurements
the laboratory is on the analytical uncertainty, since
does not equal (within error) the true value, then the
that is more readily quantified and modeled, but the
measurement is said to be biased, where the bias is
uncertainty due to sampling is equally important
the difference between the expected value or average
although more difficult to quantify.
of a large series of measurements and the true value.
An estimate of analytical uncertainty is frequently
Bias is usually considered to be systematic.
attached to a measurement (age estimate) and reflects
Precision is the closeness of agreement between a
the range of values within which the true value is
series of independent measurements obtained under
expected to lie. The uncertainty of a measurement
identical conditions. Precision depends on the distri-
describes the spread of values which might have been
bution of random errors, and is commonly computed
observed were the measurement repeated under
as the standard deviation of the results. As the stan-
IDENTICAL conditions. In such a case, the repeat
dard deviation increases, the precision decreases.
or replicate measurements will be different, and the
The archery targets in Figure 1 represent accurate
spread of values is often characterized by a standard
and precise, inaccurate and precise, accurate and
deviation, characterizing the precision of measure-
imprecise, inaccurate and imprecise measurement
ment but also the natural heterogeneity of the sample
from left to right, respectively. These and many
material in the field. To estimate the overall uncer-
other definitions can be found in the Royal Society
tainty, it may be necessary to estimate the individual
of Chemistry, Analytical Methods Committee (AMC)
components separately and then combine them using
Technical Brief No. 13, September 2003.
classical error propagation rules.

Uncertainty from Sampling


Measurement Uncertainty and Error
In the radiocarbon context, we can imagine that the
It is important to distinguish between uncertainty 14
C measurement is made on a small component of
and error: error is a single value defined below,
the whole sample (e.g., a few grains from a silo), or
uncertainty takes the form of a range.
that the archeological sampling from a midden
The error of a measurement, e, is the result of a
(which includes the materials to be dated), the secur-
measurement minus the true value and may include a
ity of the sampled materials in connection with the
random component and a systematic component. The
event being dated represent examples of uncertainty
error should always be reported with the measurement,
due to sampling. These examples also illustrate how
and the overall uncertainty is then often expressed as
difficult it is to quantify such uncertainty.
the interval ‘measurement  e’ or ‘measurement  2e’.
The actual meaning of such ranges in terms of confi-
dence or ‘plausibility’ depends on the stochastic model
Stochastic Models
(or probability distribution) chosen to model the ran-
dom error components. For a Gaussian model, the 1 There are many stochastic models, but the most
and 2 intervals represent approximately 67% and widely used (in 14C dating) is the Gaussian or normal
95% confidence, respectively. probability model.

Figure 1 Accuracy and precision.


2920 RADIOCARBON DATING/Sources of Error

The Gaussian probability model for a 14C The analytical estimate of t is provided by the
measurement X, is written as X , N(m, 2), where laboratory and will typically take into account the
m is the expected value of X and  is the standard analytical uncertainties on the individual compo-
deviation. nents which make up the conventional radiocarbon
Figure 2 shows 1,000 estimated ages (true age age.
5000 years before present (BP)), the Normal density The most basic form of the radiometric 14C age
function, with  ¼ 30 years. equation is:
 
l A0
t ¼ ln
Estimating m and s  At
The usual method of estimating m and  is based on a Where t ¼ sample age, which is the time that has
series of 14C measurements on the same material elapsed since removal of the carbonaceous material
made under identical conditions. Denoting these from the carbon cycle (e.g., death of an organism);
measurements by x1,. . . ,xn, then the estimate of m is  ¼ decay constant (ln2/t1=2) where t1=2 ¼ 5,568 years
the sample arithmetic average, and of , is s, the (Libby half-life); At ¼ the activity of the carbonac-
sample standard deviation. For the example above, eous material t years after death as measured in the
the average of all 1,000 results is 5,001 years (so we radiocarbon laboratory; and A0 ¼ ‘modern equili-
could claim the measurement is unbiased) and the brium living activity’ of the sample, again as mea-
sample standard deviation is 31 years. sured in the radiocarbon laboratory (Cook, 2005,
It is worth noting that the standard error of the this encyclopedia).
mean (s.e.m.) is a measure of precision associated A0 and At are measured in the laboratory and both
with the estimate of m and is defined as are corrected for fractionation effects. A0 is measured
pffiffiffi using standard materials (ideally NIST oxalic acid),
s= n; while At is the activity of the unknown sample. Both
will also be adjusted/corrected for background using
thus distinguishing it from the standard deviation.
samples of ‘infinite age’.
The analytical uncertainty for t will, therefore,
include uncertainty associated with modern stan-
Estimating Uncertainty
dards, background samples and fractionation. The
The conventional radiocarbon age is reported as t  t actual analytical uncertainty on t (as a function of
years BP where t represents the analytical uncertainty A0 and At) is again derived through a fairly simple error
on the measurement, as estimated by the laboratory propagation formula. However, it is also increasingly
and typically quantified as a standard deviation. common that laboratories will take a long series of

Histogram of age
Normal
140 Mean 5,001
StDev 30.69
N 1,000
120

100
Frequency

80

60

40

20

0
4,890 4,920 4,950 4,980 5,010 5,040 5,070
Age (years)

Figure 2 A Gaussian 14C model.


RADIOCARBON DATING/Sources of Error 2921

replicate measurements on a reference material and additional oxalic acid samples (now IAEA C7 and
assess the standard deviation of the set. If the stan- C8) (Le Clerq and van der Plicht, 1998). The activity
dard deviation is greater than the quoted errors on of these materials has been estimated from large
the individual estimated ages, then this would suggest numbers of measurements made by many labora-
an unaccounted source of variation and scientists tories. Recently, further natural materials from the
may chose to quote the larger of the standard devia- Third and Fourth International Radiocarbon
tion of the set and the individual quoted error, or Intercomparisons (TIRI; Gulliksen and Scott, 1995)
they may use an error multiplier approach. and FIRI (Bryant et al., 2000)) have been added to
this list. The activities of these standards and refer-
ence materials span both the applied 14C age range
How do we know Whether the Uncertainty and the chemical composition range of typical sam-
Estimate is Realistic? ples. A summary of the intercomparisons organized
within the 14C-dating community can be found in
Imagine a situation (known as repeatability condi-
Scott et al. (2003). The results from the most recent
tions) in which independent measurements are made
intercomparisons have indicated that laboratories are
on identical samples in the same laboratory, using the
generally providing accurate results, but pointed to
same equipment. Such a situation might commonly
variation in the results beyond that described by the
arise using reference materials (typically available in
quoted uncertainties. This provides some evidence
bulk), such as a large quantity of known-age wood. A
that the quoted errors are underestimates of the
laboratory will routinely prepare a large number of
laboratory precision for some laboratories. Figure 3
such samples, each with a measured age and uncer-
shows the results from FIRI (Scott, 2003) for one
tainty. If the uncertainty estimate is realistic, then the
such reference material; each horizontal line repre-
between-sample variation should be explained fully
sents the age 2 quoted by a laboratory. Such a plot
by the uncertainties on the individual measurements.
clearly shows the scatter in the results, but in addition
If this is not the case, it points to the fact that there
further analysis can reveal evidence of laboratory
are sources of error, contributing to the dispersion of
bias (if present) and also assess the reliability of
results, which have not been taken into account.
commonly quoted errors.
Another measure of whether the uncertainty esti-
Figure 4 shows the difference (offset) between a
mate is realistic can be obtained in a situation (know
laboratory’s result and the ‘true’ age (or consensus
as reproducibility conditions), where independent
value) evaluated from the FIRI intercomparison
measurements are obtained by the same method on
exercise (Scott, 2003). A small number of labora-
identical samples in different laboratories. Such a set
tories showed evidence of small but significant
of conditions is commonly encountered in a colla-
biases.
borative or proficiency trial.

Calibration
Interlaboratory Collaborative Trials
Conventional 14C ages are frequently converted to a
Proficiency testing is often used as a method for calibrated age (on the historical timescale). In radio-
assessing the accuracy of laboratories in conducting carbon terms, this means that we have a series of
particular measurements. It usually involves distri- independently known-age samples (such as tree-
buting ‘identical’ portions of the test material to rings), and in each sample, the 14C age is estimated.
each laboratory and analysis of the reported results, The relationship between the estimated age and the
which helps each laboratory assess the accuracy of true age is modeled and on the basis of the modeled
their measurement. relationship, a 14C age can be calibrated to AD/BC
The radiocarbon community has devoted consider- timescale. This relationship has been shown to be of
able care and effort to establishing and maintaining a complex, often nonlinear form which has signifi-
primary standards and reference materials and in the cant implications for the transformation of the mea-
routine organization of laboratory intercomparisons sured 14C age to a calibrated age (IntCal04). The
or collaborative trials to verify comparability of mea- error in years BP on the estimated 14C age must also
surements. From such a series of collaborative trials, undergo a transformation to give the corresponding
secondary standards or reference materials have been error on the calendar year scale. However, complex-
developed, including internationally recognized ities arise due to the complex pattern of 14C varia-
materials such as ANU-sucrose (now also known as tions. The simplest complication is that although we
IAEA-C6), Chinese-sucrose, and the IAEA C1–C6 often model the estimated 14C age using a Gaussian
series (Rozanski et al., 1992), augmented by model, once transformed or calibrated, the resulting
2922 RADIOCARBON DATING/Sources of Error

Distribution plot of Age +/- 2σ for dentro wood, D, (all laboratories)

78 69
70 67
56
16

100
39
68
22
13
47
20
29
72
43
48
20
60
58
32
81
64
52
51
25
25
23
80

59
9
1
61
72
28
37
51
27
15
37
1
82
63
55
Index of results

50
17
79
36
46
60

84
24
88
41
49
19
4
2
88
36
36
18
73
50
15
12
2
41
70 54
40

89
77
51
49
35
15
8
6
38
66
76
31
2
74
40
77
83
74
44
86
20

65
88
38
91
90
75
85
34
31
30
87
33
90
11
7
Age Values (+/–2σ).
71
42
5
5
57 +
10
0

4,000 4,200 4,400 4,600 4,800 5,000


Only Age results >4,000 shown
Age (BP)
Laboratory numbers given for each result
Figure 3 Distribution plot of ages from a collaborative trial. BP, before present.

500
400
300
200
Offset (years BP)

100
0
–100
–200
–300
–400
–500
–600

0 10 20 30 40 50 60 70 80 90 100
Laboratory identifier
Figure 4 Estimation of bias from a collaborative trial. BP, before present.

stochastic model for the calibrated age is no longer confidence intervals which can result in small, dis-
Gaussian, it is often multimodal and no longer sym- joint age ranges. The three most widely used calibra-
metric. The net effect is that often, the calibrated tion programs are Calib, BCal, and OxCal and an
result has a greater uncertainty. The most commonly example using OxCal is shown in Figure 5. The main
used calibration programs adopt a probabilistic use of the calibration program is for terrestrial sam-
approach, resulting in a calibrated-age probability ples, although special calibration data sets are avail-
distribution. Figure 5 shows a typical calibration of able for marine samples. All three programs are
a single 14C age. Commonly, probabilities are ranked based on the same internationally accepted calibra-
and summed to find the 68.3% (1) and 95.4% (2) tion data sets (IntCal04).
14
RADIOCARBON DATING/Variations in Atmospheric C 2923

Atmospheric data from Stuiver et al. (1998); OxCal v3.9 Bronk Ramsey (2003); cub r:4 sd:12 prob usp[chron]

3,900 BP
SUERC–4487 : 3,615±35BP

3,800 BP 68.2% probability


2030 BC (68.2%) 1910 BC
95.4% probability
3,700 BP
2130 BC ( 5.3%) 2080 BC
2040 BC (90.1%) 1880 BC
Radiocarbon determination

3,600 BP

3,500 BP

3,400 BP

2400 Cal BC 2200 Cal BC 2000 Cal BC 1800 Cal BC 1600 Cal BC

Calibrated date
Figure 5 Calibration of a 14C age. BP, before present.

Abbreviations Scott, E. M. (2003). The Third International Radiocarbon


Intercomparison (TIRI) and the Fourth International
BP before present Radiocarbon Intercomparison (FIRI), 1990–2002. Results,
14
C carbon-14 analyses, and conclusions. Radiocarbon 45, 135–408.
s.e.m. standard error of the mean

14
See also: Introduction: History of Dating Methods. Variations in Atmospheric C
Dating Techniques. Radiocarbon Dating: Conventional J van der Plicht, University of Groningen, Groningen,
Method; AMS Method. The Netherlands
ª 2007 Elsevier B.V. All rights reserved.

References
High-energy cosmic rays, mainly galactic and solar
Analytical Methods Committee (2003) Technical Brief No. 13,
September 2003. Part 1: Accuracy, Precision and Uncertainty.
protons, impinge on the Earth’s atmosphere. They
London: Royal Society of Chemistry. Available online at: http:// produce nuclear reactions, with spallation products
www.olinet.com/pdfs/R26_STATISTICS-TERMINOLOGY.pdf. and neutrons as the main constituents. The high-
Bryant, C., Carmi, I., Cook, G., et al. (2000). Sample requirements energy neutrons slow down by scattering and finally
and design of an inter-laboratory trial for radiocarbon labora- reach thermal energies. These thermal neutrons have
tories. NIMB 172, 355–359.
Gulliksen, S., and Scott, E. M. (1995). TIRI report. Radiocarbon
a large cross section for a nuclear reaction with nitro-
37, 820–821. gen, the main constituent of the atmosphere (78%):
14
IntCal04, 2004. Calibration issue. Radiocarbon 46. N(n,p)14C. Other reactions, such as 16O(p,3p) 14C
Le Clercq, M., van der Plicht, J., and Groening, M. (1998). New
14
and 16O(n,2pn)14C, are much less abundant. The 14C
C reference materials with activities of 15 and 50 pMC. nuclei produced are oxidized with atmospheric oxy-
Radiocarbon 40, 295–297.
Rozanski, K., Stichler, W., Gonfiantini, R., et al. (1992). The
gen to 14CO2 and hence become part of the ‘global
IAEA 14C inter-comparison exercise 1990. Radiocarbon 34, carbon cycle.’ Via photosynthesis in plants, 14C
506–519. enters the biosphere, which is in equilibrium with

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