Jull Et Al 2013 QI Reservoir Effect

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Quaternary International 299 (2013) 64e71

Contents lists available at SciVerse ScienceDirect

Quaternary International
journal homepage: www.elsevier.com/locate/quaint

Radiocarbon dating, reservoir effects, and calibration


A.J. Timothy Jull*, George S. Burr, Gregory W.L. Hodgins
NSF Arizona AMS Laboratory, University of Arizona, 1118 East Fourth St, Tucson, AZ 85721, USA

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

Article history: We summarize how radiocarbon measurements are made using accelerator mass spectrometry. We also
Available online 9 October 2012 discuss some complications inherent in the radiocarbon-dating method when calibrating radiocarbon
dates to calendar dates. For example, measurements of radiocarbon (14C) in some types of materials are
complicated by a “reservoir effect”, caused by an apparent age of the source reservoir that differs from
the contemporary atmospheric surface 14C value. In other cases, mobile carbon sources in nature can
produce mixed sources of carbon. We explore these effects and discuss their possible implications for 14C
measurements and how we can deal with them.
Ó 2012 Elsevier Ltd and INQUA. All rights reserved.

1. Introduction radiocarbon ages that are apparently older than coeval terrestrial
plant- or animal-derived material.
One of the most important aspects of the study of early humans
in America is geochronology. The dating of early humans in the
2. Accelerator mass spectrometry
New World has long been a subject of great debate. North American
anthropologists and archaeologists, until recently, favored the
AMS has become the dominant method for measurements of 14C
“Clovis First” model (Haynes, 1992, 2002; Holliday, 2000, 2009),
(radiocarbon, half-life 5730 yr), as well as other cosmogenic
where the oldest ages are approximately 12.8e13.1 ka (calibrated
radionuclides, such as 10Be, 36Cl and 26Al (Jull and Burr, 2006). The
age). This interpretation has recently been challenged by
technique is effective because it requires only a very small sample
apparently earlier dates at sites in Virginia (Lowery et al., 2010),
for radiocarbon dating. This is an important difference between this
Oregon (Gilbert et al., 2008), and most recently in Texas obtained by
method and earlier decay counting methods (Cook and van der
optically-stimulated luminescence (OSL), from 13.2 to 15.5 ka
Plicht, 2006). The number of atoms of the radionuclide in the
(Waters et al., 2011). These results still need confirmation by other
sample is measured directly, instead of waiting for individual
dating methods. Although some South American authors have
radioactive decay events. If we consider the radioactive decay
proposed even earlier dates, the consensus from well-established
equation, It is clear that it is more effective to measure atoms than
results fall within the time period from 13 to 15 ka, based on
decays:
radiocarbon dating, as the likely earliest arrival in South America
(Rothhammer and Dillehay, 2009). dN=dt ¼ lN (1)
The purpose of this paper to examine the potential caveats of
14
radiocarbon dating in an archaeological context, and identify Here, the number of atoms of C, N, is related directly to the rate
possible effects on the measurements that might lead to distortions of radioactive decay (dN/dt) through the decay constant, l. The 14C
in age determinations. We review the basis for Accelerator Mass decay rate is rate is 13.59 decays per minute per gram of C. In AMS,
Spectrometry (AMS) radiocarbon measurements and discuss how we typically measure a sample of 0.5 mg C, and we can count over
we calibrate results to convert radiocarbon ages into calendar ages. 120,000 atoms from a modern sample. If we take a counting rate of
We give examples of how reservoir effects can arise, particularly in 120,000 atoms in 1080 s, or 111 counts/second e from 0.5 mg of
marine samples, and how these can affect radiocarbon dates. These carbon, then this translates to 111  60/0.0005 ¼ 1.33  107 counts
instances include dating shell material, or dating animals or per minute per gram, a difference of 6 orders of magnitude in
humans who subsisted on a marine diet. This can result in sensitivity.
High sensitivity is achieved by accelerating sample atoms as
* Corresponding author. NSF Arizona AMS Laboratory, Department of Geo-
ions to high energies using a particle accelerator, and using nuclear
sciences, University of Arizona, 1118 East Fourth St, Tucson, AZ 85721, USA. particle detection techniques to quantify the number of 14C atoms
E-mail address: jull@email.arizona.edu (A.J.T. Jull). (Tuniz et al., 1998). Original designs of such equipment began in the

1040-6182/$ e see front matter Ó 2012 Elsevier Ltd and INQUA. All rights reserved.
http://dx.doi.org/10.1016/j.quaint.2012.10.028
A.J.T. Jull et al. / Quaternary International 299 (2013) 64e71 65

1980’s (Purser et al., 1980). Until the past 5 years or so, several animal remains. After physical inspection, samples are cleaned
million volts were typical for accelerator voltages. Today, AMS with addition of a small amount of 1 N HCl acid, 0.1% NaOH and
machines are increasingly compact, and measurements can be the sample is reacidified HCl (acid-base-acid, ABA pretreat-
made with as little as a few hundred kilovolts (e.g. Synal and ment), then washed with distilled water and dried. The dried
Wacker, 2010). There are 2 main suppliers of these machines: sample is then combusted at 900e1100  C with CuO. There are
National Electrostatics Corporation (Middleton, Wisconsin, USA) many nuances to the ABA method which require special
and High Voltage Engineering Europa (Amersfoort, the consideration on a case-by-case basis. For example, Hatté et al.
Netherlands). A summary of AMS methods is given by Jull and Burr (2001) identified potential contamination pathways in the ABA
(2006) and Burr and Jull (2009). pretreatment which can affect wood and paleosol dates and
A picture of the 3 MV AMS at the University of Arizona is shown suggested improvements to avoid them. Although charcoals
in Fig. 1 and a diagram of the design of the 3 MV AMS machine are widely regarded as an ideal material for dating, it has been
(based on an NEC accelerator) is shown in Fig. 2. In nearly all AMS shown that in some cases it is advisable to augment ABA
designs, the sample is converted to a solid (graphite), or introduced pretreatment using chromic acid (Bird et al., 1999). Rebollo
as a gas, into an ion source (Jull, 2006). The carbon is ionized by et al. (2008) examined chemical and structural changes in
bombardment with Csþ and the C ions produced are extracted charcoals pretreated with the ABA method, and by extension,
from the ion source, separated, and accelerated to high energies. natural charcoal degradation. They suggested several modifi-
The C ions pass through a stripper canal in the terminal of the cations to the ABA method based on their findings, including
accelerator (see Fig. 2) and lose electrons to become positively the use of weaker acids, eliminating the initial acid step,
charged. The charge state of carbon at the particle detector is treatment with distilled water, and agitation in the alkali step.
usually C3þ for 1e3 MV machines, and singly-charged Cþ for In another study, Ascough et al. (2011) found that for some
compact designs operating below 1 MV (e.g. Synal and Wacker, charcoals the alkali-soluble fraction normally removed from
2010). the charcoals may not be exogenous, but instead are degrada-
tion products of the charcoal itself.
2.1. Sample preparation 2. Carbonate samples are etched using 100% H3PO4 to remove
50e85% of the carbonate, dried and hydrolyzed with H3PO4 as
In order to measure a sample on the AMS, we first need to clean discussed by Burr et al. (1992).
the sample and convert it to a form usable in the machine. Some 3. For sediments, we often use selective combustion. After
basic procedures for AMS radiocarbon samples at Arizona were cleaning and drying the sample, it is combusted at 400  C in
summarized by Jull et al. (2004): w0.3 atm oxygen gas. This approach has been shown to limit
contamination from relatively old carbon, common in sedi-
1. The most basic of all pretreatments is the acid-base-acid ments (McGeehin et al., 2001).
cleaning method for treating a wide range of organic mate- 4. Textiles, parchment, canvas, art works and artifacts are given
rial, including: charcoal, wood, cellulose, plant material and the ABA pretreatment and after washing and drying, they are

Fig. 1. Picture of the 3 million volt accelerator mass spectrometer (AMS) at the University of Arizona. Photo credit: Lori Stiles, University of Arizona.
66 A.J.T. Jull et al. / Quaternary International 299 (2013) 64e71

Fig. 2. Diagram of the layout of the AMS system at the University of Arizona.

Soxhlet-extracted with hexane, followed by ethanol and finally laboratory (Donahue et al., 1990; Burr and Jull, 2009), we define the
methanol. After washing in distilled water, and drying, they are “fraction of modern carbon”, F:
combusted at up to 1100  C with CuO.
14
5. Iron artifacts are dated either by fusing the sample and C=13 C
S½25
extracting CO2, or by using wet-chemical techniques (Park Fð25Þ ¼ 14
(2)
et al., 2010). C=13 C
1950½25

Other types of samples have specialized pretreatments. Where the subscript S [25] refers to the sample renormalized to
After cleaning and combustion, samples are converted to a d13C value of 25&, and 1950 refers to the standards discussed
graphite by means of a catalytic decomposition reaction, using Fe as above, renormalized to 1950 AD, and d13C ¼ 19& for OXI
the catalyst and Zn as the reducing agent for the reaction 2CO / and 25& for OXII, or other secondary standards (Stuiver and
CO2 þ C. This step produces graphite powder that can be pressed Polach, 1977). An equivalent expression could be written using
into a target holder of Arizona design, now widely used in all NEC atomic ratios (N/N0), or activity ratios (decay rate, A/A0) for the
ion sources. The target material is pressed from both sides making sample and standard instead of the isotope ratio 14C/13C; in which
a 1 mm diameter column of graphite inside a 6 mm aluminum case N0 is the number of atoms at time zero, N is the number of
cylinder that fits into a target carousel that holds 32 or 40 targets. atoms remaining, t is time in years and l is the decay constant. We
could also substitute the isotopic ratio 14C/12C, or activity (A),
2.2. AMS measurement and calculations referenced to a zero-age value, 14C/12C0, or A0. All these values
would be normalized to d13C at 25&. It is important to point out
Measurements are made by comparing the count-rate of 14C that the decay constant l used here assumes a half-life of 5568
from a sample and rapidly switching to the stable isotope. We can years, giving a mean age (1/l) of 8033 years. To calculate an age the
then compare the isotopic ratio of the sample to a known standard. decay of 14C is written in terms of F as follows:
In the case of 14C, we use a primary (SRM-4990B, OXI) and
secondary (SRM-4990C, OXII) National Institute of Standards and Fð25Þ ¼ elt (3)
Technology (NIST) standard to determine radiocarbon dates. The
secondary standard is normalized to the consensus value of OXI. and rearranging this equation gives an expression for calculating
This material is no longer available, hence the use of OXII. The ratio the uncalibrated radiocarbon age of a sample:
of OX-II/OX-I is well-defined (Mann, 1983). Many other well-
established secondary standards are also available, which can be Age ¼ 8033 ln Fð25Þ (4)
referred back to the primary OXI value (see for example Scott et al.,
2007).
A basic assumption of radiocarbon dating is that we know the 2.3. Accuracy and precision
14
C age of the starting material when the sample was formed. This
forms the basis of the radioactive decay equation, which can be Burr et al. (2007) have summarized how the uncertainties in
expressed as a ratio of the number of atoms, the isotopic ratio radiocarbon dates are determined at the Arizona laboratory. These
relative to a stable isotope, or the activity (decay rate) ratio. In our include all sources of error, including counting statistics, error in
A.J.T. Jull et al. / Quaternary International 299 (2013) 64e71 67

the procedural blank and random machine error from the AMS a graphical model for this calculation, “The difference DR in reservoir
instrument. There are several potential pitfalls when considering age of the regional part of the ocean from which the users sample is
radiocarbon dating uncertainties. For example, radiocarbon dates derived, and the reservoir age of our model ocean, is determined
are quoted with one standard deviation uncertainties (by conven- through the use of figure 10A.”
tion), whereas calibrated radiocarbon dates are quoted at two Fig. 10A from Stuiver et al.’s paper shows a model of the oceanic
standard deviations. Often radiocarbon age uncertainties are pub- reservoir age and:
lished with no mention of how they were determined, and uncer-
tainties in reservoir corrections are often neglected. It is essential to DR ¼ Rmeasured  Rexp (9)
consider all sources of error and use appropriate statistical tech-
niques to quantify them.
Where Rmeasured is the R actually measured in the ocean water, and
Rexp is the expected value derived from the model of Stuiver and
2.4. Reservoir ages and D14C Braziunas (1993). Because this is not always easily established,
some authors report Rexp as the average oceanic value of R which is
For some samples, the initial value for modern (1950 AD) may 400 yrs (e.g. Cordero et al., 2003). So, the definition of DR (as
not be the same as the atmosphere. An excellent example is the opposed to R), depends on the oceanographic model used. By
case of the surface ocean. We know that there are offsets in marine default, this has come to be the marine model incorporated into the
samples (e.g. Dumond and Griffin, 2002; Braziunas et al. 1995) and calibration software, such as MARINE09. To avoid ambiguity, it is
there can also be offsets in other samples which are derived from therefore important that one reports the original values of R and
reservoirs (such as lakes) where the radiocarbon content of the D14C, which are not model-dependent.
carbon in the lake may not be “modern” (i.e. at the level of A0). Age
offsets of this type can be quantified in terms of the difference
between the radiocarbon content of the reservoir and contempo- 3. Radiocarbon reservoir effects
rary atmosphere. This is the age-corrected D14C value. For sample
prior to 1950 AD, D14C is defined as: The concept that there are different 14C values for different
  reservoirs has been recognized for a long time (Stuiver and Ostlund,
D14 C ¼ 1000 F elðaÞ  1 & (5) 1980). Stuiver et al. (1986) proposed the first marine radiocarbon
age calibration curve. Many studies have been conducted to
understand the differences in 14C composition among marine
Where a is the absolute age of the material in years before 1950 AD
samples (e.g. Broecker, 1963) and subsequent work related climate
(often stated as years BP in radiocarbon literature), determined
change to changes in the radiocarbon budget of the ocean (Broecker
independently.
et al., 1984, 1988; Thornalley et al., 2011). For a typical marine
A somewhat different situation arises is the sample contains
sample, there are 2 possible situations: 1) We know the actual time
bomb 14C. In this case, the true D14C should be corrected for the
of formation of a sample, either by association with a sample which
decay of the standard, as the standard has some age relative to the
measures the atmospheric age (e.g. plant material), or 2) we do not
material being studied. In this case, the value of F should be
know the exact age of the sample. In other cases (e.g. Jones et al.,
increased to get the absolute value by correcting for the time
2010) it is possible to know the actual time t, however, it is more
between the manufacture of the standard (astd) and the time of
usual that the true atmospheric age Atm(t) is not known. In this
collection of the sample (a). For OX-I, astd is 1957 AD and for OX-II,
case, it has become common to use a model-dependent value for
astd is 1977 AD.
Atm(t). This model is taken from the marine-reservoir model of
  Stuiver and Braziunas (1993) and is also incorporated into the
D14 C ¼ 1000 F elðaastd Þ  1 & (6)
current Marine09 calibration curve.
Marine effects. The marine reservoir age was defined by Stuiver
et al. (1986) as the difference between the measured radiocarbon 3.1. Speleothem dead carbon fraction
age and the atmospheric age determined independently at a known
time (t): There have been a number of attempts to use the 14C content of
speleothems and compare them to other dating methods, such as
RðtÞ ¼ 14
C age of marine sample UeTh, in order to derive information for a calibration curve. One
drawback of this approach is that speleothem carbonate also
 14 C age of atmospheric sample (7) incorporates old carbon from the soil, through which the waters
This correction factor can be determined directly from coexist- from which the carbonate precipitated have passed. Since the dis-
ing marine and terrestrially-derived plant material at a given site. solved inorganic carbon (DIC) in these waters also incorporates soil
The value of R can be related to D14C by the equation (Burr et al., carbon sources, the value of “modern” is not F ¼ 1.0.
2009): Genty and Massault (1999) developed a model to explain the
incorporation of “old” carbon into speleothem carbonate.
0 1 Fohlmeister et al. (2011) define a more complex model with three
D14 Catm
B 1000 þ 1C source components of carbon e the atmosphere, a “fast” reservoir
R ¼ 8033 lnB
@ 14
C
A (8) and a “slow” reservoir, which showed that the resulting “dead
D Cmar
þ1 carbon fraction” (DCF) should be relatively constant and in agree-
1000 ment with empirical corrections observed of about 12e15% (Genty
and Massault, 1997; Beck et al., 2001).
Vogel and Kronfeld (1997) and Beck et al. (2001) used this
2.5. DR and R information to establish a speleothem “calibration curve”, which
required a “dead carbon fraction” (DCF) correction. This correction
Finally, Stuiver et al. (1986) also introduced the concept of DR. It is usually applied as a constant offset of the fraction of modern
is important to understand the definition of DR, as they defined it as carbon for the site. This assumption appears to be somewhat
68 A.J.T. Jull et al. / Quaternary International 299 (2013) 64e71

arbitrary, but apparently works well in many cases (e.g. Southon ecosystem and attributed as much as 15e40% of the carbon in the
et al., 2011). In this case, the fraction of modern is adjusted as wood to uptake from a natural CO2 spring. Other small effects
follows: have been observed. Damon (1995) and McCormac et al. (1995)
also discuss suggest small possible differences in 14C at different
Fcorrected ¼ Fspeleothem þ DCF (10) locations between 4 and 7& (33e58 yr).

3.5. Examples of marine reservoir effects


where Fspeleothem is the measured value on the speleothem and DCF
is determined empirically or with a model.
The reservoir effect can arise in marine samples for a number of
reasons. The 14C content of the mixed layer of the ocean is an
3.2. Suess effect indication of the degree of exchange between the atmosphere and
the surface ocean, and also of upwelling from deeper layers
A final type of deviation from the expected value of “modern” (Toggweiler et al., 1993). In some regions, such as the west coast of
can arise from collection of 14C samples in areas affected by South America, we can observe large fluctuations due to upwelling
industrial or urban CO2. Although not relevant to archaeological of old carbon from the deeper ocean (e.g. Jones et al., 2009, 2010).
sampling in general (except in the industrial era, where there are Reimer and McCormac (2002) studied pre-bomb shells from the
other problems with 14C), this results in a depression of D14C due to Mediterranean Sea, which showed values of R ranging from about
the input of fossil-fuel derived carbon into the atmosphere. For 380 to 650 14C years. An example of a region with 14C close to the
example, a sample of plants collected on the University of Arizona mean sea-water value is a coral from South Vietnam, Con Dao
campus will be depressed in 14C by about D14C of 10 per mil island, that shows pre-bomb 14C values of 401e458 14C years (Dang
relative to a sample collected in a pristine area. et al., 2004).
As noted by Cordero et al. (2003), remains of sea organisms in
3.3. Soil carbon coastal sites can be abundant. It is important to know that the local
reservoir effect, R, may not be well-defined. Cordero et al. (2003)
Another type of reservoir effect arises in soils. Certain fractions compared terrestrial plant material to mollusks. In this case, the
of soils can store carbon for long periods of time, and this carbon authors assumed the oceanic average R value when calculating DR
may be isolated from the biological processes occurring in the soil A in their paper. Their observations are important because they
horizon. Hence, samples of soil clay fractions in particular can have emphasize the ambiguity of DR and the need for local calibration
substantial radiocarbon ages of thousands of radiocarbon years. (e.g. Dye, 1994; Ingram and Southon, 1996; Southon et al., 1999). In
Trumbore (2000) and Becker-Hiedemann and Scharpenseel (1992) addition, material from sites close to the southern ocean may have
discuss this extensively. It is important to emphasize here that the increasingly depleted values of 14C, and hence, large values of R.
concept of a “reservoir effect” differs from the apparent mean Angulo et al. (2007) note that the R value measured at archaeo-
residence time (AMRT) of carbon in soils. logical sites in southeastern Brazil showed evidence for large
variations from 281  44 to 1083  51 14C BP, due to effects of
3.4. Atmospheric reservoir effects seasonal upwelling from the South Atlantic.
Polar sites typically have higher values of R, with a larger 14C
It is well-known that there is an offset of radiocarbon ages offset. Dumond and Griffin (2002) discussed some examples of
determined in the Southern Hemisphere, from about 8 to 80 years, reservoir effects between co-existing plant and Walrus ivory from
as compared with the Northern Hemisphere. An intensive the Bering Sea, which gave R values of 514  57e720  53 14C
measurement program has been conducted to produce a calibra- years, and whale bone and wood, which gave R values ranging
tion curve for the Southern Hemisphere (McCormac et al., 2004). from 308 to 828  126 14C years. Berkman and Forman (1996)
Measured offsets between the two hemispheres are incorporated discuss radiocarbon reservoir effects observed in pre-bomb
into the latest version of INTCAL09 (Reimer et al., 2009). It is shells which ranged from 1300  84 before 1950 AD to about 500
important for Southern Hemisphere studies to be aware of this years less after 1950 AD. Recently, Negrete et al. (2011) observed
resource. an apparent reservoir age of w1300 years from a recently-
On a regional scale, atmospheric radiocarbon offsets, or local deceased seal. To give an example of these effects, we have
reservoir effects, may result from CO2 sources. For example, Saurer summarized available reservoir offsets, R, for a number of South
et al. (2003) observed offsets in d13C in trees in a Mediterranean American sites in Table 1.

Table 1
Some marine reservoir ages observed in South America.

Location R (yr) Material Reference


Quebrada de los Burros Peru 520  135e1290  144 yr Coexisting charcoal and shells Fontugne et al., 2004
Quebrada Jaguay Peru 200  110e730  170 yr Coexisting charcoal and shells Jones et al., 2010
Callao Bay; Sechura Bay; Salaverry Peru 504  80e819  56 Pre-bomb shells Jones et al., 2009
Northern Chile/Southern Peru coast 511  278e226  98 Coexisting charcoal and shells Ortlieb et al., 2011
Northern Chilean coast Chile 540  80 Coexisting marine and terrestrial Southon et al., 1995
material
Jabuticabeira, Santa Catarina Brazil 220  20 yre510  10 yr Eastoe et al., 2002
Ponta das Canas & Ilha do Francês, Brazil 320  44e621  46 Pre-bomb shells Angulo et al., 2005
Santa Catarina
Ilha do Mel, Parana Brazil 345  42e430  42 Pre-bomb shells Angulo et al., 2005
Tunel, Beagle channel Argentina 620  140e556  61 Coexisting materials Albero et al., 1986
Coastal sites from Punta Norte to Argentina 480  35e1520  180 Coexisting plants and mollusks Cordero et al., 2003
Beagle Channel1
Northeastern coast Argentina 269  41e2802  41 Live mollusk shells Gomez et al., 2008
A.J.T. Jull et al. / Quaternary International 299 (2013) 64e71 69

4. Calibration of the radiocarbon time scale 5. Conclusions

Libby (1955), the originator of radiocarbon dating, was the first The diversity of radiocarbon dating samples and the types of
to note that radiocarbon ages diverged from the “true” calendar measurements that can be undertaken in a given situation must be
age with his famous “Curve of Knowns”. Since about 1980, a vast considered in light of the numerous effects that can influence their
amount of time and energy has been devoted by scientists in the radiocarbon content. In the optimal case, radiocarbon dates give
field of radiocarbon dating to calibration of the radiocarbon time- robust age estimates, but under certain circumstances they can be
scale (Damon et al., 1980). This eliminated a growing discord of misleading if secondary effects are not thoroughly understood. It is
different methodologies for calibration of radiocarbon dates. This therefore necessary to study and understand potential effects in
work has resulted in a series of publications, which have estab- detail in order to correct for them, and to quantify uncertainties
lished a common radiocarbon time scale by the cross-reference of associated with them.
the measured “radiocarbon age” against material of known age.
The known-age material was originally restricted to tree rings, Acknowledgments
but has been extended to include UeTh dated corals (Stuiver,
1993) and varved marine sediment records from the Cariaco We thank our colleagues at the University of Arizona for helpful
Basin (Stuiver and van der Plicht, 1998). The International Cali- discussions. Dr. Jull thanks the organizers of the La Plata sympo-
bration team (known as IntCal) has established strict protocols for sium for their hospitality and partial support of travel to the
what kind of data is acceptable for inclusion in the calibration conference.
database. In The IntCal09 calibration dataset is incorporated into
a number of computer programs, such as Calib 5.1 (www.calib.
References
org) (Table 2).
Albero, M.C., Angiolini, F.E., Piana, E.L., 1986. Discordant ages related to reservoir
effect of associated archaeologic remains from the Tunnel site, Beagle Channel,
Table 2 Argentine Republic. Radiocarbon 28, 748e753.
Publications of the International Radiocarbon Calibration. Angulo, R.J., de Souza, M.C., Reimer, P.J., Sasaoka, S.K., 2005. Reservoir effect of the
southern and southeastern Brazilian coast. Radiocarbon 47 (1), 67e73.
First Special Calibration Issue Stuiver and Kra, 1986. Angulo, R.J., Reimer, P.J., de Souza, M.C., Scheel-Ybert, R., Tenório, M.C., Disaró, S.T.,
Calibration 1993 Stuiver, 1993. Gaspar, M.D., 2007. A tentative determination of upwelling influence on the
INTCAL98: Calibration Issue Stuiver and van der Plicht, 1998. paleosurficial marine water reservoir effect in southeastern Brazil. Radiocarbon
INTCAL04: Calibration Issue Reimer et al., 2004. 49 (3), 1255e1259.
INTCAL09: Calibration Issue Reimer et al., 2009. Ascough, P.L., Bird, M.I., Francis, S.M., Lebl, T., 2011. Alkali extraction of archaeo-
logical and geological charcoal: evidence for diagenetic degradation and
formation of humic acids. Journal of Archaeological Science 38, 69e78.
Bard, E., Hamelin, B., Fairbanks, R.G., Zindler, A., 1990. Calibration of the 14C time-
scale over the past 30,000 years using mass spectrometric UeTh ages from
The records eventually included in the most recent INTCAL09 Barbados corals. Nature 345, 405e410.
volume (Radiocarbon, 52, no. 4) include tree ring data, coral data Bard, E., Arnold, M., Fairbanks, R.G., Hamelin, B., 1993. 230The234U and 14C ages
obtained by mass-spectrometry on corals. Radiocarbon 35 (1), 191e199.
(e.g. Bard et al., 1990, 1993, 1998; Burr et al., 1998; Fairbanks Bard, E., Arnold, M., Hamelin, B., Tisnerat-Laborde, N., Cabioch, G., 1998. Radio-
et al., 2005) and perhaps more controversially, varved sedi- carbon calibration by means of mass spectrometric 230Th/234U and 14C ages of
ments from the Cariaco Basin (Hughen et al., 1998). The decision corals: an updated database including samples from Barbados, Mururoa and
Tahiti. Radiocarbon 40 (3), 1085e1092.
to include the Cariaco sediment record was explained by Stuiver Bard, E., Rostek, F., Menot-Combes, G., 2004. Radiocarbon calibration beyond 20,000
and van der Plicht (1998) as follows: “In addition, as an exception C-14 yr BP by means of planktonic foraminifera of the Iberian Margin.
to the rule, it was decided to include Late Glacial marine varves Quaternary Research 61 (2), 204e214.
Beck, J.W., Richards, D.A., Edwards, R.L., Silverman, B.W., Smart, P.L., Donahue, D.J.,
because this newly developed dataset strengthened the coral/
Herrera Osterheld, S., Burr, G.S., Calsoyas, L., Jull, A.J.T., Biddulph, D., 2001.
tree ring link considerably”. Recently, some authors have sug- Extremely large variations of atmospheric 14C concentration during the last
gested that the varve chronology may deviate from the coral glacial period. Science 292, 2453e2458.
Becker-Hiedemann, P., Scharpenseel, H.W., 1992. Studies of soil organic-matter
chronology at some points in the late Pleistocene (e.g. Southon
dynamics using natural carbon isotopes. Science of the Total Environment
et al., 2011). 118, 305e312.
Coral records appear to have wide acceptance as proxy records Berkman, P.A., Forman, S.L., 1996. Pre-bomb radiocarbon and the reservoir correc-
of atmospheric 14C at a given time, but even this might be tion for calcareous marine species in the Southern Ocean. Geophysical Research
Letters 23 (4), 363e366.
a problem. Since corals sample bicarbonate in the surface ocean, Bird, M.I., Ayliffe, L.K., Fifield, L.K., Turney, C.S.M., Cresswell, R.G., Barrows, T.T.,
not the atmosphere directly, one needs to make a reservoir David, B., 1999. Radiocarbon dating of “old” charcoal using a wet oxidation,
correction, often assumed to be around 400 yrs (e.g. Fairbanks, stepped-combustion procedure. Radiocarbon 41 (2), 127e140.
Braziunas, T.F., Fung, I.Y., Stuiver, M., 1995. The preindustrial atmospheric 14CO2
1989). Recent studies such as Fairbanks et al. (2005) and the latitudinal gradient as related to exchanges among atmospheric, oceanic and
compilation of Hughen et al. (2004) make site-specific reservoir terrestrial reservoirs. Global Biogeochemical Cycles 9 (4), 565e584.
corrections. This is an improvement, however these values are Broecker, W.S., Mix, A., Andrée, M., Oeschger, H., 1984. Radiocarbon measurements
on coexisting benthic and planktic foraminifera shells: potential for recon-
taken as constants and Pleistocene marine reservoir ages from struction ocean ventilation times over the past 20,000 years. Nuclear Instru-
a given site are known to vary by hundreds of years in some cases ments and Methods in Physics Research B 5, 331e339.
(Burr et al., 2009), so that more work needs to be done to quantify Broecker, W., Klas, M., Raganobeavan, N., Mathieu, G., Mix, A., Andree, M.,
Oeschger, H., Wolfli, W., Suter, M., Bonani, G., Hofmann, H.J., Nessi, M.,
marine reservoir age corrections in space and time. Morenzoni, E., 1988. Accelerator mass-spectrometry radiocarbon measure-
Many other geologic proxy records have been studied with the ments on marine carbonate samples from deep-sea cores and sediment traps.
intent of extending the radiocarbon calibration curve. These Radiocarbon 30 (3), 261e295.
Broecker, W.S., 1963. 14C/12C raios in surface ocean water. In: Nuclear Geophysics.
include studies of marine sediments (e.g. Voelker et al., 2000), lake
National Academy of Sciences-National Research Council Publication, p. 1075.
sediment records (Kitagawa and van der Plicht, 1998), speleothems Burr, G.S., Jull, A.J.T., 2009. Accelerator mass spectrometry for radiocarbon research.
(Beck et al., 2001), Lake Lisan sediments (Schramm et al., 2000) and In: Gross, M.L., Caprioli, R. (Eds.), Encyclopedia of Mass Spectrometry, vol. 5.
records of Atlantic foraminifera (Bard et al., 2004). These records Elsevier, Amsterdam, pp. 656e669.
Burr, G.S., Edwards, R.L., Donahue, D.J., Druffel, E.R.M., Taylor, F.W., 1992. Mass
are not currently included in the INTCAL datasets, although this spectrometric 14C and UeTh measurements in coral. Radiocarbon 34 (3),
may be reassessed in the near future. 611e618.
70 A.J.T. Jull et al. / Quaternary International 299 (2013) 64e71

Burr, G.S., Beck, J.W., Taylor, F.W., Récy, J., Edwards, R.L., Cabioch, G., Corrège, T., Ingram, B.L., Southon, J.R., 1996. Reservoir ages in eastern Pacific coastal and
Donahue, D.J., O’Malley, J.M., 1998. A coral-based radiocarbon calibration estuarine waters. Radiocarbon 38 (3), 573e582.
between 11,700 and 12,400 calendar years BP derived from 230Th ages of corals Jones, K.B., Hodgins, G.W.L., Etayo-Cadavid, M.F., Andrus, C.F.T., 2009. Upwelling
from Espiritu Santo Island, Vanuatu. Radiocarbon 40 (3), 1093e1105. signals in radiocarbon from early 20th-century Peruvian bay scallop (Argo-
Burr, G.S., Donahue, D.J., Tang, Y., Beck, J.W., McHargue, L., Biddulph, D., Cruz, R., pecten purpuratus) shells. Quaternary Research 72, 452e456.
Jull, A.J.T., 2007. Error analysis at the NSF-Arizona AMS Facility. Nuclear Jones, K.B., Hodgins, G.W.L., Etayo-Cadavid, M.F., Andrus, C.F.T., Sandweiss, D.H., 2010.
Instruments and Methods in Physics Research B 259, 149e153. Centuries of marine radiocarbon reservoir age variation within archaeological
Burr, G.S., Beck, J.W., Corrège, Cabioch, G., Taylor, F.W., Donahue, D.J., 2009. Modern Mesodesma danacium shells from southern Peru. Radiocarbon 52 (2), 1207e1214.
and Pleistocene reservoir ages inferred from the south Pacific. Radiocarbon 51 Jull, A.J.T., Burr, G.S., 2006. Accelerator mass spectrometry: is the future bigger or
(1), 319e335. smaller? Earth and Planetary Science Letters 243, 305e325.
Cook, G.T., van der Plicht, J., 2006. Radiocarbon dating: conventional method. In: Jull, A.J.T., Burr, G.S., McHargue, L.R., Lange, T.E., Lifton, N.A., Beck, J.W., Donahue, D.J.,
Elias, S. (Ed.), Encyclopedia of Quaternary Science. Elsevier, Amsterdam, 2004. New frontiers in dating of geological, paleoclimatic and anthropological
pp. 2899e2911. applications using accelerator mass spectrometric measurements of 14C and 10Be
Cordero, R.R., Panarello, H., Lanzelotti, S., Favier Dubois, C.M., 2003. Radiocarbon age in diverse samples. Global and Planetary Change 41, 309e323.
offsets between living organisms from the marine and continental reservoir in Jull, A.J.T., 2006. Radiocarbon dating: AMS method. In: Elias, S. (Ed.), Encyclopedia of
coastal localities of Patagonia(Argentina). Radiocarbon 45, 9e15. Quaternary Science. Elsevier, Amsterdam, pp. 2911e2918.
Damon, P.E., Lerman, J.C., Long, A., Bannister, B., Klein, J., Linick, T., 1980. Report of Kitagawa, H., van der Plicht, J., 1998. Atmospheric radiocarbon calibration to 45,000
the workshop on the calibration of the radiocarbon dating time scale. Radio- yr BP: late glacial fluctuations and cosmogenic isotope production. Science 279
carbon 22 (5), 947e949. (5354), 1187e1190.
Damon, P.E., 1995. Note concerning “Intercomparison of high-precision 14C Libby, W.F., 1955. Radiocarbon Dating, second ed. University of Chicago Press,
measurements at the University of Arizona and the Queen’s University of Bel- Chicago.
fast radiocarbon laboratories” by Kalin et al. (1995) and the regional effect. Lowery, D., O’Neal, M.A., Wah, J.S., Wagner, D.P., Stanford, D.J., 2010. Late Pleistocene
Radiocarbon 37 (3), 955e959. upland stratigraphy of the western Delmarva Peninsula, USA. Quaternary
Dang, P.X., Mitsuguchi, T., Kitagawa, H., Shibata, Y., Kobayashi, T., 2004. Marine Science Reviews 29 (11e12), 1472e1480.
reservoir correction in the south of Vietnam estimated from an annually- Mann, W.B., 1983. An international reference material for radiocarbon dating.
banded coral. Radiocarbon 46 (2), 657e660. Radiocarbon 25 (2), 519e527.
Donahue, D.J., Linick, T.W., Jull, A.J.T., 1990. Isotope-ratio and background correc- McCormac, F.G., Baillie, M.G.L., Pilcher, J.R., Kalin, R.M., 1995. Location-dependent
tions for accelerator mass spectrometry radiocarbon measurements. Radio- differences in the 14C content of wood. Radiocarbon 37 (2), 395e407.
carbon 32 (2), 135e142. McCormac, F.G., Hogg, A.G., Blackwell, P.G., Buck, C.E., Higham, T.F.G., Reimer, P.J.,
Dumond, D.E., Griffin, D.G., 2002. Measurements of the marine reservoir effect on 2004. SHCAL04 Southern hemisphere calibration, 0e11.0 cal ka BP. Radiocarbon
radiocarbon ages in the eastern Bering Sea. Arctic 55, 77e86. 46 (3), 1087e1092.
Dye, T., 1994. Apparent ages of marine shells e implications for archaeological McGeehin, J., Burr, G.S., Jull, A.J.T., Reines, D., Gosse, J., Davis, P.T., Muhs, D.,
dating in Hawaii. Radiocarbon 36 (1), 51e57. Southon, J., 2001. Stepped-combustion 14C dating of sediment. Radiocarbon 43
Eastoe, C.J., Fish, S., Fish, P., Gaspar, M.D., Long, A., 2002. Reservoir corrections for (2A), 255e262.
marine samples from the south Atlantic coast, Santa Catarina State, Brazil. Negrete, J., Soilbelzon, E., Tonni, E.P., Carlini, A., Soibelzon, L.H., Poljak, S.,
Radiocarbon 44 (1), 145e148. Huarte, R.A., Carbonari, J.E., 2011. Antarctic radiocarbon reservoir: the case of
Fairbanks, R.G., Mortlock, R.A., Chiu, T.C., Cao, L., Kaplan, A., Guilderson, T.P., the mummified crabeater seals (Lobodon carcinophaga) in Bodman Cape, Sey-
Fairbanks, T.W., Bloom, A.L., Grootes, P.M., Nadeau, M.J., 2005. Radiocarbon mour Island, Antarctica. Radiocarbon 53 (1), 161e166.
calibration curve spanning 0 to 50,000 years BP based on paired Ortlieb, L., Vargas, G., Saliège, J.F., 2011. Marine radiocarbon reservoir effect along
230
Th-/234U/238U and 14C dates on pristine corals. Quaternary Science Reviews the northern Chileesouthern Peru coast (14e24 S) throughout the Holocene.
24 (16e17), 1781e1796. Quaternary Research 75, 91e103.
Fairbanks, R.G., 1989. A 17,000-year glacio-eustatic sea-level record e influence of Park, J.S., Burr, G.S., Jull, A.J.T., 2010. A thermal and acid treatment for carbon
glacial melting rates on the Younger Dryas event and deep-ocean circulation. extraction from cast iron and its application to AMS dating of cast iron objects
Nature 342 (6250), 637e642. from ancient Korea. Radiocarbon 52 (3), 1312e1321.
Fohlmeister, J., Kromer, B., Mangini, A., 2011. The influence of soil organic matter age Purser, K.H., Liebert, R.B., Russo, C.J., 1980. MACS e an accelerator-based radioiso-
spectrum on the reconstruction of atmospheric 14C levels via stalagmites. tope measuring system. Radiocarbon 22 (3), 794e806.
Radiocarbon 53 (1), 99e115. Rebollo, N.T., Cohen-Ofri, I., Popovitz-Biro, R., Bar-Yosef, O., Meignen, L., Goldberg, P.,
Fontugne, M., Carré, M., Bentaleb, I., Julien, M., Lavallée, D., 2004. Radiocarbon Weiner, S., Boaretto, E., 2008. Structural characterization of charcoal exposed to
reservoir age variations in the south Peruvian upwelling during the Holocene. high and low pH: implications for 14C sample preparation and charcoal pres-
Radiocarbon 46 (2), 531e537. ervation. Radiocarbon 50 (2), 289e307.
Genty, D., Massault, M., 1997. Bomb 14C recorded in laminated speleothems: Reimer, P.J., McCormac, F.G., 2002. Marine radiocarbon reservoir corrections for the
calculation of dead carbon proportion. Radiocarbon 39 (1), 33e48. Mediterranean and Aegean seas. Radiocarbon 44 (1), 159e166.
Genty, D., Massault, M., 1999. Carbon transfer dynamics from bomb-14C and d13C Reimer, P.J., Baillie, M.G.L., Bard, E., Bayliss, A., Beck, J.W., Bertrand, C.J.H.,
time series of a laminated stalagmite from SW France e modelling and Blackwell, P.G., Buck, C.E., Burr, G.S., Cutler, K.B., Damon, P.E., Edwards, R.L.,
comparison with other stalagmite records. Geochimica et Cosmochimica Acta Fairbanks, R.G., Friedrich, M., Guilderson, T.P., Hogg, A.G., Hughen, K.A.,
63 (10), 1537e1548. Kromer, B., McCormac, G., Manning, S., Ramsey, C.B., Reimer, R.W., Remmele, S.,
Gilbert, M.T.P., Jenkins, D.L., Gotherstrom, A., Naveran, N., Sanchez, J.J., Hofreiter, M., Southon, J.R., Stuiver, M., Talamo, S., Taylor, F.W., van der Plicht, J.,
Thomsen, P.F., Binladen, J., Higham, T.F.G., Yohe, R.M., Parr, R., Cummings, L.S., Weyhenmeyer, C.E., 2004. IntCal04 Terrestrial radiocarbon age calibration, 0e
Willerslev, E., 2008. DNA from pre-Clovis human coprolites in Oregon, North 26 ka cal BP. Radiocarbon 46 (3), 1029e1058.
America. Science 320 (5877), 786e789. Reimer, P.J., Baillie, M.G.L., Bard, E., Bayliss, A., Beck, J.W., Blackwell, P.G., Bronk
Gomez, E.A., Brel, C.M., Aguirre, M.L., Martinez, D.E., 2008. Radiocarbon reservoir Ramsey, C., Buck, C.E., Burr, G.S., Edwards, R.L., Friedrich, M., Grootes, P.M.,
ages and hardwater effect for the northeastern coastal waters of Argentina. Guilderson, T.P., Hajdas, I., Heaton, T.J., Hogg, A.G., Hughen, K.A., Kaiser, K.F.,
Radiocarbon 50 (1), 119e129. Kromer, B., McCormac, F.G., Manning, S.W., Reimer, R.W., Richards, D.A.,
Hatté, C., Morvan, J., Noury, C., Paterne, M., 2001. Is classical acid-alkali-acid Southon, J.R., Talamo, S., Turney, C.S.M., van der Plicht, J., Weyhenmeyer, C.E.,
treatment responsible for contamination? An alternative proposition. Radio- 2009. INTCAL09 and MARINE09 radiocarbon age calibration curves, 0e50,000
carbon 43 (2A), 177e182. cal BP. Radiocarbon 51 (4), 1111e1150.
Haynes, C.V., 1992. Contributions of radiocarbon dating to the geochronology of the Rothhammer, F., Dillehay, T.D., 2009. The late Pleistocene colonization of South
peopling of the New World. In: Taylor, R.E., Long, A., Kra, R.S. (Eds.), Radiocarbon America: an interdisciplinary perspective. Annals of Human Genetics 73, 540e549.
Dating after Four Decades: an Interdisciplinary Perspective. Springer-Verlag, Saurer, M., Cherubini, P., Bonani, G., Siegwolf, R., 2003. Tracing carbon uptake from
New York, pp. 355e374. a natural CO2 spring into tree rings: an isotope approach. Tree Physiology 23,
Haynes, C.V., 2002. The Early Settlement of North America: the Clovis Era. Cam- 997e1004.
bridge University Press, Cambridge. Schramm, A., Stein, M., Goldstein, S.L., 2000. Calibration of the 14C time scale to >40
Holliday, V.T., 2000. The evolution of paleoindian geochronology and typology on ka by 234Ue230Th dating of Lake Lisan sediments (last glacial Dead Sea). Earth
the Great Plains. Geoarchaeology 15, 227e290. and Planetary Science Letters 175 (1e2), 27e40.
Holliday, V.T., 2009. Geoarchaeology and the search for the first Americans. Catena Scott, E.M., Cook, G.T., Naysmith, P., Bryant, C., O’Donnell, D., 2007. A report on phase
78, 310e322. I of the 5th International Radiocarbon Intercomparison (VIRI). Radiocarbon 49
Hughen, K.A., Overpeck, J.T., Lehman, S.J., Kashgarian, M., Southon, J.R., 1998. A new (2), 409e426.
14
C calibration data set for the last deglaciation based on marine varves. Southon, J.R., Rodman, A.O., True, D., 1995. A comparison of marine and terrestrial
Radiocarbon 40 (1), 483e494. radiocarbon ages from northern Chile. Radiocarbon 37 (2), 389e393.
Hughen, K.A., Baillie, M.G.L., Bard, E., Beck, J.W., Bertrand, C.J.H., Blackwell, P.G., Southon, J.R., Nelson, D.E., Vogel, J.S., 1999. A record of past ocean-atmosphere
Buck, C.E., Burr, G.S., Cutler, K.B., Damon, P.E., Edwards, R.L., Fairbanks, R.G., radiocarbon differences from the northeastern Pacific. Paleoceanography 5
Friedrich, M., Guilderson, T.P., Kromer, B., McCormac, G., Manning, S., Ramsey, C.B., (2), 197e206.
Reimer, P.J., Reimer, R.W., Remmele, S., Southon, J.R., Stuiver, M., Talamo, S., Southon, J.R., Magana, A., Cheng, H., Edwards, L., Wang, Y., 2011. A Record of
Taylor, F.W., van der Plicht, J., Weyhenmeyer, C.E., 2004. Marine04 marine radio- Deglacial Atmospheric 14C from Hulu Cave Speleothem H82. Paper CAL#6
carbon age calibration, 0e26 cal ka BP. Radiocarbon 46 (3), 1059e1086. Presented at the AMS-12 Conference, Wellington, New Zealand, March 2011.
A.J.T. Jull et al. / Quaternary International 299 (2013) 64e71 71

Stuiver, M., Braziunas, T.F., 1993. Modeling atmospheric 14C influences and 14C ages Toggweiler, J.R., Dixon, K., Broecker, W.S., 1993. The Peru upwelling and the venti-
of marine samples to 10,000 BC. Radiocarbon 35 (1), 137e189. lation of the South-Pacific thermocline. Journal of Geophysical Research-Oceans
Stuiver, M., Kra, R., 1986. Calibration issue. Radiocarbon 28 (2B), 805e1030. 96 (C11), 20467e20497.
Stuiver, M., Ostlund, H.G., 1980. GEOSECS Atlantic radiocarbon. Radiocarbon 22 (1), Trumbore, S., 2000. Age of soil organic matter and soil respiration: radiocarbon
1e24. constraints on belowground C dynamics. Ecological Applications 10 (2), 399e411.
Stuiver, M., Polach, H.A., 1977. Reporting of 14C data. Radiocarbon 19 (3), 355e363. Tuniz, C., Bird, J.R., Fink, D., Herzog, G.F., 1998. Accelerator Mass Spectrometry:
Stuiver, M., van der Plicht, J., 1998. INTCAL98: calibration issue. Radiocarbon 40 (3), Ultrasensitive Analysis for Global Science. CRC Press, Boca Raton, FL.
1041e1159. Voelker, A.H.L., Grootes, P.M., Nadeau, M.J., Sarnthein, M., 2000. Radiocarbon levels
Stuiver, M., Pearson, G.W., Braziunas, T., 1986. Radiocarbon age calibration of marine in the Iceland Sea from 25e53 ka and their link to the Earth’s magnetic field
samples back to 9000 cal yr BP. Radiocarbon 28 (2B), 980e1021. intensity. Radiocarbon 42 (3), 437e452.
Stuiver, M., 1993. Calibration 1993. Radiocarbon 35 (1), 1e244. Vogel, J.C., Kronfeld, J., 1997. Calibration of radiocarbon dates for the late Pleistocene
Synal, H.A., Wacker, L., 2010. AMS measurement technique after 30 years: possi- using U/Th dates on stalagmites. Radiocarbon 39 (1), 27e32.
bilities and limitations of low-energy systems. Nuclear Instruments and Waters, M.R., Forman, S.L., Jennings, T.A., Nordt, L.C., Driese, S.G., Feinberg, J.M.,
Methods in Physics Research B 268, 701e707. Keene, J.L., Halligan, J., Lindquist, A., Pierson, J., Hallmark, C.T., Collins, M.B.,
Thornalley, D.J.R., Barker, S., Broecker, W.S., Elderfield, H., McCave, I.M., 2011. The Wiederhold, J.E., 2011. The buttermilk creek complex and the origins of Clovis at
deglacial evolution of North Atlantic deep convection. Science 331, 202e205. the Debra L. Friedkin site, Texas. Science 331, 1599e1603.

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