Prehistoric cultures in Armenia are still poorly known; thus, accelerator mass spectrometry (AMS) radiocarbon dates are invaluable in constructing an accurate chronology. Bone samples have been collected from sites representing the Middle Paleolithic, Chalcolithic, and Early Bronze periods. Most of the bone samples are poorly preserved. We describe the separation technique for the extraction of both the bioapatite and collagen fractions. In many cases where the bone had very low organic material content, the collagen fractions yielded a younger age, although the ages of bioapatite fractions were found to be in good agreement with associated archaeological artifacts. In cases where bone was well preserved, both fractions exhibited ages in good agreement with the artifacts. The accuracy of 14C dating of bone material always depends on its degree of preservation, and each case should be carefully evaluated to determine which fraction is less contaminated in order to accurately date a burial event.

In order to reveal a possible carbon exchange between carbon dioxide of the fuel and the bone apatite during the cremation process an experiment was set up using fossil fuel. Two setups were constructed, one using natural gas and one using coal. In both experiments, a carbon substitution in the apatite was revealed.

Bones that have undergone burning at high temperatures (i.e. cremation) no longer contain organic carbon. Lanting et al. (2001) proposed that some of the original structural carbonate, formed during bioapatite formation, survives. This view is based on paired radiocarbon dating of cremated bone apatite and contemporary charcoal. However, stable carbon isotope composition of carbonate in cremated bones is consistently light compared to the untreated material and is closer to the δ13C values seen in C3 plant material. This raises the question of the origin of carbonate carbon in cremated bone apatite. That is, does the isotope signal reflect an exchange of carbon with the local cremation atmosphere and thus with carbon from the burning fuel, or is it caused by isotopic fractionation during cremation?

To study the changes in carbon isotopes (14C, 13C) of bone apatite during burning up to 800 °, a modern bovine bone was exposed to a continuous flow of an artificial atmosphere (basically a high-purity O2/N2 gas mix) under defined conditions (temperature, gas composition). To simulate the influence of the fuel carbon available under real cremation conditions, fossil CO2 was added at different concentrations. To yield cremated bone apatite properties similar to archaeological cremated bones, in terms of crystallographic criteria, water vapor had to be added to the atmosphere in the oven. Infrared vibrational spectra reveal large increases in crystal size and loss of carbonate upon cremation. The isotope results indicate an effective carbon exchange between bone apatite carbonate and CO2 in the combustion gases depending on temperature and CO2 concentration. 14C dates on archaeological cremated bone apatite may thus suffer from an old-wood effect. Paired 13C and 14C values indicate that in addition to this exchange, isotope fractionation between CO2 and carbonate, and admixture of carbon from other sources such as possibly collagen or atmospheric CO2, may play a role in determining the final composition of the apatite carbonate.

During the laboratory pretreatment of samples for radiocarbon dating, small amounts of carbon may be added to a sample. Contamination can be incorporated at any stage: during chemical pretreatment, combustion to CO2, graphitization, or accelerator mass spectrometry (AMS) measurement. Such carbon contamination is often modern in age, and so can have an especially severe effect on samples older than ∼25 ka BP. During the extraction of collagen from bone using the ultrafiltration protocol at the Oxford Radiocarbon Accelerator Unit (ORAU), small amounts of young carbon are added to the sample. Currently, this contamination is poorly characterized when less than 10 mg of collagen is extracted from a bone. Demand to date small collagen samples with 14C concentrations that approach the detection limit of AMS measurement has increased recently with the growing interest in, for example, directly dating Neanderthal remains and Upper Paleolithic bone artifacts. This paper aims to reduce the minimum collagen sample size required to produce a reliable date from 10 to 5 mg by re-examining the combustion background and subsequently the pretreatment background for bone. The average of 136 measurements of directly combusted nylon suggests that 0.0007 ± 0.001 mg of modern carbon is added to each sample, although the distribution is positively skewed. Regression analysis of the measurements of 52 collagen samples extracted from a bone of background age results in a background of just less than 50,000 BP for bone treated at ORAU.

Isolation of bone collagen for radiocarbon dating is a labor-intensive and time-consuming process that sometimes results in unacceptably low protein recovery. In preliminary studies reported here, micro-computed tomography (microCT), a nondestructive technique that uses X-rays to produce high-resolution three-dimensional images of mineralized materials such as bone, offers promise as a suitable prescreening option for bones of questionable preservation. We have found that the bone volume fraction calculated by the scanner software correlates well with collagen recovery in 4 analyzed bones from Etton, United Kingdom.

Since the development of accelerator mass spectrometry (AMS) for radiocarbon dating in the late 1970s, its ability to date small samples of bone has been of huge importance in archaeology and Quaternary paleoecology. The conventional approach to sample preparation has been to extract and gelatinize protein, which is then combusted and graphitized for analysis. However, this “bulk protein” can contain a heterogeneous mixture of non-collagenous molecules, including humic acids and other soil components that may be of a different age than the bone and therefore affect the accuracy of its 14C date. Sample pretreatment methods have been an important area of development in recent years but still show inadequacies for the dating of severely contaminated bone. The idea of isolating and dating individual compounds such as single amino acids, to improve dating accuracy, has been discussed in the literature since the 1960s. Hydroxyproline, for example, makes up over 10% of bone collagen but is extremely rare in most other animal proteins, increasing the chances of its presence being endogenous to the individual being dated. Its successful isolation has therefore been considered a potential “gold standard” for dating archaeological bone; however, extracting and suitably purifying single amino acids from bone has proved a challenging task.

Within a project on Stone Age sites of NE Germany, 26 burials from the Ostorf cemetery and some further Neolithic sites have been analyzed by more than 40 accelerator mass spectrometry (AMS) dates. We here present the results of stable isotope and radiocarbon measurements together with reference 14C dates on grave goods from terrestrial animals such as tooth pendants found in 10 of the graves. Age differences between human individuals and their associated grave goods are used to calculate 14C reservoir effects. The resulting substantial reservoir effects have revealed misleadingly high 14C ages of their remains, which originally indicated a surprisingly early occurrence of graves and long-term use of this Neolithic burial site. We demonstrate that in order to 14C date the human bones from Ostorf cemetery, it is of utmost importance to distinguish between terrestrial- and freshwater-influenced diet. The latter may result in significantly higher than marine reservoir ages with apparent 14C ages up to ∼800 yr too old. The carbon and nitrogen isotopic composition may provide a basis for or an indicator of necessary corrections of dates on humans where no datable grave goods of terrestrial origin such as tooth pendants or tusks are available. Based on the associated age control animals, there is no evidence that the dated earliest burials occurred any earlier than 3300 BC, in contrast to the original first impression of the grave site (∼3800 BC).

This investigation concerns human teeth and bones from the site of Natfieh, north Jordan. Nitrogen and carbon isotope analyses were used to model the paleo-economy by reconstructing Natfieh's paleodiet during a specific time period. 14C dating of human teeth and bones from the site of Natfieh, north Jordan, demonstrate that they belong to the Early Roman period and match the archaeological date from the tomb and grave goods typology. Stable isotope analyses of these humans have provided new information about the subsistence and society of individuals buried at Natfieh. Natfieh is today agriculturally productive and must have been so in antiquity with most of the foodstuffs having been produced locally. The long distance between Natfieh and the closest aquatic food source (Mediterranean Sea and Lake Tiberias) and the high cost of land transportation might be the reason for the low consumption of marine protein. The results agree with past research on the Roman diet showing that plants were the common source of food for the Romans and fish may have been restricted to elite members of the society.

The influence of geothermally derived carbon on the radiocarbon dating of human bone from archaeological sites is poorly understood and has rarely been rigorously examined. This study identifies a previously unknown reservoir effect at the archaeological site of Klin-Yar in the Russian North Caucasus. AMS-dated human bones yielded results that were older than expected when compared with dates of coins found in the same grave contexts. We investigated the reasons for this offset by AMS dating modern plant, fish, and water samples to examine the source of the old carbon. We identified a potential source in geothermally derived riverine and spring water, with an apparent age of several thousand years, and hypothesize that carbon from here is being transferred through the food chain to humans. If humans consume resources from the local rivers, such as fish, then they ought to be affected by this reservoir offset. An extensive analysis of carbon and nitrogen isotopes of human and animal bone showed evidence for a mixed diet that may be masking the amount of freshwater-derived protein being consumed. Due to the highly variable nature of the 14C offset (0 to ∼350 yr), no suitable average correction factor is applicable to correct for the human dates at the site. A 14C chronology based on dates obtained from terrestrial ungulate bones, which we subsequently obtained, is instead a more reliable indicator of age.

The relative contribution of marine-derived carbon in the ancient diet is essential for correcting the marine reservoir effect on the radiocarbon age of archaeological human remains. In this study, we evaluated the marine protein consumption of 3 human populations from the Okhotsk culture (about AD 550–1200) in Hokkaido, Japan, based on stable carbon and nitrogen isotopic compositions in bulk bone collagen as well as the nitrogen isotopic composition of glutamic acid and phenylalanine. Despite the similarity of carbon and nitrogen isotopic composition of bulk collagens, nitrogen isotopic composition of their constituent amino acids suggests differences in fur seal contributions among northern Hokkaido (0–24% for Kafukai 1, 0–10% for Hamanaka 2) and eastern Hokkaido (78–80% for Moyoro) populations. It suggests that nitrogen composition of glutamic acid and phenylalanine could provide a detailed picture of ancient human subsistence.

In this study, δ13C and δ15N of bone samples from 83 skeletons (79 humans, 2 horses, and 2 dogs) excavated from pagan and early Christian graves from 21 localities in Iceland are used to reconstruct diet of the early settlers in Iceland and possible differences in diet depending on the distance between the excavation site and the seashore. We have radiocarbon dated 47 of these skeletons and used the carbon isotopic composition (δ13C) to estimate and correct for the marine reservoir effect (the 14C difference between terrestrial and mixed marine organisms). The reservoir-corrected ages lie in the range of AD 780–1270 (68.2% probability). Reservoir age corrections were checked by comparing 14C dates of a horse (terrestrial diet), a dog (highly marine diet), and a human (mixed diet) from the same burial. The range in measured marine protein percentage in individual diet is from about 10% up to 55%, mostly depending on the geographical position (distance from the sea) of the excavation site. We had access to the skeleton (AAR-5908) of the Skálholt bishop Páll Jónsson whose remains are enshrined at the Episcopal residence in Skálholt, southern Iceland. According to written sources, the bishop died in AD 1211. Using our dietary reconstruction, his bones were about 17% marine, which is within the range of human skeletons from the same area, and the reservoir-corrected calibrated 14C age of the skeleton is in accord with the historical date.

In order to verify the relative dating based on pot type morphology and decoration of the Swifterbant pottery collected at the Final Mesolithic site of Doel “Deurganckdok” (Belgium) and of the Late Iron Age pottery excavated at Grijpskerke (the Netherlands), direct radiocarbon dates were obtained on charred food residue preserved on the inner surface of numerous potsherds. In addition, a number of indirect 14C dates were obtained from samples of organic material. In the case of Doel, the results indicate an important incompatibility between the charred food residue dates and the other dates, the former being systematically older. This difference may be explained by a reservoir effect of the charred food residue, caused by the processing of (freshwater) fish. The 14C dates for the Grijpskerke site are in agreement between the charred food residue and the organic material. The stable isotopes of the charred food residue were analyzed to demonstrate fish processing in the pottery, but the results were inconclusive.

While radiocarbon is widely applied in dating ancient samples, recent studies reveal that 14C concentrations in modern samples can also yield precise ages due to the atmospheric testing of thermonuclear devices between 1950 and 1963. 14C concentrations in both enamel and organic matter of 13 teeth from 2 areas in China were examined to evaluate and improve this method of forensic investigation. Choosing enamel near the cervix of the tooth can reduce the error caused by the difference between the sample formation time and whole enamel formation time because tooth enamel formations take a long time to complete. A proper regional data set will be helpful to get an accurate result when calculating the age of the sample (T1) by the CALIBomb program. By subtracting the enamel formation time (t), the birth date of an individual (T2) can be confirmed by enamel F14C from 2 teeth formed at different ages. Calculated enamel formation dates by 14C concentration are basically consistent with corresponding actual values, with a mean error of 1.9 yr for all results and 0.2 yr for the samples formed after AD 1960. This method is more effective for dating samples completed after AD 1960. We also found that 14C concentrations in organic matter of tooth roots are much lower than atmospheric concentrations in root formation years, suggesting that the organic material keeps turning over even after tooth formation is complete. This might be a potential tool for identification of death age to extract a proper component for 14C dating. We also observed that δ13C values between hydroxyapatite and organic matter indicate that isotopic fractionation during the biomineralization is 8–9%‰ more positive in mineral fractions than in organic matter.

The article reports the first radiocarbon dating of a live African baobab (Adansonia digitata L.), by investigating wood samples collected from 2 inner cavities of the very large 2-stemmed Platland tree of South Africa. Some 16 segments extracted from determined positions of the samples, which correspond to a depth of up to 15–20 cm in the wood, were processed and analyzed by accelerator mass spectrometry (AMS). Calibrated ages of segments are not correlated with their positions in the stems of the tree. Dating results indicate that the segments originate from new growth layers, with a thickness of several centimeters, which cover the original old wood. Four new growth layers were dated before the reference year AD 1950 and 2 layers were dated post-AD 1950, in the post-bomb period. Formation of these layers was triggered by major damage inside the cavities. Fire episodes are the only possible explanation for such successive major wounds over large areas or over the entire area of the inner cavities of the Platland tree, able to trigger regrowth.

In 2008, a large African baobab (Adansonia digitata L.) from Makulu Makete, South Africa, split vertically into 2 sections, revealing a large enclosed cavity. Several wood samples collected from the cavity were processed and radiocarbon dated by accelerator mass spectrometry (AMS) for determining the age and growth rate dynamics of the tree. The 14C date of the oldest sample was found to be of 1016 ± 22 BP, which corresponds to a calibrated age of 1000 ± 15 yr. Thus, the Makulu Makete tree, which eventually collapsed to the ground and died, becomes the second oldest African baobab dated accurately to at least 1000 yr. The conventional growth rate of the trunk, estimated by the radial increase, declined gradually over its life cycle. However, the growth rate expressed more adequately by the cross-sectional area increase and by the volume increase accelerated up to the age of 650 yr and remained almost constant over the past 450 yr.

One critical variable in the successful application of radiocarbon dating is the effective removal of carbonaceous contaminants. In the case of marine carbonates, contamination appears usually in the form of secondary low-magnesium calcite, the stable polymorph of calcium carbonate and byproduct of the post-mortem recrystallization or replacement of the autochthonous phase, originally in the form of high-magnesium calcite or aragonite. Depending on the nature of the depositional environment, the secondary phase may be contemporary in age with the original shell carbonate and may have even been derived from it by dissolution-recrystallization processes, or can be an exogenous contaminant of younger or older age. The limited ability of current pretreatment protocols to detect and remove the secondary mineralogical phases prior to dating carbonates has been one of the reasons marine shell and coral 14C determinations are often difficult to validate in terms of their reliability. We have developed a new pretreatment protocol designed to achieve greater reliability and accuracy in the dating of this material. The method entails 2 steps. The first one involves the improved detection and quantification of secondary calcite in aragonite using X-ray diffraction, at a precision of ∼0.1% and ∼0.8%, respectively. Next, where this is required, a novel density separation step using non-toxic heavy liquids (CarDS) is applied to the diagenetic sample. This enables the clear separation of calcite and aragonite, with only the latter kept for dating. We have applied the new steps, screening and separation, on standard and archaeological examples and our initial results suggest that it is successful and reproducible. In this paper, we describe the method and initial results.

There is a great scientific demand for an assessment of the sources and formation processes of atmospheric carbonaceous aerosols since they strongly influence the global radiation balance and affect public health. Much attention in atmospheric studies has been paid to dicarboxylic acids (DCAs) due to their abundance at substantially different sites and their potential influence on cloud formation processes. Nevertheless, sources of oxalic acid (HOOCCOOH) and other DCAs are not well understood yet. In order to quantify contributions of fossil and non-fossil sources, a method for the preparative separation of oxalic acid and other DCAs from aerosols for compound-specific radiocarbon analysis (CSRA) has been developed. This method consists of a water extraction of aerosols collected on quartz-fiber filters followed by 2 consecutive liquid chromatography (LC) steps on different chromatography columns (2D-chromatography). Through the use of aqueous, completely non-organic eluents and single injections into liquid chromatography, low blank levels are achieved with total oxalic acid recoveries of up to 66%. Upon separation, 14C measurements of small samples (containing typically 10–20 μg carbon) are conducted at the gas ion source of the 200kV accelerator mass spectrometry facility MICADAS. The method is verified with processed reference materials, artificial mixtures of oxalic acid with typical matrix components, and a standard addition of ambient aerosols. Two exemplary field samples show dominant non-fossil sources of oxalic acid.

Atmospheric carbonaceous aerosol is traditionally divided into organic carbon (OC) and elemental carbon (EC). Their respective carbon amounts are usually analyzed by means of an OC/EC analyzer and their fossil and non-fossil origins can be determined by radiocarbon analysis, which has proven to be a powerful tool for carbonaceous aerosol source apportionment. Thus far, separation of OC and EC has been performed off-line by manual and time-consuming techniques. We present an on-line system that couples a commercial OC/EC analyzer with the gas ion source of the accelerator mass spectrometer (AMS) MICADAS and its CO2 feeding system. The performance achieved with reference materials and blanks are discussed to demonstrate the potential of this coupling for source apportionment of atmospheric carbonaceous particulate matter.

We describe progress in developing a novel miniaturized laser-heated “microfurnace” aimed at preparing ultra-small (∼5 μg) graphite samples from CO2 (Smith et al. 2006, 2007, 2010). Recent effort has focused on automation of the process using a LabVIEW interface, which has permitted feedback control of the catalyst temperature as the reaction proceeds and the logging of reaction parameters. We trialed a number of different pure iron catalysts as well as Fe2O3 (which is reduced in situ to iron) and discuss the reaction rates. We studied the graphite morphology by scanning electron microscopy (SEM) and found there is a marked difference in graphite morphology with catalyst type. We assessed how each catalyst performs in the cesium sputter ion source of the ANTARES Accelerator Mass Spectrometry (AMS) facility. We utilized a quadrupole mass spectrometer to study the gas composition during the reaction, in order to better understand the underlying chemical reactions for such small samples and to better estimate the overall efficiency of the process. Results show that all CO2 is converted to CO by reduction on the iron catalyst within a few minutes of applying laser power. The reaction pressure stabilizes after 40 min; however, some CO is not converted to graphite. The cold trap temperature of –80 ° is effective at trapping H2O, so there is little CH4 production.

The Lower Danube Basin covers the Romanian-Bulgarian sub-basin downstream from Cazane Gorge and the sub-basins of the Siret and Prut rivers. To extensively survey the Romanian nuclear power plant impact on the Danube water, tritium and radiocarbon baseline values are required. Therefore, the reported study tried to establish these values based on a 2-yr sampling campaign covering 975 km of the Danube from Cazane Gorge to Tulcea. The tributaries Cerna, Jiu, Olt, and Arges were also included in this study. During the sampling campaigns, tritium concentration of different sampling locations showed values between 7 ± 2.1 and 33.5 ± 2.3 TU. Measured 14C activity for the same locations ranged between 88.45 ± 1.46 and 112.36 ± 1.56 pMC. Lower values were recorded for tributaries: between 8.3 ± 2.1 and 12.2 ± 2.2 TU for tritium and between 67.3 ± 1.29 and 86.04 ± 1.42 pMC for 14C. Despite the nuclear activity in the observed areas, tritium and 14C activities presented slightly higher values for specific locations without any influence on Danube River water.