We describe the design, construction, and testing of a new, simplified in situ radiocarbon extraction system at the University of Arizona. Blank levels for the new system are low ((234 ± 11) x 103 atoms (1 σ; n = 7)) and stable. The precision of a given measurement depends on the concentration of 14C, but is typically <5% for concentrations of 100 x 103 atoms g–1 or more. The new system is relatively small and easy to construct, costs significantly less than the original in situ14C extraction system at Arizona, and lends itself to future automation.

Chemical pretreatment and extraction techniques have been developed previously to extract in situ cosmogenic radiocarbon (in situ14C) from quartz and carbonate. These minerals can be found in most environments on Earth, but are usually absent from mafic terrains. To fill this gap, we conducted numerous experiments aimed at extracting in situ14C from olivine ((Fe,Mg)2SiO4). We were able to extract a stable and reproducible in situ14C component from olivine using stepped heating and a lithium metaborate (LiBO2) flux, following treatment with dilute HNO3 over a variety of experimental conditions. However, measured concentrations for samples from the Tabernacle Hill basalt flow (17.3 ± 0.3 ka4) in central Utah and the McCarty's basalt flow (3.0 ± 0.2 ka) in western New Mexico were significantly lower than expected based on exposure of olivine in our samples to cosmic rays at each site. The source of the discrepancy is not clear. We speculate that in situ14C atoms may not have been released from Mg-rich crystal lattices (the olivine composition at both sites was ∼Fo65Fa35). Alternatively, a portion of the 14C atoms released from the olivine grains may have become trapped in synthetic spinel-like minerals that were created in the olivine-flux mixture during the extraction process, or were simply retained in the mixture itself. Regardless, the magnitude of the discrepancy appears to be inversely proportional to the Fe/(Fe+Mg) ratio of the olivine separates. If we apply a simple correction factor based on the chemical composition of the separates, then corrected in situ14C concentrations are similar to theoretical values at both sites. At this time, we do not know if this agreement is fortuitous or real. Future research should include measurement of in situ14C concentrations in olivine from known-age basalt flows with different chemical compositions (i.e. more Fe-rich) to determine if this correction is robust for all olivine-bearing rocks.

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.

The radiocarbon content of atmospheric CO2 (Δ14CO2) has long been of interest to atmospheric and Earth system researchers. Recent improvements in 14C measurement precision and reduction in sample size requirements have now made it possible to measure Δ14CO2 within existing trace gas sampling networks, most notably as a method to quantify recently added fossil-fuel-derived CO2 in the atmosphere. At INSTAAR, in collaboration with NOAA/ESRL, ∼600 atmospheric samples from around the globe are prepared each year, and that number is anticipated to grow in connection with various monitoring and data assimilation efforts. To accommodate the growing demand and reduce per sample costs, we developed an automated extraction system to quantitatively isolate CO2 from whole air for AMS 14C analysis. Twenty samples can be extracted in 1 fully automated run, taking 10–12 hr to complete and requiring only about 1 hr of operator time, a substantial improvement over the manual extraction system. CO2 is extracted cryogenically by flowing the whole air over a liquid nitrogen trap, after first removing water in a trap at –85 °C. Large volume vacuum lines are used to extract ∼30 μmol of CO2 in less than 10 min, keeping contamination from leaks to a minimum and allowing rapid processing and greater throughput. δ13C measurements on the resultant CO2 demonstrate that extraction is quantitative, and extractions of 14C-free air show that no significant modern contamination occurs. Replicate analyses of standard materials indicate that both mean values and precision are comparable to those for the manual extraction system.

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.

To be able to successfully measure radiocarbon with accelerator mass spectrometry (AMS) in atmospheric aerosol samples, graphitization of small sample sizes (<50 μg carbon) must provide reproducible results. At Lund University, a graphitization line optimized for small samples has been constructed. Attention has been given to minimize the reduction reactor volume and each reactor is equipped with a very small pressure transducer that enables constant monitoring of the reaction. Samples as small as 25 μg of carbon have been successfully analyzed, and the mass detection limit of the system has probably not been reached.

Many previous studies on the sample preparation of various kinds of radiocarbon dating samples by accelerator mass spectrometry (AMS) have been examined at KIGAM (Korea Institute of Geoscience and Mineral Resources) and our own procedures have been established. Furthermore, an automated reduction system has been developed. The volume of the reduction region was minimized to improve the reduction yield, and air-actuated pneumatic valves and solenoid arrays were used for computer control of the system. Operation of all the valves and vacuum pumps and signals from the temperature sensors and pressure gauges were interfaced to a personal computer with an A/D board. A computer program was also developed to perform automatic operation of the reduction system. This system consistently shows a higher reduction yield than 90%. The reduction time of the system is currently 140 min.

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.

In this paper, we describe improvements to the in situ cosmogenic radiocarbon extraction system at SUERC made since 2004, highlighting the factors that potentially control the reduction of analytical variability. We also present new results on system blanks and of measurements of in situ14C in shielded quartz and a surface quartz sample used at the University of Arizona as an in situ14C standard (PP-4). The SUERC in situ14C extraction system was built in 2001 and is based on a combustion technique following the design of the extraction system at the University of Arizona. Our preliminary results suggest that the continuous running of the extraction system and the monitoring of gas collecting time and of the temperature of the cryogenic traps used in the gas cleaning steps are key to maintaining low and stable system blanks. Our latest average system blank is 2.02 ± 0.23 x 10514C atoms. This is consistent with those recently published by the University of Arizona and ETH in situ14C labs. Measurements of in situ14C concentrations in sample PP-4 yield an average of 3.82 ± 0.23 x 105 atoms g–1 quartz, again consistent with published values.

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).

Since iron artifacts generally contain trace amounts of carbon, an iron sample needs to be relatively large, as compared to other materials, and a specially designed combustion system is required. An elemental analyzer (EA) was used for the combustion of iron without any special chemical treatment. CO2 gas with 1 mg of carbon was obtained from the combustion of an iron artifact by using an EA and reduced to graphite for accelerator mass spectrometry (AMS) measurement. In this work, AMS dating results done at the Korea Institute of Geoscience and Mineral Resources (KIGAM) for several ancient iron artifacts are presented and compared with independently estimated ages. This method was found to be useful for the pretreatment of iron artifacts that contained >0.1% carbon. A simple pretreatment method using an EA was also applied to calcium carbonate (CaCO3) samples. Samples were preheated overnight at 100–300 °C, without any special chemical treatment. This removed modern CO2 contamination and the background level decreased to a comparable value measured in samples treated with phosphoric acid under vacuum.

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.

Coastal archaeological sites that lack organic remains for radiocarbon dating are often abundant sources of molluscan shells. As a substitute for materials such as bone and charcoal, shells can be analyzed with 14C dating to determine a site's age. Despite their being convenient, non-mobile archaeological artifacts, molluscan shells are plagued by several issues, including carbonate remodeling, in which aragonite in shells is converted to calcite as predicted by thermodynamics. We present here a carbonate density separation technique that addresses the issue of carbonate remodeling. Using a density fractionation with bromoform, aragonite concentrations are enriched in shells that have undergone significant remodeling. The technique has been applied to archaeological shells and has returned dates that are younger than those previously determined for the same shells.

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.

A method of thermal and acid treatments was developed at the Archaeo-metallurgy Laboratory of Hongik University in Korea to extract carbon from cast iron, and carbon objects thus prepared from cast iron artifacts of ancient Korea were dated at the University of Arizona's AMS Facility. The thermal treatments consist of heating a specimen to ∼1000 °C in a controlled environment with reduced oxygen potential, then cooling it rapidly to room temperature. The heating causes the cementite phase in white cast iron to be graphitized and the quenching suppresses pearlite formation. The specimen then consists of flakes of graphite embedded in a matrix of martensite. The next stage of the treatment is to dissolve the martensite matrix in a solution of nitric and hydrochloric acids to release the graphite as a powder. This material is then cleaned, dried, and pressed into target holders for accelerator mass spectrometry (AMS) analysis. The method was applied to a collection of artifacts from the Korean Three Kingdoms period (about AD 300–668) and the AMS results were compared with chronological estimates from other means.

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.

The Keck Carbon Cycle AMS facility at the University of California, Irvine (KCCAMS/UCI) has developed protocols for analyzing radiocarbon in samples as small as ∼0.001 mg of carbon (C). Mass-balance background corrections for modern and 14C-dead carbon contamination (MC and DC, respectively) can be assessed by measuring 14C-free and modern standards, respectively, using the same sample processing techniques that are applied to unknown samples. This approach can be validated by measuring secondary standards of similar size and 14C composition to the unknown samples. Ordinary sample processing (such as ABA or leaching pretreatment, combustion/graphitization, and handling) introduces MC contamination of ∼0.6 ± 0.3 μg C, while DC is ∼0.3 ± 0.15 μg C. Today, the laboratory routinely analyzes graphite samples as small as 0.015 mg C for external submissions and ≅0.001 mg C for internal research activities with a precision of ∼1% for ∼0.010 mg C. However, when analyzing ultra-small samples isolated by a series of complex chemical and chromatographic methods (such as individual compounds), integrated procedural blanks may be far larger and more variable than those associated with combustion/graphitization alone. In some instances, the mass ratio of these blanks to the compounds of interest may be so high that the reported 14C results are meaningless. Thus, the abundance and variability of both MC and DC contamination encountered during ultra-small sample analysis must be carefully and thoroughly evaluated. Four case studies are presented to illustrate how extraction chemistry blanks are determined.

Charcoal is the result of natural and anthropogenic burning events, when biomass is exposed to elevated temperatures under conditions of restricted oxygen. This process produces a range of materials, collectively known as pyrogenic carbon, the most inert fraction of which is known as black carbon (BC). BC degrades extremely slowly and is resistant to diagenetic alteration involving the addition of exogenous carbon, making it a useful target substance for radiocarbon dating particularly of more ancient samples, where contamination issues are critical. We present results of tests using a new method for the quantification and isolation of BC, known as hydropyrolysis (hypy). Results show controlled reductive removal of non-BC organic components in charcoal samples, including lignocellulosic and humic material. The process is reproducible and rapid, making hypy a promising new approach not only for isolation of purified BC for 14C measurement but also in quantification of different labile and resistant sample C fractions.