Radiocarbon 52 (3)

Discusses the aims of and methodology behind the project. PP-B

The Bayesian CAR (continuous autoregressive) model for accelerator mass spectrometry (AMS) data analysis delivers uncertainties with less scatter and bias. Better detection and estimation of the instrumental error of the AMS machine are also achieved. Presently, the main disadvantage is the several-hour duration of the analysis. The Markov chain Monte Carlo (MCMC) program for CAR model analysis, car4ams, has been made freely available under the GPL license. Included in the package is an R program that analyzes the car4ams output and summarizes the results in graphical and spreadsheet formats. Describes the main properties of the CAR analysis and the use of the 2 parts of the program package for radiocarbon AMS data analysis.\r\n

Bayesian sequencing of radiocarbon dates deals with the problem that in most cases there does not exist an unambiguous way to define the so-called prior function, which represents information in addition to the result of the 14C measurements alone. However, a random choice of a particular prior function can lead to biased results. "Robust Bayesian analysis," which uses a whole set of prior functions, is introduced and argued to be a more reliable method. The most important aspects of the mathematical foundation and of the practical realization of the method are described. As a general result, robust Bayesian analysis leads to higher accuracy, but reduced precision. It is suggested that investigations indicate that it seems possible to establish robust analysis for practical applications.

Describes an automatic water sampling unit developed to monitor the radioactive emission (radiocarbon and other corrosion and fission products) from nuclear facilities into the groundwater.

Presents a time-saving modification to the ultraviolet (UV) oxidation method for analyzing dissolved organic carbon (DOC) concentration, ∆14C, and δ13C measurements in seawater and standard materials. A low background (~0.2 ± 0.2 μM) was reported for pre-irradiated Milli-Q (MQ) water that was used to dilute samples for DOC 14C analysis (Beaupré et al. 2007). MQ water without pre-irradiation (background ~0.9 ± 0.2 μM) was used to dilute the sample. This method is suitable for small-volume, high-concentration samples (mass of sample DOC overwhelms mass of MQ water DOC). An acceptable precision of ∆14C measurements (5-9'°) is maintained. This revised method reduces the preparation time for diluted DOC ∆14C samples from 2 days to 1 day.

Describes 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 10^3 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 10^3 atoms g^(-1) or more. The new system is relatively small and easy to construct, costs significantly less than the original in situ 14C extraction system at Arizona, and lends itself to future automation.

Describes the development of 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.

Describes the process of establishing methods for sample preparation of various kinds of radiocarbon dating samples by accelerator mass spectrometry (AMS) at KIGAM (Korea Institute of Geoscience and Mineral Resources). Also describes 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 th

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. 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.

Describes protocols developed 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. Presents 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.

The main methods applied to clean plant material for radiocarbon dating are not compound-specific and generally remove only the easily exchangeable components by an acid-base-acid sequence and additional optional steps like Soxhlet extraction to remove resins and oxidative bleaching with NaClO2. The products are normally clean enough for standard 14C measurement, but in some cases it is desirable to have pure cellulose, which remains unchanged and immobile over longer time ranges, better representing the original plant material. In this work, 2 more compound-specific but still simple methods were tested to separate the cellulose from wood. The viscose method is based on the xanthification process used in the textile industry, where the alkali-cellulose with CS2 forms a soluble cellulose xanthate, which is then extracted and cellulose is recovered. The second procedure is based on the wood/cellulose dissolution in ionic liquid 1-butyl-3-methylimidazolium chloride [BMIM]Cl, when the dissolved cellulose could be precipitated again by simply adding a water-acetone mixture. This process was recently reported, but still not used in sample preparation procedures for 14C dating.

The reaction conditions for the graphitization of CO2 with hydrogen were optimized for a fast production of high-quality carbon samples for accelerator mass spectrometry (AMS) measurement. The iron catalyst in use is first oxidized by heating with air to remove possible carbon and other impurities and then after evacuation reduced back to iron with hydrogen in several flushing steps to remove any iron oxide. The optimum conditions for a fast graphitization reaction were experimentally determined by changing the reaction temperatures and the H2/CO2 ratio. The resulting graphite samples were measured by AMS to find the smallest isotopic changes (δ13C) at a minimum of molecular fragment formation (13CH current). The improvements are based on thermodynamic data and are explained with Baur-Glaessner diagrams.

Twenty years after the first International Radiocarbon Database Workshop, and 13 yr after the setup of a preliminary structure for a worldwide database on 14C dates of soils, sound reasons and excuses for not establishing a real and globally accessible database are argued to have diminished. Climate change itself is widely accepted as reality now, and the strong demand of the modeling community for reliable data of the carbon pool--especially in soils--has been maintained. With the steadily increasing capacity of 14C dating facilities, these data can be and are produced. Nevertheless, they still cannot be accessed easily and equally enough. Now, decreased costs of hardware and recent developments of the internet enable the IRSDB to be implemented, in a joint effort. As a seed, a test server has been set up, with open-source software, housing the database in alpha-stage, a web interface, and a community portal. Thus, the development of the design as well as the data input of the database is done in close collaboration of the users of the database, the laboratories, soil scientists, archaeologists, modelers, other scientists, and interested laypersons. In order to guarantee the longtime independence of the availability and usability of the database from vendors or changing standards, only widely used open-source software and open standards are used. Therefore, the development of plug-ins for data input from laboratory databases or output to different required formats as well as interfaces to GIS and other software is possible. A version control system takes care of the integrity of the data.