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Here we report results of a direct inter-comparison of the ability of three radiocarbon pre-treatment techniques to remove radiocarbon contamination introduced by exposing known-radiocarbon-free charcoal made at three different temperatures (300, 400 and 500 °C) to environmental contamination on a rainforest floor for one to three years. The initial charcoal had no measureable radiocarbon, but 14C activity increased after environmental exposure to ∼1 pMC after one year (apparent age of ∼40,000 yrs BP) and ∼5 pMC after three years (apparent age of ∼25,000 years). For the 400 and 500 °C samples, all techniques were able to reduce contamination by >90%. Acid–base oxidation (ABOX) provided the most reliable decontamination, reducing the radiocarbon activity of the one year samples to background, and reducing the radiocarbon activity of the three year samples to 0.04 ± 0.02 pMC or less (apparent age >56,900 yrs BP). The performance of ABOX was superior to that of both acid–base–acid (ABA) and hydrogen pyrolysis (hypy) treatments, with ABA performing better than hypy in most cases. No technique was able to fully remove decontamination from the 300 °C charcoal (although ABOX again removed the most contamination), likely due to the incompletely pyrolized nature of the charcoal which is dominated by aromatic clusters of small ring size. All the techniques rely on removing contaminant carbon faster than indigenous carbon and this condition is not met in the case of charcoal produced at temperatures below ∼350 °C. While all pre-treatments are useful for routine sample processing, the results suggest that ABOX is the only technique that can provide reliable decontamination of charcoal of an age close to the dating limit of the radiocarbon dating technique. [ABSTRACT FROM AUTHOR]

Abstract: This study investigates the potential of low-temperature oxygen plasma ashing as a technique for decontaminating charcoal and wood samples prior to radiocarbon dating. Plasma ashing is demonstrated to be rapid, controllable and surface-specific. Different organic materials clearly ash at different rates, however, the ability of plasma ashing to selectively ash different organic components is limited in heterogeneous sample matrices. This is because oxidation is confined to the immediate sample surface. Comparison of radiocarbon dates obtained from identical aliquots of contaminated ancient charcoal pre-treated by acid–base–acid (ABA), acid–base-oxidation-stepped combustion (ABOx-SC) and plasma ashing suggests that the technique performs as well as the ABA pre-treatment but does not remove as much contamination as the ABOx-SC technique. Plasma ashing may be particularly useful in cases where sample size is limiting. [ABSTRACT FROM AUTHOR]

Abstract: The first results concerning the potential of hydrogen pyrolysis (hypy) as a new tool for the quantification and isolation of Black Carbon (BC) for radiocarbon analysis are reported. BC is a highly stable form of carbon, produced during pyrolysis of biomass to materials such as charcoal. Isolation and quantification of this component is therefore of great interest in radiocarbon measurement, particularly for more ancient samples, where contamination issues become more critical. Hypy has been demonstrated to reliably separate labile and refractory carbonaceous sample components for engineering and geological applications, but its potential in 14C geochronological investigation has previously been unexplored. Here, we test the hypy technique using a selection of soil standard samples and ancient charcoals from deposits of geological and archaeological significance. The results show that hypy can effectively and reproducibly isolate different carbon fractions within a variety of sample types and thus has the potential to provide a rapid and robust pre-treatment technique for radiocarbon analysis. Hypy has the additional advantage that the non-BC fraction removed from a sample can be quantitatively collected for subsequent further analysis. The technique represents a promising new approach not only for ensuring reliable decontamination of pyrogenic carbon samples prior to radiocarbon dating, but also for BC quantification in a variety of environmental matrices. [Copyright &y& Elsevier]

Pyrogenic carbon (charcoal, black carbon, elemental carbon) is one of the most common materials used for radiocarbon dating of terrestrial samples. However, exogenous carbon contamination can compromise the accuracy of radiocarbon ages. This study presents the results of two chemical pretreatments prior to hydrogen pyrolysis (hypy) as improved protocols for the isolation and decontamination of pyrogenic carbon, i) a simple acid-oxidation step (A-Ox/hypy) and ii) acid-base-acid (ABA/hypy). The A-Ox/hypy protocol uses HNO 3 and H 2 O 2 , while ABA/hypy uses HCl and NaOH. Both pretreatments remove labile and inorganic carbon before hypy, decreasing the potential for in situ production of pyrogenic carbon during the hypy reaction. The effectiveness of each protocol was directly measured on charcoal artificially produced at 350 °C, 450 °C and 550 °C from radiocarbon-free wood, and exposed to environmental contamination for 1–3 yrs. The results show a >94% reduction in carbon contamination for the 450 °C and 550 °C charcoal samples occurred using A-Ox/hypy, but this treatment was less effective for the 350 °C charcoal. A >99% reduction in carbon contamination in all charcoal samples examined occurred using ABA/hypy. The A-Ox/hypy protocol was further tested on cave guano sediments, which had previously reported erroneous dates following simple organic solvent extraction followed by ABA pretreatment. Effective decontamination was achieved using A-Ox/hypy on the guano, which corrected a radiocarbon age reversal. Overall, ABA/hypy effectively decontaminated the charcoals and was a more efficient pretreatment for charcoal than A-Ox/hypy, however resulting in larger sample mass loss. Therefore, ABA/hypy is the recommended protocol for older (>30,000 14C yr BP) charcoal or sediment samples, or where date accuracy is imperative, while A-Ox/hypy represents an improved protocol for the quick and cost-effective measurement of younger samples (<30,000 14C yr BP) when sample size is of concern. • A-Ox/hypy (HNO 3 , H 2 O 2 and hydrogen pyrolysis) a new pretreatment for 14C dating. • Hypy removes remaining carbon contamination after ABA (acid-base-acid). • ABA and hypy pretreatment was effective in removing contamination. • A-Ox/hypy pretreatment was not as effective. [ABSTRACT FROM AUTHOR]