Natural Abundance of Carbon Isotopes (14C, 13C) in Lichens and Calcium Oxalate Pruina: Implications for Archaeological and Paleoenvironmental Studies
Marion County Arkansas
Val Verde County Texas
accelerator mass spectra
alkaline earth metals
C 13 C 12
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CitationBeazley, M. J., Rickman, R. D., Ingram, D. K., Boutton, T. W., & Russ, J. (2002). Natural abundances of carbon isotopes (14C, 13C) in lichens and calcium oxalate pruina: Implications for archaeological and paleoenvironmental studies. Radiocarbon, 44(3), 676-683.
AbstractRadiocarbon ages of calcium oxalate that occurs naturally on rock surfaces have been used recently in archaeological and paleoenvironmental studies. Oxalate rock coatings are found globally, with most appearing to be residues from epilithic lichens. To explore the source(s) of carbon used by these organisms for the production of oxalate we measured the natural abundances of 14C and 13C in 5 oxalate-producing lichen species, 3 growing on limestone in southwestern Texas and 2 on sandstone in Arkansas. We also examined the distribution of the isotopes between the calcium oxalate and lichen tissues by separating these components and measuring the 13C/C independently. The results demonstrate that the limestone species were slightly enriched in 14C, by 1.7 per mil, relative to the sandstone species, which suggests that "dead" carbon from the limestone substrate does not constitute a significant source of carbon for the production of oxalate. The calcium oxalate produced by the lichens is also enriched in 13C by 6.5 per mil compared to the lichen tissues, demonstrating that there is a large carbon isotope discrimination during oxalate biosynthesis. These results support the reliability of 14C ages of calcium oxalate rock coatings used for archaeological and paleoclimate studies.
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Iron-Manganese System for Preparation of Radiocarbon AMS Targets: Characterization of Procedural Chemical-Isotopic Blanks and FractionationVerkouteren, R. Michael; Klinedinst, Donna B.; Currie, Lloyd A. (Department of Geosciences, The University of Arizona, 1997-01-01)We report a practical system to mass-produce accelerator mass spectrometry (AMS) targets with 10-100 micrograms carbon samples. Carbon dioxide is reduced quantitatively to graphite on iron fibers via manganese metal, and the Fe-C fibers are melted into a bead suitable for AMS. Pretreatment, reduction and melting processes occur in sealed quartz tubes, allowing parallel processing for otherwise time-intensive procedures. Chemical and isotopic (13C, 14C) blanks, target yields and isotopic fractionation were investigated with respect to levels of sample size, amounts of Fe and Mn, pretreatment and reduction time, and hydrogen pressure. With 7-day pretreatments, carbon blanks exhibited a lognormal mass distribution of 1.44 micrograms (central mean) with a dispersion of 0.50 micrograms (standard deviation). Reductions of 10 micrograms carbon onto targets were complete in 3-6 h with all targets, after correction for the blank, reflecting the 13C signature of the starting material. The 100 micrograms carbon samples required at least 15 h for reduction; shorter durations resulted in isotopic fractionation as a function of chemical yield. The trend in the 13C data suggested the presence of kinetic isotope effects during the reduction. The observed CO2-graphite 13C fractionation factor was 3-4% smaller than the equilibrium value in the simple Rayleigh model. The presence of hydrogen promoted methane formation in yields up to 25%. Fe-C beaded targets were made from NIST Standard Reference Materials and compared with graphitic standards. Although the 12C ion currents from the beads were one to two orders of magnitude lower than currents from the graphite, measurements of the beaded standards were reproducible and internally consistent. Measurement reproducibility was limited mainly by Poisson counting statistics and blank variability, translating to 14C uncertainties of 5-1% for 10-100 micrograms carbon samples, respectively. A bias of 5-7% (relative) was observed between the beaded and graphitic targets, possibly due to variations in sputtering fractionation dependent on sample size, chemical form and beam geometry.
Systematic Investigations of 14C Measurements at the Vienna Environmental Research AcceleratorRom, Werner; Golser, Robin; Kutschera, Walter; Priller, Alfred; Steier, Peter; Wild, Eva (Department of Geosciences, The University of Arizona, 1998-01-01)A newly operating accelerator mass spectrometry (AMS) facility such as VERA has to go through an extensive testing phase in order to establish optimal conditions for 14C measurements, especially in the field of archaeological samples where an overall precision of 0.5% is desirable. We discuss the results of our measurements at the milligram carbon level as they relate to long-term stability, reproducibility, precision and isotope fractionation.
On Correcting 14C Ages of Gastropod Shell Carbonate for FractionationPigati, Jeffrey S. (Department of Geosciences, The University of Arizona, 2002-01-01)Correcting the 14C age of a sample for fractionation is straightforward if the measured carbon was derived entirely from the atmosphere, either directly or through chemical and/or biological reactions that originated with atmospheric carbon. This correction is complicated in the case of gastropods that incorporate carbon from limestone or secondary carbonate (e.g. Soil carbonate) during shell formation. The carbon isotopic composition of such gastropod shells is determined by fractionation, as well as mixing of carbon from sources with different isotopic values. Only the component of shell carbonate derived from atmospheric carbon should be corrected for fractionation. In this paper, the author derives a new expression for correcting the measured 14C activity of gastropod shells for fractionation, and describe an iterative approach that allows the corrected 14C activity and the fraction of shell carbonate derived from atmospheric carbon to be determined simultaneously.