An independent assessment of uncertainty for radiocarbon analysis with the new generation high-yield accelerator mass spectrometers

ABSTRACT. The radiocarbon dating facility at the Centre for Isotope Research, University of Groningen went through a major upgrade in 2017 and this included installation of a MICADAS accelerator mass spectrometer (AMS). In the first 18 months, we performed 4000 sample and 3000 reference measurements. A careful evaluation of those measurement results is presented, to characterize the various sources of uncertainty and to ultimately assign, for every sample measurement, a realistic expanded uncertainty. This analysis was performed on the measurements of secondary references and sample duplicates in various phases of their processing steps. The final expanded uncertainty includes both the 14C measurement uncertainties and uncertainties originating from pretreatment steps. Where the 14C measurement uncertainty includes straightforward uncertainties arising from Poisson statistics, background subtraction, calibration on Oxalic Acid II and δ13C correction, the uncertainties originating from pretreatment steps are based on the spread of actual measurement results for secondary references and sample duplicates. We show that the 14C measurement uncertainty requires expansion, depending on the number of processing steps involved prior to a 14C measurement, by a maximum factor of 1.6 at our laboratory. By using these expansion (multiplication) factors, we make our reported uncertainty both more realistic and reliable

USGS44, a new high purity calcium carbonate reference material for δ13 C measurements

RATIONALE: The stable carbon isotopic (δ13 C) reference material (RM) LSVEC Li2 CO3 has been found to be unsuitable for δ13 C standardization work because its δ13 C value increases with exposure to atmospheric CO2 . A new CaCO3 RM, USGS44, has been prepared to alleviate this situation. METHODS: USGS44 was prepared from 8 kg of Merck high purity CaCO3 . Two sets of δ13 C values of USGS44 were determined. The first set of values was determined by on-line combustion, continuous-flow (CF) isotope-ratio mass spectrometry (IRMS) of NBS 19 CaCO3 (δ13 CVPDB = +1.95 milliurey (mUr) exactly, where mUr = 0.001 = 1 ‰), and LSVEC Li2 CO3 (δ13 CVPDB = -46.6 mUr exactly), and normalized to the two-anchor δ13 CVPDB-LSVEC isotope-delta scale. The second set of values was obtained by dual-inlet (DI) IRMS of CO2 evolved by reaction of H3 PO4 with carbonates, corrected for cross contamination, and normalized to the single anchor δ13 CVPDB scale. RESULTS: USGS44 is stable and isotopically homogeneous to within 0.02 mUr in 100-μg amounts. It has a δ13 CVPDB-LSVEC value of -42.21 ± 0.05 mUr. Single-anchor δ13 CVPDB values of -42.08 ± 0.01 and -41.99 ± 0.02 mUr were determined by DI-IRMS with corrections for cross contamination. CONCLUSIONS: The new high-purity, well homogenized calcium carbonate isotopic reference material USGS44 is stable and has a δ13 CVPDB-LSVEC value of -42.21 ± 0.05 mUr for both EA-IRMS and DI-IRMS measurements. As a carbonate relatively depleted in 13 C, it is intended for daily use as a secondary isotopic reference material to normalize stable carbon isotope-delta measurements to the δ13 CVPDB-LSVEC scale. It is useful in quantifying drift with time, determining mass-dependent isotopic fractionation (linearity correction), and adjusting isotope-ratio-scale contraction. Due to its fine grain size (smaller than 63 μm), it is not suitable as a δ18 O reference material. A δ13 CVPDB-LSVEC value of -29.99 ± 0.05 mUr was determined for NBS 22 oil

Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils

An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ^2H_(VSMOW-SLAP) values from −210.8 to +397.0 mUr or ‰, for δ^(13)C_(VPDB-LSVEC) from −40.81 to +0.49 mUr and for δ^(15)N_(Air) from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C_(16) n-alkanes, n-C_(20)-fatty acid methyl esters (FAMEs), glycines, and L-valines, together with polyethylene powder and string, one n-C_(17)-FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a ^2H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ2H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain ^(13)C and carbon-bound organic ^2H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies

Dating of Cremated Bones

From the 17th International Radiocarbon Conference held in Jerusalem, Israel, June 18-23, 2000.When dating unburnt bone, bone collagen, the organic fraction of the bone, is used. Collagen does not survive the heat of the cremation pyre, so dating of cremated bone has been considered impossible. Structural carbonate in the mineral fraction of the bone, however, survives the cremation process. We developed a method of dating cremated bone by accelerator mass spectrometry (AMS), using this carbonate fraction. Here we present results for a variety of prehistoric sites and ages, showing a remarkable success rate for this method.The Radiocarbon archives are made available by Radiocarbon and the University of Arizona Libraries. Contact [email protected] for further information.Migrated from OJS platform February 202

Contamination on AMS Sample Targets by Modern Carbon is Inevitable

Accelerator mass spectrometry (AMS) measurements of the radiocarbon content in very old samples are often challenging and carry large relative uncertainties due to possible contaminations acquired during the preparation and storage steps. In case of such old samples, the natural surrounding levels of C-14 from gases in the atmosphere, which may well be the source of contamination among others, are 2-3 orders of magnitude higher than the samples themselves. Hence, serious efforts are taken during the preparation steps to have the samples pristine until measurements are performed. As samples often have to be temporarily stored until AMS measurements can be performed, storage conditions also become extremely crucial. Here we describe an assessment of this process of contamination in background AMS samples. Samples, both as pressed graphite (on AMS targets) and graphite powder, were stored in various storage conditions (CO2-spiked air) to investigate the extent of contamination. The experiments clearly show that the pressed targets are more vulnerable to contamination than the unpressed graphite. Experiments conducted with enriched CO2-spiked laboratory air also reveal that the contaminating carbon is not only limited to the target surface but also penetrates into the matrix. A combination of measurements on understanding the chemical nature of the graphitization product, combined with long-available knowledge on "adventitious carbon" from the surface science community, brought us to the conclusion that contamination is to a certain extent inevitable. However, it can be minimized, and should be dealt with by sputter-cleaning the samples individually before the actual measurement