Absolute isotopic abundance ratios and the accuracy of Δ47 measurements

Clumped isotope measurements aim to quantify some statistical properties of the isotopologue population in a given sample, which requires prior knowledge of the absolute isotopic abundance ratios in reference materials such as VSMOW or VPDB. In the case of CO2, matters are further complicated by the need to define a mass-dependent fractionation law linking the three stable isotopes of oxygen. Conversion from raw mass spectrometric data to mass-47 anomalies (Delta(47)) thus relies on four external parameters: the (C-13/C-12) ratio of VPDB, the (O-17/O-16) and (O-18/O-16) ratios of VSMOW (or VPDB-CO2), and the slope of the triple oxygen isotope line (lambda). Here we investigate the influence that these isotopic parameters exert on measured Delta(47) values, using (a) real-world data corresponding to seven months of measurements; (b) simple simulations based on randomly generated data; (c) precise comparisons between water-equilibrated CO2 samples and between carbonate standards believed to share quasi-identical Delta(47) values; and (d) reprocessing of two carbonate calibration data sets with different slopes of Delta(47) versus T. We demonstrate that the use of different sets of isotopic parameters generally produces systematic offsets as large as 0.04% in measured Delta(47) values, even after following the established standardization procedures. What's more, even using a single set of isotopic parameters can produce intra-and inter-laboratory discrepancies in measured Delta(47) values, if some of these parameters are inaccurate, and depending on the isotopic compositions of the standards used for conversion to the absolute scale of Dennis et al. (2011), these errors should correlate strongly with either delta C-13 or delta O-18, or more weakly with both. Based on measurements of samples expected to display quasi-identical Delta(47) values, such as 25 degrees C water-equilibrated CO2 with different carbon and oxygen isotope compositions, or high-temperature standards ETH-1 and ETH-2, we conclude that the traditional set of isotopic parameters used in all early clumped isotope studies produces large, systematic errors controlled by the relative bulk isotopic compositions of samples and standards. These errors are likely to be one of the key factors responsible for current inter-laboratory discrepancies, but cannot easily explain the conflicting carbonate calibration slopes obtained by different groups. By contrast, the isotopic parameters of Brand et al. (2010) appear to yield accurate Delta(47) values regardless of bulk isotopic composition. Based on these findings, we offer recommendations aiming to minimize errors related to the choice of isotopic parameters. (C) 2016 Elsevier B.V. All rights reserved.