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  1. Abstract

    A few key methodological uncertainties remain for the carbonate clumped isotope community. One is how to compare data among published data sets that are not anchored to the InterCarb Carbon Dioxide Equilibrium Scale (I‐CDES). A second is how temperature calibrations of calcite compare to those of other carbonate minerals in the I‐CDES—particularly dolomite and apatite—which can elucidate several Earth system dynamics. Previous calibrations of the clumped isotope thermometer for dolomite are discrepant from one another and variably (dis)agree with calibrations developed for calcite; apatite calibrations have not yet been compared between laboratories using carbonate‐based standardization. Here we report I‐CDES standardized values for a suite of 11 carbonates that are commonly measured by the clumped isotope community to aid future comparisons of non‐I‐CDES data sets. In addition, 17 dolomite samples (25–1,200°C) and five apatite samples (1–38°C) of known precipitation temperature were measured using carbonate‐based standardization. Excellent agreement between calcites and dolomites heated to similar temperatures (1,100–1,200°C) suggests no mineral‐specific differences in absolute acid fractionation factor. We show that calcite and dolomite regressions largely agree but are sensitive to sample characteristics, regression method, and how equations are statistically compared. We suggest that there is no need for a dolomite‐specific clumped isotope calibration, although our results suggest that further work is necessary to determine the influence of sample characteristics on this relationship. The apatite calibration equation defined in this study is statistically indistinguishable from calcite‐based calibrations; we corroborate previous findings that an apatite‐specific calibration is unnecessary.

     
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  2. Abstract

    The clumped isotopic composition of carbonate‐derived CO2(denoted Δ47) is a function of carbonate formation temperature and in natural samples can act as a recorder of paleoclimate, burial, or diagenetic conditions. The absolute abundance of heavy isotopes in the universal standards VPDB and VSMOW (defined by four parameters:R13VPDB,R17VSMOW,R18VSMOW, andλ) impact calculated Δ47values. Here, we investigate whether use of updated and more accurate values for these parameters can remove observed interlaboratory differences in the measured T‐Δ47relationship. Using the updated parameters, we reprocess 14 published calibration data sets measured in 11 different laboratories, representing many mineralogies, bulk compositions, sample types, reaction temperatures, and sample preparation and analysis methods. Exploiting this large composite data set (n= 1,253 sample replicates), we investigate the possibility for a “universal” clumped isotope calibration. We find that applying updated parameters improves the T‐Δ47relationship (reduces residuals) within most labs and improves overall agreement but does not eliminate all interlaboratory differences. We reaffirm earlier findings that different mineralogies do not require different calibration equations and that cleaning procedures, method of pressure baseline correction, and mass spectrometer type do not affect interlaboratory agreement. We also present new estimates of the temperature dependence of the acid digestion fractionation for Δ47(Δ*25‐X), based on combining reprocessed data from four studies, and new theoretical equilibrium values to be used in calculation of the empirical transfer function. Overall, we have ruled out a number of possible causes of interlaboratory disagreement in the T‐Δ47relationship, but many more remain to be investigated.

     
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  3. Abstract

    Increased use and improved methodology of carbonate clumped isotope thermometry has greatly enhanced our ability to interrogate a suite of Earth‐system processes. However, interlaboratory discrepancies in quantifying carbonate clumped isotope (Δ47) measurements persist, and their specific sources remain unclear. To address interlaboratory differences, we first provide consensus values from the clumped isotope community for four carbonate standards relative to heated and equilibrated gases with 1,819 individual analyses from 10 laboratories. Then we analyzed the four carbonate standards along with three additional standards, spanning a broad range of δ47and Δ47values, for a total of 5,329 analyses on 25 individual mass spectrometers from 22 different laboratories. Treating three of the materials as known standards and the other four as unknowns, we find that the use of carbonate reference materials is a robust method for standardization that yields interlaboratory discrepancies entirely consistent with intralaboratory analytical uncertainties. Carbonate reference materials, along with measurement and data processing practices described herein, provide the carbonate clumped isotope community with a robust approach to achieve interlaboratory agreement as we continue to use and improve this powerful geochemical tool. We propose that carbonate clumped isotope data normalized to the carbonate reference materials described in this publication should be reported as Δ47(I‐CDES) values for Intercarb‐Carbon Dioxide Equilibrium Scale.

     
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