Open AccessEffects of Improved 17 O Correction on Interlaboratory Agreement in Clumped Isotope Calibrations, Estimates of Mineral‐Specific Offsets, and Temperature Dependence of Acid Digestion Fractionation
Author(s) -
Petersen S. V.,
Defliese W. F.,
Saenger C.,
Daëron M.,
Huntington K. W.,
John C. M.,
Kelson J. R.,
Bernasconi S. M.,
Colman A. S.,
Kluge T.,
Olack G. A.,
Schauer A. J.,
Bajnai D.,
Bonifacie M.,
Breitenbach S. F. M.,
Fiebig J.,
Fernandez A. B.,
Henkes G. A.,
Hodell D.,
Katz A.,
Kele S.,
Lohmann K. C.,
Passey B. H.,
Peral M. Y.,
Petrizzo D. A.,
Rosenheim B. E.,
Tripati A.,
Venturelli R.,
Young E. D.,
Winkelstern I. Z.
Publication year - 2019
Publication title -
geochemistry, geophysics, geosystems
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.928
H-Index - 136
ISSN - 1525-2027
DOI - 10.1029/2018gc008127
Subject(s) - calibration , fractionation , isotope , carbonate , mineralogy , geology , equilibrium fractionation , diagenesis , analytical chemistry (journal) , chemistry , isotope fractionation , statistics , mathematics , environmental chemistry , chromatography , physics , organic chemistry , quantum mechanics
The clumped isotopic composition of carbonate‐derived CO 2 (denoted Δ 47 ) 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: R 13 VPDB , R 17 VSMOW , R 18 VSMOW , and λ ) impact calculated Δ 47 values. Here, we investigate whether use of updated and more accurate values for these parameters can remove observed interlaboratory differences in the measured T‐Δ 47 relationship. 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‐Δ 47 relationship (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 Δ 47 (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‐Δ 47 relationship, but many more remain to be investigated.