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Rapid and precise measurement of carbonate clumped isotopes using laser spectroscopy

Nitzan Yanay, Zhennan Wang, David L. Dettman, Jay Quade, Katharine W. Huntington, Andrew J. Schauer, David D. Nelson, J. Barry McManus, Kaustubh Thirumalai, Saburo Sakai, Anna Rebaza Morillo, Ananya Mallik

2022Science Advances29 citationsDOIOpen Access PDF

Abstract

Carbonate clumped isotope abundance is an important paleothermometer, but measurement is difficult, slow, and subject to cardinal mass ( m/z ) interferences using isotope ratio mass spectrometry (IRMS). Here, we describe an optical spectroscopic measurement of carbonate clumped isotopes. We have adapted a tunable infrared laser differential absorption spectrometer (TILDAS) system to measure the abundances of four CO 2 isotopologues used for clumped isotope thermometry. TILDAS achieves the same precision (0.01‰ SE) as IRMS measurements rapidly (∼50 min per carbonate analysis) and using small samples (<2 mg of calcite), without making assumptions about 17 O abundance in the sample. A temperature calibration based on 406 analyses of CO 2 produced by digestion of 51 synthetic carbonates equilibrated at 6° to 1100°C is consistent with results for natural carbonates and previous calibrations. Our system results were indistinguishable from IRMS systems after replicating the InterCarb interlaboratory calibration. Measurement by TILDAS could change the landscape for clumped isotope analysis.

Topics & Concepts

IsotopologueCarbonateIsotopeCalciteCalibrationMass spectrometryStable isotope ratioAnalytical Chemistry (journal)SpectroscopyIsotope analysisAbundance (ecology)MineralogyChemistryGeologyEnvironmental chemistryEcologyPhysicsBiologyChromatographyMoleculeQuantum mechanicsOceanographyOrganic chemistryIsotope Analysis in EcologyGeology and Paleoclimatology ResearchSpectroscopy and Laser Applications
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