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Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures.

ABSTRACT: Surface temperature is a fundamental parameter of Earth's climate. Its evolution through time is commonly reconstructed using the oxygen isotope and the clumped isotope compositions of carbonate archives. However, reaction kinetics involved in the precipitation of carbonates can introduce inaccuracies in the derived temperatures. Here, we show that dual clumped isotope analyses, i.e., simultaneous ?47 and ?48 measurements on the single carbonate phase, can identify the origin and quantify the extent of these kinetic biases. Our results verify theoretical predictions and evidence that the isotopic disequilibrium commonly observed in speleothems and scleractinian coral skeletons is inherited from the dissolved inorganic carbon pool of their parent solutions. Further, we show that dual clumped isotope thermometry can achieve reliable palaeotemperature reconstructions, devoid of kinetic bias. Analysis of a belemnite rostrum implies that it precipitated near isotopic equilibrium and confirms the warmer-than-present temperatures during the Early Cretaceous at southern high latitudes.

SUBMITTER: Bajnai D

PROVIDER: S-EPMC7418028 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures.

Bajnai David D Guo Weifu W Spötl Christoph C Coplen Tyler B TB Methner Katharina K Löffler Niklas N Krsnik Emilija E Gischler Eberhard E Hansen Maximilian M Henkel Daniela D Price Gregory D GD Raddatz Jacek J Scholz Denis D Fiebig Jens J

Nature communications 20200810 1

Surface temperature is a fundamental parameter of Earth's climate. Its evolution through time is commonly reconstructed using the oxygen isotope and the clumped isotope compositions of carbonate archives. However, reaction kinetics involved in the precipitation of carbonates can introduce inaccuracies in the derived temperatures. Here, we show that dual clumped isotope analyses, i.e., simultaneous ∆<sub>47</sub> and ∆<sub>48</sub> measurements on the single carbonate phase, can identify the orig ...[more]

PMID: 32778658

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Project description:RationaleClumped isotope geochemistry examines the pairing or clumping of heavy isotopes in molecules and provides information about the thermodynamic and kinetic controls on their formation. The first clumped isotope measurements of carbonate minerals were first published 15 years ago, and since then, interlaboratory offsets have been observed, and laboratory and community practices for measurement, data analysis, and instrumentation have evolved. Here we briefly review historical and recent developments for measurements, share Tripati Lab practices for four different instrument configurations, test a recently published proposal for carbonate-based standardization on multiple instruments using multi-year data sets, and report values for 21 different carbonate standards that allow for recalculations of previously published data sets.MethodsWe examine data from 4628 standard measurements on Thermo MAT 253 and Nu Perspective IS mass spectrometers, using a common acid bath (90°C) and small-sample (70°C) individual reaction vessels. Each configuration was investigated by treating some standards as anchors (working standards) and the remainder as unknowns (consistency standards).ResultsWe show that different acid digestion systems and mass spectrometer models yield indistinguishable results when instrument drift is well characterized. For linearity correction, mixed gas-and-carbonate standardization or carbonate-only standardization yields similar results. No difference is observed in the use of three or eight working standards for the construction of transfer functions.ConclusionsWe show that all configurations yield similar results if instrument drift is robustly characterized and validate a recent proposal for carbonate-based standardization using large multiyear data sets. Δ47 values are reported for 21 carbonate standards on both the absolute reference frame (ARF; also refered to as the Carbon Dioxide Equilibrated Scale or CDES) and the new InterCarb-Carbon Dioxide Equilibrium Scale (I-CDES) reference frame, facilitating intercomparison of data from a diversity of labs and instrument configurations and restandardization of a broad range of sample sets between 2006, when the first carbonate measurements were published, and the present.

Dataset Information

Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures.

Publications

Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures.

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