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Density functional theory and ab initio molecular dynamics reveal atomistic mechanisms for carbonate clumped isotope reordering.

ABSTRACT: Carbon (¹³C) and oxygen (¹⁸O) isotopes in carbonates form clumped isotope species inversely correlated with temperature, providing a valuable paleothermometer for sedimentary carbonates and fossils. However, this signal resets ("reorders") with increasing temperature after burial. Research on reordering kinetics has characterized reordering rates and hypothesized the effects of impurities and trapped water, but the atomistic mechanism remains obscure. This work studies carbonate-clumped isotope reordering in calcite via first-principles simulations. We developed an atomistic view of the isotope exchange reaction between carbonate pairs in calcite, discovering a preferred configuration and elucidating how Mg²⁺ substitution and Ca²⁺ vacancies lower the free energy of activation (ΔA^‡) compared to pristine calcite. Regarding water-assisted isotopic exchange, the H⁺-O coordination distorts the transition state configuration and reduces ΔA^‡. We proposed a water-mediated exchange mechanism showing the lowest ΔA^‡ involving a reaction pathway with a hydroxylated four-coordinated carbon atom, confirming that internal water facilitates clumped isotope reordering.

SUBMITTER: Perez-Beltran S

PROVIDER: S-EPMC10306293 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

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Density functional theory and ab initio molecular dynamics reveal atomistic mechanisms for carbonate clumped isotope reordering.

Perez-Beltran Saul S Zaheer Wasif W Sun Zeyang Z Defliese William F WF Banerjee Sarbajit S Grossman Ethan L EL

Science advances 20230628 26

Carbon (<sup>13</sup>C) and oxygen (<sup>18</sup>O) isotopes in carbonates form clumped isotope species inversely correlated with temperature, providing a valuable paleothermometer for sedimentary carbonates and fossils. However, this signal resets ("reorders") with increasing temperature after burial. Research on reordering kinetics has characterized reordering rates and hypothesized the effects of impurities and trapped water, but the atomistic mechanism remains obscure. This work studies carb ...[more]

PMID: 37379381

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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.

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Density functional theory and ab initio molecular dynamics reveal atomistic mechanisms for carbonate clumped isotope reordering.

Publications

Density functional theory and ab initio molecular dynamics reveal atomistic mechanisms for carbonate clumped isotope reordering.

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