δ13 C and δ18 O heterogeneities in carbonates: Nonlinear mixing in the application of dual-carbonate-clumped isotope thermometer.

RATIONALE: Dual-carbonate-clumped isotope thermometry assumes any departure from Δ47 and Δ48 co-equilibrium is due to disequilibrium processes; however, the effects of endmember mixing have not been evaluated for Δ48 . We show that variations in δ13 C and δ18 O values within a sample can lead to offsets in Δ47 and Δ48 that can be mistaken for kinetic fractionation. METHODS: A numerical mixing model was developed to calculate the Δ48 and Δ47 values of samples with heterogeneous isotope compositions. The model was used to test a variety of possible endmember mixing scenarios and produce a dataset of mixing offsets in both Δ48 and Δ47 . RESULTS: Different mixing patterns arise from endmember mixing, with different patterns between Δ48 and Δ47 . Δ47 can be both positively and negatively offset from equilibrium values by mixing; however, Δ48 can only be offset in a positive direction, producing an underestimate of formation temperature. The overall results suggest that endmember mixing can mimic kinetic fractionation caused by CO2 degassing in dual-clumped isotope measurements. CONCLUSIONS: Mixing between endmembers can result in patterns that resemble that of CO2 degassing. However, these effects require a variation of greater than 5‰ in endmember δ18 O values to have a significant effect relative to measurement errors on Δ48 with the detection limits of modern mass spectrometers. Δ47 remains more sensitive to endmember mixing effects and will display measurable mixing effects at 2‰ variation or less in endmember isotopic values.

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

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.

Effects of different constants and standards on the reproducibility of carbonate clumped isotope (Δ47 ) measurements: Insights from a long-term dataset.

RATIONALE: Carbonate clumped isotope (Δ47 ) thermometry examines the temperature-dependent excess abundance of the 13 C-18 O bond in the carbonate lattice. Inconsistent temperature calibrations and standard values have been reported among laboratories, which has led to the use of equilibrated gases and carbonate standards for standardization. Furthermore, different acid fractionation factors and isotopic parameter sets have been proposed for improving inter-laboratory data comparability. However, few long-term datasets have been generated to explore the effects of these factors on the long-term reproducibility of Δ47 data within a laboratory. METHODS: Four standards (ISTB-1, NBS-19, GBWO4416, and GB04417) were analyzed as unknowns by isotope ratio mass spectrometry from 2015 to 2019. The values of Δ47 were calibrated using the ETH standards. We investigated the Assonov, Brand, and Gonfiantini isotope parameter sets for carbon and oxygen isotopes, as well as two correction schemes of equilibrated gas and carbonate standardization, using the same sample measurements to determine which procedures enhanced reproducibility. ISTB-1 (calcite) and ZK312-346W (dolomite) were measured to determine the 90°C acid fractionation factor. RESULTS: The corrected 90°C acid fractionation factors are 0.076 ± 0.008‰ for ISTB-1 and 0.077 ± 0.009‰ for ZK312-346W. The choice of isotope parameter set had no significant influence on final Δ47 values in this study. However, using the Assonov parameters to calculate Δ47 values improved the reproducibility of the results. The use of carbonate standards improved reproducibility through time compared with the use of equilibrated gases for standardization. CONCLUSIONS: At 90°C, the acid fractionation factors of calcite and dolomite are statistically indistinguishable. We find an insignificant effect from changing the isotope parameter set, suggesting that the choice of isotope parameter set among laboratories is not a major factor affecting inter-laboratory reproducibility. We find that using carbonate standards improved the reproducibility of results, suggesting that the use of carbonate standards may help to achieve inter-laboratory comparability of results in future studies.

Analytical effects on clumped isotope thermometry: Comparison of a common sample set analyzed using multiple instruments, types of standards, and standardization windows.

RATIONALE: Carbonate clumped isotope geothermometry is being increasingly used in multiple disciplines in the geosciences. However, potential interlaboratory issues are arising from different standardization procedures that may contribute to the multiple Δ47 -temperature calibrations reported in the literature. We investigate this issue by comparing a common temperature calibration sample set across three different mass spectrometers, using multiple standardization methods. METHODS: The same temperature calibration sample set was analyzed on three different mass spectrometers. Several standardization methods were utilized, including the use of carbonate versus gas standards, and different types of background correction were applied to the raw data. RESULTS: All standardization types applied resulted in statistically indistinguishable Δ47 -temperature slopes, with the exception of standardization calculations that did not correct for background effects. Some instruments and standardizations showed different intercepts relative to each other. The use of carbonate standards improved comparability between different instruments relative to gas standards. CONCLUSIONS: Our results show that background effects are the largest factor potentially affecting Δ47 results, and there may be an improvement in interlaboratory precision using carbonate standards. Critically, all techniques used for standardizing Δ47 results converge on a common slope as long as background effects are properly corrected. The use of carbonate standards is recommended as a component of standardization procedures.

Non-linear mixing effects on mass-47 CO2 clumped isotope thermometry: Patterns and implications.

RATIONALE: Mass-47 CO(2) clumped isotope thermometry requires relatively large (~20 mg) samples of carbonate minerals due to detection limits and shot noise in gas source isotope ratio mass spectrometry (IRMS). However, it is unreasonable to assume that natural geologic materials are homogenous on the scale required for sampling. We show that sample heterogeneities can cause offsets from equilibrium Δ(47) values that are controlled solely by end member mixing and are independent of equilibrium temperatures. METHODS: A numerical model was built to simulate and quantify the effects of end member mixing on Δ(47). The model was run in multiple possible configurations to produce a dataset of mixing effects. We verified that the model accurately simulated real phenomena by comparing two artificial laboratory mixtures measured using IRMS to model output. RESULTS: Mixing effects were found to be dependent on end member isotopic composition in δ(13)C and δ(18)O values, and independent of end member Δ(47) values. Both positive and negative offsets from equilibrium Δ(47) can occur, and the sign is dependent on the interaction between end member isotopic compositions. The overall magnitude of mixing offsets is controlled by the amount of variability within a sample; the larger the disparity between end member compositions, the larger the mixing offset. CONCLUSIONS: Samples varying by less than 2 ‰ in both δ(13)C and δ(18)O values have mixing offsets below current IRMS detection limits. We recommend the use of isotopic subsampling for δ(13)C and δ(18)O values to determine sample heterogeneity, and to evaluate any potential mixing effects in samples suspected of being heterogonous.