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Carbonate clumped isotope thermometry (Δ47) is a temperature proxy that is becoming more widely used in the geosciences. Most calibration studies have used ordinary least squares linear regressions...

Rationale: Clumped 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. Methods: We 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). Results: We 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. Conclusions: We 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. Δ 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.

Carbonate clumped isotope (Δ ) thermometry examines the temperature-dependent excess abundance of the C- O bond in the carbonate lattice. Inconsistent temperature calibrations and standard values have been reported among laboratories, which has led to use of equilibrated gases and carbonate standards for standardization. Furthermore, different acid fractionation factors and isotopic parameter sets have been proposed to improve 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 Δ data within a laboratory. Four standards (ISTB-1, NBS-19, GBWO4416, and GB04417) were analyzed as unknowns from 2015 to 2019. Δ values 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. 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 Δ values in this study. However, using the Assonov parameters to calculate Δ values improved the reproducibility of results. The use of carbonate standards improved reproducibility through time compared to use of equilibrated gases for standardization. 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 interlaboratory reproducibility. We find that using carbonate standards improved the reproducibility of results, suggesting that the use of carbonate standards may help achieve interlaboratory comparability of results in future studies.

Carbonate clumped isotope thermometry is a useful tool practised in studies of temperature history and fluid composition of surface and subsurface environments, with application to both inorganic a...

© 2014 John Wiley & Sons Ltd. Quantitative tools for deciphering the environment of microbialite formation are relatively limited. For example, the oxygen isotope carbonate-water geothermometer requires assumptions about the isotopic composition of the water of formation. We explored the utility of using 'clumped' isotope thermometry as a tool to study the temperatures of microbialite formation. We studied microbialites recovered from water depths of 10-55 m in Pavilion Lake, and 10-25 m in Kelly Lake, spanning the thermocline in both lakes. We determined the temperature of carbonate growth and the18O/16O ratio of the waters that microbialites grew in. Results were then compared to current limnological data from the lakes to reconstruct the history of microbialite formation. Modern microbialites collected at shallow depths (11.7 m) in both lakes yield clumped isotope-based temperatures of formation that are within error of summer water temperatures, suggesting that clumped isotope analyses may be used to reconstruct past climates and to probe the environments in which microbialites formed. The deepest microbialites (21.7-55 m) were recovered from below the present-day thermoclines in both lakes and yield radioisotope ages indicating they primarily formed earlier in the Holocene. During this time, pollen data and our reconstructed water18O/16O ratios indicate a period of aridity, with lower lake levels. At present, there is a close association between both photosynthetic and heterotrophic communities, and carbonate precipitation/microbialite formation, with biosignatures of photosynthetic influences on carbonate detected in microbialites from the photic zone and above the thermocline (i.e., depths of generally