The clumped isotopic composition of carbonate‐derived CO2 (denoted Δ47) is a function of carbonate formation temperature and in natural samples can act as a recorder of paleoclimate, burial, or diagenetic conditions. The absolute abundance of heavy isotopes in the universal standards VPDB and VSMOW (defined by four parameters: R13VPDB, R17VSMOW, R18VSMOW, and λ) impact calculated Δ47 values. Here, we investigate whether use of updated and more accurate values for these parameters can remove observed interlaboratory differences in the measured T‐Δ47 relationship. Using the updated parameters, we reprocess 14 published calibration data sets measured in 11 different laboratories, representing many mineralogies, bulk compositions, sample types, reaction temperatures, and sample preparation and analysis methods. Exploiting this large composite data set (n = 1,253 sample replicates), we investigate the possibility for a “universal” clumped isotope calibration. We find that applying updated parameters improves the T‐Δ47 relationship (reduces residuals) within most labs and improves overall agreement but does not eliminate all interlaboratory differences. We reaffirm earlier findings that different mineralogies do not require different calibration equations and that cleaning procedures, method of pressure baseline correction, and mass spectrometer type do not affect interlaboratory agreement. We also present new estimates of the temperature dependence of the acid digestion fractionation for Δ47 (Δ*25‐X), based on combining reprocessed data from four studies, and new theoretical equilibrium values to be used in calculation of the empirical transfer function. Overall, we have ruled out a number of possible causes of interlaboratory disagreement in the T‐Δ47 relationship, but many more remain to be investigated.

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a b s t r a c tGrowing pressure on sustainable water resource allocation in the context of global development and rapid environmental change demands rigorous knowledge of how regional water cycles change through time. One of the most attractive and widely utilized approaches for gaining this knowledge is the analysis of lake carbonate stable isotopic compositions. However, endogenic carbonate archives are sensitive to a variety of natural processes and conditions leaving isotopic datasets largely underdetermined. As a consequence, isotopic researchers are often required to assume values for multiple parameters, including temperature of carbonate formation or lake water d 18 O, in order to interpret changes in hydrologic conditions. Here, we review and analyze a global compilation of 57 lacustrine dual carbon and oxygen stable isotope records with a topical focus on the effects of shifting hydrologic balance on endogenic carbonate isotopic compositions.Through integration of multiple large datasets we show that lake carbonate d 18 O values and the lake waters from which they are derived are often shifted by >þ10‰ relative to source waters discharging into the lake. The global pattern of d 18 O and d 13 C covariation observed in >70% of the records studied and in several evaporation experiments demonstrates that isotopic fractionations associated with lake water evaporation cause the heavy carbon and oxygen isotope enrichments observed in most lakes and lake carbonate records. Modeled endogenic calcite compositions in isotopic equilibrium with lake source waters further demonstrate that evaporation effects can be extreme even in lake records where d 18 O and d 13 C covariation is absent. Aridisol pedogenic carbonates show similar isotopic responses to evaporation, and the relevance of evaporative modification to paleoclimatic and paleotopographic research using endogenic carbonate proxies are discussed.Recent advances in stable isotope research techniques present unprecedented opportunities to overcome the underdetermined nature of stable isotopic data through integration of multiple isotopic proxies, including dual element 13 C-excess values and clumped isotope temperature estimates. We demonstrate the utility of applying these multi-proxy approaches to the interpretation of paleohydroclimatic conditions in ancient lake systems. Understanding past, present, and future hydroclimatic systems is a global imperative. Significant progress should be expected as these modern research techniques become more widely applied and integrated with traditional stable isotopic proxies.

Methane cold seep systems typically exhibit extensive buildups of authigenic carbonate minerals, resulting from local increases in alkalinity driven by methane oxidation. Here, we demonstrate that modern seep authigenic carbonates exhibit anomalously low clumped isotope values (Δ47), as much as ∼0.2‰ lower than expected values. In modern seeps, this range of disequilibrium translates into apparent temperatures that are always warmer than ambient temperatures, by up to 50 °C. We examine various mechanisms that may induce disequilibrium behaviour in modern seep carbonates, and suggest that the observed values result from several factors including kinetic isotopic effects during methane oxidation, mixing of inorganic carbon pools, pH effects and rapid precipitation. Ancient seep carbonates studied here also exhibit potential disequilibrium signals. Ultimately, these findings indicate the predominance of disequilibrium clumped isotope behaviour in modern cold seep carbonates that must be considered when characterizing environmental conditions in both modern and ancient cold seep settings.

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.

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

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.

The warm climate of Bermuda today is modulated by the nearby presence of the Gulf Stream current. However, iceberg scours in the Florida Strait and the presence of ice‐rafted debris in Bermuda Rise sediments indicate that, during the last deglaciation, icebergs discharged from the Laurentide Ice Sheet traveled as far south as subtropical latitudes. We present evidence that an event of similar magnitude affected the subtropics during the Last Interglacial, potentially due to melting of the Greenland Ice Sheet. Using the clumped isotope paleothermometer, we found temperatures ~10°C colder and seawater δ18O values ~2‰ lower than modern in Last Interglacial Cittarium pica shells from Grape Bay, Bermuda. In contrast, Last Interglacial shells from Rocky Bay, Bermuda, record temperatures only slightly colder and seawater δ18O values similar to modern, likely representing more typical Last Interglacial conditions in Bermuda outside of a meltwater event. The significantly colder ocean temperatures observed in Grape Bay samples illustrate the extreme sensitivity of Bermudian climate to broad‐scale ocean circulation changes. They indicate routine meltwater transport in the North Atlantic to near‐equatorial latitudes, which would likely have resulted in disruption of the Atlantic Meridional Overturning Circulation. These data demonstrate that future melting of the Greenland Ice Sheet, a potential source of the Last Interglacial meltwater event, could have dramatic climate effects outside of the high latitudes.