The geochemistry of multiply substituted isotopologues ('clumped-isotope' geochemistry) examines the abundances in natural materials of molecules, formula units or moieties that contain more than one rare isotope (e.g. (13)C(18)O(16)O, (18)O(18)O, (15)N(2), (13)C(18)O(16)O(2) (2-)). Such species form the basis of carbonate clumped-isotope thermometry and undergo distinctive fractionations during a variety of natural processes, but initial reports have provided few details of their analysis. In this study, we present detailed data and arguments regarding the theoretical and practical limits of precision, methods of standardization, instrument linearity and related issues for clumped-isotope analysis by dual-inlet gas-source isotope ratio mass spectrometry (IRMS). We demonstrate long-term stability and subtenth per mil precision in 47/44 ratios for counting systems consisting of a Faraday cup registered through a 10(12) ohm resistor on three Thermo-Finnigan 253 IRMS systems. Based on the analyses of heated CO(2) gases, which have a stochastic distribution of isotopes among possible isotopologues, we document and correct for (1) isotopic exchange among analyte CO(2) molecules and (2) subtle nonlinearity in the relationship between actual and measured 47/44 ratios. External precisions of approximately 0.01 per thousand are routinely achieved for measurements of the mass-47 anomaly (a measure mostly of the abundance anomaly of (13)C-(18)O bonds) and follow counting statistics. The present technical limit to precision intrinsic to our methods and instrumentation is approximately 5 parts per million (ppm), whereas precisions of measurements of heterogeneous natural materials are more typically approximately 10 ppm (both 1 s.e.). These correspond to errors in carbonate clumped-isotope thermometry of +/-1.2 degrees C and +/-2.4 degrees C, respectively.

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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The potential for carbonate clumped isotope thermometry to independently constrain both the formation temperature of carbonate minerals and fluid oxygen isotope composition allows insight into long‐standing questions in the Earth sciences, but remaining discrepancies between calibration schemes hamper interpretation of temperature measurements. To address discrepancies between calibrations, we designed and analyzed a sample suite (41 total samples) with broad applicability across the geosciences, with an exceptionally wide range of formation temperatures, precipitation methods, and mineralogies. We see no statistically significant offset between sample types, although the comparison of calcite and dolomite remains inconclusive. When data are reduced identically, the regression defined by this study is nearly identical to that defined by four previous calibration studies that used carbonate‐based standardization; we combine these data to present a composite carbonate‐standardized regression equation. Agreement across a wide range of temperature and sample types demonstrates a unified, broadly applicable clumped isotope thermometer calibration.

The exclusive use of carbonate reference materials is a robust method for the standardization of clumped isotope measurements • Measurements using different acid temperatures, designs of preparation lines, and mass spectrometers are statistically indistinguishable • We propose new consensus values for a set of 7 carbonate reference materials and updated guidelines to report clumped isotope measurements

The elevation history of Earth's surface is key to understanding the geodynamic processes responsible for the rise of plateaus. We investigate the timing of Colorado Plateau uplift by estimating depositional temperatures of Tertiary lake sediments that blanket the plateau interior and adjacent lowlands using carbonate clumped isotope paleothermometry (a measure of the temperature‐dependent enrichment of 13C‐18O bonds in carbonates). Comparison of modern and ancient samples deposited near sea level provides an opportunity to quantify the influence of climate and therefore assess the contribution of changes in elevation to the variations of surface temperature on the plateau. Analysis of modern lake calcite from 350 to 3300 m elevation in the southwestern United States reveals a lake water carbonate temperature (LCT) lapse rate of 4.2 ± 0.6°C/km. Analysis of Miocene deposits from 88 to 1900 m elevation in the Colorado River drainage suggests that the ancient LCT lapse rate was 4.1 ± 0.7°C/km, and temperatures were 7.7 ± 2.0°C warmer at any one elevation than predicted by the modern trend. The inferred cooling is plausible in light of Pliocene temperature estimates off the coast of California, and the consistency of lapse rates through time supports the interpretation that there has been little or no elevation change for any of the samples since 6 Ma. Together with previous paleorelief estimates from apatite (U‐Th)/He data from the Grand Canyon, our results suggest most or all of the plateau's lithospheric buoyancy was acquired ∼80–60 Ma and do not support explanations that ascribe most plateau uplift to Oligocene or younger disposal of either the Farallon or North American mantle lithosphere.

The O correction strategy employed by CO and carbonate clumped-isotope researchers can have a large effect on the accuracy of Δ values. Use of the traditional O correction may have caused errors in published studies as large as 0.1 ‰ and may account for Δ differences among laboratories and disagreement among previously published carbonate clumped isotope thermometry calibrations. Copyright © 2016 John Wiley & Sons, Ltd.

[1] In the Himalaya and other active convergent orogens, linear relationships between thermochronometer sample age and elevation are often used to estimate long-term exhumation rates. In these regions, high-relief topography and nonvertical exhumation pathways may invalidate such one-dimensional (1-D) interpretations and lead to significant errors. To quantify these errors, we integrate apatite fission track (AFT) ages from the central Himalaya with a 3-D coupled thermokinematic model, from which sample cooling ages are predicted using a cooling-rate-dependent algorithm. By changing the slip partitioning between faults near the Main Central thrust and the Main Frontal thrust system at the Himalayan range front, we are able to explore the significance of different tectonic scenarios on predicted thermochronometer ages. We find that the predicted AFT cooling ages are not sensitive to the different slip partitioning scenarios but depend strongly on erosion rate: Predicted ages are most consistent with kinematic models that produce erosion rates of 1.8-5.0 mm/yr. This range is considerably smaller than that derived from regression lines through the data (À2.6-12.2 mm/yr). The pattern of observed AFT ages shows more complexity than our models predict. None of the kinematic scenarios are able to fit >80% of all of the AFT data, most likely because erosion is spatially variable. Such complexities notwithstanding, we conclude that the use of thermokinematic modeling and thermochronologic data sets to explore detailed fault kinematics in rapidly eroding active orogens has great promise but requires integration of higher-temperature (>$350°C) data sets to maximize effectiveness.