About a decade after its introduction, the field of carbonate clumped isotope thermometry is rapidly expanding because of the large number of possible applications and its potential to solve long‐standing questions in Earth Sciences. Major factors limiting the application of this method are the very high analytical precision required for meaningful interpretations, the relatively complex sample preparation procedures, and the mass spectrometric corrections needed. In this paper we first briefly review the evolution of the analytical and standardization procedures and discuss the major remaining sources of uncertainty. We propose that the use of carbonate standards to project the results to the carbon dioxide equilibrium scale can improve interlaboratory data comparability and help to solve long‐standing discrepancies between laboratories and temperature calibrations. The use of carbonates reduces uncertainties related to gas preparation and cleaning procedures and ensures equal treatment of samples and standards. We present a set of carbonate standards of diverse composition, discuss how they can be used to correct for mass spectrometric biases, and demonstrate that their use significantly improves the comparability among four laboratories. We propose that the use of these standards or of a similar set of carbonate standards will improve the comparability of data across laboratories.

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.

Considerable efforts have been made to calibrate the D 47 paleothermometer, which derives from the quantity of 13 C-18 O bonds in carbon dioxide produced during acid digestion of carbonate minerals versus its expected stochastic abundance, in a range of materials. However the impacts of precipitation rate, ionic strength, and pH on carbonate D 47 values are still unclear. Here we present a set of 75 measurements of D 47 values from inorganic calcites grown under well-controlled experimental conditions, where we evaluate the impact on D 47 values of precipitation rate (log R = 1.8-4.4 lmol/m 2 /h), pH (8.3-10.5; NBS pH scale), and ionic strength (I = 35-832 mM). With the data available and at the current instrumental resolution, our study does not resolve any clear effects of pH, ionic strength, growth rate effects on measured D 47 when compared in magnitude to the effects on d 18 O over most of the ranges of parameters sampled by our analyses. If these relationships exist, they must be smaller than our current ability to resolve them within our dataset. Under our experimental conditions, a D 47-temperature equation, which is apparently insensitive to variation in pH, precipitation rate, and ionic strength over the range of variables sampled, can be written as D 47 ¼ ð0:0387 AE 0:0072Þ Â 10 6 =T 2 þ ð0:2532 AE 0:0829Þ ðr 2 ¼ 0:9998; p ¼ 0:009Þ where D 47 values were reported on the absolute D 47 reference frame after normalizing to conventional 25°C reaction temperature using an acid fractionation factor of À0.00141&°C À1 .

This study demonstrates that by using a Kiel IV-253 Plus system with LIDI it is possible to achieve the same analytical precision as conventional DI measurements with at least a factor of 40 less sample material. With the new 10 ohm resistor technology there is the potential to reduce the required sample material even more. This opens new avenues of research in paleoceanography, paleoclimatology, low-temperature diagenesis and other currently sample size limited applications. Copyright © 2017 John Wiley & Sons, Ltd.

The middle Miocene is an important analogue for potential future warm climates. However, few independent deep ocean temperature records exist, though these are important for climate model validation and estimates of changes in ice volume. Existing records, all based on the foraminiferal Mg/Ca proxy, suggest that bottom water temperatures were 5–8°C warmer than present. In order to improve confidence in these bottom water temperature reconstructions, we generated a new record using carbonate clumped isotopes (Δ47) and compared our results with Mg/Ca‐based estimates for the Indian Ocean at ODP Site 761. Our results indicate temperatures of 11.0 ± 1.7°C during the middle Miocene Climatic Optimum (MCO, 14.7–17 Ma) and 8.1 ± 1.9°C after the middle Miocene Climate Transition (MCT, 13.0–14.7 Ma), values 6 to 9°C warmer than present. Our record also indicates cooling across the MCT of 2.9 ± 2.5°C (uncertainties 95% confidence level). The Mg/Ca record derived from the same samples indicates temperatures well within uncertainty of Δ47. As the two proxies are affected by different non‐thermal biases, the good agreement provides confidence in these reconstructed temperatures. Our Δ47 temperature record implies a ~0.6‰ seawater δ18O change over the MCT, in good agreement with previously published values from other sites. Our data furthermore confirm overall high seawater δ18O values across the middle Miocene, at face value suggesting ice volumes exceeding present‐day despite the warm bottom water temperatures. This finding suggests previously underappreciated additional influences on seawater δ18O and/or a decoupling of ice volume and ocean temperature.