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Rationale The clumped isotope paleothermometer, a new proxy widely applicable in studies of paleoclimate, tectonics, and paleontology, relates the abundance of doubly substituted isotopologues of carbonate-derived CO2 to the temperature of formation of the carbonate phase. As this technique becomes more widely used, more is discovered about the effects of everyday laboratory procedures on the clumped isotopic composition of CO2 gas. Methods Preparation of CO2 for clumped isotope analysis requires the removal of isobaric contaminants prior to measurement, achieved dynamically by passing the CO2 through a gas chromatography column using a helium carrier gas or cryogenically pumping CO2 through a static trap filled with Porapak™ Q (PPQ) material. The stable and clumped isotopic compositions of carbonate standards prepared at PPQ trap temperatures between −40°C and −10°C were measured by isotope ratio mass spectrometry to evaluate potential artifacts introduced by the static PPQ trap method. Results The stable isotopic composition of carbonates run at temperatures below −20°C was fractionated, despite achieving >99% retrieval of gas at temperatures as cold as −30°C. The δ13C and δ18O values decreased by ~0.01 and ~0.03 ‰/(°C below −20°C). The raw Δ47 values decreased by 0.003–0.005 ‰/(°C below −20°C), but the final reference-frame-corrected values (Δ47-RFAC) were unaffected as long as the carbonate samples and standard gases were prepared identically. Conclusions Preparing carbonate samples for clumped isotope analysis using a PPQ trap that is too cold can result in erroneous stable isotopic compositions. New and existing labs using the static PPQ trap cleaning procedure should determine the ideal PPQ trap temperature for their particular system through monitoring not only yield through the PPQ trap, but also stable isotopic composition at various PPQ trap temperatures. Copyright © 2015 John Wiley & Sons, Ltd.

RATIONALE The measurement of multiply substituted isotopologues of CO2 derived from carbonate has allowed the reconstruction of paleotemperatures from a single phase (CaCO3), circumventing uncertainty inherent in other isotopic paleothermometers. Traditional analytical techniques require relatively large amounts of carbonate (3–8 mg per replicate), which limits the applicability of the clumped isotope proxy to certain geological materials such as marine microfossils, commonly used for paleoclimate reconstructions. METHODS Clumped isotope ratio measurements of small samples were made on a new, high-efficiency, dual-reservoir sample-preparation inlet system attached to a Thermo-Finnigan MAT 253 mass spectrometer. Sample gas produced on the inlet is introduced from a 10 mL reservoir directly into the source via a capillary. Reference gas fills an identical 10 mL reservoir installed between the reference bellows and the capillary. The gas pressures in the two reservoirs are initially balanced, and are allowed to decrease together over the run. RESULTS Carbonate samples from 1 mg to 2.6 mg produced Δ47 values equivalent to those from the traditional two-bellows method with identical single-sample precision (1 SE = 0.005–0.015‰) and external standard error (SE = 0.006–0.015‰, n = 4–6). The size of sample needed to achieve good precision is controlled by the sensitivity of the mass spectrometer and the size of the fixed reservoirs and adjacent U-trap installed on our inlet. CONCLUSIONS The high-precision clumped isotope measurements of small aliquots of carbonate obtained in this method allows for the application of this proxy to a wider range of geological sample materials, such as marine microfossils, that until now have been nearly impossible to analyze given sample size limitation. Copyright © 2014 John Wiley & Sons, Ltd.