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Recently, methane (CH(4)) of possible abiogenic origin has been reported from many localities within Earth's crust. However, little is known about the mechanisms of abiogenic methane formation, or about isotopic fractionation during such processes. Here, a hydrothermally formed nickel-iron alloy was shown to catalyze the otherwise prohibitively slow formation of abiogenic CH(4) from dissolved bicarbonate (HCO(3)-) under hydrothermal conditions. Isotopic fractionation by the catalyst resulted in delta(13)C values of the CH(4) formed that are as low as those typically observed for microbial methane, with similarly high CH(4)/(C(2)H(6) + C(3)H(8)) ratios. These results, combined with the increasing recognition of nickel-iron alloy occurrence in oceanic crusts, suggest that abiogenic methane may be more widespread than previously thought.

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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.

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The Craig-Gordon model (C-G model) [H. Craig, L.I. Gordon. Deuterium and oxygen 18 variations in the ocean and the marine atmosphere. In Stable Isotopes in Oceanographic Studies and Paleotemperatures, E. Tongiorgi (Ed.), pp. 9-130, Laboratorio di Geologia Nucleare, Pisa (1965).] has been synonymous with the isotope effects associated with the evaporation of water from surface waters, soils, and vegetations, which in turn constitutes a critical component of the global water cycle. On the occasion of the four decades of its successful applications to isotope geochemistry and hydrology, an attempt is made to: (a) examine its physical background within the framework of modern evaporation models, (b) evaluate our current knowledge of the environmental parameters of the C-G model, and (c) comment on a general strategy for the use of these parameters in field applications. Despite its simplistic representation of evaporation processes at the water-air interface, the C-G model appears to be adequate to provide the isotopic composition of the evaporation flux. This is largely due to its nature for representing isotopic compositions (a ratio of two fluxes of different isotopic water molecules) under the same environmental conditions. Among many environmental parameters that are included in the C-G model, accurate description and calculations are still problematic of the kinetic isotope effects that occur in a diffusion-dominated thin layer of air next to the water-air interface. In field applications, it is of importance to accurately evaluate several environmental parameters, particularly the relative humidity and isotopic compositions of the 'free-atmosphere', for a system under investigation over a given time-scale of interest (e.g., hourly to daily to seasonally). With a growing interest in the studies of water cycles of different spatial and temporal scales, including paleoclimate and water resource studies, the importance and utility of the C-G model is also likely to grow in the future.

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