We report measurements of resolved 12 CH 2 D 2 and 13 CH 3 D at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve 12 CH 2 D 2 from 13 CH 3 D provides unprecedented insights into the origin and evolution of CH 4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Δ 12 CH 2 D 2 and Δ 13 CH 3 D temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH 4/ H 2 D/H exchange, underscoring the importance of reliable thermometry based on the CH 4 molecules themselves. Where Δ 12 CH 2 D 2 and Δ 13 CH 3 D values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide novel information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis versus biological processes. Deficits in 12 CH 2 D 2 compared with equilibrium values in CH 4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in 13 CH 3 D that accompany the low 12 CH 2 D 2 abundances produced by abiotic reactions. The tunneling signature may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Δ 12 CH 2 D 2 values are a key tracer of microbial recycling.
Fischer-Tropsch type (FTT) synthesis has long been proposed to account for the existence of hydrocarbons in hydrothermal fluids. We show that iron- and chromium-bearing minerals catalyze the abiotic formation of hydrocarbons. In addition to production of methane (CH4aq), we report abiotic generation of ethane (C2H6aq) and propane (C3H8aq) by mineral-catalyzed hydrothermal reactions at 390 degrees C and 400 bars. Results suggest that the chromium component in ultramafic rocks could be an important factor for FTT synthesis during water-rock interaction in mid-ocean ridge hydrothermal systems. This in turn could help to support microbial communities now recognized in the subsurface at deep-sea vents.
[1] In June 1999, an intense swarm of earthquakes occurred on the Endeavour segment of the Juan de Fuca Ridge influencing hydrothermal activity in and around the Main Endeavour Field (MEF). Here we report the dissolved concentrations of 31 species from five high-temperature vents sampled 3 months after the seismic event. The spatial variability of vent fluid chemistry is extreme. Vapor-dominated vent fluids at Cantilever and Sully sites have high measured temperatures (375°-379°C), high dissolved gas and boron concentrations, but low SiO 2 . Modeling results indicate that these fluids can be accounted for by supercritical phase separation and brine condensation. Other vent fluids have moderate temperatures (340°-366°C) and chloride concentrations (208-426 mmol/kg), and may result from mixing of supercritical, vapor-rich fluids with evolved seawater. Phase equilibria calculations indicate that in addition to chloride, redox, temperature, and especially pressure play key roles in accounting for compositional variability of vent fluids at MEF. In comparison with earlier (1988) data, the 1999 data set reveals significantly lower chloride concentrations and higher boron, whereas alkali and alkaline earth cations are lower by 10-20% in keeping with chloride decrease. That dissolved chloride, boron, and other elements returned to preevent levels when again sampled in 2000 provide additional data documenting the inherently dynamic nature of hydrothermal systems at mid-ocean ridges.
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