Clumped isotopologue constraints on the origin of methane at seafloor hot springs

Apparent equilibrium temperatures retrieved from methane clumped isotopologue analyses average 310-42+53 °C, with no apparent relation to the wide range of fluid temperatures (96-370 °C) and chemical compositions (pH, [H2], [∑CO2], [CH4]) represented. Combined with very similar bulk stable isotope ratios (13C/12C and D/H) of methane across the suite of hydrothermal fluids, all available geochemical and isotopic data suggest a common mechanism of methane generation at depth that is disconnected from active fluid circulation. Attainment of equilibrium amongst methane isotopologues at temperatures of ca. 270-360 °C is compatible with the thermodynamically-favorable reduction of CO2 to CH4 at temperatures at or below ca. 400 °C under redox conditions characterizing intrusive rocks derived from sub-ridge melts. Collectively, the observations support a model where methane-rich aqueous fluids, known to be trapped in rocks of the oceanic lithosphere, are liberated from host rocks during hydrothermal circulation and perhaps represent the major source of methane venting with thermal waters at unsedimented hydrothermal fields. The results also provide further evidence that water-rock reactions occurring at temperatures lower than 200 °C do not contribute significantly to the quantities of methane venting at mid-ocean ridge hot springs.