Hydrothermal carbon reduction in the absence of minerals

Abiotic synthesis of CH4 in seafloor hydrothermal fluids is generally assumed to occur via heterogeneous reactions on mineral surfaces. Stepwise homogeneous reduction of CO2 has, however, been suggested as an alternative (but sluggish) abiotic pathway to CH4, potentially via metastable species of intermediate oxidation states. In this study, we examine the effect of two temperature-dependent methylated species − methanol (CH3OH) and methanethiol (CH3SH), on homogeneous CH4 formation rates under long-term simulated hydrothermal conditions. Aqueous solutions containing formic acid (H13COOH, generating 13CO2 and H2) were heated with and without H2S at 300–325 °C (35 MPa) in a flexible Au reaction cell over several years without added minerals. Substantial 13C-labeled CH4 and CH3OH production from 13CO2 was observed over 4.3 yr, with aqueous CH4 formation varying with CH3OH abundance – a strong function of dissolved H2 abundance and, inversely, temperature. CH4 production was slower at 325 °C with lower CH3OH concentrations (in equilibrium with CO2 and H2), and faster at 300 °C, accompanying an equilibrium-controlled increase in CH3OH. Fastest CH4 production occurred at 300 °C following injection of H2S and H13COOH, which led to rapid formation (<4 days) of 13C-labeled CH3SH that subsequently decomposed over a further 0.8 yr, partly to 13CH4. Heating aqueous 13CH4 to 345–387 °C (33–35 MPa) in the presence of an oxidizing hematite-magnetite-pyrite assemblage, however, yielded no detectable CH3SH after 112 days indicating the reverse reaction is inhibited under favorable thermodynamics. Neither direct reduction of CO2 to CH3SH nor CO2-CH3SH equilibrium were evident at 300 °C, implying CH3SH and CH3OH play disparate roles in homogeneous carbon reduction to CH4. Longer chain hydrocarbons (C2+ alkanes) remained low throughout the experiments. CH3SH abundances previously reported in vent fluids at the Von Damm hydrothermal field correlate strongly with demonstrably abiotic HCOOH there, suggesting the reduction of HCOOH to CH3SH observed in this study may also occur in vent fluids. A comparison of mineral-free 13CH4 production rates reported here with 13CO2 reduction experiments involving minerals indicates that homogeneous reduction proceeds at similar rates to purported transition metal-catalyzed 13CH4 production, and is generally faster than experiments with either added olivine or ultramafic rock. Previous claims of substantial mineral-catalyzed abiogenic CH4 production are therefore not supported by our study. Homogeneous CO2 reduction may be a significant source of methylated compounds and CH4 in hydrothermal fluids characterized by decadal (or longer) residence times, such as those found in mineral-hosted inclusions or occluded fractures in igneous basement, requiring only moderate temperatures and abundant H2 to proceed.