Origin of methane in serpentinite-hosted hydrothermal systems: The CH4-H2-H2O hydrogen isotope systematics of the Hakuba Happo hot spring

•New onland serpentinite-hosted hydrothermal system is studied.•Hydrogen isotopes indicate that abiotic CH4 is produced from H2O not form H2.•Serpentinite-hosted methane may not been produced via Fischer-Tropsch-type synthesis.

Serpentinite-hosted hydrothermal systems have attracted considerable attention as sites of abiotic organic synthesis and as habitats for the earliest microbial communities. Here, we report a systematic isotopic study of a new serpentinite-hosted system: the Hakuba Happo hot spring in the Shiroumadake area, Japan (36°42′N, 137°48′E). We collected water directly from the hot spring from two drilling wells more than 500 m deep; all water samples were strongly alkaline (pH>10) and rich in H2 (201-664 μmol/L) and CH4 (124-201 μmol/L). Despite the relatively low temperatures (50-60 °C), thermodynamic calculations suggest that the H2 was likely derived from serpentinization reactions. Hydrogen isotope compositions for Happo #1 (Happo #3) were found to be as follows: δD-H2=−700‰ (−710‰), δD-CH4=−210‰ (−300‰), and δD-H2O=−85‰ (−84‰). The carbon isotope compositions of methane from Happo #1 and #3 were found to be δC13=−34.5‰ and −33.9‰, respectively. The CH4-H2-H2O hydrogen isotope systematics indicate that at least two different mechanisms were responsible for methane formation. Happo #1 has a similar hydrogen isotope compositions to other serpentinite-hosted systems reported previously. The elevated δD-CH4 (with respect to the equilibrium relationship) suggests that the hydrogen of the Happo #1 methane was not sourced from molecular hydrogen but was derived directly from water. This implies that the methane may not have been produced via the Fischer-Tropsch-type (FTT) synthesis but possibly by the hydration of olivine. Conversely, the depleted δD-CH4 (with respect to the equilibrium relationship) in Happo #3 suggests the incorporation of biological methane. Based on a comparison of the hydrogen isotope systematics of our results with those of other serpentinite-hosted hydrothermal systems, we suggest that abiotic CH4 production directly from H2O (without mediation by H2) may be more common in serpentinite-hosted systems. Hydration of olivine may play a more significant role in abiotic methane production than previously thought.

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