Molecular hydrogen (H 2 ) is derived from the hydrothermal alteration of olivine-rich planetary crust. Abiotic and biotic processes consume H 2 to produce methane (CH 4 ); however, the extent of either process is unknown. Here, we assess the temporal dependence and limit of abiotic CH 4 related to the presence and formation of mineral catalysts during olivine hydrolysis (i.e., serpentinization) at 200°C and 0.03 gigapascal. Results indicate that the rate of CH 4 production increases to a maximum value related to magnetite catalyzation. By identifying the dynamics of CH 4 production, we kinetically model how the H 2 to CH 4 ratio may be used to assess the origin of CH 4 in deep subsurface serpentinization systems on Earth and Mars. Based on our model and available field data, low H 2 ∕CH 4 ratios (less than approximately 40) indicate that life is likely present and active.kinetics | molecular hydrogen | Fischer-Tropsch type reactions | methanogenesis O livine hydrolysis (i.e., serpentinization) is a major pathway related to the near-surface synthesis of molecular hydrogen (H 2 ) on Earth, Mars, and, potentially, other planets and satellites (1-4). Molecular hydrogen from serpentinization can chemically reduce carbon (e.g., HCO 3 − , HCOOH, CO, CO 2 ) to form CH 4 or can be converted to CH 4 via microbial processes (i.e., methanogenesis) (1, 3, 5-12). Although CH 4 formation is thermodynamically favorable over a range of pressure (P) and temperature (T) (13, 14), CH 4 production via Fischer-Tropsch type (FTT) reactions is slow without the aid of mineral catalysts (3,9,15,16). To understand the limits of abiotic CH 4 production, it is imperative to assess the role of mineral catalysts, both those initially present in the system and those formed during the process of serpentinization.Chromite (FeCr 2 O 4 ), a primary mineral common in serpentinization systems, has been shown to enhance FTT synthesis reactions (17). Additionally, secondary minerals such as magnetite (Fe 3 O 4 ) and/or awaruite (Ni 3 Fe) are produced during olivine hydrolysis, providing increased opportunities for FTT catalysis (13,15,(18)(19)(20)(21). Here, we evaluate the rate of abiotic CH 4 production for systems catalyzed both by chromite and secondary minerals (magnetite and awaruite) in experimental systems undergoing serpentinization at 200°C and 0.03 gigapascal (GPa), conditions similar to hydrothermally altered peridotite in midocean ridge environments on Earth or at approximately 5 km depth in the Martian subsurface. By measuring H 2 and CH 4 formed during olivine hydrolysis, mineral-catalyzed CH 4 production can be differentiated from biogenic CH 4 production through a consideration of the H 2 -CH 4 kinetic balance.
Experimental ProceduresSerpentinization experiments were carried out in the WaterRock Interaction Laboratory (US Geological Survey, Menlo Park, CA) using the parameters listed in