Abiogenic methane formation and isotopic fractionation under hydrothermal conditions

Recently, methane (CH(4)) of possible abiogenic origin has been reported from many localities within Earth's crust. However, little is known about the mechanisms of abiogenic methane formation, or about isotopic fractionation during such processes. Here, a hydrothermally formed nickel-iron alloy was shown to catalyze the otherwise prohibitively slow formation of abiogenic CH(4) from dissolved bicarbonate (HCO(3)-) under hydrothermal conditions. Isotopic fractionation by the catalyst resulted in delta(13)C values of the CH(4) formed that are as low as those typically observed for microbial methane, with similarly high CH(4)/(C(2)H(6) + C(3)H(8)) ratios. These results, combined with the increasing recognition of nickel-iron alloy occurrence in oceanic crusts, suggest that abiogenic methane may be more widespread than previously thought.