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Thermochemical oxidation of methane (TOM) by high-valence metal oxides in geological systems and its potential role as a methane sink remain poorly understood. Here we present evidence of TOM induced by high-valence metal oxides in the Junggar Basin, located in northwestern China. During diagenesis, methane from deeper source strata is abiotically oxidized by high-valence Mn(Fe) oxides at 90 to 135 °C, releasing  13 C-depleted CO 2 , soluble Mn 2+  and Fe 2+ . Mn generally plays the dominant role compared to Fe, due to its lower Gibbs free energy increment during oxidation. Both CO 2  and metal ions are then incorporated into authigenic calcites, which are characterized by extremely negative δ 13 C values (−70 to −22.5‰) and high Mn content (average MnO = 5 wt.%). We estimate that as much as 1224 Tg of methane could be oxidized in the study area. TOM is unfavorable for gas accumulation but may act as a major methane sink in the deep crustal carbon cycle.

Thermochemical oxidation of methane induced by high-valence metal oxides in a sedimentary basin