Methane in the environment is produced by both biotic and abiotic processes. Biomethanation involves the formation of methane by microbes that live in oxygen-free environments. Abiotic methane formation proceeds under conditions at elevated temperature and/or pressure. Here we present a chemical reaction that readily forms methane from organosulphur compounds under highly oxidative conditions at ambient atmospheric pressure and temperature. When using iron(II/III), hydrogen peroxide and ascorbic acid as reagents, S-methyl groups of organosulphur compounds are efficiently converted into methane. In a first step, methyl sulphides are oxidized to the corresponding sulphoxides. In the next step, demethylation of the sulphoxide via homolytic bond cleavage leads to methyl radical formation and finally to methane in high yields. Because sulphoxidation of methyl sulphides is ubiquitous in the environment, this novel chemical route might mimic methane formation in living aerobic organisms.
Methane plays an important role as a radiatively and chemically active gas in our atmosphere. Until recently, sources of atmospheric methane in the biosphere have been attributed to strictly anaerobic microbial processes during degradation of organic matter. However, a large fraction of methane produced in the anoxic soil layers does not reach the atmosphere due to methanotrophic consumption in the overlaying oxic soil. Although methane fluxes from aerobic soils have been observed, an alternative source other than methanogenesis has not been identified thus far. <br></br> Here we provide evidence for non-microbial methane formation in soils under oxic conditions. We found that soils release methane upon heating and other environmental factors like ultraviolet irradiation, and drying-rewetting cycles. We suggest that chemical formation of methane during degradation of soil organic matter may represent the missing soil source that is needed to fully understand the methane cycle in aerobic soils. Although the emission fluxes are relatively low when compared to those from wetlands, they may be important in warm and wet regions subjected to ultraviolet radiation. We suggest that this methane source is highly sensitive to global change
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