Carbon isotope equilibration during sulphate-limited anaerobic oxidation of methane

Abstract

Collectively, marine sediments comprise the largest reservoir of methane on Earth. The flux of methane from the sea bed to the overlying water column is mitigated by the sulphate-dependent anaerobic oxidation of methane by marine microbes within a discrete sedimentary horizon termed the sulphate–methane transition zone. According to conventional isotope systematics, the biological consumption of methane leaves a residue of methane enriched in 13 C (refs 1–3). However, in many instances the methane within sulphate–methane transition zones is depleted in 13 C, consistent with the production of methane, and interpreted as evidence for the intertwined anaerobic oxidation and production of methane 4–6 . Here, we report results from experiments in which we incubated cultures of microbial methane consumers with methane and low levels of sulphate, and monitored the stable isotope composition of the methane and dissolved inorganic carbon pools over time. Residual methane became progressively enriched in 13 C at sulphate concentrations above 0.5 mM, and progressively depleted in 13 C below this threshold. We attribute the shift to 13 C depletion during the anaerobic oxidation of methane at low sulphate concentrations to the microbially mediated carbon isotope equilibration between methane and carbon dioxide. We suggest that this isotopic e ect could help to explain the 13 C-depletion of methane in subseafloor sulphate–methane transition zones.