Anaerobic methanotrophy and the rise of atmospheric oxygen.

In modern marine sediments, the anoxic decomposition of organic matter generates a significant flux of methane that is oxidized microbially with sulphate under the seafloor and never reaches the atmosphere. In contrast, prior to ca 2.4Gyr ago, the ocean had little sulphate to support anaerobic oxidation of methane (AOM) and the ocean should have been an important methane source. As atmospheric O2 and seawater sulphate levels rose on the early Earth, AOM would have increasingly throttled the release of methane. We use a biogeochemical model to simulate the response of early atmospheric O2 and CH4 to changes in marine AOM as sulphate levels increased. Semi-empirical relationships are used to parameterize global AOM rates and the evolution of sulphate levels. Despite broad uncertainties in these relationships, atmospheric O2 concentrations generally rise more rapidly and to higher levels (of order approx. 10(-3) bar versus approx. 10(-4) bar) as a result of including AOM in the model. Methane levels collapse prior to any significant rise in O2, but counter-intuitively, methane re-rises after O2 rises to higher levels when AOM is included. As O2 concentrations increase, shielding of the troposphere by stratospheric ozone slows the effective reaction rate between oxygen and methane. This effect dominates over the decrease in the methane source associated with AOM. Thus, even with the inclusion of AOM, the simulated Late Palaeoproterozoic atmosphere has a climatologically significant level of methane of approximately 50ppmv.