Two-billion-year-old evaporites capture Earth's great oxidation.

Major changes in atmospheric and ocean chemistry occurred in the Paleoproterozoic era (2.5 to 1.6 billion years ago). Increasing oxidation dramatically changed Earth's surface, but few quantitative constraints exist on this important transition. This study describes the sedimentology, mineralogy, and geochemistry of a 2-billion-year-old, ~800-meter-thick evaporite succession from the Onega Basin in Russian Karelia. The deposit consists of a basal unit dominated by halite (~100 meters) followed by units dominated by anhydrite-magnesite (~500 meters) and dolomite-magnesite (~200 meters). The evaporite minerals robustly constrain marine sulfate concentrations to at least 10 millimoles per kilogram of water, representing an oxidant reservoir equivalent to more than 20% of the modern ocean-atmosphere oxidizing capacity. These results show that substantial amounts of surface oxidant accumulated during this critical transition in Earth's oxygenation.

High rates of anaerobic methanotrophy at low sulfate concentrations with implications for past and present methane levels.

Despite the importance of the anaerobic oxidation of methane (AOM) to global biogeochemical cycles, the relationship between sulfate concentration and the rate of AOM has not been previously experimentally constrained. Here, we present measurements showing substantial methane oxidation at low sulfate concentrations, with no significant decrease in the rate of AOM until sulfate levels are well below 1 mM. At sulfate levels below 1 mM, there appears to be a strong decoupling of AOM and sulfate reduction, with a (13)C-label transferred from methane to carbon dioxide occurring at a rate almost an order of magnitude faster than the observed rate of sulfate reduction. These results allow for the possibility that high rates of AOM occurred in the Archean oceans and that high rates of AOM may be found in freshwater environments (lakes, rivers, etc.) and deep ocean sediments today.

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.