Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event

The early Earth was characterized by the absence of oxygen in the ocean–atmosphere system, in contrast to the well-oxygenated conditions that prevail today. Atmospheric concentrations first rose to appreciable levels during the Great Oxidation Event, roughly 2.5–2.3 Gyr ago. The evolution of oxygenic photosynthesis is generally accepted to have been the ultimate cause of this rise, but it has proved difficult to constrain the timing of this evolutionary innovation. The oxidation of manganese in the water column requires substantial free oxygen concentrations, and thus any indication that Mn oxides were present in ancient environments would imply that oxygenic photosynthesis was ongoing. Mn oxides are not commonly preserved in ancient rocks, but there is a large fractionation of molybdenum isotopes associated with the sorption of Mo onto the Mn oxides that would be retained. Here we report Mo isotopes from rocks of the Sinqeni Formation, Pongola Supergroup, South Africa. These rocks formed no less than 2.95 Gyr ago in a nearshore setting. The Mo isotopic signature is consistent with interaction with Mn oxides. We therefore infer that oxygen produced through oxygenic photosynthesis began to accumulate in shallow marine settings at least half a billion years before the accumulation of significant levels of atmospheric oxygen

Micro-scale sulphur isotope evidence for sulphur cycling in the late Archean shallow ocean

We report in situ secondary ion mass spectrometer sulphur isotope data for sedimentary pyrite from the 2.52 Ga Upper Campbellrand Subgroup, Transvaal, South Africa. The analysed sedimentary rocks represent a transition in depositional environment from very shallow to deeper water, with strong sedimentological, facies distribution and geochemical evidence for the presence of a shallow redox chemocline. Data were obtained directly in thin section in order to preserve petrographic context. They reveal a very large extent of isotopic fractionation both in mass- independent (MIF) and in mass-dependent fractionation (MDF) on unprecedentedly small scale. in the shallow-water microbical carbonates, three types of pyrite were identified. The texturally oldest pyrite is found as small, isotopically little fractionated grains in the microbial mats. Large (several mm) spheroidal pyrite concretions, which postdate the mat pyrite, record strong evidence for an origin by bacterial sulphate reduction. Rare pyrite surrounding late fenestral calcite is inferred to have formed from recycled bacterial pyrite on account of the slope of its correlated MIF and MDF array. This latter type of pyrite was also found in an interbedded black shale and a carbonate laminite. In a deeper water chert, pyrite with very heavy sulphur indicates partial to almost complete sulphate reduction across a chemocline whose existence has been inferred independently. The combined picture from all the studied samples is that of a sulphate availability-limited environment, in which sulphur was cycled between reservoirs according to changing redox conditions established across the chemocline. Cycling apparently reduced the extent of recorded sulphur isotope fractionation relative to what is expected from projection in the correlated MIF and MDF arrays. This is consistent with regionally relatively high free oxygen concentrations in the shallow water, permitting locally strong MDF. Our new observations add to the growing evidence for a complex, fluctuating evolution of free atmospheric oxygen between c. 2.7 Ga and 2.3 Ga