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.