Sulphur cycling in a Neoarchaean microbial mat.

Multiple sulphur (S) isotope ratios are powerful proxies to understand the complexity of S biogeochemical cycling through Deep Time. The disappearance of a sulphur mass-independent fractionation (S-MIF) signal in rocks <~2.4 Ga has been used to date a dramatic rise in atmospheric oxygen levels. However, intricacies of the S-cycle before the Great Oxidation Event remain poorly understood. For example, the isotope composition of coeval atmospherically derived sulphur species is still debated. Furthermore, variation in Archaean pyrite δ S values has been widely attributed to microbial sulphate reduction (MSR). While petrographic evidence for Archaean early-diagenetic pyrite formation is common, textural evidence for the presence and distribution of MSR remains enigmatic. We combined detailed petrographic and in situ, high-resolution multiple S-isotope studies (δ S and Δ S) using secondary ion mass spectrometry (SIMS) to document the S-isotope signatures of exceptionally well-preserved, pyritised microbialites in shales from the ~2.65-Ga Lokammona Formation, Ghaap Group, South Africa. The presence of MSR in this Neoarchaean microbial mat is supported by typical biogenic textures including wavy crinkled laminae, and early-diagenetic pyrite containing <26‰ μm-scale variations in δ S and Δ S = -0.21 ± 0.65‰ (±1σ). These large variations in δ S values suggest Rayleigh distillation of a limited sulphate pool during high rates of MSR. Furthermore, we identified a second, morphologically distinct pyrite phase that precipitated after lithification, with δ S = 8.36 ± 1.16‰ and Δ S = 5.54 ± 1.53‰ (±1σ). We propose that the S-MIF signature of this secondary pyrite does not reflect contemporaneous atmospheric processes at the time of deposition; instead, it formed by the influx of later-stage sulphur-bearing fluids containing an inherited atmospheric S-MIF signal and/or from magnetic isotope effects during thermochemical sulphate reduction. These insights highlight the complementary nature of petrography and SIMS studies to resolve multigenerational pyrite formation pathways in the geological record.