Multiple sulphur isotope record of Paleoarchean sedimentary rocks across the Onverwacht Group, Barberton Greenstone Belt, South Africa

This study presents multiple sulphur isotope (³²S, ³³S, ³⁴S, ³⁶S) data on pyrites from silicified volcano-sedimentary rocks of the Paleoarchean Onverwacht Group of the Barberton greenstone belt, South Africa. These rocks include seafloor cherts and felsic conglomerates that were deposited in shallow marine environments preserving a record of atmospheric and biogeochemical conditions on the early Earth. A strong variation in mass independent sulphur isotope fractionation (MIF-S) anomalies is found in the cherts, with Δ³³S ranging between −0.26‰ and 3.42‰. We explore possible depositional and preservational factors that could explain some of this variation seen in MIF-S. Evidence for microbial activity is recorded by the c. 3.45 Ga Hooggenoeg Formation Chert (HC4) preserving a contribution of microbial sulphate reduction (−Δ³³S and –δ³⁴S), and a c. 3.33 Ga Kromberg Formation Chert (KC5) recording a possible contribution of microbial elemental sulphur disproportionation (+Δ³³S and –δ³⁴S). Pyrites from a rhyo-dacitic conglomerate of the Noisy Formation do not plot along a previously proposed global Felsic Volcanic Array, and this excludes short-lived pulses of intense felsic volcanic gas emissions as the dominant control on Archean MIF-S. Rather, we suggest that the MIF-S signals measured reflect dilution during marine deposition, early diagenetic modification, and mixing with volcanic/hydrothermal S sources. Given the expanded stratigraphic interval (3.47–3.22 Ga) now sampled from across the Barberton Supergroup, we conclude that large MIF-S exceeding >4‰ is atypical of Paleoarchean near-surface environments on the Kaapvaal Craton.