Iron and sulfur isotope constraints on redox conditions associated with the 3.2 Ga barite deposits of the Mapepe Formation (Barberton Greenstone Belt, South Africa)

The occurrence of Early Archean barite deposits is intriguing since this type of sediment requires high availability of dissolved sulfate (SO42-), the oxidized form of sulfur, although most authors argued that the Archean eon was dominated by reducing conditions, with low oceanic sulfate concentration (< 10 mu M) relative to present day levels of 28,000 mu M. In order to better assess the redox state of the paleo-atmosphere and -oceans, we examined Fe and S isotope compositions in a sedimentary sequence from the 3.2 Ga-old Mendon and Mapepe formations (Kaapvaal craton, South Africa), recovered from the drill-core BBDP2 of the Barberton Barite Drilling Project. Major elements were also analyzed to constrain the respective imprints of detrital vs metasomatic processes, in particular using Al, Ti and K interrelations. Bulk rock Fe isotope compositions are linked to mineralogy, with delta(56) Fe values varying between - 2.04% in Fe sulfide-dominated barite beds, to + 2.14% in Fe oxide-bearing cherts. delta S-34 values of sulfides vary between -10.84 and +3.56%, with Delta S-33 in a range comprised between -0.35 and +2.55%, thus supporting an O-2-depleted atmosphere (< 10 - 5 PAL). Iron isotope variations together with major element correlations show that, although the sediments experienced a pervasive stage of hydrothermal alteration, the rocks preserved a primary/authigenic signature predating subsequent hydrothermal stage. Highly positive delta 56 Fe values recorded in primary Fe-oxides from ferruginous cherts support partial Fe oxidation in a reducing oceanic environment (O-2 < 10(-4) mu M), but are incompatible with a model of complete oxidation at the redox boundary of a stratified water column. Iron oxide precipitation under low O2 levels was likely mediated by anoxygenic photosynthesis, and/or abiotic photo-oxidation processes. Our results are consistent with global anoxic conditions in the 3.2 Ga-old sediments, implying that the barite deposits were most likely sourced by atmospheric photolysis of S gases produced by large subaerial volcanic events, and possibly SO42- produced by magmatic SO2 disproportionation in hydrothermal systems. (C) 2017 Elsevier Ltd. All rights reserved.