Paleoarchean sulfur cycling: Multiple sulfur isotope constraints from the Barberton Greenstone Belt, South Africa

Abstract

Mass-dependent and mass-independent sulfur isotope fractionation archived in volcanic and sedimentary rocks from the Barberton Greenstone Belt (3550-3215. Ma), South Africa, provide constraints for sulfur cycling on the early Earth. Four different sample suites were studied: komatiites and tholeiites, barite, massive and disseminated sulfide ores, and non-mineralized black shales.Variable but generally slightly positive δ34S values between -0.7 and +5.2‰, negative δ33S values between -0.50 and -0.09‰, and a negative correlation between δ34S and δ33S as well as between δ33S and δ36S for komatiites and tholeiites from the Komati Formation and from the Weltevreden Formation are outside the expected range of unfractionated juvenile sulfur. Instead, results suggest alteration of oceanic crustal rock sulfur through interactions with fluids that most likely derived their sulfur from seawater.Barite from the Mapepe Formation displays positive δ34S values between +3.1 and +8.1‰ and negative δ33S values between -0.77 and -0.34‰. The mass-independent sulfur isotope fractionation indicates an atmospheric sulfur source, notably photolytic sulfate, whereas the positive δ34S values suggest bacterial sulfate reduction of the marine sulfate reservoir.Non-mineralized black shale samples from the presumed stratigraphic equivalent of the Mapepe Formation show positive δ34S values between 0.0 and +1.3‰ and positive δ33S values between +0.59 and +2.45‰. These results are interpreted to result from the reduction of photolytic elemental sulfur, carrying a positive δ33S signature.Positive δ34S values ranging from +0.7 to +3.5‰ and slightly negative δ33S values between -0.17 and -0.12‰ characterize massive and disseminated sulfides from the Bien Venue Prospect. Results suggest unfractionated juvenile magmatic sulfur source as the primary sulfur source, but a contribution from recycled seawater sulfate, which would be indicative of submarine hydrothermal activity, cannot be ruled out.Massive and disseminated sulfides from the M'hlati prospect are distinctly different from massive and disseminated sulfide from the Bien Venue Prospect. They show negative δ34S values between -1.2 and -0.1‰ and positive δ33S values between +2.66 and +3.17‰, thus, displaying a sizeable mass-independent sulfur isotopic fractionation. Again, these samples clearly exhibit the incorporation of an atmospheric MIF-S signal. The source of sulfur for these samples has positive δ33S values, suggesting a connection with photolytic elemental sulfur.In conclusion, the sulfur isotope signatures in Paleoarchean rocks from the Barberton Greenstone Belt are diverse and indicate the incorporation of different sources of sulfur. For komatiites and tholeiites, barite and massive and possibly also disseminated sulfides from Bien Venue, multiple sulfur isotopes are related to ambient seawater sulfate and its photolytic origin, while massive and disseminated sulfides from M'hlati and non-mineralized black shales are related to a second (photolytic elemental sulfur) end member.