Dynamic interplay of biogeochemical C, S, and Ba cycles in response to Shuram oxygenation event

Compared with Phanerozoic strata, sulfate minerals are relatively rare in the Precambrian record likely due to the lower concentrations of sulfate in dominantly anoxic oceans. Here, we present a compilation of sulfate minerals that are stratigraphically associated with the Ediacaran Shuram excursion (SE) — the largest negative δ13C excursion in Earth history. We evaluated 15 SE sections, all of which reveal the presence of sulfate minerals and/or concentration enrichment in carbonate-associated sulfate, suggesting a rise in sulfate reservoir. Notably, where data are available, the SE also reveals considerable enrichments in [Ba] relative to pre- and post-SE intervals. We propose that elevated seawater sulfate concentrations during the SE may have faciliated authigenesis of sulfate minerals. At the same time, the rise of Ba concentrations in shelf environments further facilitated barite deposition. A larger sulfate reservoir would stimulate microbial sulfate reduction and anaerobic oxidation of organic matter (including methane), contributing to the genesis of the SE. The existence of sulfate minerals throughout the SE suggests that oxidant pools were not depleted at that time, which challenges previous modelling results. Our study highlights the dynamic interplay of biogeochemical C, S, and Ba cycles in response to the Shuram oxygenation event.Thematic collection: This article is part of the Sulfur in the Earth system collection available at: https://www.lyellcollection.org/cc/sulfur-in-the-earth-systemSupplementary material:https://doi.org/10.6084/m9.figshare.c.5602560

Revisiting Ediacaran sulfur isotope chemostratigraphy with in situ nanoSIMS analysis of sedimentary pyrite

Reconstructions of ancient sulfur cycling and redox conditions commonly rely on sulfur isotope measurements of sedimentary rocks and minerals. Ediacaran strata (635–541 Ma) record a large range of values in bulk sulfur isotope difference (Δ34S) between carbonate-associated sulfate (δ34SCAS) and sedimentary pyrite (δ34Spy), which has been interpreted as evidence of marine sulfate reservoir size change in space and time. However, bulk δ34Spy measurements could be misleading because pyrite forms under syngenetic, diagenetic, and metamorphic conditions, which differentially affect its isotope signature. Fortunately, these processes also impart recognizable changes in pyrite morphology. To tease apart the complexity of Ediacaran bulk δ34Spy measurements, we used scanning electron microscopy and nanoscale secondary ion mass spectrometry to probe the morphology and geochemistry of sedimentary pyrite in an Ediacaran drill core of the South China block. Pyrite occurs as both framboidal and euhedral to subhedral crystals, which show largely distinct negative and positive δ34Spy values, respectively. Bulk δ34Spy measurements, therefore, reflect mixed signals derived from a combination of syndepositional and diagenetic processes. Whereas euhedral to subhedral crystals originated during diagenesis, the framboids likely formed in a euxinic seawater column or in shallow marine sediment. Although none of the forms of pyrite precisely record seawater chemistry, in situ framboid measurements may provide a more faithful record of the maximum isotope fractionation from seawater sulfate. Based on data from in situ measurements, the early Ediacaran ocean likely contained a larger seawater sulfate reservoir than suggested by bulk analyses.

An enormous sulfur isotope excursion indicates marine anoxia during the end-Triassic mass extinction

The role of ocean anoxia as a cause of the end-Triassic marine mass extinction is widely debated. Here, we present carbonate-associated sulfate δ34S data from sections spanning the Late Triassic–Early Jurassic transition, which document synchronous large positive excursions on a global scale occurring in ~50 thousand years. Biogeochemical modeling demonstrates that this S isotope perturbation is best explained by a fivefold increase in global pyrite burial, consistent with large-scale development of marine anoxia on the Panthalassa margin and northwest European shelf. This pyrite burial event coincides with the loss of Triassic taxa seen in the studied sections. Modeling results also indicate that the pre-event ocean sulfate concentration was low (<1 millimolar), a common feature of many Phanerozoic deoxygenation events. We propose that sulfate scarcity preconditions oceans for the development of anoxia during rapid warming events by increasing the benthic methane flux and the resulting bottom-water oxygen demand.