Quantifying the Seawater Sulfate Concentration in the Cambrian Ocean

Although the earliest animals might have evolved in certain “sweet spots” in the last 10 million years of Ediacaran (550–541 Ma), the Cambrian explosion requires sufficiently high levels of oxygen (O2) in the atmosphere and diverse habitable niches in the substantively oxygenated seafloor. However, previous studies indicate that the marine redox landscape was temporally oscillatory and spatially heterogeneous, suggesting the decoupling of atmospheric oxygenation and oceanic oxidation. The seawater sulfate concentration is controlled by both the atmospheric O2 level and the marine redox condition, with sulfide oxidation in continents as the major source, and sulfate reduction and pyrite burial as the major sink of seawater sulfate. It is thus important to quantify the sulfate concentration on the eve of the Cambrian explosion. In this study, we measured the pyrite contents and pyrite sulfur isotopes of black shale samples from the Yurtus Formation (Cambrian Series 2) in the Tarim Block, northwestern China. A numerical model is developed to calculate the seawater sulfate concentration using the pyrite content and pyrite sulfur isotope data. We first calibrate some key parameters based on observations from modern marine sediments. Then, the Monte Carlo simulation is applied to reduce the uncertainty raised by loosely confined parameters. Based on the geochemical data from both Tarim and Yangtze blocks, the modeling results indicate the seawater sulfate concentration of 8.9–14 mM, suggesting the seawater sulfate concentration was already 30–50% of the present level (28 mM). High seawater sulfate concentration might be attributed to the enhanced terrestrial sulfate input and widespread ocean oxygenation on the eve of the Cambrian explosion.

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.

Fluid inclusions, H-O-S isotopic characteristics and genesis of the Chambishi copper deposit, Zambia

In this paper, fluid inclusions and H-O-S isotope geochemistry of the Chambishi copper deposit in Zambia are studied. According to the fluid inclusion in quartz and H-O-S isotope characteristics, it is concluded that ore-forming hydrothermal fluid is derived from mantle source and crust source magma mingling, the cause of copper precipitation, sedimentary type sulfur layered mineralization are mainly from diagenetic sulfides and seawater sulfate. Sulfate is mainly reduced by thermochemical method. The hydrothermal vein mineralization of Chambishi copper deposit is closely related to the magmatic activity in the middle Neoproterozoic, and the sedimentary stratified mineralization is mainly related to the large-scale orogeny and regional metamorphism in the late Neoproterozoic.

Significant Fluctuation in the Global Sulfate Reservoir and Oceanic Redox State During the Late Devonian Mass Extinction

Sulfate plays an important role in the biosphere, hydrosphere, atmosphere, and lithosphere, and its concentration might have fluctuated greatly throughout the Earth’s history, in response to perturbations in the ocean-atmosphere system. Coupling high-resolution experimental results with an inverse modeling approach, we, here, show an unprecedented dynamic in the global sulfate reservoir during the Frasnian-Famennian (F-F) mass extinction, as one of the “Big five” Phanerozoic biotic crises. Notably, our results indicate that, in a relatively short time scale (~ 200 thousand years), seawater sulfate concentration would have dropped from several mM before the Upper Kellwasser Horizon (UKH) to a few hundreds of µM or perhaps lower at the dawn and during the UKH (more than 100 times lower than the modern level), and returned to around mM range after the event. The extremely low oceanic sulfate concentrations during the UKH would have enhanced the biological production of methane, leading to an increase in the methane efflux from the ocean and a warmer climate. Taken together, our findings indicate that the instability in the global sulfate reservoir may have played a major role in driving the Phanerozoic biological crises.

Volcanic controls on seawater sulfate over the past 120 million years

Changes in the geological sulfur cycle are inferred from the sulfur isotopic composition of marine barite. The structure of the34S/32S record from the Mesozoic to present, which includes ∼50- and 100-Ma stepwise increases, has been interpreted as the result of microbial isotope effects or abrupt changes to tectonics and associated pyrite burial. Untangling the physical processes that govern the marine sulfur cycle and associated isotopic change is critical to understanding how climate, atmospheric oxygenation, and marine ecology have coevolved over geologic time. Here we demonstrate that the sulfur outgassing associated with emplacement of large igneous provinces can produce the apparent stepwise jumps in the isotopic record when coupled to long-term changes in burial efficiency. The record of large igneous provinces map onto the required outgassing events in our model, with the two largest steps in the sulfur isotope record coinciding with the emplacement of large igneous provinces into volatile-rich sedimentary basins. This solution provides a quantitative picture of the last 120 My of change in the ocean’s largest oxidant reservoir.