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Abstract Estimating dissolved oxygen (O2) concentrations in seawater during the Neoproterozoic is central to testing hypotheses about the role of O2 in animal evolution. Here we apply the thallium (Tl) isotope redox proxy to samples stratigraphically below the ca. 810-million-year-old (Ma) Bitter Springs Carbon Isotope Excursion and spanning the interval between the two Snowball Earth glaciations (ca. 662–650 Ma) to constrain the evolution of Neoproterozoic bottom water redox conditions. Thallium isotopes can be used to reconstruct the global extent of oxygenated oceanic bottom waters because the primary control on seawater Tl isotope compositions (ε205Tl) over million-year time scales is changes in the amount of 205Tl removal by Mn oxides on the seafloor. Samples spanning an ~20-m.y. period preceding the Bitter Springs excursion from the Tonian Reefal Assemblage (n = 18/30) yield ε205Tlauth values lower than global oceanic inputs (ε205Tl ~–2±), with some samples approaching the modern seawater ε205Tl value of –6±. These sustained low ε205Tlauth values require enhanced burial of Mn oxides elsewhere on the seafloor, which we interpret as evidence for the oxygenation of the deep ocean in the Tonian. In contrast, the majority of samples from the Cryogenian Hay Creek Group (n = 13/16) yield ε205Tlauth values similar to global oceanic inputs, suggesting that the deep ocean was not ventilated at this time. This indicates that Earth’s deep ocean was not gradually oxygenated throughout the Neoproterozoic, but rather experienced intervals of increased and decreased O2 concentrations. 

The Early Paleozoic radiation of diverse animal life is commonly connected to a well-ventilated global ocean. Yet the oxygenation history of Paleozoic deep oceans remains debated. Using thallium (Tl) isotope ratios in deep-marine mudrocks, we reconstruct the history of deep marine oxygenation from ~485 to 380 million years ago. Thallium isotopes can track bottom water oxygenation indirectly through their sensitivity to seafloor Mn oxide burial. We apply Tl isotopes to a global set of mudrocks, placing a particular focus on the Road River Group of Yukon, Canada. Our data reveal an oscillatory pattern in seawater Tl isotope ratios and, in turn, a dynamic ocean ventilation history. A long-lived deep ocean oxygenation episode is identified between ~405 and 386 million years ago. These short-term dynamics are superimposed on a muted positive ocean oxygenation trend over the entire Early and Middle Paleozoic. Sustained O₂accumulation in global marine bottom waters occurred sometime after ~380 million years ago according to our dataset. 

Ferruginous conditions, defined by anoxia and abundant dissolved ferrous iron (Fe2+aq), dominated the Precambrian oceans but are essentially non-existent in a modern, oxygenated world. Ferruginous meromictic lakes represent natural laboratories to ground truth our understanding of the stable Fe isotope proxy, which has been used extensively in interpreting the origins of Fe-rich sedimentary rocks like iron formations (IFs) and the interactions of early life with high-Fe2+aq conditions. Here we report comprehensive geochemical and Fe isotopic analyses of samples collected in May and August 2022, and March 2023, from Deming Lake, Minnesota, a ferruginous meromictic lake that undergoes surface freezing in winter and never becomes euxinic. Through chemical and Fe isotopic analyses of different putative Fe sources to Deming Lake; including eolian input trapped in winter ice cover, nearby bogs, and regional groundwaters sampled at surface springs; we find that a groundwater source provides the best chemical and Fe isotopic match for Deming Lake and can support Fe2+aq-rich waters at depth that maintain a permanent chemocline at ~12 m. The ice-free Deming Lake water column can be split into three layers dominated by distinct Fe cycling regimes. Layer (I) extends from the lake surface to the base of the oxycline at ~6 m, and its Fe cycling is dominated by isotopically light Fe uptake into biomass, likely from stabilized dissolved Fe3+, with variable eolian lithogenic influences. Layer (II) extends between the oxycline and the chemocline at ~12 m and is dominated by partial Fe2+aq oxidation on approach to the oxycline, with the formation of variably isotopically heavy Fe3+-bearing particles. Layer (III) underlies the chemocline and is defined by Fe2+ phosphate (vivianite) and carbonate saturation and precipitation under anoxic, Fe2+aq-rich conditions with little Fe isotopic fractionation. The ice-covered winter water column features more homogenous Fe chemistry above the chemocline, which we attribute to seasonal homogenization of Layers (I) and (II), with suppressed ferric particle formation. Authigenic Fe minerals with non-crustal (light) Fe isotopic compositions only appreciably accumulate in sediments in Deming Lake underlying the chemocline. All sediments deposited above 12 m appear crustal in their Fe isotopic, Mn/Fe, and Fe/Al ratios, likely revealing efficient reductive dissolution of Fe3+-bearing lake precipitates and remineralization of Fe-bearing biomass. We find limited fractionation of Fe isotopes in the ice-covered water column and suggest this provides evidence that substantial delivery of oxidants is required to generate highly fractionated Fe isotopic compositions in Sturtian Snowball era IFs. By comparing Fe isotopic and Mn/Fe fractionation trends in the different Deming Lake layers, we also suggest that correlations between these two parameters in giant early Paleoproterozoic IFs requires the simultaneous deposition of multiple authigenic phases on the ancient seafloor. Finally, high-precision triple Fe isotopic analyses of dissolved Fe impacted by extensive oxidation near the Deming Lake oxycline reveal that the slope of the mass fractionation law for natural, O2-mediated Fe2+aq oxidation is identical to those previously defined for both UV photo-oxidation, and for an array of highly fractionated Paleoproterozoic IFs. 

Abstract The Ediacaran Period (~635–539 Ma) is marked by the emergence and diversification of complex metazoans linked to ocean redox changes, but the processes and mechanism of the redox evolution in the Ediacaran ocean are intensely debated. Here we use mercury isotope compositions from multiple black shale sections of the Doushantuo Formation in South China to reconstruct Ediacaran oceanic redox conditions. Mercury isotopes show compelling evidence for recurrent and spatially dynamic photic zone euxinia (PZE) on the continental margin of South China during time intervals coincident with previously identified ocean oxygenation events. We suggest that PZE was driven by increased availability of sulfate and nutrients from a transiently oxygenated ocean, but PZE may have also initiated negative feedbacks that inhibited oxygen production by promoting anoxygenic photosynthesis and limiting the habitable space for eukaryotes, hence abating the long-term rise of oxygen and restricting the Ediacaran expansion of macroscopic oxygen-demanding animals. 

ABSTRACT The geologically rapid appearance of most extant animal groups in the Cambrian fossil record is often linked to enhanced ocean oxygenation. However, conflicting reconstructions of the Cambrian redox landscape make it difficult to determine the extent of ocean oxygenation during this significant biotic event, particularly regarding the redox state of the global deep ocean. In this study, we present authigenic thallium isotope compositions (ε²⁰⁵Tl_auth) for two shale sequences from South China (Qingjiang and Weng'an) that span the Cambrian Stage 2–3 boundary to the appearance of the Qingjiang biota, approximately 521–518 million years ago (Ma), a timeframe that chronicles a particularly rapid interval of metazoan diversification and radiation in the broader Cambrian explosion. If this event occurred amid modern‐like extents of global ocean oxygenation, we would expect a significant increase in the global extent of seafloor Mn‐oxide burial to drive lower ε²⁰⁵Tl_authvalues near the modern open‐ocean composition of −6‱. Instead, we observe broadly stable ε²⁰⁵Tl_authvalues of around −3 to −4‱ in both studied sections. The lack of any significant Tl isotope shifts in our dataset argues against a short‐term global ocean oxygenation event and suggests the global deep ocean was not characterized by modern extents of oxygenation 521–518 Ma. We reinterpret contemporaneous near‐modern Mo and U isotope compositions to signal a relatively minor increase in marine oxygenation, likely limited to the continental shelves. However, ε²⁰⁵Tl_authlower than the average isotopic composition of approximately −2‱ in Ediacaran shales suggests a shift to comparatively better‐oxygenated conditions sometime between ~555 Ma and 521 Ma. If diversification at this time was linked to increased ocean oxygen levels, these changes were likely more dominant in the relatively shallow‐water settings of continental shelves most densely populated by Cambrian animals and were incapable of dramatically altering seawater Tl isotope mass balance through seafloor Mn‐oxide burial.