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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. 

Abstract Reconstructing past oxygen fluctuations in oxygen minimum zones (OMZs) is crucial for understanding their response to climate change. Numerous studies suggest better oxygenation in the Arabian Sea OMZ during the Last Glacial Maximum (LGM) compared to the Holocene. However, bottom water oxygen (BWO) variability during the Penultimate Glacial Cycle (Marine Isotope Stage [MIS] 6 to MIS 5e, ∼140–115 ka B.P.) remains poorly constrained. This study reconstructs BWO variations during this period from sediment core TN041‐8JPC in the western Arabian Sea OMZ, utilizing proxies including benthic foraminiferal surface porosity, redox‐sensitive trace metal enrichment factors (e.g., U_EF), and U/Ba ratios. Bottom water oxygen concentrations were 24.4 ± 5.9 μmol/kg during MIS 6 and 16.8 ± 6.5 μmol/kg during MIS 5e, with all proxies indicating higher BWO in MIS 6 than in MIS 5e. However, these proxies show different patterns within MIS 5e, indicating that U_EFand U/Ba ratios may be limited to recording average BWO in glacial and interglacial (quasi)steady states. We propose that the intensified OMZ during MIS 5e, relative to MIS 6, was driven by higher productivity, temperature‐induced reductions in oxygen solubility, and reduced delivery of Southern‐sourced intermediate waters. In contrast, the intensified OMZ during the Holocene, compared to the LGM, was likely influenced by lower oxygen solubility, reduced Southern water delivery, and winter convective mixing rather than productivity. This study highlights a general trend of weaker OMZs in glacial than interglacial periods, though the mechanisms may not be identical, offering insights into OMZ dynamics under climate change in the past. 

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. 

Abstract Oxic pelagic clays are an important component of seafloor sediment that may hold valuable information about past ocean chemistry due to their affinity for and accumulation of biogeochemically important metals. We present a new approach to calculating site‐specific sedimentation rates (SRs) by comparing authigenic sediment thorium isotope compositions (²³⁰Th/²³²Th) to seawater dissolved²³⁰Th/²³²Th in a suite of deep (>3,000 m) pelagic core sites. We extracted the authigenic sediment fraction using an HHAc leach protocol, which major element chemistry (Al, Mn, Fe, Ti) suggested was less affected by lithogenic contamination than the HCl leach. Four different methods were tested for extracting the appropriate initial²³⁰Th/²³²Th from seawater: using either the nearest water column station (methods 1 and 2) or a regionally averaged profile (methods 3 and 4) and using either the bottommost profile measurement (methods 1 and 3) or linear regression of the profile and extrapolation to the seafloor (methods 2 and 4). Method 3 outperformed the other methods in reconstructing previously published SRs from pelagic clays in the North Pacific. The new thorium‐based SRs were then combined with estimates from the total sediment thickness on ocean crust and non‐lithogenic cobalt accumulation to determine the best estimates for SRs of oxic pelagic clays. The Pacific has the lowest SR (median 0.28 cm/kyr), while the Atlantic is higher (median 0.46 cm/kyr) and the Indian Ocean is highest (median 0.75 cm/kyr). These new estimates are consistent with the expected spatial patterns of sedimentation, but they revise the absolute SR values downward from available gridded SR maps. 

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.