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Reconstructing Earth's oxygenation history is key to deciphering environmental controls on early biospheric evolution. During the mid-Proterozoic Eon, low (but potentially variable) atmospheric p O 2 led to highly heterogeneous marine redox conditions, with most studies indicating a relatively shallow depth of oxygen penetration. The relative proportion of oxic, anoxic and iron-rich (ferruginous), and anoxic and sulfide-rich (euxinic) conditions on the global seafloor is difficult to quantify, however, due to a general reliance on local redox proxies applied to the temporally discontinuous black shale record. It is particularly important to constrain the global prevalence of euxinic bottom waters because sulfide toxicity has been implicated as a primary constraint on evolution in mid-Proterozoic oceans and limits the solubility of bioessential trace metals such as copper, zinc, and molybdenum. Here, we present a suite of new uranium (U) isotope data from marine carbonate rocks that span the entire mid-Proterozoic interval (∼1.8 to 0.8 Ga). U-isotopes in well-preserved carbonate rocks represent a powerful new proxy that can be used to quantitatively constrain the global extent of marine euxinia. The median δ 238 U value for mid-Proterozoic carbonate samples is −0.43‰, which is lower than the median value for modern post-depositional carbonate sediments from the Bahamas, yet significantly higher than carbonate δ 238 U values recorded during other times of expanded anoxia in Earth history, such as during the end-Permian mass extinction. When paired with a three-sink isotope mass balance model, our data indicate that no more than 7% of the global seafloor was euxinic during the mid-Proterozoic Eon, although transient pulses of expanded euxinia are recorded. Although these results challenge early expectations of a sulfide-rich mid-Proterozoic ocean, they are consistent with more recent inferences from the black shale trace metal record. Evidence therefore indicates that euxinic bottom waters were relatively limited in their spatial extent in the mid-Proterozoic oceans. • Uranium isotopes in marine carbonate constrain Proterozoic seafloor euxinia. • Median Proterozoic δ 238U (−0.43‰) lower than modern Bahamian carbonate. • Median Proterozoic δ 238U higher than end-Ediacaran and Permo-Triassic carbonate. • Mass balance model suggests that at maximum 7% of seafloor was euxinic. • Mid-Proterozoic euxinia was less prevalent than previously envisaged. [ABSTRACT FROM AUTHOR]

In marine sediments, authigenic uranium (U) enrichments and U isotope compositions are important tools for interpreting changes in redox conditions, however, their use as paleoproxies requires a comprehensive understanding of the dominant processes that contribute to sediments becoming enriched or depleted. This study focuses on the U content and 238U/235U ratio of organic-rich surface sediments from the Namibian continental margin, where high productivity results in an expanded oxygen minimum zone (OMZ). The investigated core sample sites are located on the shelf, shelf break, and slope where bottom water redox conditions vary from anoxic to suboxic to oxic, respectively. While all cores have relatively high total organic carbon (TOC) contents (up to 12 wt.%), each location displays a unique U to TOC relationship. Shelf sediment exhibit a fair correlation between U and TOC, while the shelf break and slope sediments show a pronounced decoupling of U and TOC. On the Namibia continental margin, particle-rich nepheloid layers transport organic-rich deposits from within the OMZ, through oxic water, to be redeposited on the slope. Due to the sensitivity of U to changes in redox conditions, this lateral movement results in the release of the reduced U phases back into the water column through oxidation while transporting the partially remineralized organic carbon to the slope. Oxidation of U during transport does not alter the average primary 238U/235U isotopic signature in redeposited sediment, and the combination of high TOC, low U content and high δ 238 U values may become a useful tool for the identification of the boundaries of ancient OMZs. • Slope sediments underlying oxic water column reveal abundant organic carbon deposits. • Decoupling of uranium and organic carbon in Namibia Continental Margin sediment is related to sediment redeposition. • Primary uranium isotope signal preserved during sediment transport. [ABSTRACT FROM AUTHOR]

Abstract The Late Devonian extinction ranks as one of the 'big five' Phanerozoic extinctions affecting up to 80% of marine species and is characterized by two major extinction events that are separated by <3 My. The leading hypotheses explaining both extinction events are global cooling and/or widespread marine anoxia. We test the marine anoxia hypothesis by analyzing uranium isotopes (δ 238 U) across a ∼7 My interval of well-dated Upper Devonian marine limestones from the Devil's Gate Formation in Nevada, USA. The measured δ 238 U curve shows no co-variation with local sediment-derived redox trends, water-depth dependent facies changes, redox-sensitive metals, TOC, or diagnostic elemental ratios. From these relationships, we infer that the δ 238 U curve represents global seawater redox conditions. Two negative δ 238 U excursions (indicating more reducing seawater) are observed with durations of ∼3.8 My (late Frasnian) and ∼1.1 My (early Famennian), respectively. Steady-state modeling of the observed −0.2 to −0.3‰ shifts in δ 238 U points to a ∼5–15% increase in the total area of anoxic seafloor during these excursions. The late Frasnian negative excursion is broadly coincident with the first extinction event (late rhenana Zone or lower Kellwasser event), whereas the early Famennian negative excursion (lower-middle triangularis zones) occurs after the most intense Frasnian–Famennian boundary (F–F) extinction event (upper Kellwasser event). Compilations of local sediment redox conditions from Upper Devonian marine deposits with conodont zone-level age control indicates that the extinction events were coincident with widespread anoxic deposits accumulating in subtropical epeiric sea and some open ocean settings, supporting previous interpretations that widespread marine anoxia had an important influence on the Late Devonian extinctions. The temporal relationships between global-ocean redox trends represented by the δ 238 U curve and the newly compiled subtropical marine redox sediment trends indicates that local epeiric seawaters carried a similar U-isotopic composition as the open ocean for the majority of the studied interval except for a brief interval (<500 ky) spanning the F–F boundary. Highlights • Late Devonian δ 238 U trends from marine limestones record two widespread anoxic events. • Late Frasnian global anoxia coincides with lower Kellwasser extinction event. • Epeiric sea anoxia but not global ocean anoxia associated with Upper Kellwasser extinction event. • Late Devonian epeiric seas in relatively good redox communication with open oceans. [ABSTRACT FROM AUTHOR]

• High-resolution U isotopes used to investigate middle Paleozoic seawater redox trends. • Rapid oxygenation event near Early-Middle Devonian boundary (∼395 Ma). • Oxygenation coeval with rapid diversification of shallow-rooted Late Eophytic flora. • Lack of redox response to later Devonian evolution of deep-rooted arborescent forests. The middle Paleozoic (∼420-350 Myr) records a major increase in ocean-atmosphere oxygen levels; however, the timing and pattern of oxygenation are poorly constrained. Two well-dated North American locations in Nevada and Illinois were used to generate a high-resolution U-isotopic profile (δ 238 U) spanning ∼70 Myr of the middle Paleozoic. Stratigraphic and geochemical data support the interpretation that the Nevada profile represents a near-primary record of global-ocean redox variations. First-order δ 238 U trends indicate strongly reducing oceans during the late Silurian and Early Devonian, terminated by a major oxygenation event near the Emsian-Eifelian boundary (∼395 Ma). More oxic seawater conditions persisted for the next 30+ Myr, but were punctuated by multiple Myr-scale anoxic events during the Middle-Late Devonian and Early Mississippian that correlate with known global biotic crises, positive δ 13 C excursions, and widespread organic-rich facies deposition. The timing of the ∼395 Ma oxygenation event suggests that the O 2 rise was the result of increased photosynthesis and organic carbon burial linked to diversification of late Silurian to earliest Middle Devonian terrestrial plants, rather than to subsequent Devonian increases in terrestrial plant root depth, tree height, lignin content, or seed reproduction. These findings demonstrate that early colonization of continents by relatively small, shallowly rooted plants with geographically limited ranges was sufficient to drive long-term oxygenation of the ocean-atmosphere system, paving the way for the evolution of large, mobile animals that have dominated the Earth's surface since the middle Paleozoic. [ABSTRACT FROM AUTHOR]

• Glacial diamictites record changes in chemical weathering of the crust. • Diamictites formed before the GOE have similar δ 98 Mo values as igneous rocks. • Diamictites that formed after the GOE retain isotopically light Mo. • The onset of the GOE drove Mo isotope fractionation during crustal weathering. • The weathered continental crust is an isotopically light Mo reservoir. Molybdenum isotopes in twenty-four composites of glacial diamictites spanning depositional ages of 2900 to 300 Ma show a systematic shift to lighter compositions and a decrease in Mo concentration over time. The diamictites fall into three age groups relative to the Great Oxidation Event (GOE): pre-GOE (2.43 – 2.90 Ga), syn-GOE (2.20 – 2.39 Ga), and post-GOE (0.33 – 0.75 Ga). Pre-GOE composites have an average δ 98 Mo NIST3134 of +0.03‰ (± 0.18‰), syn-GOE composites average − 0.29 ‰ (± 0.60‰), and post-GOE composites average − 0.45 ‰ (± 0.51‰). These groups are statistically different at p=0.05. We use the pre-GOE data to estimate the average Archean upper continental crust (UCC) δ 98 Mo signature as +0.03 ± 0.18‰ (2 σ), which falls within the range of previous estimates of modern igneous rocks. As the diamictites represent a mixture of igneous and weathered crust, the shift to lighter Mo values over time likely reflects Mo isotope fractionation during oxidative weathering and increased retention of light Mo isotopes in weathered regolith and soils. We hypothesize that this fractionation is due to the mobilization of oxidized Mo following the GOE, and subsequent adsorption of light Mo onto Fe-Mn oxides and/or organic matter in weathered regolith. We conclude that Mo isotopes in continental weathering products record the rise of atmospheric oxygen and onset of oxidative weathering. As the regolith formed under oxidative conditions is isotopically lighter than average continental igneous rocks, mass balance dictates that Mo isotope fractionation during oxidative weathering should result in isotopically heavy groundwater and river water, which is observed in modern systems. [ABSTRACT FROM AUTHOR]

The timing and causation of the Capitanian (late Middle Permian) biocrisis remain controversial. Here, a detailed uranium-isotopic (δ 238 U) profile was generated for the mid-Capitanian to lower Wuchiapingian of the Penglaitan section (the Guadalupian/Lopingian Permian global stratotype) in South China for the purpose of investigating relationships between the biocrisis and coeval oceanic anoxic events (OAEs). Negative δ 238 U excursions indicate two distinct OAEs, a mid-Capitanian (OAE-C1) and an end-Capitanian (OAE-C2) event. Mass balance modeling shows that the anoxic sink of uranium (F anox ; i.e., the fraction of the total U burial flux) and anoxic seafloor area (F area ; i.e., the fraction of total seafloor area) increased during each OAE. A dynamic mass balance model yields increases of F anox from <30% to >60% and F area from ∼1% to ∼4-7% during each OAE. These two OAEs coincided with two extinction episodes during the Capitanian biocrisis, supporting a causal relationship between oceanic anoxia and mass extinction during the Middle Permian. The most likely driver of middle to late Capitanian global warming and oceanic anoxia was episodic magmatism of the Emeishan Large Igneous Province. • New carbonate uranium isotope profile for the Capitanian (late Middle Permian). • Two negative δ 238 U excursions, in the mid-Capitanian and end-Capitanian intervals. • δ 238 U records two global oceanic anoxic events (4-7X expansion of anoxic seafloor). • These anoxic events coincided with two episodes of the Capitanian biocrisis. • Emeishan Large Igneous Province triggered global warming and oceanic anoxic events. [ABSTRACT FROM AUTHOR]

The nature of ocean redox chemistry between the Cryogenian Sturtian and Marinoan glaciations (ca. 663–654 Ma) is important for understanding the relationship between environmental conditions and the subsequent emergence and expansion of early animals. The Cryogenian-to-Ediacaran stratigraphic succession of the Nanhua Basin in South China provides a nearly complete sedimentary record of the Cryogenian, including a continuous record of interglacial sedimentation. Here, we present a high-resolution pyrite Fe isotope record for a ∼120-m-long drill-core (ZK105) through Sturtian glacial diamictites and the overlying interglacial sediments in the Nanhua Basin to explore changes in marine chemistry during the late Cryogenian. Our pyrite Fe isotope profile exhibits significant stratigraphic variation: Interval I, comprising middle to upper Tiesi'ao diamictites (correlative with the Sturtian glaciation), is characterized by light, modern seawater-like Fe isotope compositions; Interval II, comprising uppermost Tiesi'ao diamictites and the basal organic-rich Datangpo Formation, is characterized by an abrupt shift to heavier Fe isotope compositions; and Interval III, comprising organic-poor grey shales in the middle Datangpo Formation, is characterized by the return of lighter, seawater-like Fe isotope compositions. We infer that Interval I pyrite was deposited in a predominantly anoxic glacial Nanhua Basin through reaction of dissolved Fe 2+ and H 2 S mediated by microbial sulfate reduction (MSR). The shift to heavier pyrite Fe isotope values in Interval II is interpreted as partial oxidation of ferrous iron to ferric iron and subsequent near-quantitative reduction and transformation of Fe-oxyhydroxides to pyrite through coupling with oxidation of organic matter in the local diagenetic environment. In Interval III, near-quantitative oxidation of ferrous iron to Fe-oxyhydroxides followed by near-quantitative reduction and conversion to pyrite in the local diagenetic environment was likely responsible for the return of lighter, seawater-like Fe isotope compositions in pyrite. Our pyrite Fe isotope profile thus records increased oxygenation in the Nanhua Basin between the Sturtian and Marinoan glaciations. The increased oxygenation of Nanhua Basin seawater deduced from pyrite Fe isotopes could have resulted from either local or global controls. Further work will be needed to determine whether this increasing oxygenation extended to the global scale. [ABSTRACT FROM AUTHOR]

• We present the first U isotope data across the Late Devonian Hangenberg Crisis. • Our δ 238 U data show three negative shifts punctuated by two short positive events. • The positive δ 238 U events were associated with sulfidic porewater redox conditions. • Marine anoxia expanded to cover >5% seafloor area in the latest Devonian oceans. • Marine anoxia was likely an important kill mechanism for the Hangenberg Crisis. The global Hangenberg Crisis near the Devonian-Carboniferous boundary (DCB) represents one of the major Phanerozoic mass extinction events, which shaped the roots of modern vertebrate biodiversity. Marine anoxia has been cited as the proximate kill mechanism for this event. However, the detailed timing, duration, and extent of global marine redox chemistry changes across this critical interval remain controversial because most of the studies to date only constrain changes in local or regional redox chemistry. Thus, opinions on the significance of anoxia as a kill mechanism are variable—from anoxia being a primary driver to being relatively unimportant. In this study, we explore the evolution of global marine redox chemistry using U isotopes of marine limestones. The δ 238 U trends at Long'an section in South China document systematic oscillations with three negative shifts punctuated by two positive events in between. The magnitude of the δ 238 U oscillations implies that the sediments do not record contemporaneous seawater with a constant offset at all times. The lack of covariation between δ 238 U data and diagenetic indicators (e.g., Mn and Sr contents, Mn/Sr ratio, δ 18 O) suggests that the δ 238 U trends are not produced by the same post-depositional diagenetic processes. Instead, trace-metal enrichments suggest that more reducing conditions prevailed during the deposition of the two positive events. We present plausible model scenarios that fit the observed δ 238 U trends in the context of redox-sensitive trace metal data suggesting marine anoxia expanded in the latest Devonian oceans to cover >5% of the continental shelf seafloor area. The rapid expansion of marine anoxia coincident with the onset of the Hangenberg Crisis supports marine anoxia as an important kill mechanism. Biogeochemical modeling of the coupled C-P-U cycles suggests that intensified continental weathering, for example, assisted by the spread of seed plants with deeper root systems at this time, could have triggered expansion of marine anoxia and other global changes (e.g., positive excursion in δ 13 C carb and decrease in sea surface temperature) in the latest Devonian. The anoxic event is inferred to have been transient as climatic cooling would have reduced weathering fluxes. [ABSTRACT FROM AUTHOR]