The 260-million-year-old Emeishan volcanic province of southwest China overlies and is interbedded with Middle Permian carbonates that contain a record of the Guadalupian mass extinction. Sections in the region thus provide an opportunity to directly monitor the relative timing of extinction and volcanism within the same locations. These show that the onset of volcanism was marked by both large phreatomagmatic eruptions and extinctions amongst fusulinacean foraminifers and calcareous algae. The temporal coincidence of these two phenomena supports the idea of a cause-and-effect relationship. The crisis predates the onset of a major negative carbon isotope excursion that points to subsequent severe disturbance of the ocean-atmosphere carbon cycle.

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Emerging evidence suggests that atmospheric oxygen may have varied before rising irreversibly ∼2.4 billion years ago, during the Great Oxidation Event (GOE). Significantly, however, pre-GOE atmospheric aberrations toward more reducing conditions-featuring a methane-derived organic-haze-have recently been suggested, yet their occurrence, causes, and significance remain underexplored. To examine the role of haze formation in Earth's history, we targeted an episode of inferred haze development. Our redox-controlled (Fespeciation) carbon-and sulfur-isotope record reveals sustained systematic stratigraphic covariance, precluding nonatmospheric explanations. Photochemical models corroborate this inference, showing Δ 36 S/Δ 33 S ratios are sensitive to the presence of haze. Exploiting existing age constraints, we estimate that organic haze developed rapidly, stabilizing within ∼0.3 ± 0.1 million years (Myr), and persisted for upward of ∼1.4 ± 0.4 Myr. Given these temporal constraints, and the elevated atmospheric CO 2 concentrations in the Archean, the sustained methane fluxes necessary for haze formation can only be reconciled with a biological source. Correlative δ 13 C Org and total organic carbon measurements support the interpretation that atmospheric haze was a transient response of the biosphere to increased nutrient availability, with methane fluxes controlled by the relative availability of organic carbon and sulfate. Elevated atmospheric methane concentrations during haze episodes would have expedited planetary hydrogen loss, with a single episode of haze development providing up to 2.6-18 × 10 18 moles of O 2 equivalents to the Earth system. Our findings suggest the Neoarchean likely represented a unique state of the Earth system where haze development played a pivotal role in planetary oxidation, hastening the contingent biological innovations that followed.sulfur mass-independent fractionation | organic haze | planetary oxidation | hydrogen loss | Neoarchean

The exceptionally organic-rich rocks of the 1.98 Ga Zaonega Formation deposited in the Onega Basin, NW Russia, have refined our understanding of Earth System evolution during the Paleoproterozoic rise in atmospheric oxygen. These rocks were formed in vent-or seepinfluenced settings contemporaneous with voluminous mafic volcanism and contain strongly 13 C-depleted organic matter. Here we report new isotopic (δ 34 S, Δ 33 S, Δ 36 S, δ 13 Corg) and mineralogical, major element, total sulphur and organic carbon data for the upper part of the Zaonega Formation, which was deposited shortly after the termination of the Lomagundi-Jatuli positive carbon isotope excursion. The data were collected on a recently obtained 102 m drillcore section and show a δ 13 Corg shift from-38‰ to-25‰. Sedimentary sulphides have δ 34 S values typically between +15‰ and +25‰ reflecting closed-system sulphur isotope behaviour

The bioavailability of essential nutrients such as nitrogen (N) and phosphorus (P) has fluctuated with the chemical evolution of Earth surface environments over geologic timescales. However, significant uncertainty remains over the evolution of Earth's early nitrogen cycle, particularly how and when it responded to the evolution of oxygenic photosynthesis. Here we apply multi-proxy geochemical analyses (Fe speciation,  13 C and δ 15 N) to exceptionally well-preserved shales from the approximately 2.7 Ga Manjeri Formation in the Belingwe Greenstone Belt, Zimbabwe, to evaluate the redox status of Earth's early nitrogen cycle and decipher feedbacks associated with the initial stages of planetary oxygenation. These continental shelf sediments have previously been linked to early cyanobacterial oxygen production, and provide a direct test of conflicting hypotheses concerning the importance of nitrogen oxyanions in the Late Archean. Our data reveal a dominantly anaerobic marine nitrogen cycle, where ammonium-replete ferruginous waters underlay an ephemeral oxygen oasis. Driven by the emergence of oxygenic photosynthesis, increased primary productivity could have periodically strengthened export production, allowing for accumulation of ammonium in the water column during organic matter degradation. Restricted oxygen availability could have allowed upwelling ammonium to reach the photic zone, providing ample nitrogen to fuel a prolific Late Archean biosphere.

The marine nitrogen cycle is dominated by redox-controlled biogeochemical processes and, therefore, is likely to have been revolutionised in response to Earth-surface oxygenation. The details, timing, and trajectory of nitrogen cycle evolution, however, remain elusive. Here we couple nitrogen and carbon isotope records from multiple drillcores through the Rooihoogte–Timeball Hill Formations from across the Carletonville area of the Kaapvaal Craton where the Great Oxygenation Event (GOE) and its aftermath are recorded. Our data reveal that aerobic nitrogen cycling, featuring metabolisms involving nitrogen oxyanions, was well established prior to the GOE and that ammonium may have dominated the dissolved nitrogen inventory. Pronounced signals of diazotrophy imply a stepwise evolution, with a temporary intermediate stage where both ammonium and nitrate may have been scarce. We suggest that the emergence of the modern nitrogen cycle, with metabolic processes that approximate their contemporary balance, was retarded by low environmental oxygen availability.