Major changes in atmospheric and ocean chemistry occurred in the Paleoproterozoic era (2.5 to 1.6 billion years ago). Increasing oxidation dramatically changed Earth's surface, but few quantitative constraints exist on this important transition. This study describes the sedimentology, mineralogy, and geochemistry of a 2-billion-year-old, ~800-meter-thick evaporite succession from the Onega Basin in Russian Karelia. The deposit consists of a basal unit dominated by halite (~100 meters) followed by units dominated by anhydrite-magnesite (~500 meters) and dolomite-magnesite (~200 meters). The evaporite minerals robustly constrain marine sulfate concentrations to at least 10 millimoles per kilogram of water, representing an oxidant reservoir equivalent to more than 20% of the modern ocean-atmosphere oxidizing capacity. These results show that substantial amounts of surface oxidant accumulated during this critical transition in Earth's oxygenation.

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

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The pyrite sulfur isotope record of the 1.98 Ga Zaonega Formation in the Onega Basin, NW Russia, has played a central role in understanding ocean-atmosphere composition and infering worldwide fluctuations of the seawater sulfate reservoir during the pivotal times of the Paleoproterozoic Era. That, in turn, has led to a concept that Earth's atmospheric oxygen levels underwent global-scale changes. Here we present a steady-state isotope mass-balance model to gain insight into the mechanisms governing the sulfur cycle and sulfate reservoir during deposition of the organic-rich Zaonega Formation. We demonstrate that coupling between high microbial sulfate reduction rates and effective sulfate removal by pyrite precipitation can lead to Rayleigh distillation of the basinal sulfate reservoir and development of high amplitude positive δ 34 S excursions. This modelling approach illustrates that secular changes in sedimentary pyrite isotope trends can be explained by processes that reflect local (basin-scale) fluctuations in sulfur cycling rather than global mechanisms.

The Paleoproterozoic Zaonega Formation in Karelia, NW Russia, has played a key role in understanding the environmental conditions postdating the Great Oxidation and Lomagundi-Jatuli Events. Its carbonate-and organic-rich rocks (shungite) define the postulated Shunga Event representing an accumulation of very organic-rich sediments at c. 2 Ga and are central in ideas about changing ocean-atmosphere composition in the wake of those worldwide biogeochemical phenomena. Our work focussed on a key interval of carbonate rocks in the upper part of the Formation to: (i) obtain new high-resolution carbon, oxygen and strontium isotope data complemented by detailed petrography and mineralogical characterisation and (ii) expand upon previous studies by using our data to constrain geochemical modelling and show in greater detail how magmatic hydrothermal fluids induced dedolomitisation and altered geochemical signals. Our findings show that the δ 13 C carb of calcite-rich intervals are the most altered, with values between -16.9 to 0.6‰, whereas the dolomite-dominated parts retain the best-preserved (i.e. most original) values. Those define a trend of steadily ACCEPTED MANUSCRIPT A C C E P T E D M A N U S C R I P T 2increasing δ 13 C carb , from -6 to +0.5‰, which we interpret as a return to normal marine conditions and carbonate-carbon values following the Lomagundi-Jatuli Event.

The c. 2.0 Ga Zaonega Formation of the Onega Basin (NW Russia) has been central in efforts to understand what led to the initial rise (Great Oxidation Event, GOE) and postulated fall in free atmospheric oxygen and associated high-amplitude carbon cycle excursions, the Lomagundi-Jatuli Event (LJE) and subsequent Shunga Event during Paleoproterozoic time.The Formation accumulated shortly after the LJE and encompasses both the recovery in the carbon cycle and hypothesised contraction of the oceanic oxidant pool. However, interpreting the correct environmental context recorded by geochemical signatures in the Zaonega rocks is difficult due to a complex depositional and diagenetic history. In order to robustly constrain that history, we undertook a multiproxy study (mineralogy, petrography, carbon isotope and rare earth element composition) of carbonate beds in the upper part of the Zaonega Formation recovered in the 102-m composite section of the OnZap drill-cores. Our findings differentiate primary environmental signatures from secondary overprinting and show that: (i) the bestpreserved carbonate beds define an upwards increasing δ 13 Ccarb trend from c. -5.4‰ to near 0‰; and that (ii) large intra-bed δ 13 Ccarb variations reflect varying contributions of methanotrophic dissolved inorganic carbon (DIC) to the basinal DIC pool. Rare earth element and yttrium (REYSN) patterns confirm a marine origin of the carbonate beds whereas a consistent positive EuSN anomaly suggests a strong high temperature hydrothermal input during accumulation of the Zaonega Formation. Importantly, the presence of a negative CeSN anomaly in the REYSN pattern indicates an oxygenated atmosphere-ocean system shortly after the LJE and indicates that models invoking a fall in oxygen at that time require reassessment.

Geobiology explores how Earth's system has changed over the course of geologic history and how living organisms on this planet are impacted by or are indeed causing these changes. For decades, geologists, paleontologists, and geochemists have generated data to investigate these topics. Foundational efforts in sedimentaryThis is an open access article under the terms of the Creat ive Commo ns Attri bution-NonCo mmercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

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