Early planetary degassing and atmospheric escape are two major, yet unconstrained, processes that shaped early Earth. Modeling predicts that the atmospheric 20Ne/22Ne ratio is sensitive to solar-Ne mantle degassing over geological time. Until the Great Oxidation Event, atmospheric escape progressively depletes the atmosphere in Xe, leaving an isotopic imprint. However, the quantity of xenon in the ancient atmosphere remains largely unknown. In this study, we analyzed noble gases in Archean hydrothermal quartz fluid inclusions and show that a modern atmospheric 20Ne/22Ne ratio was almost reached 2.7 Ga ago, implying intense mantle degassing during the first 1.7 billion years of Earth's history, three orders of magnitude higher than today. Furthermore, we determine an Archean atmospheric Xe/Kr ratio, 2.3 times higher than today, consistent with models of Xe depletion over time through atmospheric escape.

Sedimentological evidence and detrital zircon provenance analysis show that the Amazonian Craton, Brazil, was subjected to large-scale subaerial erosion by c. 2.7 Ga. To assess weathering conditions attending the emergence of the Amazonian Craton, we used the chemical composition of terrigenous sediments deposited in the Carajas Basin, SE Amazonian Craton, between c. 2.7 and 2.6 Ga. Results from 41 samples collected in two drill cores along 150 and 250 m thick intervals show that emerged lands have been affected by strong chemical weathering conditions, similar in intensity to those occurring in the present-day inter-tropical belt. These intense chemical weathering conditions were probably due to the conjunction of warm temperatures (potentially as high as 22 +/- 3 degrees C), abundant precipitation (mean annual precipitation estimated at 1540 +/- 150 mm) and high atmospheric CO2 content (pCO(2) >= 10 times the present atmospheric level) that enhanced the chemical alteration of labile minerals. These intense weathering conditions contrast with those inferred in other cratons, which suggests that regionally contrasted climates existed during the Neoarchean.

Plate tectonics exerts a first-order control on the interaction between Earth’s reservoirs. Atmospherically-altered surface materials are recycled to the mantle via subduction, while volatiles from the mantle are liberated to the atmosphere via volcanism. This cycle regulates much of Earth’s climate, ocean levels and metallogenetic processes within the continental crust. However, the interplay between Earth’s atmospheric changes and the geochemical evolution of mantle-derived magmas has remained obscure for the ancient geological history. This has led to multiple conflicting models for the crustal evolution in the early Earth. A time-integrated evolution of the mantle-crust-atmosphere-hydrosphere interaction is yet to be fully established. For instance, secular change of the ocean and atmosphere system is evident from several proxies but the feedback of these changes to magmatic and geochemical processes in the lithosphere remain unclear. Moreover, no clear consensus has been reached on the timing of modern-style plate tectonic initiation and the evolution of net growth of the continental crust. To explain overt and cryptic global trends in the geochemistry of magmatic rocks, a better understanding of mineral reactions and how these control trace element evolution in magmas at the lithosphere-scale is paramount. For example, the elemental and isotopic composition of apatite inclusions hosted by zircon offers a way to better understand the evolution of magmas and, to some extent, the nature of magma sources. These proxies rely on the robust data acquisition of other isotope systems with different geochemical behaviour, such as U-Pb and Lu-Hf analyses in the host zircon crystal. A combination of methods and proxies including the elemental composition of apatite via EPMA and the oxygen fugacity based on sulphur speciation via μ-XANES of apatite inclusions was applied to ancient sub-arc magmas formed in regions akin to modern subduction zones. These magmas share a common mantle source but crystallised more than 200 million years apart (at 2.35 and 2.13 billion years ago). Importantly, they bracket the Great Oxidation Event, when atmospheric oxygen levels increased by five orders of magnitude, causing a permanent and dramatic change in Earth’s surface chemistry. As such, these sub-arc magmas were investigated as potential tracers of the interaction between Earth’s atmosphere and the mantle. The information from several inclusions from co-magmatic rocks can then be interpreted in the light of U-Pb, Lu-Hf, trace elements and oxygen isotope analyses of the host zircon grains. Altogether, the results show a shift in oxygen fugacity of sub-arc magmas across the Great Oxidation Event. The change in oxygen fugacity is thought to be caused by recycling into the mantle of sediments that had been geochemically altered at the surface by the increase in atmospheric oxygen levels. This study opens a wide window of opportunities for the time-integrated investigation of the interaction between atmosphere and oceans with the evolving terrestrial mantle.

Banded iron formations (BIFs) are chemical sedimentary rocks commonly utilized for exploring the chemistry and redox state of the Precambrian ocean. Despite their significance, many aspects regarding the crystallization pathways of iron oxides in BIFs remain loosely constrained. In this study, we combine magnetic properties characterization with high-resolution optical and electron imaging of finely laminated BIFs from the 2.7 Ga Carajás Formation, Brazil, to investigate their nature and potential for preserving ancient environmental conditions. Our findings reveal that magnetite, in the form of large 0.1-0.5 mm crystals, is the main iron oxide, with an overall averaged saturation magnetization (Ms) of 25 Am2/kg (corresponding to ~27 wt% of magnetite) over the studied 230 m of the sequence. Nevertheless, the non-negligible contribution of minerals with higher coercivity suggests variable proportions of hematite along the core. Additionally, we observe non-uniform behavior in magnetite grains, with distinct populations identified through low-temperature measurements of the Verwey transition. Petrographic observations indicate that the original sediment was an Fe-Si mud consisting of a ferrihydrite-silica mixture formed in the water column. This assemblage was rapidly transformed into nano-scale hematite embedded in silica as indicated by a honeycomb structure composed of Si-spherules distributed in a microscale hematite matrix. Textural relationships show that the nucleation of magnetite started during or soon after the formation of hematite, as indicated by the preservation of the Si-spherules within magnetite cores. Further magnetite overgrowth stages are characterized by inclusion-free rims, associated with continuous Si supply during the evolving diagenetic or early metamorphic stages. These findings, combined with existing literature, suggest that ferrihydrite precipitated alongside Si and organic material, later crystallizing as hematite on the seafloor. Anaerobic respiration by Fe(III)-reducing microorganisms likely contributed to early magnetite formation in a fluid-saturated, unconsolidated sediment. Subsequent low-grade metamorphism and Si mobilization led to palisade quartz precipitation and a second stage of magnetite growth likely formed at the expense of matrix hematite through thermochemical Fe(III) reduction. Low-temperature magnetic analyses revealed that the two generations of magnetite core and rim are associated with specific stoichiometry.

Sulfur is a critical component of Earth’s surface evolution owing to its dynamic roles as a redox buffer and nutrient as well as forming the basis for some of Earth’s earliest metabolisms. In this Review, we provide a broad-scale reconstruction of the biogeochemical sulfur cycle and its evolution through time. Insights gleaned through microscale observations, diagenetic modelling and organic sulfur together with traditional bulk sulfur isotope measurements highlight that links between variations in the isotopic composition of reduced and oxidized sulfur species are more complex than previously assumed. The most up-to-date evidence suggests that marine sulfate concentrations have been variable, but generally characterized by background levels (μM to low mM) substantially lower than today’s oceans (28 mM), for most of Earth’s history. The shift towards relatively stable modern-like marine sulfate cycling conditions started in the Phanerozoic eon, with the exceptions of oceanic anoxic events (OAEs). Feedbacks between ocean deoxygenation, climate and sulfur, iron, carbon and nutrient cycles are in need of further study to quantify the importance of key processes that both drove OAEs as well as maintained the low sulfate conditions that characterized the majority of Earth’s past. Modern low-sulfate systems, such as certain lakes and marine basins, could be key to further understanding such feedbacks and therefore Earth’s early sulfur cycle. Future research further constraining Earth’s past sulfur cycle may offer critical insights into the potential impacts of modern anthropogenically driven ocean deoxygenation. The redox transformations of sulfur mean it is a key component of global biogeochemical cycles. This Review explores the sulfur cycle over geological time, including its role during major climate perturbations, oceanic anoxic events and the evolution of life.

The nitrogen isotopic composition of sedimentary rocks (δ15N) can trace redox-dependent biological pathways and early Earth oxygenation1,2. However, there is no substantial change in the sedimentary δ15N record across the Great Oxidation Event about 2.45 billion years ago (Ga)3, a prominent redox change. This argues for a temporal decoupling between the emergence of the first oxygen-based oxidative pathways of the nitrogen cycle and the accumulation of atmospheric oxygen after 2.45 Ga (ref. 3). The transition between both states shows strongly positive δ15N values (10-50‰) in rocks deposited between 2.8 Ga and 2.6 Ga, but their origin and spatial extent remain uncertain4,5. Here we report strongly positive δ15N values (>30‰) in the 2.68-Gyr-old shallow to deep marine sedimentary deposit of the Serra Sul Formation6, Amazonian Craton, Brazil. Our findings are best explained by regionally variable extents of ammonium oxidation to N2 or N2O tied to a cryptic oxygen cycle, implying that oxygenic photosynthesis was operating at 2.7 Ga. Molecular oxygen production probably shifted the redox potential so that an intermediate N cycle based on ammonium oxidation developed before nitrate accumulation in surface waters. We propose to name this period, when strongly positive nitrogen isotopic compositions are superimposed on the usual range of Precambrian δ15N values, the Nitrogen Isotope Event. We suggest that it marks the earliest steps of the biogeochemical reorganizations that led to the Great Oxidation Event.

The chemical exchange between the atmosphere, crust and mantle depends on sediment recycling via subduction. However, it remains unclear how atmospherically modified sediment may affect mantle oxygen fugacity through time. The Great Oxidation Event, among the most important atmospheric changes on Earth, offers an opportunity to investigate changes in magmatism related to surface–mantle interactions. Here we use sulfur K-edge micro X-ray absorption near-edge structure spectroscopy to measure the relative abundances of S 6+ , S 4+ and S 2− state in apatite inclusions hosted in 2.4–2.1-billion-year-old igneous zircons from the Mineiro Belt, Brazil. The host magmas record intracrustal melting of juvenile crust and the involvement of recycled sediments in the sub-arc mantle wedge. Unaltered apatite inclusions reveal a change from reduced to more oxidized magmas from pre- to post-Great Oxidation Event during the early Proterozoic. We argue that this change is a direct result of deep subduction of oxidized sediments and thus evidence of mantle–atmosphere interaction across the Great Oxidation Event. This suggests that the onset of sediment recycling in the Archaean provided atmospheric access to the mantle, and early ‘whiffs’ of oxygen may have already contributed to a localized increase of calc-alkaline magmatism and related ore deposits on Earth.

The availability of nutrients in seawater, such as dissolved phosphorus (P), is thought to have regulated the evolution and activity of microbial life in Earth's early oceans. Marine concentrations of bioavailable phosphorus spanning the Archean Eon remain a topic of debate, with variable estimates indicating either low (0.04 to 0.13 mu M P) or high (10 to 100 mu M P) dissolved P in seawater. The large uncertainty on these estimates reflects in part a lack of clear proxy signals recorded in sedimentary rocks. Contrary to some recent views, we show here that iron formations (IFs) are reliable recorders of past phosphorus concentrations and preserved a primary seawater signature. Using measured P and iron (Fe) contents in Neoarchean IF from Carajas (Brazil), we demonstrate for the first time a clear partitioning coefficient relationship in the P-Fe systematics of this IF, which, in combination with experimental and Archean literature data, permits us to constrain Archean seawater to a mean value of 0.063 +/- 0.05 mu M dissolved phosphorus. Our data set suggests that low-phosphorus conditions prevailed throughout the first half of Earth's history, likely as the result of limited continental emergence and marine P removal by iron oxyhydroxide precipitation, supporting prior suggestions that changes in ancient marine P availability at the end of the Archean modulated marine productivity, and ultimately, the redox state of Earth's early oceans and atmosphere.

The emplacement of Large Igneous Provinces (LIPs) during the Neoarchean is thought to have influenced the Earth's surface by modulating global climate and the supply of nutrients to the oceans. However, the links between Neoarchean LIPs and Earth's surface changes are complex and not fully understood due to a lack of sedimentological constraints documenting the relationships between magmatic activity and concomitant depositional environments. At ca. 2.75 Ga, the Amazonia Craton witnessed the emplacement of the Parauapebas LIP, which is mainly composed of vesicular basalts and associated volcaniclastic rocks. The Caraj ' as Formation conformably overlies the basalts of the Parauapebas LIP. It comprises extensive iron formations (IFs) interbedded with minor carbonate and volcaniclastic horizons, which were deposited in various shallow to deep-water settings. Zircon U-Pb dating of volcaniclastic layers yielded ages between 2732 +/- 5 Ma and 2720 +/- 6 Ma, which indicates that the volcanic activity continued 30-40 Myrs after the main peak in magmatic activity of the Parauapebas LIP. Above the Caraj ' as Formation, the Igarape ' Bahia Group consists mainly of terrigenous sediments that are interleaved at their base with minor IFs. This group does not preserve evidence of contemporaneous volcanic activity and comprises detrital zircon populations with ages between ca. 3.0 and 2.7 Ga. The few IFs horizons at the base of the Igarape ' Bahia Group could reflect a long-lasting hydrothermal activity linked with the emplacement of the Parauapebas LIP. This LIP thus exerted a major control on depositional environments both in space and time by favoring the deposition of IFs (e.g., in shallow to deep-water settings) during a period that exceeded 30 Myrs.

Despite representing one of the largest cratons on Earth, the early geological evolution of the Amazonia Craton remains poorly known due to relatively poor exposure and because younger metamorphic and tectonic events have obscured initial information. In this study, we investigated the sedimentary archives of the Carajás Basin to unravel the early geological evolution of the southeastern Amazonia Craton. The Carajás Basin contains sedimentary rocks that were deposited throughout a long period spanning more than one billion years from the Mesoarchean to the Paleoproterozoic. The oldest archives preserved in this basin consist of a few ca. 3.6 Ga detrital zircon grains showing that the geological roots of the Amazonia Craton were already formed by the Eoarchean. During the Paleoarchean or the early Mesoarchean（＜3.1 Ga）, the Carajás Basin was large and rigid enough to sustain the formation and preservation of the Rio Novo Group greenstone belt. Later, during the Neoarchean, at ca. 2.7 Ga, the southeastern Amazonia Craton witnessed the emplacement of the Parauapebas Large Igneous Province（LIP） that probably covered a large part of the craton and was associated with the deposition of some of the world largest iron formations. The emplacement of this LIP immediately preceded a period of continental extension that formed a rift infilled first by iron formations followed by terrigenous sediments. This major change of sedimentary regime might have been controlled by the regional tectonic evolution of the Amazonia Craton and its emergence above sea-level. During the Paleoproterozoic, at ca. 2.1 Ga, the Rio Fresco Group, consisting of terrigenous sediments from the interior of the Amazonia Craton, was deposited in the Carajás Basin. At that time, the Amazonian lithosphere could have either underwent thermal subsidence forming a large intracratonic basin or could have been deformed by long wavelength flexures that induced the formation of basins and swells throughout the craton under the influence of the growing Transamazonian mountain belt.

The nitrogen isotopic composition of sedimentary rocks is controlled by metabolic activity and redox speciation in the water column. Therefore, changes in the dominating nitrogen biogeochemical cycle's pathways have frequently been used to uncover the joint evolution of the atmosphere, the ocean and the biosphere. The transition from anoxic to oxygenated environments leading to the Great Oxidation Event (GOE) deserves a particular focus, especially as its timing and mechanisms remain debated

The iron isotope composition of iron-bearing carbonates is commonly used to obtain insights into ancient environmental conditions. However, it is often challenging to target only Fe-carbonates (e.g. siderite and ankerite) from samples containing a variety of other Fe-bearing minerals, such as observed in Precambrian iron formations. Chemical extraction (i.e. leaching) methods of Fe-carbonates could be an alternative to in-situ measurements and/or micro-drilling techniques applied to isotopic studies. Yet, only a few studies have looked at the effects of leaching carbonates (e.g. partial and/or total dissolution) on their Fe isotope composition. Here, we tested several leaching protocols, using 5 to 20% acetic acid (HAc) and 0.4 M HCl, on a siderite standard and three natural samples, including an iron formation, Fe-rich and Fe-poor carbonates. We showed that carbonate mineralogy has a strong control on how much of each mineral phase was being dissolved, and that variations in HAc concentration from 5% to 20% are less likely to change how much siderite dissolves (e.g. similar to 30% dissolution) under a 12 h period at room temperature. Importantly, the Fe isotope composition of partially dissolved siderite had indistinguishable values within error from the whole-rock composition (i.e. complete dissolution) as shown with HAc and HCl attacks. Carbonates from the three natural samples were almost completely dissolved under the same protocol with 5 to 20% HAc, while 0.4 M HCl attacks dissolved additional mineralogical phases, which might contribute to the Fe leachate. Moreover, the iron isotope composition of carbonate leachates was preserved without generating anomalous results. Hence, weak chemical leaches represent a reliable tool to study Fe isotopic composition of carbonate to understand how the Fe cycle was operating throughout Earth's history.

Sulfur mass-independent fractionation (S-MIF) preserved in Archean sedimentary pyrite is interpreted to reflect atmospheric chemistry. Small ranges in Delta S-33 that expanded into larger fractionations leading up to the Great Oxygenation Event (GOE; 2.45-2.2 Ga) are disproportionately represented by sequences from the Kaapvaal and Pilbara Cratons. These patterns of S-MIF attenuation and enhancement may differ from the timing and magnitude of minor sulfur isotope fractionations reported from other cratons, thus obscuring local for global sulfur cycling dynamics. By expanding the Delta S-33 record to include the relatively underrepresented Sao Francisco Craton in Brazil, we suggest that marine biogeochemistry affected S-MIF preservation prior to the GOE. In an early Neoarchean sequence (2763-2730 Ma) from the Rio das Velhas Greenstone Belt, we propose that low delta C-13(org) (<-30 parts per thousand) and dampened Delta S-33 (0.4 parts per thousand to -0.7 parts per thousand) in banded iron formation reflect the marine diagenetic process of anaerobic methane oxidation. The overlying black shale (TOC up to 7.8%) with higher delta C-13(org) (-33.4 parts per thousand to -19.2 parts per thousand) and expanded Delta S-33 (2.3 parts per thousand +/- 0.8 parts per thousand), recorded oxidative sulfur cycling that resulted in enhance preservation of S-MIF input from atmospheric sources of elemental sulfur. The sequence culminates in a metasandstone, where concomitant changes to more uniform delta C-13(org) (-30 parts per thousand to -25 parts per thousand), potentially associated with the RuBisCO I enzyme, and near-zero Delta S-33 (-0.04 parts per thousand to 0.38 parts per thousand) is mainly interpreted as evidence for local oxygen production. When placed in the context of other sequences worldwide, the Rio das Velhas helps differentiate the influences of global atmospheric chemistry and local marine diagenesis in Archean biogeochemical processes. Our data suggest that prokaryotic sulfur, iron, and methane cycles might have an underestimated role in pre-GOE sulfur minor isotope records. (C) 2021 China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Triple oxygen isotope (Delta O-17 with delta O-18) signals of H2O and O-2 found in sulfate of oxidative weathering origin offer promising constraints on modern and ancient weathering, hydrology, atmospheric gas concentrations, and bioproductivity. However, interpretations of the sulfate-water-O-2 system rely on assuming fixed oxygen-isotope fractionations between sulfate and water, which, contrastingly, are shown to vary widely in sign and amplitude. Instead, here we anchor sulfate-water-O-2 triple oxygen isotope systematics on the homogeneous composition of atmospheric O(2 )with empirical constraints and modeling. Our resulting framework does not require a priori assumptions of the O-2- versus H2O-oxygen ratio in sulfate and accounts for the signals of mass-dependent and mass-independent fractionation in the Delta O-17 and delta O-18 of sulfate's O-2-oxygen source. Within this framework, new Delta O-17 measurements of sulfate constrain similar to 2.3 Ga Paleoproterozoic gross primary productivity to between 6 and 160 times present-day levels, with important implications for the biological carbon cycle response to high CO2 concentrations prevalent on the early Earth.

Vase-shaped microfossils (VSMs) attributed to testate amoebae occur globally in diverse assemblages in Tonian rocks. These microfossils have thus been considered a potential biostratigraphic tool, especially for the interval between 789 and 729 Ma. Here we report a diverse and well-preserved in situ VSM assemblage, including several taxa previously considered as Tonian, within glacially influenced deposits for which sedimentological data support a Cryogenian age. However, the more robust recent multi-proxy correlation proposed by Freitas et al. (2021) indicates a Marinoan age for the studied succession. Detrital zircon data provide a maximum depositional weighted mean age of 749 +/- 3 Ma for the VSM-bearing, organic-rich, fine-grained deposits within the Marinoan sequence in the Urucum Formation. Nine taxa are described from the fine-grained deposits in the upper Urucum Formation, Jacadigo Group, Brazil: Cycliocyrillium simplex, Bonniea dacruchares, Bonniea pytinaia, Bombycion micron, Limeta lageniformis, Palaeoarcella athanata, Trigonocyrillium horodyskii, Pakupaku kabin and cf. Taruma rata. The discovery of well-preserved in situ VSMs attributable to specific Tonian taxa within a Cryogenian succession challenges previous thinking that these organisms disappeared from marine ecosystems at the end of the Tonian.