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Sedimentary rocks and minerals formed during the final two-hundred million years of the Archean Eon (2.7 to 2.5 billion years ago, or Ga) are more depleted in 56Fe than at any other time in Earth’s past. Three hypotheses are proposed to explain these 56Fe depletions: (1) a very negative late-Archean seawater δ56Fe value, (2) “shuttling” of isotopically light Fe across the chemocline in redox-stratified settings, and (3) pyrite formation in an Fe(II)-rich ocean. Each of these scenarios has different implications for the initial oxidation of Earth’s surface, the climax of which – the Great Oxidation Event – immediately post-dates the appearance of these 56Fe depletions in the rock record. To help inform this debate, we measured the Fe isotope ratios of 120 shale and pyrite samples from Western Australia (Mt. McRae Shale and Jeerinah Formation) and South Africa (Klein Naute Formation) deposited between ∼2.65 Ga and ∼2.50 Ga. As in previous studies, we also find very strong sedimentary 56Fe depletions, to as low as δ56Fe = −2.06 ± 0.08‰ in bulk shales and δ56Fe = −2.31 ± 0.08‰ in pyrite. Some, but not all, of the severest 56Fe depletions appear alongside evidence of an Fe shuttle and local pyrite formation. These processes need not be mutually exclusive, and some combination of them likely played a partial, probably faciliatory role in driving some strong 56Fe depletions in our dataset. Most interestingly, and with little exception, the severest 56Fe depletions appear in samples deposited farther from shore under H2S-rich and anoxic (“euxinic”) conditions. We find it difficult to explain this connection without invoking the persistent presence of a very negative global seawater δ56Fe value during the latest Archean, one that was most consistently captured in sediments formed in distal euxinic settings. In order to impart this isotopic effect on seawater, the global seawater Fe(II) reservoir needed to have been partially oxidized during at least the final few hundreds of millions of years leading up to the Great Oxidation Event. Our new data add support to the idea that Earth’s initial oxidation was a long and protracted process rather than a rapid event.

Earth’s Great Oxidation Event (GOE), ca. 2.5–2.0 Ga, was one of the most extreme environmental perturbations in the history of the planet. In addition to the first sustained accumulation of O2 in the atmosphere, the latter half of the GOE is associated with a very large positive carbon isotope excursion, both in terms of magnitude and inferred duration. The end of the GOE may have been associated with a decrease in atmospheric oxygen levels, although this transition remains poorly understood. We test if this suggested decline in atmospheric O2 is reflected in the molybdenum stable isotope compositions (δ98Mo) and Ce anomalies of a large number (N = 299) of carbonate sedimentary rocks collected from Finnish Lapland and the Canadian Labrador Trough and Belcher Group, which collectively span ca. 2.1–1.88 Ga. Clear evidence for a shift in redox conditions across the end-GOE is obscured by coupled stratigraphic variations in δ98Mo values, Ce anomalies, and Mn concentrations, suggesting local controls on these redox proxies as a function of depositional environment, likely as a result of particulate shuttling of Mo and Ce associated with Mn redox cycling across a chemocline. The most negative Ce anomalies recorded in the Belcher Group (

The newly discovered Bibole banded iron formations are located within the Nyong Group at the northwest of the Congo Craton in Cameroon. The Bibole banded iron formations comprise oxide (quartz-magnetite) and mixed oxide-silicate (chlorite-magnetite) facies banded iron formations, which are interbedded with felsic gneiss, phyllite and quartz-chlorite schist. Geochemical studies of the quartz-magnetite banded iron formations and chlorite-magnetite banded iron formations reveal that they are composed of >95 wt % Fe2O3 plus SiO2 and have low concentrations of Al2O3, TiO2 and high field strength elements. This indicates that the Bibole banded iron formations were not significantly contaminated by detrital materials. Post-Archaean Australian Shale–normalized rare earth element and yttrium patterns are characterized by positive La and Y anomalies, a relative depletion of light rare earth elements compared to heavy rare earth elements and positive Eu anomalies (average of 1.86 and 1.15 for the quartz-magnetite banded iron formations and chlorite-magnetite banded iron formations, respectively), suggesting the influence of low-temperature hydrothermal fluids and seawater. The quartz-magnetite banded iron formations display true negative Ce anomalies, while the chlorite-magnetite banded iron formations lack Ce anomalies. Combined with their distinct Eu anomalies consistent with Algoma- and Superior-type banded iron formations, we suggest that the Bibole banded iron formations were deposited under oxic to suboxic conditions in an extensional basin. SIMS U–Pb data indicate that the Bibole banded iron formations were deposited at 2466 Ma and experienced metamorphism and metasomatism at 2078 Ma during the Eburnean/Trans-Amazonian orogeny. Overall, these findings suggest that the studied banded iron formations probably marked the onset of the rise of atmospheric oxygen, also known as the Great Oxidation Event in the Congo Craton.

Proterozoic continental sedimentary basins contain a unique record of the evolving Earth in their sedimentology and stratigraphy and in the large-scale, redox-sensitive mineral deposits they host. The Paleoproterozoic (Stratherian) Kombolgie Basin, located on the Arnhem Land Plateau, Northern Territory, is an exceptionally well preserved, early part of the larger McArthur Basin in northern Australia. This intracratonic basin is filled with 1 to 2 km-thick, relatively undeformed, nearly flat-lying, siliciclastic rocks of the Kombolgie Subgroup. Numerous drill cores and outcrop exposures from across the basin allow sedimentary fabrics, structures, and stratigraphic relationships to be studied in great detail, providing an extensive stratigraphic framework and record of basin development and evolution. Tectonic events controlled the internal stratigraphic architecture of the basin and led to the formation of three unconformity-bounded sequences that are punctuated by volcanic events. The first sequence records the onset of basin formation and is comprised of coarse-grained sandstone and polymict lithic conglomerate deposited in proximal braided rivers that transported sediment away from basin margins and intra-basin paleohighs associated with major uranium mineralization. Paleo-currents in the upper half of this lower sequence, as well as those of overlying sequences, are directed southward and indicate that the major intra-basin topographic highs no longer existed. The middle sequence has a similar pattern of coarse-grained fluvial facies, followed by distal fluvial facies, and finally interbedded marine and eolian facies. An interval marked by mud-rich, fine-grained sandstones and mud-cracked siltstones representing tidal deposition tops this sequence. The uppermost sequence is dominated by distal fluvial and marine facies that contain halite casts, gypsum nodules, stromatolites, phosphate, and “glauconite” (a blue-green mica group mineral), indicating a marine transgression. The repeating pattern of stratigraphic sequences initiated by regional tectonic events produced well-defined coarse-grained diagenetic aquifers capped by intensely cemented distal fluvial, shoreface, eolian, and even volcanic units, and led to a well-defined heterogenous hydrostratigraphy. Basinal brines migrated within this hydrostratigraphy and, combined with paleotopography, dolerite intrusion, faulting, and intense burial diagenesis, led to the economically important uranium deposits the Kombolgie Basin hosts. Proterozoic sedimentary basins host many of Earth's largest high-grade iron and uranium deposits that formed in response to the initial oxygenation of the hydrosphere and atmosphere following the Great Oxygenation Event. Unconformity-related uranium mineralization like that found in the Kombolgie Basin highlights the interconnected role that oxygenation of the Earth, sedimentology, stratigraphy, and diagenesis played in creating these deposits.

Sustainable life on Earth could not exist without breathable air or molecular oxygen, which makes up 21% of the atmosphere we breathe today. Oxygen did not always exist in the atmosphere, and it is believed that it evolved in a period in Earth's history around 2.33 billion years ago, known as the Great Oxygenation Event (GOE). Prior to this time, in the first 2 billion years since Earth was formed, oxygen was not present in the atmosphere. Earth's atmosphere was initially extremely hot, composed of about 75% hydrogen and 25% helium, which was identical to the atmosphere of most stars [1], [2]. In fact, hydrogen is the most common element in the universe today, composed of 90% of all matter, but being the lightest in weight of all gases, when the Earth cooled, it almost completely drifted off into space.

The Archean-Proterozoic transition marks a time of fundamental geologic, biologic, and atmospheric changes to the Earth system, including oxygenation of the atmosphere (termed the Great Oxygenation Event; GOE), and the emergence of continents above sea level. The impacts of the GOE on Earth’s surface environment are imprinted on the geologic record, including the disappearance of mass-independent fractionation of sulfur isotopes (S-MIF). Temporally overlapping geologic and geochemical observations (e.g. a change in oxygen isotope ratio of sediments and an increase in subaerial volcanism) imply the widespread subaerial emergence of continents was coeval with atmospheric oxygenation. Here we present triple sulfur isotope ratios in pyrite and oxygen isotope ratios in garnet and zircon in a global suite of Archean and Proterozoic granitoids derived from the partial melting of sedimentary protoliths. These crustal melts record an increase in average garnet and zircon δ18O from 7.2‰ before 2.3 Ga to 10.0‰ post-2.3 Ga. Pre-2.3 Ga granitoids show small S-MIF signatures with Δ33S ranging from −0.29‰ to 0.13‰, whereas post-2.3 Ga granitoids record S-MDF (i.e. Δ33S = 0‰). The combination of sulfur and oxygen isotope signatures in the same sample with zircon U-Pb geochronology provides new insights on a potential causal link between the emergence of continents and Paleoproterozoic atmospheric oxygenation.

Banded iron formations (BIFs) were deposited before and concurrent with the Great Oxidation Event at ∼2.33 Ga. They provide useful archives that document the transformation of the Precambrian hydrosphere from anoxic to progressively oxygenated conditions. Their formation involves removal of oceanic Fe by either inorganic or biologically promoted Fe

From the Archean toward the Proterozoic, the Earth's atmosphere underwent a major shift from anoxic to oxic conditions, around 2.4 to 2.1 Gyr, known as the Great Oxidation Event (GOE). This rapid transition may be related to an atmospheric instability caused by the formation of the ozone layer. Previous works were all based on 1D photochemical models. Here, we revisit the GOE with a 3D photochemical-climate model to investigate the possible impact of the atmospheric circulation and the coupling between the climate and the dynamics of the oxidation. We show that the diurnal, seasonal and transport variations do not bring significant changes compared to 1D models. Nevertheless, we highlight a temperature dependence for atmospheric photochemical losses. A cooling during the late Archean could then have favored the triggering of the oxygenation. In addition, we show that the Huronian glaciations, which took place during the GOE, could have introduced a fluctuation in the evolution of the oxygen level. Finally, we show that the oxygen overshoot which is expected to have occurred just after the GOE, was likely accompanied by a methane overshoot. Such high methane concentrations could have had climatic consequences and could have played a role in the dynamics of the Huronian glaciations.

The Great Oxygenation Event (GOE), ca. 2.4 billion years ago, transformed life and environments on Earth. Its causes, however, are debated. We mathematically analyze the GOE in terms of ecological dynamics coupled with a changing Earth. Anoxygenic photosynthetic bacteria initially dominate over cyanobacteria, but their success depends on the availability of suitable electron donors that are vulnerable to oxidation. The GOE is triggered when the difference between the influxes of relevant reductants and phosphate falls below a critical value that is an increasing function of the reproductive rate of cyanobacteria. The transition can be either gradual and reversible or sudden and irreversible, depending on sources and sinks of oxygen. Increasing sources and decreasing sinks of oxygen can also trigger the GOE, but this possibility depends strongly on migration of cyanobacteria from privileged sites. Our model links ecological dynamics to planetary change, with geophysical evolution determining the relevant time scales., The Great Oxygenation Event (GOE) 2.4 billion years ago is believed to have been critical for the evolution of complex life. Here, Olejarz et al. propose a model suggesting that competition between major bacterial groups could have triggered the GOE in a feedback loop with geophysical processes.

The rise of molecular oxygen (O2) in the atmosphere and oceans was one of the most consequential changes in Earth's history. While most research focuses on the Great Oxidation Event (GOE) near the start of the Proterozoic Eon—after which O2became irreversibly greater than 0.1% of the atmosphere—many lines of evidence indicate a smaller oxygenation event before this time, at the end of the Archean Eon (2.5 billion years ago). Additional evidence of mild environmental oxidation—probably by O2—is found throughout the Archean. This emerging evidence suggests that the GOE might be best regarded as the climax of a broader First Redox Revolution (FRR) of the Earth system characterized by two or more earlier Archean Oxidation Events (AOEs). Understanding the timing and tempo of this revolution is key to unraveling the drivers of Earth's evolution as an inhabited world—and has implications for the search for life on worlds beyond our own. ▪ Many inorganic geochemical proxies suggest that biological O2production preceded Earth's GOE by perhaps more than 1 billion years. ▪ Early O2accumulation may have been dynamic, with at least two AOEs predating the GOE. If so, the GOE was the climax of an extended period of environmental redox instability. ▪ We should broaden our focus to examine and understand the entirety of Earth's FRR.

The oxygenation of early Earth’s atmosphere during the Great Oxidation Event, is generally accepted to have been caused by oceanic Cyanobacterial oxygenic photosynthesis. Recent studies suggest that Fe(II) toxicity delayed the Cyanobacterial expansion necessary for the GOE. This study investigates the effects of Fe(II) on two Cyanobacteria, Pseudanabaena sp. PCC7367 and Synechococcus sp. PCC7336, in a simulated shallow-water marine Archean environment. A similar Fe(II) toxicity response was observed as reported for closed batch cultures. This toxicity was not observed in cultures provided with continuous gaseous exchange that showed significantly shorter doubling times than the closed-culture system, even with repeated nocturnal addition of Fe(II) for 12 days. The green rust (GR) formed under high Fe(II) conditions, was not found to be directly toxic to Pseudanabaena sp. PCC7367. In summary, we present evidence of diurnal Fe cycling in a simulated shallow-water marine environment for two ancestral strains of Cyanobacteria, with increased O2 production under anoxic conditions., Cyanobacterial photosynthesis is thought to have oxygenated Earth’s atmosphere during the Great Oxidation Event, but these organisms had to overcome the toxic effects of iron. Here the authors simulate Archaean conditions in Cyanobacterial cultures and find that gas exchange and rust formation alleviated iron toxicity.

The age of carbonate rocks of the Tim Formation of the Oskol Group of the Kursk block, Sarmatia, is limited to 2.22–2.10 Ga on the basis of new data on δ13C and 87Sr/86Sr. Carbonate rocks with an anomalously high value of δ13С (about +11‰ V-PDB) have been revealed for the first time among the Paleoproterozoic sediments of Sarmatia. The distinct negative cerium anomaly [(Ce/Ce*)SN] indicates the formation of limestones after the Great Oxidation Event (GOE) in the early Paleoproterozoic. The minimum value of 87Sr/86Sr (0.7055–0.7058) in the limestones suggests that the Tim paleobasin was partially isolated from the ocean.

Abundant geologic evidence shows that atmospheric oxygen levels were negligible until the Great Oxidation Event (GOE) at 2.4–2.1 Ga. The burial of organic matter is balanced by the release of oxygen, and if the release rate exceeds efficient oxygen sinks, atmospheric oxygen can accumulate until limited by oxidative weathering. The organic burial rate relative to the total carbon burial rate can be inferred from the carbon isotope record in sedimentary carbonates and organic matter, which provides a proxy for the oxygen source flux through time. Because there are no large secular trends in the carbon isotope record over time, it is commonly assumed that the oxygen source flux changed only modestly. Therefore, declines in oxygen sinks have been used to explain the GOE. However, the average isotopic value of carbon fluxes into the atmosphere–ocean system can evolve due to changing proportions of weathering and outgassing inputs. If so, large secular changes in organic burial would be possible despite unchanging carbon isotope values in sedimentary rocks. Here, we present an inverse analysis using a self‐consistent carbon cycle model to determine the maximum change in organic burial since ~4 Ga allowed by the carbon isotope record and other geological proxies. We find that fractional organic burial may have increased by 2–5 times since the Archean. This happens because O2‐dependent continental weathering of 13C‐depleted organics changes carbon isotope inputs to the atmosphere–ocean system. This increase in relative organic burial is consistent with an anoxic‐to‐oxic atmospheric transition around 2.4 Ga without declining oxygen sinks, although these likely contributed. Moreover, our inverse analysis suggests that the Archean absolute organic burial flux was comparable to modern, implying high organic burial efficiency and ruling out very low Archean primary productivity.

As an important contributor to the habitability of our planet, the oxygen cycle is interconnected with the emergence and evolution of complex life and is also the basis to establish Earth system science. Investigating the global oxygen cycle provides valuable information on the evolution of the Earth system, the habitability of our planet in the geologic past, and the future of human life. Numerous investigations have expanded our knowledge of the oxygen cycle in the fields of geology, geochemistry, geobiology, and atmospheric science. However, these studies were conducted separately, which has led to one-sided understandings of this critical scientific issue and an incomplete synthesis of the interactions between the different spheres of the Earth system. This review presents a five-sphere coupled model of the Earth system and clarifies the core position of the oxygen cycle in Earth system science. Based on previous research, this review comprehensively summarizes the evolution of the oxygen cycle in geological time, with a special focus on the Great Oxidation Event (GOE) and the mass extinctions, as well as the possible connections between the oxygen content and biological evolution. The possible links between the oxygen cycle and biodiversity in geologic history have profound implications for exploring the habitability of Earth in history and guiding the future of humanity. Since the Anthropocene, anthropogenic activities have gradually steered the Earth system away from its established trajectory and had a powerful impact on the oxygen cycle. The human-induced disturbance of the global oxygen cycle, if not controlled, could greatly reduce the habitability of our planet.

Production of molecular oxygen was a turning point in the Earth’s history. The geological record indicates the Great Oxidation Event, which marked a permanent transition to an oxidizing atmosphere around 2.4 Ga. However, the degree to which oxygen was available to life before oxygenation of the atmosphere remains unknown. Here, phylogenetic analysis of all known oxygen-utilizing and -producing enzymes (O2-enzymes) indicates that oxygen became widely available to living organisms well before the Great Oxidation Event. About 60% of the O2-enzyme families whose birth can be dated appear to have emerged at the separation of terrestrial and marine bacteria (22 families, compared to two families assigned to the last universal common ancestor). This node, dubbed the last universal oxygen ancestor, coincides with a burst of emergence of both oxygenases and other oxidoreductases, thus suggesting a wider availability of oxygen around 3.1 Ga. Phylogenetic dating of O2-utilizing enzymes indicates a burst of emergence several hundred million years before the Great Oxidation Event.

Reduced greenhouse gases such as methane (CH4) and hydrogen (H2) might be the only tenable solution to explain warming of the ancient Martian climate, but direct geological evidence that a reduced atmosphere actually existed on Mars has been lacking. Here we report widespread, strong Fe loss in chemically weathered bedrock sections in the Mawrth Vallis region and other 3–4-billion-year-old terrains on Mars. The separation of Fe from Al in Martian palaeosols, which is comparable to trends observed in palaeosols before the Great Oxidation Event on Earth, suggests that the ancient Martian surface was chemically weathered under a reducing greenhouse atmosphere. Although for different reasons than on Earth, Mars underwent an oxidation event of its own in the late Noachian that forever changed the geological path of the planet. A comparative analysis of weathered bedrock in the Mawrth Vallis region of Mars and on Hainan Island, China, provides geological evidence for a reduced greenhouse atmosphere on early Mars, as there was on early Earth.

Iron mobilization during continental weathering was pervasive before the Great Oxidation Event (GOE) that started at around 2.43 billion years (Ga) ago, due to the soluble nature of reduced iron. However, various geochemical proxies indicate transient oxygenation during deposition of the Mesoarchean (∼2.95 Ga) Pongola Supergroup, South Africa, which suggests that continental weathering could have also occurred under transiently oxic conditions before the GOE. We analyzed trace elemental and Fe, Ti, and Cr isotopic compositions of the ca. 2.95 Ga Denny Dalton paleosol in the Pongola Supergroup to better understand continental weathering and redox conditions in the ancient critical zone, and the nature of geochemical fluxes from the continents to the oceans and marine sediments. Iron isotope systematics are consistent with a model where Fe was released during intense leaching from the paleosol to concentrate in Fe-rich groundwaters in the deeper part of the soil horizon. We show for the first time that Fe isotopic fractionation during Mesoarchean continental weathering was limited, and Fe enrichments and depletions are coupled with those of divalent transition metals, Co, Ni, and particularly Zn. This suggests that Fe redox cycling was not involved in paleosol formation, and Fe2+ was mobilized under anoxic conditions. Chromium isotopes are also unfractionated relative to the parent igneous rock in this paleosol, which precludes removal of isotopically heavy Cr6+ and thus supports anoxic continental weathering. We show that previously reported Cr isotopic fractionation in another Denny Dalton paleosol profile does not follow a Cr6+ leaching trend, but instead scales with Cr enrichment and may reveal Cr enrichment from post-burial fluids. Thus, there is no clear evidence for an oxidative continental weathering during deposition of the Pongola Supergroup. Titanium isotopes are not significantly fractionated in the paleosol, suggesting that continental weathering and erosion in the Archean did not fractionate Ti isotopes. Similarly, Ni/Co and Th/Sc ratios are reasonably conserved, which validates their use as a robust proxy for upper continental crust composition in shales, whereas La/Sc, Cr/Zn and Cr/U ratios are highly variable relative to the provenance composition, which suggests that caution should be used when applying these ratios in shale studies of the ancient upper continental crust composition.

Manganese (Mn) oxides have been prevalent on Earth since before the Great Oxidation Event and the Mn cycle is one of the most important biogeochemical processes on the Earth's surface. In sunlit natural environments, the photochemistry of Mn oxides has been discovered to enable solar energy harvesting and conversion in both geological and biological systems. One of the most widespread Mn oxides is birnessite, which is a semiconducting layered mineral that actively drives Mn photochemical cycling in Nature. The oxygen-evolving centre in biological photosystem II (PSII) is also a Mn-cluster of Mn4CaO5, which transforms into a birnessite-like structure during the photocatalytic oxygen evolution process. This phenomenon draws the potential parallel of Mn-functioned photoreactions between the organic and inorganic world. The Mn photoredox cycling involves both the photo-oxidation of Mn(II) and the photoreductive dissolution of Mn(IV/III) oxides. In Nature, the occurrence of Mn(IV/III) photoreduction is usually accompanied with the oxidative degradation of natural organics. For Mn(II) oxidation into Mn oxides, mechanisms of biological catalysis mediated by microorganisms (such asPseudomonas putidaandBacillusspecies) and abiotic photoreactions by semiconducting minerals or reactive oxygen species have both been proposed. In particular, anaerobic Mn(II) photo-oxidation processes have been demonstrated experimentally, which shed light on Mn oxide emergence before atmospheric oxygenation on Earth. This review provides a comprehensive and up-to-date elaboration of Mn oxide photoredox cycling in Nature, and gives brand-new insight into the photochemical properties of semiconducting Mn oxides widespread on the Earth's surface.

Drill core and outcrop samples of pure marine chemical sediments (banded iron formation (BIF), manganese formation (MnF), jaspilites, lutites, and cherts) from the transition of the ~2426 Ma old Ongeluk Formation into the 2413 Ma old Hotazel Formation, Transvaal Supergroup, South Africa, reveal remarkable changes of seawater chemistry in the Transvaal Ocean. Similar to pre-Ongeluk chemical sediments, the shale-normalized rare earths and yttrium (REYSN) patterns of jaspilites intercalated with the volcanic rocks of the Ongeluk large igneous province and directly overlying cherts do not show positive EuSN anomalies, indicating that high-temperature (>250 °C) hydrothermal fluids did not contribute significantly to the REY budget of ambient waters. However, a 10 cm drill core section in the lower Hotazel Formation is characterized by conspicuous positive EuSN anomalies, revealing temporary inflow of water masses strongly affected by high-temperature hydrothermal fluids. After this short episode, the REYSN pattern of Transvaal seawater returned to that of pre-Ongeluk times, showing heavy REYSN enrichment, positive LaSN, GdSN and YSN anomalies, but no CeSN or EuSN anomalies. Higher up in the stratigraphy, the Hotazel Formation shows negative CeSN anomalies in some of the lutites, BIFs and MnFs, reflecting Ce depletion in ambient seawater. All Hotazel lutite, BIF, and MnF samples studied show unradiogenic eNd(t) values (−0.5 ± 0.2 to −2.4 ± 0.2), indicating a mostly continental REY source. The REY distribution and Nd isotope data combined suggest that oxidative terrestrial weathering of this continental crustal source supplied most of the dissolved REY to local “Transvaal seawater”. Precipitation of the Hotazel lutites, BIFs and MnFs with negative CeSN anomalies, therefore, suggests that oxic conditions prevailed on the Kaapvaal Craton and in Hotazel seawater already at ~2.413 Ga, i.e. 80 m.y. before the disappearance of mass-independent sulfur isotope fractionation (MIF-S) that defines the Great Oxidation Event at ~2.33 Ga.

Aerobic lifeforms, including humans, thrive because of abundant atmospheric O2, but for much of Earth history O2 levels were low. Even after evidence for oxygenic photosynthesis appeared, the atmosphere remained anoxic for hundreds of millions of years until the ~2.4 Ga Great Oxidation Event. The delay of atmospheric oxygenation and its timing remain poorly understood. Two recent studies reveal that the mantle gradually oxidized from the Archean onwards, leading to speculation that such oxidation enabled atmospheric oxygenation. But whether this mechanism works has not been quantitatively examined. Here, we show that these data imply that reducing Archean volcanic gases could have prevented atmospheric O2 from accumulating until ~2.5 Ga with ≥95% probability. For two decades, mantle oxidation has been dismissed as a key driver of the evolution of O2 and aerobic life. Our findings warrant a reconsideration for Earth and Earth-like exoplanets., The early Earth’s atmosphere had very low oxygen levels for hundreds of millions of years, until the 2.4 Ga Great Oxidation Event, which remains poorly understood. Here, the authors show that reducing Archean volcanic gases could have prevented atmospheric O2 from accumulating, and therefore mantle oxidation was likely very important in setting the evolution of O2 and aerobic life.

In order to determine whether sulfides are major reservoirs for Mo in the upper continental crust (UCC), we determined the composition and mode of occurrence of sulfides and evaluated their contribution to the molybdenum budget in twelve glacial diamictites with ages ranging from 2900 to 300 Ma. The diamictites provide a snapshot of UCC mineralogy and composition at the time of their deposition and show systematic depletion in bulk rock Mo concentrations after the Great Oxidation Event (GOE), reflecting the effects of oxidative weathering in their provenance (Gaschnig et al., 2014; Li et al., 2016). Sulfides are generally confined to Archean and Paleoproterozoic diamictites, although they also have been found in one Phanerozoic sample with an ancient provenance. We classify the sulfides based on their compositions and morphologies. Detrital sulfides are generally rounded, may be a single mineral, or an assemblage of minerals, and show a very wide range in mineralogy, including a single molybdenite grain. Sedimentary sulfides are pyrites, generally with framboidal-like textures. Pyrites also include non-framboidal textured authigenic pyrites. Epigenetic sulfides consist of irregular pyrrhotite aggregates (sometimes pyrrhotite intergrown with chalcopyrite and cobaltite), late-stage euhedral pyrites and pyrite aggregates in veins. High Mo concentrations (up to ∼230 ppm) are found in some sedimentary framboidal-like pyrites from the Mesoarchean Coronation and Paleoproterozoic Makganyene Formations, epigenetic pyrrhotite aggregates and chalcopyrite in the Ramsay Lake diamictite, and in detrital sulfides in Timeball Hill diamictites that may have originated from hydrothermal fluids in the sedimentary basins. Other detrital sulfides have widely variable Mo concentrations (0.5–36 ppm). Mass balance calculations show that sulfides can account for only

Significance The oxygenation of the atmosphere about 2.4 billion years ago remodeled global cycles of toxic, redox-sensitive metal(loids), including that of arsenic, which must have represented a cataclysm in the history of life. Our understanding of biological adaptations surrounding this key transition remains unexplored. By estimating the timing of genetic systems for arsenic detoxification, we reveal an expansion of enzymes and pathways that accompanied adaptations to the biotoxicity of oxidized arsenic species produced by Great Oxidation Event. These include enzymes originated via convergent evolution and pathways that use oxygen for enzymatic catalysis. Our results illustrate how life thrived under the stress of metal(loid) toxicity and provide insights into environmental biogeochemical cycling and microbial evolution., The rise of oxygen on the early Earth about 2.4 billion years ago reorganized the redox cycle of harmful metal(loids), including that of arsenic, which doubtlessly imposed substantial barriers to the physiology and diversification of life. Evaluating the adaptive biological responses to these environmental challenges is inherently difficult because of the paucity of fossil records. Here we applied molecular clock analyses to 13 gene families participating in principal pathways of arsenic resistance and cycling, to explore the nature of early arsenic biogeocycles and decipher feedbacks associated with planetary oxygenation. Our results reveal the advent of nascent arsenic resistance systems under the anoxic environment predating the Great Oxidation Event (GOE), with the primary function of detoxifying reduced arsenic compounds that were abundant in Archean environments. To cope with the increased toxicity of oxidized arsenic species that occurred as oxygen built up in Earth’s atmosphere, we found that parts of preexisting detoxification systems for trivalent arsenicals were merged with newly emerged pathways that originated via convergent evolution. Further expansion of arsenic resistance systems was made feasible by incorporation of oxygen-dependent enzymatic pathways into the detoxification network. These genetic innovations, together with adaptive responses to other redox-sensitive metals, provided organisms with novel mechanisms for adaption to changes in global biogeocycles that emerged as a consequence of the GOE.

Evolving atmospheric oxygen levels during the early Earth history had a profound impact on Earth’s surface processes, especially on the mineralization of redox-sensitive elements such as iron (Fe) ...

Accelerated precipitation of Mn-rich rocks in the early Paleoproterozoic ocean is considered to reflect the irreversible rise of oxygen in the atmosphere during the Great Oxidation Event (GOE), 2.501–2.220 billion years ago. But the precipitation conditions, pathways, mechanisms, and linkages to ocean redox, broadly remain unresolved. The Lagoa do Riacho Mn deposit in Borborema Province, northeastern Brazil, Ceara state, consists mainly of manganese-rich and manganese-poor silicates deposited during the GOE epoch. Negative Ce anomalies in the manganese-poor silicates point to the scavenging of Ce3+ onto Mn-oxyhydroxide reactive surfaces in the oxygenated surface waters. In contrast, samples with positive Ce anomalies, predominantly associated with the manganese-rich silicates, indicate a reductive dissolution of Mn-oxyhydroxides across a redoxcline, enriching the anoxic bottom water with Ce and Mn2+. A paleoredox reconstruction based on couple Mn, Mo, and U systematics supports the existence of the proposed Mn-oxide redox shuttle that enriched the anoxic sediment pile with Mn precipitated from the oxygenated shallow surface waters. This study uncovers a unique pathway in Paleoproterozoic Mn mineralization involving the transfer of Mn oxides from an oxygenated upper ocean reservoir to a predominantly deep anoxic silicate reservoir that was subsequently metamorphosed. The proposed Mn oxide sink switch mechanism is different from the commonly reported reductive transfer of Mn to a diagenetic carbonate sink during the Paleoproterozoic.

The appearance of oxygenic photosynthesis in cyanobacteria is a major event in evolution. It had an irreversible impact on the Earth, promoting the Great Oxygenation Event (GOE) ~2.4 billion years ago. Ancient cyanobacteria predating the GOE were Gloeobacter-type cells lacking thylakoids, which hosted photosystems in their cytoplasmic membrane. The driver of the GOE was proposed to be the transition from unicellular to filamentous cyanobacteria. However, the appearance of thylakoids expanded the photosynthetic surface to such an extent that it introduced a multiplier effect, which would be more coherent with an impact on the atmosphere. Primitive thylakoids self-organize as concentric parietal uninterrupted multilayers. There is no robust evidence for an origin of thylakoids via a vesicular-based scenario. This review reports studies supporting that hexagonal II-forming glucolipids and galactolipids at the periphery of the cytosolic membrane could be turned, within nanoseconds and without any external source of energy, into membrane multilayers. Comparison of lipid biosynthetic pathways shows that ancient cyanobacteria contained only one anionic lamellar-forming lipid, phosphatidylglycerol. The acquisition of sulfoquinovosyldiacylglycerol biosynthesis correlates with thylakoid emergence, possibly enabling sufficient provision of anionic lipids to trigger a hexagonal II-to-lamellar phase transition. With this non-vesicular lipid-phase transition, a framework is also available to re-examine the role of companion proteins in thylakoid biogenesis.

The geological record following the c. 2.3 billion years old Great Oxidation Event includes evidence for anomalously high burial of organic carbon and the emergence of widespread mountain building. Both carbon burial and orogeny occurred globally over the period 2.1 to 1.8 billion years ago. Prolific cyanobacteria were preserved as peak black shale sedimentation and abundant graphite. In numerous orogens, the exceptionally carbonaceous sediments were strongly deformed by thrusting, folding, and shearing. Here an assessment of the timing of Palaeoproterozoic carbon burial and peak deformation/metamorphism in 20 orogens shows that orogeny consistently occurred less than 200 million years after sedimentation, in a time frame comparable to that of orogens through the Phanerozoic. This implies that the high carbon burial played a critical role in reducing frictional strength and lubricating compressive deformation, which allowed crustal thickening to build Palaeoproterozoic mountain belts. Further, this episode left a legacy of weakening and deformation in 2 billion year-old crust which has supported subsequent orogenies up to the building of the Himalayas today. The link between Palaeoproterozoic biomass and long-term deformation of the Earth’s crust demonstrates the integral relationship between biosphere and lithosphere. High burial of organic carbon in sediments around 2 billion years ago acted to enhance crustal deformation and led to intensified mountain building both in the Paleoproterozoic and since, suggests an assessment of the timing of carbon burial and deformation

Introductory paragraphCyanobacteria oxygenated Earth’s atmosphere during the Great Oxygenation Event (GOE) through oxygenic photosynthesis. Their high iron requirement was presumed met by high levels of Fe(II) in the anoxic Archean ocean. Here we show that most basal Cyanobacteria cannot synthesize the primary Fe(II) transporter, FeoB. Relaxed molecular clock analyses estimate the arrival of FeoB, as well as the Fe(III) transporters, cFTR1 and FutB, in the Cyanobacteria after the GOE. Furthermore Pseudanabaena sp. PCC7367, a basal marine, benthic strain grown under simulated Archean conditions, constitutively expressed cftr1, even after the addition of Fe(II). By utilizing gene expression studies under a simulated Archean atmosphere, as well as comparative genomics, phylogenetics and molecular clock analyses, this study identified a need to reappraise iron uptake in ancestral Cyanobacteria, as genetic profiling suggests that scavenging of siderophore bound Fe(III), rather than Fe(II), appears to have been the means of iron acquisition prior to the GOE.

Description, New modeling of early Mo cycle places constraints on Archean O2., Evidence continues to emerge for the production and low-level accumulation of molecular oxygen (O2) at Earth’s surface before the Great Oxidation Event. Quantifying this early O2 has proven difficult. Here, we use the distribution and isotopic composition of molybdenum in the ancient sedimentary record to quantify Archean Mo cycling, which allows us to calculate lower limits for atmospheric O2 partial pressures (PO2) and O2 production fluxes during the Archean. We consider two end-member scenarios. First, if O2 was evenly distributed throughout the atmosphere, then PO2 > 10–6.9 present atmospheric level was required for large periods of time during the Archean eon. Alternatively, if O2 accumulation was instead spatially restricted (e.g., occurring only near the sites of O2 production), then O2 production fluxes >0.01 Tmol O2/year were required. Archean O2 levels were vanishingly low according to our calculations but substantially above those predicted for an abiotic Earth system.