Paleoproterozoic Great Oxidation Event Research Articles

Timing the evolution of phosphorus-cycling enzymes through geological time using phylogenomics

Phosphorus plays a crucial role in controlling biological productivity, but geological estimates of phosphate concentrations in the Precambrian ocean, during life’s origin and early evolution, vary over several orders of magnitude. While reduced phosphorus species may have served as alternative substrates to phosphate, their bioavailability on the early Earth remains unknown. Here, we reconstruct the phylogenomic record of life on Earth and find that phosphate transporting genes (pnas) evolved in the Paleoarchean (ca. 3.6-3.2 Ga) and are consistent with phosphate concentrations above modern levels ( > 3 µM). The first gene optimized for low phosphate levels (pstS; <1 µM) appeared around the same time or in the Mesoarchean depending on the reconstruction method. Most enzymatic pathways for metabolising reduced phosphorus emerged and expanded across the tree of life later. This includes phosphonate-catabolising CP-lyases, phosphite-oxidising pathways and hypophosphite-oxidising pathways. CP-lyases are particularly abundant in dissolved phosphate concentrations below 0.1 µM. Our results thus indicate at least local regions of declining phosphate levels through the Archean, possibly linked to phosphate-scavenging Fe(III), which may have limited productivity. However, reduced phosphorus species did not become widely used until after the Paleoproterozoic Great Oxidation Event (2.3 Ga), possibly linked to expansion of the biosphere at that time.

The Evolution of Mineral Hardness Reveals Both Changing Parageneses and Preservational Bias in the Mineralogical Record

A survey of the average Mohs hardness of minerals throughout Earth’s history reveals a significant and systematic decrease from &gt;6 in presolar grains to ~5 for Archean lithologies to &lt;4 for Phanerozoic minerals. Two primary factors contribute to this temporal decrease in the average Mohs hardness. First, selective losses of softer minerals throughout billions of years of near-surface processing lead to preservational biases in the mineral record. Second, changes in the processes of mineral formation play a significant role because more ancient refractory stellar phases and primary igneous minerals of the Hadean/Archean Eon are intrinsically harder than more recently weathered products, especially following the Paleoproterozoic Great Oxidation Event and the production of Phanerozoic biominerals. Additionally, anthropogenic sampling biases resulting from the selective exploration and curation of the mineralogical record may be superimposed on these two factors.

Origin of Banded Iron Formations: Links with Paleoclimate, Paleoenvironment, and Major Geological Processes

Banded iron-formations (BIFs) are marine chemical sedimentary rocks composed of siliceous and ferric materials, usually with typical thin layers or sheet structures. BIFs not only record a wealth of information about the state and evolution of the lithosphere, atmosphere, hydrosphere, and biosphere but also host the majority of the economic iron resources in the world. Here, we summarize the types, mineralogical, and geochemical characteristics of BIFs; analyze their formation conditions, their oxidative mechanism, and the absence causes of BIFs; and elucidate the associations between BIFs and major atmospheric oxidation events (Paleoproterozoic great oxidation event (2.4~2.1 Ga) and Neoproterozoic oxidation event (0.8~0.55 Ga)). BIFs are intimately associated with enhanced submarine magmatic–hydrothermal activities. Finally, it is concluded that the deposition and demise of BIFs are closely related to major geological events, and these major geological events interact with each other, jointly constraining the evolution of the atmospheric and marine environment and of geo-biological and geodynamic processes.

Redox-stratified seawater during the GOE: Evidences from rare earth elemental and C-O isotopic compositions of Paleoproterozoic BIF and carbonate rocks from the Taihua Group, North China Craton

The Paleoproterozoic Great Oxidation Event (GOE) is known for the dramatic change in atmospheric composition that led to oxygen becoming a persistent component of global surface processes. Drastic environmental changes greatly affected ocean and atmosphere chemistry. However, the distribution of dissolved oxygen in the ocean during the GOE is still unclear as rare contemporary sediment-records have been found. In order to identify the redox state of both shallow and deep water, and reveal the ocean redox structure during this time, we present new major and trace elemental and C-O isotopic data of bulk samples of the banded iron formation (BIF), dolomitic marble, and graphite-bearing marble of the early Paleoproterozoic upper Taihua Group in the Lushan area, southern margin of the North China Craton (NCC). The BIF samples exhibit typical major and trace element characteristics akin to very pure marine chemical sediments, such as the shale-normalized positive La, Ga, and Y anomalies, indicative of a marine depositional setting. In these BIF samples, both negative Ce anomalies and the lack of Ce anomalies reflect the presence of both oxic and suboxic/anoxic water in the ocean. Samples of the dolomitic marble are characterized by extremely low amounts of crustal material (such as Al, Ti, Zr, Hf) and high Y/Ho ratios (46–66), also implying a pure marine chemical origin. Excluding some contaminated samples, the rest of the graphite-bearing marble samples display similar features of the dolomitic marble. Significant positive Ce anomalies and high light to heavy REE (Pr/Yb(SN)) ratios in both dolomitic marble and graphite-bearing marble are essentially consistent with the 2.2–2.1 Ga carbonates from the Guanmenshan Formation of the Liaohe Group in the NE Sino-Korean Craton. Combined with the Ce anomalies in the BIF samples, we consider that the seawater when the upper Taihua Group deposited was redox-stratified from oxic shallow water to deeper anoxic water. Besides, the graphite-bearing marble record coeval surface water in the column that was enriched in nutritive materials and beneficial to microbiology and high productivity. Moreover, the early Paleoproterozoic IFs in the Songshan Group and the Lüliang Group in the NCC also exhibit significant both positive and negative Ce anomalies and enrichment of redox sensitive elements. These evidences, therefore, suggest that redox-stratified seawater occurred extensively during the GOE.

Re-appearance of precipitated aragonite crystal fans as evidence for expansion of oceanic dissolved inorganic carbon reservoir in the aftermath of the Lomagundi-Jatuli Event

The initial accumulation of atmospheric oxygen is marked by the unprecedented positive δ13Ccarb excursions of the Lomagundi-Jatuli Event (LJE) and records an interval of abnormal O2 production through elevated rates of organic carbon burial. Emerging evidence suggests that the post-LJE atmosphere-ocean system might have suffered a significant deoxygenation. These dynamic perturbations in the oceanic redox state and biogeochemical cycles would have led to fundamental changes in carbonate precipitation dynamics. Here, we report the discovery of centimeter-sized crystal fans in the post-LJE Huaiyincun Formation, Hutuo Supergroup in the North China Craton. The hexagonal cross-sections and square terminations suggest that these fan-like dolomitic structures were originally aragonite crystal fans (ACF). Variations of stromatolite morphology and frequent occurrences of storm-related deposits in the Huaiyincun Formation point to repeated cycles of sea level changes. The bedding-parallel distribution of the ACF and the homogeneous δ13C values of the ACF-bearing dolostones are consistent with a primary depositional origin for the ACF. An updated compilation of published records of ACF throughout geological history highlights a clear absence of ACF from the initiation of the Paleoproterozoic Great Oxidation Event until the end of the LJE, and a global reappearance of ACF in the post-LJE late Paleoproterozoic. We propose that the reappearance of ACF is in agreement with the expansion of the oceanic dissolved inorganic carbon reservoir. At the same time, consumption of dissolved oxygen during the oxidation of organic matter might have been stimulated by ferruginous deep seawater, facilitating the formation of Huiayincun ACF.

Proterozoic supercontinent break-up as a driver for oxygenation events and subsequent carbon isotope excursions.

Oxygen and carbon are 2 elements critical for life on Earth. Earth's most dramatic oxygenation events and carbon isotope excursions (CIE) occurred during the Proterozoic, including the Paleoproterozoic Great Oxidation Event and the associated Lomagundi CIE, the Neoproterozoic Oxygenation event, and the Shuram negative CIE during the late Neoproterozoic. A specific pattern of a long-lived positive CIE followed by a negative CIE is observed in association with oxygenation events during the Paleo- and Neo-proterozoic. We present results from a carbon cycle model designed to couple the surface and interior cycling of carbon that reproduce this pattern. The model assumes organic carbon resides in the mantle longer than carbonate, leading to systematic temporal variations in the δ13C of volcanic CO2 emissions. When the model is perturbed by periods of enhanced continental weathering, increased amounts of carbonate and organic carbon are buried. Increased deposition of organic carbon allows O2 accumulation, while positive CIEs are driven by rapid release of subducted carbonate-derived CO2 at arcs. The subsequent negative CIEs are driven by the delayed release of organic C-derived CO2 at ocean islands. Our model reproduces the sequences observed in the Paleo- and Neo-proterozoic, that is oxygenation accompanied by a positive CIE followed by a negative CIE. Periods of enhanced weathering correspond temporally to supercontinent break-up, suggesting an important connection between global tectonics and the evolution of oxygen and carbon on Earth.

The Great Oxidation Event preceded a Paleoproterozoic “snowball Earth”

The inability to resolve the exact temporal relationship between two pivotal events in Earth history, the Paleoproterozoic Great Oxidation Event (GOE) and the first "snowball Earth" global glaciation, has precluded assessing causality between changing atmospheric composition and ancient climate change. Here we present temporally resolved quadruple sulfur isotope measurements (δ34S, ∆33S, and ∆36S) from the Paleoproterozoic Seidorechka and Polisarka Sedimentary Formations on the Fennoscandian Shield, northwest Russia, that address this issue. Sulfides in the former preserve evidence of mass-independent fractionation of sulfur isotopes (S-MIF) falling within uncertainty of the Archean reference array with a ∆36S/∆33S slope of -1.8 and have small negative ∆33S values, whereas in the latter mass-dependent fractionation of sulfur isotopes (S-MDF) is evident, with a ∆36S/∆33S slope of -8.8. These trends, combined with geochronological constraints, place the S-MIF/S-MDF transition, the key indicator of the GOE, between 2,501.5 ± 1.7 Ma and 2,434 ± 6.6 Ma. These are the tightest temporal and stratigraphic constraints yet for the S-MIF/S-MDF transition and show that its timing in Fennoscandia is consistent with the S-MIF/S-MDF transition in North America and South Africa. Further, the glacigenic part of the Polisarka Formation occurs 60 m above the sedimentary succession containing S-MDF signals. Hence, our findings confirm unambiguously that the S-MIF/S-MDF transition preceded the Paleoproterozoic snowball Earth. Resolution of this temporal relationship constrains cause-and-effect drivers of Earth's oxygenation, specifically ruling out conceptual models in which global glaciation precedes or causes the evolution of oxygenic photosynthesis.

Mo isotopic response to the end of Neoproterozoic Marinoan glaciation: Evidence from a sedimentary profile in South China

In the geological time, atmosphere and ocean have experienced two important oxidation events which are the Paleoproterozoic Great Oxidation Event and the Neoproterozoic Oxidation Event. These events had a great influence on the origin and evolution of life and the system of atmosphere, ocean and earth surface. The record of early metazoan fossils and the radiation of marine algae occurred following the Marinoan glaciation in the Neoproterozoic. Hence, an ocean oxygenation event at the boundary of Cryogenian and Ediacaran is closely associated with the biological evolution. Here, we present new TOC contents, Mo concentrations, C-O-Mo isotopic data of sedimentary rocks collected across the boundary (~635 Ma) between the Nantuo and Doushantuo Formations in the Shennongjia area, South China. Based on the isotopic data, three intervals can be distinguished: Interval I, the Nantuo Formation beneath the cap carbonate of the Doushantuo Formation, has the highest TOC (0.03%) and Mo concentration (5.494 ppm) and similar tendency of the δ13C values and the δ98Mo values, which represent the enhanced chemical weathering, the raised nutrient input and the higher primary productivity. Interval II, the cap carbonate, possesses low TOC and Mo concentrations and the consistently diminished carbon composition and the fluctuating δ98Mo values. Interval III, the sediments above the cap carbonate of the Doushantuo Formation, is characterized by low TOC and Mo concentration, which is similar with the Interval II, but displays decreasing δ13C values and increasing δ98Mo values. These features of the Interval II and III were contributed by the end of high intensity chemical weathering, resulting in the atmosphere and shallow-ocean enriching oxygen. The δ98Mo values elevated until the interval III, indicating that the response of Mo isotope system lagged the shallow-ocean oxygenation. Our data, therefore, indicate an oxygenation from the Cryogenian to Ediacaran, which is in good agreement with the emergence of the Ediacaran biota.

The onset of oxidative weathering traced by uranium isotopes

The invention of photosynthesis was a key interval in Earth’s history, initiating major changes in the evolution of the oceans and atmosphere. Many studies suggest that oxygen levels were already enhanced before the Paleoproterozoic Great Oxidation Event (GOE, 2.45–2.32 Ga). However, the timing of the onset of photosynthetic oxygenation, as well as spatio-temporal fluctuations of atmospheric and oceanic oxygen levels are highly debated. Here, we present a new and substantial uranium (U) isotope dataset comprising marine sediments, e.g. black shales, carbonates and iron-rich sedimentary rocks, from the Hamersley Basin (Western Australia), Kaapvaal and Zimbabwe Cratons (both southern Africa) with depositional ages ranging from 3.4 to 2.2 Ga. Sub-recent U mobilization was monitored by analyzing 234U along with δ238U, and detrital U contribution was monitored with [Al]/[U] or [Th]/[U] ratios. Samples with significant authigenic U enrichment (EFU > 2), relative to post-Archean Australian Shale (PAAS), exhibit authigenic δ238U ranging from −0.96 to −0.02‰ (±0.05‰, 2 s.d. long-term reproducibility), which deviates markedly from typical δ238U of the continental crust (−0.40 to −0.20‰). Remarkably, we find increased δ238U variability in the upper Ghaap Group (2.50–2.47 Ga, carbonates and black shales) and the lower Pretoria Group (2.42–2.32 Ga, Duitschland Formation, shales) of the Kaapvaal Craton. The predominantly light U isotope composition of those samples is likely explained by U isotope fractionation related to the onset of partial U mobilization during slow oxidative weathering of uraninite shortly before and during the GOE. The lack of low δ238U values in the Timeball Hill Formation (overlying the Duitschland Formation) indicate the onset of quantitative U mobilization during (modern-style) oxidative weathering of uraninite and other U-bearing minerals with limited U isotope fractionation. These limited U isotope variations measured in the Paleoproterozoic Timeball Hill Formation further suggest that, in contrast to modern oceans, in the period following the GOE, U was largely quantitatively reduced and removed from the water column of the Transvaal basin which remained mainly anoxic at depth.

Synsedimentary fault control on the deposition of the Duitschland Formation (South Africa): Implications for depositional settings, Paleoproterozoic stratigraphic correlations, and the GOE

The Paleoproterozoic Great Oxidation Event (GOE) marks the first significant oxidation of atmosphere and surface environments, and is causally associated with the global disappearance of mass-independent sulfur isotope fractionation (MIF-S). However, fundamental sedimentary aspects of successions recording this event (e.g. depositional environment, tectonic setting and stratigraphic correlation) are poorly constrained and often debated, restricting full understanding of causes and effects related to the GOE. In South Africa, MIF-S disappears across the ‘mid-Duitschland unconformity’ (MDU) in the Duitschland Formation (Transvaal Supergroup). New sedimentological observations of the lower Duitschland Formation have identified up to 5 times thicker and more diverse chert-pebble conglomerates than previously documented. New facies observed include lenticular conglomerates which incise cross-bedded dolomites, and imbricated conglomerates. The overlying MDU is angular in nature, recording an ∼15° N dip of the lower Duitschland strata; elsewhere it possesses a disconformable geometry. A new depositional model is proposed where shallow-marine carbonate (ramp) deposition interfaced with wave-influenced Gilbert-type fan deltas in an isolated depocentre produced during synsedimentary faulting. There is no evidence that the MDU formed due to direct glaciation as proposed previously. However, glacio-eustatic changes may have had an influence. This study supports the lithostratigraphic correlation of the Duitschland and Rooihoogte formations. This interpretation challenges the idea that they are separate lithostratigraphic units that record oscillations in MIF-S; this apparent oscillation in MIF-S is a stratigraphic artefact. The correlation proposed in this study implies a unique MIF-S signal and has important consequences for differentiating true spatiotemporal oscillations in MIF-S chemistry from artificial variations caused by unresolved stratigraphic relations.

Dating the Gaofan and Hutuo Groups – Targets to investigate the Paleoproterozoic Great Oxidation Event in North China

There are several sedimentary units in North China that are proposed to be associated with the Paleoproterozoic Great Oxidation Event (GOE) and/or subsequent events; however, few of them have been precisely dated. In this study, deposition age of the greenschist facies Gaofan and Hutuo Groups is determined. Zircon grains liberated from a tuff layer (metamorphosed to sericite-quartz schist) in the upper part of the Mohe Formation (the second of the three formations of the Gaofan Group) yield a weighted average 207Pb/206Pb age of 2186±8Ma (n=7, MSWD=1.3), representing time of deposition. This age and the detrital zircon U-Pb ages of the basal feldspar quartzite (meta-siltstone), as well as the initial deposition age of the unconformably overlying Hutuo Group, confine the deposition age of the Gaofan Group to 2350–2150Ma. This result negates the Gaofan Group as one subgroup of the 2560–2510Ma Wutai greenstone belt. Zircons from the Banlaoyao mafic sill (meta-diabase) that intruded the Dongye Subgroup of the Hutuo Group yield an upper intercept U-Pb age of 2057±25Ma (n=14, MSWD=1.3), representing time of crystallization. Considering the age of the basalt in the first formation of the Doucun Subgroup and the tuff in the first formation of the Dongye Subgroup, the deposition age of the Doucun and Dongye Subgroups of the Hutuo Group is confined to 2150–2090Ma and 2090–2060Ma, respectively. These age brackets, as well as the available carbon and nitrogen isotope data indicate that the Zhangxianbu Formation of the Gaofan Group possibly recorded the GOE; whereas the Mohe-Yaokouqian Formations of the Gaofan Group and the Doucun-Dongye Subgroups of the Hutuo Group recorded the subsequent Lomagundi-Jatuli Event (LJE). However, the Lomagundi-Jatuli carbon excursions are hardly distinguishable from the Gaofan Group and the Doucun Subgroup (Hutuo Group) as both units consist of little inorganic carbon but terrestrial clastic turbidites.

Atmospheric oxygen regulation at low Proterozoic levels by incomplete oxidative weathering of sedimentary organic carbon

It is unclear why atmospheric oxygen remained trapped at low levels for more than 1.5 billion years following the Paleoproterozoic Great Oxidation Event. Here, we use models for erosion, weathering and biogeochemical cycling to show that this can be explained by the tectonic recycling of previously accumulated sedimentary organic carbon, combined with the oxygen sensitivity of oxidative weathering. Our results indicate a strong negative feedback regime when atmospheric oxygen concentration is of order pO2∼0.1 PAL (present atmospheric level), but that stability is lost at pO2<0.01 PAL. Within these limits, the carbonate carbon isotope (δ13C) record becomes insensitive to changes in organic carbon burial rate, due to counterbalancing changes in the weathering of isotopically light organic carbon. This can explain the lack of secular trend in the Precambrian δ13C record, and reopens the possibility that increased biological productivity and resultant organic carbon burial drove the Great Oxidation Event.

Selenium isotopes record extensive marine suboxia during the Great Oxidation Event

It has been proposed that an "oxygen overshoot" occurred during the early Paleoproterozoic Great Oxidation Event (GOE) in association with the extreme positive carbon isotopic excursion known as the Lomagundi Event. Moreover, it has also been suggested that environmental oxygen levels then crashed to very low levels during the subsequent extremely negative Shunga-Francevillian carbon isotopic anomaly. These redox fluctuations could have profoundly influenced the course of eukaryotic evolution, as eukaryotes have several metabolic processes that are obligately aerobic. Here we investigate the magnitude of these proposed oxygen perturbations using selenium (Se) geochemistry, which is sensitive to redox transitions across suboxic conditions. We find that δ82/78Se values in offshore shales show a positive excursion from 2.32 Ga until 2.1 Ga (mean +1.03 ± 0.67‰). Selenium abundances and Se/TOC (total organic carbon) ratios similarly show a peak during this interval. Together these data suggest that during the GOE there was pervasive suboxia in near-shore environments, allowing nonquantitative Se reduction to drive the residual Se oxyanions isotopically heavy. This implies O2 levels of >0.4 μM in these settings. Unlike in the late Neoproterozoic and Phanerozoic, when negative δ82/78Se values are observed in offshore environments, only a single formation, evidently the shallowest, shows evidence of negative δ82/78Se. This suggests that there was no upwelling of Se oxyanions from an oxic deep-ocean reservoir, which is consistent with previous estimates that the deep ocean remained anoxic throughout the GOE. The abrupt decline in δ82/78Se and Se/TOC values during the subsequent Shunga-Francevillian anomaly indicates a widespread decrease in surface oxygenation.

Coupled sulfur, iron and molybdenum isotope data from black shales of the Teplá-Barrandian unit argue against deep ocean oxygenation during the Ediacaran

The Earth’s atmosphere and hydrosphere changed from an Archean anoxic to a modern oxygenated world in two major steps, the Paleoproterozoic Great Oxidation Event (2.4–2.3 billion years ago) and the Neoproterozoic Oxidation Event (0.8–0.5 billion years ago). Both events had a strong influence on the availability of redox sensitive and bio-essential metals within the ocean and are, thus, strongly linked to fundamental biological innovations and diversification. Biological diversification during the Precambrian–Cambrian transition between 555 and 540 million years ago may have been driven by ocean–atmosphere oxygenation. The exact timing and the extent of (deep) ocean oxygenation within this time period remains unresolved though.Here we present major and trace element compositions as well as Mo, S and Fe isotopic data of organic-rich black shales from the Teplá-Barrandian unit, Czech Republic. New in situ zircon U–Pb ages provide a maximum depositional age of 559.8±3.8 million years. Black shales with strong metal enrichment show low δ56Fe values due to the dominance of authigenic pyrite-Fe with δ56Fe values around −0.6‰ over detrital Fe with δ56Fe values around 0.1‰. Samples with lower authigenic metal enrichment show relatively low Mo/TOC ratios and increasing δ34S values, which is interpreted to reflect basinal restriction and longer seawater renewal times. In analogy to the modern Black Sea, the accompanied depletion of basinal Moaq due to near quantitative Mo removal might have led to the preservation of the seawater δ98Mo in the respective black shales. Our best estimate for this seawater Mo isotopic composition <560 million years ago is +1.2‰ in δ98Mo, which is nearly identical to seawater δ98Mo values inferred from Mid-Proterozoic black shales. The lack of higher δ98Mo values in black shales (and seawater) argues against contemporaneous Mn oxide formation in well oxygenated deep sea settings, which would preferentially adsorb isotopically light Mo leaving behind an isotopically heavy ocean. By contrast, the deep ocean might have remained ferruginous with the hydrothermal Fe still outbalancing surficial oxygen production. Our results therefore contribute to a growing data set, which suggests limited deep water oxygenation during major biological innovations in the late Ediacaran period.

The evolution of the global selenium cycle: Secular trends in Se isotopes and abundances

The Earth’s surface has undergone major transitions in its redox state over the past three billion years, which have affected the mobility and distribution of many elements. Here we use Se isotopic and abundance measurements of marine and non-marine mudrocks to reconstruct the evolution of the biogeochemical Se cycle from ∼3.2Gyr onwards. The six stable isotopes of Se are predominantly fractionated during redox reactions under suboxic conditions, which makes Se a potentially valuable new tool for identifying intermediate stages from an anoxic to a fully oxygenated world. δ82/78Se shows small fractionations of mostly less than 2‰ throughout Earth’s history and all are mass-dependent within error. In the Archean, especially after 2.7Gyr, we find an isotopic enrichment in marine (+0.37±0.27‰) relative to non-marine samples (−0.28±0.67‰), paired with increasing Se abundances. Student t-tests show that these trends are statistically significant. Although we cannot completely rule out the possibility of volcanic Se addition, these trends may indicate the onset of oxidative weathering on land, followed by non-quantitative reduction of Se oxyanions during fluvial transport. The Paleoproterozoic Great Oxidation Event (GOE) is not reflected in the marine δ82/78Se record. However, we find a major inflection in the secular δ82/78Se trend during the Neoproterozoic, from a Precambrian mean of +0.42±0.45‰ to a Phanerozoic mean of −0.19±0.59‰. This drop probably reflects the oxygenation of the deep ocean at this time, stabilizing Se oxyanions throughout the water column. Since then, reduction of Se oxyanions has likely been restricted to anoxic basins and diagenetic environments in sediments. In light of recent Cr isotope data, it is likely that oxidative weathering before the Neoproterozoic produced Se oxyanions in the intermediate redox state SeIV, whereas the fully oxidized species SeVI became more abundant after the Neoproterozoic rise of atmospheric oxygen.

Selenium isotopes support free O2 in the latest Archean

Selenium (Se) undergoes redox transformations and isotopic fractionations at relatively high redox potentials and could therefore provide insight into changes in oceanic and atmospheric O2 levels over Earth’s history. We test this idea with Se data from the 2.5 Ga Mount McRae Shale (Hamersley Basin, Australia), which records temporary enrichments in abundances and isotopes of other redox-sensitive elements indicating a “whiff of oxygen” in Earth’s atmosphere before the Great Oxidation Event. Se isotopic ratios expressed as δ82/78Se and abundances relative to crustal background show significant positive excursions of up to 1.1‰ and an enrichment 13 times above background, respectively, overlapping with excursions in Mo and N isotopes and abundances. Because Se has a relatively high redox potential and photosynthetic oxidation pathways are unknown, our data thus suggest that Se was mobilized by free O2 during this interval. The isotopic fractionation likely occurred during transport of Se oxyanions from the site of weathering to the outer shelf. Although O2 could have been produced locally on land and may not necessarily have increased in the global atmosphere, our results strengthen the inference of an early origin of oxygenic photosynthesis long before the Paleoproterozoic Great Oxidation Event. This is the first report of a Se isotope excursion in the Precambrian rock record, and it confirms that Se isotopes can serve as a useful redox proxy in deep time.

Uranium isotope fractionation suggests oxidative uranium mobilization at 2.50 Ga

Geochemical data from late Archean sedimentary rocks point to photosynthetic O2 production and at least intermittent occurrences of locally mild oxidative weathering and surface ocean oxygenation (“oxygen oases”) prior to the early Paleoproterozoic Great Oxidation Event. For example, distinctive authigenic enrichments of Mo and Re in euxinic (anoxic and sulfidic) black shales are best explained by the oxidative mobilization of these metals from crustal sulfide minerals and their accumulation as oxyanions in seawater. In contrast, it is not clear if low U enrichments in the same shales reflect negligible oxidation of U from the upper crust or a very small oceanic U inventory that was derived from oxidative U mobilization. Here, we report U isotope data for the 2.50Ga Mt. McRae Shale (Hamersley basin, Western Australia), which provides a more sensitive test for the presence or absence of authigenic U compared to U concentrations and enrichment factors normalized to average shale or upper crustal compositions (that may not be representative of the local detrital composition). We find instances where the U isotope composition in the upper Mt. McRae Shale (δ238U=−0.2 to 0.0‰ relative to standard SRM950a) is isotopically heavier than average upper crust (δ238U=−0.31±0.14 [2SD] based on granitoids and basalts). The high δ238U values point to U isotope fractionation in the late Archean marine environment and hence indicate the presence of a small amount of dissolved U in seawater and authigenic U in the Mt. McRae Shale. Volume-dependent equilibrium isotope fractionation during the reduction of dissolved UVI to insoluble UIV, like that observed in the modern Black Sea, may explain the high δ238U signatures if U removal from bottom waters was not quantitative. Alternatively, quantitative U removal would require that late Archean seawater had high δ238U, which could have arisen from the preferential sequestration of 235U to Fe (oxyhydr)oxide minerals elsewhere in the Hamersley basin. The supracrustal δ238U signatures are associated with some of the highest Mo and Re enrichments in the Mt. McRae Shale as well as distinctive Mo, S and N isotope signatures that are indicative of mild environmental oxygenation. Hence, our findings suggest that small amounts of U were oxidatively mobilized from the upper crust at 2.50Ga. Unlike Mo and Re, however, U oxidation may not have occurred on land. Instead, we hypothesize that oxidative U mobilization occurred by submarine weathering in an oxygen oasis.

Single cell gas flotation separator with filter media

Geochemical data from late Archean sedimentary rocks point to photosynthetic O2 production and at least intermittent occurrences of locally mild oxidative weathering and surface ocean oxygenation (“oxygen oases”) prior to the early Paleoproterozoic Great Oxidation Event. For example, distinctive authigenic enrichments of Mo and Re in euxinic (anoxic and sulfidic) black shales are best explained by the oxidative mobilization of these metals from crustal sulfide minerals and their accumulation as oxyanions in seawater. In contrast, it is not clear if low U enrichments in the same shales reflect negligible oxidation of U from the upper crust or a very small oceanic U inventory that was derived from oxidative U mobilization. Here, we report U isotope data for the 2.50 Ga Mt. McRae Shale (Hamersley basin, Western Australia), which provides a more sensitive test for the presence or absence of authigenic U compared to U concentrations and enrichment factors normalized to average shale or upper crustal compositions (that may not be representative of the local detrital composition). We find instances where the U isotope composition in the upper Mt. McRae Shale (δ238U = − 0.2 to 0.0‰ relative to standard SRM950a) is isotopically heavier than average upper crust (δ238U = − 0.31 ± 0.14 [2SD] based on granitoids and basalts). The high δ238U values point to U isotope fractionation in the late Archean marine environment and hence indicate the presence of a small amount of dissolved U in seawater and authigenic U in the Mt. McRae Shale. Volume-dependent equilibrium isotope fractionation during the reduction of dissolved UVI to insoluble UIV, like that observed in the modern Black Sea, may explain the high δ238U signatures if U removal from bottom waters was not quantitative. Alternatively, quantitative U removal would require that late Archean seawater had high δ238U, which could have arisen from the preferential sequestration of 235U to Fe (oxyhydr)oxide minerals elsewhere in the Hamersley basin. The supracrustal δ238U signatures are associated with some of the highest Mo and Re enrichments in the Mt. McRae Shale as well as distinctive Mo, S and N isotope signatures that are indicative of mild environmental oxygenation. Hence, our findings suggest that small amounts of U were oxidatively mobilized from the upper crust at 2.50 Ga. Unlike Mo and Re, however, U oxidation may not have occurred on land. Instead, we hypothesize that oxidative U mobilization occurred by submarine weathering in an oxygen oasis.

Process for treating iron-containing sulfidic rocks and ores

Geochemical data from late Archean sedimentary rocks point to photosynthetic O2 production and at least intermittent occurrences of locally mild oxidative weathering and surface ocean oxygenation (“oxygen oases”) prior to the early Paleoproterozoic Great Oxidation Event. For example, distinctive authigenic enrichments of Mo and Re in euxinic (anoxic and sulfidic) black shales are best explained by the oxidative mobilization of these metals from crustal sulfide minerals and their accumulation as oxyanions in seawater. In contrast, it is not clear if low U enrichments in the same shales reflect negligible oxidation of U from the upper crust or a very small oceanic U inventory that was derived from oxidative U mobilization. Here, we report U isotope data for the 2.50 Ga Mt. McRae Shale (Hamersley basin, Western Australia), which provides a more sensitive test for the presence or absence of authigenic U compared to U concentrations and enrichment factors normalized to average shale or upper crustal compositions (that may not be representative of the local detrital composition). We find instances where the U isotope composition in the upper Mt. McRae Shale (δ238U = − 0.2 to 0.0‰ relative to standard SRM950a) is isotopically heavier than average upper crust (δ238U = − 0.31 ± 0.14 [2SD] based on granitoids and basalts). The high δ238U values point to U isotope fractionation in the late Archean marine environment and hence indicate the presence of a small amount of dissolved U in seawater and authigenic U in the Mt. McRae Shale. Volume-dependent equilibrium isotope fractionation during the reduction of dissolved UVI to insoluble UIV, like that observed in the modern Black Sea, may explain the high δ238U signatures if U removal from bottom waters was not quantitative. Alternatively, quantitative U removal would require that late Archean seawater had high δ238U, which could have arisen from the preferential sequestration of 235U to Fe (oxyhydr)oxide minerals elsewhere in the Hamersley basin. The supracrustal δ238U signatures are associated with some of the highest Mo and Re enrichments in the Mt. McRae Shale as well as distinctive Mo, S and N isotope signatures that are indicative of mild environmental oxygenation. Hence, our findings suggest that small amounts of U were oxidatively mobilized from the upper crust at 2.50 Ga. Unlike Mo and Re, however, U oxidation may not have occurred on land. Instead, we hypothesize that oxidative U mobilization occurred by submarine weathering in an oxygen oasis.