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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 μM P) or high (10 to 100 μM 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 Carajás (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 μM 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. Classification: Physical Sciences, Earth, Atmospheric and Planetary Sciences

Precambrian metasediments provide a unique archive for understanding Earth’s earliest biosphere, however traces of microbial life preserved in ancient rocks are often controversial. In this study we leveraged several micro- to nano-scale techniques to study filamentous structures previously reported in clastic sediments of the 3.22 Ga Moodies Group, Barberton Greenstone Belt, S. Africa. We performed petrographic, mineralogical, electron microprobe, confocal fluorescence and electron microscopy analyses of these structures in order to evaluate their biogenicity and syngenecity. We also examined drill core samples of deep-water iron formations from the 2.46 Ga Joffre member of the Brockman Iron Formation (Hamersley Basin, W. Australia) to better understand their potential biogenicity. In both cases, we aimed to resolve primary vs. secondary mineral assemblages and their relation to filamentous or sedimentary structures. In the Moodies Group samples, filamentous structures were resolved by confocal imaging and revealed to be crosscut by later metamorphic phases, highlighting their syngenetic nature. Three-dimensional imaging reveals that while the filamentous structures are not necessarily associated with grain boundaries (e.g., as organic coatings), they form both sheets and filaments, complicating their interpretation but not ruling out a biological origin. No organic microstructures appeared to be preserved in our Dales Gorge samples. We also examined the possible application of electron paramagnetic resonance spectroscopy (EPR) to carbonaceous matter in ancient silica-rich matrices, similar to Bourbin et al. (2013), using samples from the Brockman iron formation. While resonance associated with organic matter was largely unresolvable in the Brockman iron formation samples due to their low organic matter contents, large effects on the EPR spectra were apparent stemming from the presence of magnetic iron minerals, highlighting the need to carefully consider sample composition in EPR analyses targeting ancient organic matter. Collectively, this study highlights the added value of micro- to nano-scale techniques as applied to Precambrian metasediments containing traces of ancient life, for example in revealing the pre-metamorphic emplacement and three-dimensional structure of filaments in the Moodies Group, but also the potential drawbacks and pitfalls, such as the case of strong magnetic mineral interference in EPR analysis of organic matter in trace abundance in the Dales Gorge.

The Fezouata Shale in Morocco is the most diverse Lower Ordovician unit yielding soft-tissue preservation. Iron played a crucial role in the preservation of soft parts in this formation through the damage of bacterial membranes under oxic conditions and the pyritization of soft parts under the activity of bacterial sulphate reduction. However, the origin of Fe in this formation remains largely speculative. Herein, trace and rare earth elements were investigated in drilled-core sediments from the Fezouata Shale. It is shown that a correlation exists between Fe and Al suggesting that most Fe has a detrital source. Elemental concentrations in the Fezouata Shale are most comparable to rivers and are the least similar to loess and sediments deposited near active island arcs. In this sense, continental weathering and its related Fe in river fluxes dictated occurrences of exceptional fossil preservation in the Fezouata Shale.

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 evolution of oxygenic photosynthesis fundamentally altered the global environment, but the history of this metabolism prior to the Great Oxidation Event (GOE) at ca. 2.4 Ga remains unclear. Increasing evidence suggests that non-marine microbial mats served as localized “oxygen oases” for hundreds of millions of years before the GOE, though direct examination of redox proxies in Archean lacustrine microbial deposits remains relatively limited. We report spatially distinct patterns of positive and negative cerium (Ce) anomalies in lacustrine stromatolites from the 2.74 Ga Ventersdorp Supergroup (Hartbeesfontein Basin, South Africa), which indicate that dynamic redox conditions within ancient microbial communities were driven by oxygenic photosynthesis. Petrographic analyses and rare earth element signatures support a primary origin for Ce anomalies in stromatolite oxides. Oxides surrounding former bubbles entrained in mats (preserved as fenestrae) exhibit positive Ce anomalies, while oxides in stromatolite laminae typically contain strong negative Ce anomalies. The spatial patterns of Ce anomalies in Ventersdorp stromatolites are most parsimoniously explained by localized Ce oxidation and scavenging around oxygen bubbles produced by photosynthesis in microbial mats. Our new data from Ventersdorp stromatolites supports the presence of oxygenic photosynthesis ~300 m.y. before the GOE, and add to the growing evidence for early oxygen oases in Archean non-marine deposits.

In the oligotrophic bottom waters of a post-mining lake (Lake Medard, Czechia), ferruginous conditions occur without quantitative sulfate depletion. The dissolved organic matter supply to the deep waters is small and, accordingly, sulfate reduction promoting precipitation of stable ferrous sulfides is limited. In line with these observations, an isotopically constrained estimate of the rates of planktonic sulfate reduction (SRR) suggests that despite a high genetic potential—as determined by genome analyses, SRR are limited by substrate competition exerted by nitrogen and iron respiring prokaryotes. The microbial succession across the nitrogenous and ferruginous zones of the bottom water column also indicates a sustained genetic potential for chemolithotrophic sulfur oxidation, probably accompanied by disproportionation of S intermediates[1].The bottom waters displayed dissolved Fe concentrations (~0.1 to 33 µM) and δ56Fe values (-1.77 ± 0.03 ‰ to +0.12 ± 0.05 ‰) that increase across the redoxcline and towards the anoxic sediment-water interface (SWI). These parameters pinpoint diffusive transport and partial oxidation of dissolved ferrous iron (Fe(II)) sourced from the lakebed, depletion of the residual Fe(II) in heavy isotopes at the redoxcline and enrichment near the SWI linked to monosulfide precipitation. In the carbonate-buffered lake sediments, however, sulfur re-oxidation appears to prevent substantial stabilization of iron monosulfides as pyrite, but it enables the interstitial precipitation of small proportions of equant microcrystalline gypsum. This gypsum isotopically fingerprints sulfur oxidation proceeding at near equilibrium with the ambient anoxic waters, whilst authigenic pyrite-sulfur displays a 38 to 27 ‰ isotopic offset from ambient sulfate, suggestive of incomplete sulfate reduction and indicative of the openness of the system[1].Overall, our results demonstrate that under transitional redox states producing the meromictic stability described here, the simple biogeochemical zonation models based on energetic considerations of pure phases at standard conditions may not accurately describe the overlapping zonation of dissimilatory iron and sulfur reduction. Vigorous sulfur and iron co-recycling in the water column can be fuelled by ferric and manganic particulate matter and notably by the redeposited siderite stocks of the upper anoxic sediments. In the absence of ferruginous coastal zones today, the current water column redox stratification in the post-mining Lake Medard has scientific value for (i) testing emerging hypotheses on how a few interlinked biogeochemical cycles operated in low productivity nearshore paleoenvironments during transitional states between ferruginous and euxinic conditions; and (ii) to acquire insight on potential avenues for early diagenetic overprinting of redox proxy signals in ferruginous-type sediments.[1] Petrash, D. A., Steenbergen, I. M., Valero, A., Meador, T. B., Pačes, T., and Thomazo, C.: Aqueous system-level processes and prokaryote assemblages in the ferruginous and sulfate-rich bottom waters of a post-mining lake, Biogeosciences Discuss. [preprint], https://doi.org/10.5194/bg-2021-253, in review, 2021.

Ratios of phosphorous (P) to iron (Fe) in Precambrian banded iron formations (BIFs) have previously been used to estimate dissolved seawater phosphate concentrations in the ancient oceans. Such studies rely on an assumed composition of the primary iron minerals, the concentrations of the major ions in seawater, and empirical partitioning coefficients for phosphate sorption to Fe(III) (oxyhydr)oxides. There is limited data, however, regarding the post-depositional stability of phosphate associated with presumed primary BIF iron minerals, such as ferrihydrite under low-grade metamorphic temperature and pressure conditions. Here we experimentally formed ferrihydrite in the presence of silica, which was abundant in the Precambrian oceans, and then incubated it at 170 °C and 1.2 kbar in the presence or absence of organic carbon (Corg; either glucose or microbial biomass) as a proxy for ancient planktonic biomass. We found that the post-metamorphic mineral assemblage resulting from thermochemical Fe(III) reduction of Si-doped ferrihydrite depended on Corg reactivity: In the presence of highly reactive glucose, siderite, magnetite, and vivianite were formed, with less than 1.2 mol% of phosphate (0.5 M NaCl extractable) being mobilized. In contrast, the reaction of Si-doped ferrihydrite with less reactive microbial biomass resulted in the formation of hematite and siderite, but not vivianite, and approximately 10 mol% of phosphate was remobilized into the pore fluids. Collectively, our data suggest that the fidelity with which BIFs record ancient oceanic phosphate concentrations depends on the mineralogy and diagenetic history of individual BIFs but should be reliable within 10%.

The Apex chert unit (∼3.46 Ga, Pilbara Craton, Australia) constitutes one of the oldest sedimentary units on Earth in which putative carbonaceous microfossils have been reported. The source of carbonaceous matter (CM) in this unit, however, is hotly debated. Hydrothermal fluids have circulated through the underlying crust and up into the bedded unit; these fluids could have remobilized sedimentary microbial biomass, generated abiological hydrocarbons, or harbored in situ chemolithoautotrophic microbial communities. Are there parts of the unit where microfossils might be best preserved? A potential fossil microbiota – if present – would probably be best preserved in the stratiform portion of the unit where hydrothermal influence seems to have been lowest. In order to shed light on the history of hydrothermal overprinting and the source of carbonaceous fractions in the Apex chert, we correlate here at a high spatial resolution petrographic observations and trace element analyses over a transect from the dyke where putative microfossils were found to the stratiform part where remnants of microbial mats were found. The layered, stratiform part of the unit has positive La anomalies up to 1.7, and Light Rare Earth Element depletions, indicating a seawater source. However, as far as 300 m from the dyke, the stratiform part also shows hydrothermal brecciation, high Eu anomalies (2–12; µ = 4.2) and chondritic Y/Ho ratios (24.3–30.3; µ = 27.0), indicating that hydrothermal fluids have laterally infiltrated over large distances. Overall, the pervasive influence of hydrothermal fluids throughout the entire unit and the presence of carbonaceous matter both in the sedimentary part and the hydrothermal dyke is consistent with a ‘hydrothermal pump’ model that was earlier proposed for the nearby Dresser Formation. In this model, organic matter from surface environments is circulated along with hydrothermal fluids and redistributed in the crust and overlying sediments, therefore complicating paleobiological interpretations. Raman measurements show that most of the CM experienced temperatures of ∼350 °C, while some samples contain CM with a variable, but markedly lower maturity (temperature ranging from 200 to 350 °C). Correlation to texture points out a potential mixing of pre-metamorphic CM with post-metamorphic CM during late hydrothermal events.

Microbial mats floating within multiple hydrothermally sourced streams in El Tatio, Chile, frequently exhibit brittle siliceous crusts (~1 mm thick) above the air-water interface. The partially silicified mats contain a diverse assemblage of microbial clades and metabolisms, including cyanobacteria performing oxygenic photosynthesis. Surficial crusts are composed of several amorphous silica layers containing well-preserved filaments (most likely cyanobacteria) and other cellular textures overlying EPS-rich unsilicified mats. Environmental logs, silica crust distribution, and microbial preservation patterns provide evidence for crust formation via repeated cycles of evaporation and silica precipitation. Within the mats, in situ microelectrode profiling reveals that daytime oxygen concentrations and pH values are diminished beneath silica crusts compared with adjacent unencrusted communities, indicating localized inhibition of oxygenic photosynthesis due to light attenuation. As a result, aqueous conditions under encrusted mats have a higher saturation state with regard to amorphous silica compared with adjacent, more active mats where high pH increases silica solubility, likely forming a modest feedback loop between diminished photosynthesis and crust precipitation. However, no fully lithified sinters are associated with floating encrusted mats in El Tatio streams, as both subaqueous and subaerial silica precipitation are limited by undersaturated, low-SiO2 (

International audience; Natural stable isotopes ratios (δ13Ccarb and δ18Ocarb) of carbonates archived in the geological record are routinely used to reconstruct local and global paleo temperatures and the secular evolution of the biogeochemical carbon cycle. The state-of-the-art technique, employed since the mid 20th century, to measure these isotopic ratios starts with field sampling followed by several steps of physical and chemical laboratory preparation including: (i) microdrilling and/or sawing and crushing, (ii) CO2 release by wet acid digestion, (iii) gas equilibration, purification and transfer, before (iv) gas phase IRMS measurements. While these steps are time and resource consuming, they provide accurate measurements of δ13Ccarb, δ18Ocarb and carbonate contents. This study presents a new protocol involving a compact and modernized laser calcination system that decreases drastically the analyses time by reducing the number of preparations steps together with offering the possibility of performing spatially resolved analysis at the mm scale. This new method is based on the use of a fiber coupled laser diode device emitting 30 W in the near infrared at 880 nm. The energy provided by the laser source induces the decomposition of calcium carbonate into lime and carbon dioxide. In this work, the CO2 was collected in sample tubes under a controlled atmosphere for offline analysis, however additional developments should permit online analysis in the near future.We analyzed 9 different types of carbonate minerals encompassing a range of isotopic compositions VPDB between +3.3 and − 18.2‰ and between −1.7 and − 14.6‰ for δ13Ccarb and δ18Ocarb, respectively. A comparison of isotopic results was performed for carbonate zones analyzed both by classic methods (micro-drilling followed by acid digestion) and laser calcination. This isotopic cross-calibration exercise shows a direct positive co-variation between both methods with a correlation coefficient of 0.99 and a regression slope of 1 within uncertainties for the δ13Ccarb values. The δ18Ocarb values also compared well with a correlation coefficient of 0.96, suggesting a constant gas-solid phase isotopic equilibrium between carbon dioxide and lime. The reproducibility of our laser calcination method performed on replicate analyses of dolomite, siderite and malachite shows a 1σ standard deviation of 0.31 and 0.77 for δ13Ccarb and δ18Ocarb, respectively. These reproducibilities are within the observed isotopic natural inhomogeneity of samples (up to 1.3 and 0.57‰ for the δ13Ccarb and δ18Ocarb, respectively) as assessed by microdrilling and acid digestion.Based on the suit of samples analyzed in this study, we demonstrate that (i) fiber coupled laser diode calcination enables accurate and reproducible C and O isotopic characterization of natural carbonates, (ii) physical effects during calcination do not introduce any isotopic fractionation for C and is accompanied by a constant isotopic offset for O over a range of isotopic compositions and mineral matrices. These findings pave the way for a new range of possibilities for carbonate δ13C and δ18O measurements directly in the field using rapid, portable, and easy to manipulate laser preparation devices paired with CRDS/IRIS optical-mass spectrometers.

International audience

Development of Archean paleosols and patterns of Precambrian rock weathering suggest colonization of continents by subaerial microbial mats long before evolution of land plants in the Phanerozoic Eon. Modern analogues for such mats, however, have not been reported, and possible biogeochemical roles of these mats in the past remain largely conceptual. We show that photosynthetic, subaerial microbial mats from Indonesia grow on mafic bedrocks at ambient temperatures and form distinct layers with features similar to Precambrian mats and paleosols. Such subaerial mats could have supported a substantial aerobic biosphere, including nitrification and methanotrophy, and promoted methane emissions and oxidative weathering under ostensibly anoxic Precambrian atmospheres. High C-turnover rates and cell abundances would have made these mats prime locations for early microbial diversification. Growth of landmass in the late Archean to early Proterozoic Eons could have reorganized biogeochemical cycles between land and sea impacting atmospheric chemistry and climate., Microbes venturing onto land could have impacted biogeochemical cycles billions of years before terrestrial plants, but insight into this process on ancient Earth has remained elusive. With the discovery and analysis of microbial mats analogous to those of the Precambrian, Finke and colleagues infer how these microbial jungles likely shaped ecology and climate.

International audience; Microbial activity is often invoked as a direct or indirect contributor to the precipitation of ancient chemical sedimentary rocks such as Precambrian iron formations (IFs). Determining a specific metabolic pathway from the geological record remains a challenge, however, due to a lack of constraints on the initial conditions and microbially induced redox reactions involved in the formation of iron oxides. Thus, there is ongoing debate concerning the role of photoferrotrophy, that is the process by which inorganic carbon is fixed into organic matter using light as an energy source and Fe(II) as an electron donor, in the deposition of IFs. Here, we examine ~2.74‐Ga‐old Neoarchean IFs and associated carbonates from the Carajás Mineral Province, Brazil, to reconstruct redox conditions and to infer the oxidizing mechanism that allowed one of the world's largest iron deposits to form. The absence of cerium (Ce) anomalies reveals that conditions were pervasively anoxic during IF deposition, while unprecedented europium (Eu) anomalies imply that Fe was supplied by intense hydrothermal activity. A positive and homogeneous Fe isotopic signal in space and time in these IFs indicates a low degree of partial oxidation of Fe(II), which, combined with the presence of 13C‐depleted organic matter, points to a photoautotrophic metabolic driver. Collectively, our results argue in favor of reducing conditions during IF deposition and suggest anoxygenic photosynthesis as the most plausible mechanism responsible for Fe oxidation in the Carajás Basin.

The aim of FeLINE project (Fer Ligands In the aulNe Estuary) was to determine the distribution of iron and associated ligands concentrations along the land sea continuum of the Iroise Sea (Bay of Brest, France). Iron porphyrin like ligands (Fe-Py) such as heme and hemoproteins are relevant complexes in iron biogeochemical cycling as they can persist in seawater and on marine particulates. This work reveals for the first time the distribution of Fe-Py concentrations (dissolved plus reactive particulate) along a temperate macrotidal estuary. Unfiltered samples were collected in October 2019 across a transect of the Aulne river and estuary / Rade of Brest / Iroise Sea during low tidal coefficient (39). Fe-Py concentrations were determined using flow injection analysis with chemiluminescence detection adapted from Vong et al. (2007). Various interferences (organic, metallic, pH and salinity) were tested. The detection limit attained was 11 pmol.l-1 and the time of analysis 1min30s per sample. The Fe-Py concentrations varied from 0.007 ±0.002 nmol.l-1 for S=33.98 and 1.177 ±0.007 nmol.l-1 for S = 0.92. The Fe-Py concentrations clearly showed a non-conservative behavior due to various processes other than simple mixing of natural and seawater. The highest values revealing a Fe-Py enrichment were observed in the Estuarine Turbidity Maximum (ETM) for which concentrations varied between 1.177 ±0.007, S = 5.2 and 0.738 ±0.004 nmol.l-1 S = 8.59. This positive anomaly of Fe-Py concentrations (40%) also corresponded to the lowest pH values (pH =7.27-7.32). The distal part of the transect displayed a negative anomaly for salinities comprised between 15 and 25 (loss of 37%). The four last points geographically corresponding to the Bay of Brest (S>35) exhibited low and stable Fe-Py concentrations of 0.007±0.002 and 0.024 ± 0.003 nmol.l-1. The supply and removal fluxes were respectively estimated at 2.4±0.2g/d and 8.1 ± 0.8g/d, revealing an average Fe-Py removal of 39.8% that is probably due to particle flocculation.

International audience

The Zaonega Formation in northwest Russia (~2.0 billion years old) is amongst the most complete successions that record the middle of the Palaeoproterozoic era. As such, geochemical data from the formation have played a central role in framing the debate over redox dynamics in the aftermath of the Great Oxidation Event (GOE). However, uncertainty over local redox conditions and the degree of hydrographic restriction in the formation has led to contradictory interpretations regarding global oxygen (O2) fugacity. Here, we provide new iron (Fe) isotope data together with major and trace element concentrations to constrain the local physiochemical conditions. The Zaonega Formation sediments show authigenic Fe accumulation (Fe/Al ≫ 1 wt.%/wt.%) and δ56Fe ranging from −0.58‰ to +0.60‰. Many of the data fall on a negative Fe/Al versus δ56Fe trend, diagnostic of a benthic Fe shuttle, which implies that Zaonega Formation rocks formed in a redox-stratified and semi-restricted basin. However, basin restriction did not coincide with diminished trace metal enrichment, likely due to episodes of deep-water exchange with metal-rich oxygenated seawater, as evidenced by simultaneous authigenic Fe(III) precipitation. If so, the Onega Basin maintained a connection that allowed its sediments to record signals of global ocean chemistry despite significant basinal effects.

5 pages; International audience; Stable isotope signatures of elements related to life such as carbon and nitrogen can be powerful biomarkers that provide key information on the biological origin of organic remains and their paleoenvironments. Marked advances have been achieved in the last decade in our understanding of the coupled evolution of biological carbon and nitrogen cycling and the chemical evolution of the early Earth thanks, in part, to isotopic signatures preserved in fossilized microbial mats and organic matter of marine origin. However, the geologic record of the early continental biosphere, as well as its evolution and biosignatures, is still poorly constrained. Following a recent report of direct fossil evidence of life on land at 3.22 Ga, we compare here the carbon and nitrogen isotopic signals of this continental Archean biosphere with biosignatures of cyanobacteria biological soil crusts (cyanoBSCs) colonizing modern arid environments. We report the first extended δ13C and δ15N data set from modern cyanoBSCs and show that these modern communities harbor specific isotopic biosignatures that compare well with continental Archean organic remains. We therefore suggest that cyanoBSCs are likely relevant analogs for the earliest continental ecosystems. As such, they can provide key information on the timing, extent, and possibly mechanism of colonization of the early Earth's emergent landmasses.

The shallow marine depositional and early diagenetic conditions in the predominantly anoxic oceans that followed the Great Oxygenation Event (GOE) remain to be fully understood. In post-GOE coastlines, ferruginous seawater was locally admixed with oxidised freshwater carrying products from the enhanced weathering of sulfides on land, to form coastal aquifers likely exhibiting sulfate concentrations significantly higher than those generally estimated for Proterozoic open oceans; e.g., < 400 μM1. Also, there is mounting petrographic evidence for pseudomorphs after gypsum (or anhydrite) in Paleoproterozoic shallow marine facies, indicating that the penecontemporaneous oxidised sulfur levels in peritidal to intertidal settings were high enough to allow for the formation of primary sulfate minerals. The study of such ancient coastal depositional/early diagenetic conditions throughout modern systems is not straightforward since most of the purposed analogues to Precambrian ferruginous oceans lack environmentally relevant sulfate levels. A combination of spectroscopic and physicochemical measurements of the bottom waters of a meromictic, post-mining lake featuring a dysoxic hypolimnion and an anoxic monimolimnion reveals relatively high concentrations of sulfate ([SO42-]= 19 ± 2 mM) and dissolved iron ([Fe(II)]= 127 ± 17 μM), with redox gradients marked by changes in Fe and N speciation2. The oligotrophic artificial lake—known as Lake Medard (Czech Republic)—also features a depth-dependent co-variation in the abundance of volatile fatty acids, pH and alkalinity, together with a lack of dissolved sulfide, which can only be detected (at near quantification limits) in the 60 m depth sediment-water interface (SWI). Within the hypolimnion, changes in the relative abundance of bacterioplankton taxa point to prokaryotes (mostly Proteobacteria) being important for the co-recycling of dissolved C, N, and Fe stocks, but exerting limited sulfate reduction. In the clayey anoxic sediments there is no accumulation of authigenic sulfides but gypsum, and early diagenetic siderite acts as a significant Fe(II) sink. Preservation of P-bearing FeOOH polymorphs were also observed by using a combination of high-resolution synchrotron-based in situ XRF and XRD analyses. In the sediment pile accessory amounts of pyrite (≤ 0.5 wt. %) can be detected as depth increase, suggesting that a high turnover rate of reduced sulfur occurs towards the SWI. Such effect could be tied to sulfur disproportionation. The meromictic, oligotrophic, ferruginous and sulfate-rich study site exhibits chemical conditions that, via extrapolation, could provide insight int the microbial and abiotic pathways that controlled the coupled iron and sulfur geochemistry of shallow marine Paleoproterozoic coastal zones. A study of dissolved sulfate-bound oxygen and sulfur, and iron isotope ratios of the bottom water column is currently underway to constrain iron- vs. sulfate-reducing activity and ongoing re-oxidation processes.1Fakhraee, M., Hancisse, O., Canfield, D.E. et al. Proterozoic seawater sulfate scarcity and the evolution of ocean–atmosphere chemistry. Nat. Geosci. 12, 375–380 (2019).2Petrash, D.A., Jan, J., Sirová, D., et al. Iron and nitrogen cycling, bacterioplankton community composition and mineral transformations involving phosphorus stabilisation in the ferruginous hypolimnion of a post-mining lake. Environ. Sci. Process. Impacts 20, 1414–1426 (2018).

The oceans probably remained well-oxygenated for millions of years after the Palaeoproterozoic Lomagundi-Jatuli Event, according to high concentrations and isotope signatures of redox-sensitive metals in the 2-billion-year-old Zaonega Formation, Russia. The approximately 2,220-2,060 million years old Lomagundi-Jatuli Event was the longest positive carbon isotope excursion in Earth history and is traditionally interpreted to reflect an increased organic carbon burial and a transient rise in atmospheric O-2. However, it is widely held that O-2 levels collapsed for more than a billion years after this. Here we show that black shales postdating the Lomagundi-Jatuli Event from the approximately 2,000 million years old Zaonega Formation contain the highest redox-sensitive trace metal concentrations reported in sediments deposited before the Neoproterozoic (maximum concentrations of Mo = 1,009 mu g g(-1), U = 238 mu g g(-1) and Re = 516 ng g(-1)). This unit also contains the most positive Precambrian shale U isotope values measured to date (maximum U-238/U-235 ratio of 0.79 parts per thousand), which provides novel evidence that there was a transition to modern-like biogeochemical cycling during the Palaeoproterozoic. Although these records do not preclude a return to anoxia during the Palaeoproterozoic, they uniquely suggest that the oceans remained well-oxygenated millions of years after the termination of the Lomagundi-Jatuli Event.

The Fezouata Shale in Morocco is the only Lower Ordovician Lagerstatte to yield a diverse exceptionally preserved marine fauna. Sediments of this formation have yielded soft to lightly sclerotized taxa that were previously unknown from the Ordovician. Yet the taphonomic pathway of fossils from this formation remains poorly understood. Here, based on drill core material, a close association between exceptional preservation and a specific sedimentary facies is evidenced in the Fezouata Shale. This facies corresponds to calm sea-bottoms, sporadically smothered by distal storm deposits. The patterns of exceptional preservation in this facies indicate that most animals were dead and decayed on the seafloor prior to their burial by distal storm deposits. Furthermore, contrasted elemental and molecular compositions between fresh-cored and altered materials show that surface deposits of the Fezouata Shale were substantially affected by recent weathering. This weathering resulted in the leaching of organic materials from fossils originally preserved as carbonaceous compressions and the transformation of pyrite into iron oxides. Understanding the processes behind the current patterns of soft tissue preservation in the Fezouata Shale is essential prior to any palaeontological description, especially of taxa with no current representatives.

International audience; The large manganese (Mn) deposit at Obrochishte (NE Bulgaria) is part of a cluster of similar Early Oligocene deposits located around present-day Black Sea. They collectively constitute the Earth's second largest endowment of Mn, after the Kalahari Manganese Field in Africa. We have employed a battery of isotopic techniques (C, O, Fe, Sr, Nd, Pb) to help understand the genesis of this deposit. Carbon isotope data indicates that some sections of the Mn-ore layer have diagenetic MnCO3 mineralization, formed by reaction of Mn oxides with organic carbon (C-org, whereas other sections have MnCO3 precipitated directly from the seawater column. Oxygen isotopes show that the high-grade Mn mineralization had seawater as the fluid source, whereas some lower-grade sections had a mix of ground water and seawater as fluid sources. Sr and Nd isotope values of ore leachates also indicate that the Mn deposition occurred in normal Early Oligocene seawater. Nd and Pb isotope values suggest that the clastic host sediments were sourced from continental bedrock rather than younger arc volcanic rocks to the west. Iron isotope composition of the Mn ore implies deposition in a redox-stratified basin, similar to the modern Black Sea, with much of the Fe sequestered in deep, anoxic-euxinic water as sulfides. Similar to the modern Black Sea, most of the detrital Fe was transferred from shallow oxic sediments into deep, anoxic-euxinic water by an "iron shuttle" and remobilized Mn sequestered in the upper suboxic water layer. However, during the Oligocene, the "iron shuttle" operated intermittently due to the chemocline falling mostly below the shelf break, thereby limiting the efficiency of the shuttle mechanism. We propose a model for the Lower Oligocene strata in which intense weathering during the Eocene weathering phase produced a thick lateritic crust on the southern European continent. The drastic sea-level drop at the end of the Eocene initiated downcutting of streams through this weathered material, transferring Fe- and Mn-oxides to the redox-stratified Western Black Sea. Here, these oxides were partly or entirely dissolved in the suboxic (Mn-oxides partly, Fe-oxyhydroxides entirely dissolved) and anoxic-euxinic (Mn-oxides entirely dissolved, dissolved Fe2+ re-precipitated) water layers. Eventually, Fe was re-precipitated as sulfide in the deep anoxic-euxinic water, while Mn accumulated in the suboxic water layer. Transgression in the Early Oligocene brought this Mn-rich water onto the shallow shelf where it precipitated as Mn-oxide, then converted to Mn-carbonates during early diagenesis. Some Mn was also contributed by submarine groundwater discharge. Further transgression brought lower-oxygen water onto the shelf and Mn-carbonate precipitated directly from the water column. The findings from this work provide insights about the unique Oligocene geochemical event in the region that lead to the formation of the 2nd largest cluster of Mn deposits in the world.

International audience; Precambrian banded iron formations (BIF) are chemical sedimentary deposits whose trace element signatures have been widely used to interrogate the chemical composition and redox state of ancient seawater. Here we investigated trace element signatures in BIF of the 3.22 Ga Moodies Group, Barberton Greenstone Belt (South Africa), which are interbedded with near-shore siliciclastic sedimentary rocks and represent one of the oldest known shallow-water occurrences of BIF. Unusual rare earth element (REE) signatures, notably with pronounced negative Ce anomalies in shale-normalized spectra, have been previously reported for chemical sediments of the Moodies Group, which we confirm here through an expanded dataset for Moodies BIF spanning three different localities. We find negative Ce anomalies as low as 0.2 Ce/Ce* that are associated with unusual enrichment of LREE relative to HREE in the sample set. While total REE abundances and certain REE features appear strongly related to the concentration of detrital indicators (e.g., Zr), and are likely primary, other features, notably LREE enrichment, cannot be explained as a primary feature of the sediment. This is better explained by later addition of REE from a LREE-enriched but Ce-depleted fluid that generated the significant negative Ce anomalies observed in surface samples of Moodies Group BIF. This REE addition event influenced both Sm-Nd and La-Ce isotope systematics, the latter yielding an isochron of 60 +/- 32 Ma, thus constraining the timing of emplacement of the negative Ce anomalies to the past 100 Ma, possibly upon surface exposure of the Barberton Greenstone Belt to wetter conditions during the Cenozoic. Our findings constitute a cautionary tale in that even the most immobile elemental redox proxies may be more sensitive to post-depositional modification than previously thought, and demonstrate the clear advantage offered by paleoredox proxies coupled to radiometric geochronometers to enable the direct dating of ancient signals of Earth surface oxygenation.

The colonization of emergent continental landmass by microbial life was an evolutionary step of paramount importance in Earth history. Here we report direct fossil evidence for life on land 3,220 million years ago (Ma) in the form of terrestrial microbial mats draping fluvial conglomerates and gravelly sandstones of the Moodies Group, South Africa. Combined field, petrographic, carbon isotope and Raman spectroscopic analyses confirm the synsedimentary origin and biogenicity of these unique fossil mats as well as their fluvial habitat. The carbon isotope compositions of organic matter (δ13Corg) from these mats define a narrow range centred on −21‰, in contrast to fossil mats of marine origin from nearby tidal deposits that show δ13Corg values as low as −34‰. Bulk nitrogen isotope compositions (2

Ever since it was first proposed that the Earth completely froze during glaciations ∼ 640 million years ago evidence supporting this hypothesis has been increasing, primarily from samples of carbonates directly overlying glacial diamictites, termed cap carbonates. However, this was not the first extensive glacial period that affected planet Earth: ∼1750 million years prior to Neoproterozoic glaciations the Earth went through its first major glacial episode, the early Paleoproterozoic Huronian glaciations. The second Huronian ice advance deposited the Bruce Formation, with its overlying cap carbonate, the Espanola Formation. This up to ∼ 300 m thick succession of limestone, siltstone, dolostone and sandstone overlies diamictite containing a dropstone-bearing layer with δ13Ccarb of −10‰. The 12C-enriched interval also has rare earth element (REE) patterns with negative Eu anomalies, radiogenic Sr isotopes, and negative eNd(0) in the carbonate. The first of these observations is probably due to highly reducing conditions in the sediment, and the possible thawing of methane-rich areas, releasing fluids that mixed with the overlying bottom waters; the last two reflect the diagenetic incorporation into the carbonate of radiogenic Sr, and derivation of REEs, including Nd, from abundant silty loess. This infers a stratified water mass with a relatively stagnant bottom layer during disintegration of an ice shelf. Above this REE patterns through the basal Espanola become increasingly more light depleted upwards, C becomes heavier, Sr is less radiogenic, eNd(0) is near 0 and one area has up to ∼ 1300 ppm Ba incorporated into the carbonate, indicating breakdown of water-mass stratification. Vertically over ∼ 200 m δ13Ccarb increases from −4.5 to −2.5‰ as the environment shallowed incorporating gradually increasing amounts of seawater into the freshwater plume, which initially extended to depths below wave base. Strata deposited in the upper Espanola near the strandline contain layers of Fe-Mn-rich dolomite with positive Eu anomalies reflecting Paleoproterozioc seawater composition dominating even the nearshore by this time. These observations are similar to those from Neoproterozoic cap carbonates, and provide new evidence for the possibly snowball Earth-like nature of the ∼ 2.4 Ga Bruce glaciation.

Although dissolved concentrations of germanium (Ge) and silicon (Si) in modern seawater are tightly correlated, uncertainties still exist in the modern marine Ge cycle. Germanium stable isotope systematics in marine systems should provide additional constraints on marine Ge sources and sinks, however the low concentration of Ge in seawater presents an analytical challenge for isotopic measurement. Here, we present a new method of pre-concentration of inorganic Ge from seawater which was applied to measure three Ge isotope profiles in the Southern Ocean and deep seawater from the Atlantic and Pacific Oceans. Germanium isotopic measurements were performed on Ge amounts as low as 2.6 ng using a double-spike approach and a hydride generation system coupled to a MC-ICP-MS. Germanium was co-precipitated with iron hydroxide and then purified through anion-exchange chromatography. Results for the deep (i.e. > 1000 m depth) Pacific Ocean off Hawaii (nearby Loihi Seamount) and the deep Atlantic off Bermuda (BATS station) showed nearly identical δ74/70Ge values at 3.19 ± 0.31 ‰ (2SD, n = 9) and 2.93 ± 0.10 ‰ (2SD, n = 2), respectively. Vertical distributions of Ge concentration and isotope composition in the deep Southern Ocean for water depth > 1300 m yielded an average δ74/70Ge = 3.13 ± 0.25 ‰ (2SD, n = 14) and Ge/Si = 0.80 ± 0.09 mol/mol (2SD, n = 12). Significant variations in δ74/70Ge, from 2.62 to 3.71 ‰, were measured in the first 1000 m in one station of the Southern Ocean near Sars Seamount in the Drake Passage, with the heaviest values measured in surface waters. Isotope fractionation by diatoms during opal biomineralization may explain the enrichment in heavy isotopes for both Ge and Si in surface seawater. However, examination of both oceanographic parameters and δ74/70Ge values suggest also that water mass mixing and potential contribution of shelf-derived Ge also could contribute to the variations. Combining these results with new Ge isotope data for deep-sea sponges sampled nearby allowed us to determine a Ge isotope fractionation factor of -0.87 ± 0.37 ‰ (2SD, n = 12) during Ge uptake by sponges. Although Ge has long been considered as a geochemical twin of Si, this work underpins fundamental differences in their isotopic behaviors both during biomineralization processes and in their oceanic distributions. This suggests that combined with Si isotopes, Ge isotopes hold significant promise as a complementary proxy for delineating biological versus source effects in the evolution of the marine silicon cycle through time.

Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages has yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth's ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies.

After permanent atmospheric oxygenation, anomalous sulfur isotope compositions were lost from sedimentary rocks, demonstrating that atmospheric chemistry ceded its control of Earth’s surficial sulfur cycle to weathering. However, mixed signals of anoxia and oxygenation in the sulfur isotope record between 2.5 to 2.3 billion years (Ga) ago require independent clarification, for example via oxygen isotopes in sulfate. Here we show, The loss of anomalous sulfur isotope compositions from sedimentary rocks has been considered a symptom of permanent atmospheric oxygenation. Here the authors show sulfur and oxygen isotope evidence from