Milankovitch cycles in banded iron formations constrain the Earth-Moon system 2.46 billion years ago.

The long-term history of the Earth-Moon system as reconstructed from the geological record remains unclear when based on fossil growth bands and tidal laminations. A possibly more robust method is provided by the sedimentary record of Milankovitch cycles (climatic precession, obliquity, and orbital eccentricity), whose relative ratios in periodicity change over time as a function of a decreasing Earth spin rate and increasing lunar distance. However, for the critical older portion of Earth's history where information on Earth-Moon dynamics is sparse, suitable sedimentary successions in which these cycles are recorded remain largely unknown, leaving this method unexplored. Here we present results of cyclostratigraphic analysis and high-precision U-Pb zircon dating of the lower Paleoproterozoic Joffre Member of the Brockman Iron Formation, NW Australia, providing evidence for Milankovitch forcing of regular lithological alternations related to Earth's climatic precession and orbital eccentricity cycles. Combining visual and statistical tools to determine their hierarchical relation, we estimate an astronomical precession frequency of 108.6 ± 8.5 arcsec/y, corresponding to an Earth-Moon distance of 321,800 ± 6,500 km and a daylength of 16.9 ± 0.2 h at 2.46 Ga. With this robust cyclostratigraphic approach, we extend the oldest reliable datum for the lunar recession history by more than 1 billion years and provide a critical reference point for future modeling and geological investigation of Precambrian Earth-Moon system evolution.

Effect of Ni2+, Zn2+, and Co2+ on green rust transformation to magnetite.

In this study, we investigated Ni2+, Zn2+, and Co2+ mineralogical incorporation and its effect on green rust transformation to magnetite. Mineral transformation experiments were conducted by heating green rust suspensions at 85 °C in the presence of Ni2+, Zn2+, or Co2+ under strict anoxic conditions. Transmission electron microscopy and powder X-ray diffraction showed the conversion of hexagonal green rust platelets to fine grained cubic magnetite crystals. The addition of Ni2+, Zn2+, and Co2+ resulted in faster rates of mineral transformation. The conversion of green rust to magnetite was concurrent to significant increases in metal uptake, demonstrating a strong affinity for metal sorption/co-precipitation by magnetite. Dissolution ratio curves showed that Ni2+, Zn2+, and Co2+ cations were incorporated into the mineral structure during magnetite crystal growth. The results indicate that the transformation of green rust to magnetite is accelerated by metal impurities, and that magnetite is a highly effective scavenger of trace metals during mineral transformation. The implications for using diagenetic magnetite from green rust precursors as paleo-proxies of Precambrian ocean chemistry are discussed.

Water near its Supercritical Point and at Alkaline pH for the Production of Ferric Oxides and Silicates in Anoxic Conditions. A New Hypothesis for the Synthesis of Minerals Observed in Banded Iron Formations and for the Related Geobiotropic Chemistry inside Fluid Inclusions.

An alternative hypothesis for the origin of the banded iron formations and the synthesis of prebiotic molecules is presented here. I show the importance of considering water near its supercritical point and at alkaline pH. It is based on the chemical equation for the anoxic oxidation of ferrous iron into ferric iron at high-subcritical conditions of water and high pH, that I extract from E-pH diagrams drawn for corrosion purposes (Geophysical Research Abstracts Vol 15, EGU2013-22 Bassez 2013, Orig Life Evol Biosph 45(1):5-13, Bassez 2015, Procedia Earth Planet Sci 17, 492-495, Bassez 2017a, Orig Life Evol Biosph 47:453-480, Bassez 2017b). The sudden change in solubility of silica, SiO2, at the critical point of water is also considered. It is shown that under these temperatures and pressures, ferric oxides and ferric silicates can form in anoxic terrains. No FeII oxidation by UV light, neither by oxygen is needed to explain the minerals of the Banded Iron Formations. The intervention of any kind of microorganisms, either sulfate-reducing, or FeII-oxidizing or O2-producing, is not required. The chemical equation for the anoxic oxidation of ferrous iron is applied to the hydrolyses of fayalite, Fe2SiO4 and ferrosilite, FeSiO3. It is shown that the BIF minerals of the Hamersley Group, Western Australia, and the Transvaal Supergroup, South Africa, are those of fayalite and ferrosilite hydrolyses and carbonations. The dissolution of crustal fayalite and ferrosilite during water-rock interaction needs to occur at T&P just below the critical point of water and in a rising water which is undersaturated in SiO2. Minerals of BIFs which can then be ejected at the surface from venting arcs are ferric oxide hydroxides, hematite, FeIII-greenalite, siderite. The greenalite dehydrated product minnesotaite forms when rising water becomes supersaturated in SiO2, as also riebeckite and stilpnomelane. Long lengths of siderite without ferric oxides neither ferric silicates can occur since the exothermic siderite formation is not so much dependent in T&P. It is also shown that the H2 which is released during hydrolysis/oxidation of fayalite/ferrosilite can lead to components of life, such as macromolecules of amino acids which are synthesized from mixtures of (CO, N2, H2O) in Sabatier-Senderens/Fischer-Tropsch & Haber-Bosch reactions or microwave or gamma-ray excitation reactions. I propose that such geobiotropic synthesis may occur inside fluid inclusions of BIFs, in the silica chert, hematite, FeIII-greenalite or siderite. Therefore, the combination of high-subcritical conditions of water, high solubility of SiO2 at these T&P values, formation of CO also at these T&P, high pH and anoxic water, leads to the formation of ferric minerals and prebiotic molecules in the process of geobiotropy.

Anoxic photochemical oxidation of siderite generates molecular hydrogen and iron oxides.

Photochemical reactions of minerals are underappreciated processes that can make or break chemical bonds. We report the photooxidation of siderite (FeCO3) by UV radiation to produce hydrogen gas and iron oxides via a two-photon reaction. The calculated quantum yield for the reaction suggests photooxidation of siderite would have been a significant source of molecular hydrogen for the first half of Earth's history. Further, experimental results indicate this abiotic, photochemical process may have led to the formation of iron oxides under anoxic conditions. The reaction would have continued through the Archean to at least the early phases of the Great Oxidation Event, and provided a mechanism for oxidizing the atmosphere through the loss of hydrogen to space, while simultaneously providing a key reductant for microbial metabolism. We propose that the photochemistry of Earth-abundant minerals with wide band gaps would have potentially played a critical role in shaping the biogeochemical evolution of early Earth.

Exploring the secondary mineral products generated by microbial iron respiration in Archean ocean simulations.

Marine chemical sedimentary deposits known as Banded Iron Formations (BIFs) archive Archean ocean chemistry and, potentially, signs of ancient microbial life. BIFs contain a diversity of iron- and silica-rich minerals in disequilibrium, and thus many interpretations of these phases suggest they formed secondarily during early diagenetic processes. One such hypothesis posits that the early diagenetic microbial respiration of primary iron(III) oxides in BIFs resulted in the formation of other iron phases, including the iron-rich silicates, carbonates, and magnetite common in BIF assemblages. Here, we simulated this proposed pathway in laboratory incubations combining a model dissimilatory iron-reducing (DIR) bacterium, Shewanella putrefaciens CN32, and the ferric oxyhydroxide mineral ferrihydrite under conditions mimicking the predicted Archean seawater geochemistry. We assessed the impact of dissolved silica, calcium, and magnesium on the bioreduced precipitates. After harvesting the solid products from these experiments, we analyzed the reduced mineral phases using Raman spectroscopy, electron microscopy, powder x-ray diffraction, and spectrophotometric techniques to identify mineral precipitates and track the bulk distributions of Fe(II) and Fe(III). These techniques detected a diverse range of calcium carbonate morphologies and polymorphism in incubations with calcium, as well as secondary ferric oxide phases like goethite in silica-free experiments. We also identified aggregates of curling, iron- and silica-rich amorphous precipitates in all incubations amended with silica. Although ferric oxides persist even in our electron acceptor-limited incubations, our observations indicate that microbial iron reduction of ferrihydrite is a viable pathway for the formation of early iron silicate phases. This finding allows us to draw parallels between our experimental proto-silicates and the recently characterized iron silicate nanoinclusions in BIF chert deposits, suggesting that early iron silicates could possibly be signatures of iron-reducing metabolisms on early Earth.

Microbial processes during deposition and diagenesis of Banded Iron Formations.

Banded Iron Formations (BIFs) are marine chemical sediments consisting of alternating iron (Fe)-rich and silica (Si)-rich bands which were deposited throughout much of the Precambrian era. BIFs represent important proxies for the geochemical composition of Precambrian seawater and provide evidence for early microbial life. Iron present in BIFs was likely precipitated in the form of Fe3+ (Fe(III)) minerals, such as ferrihydrite (Fe(OH)3), either through the metabolic activity of anoxygenic photoautotrophic Fe2+ (Fe(II))-oxidizing bacteria (photoferrotrophs), by microaerophilic bacteria, or by the oxidation of dissolved Fe(II) by O2 produced by early cyanobacteria. However, in addition to oxidized Fe-bearing minerals such as hematite (FeIII 2O3), (partially) reduced minerals such as magnetite (FeIIFeIII 2O4) and siderite (FeIICO3) are found in BIFs as well. The presence of reduced Fe in BIFs has been suggested to reflect the reduction of primary Fe(III) minerals by dissimilatory Fe(III)-reducing bacteria, or by metamorphic (high pressure and temperature) reactions occurring in presence of buried organic matter. Here, we present the current understanding of the role of Fe-metabolizing bacteria in the deposition of BIFs, as well as competing hypotheses that favor an abiotic model for BIF deposition. We also discuss the potential abiotic and microbial reduction of Fe(III) in BIFs after deposition. Further, we review the availability of essential nutrients (e.g. P and Ni) and their implications on early Earth biogeochemistry. Overall, the combined results of various ancient seawater analogue experiments aimed at assessing microbial iron cycling pathways, coupled with the analysis of the BIF rock record, point towards a strong biotic influence during BIF genesis.

Determination of rare earth elements in Fe-minerals using external calibration by LA-ICP-MS and application on Cauê Iron Formation (Brazil).

The rare earth elements (REE) composition in Fe-mineral phases is an important tool in iron formation studies to obtain information about parent rocks and environmental and paragenetic processes. However, the determination of REE presents some difficulties, such as the low concentration of these elements, matrix complexity and lack of iron matrix certified reference materials. The aim of the present work is to propose an analytical method to determine the REE plus Y (REE + Y) contents at trace levels in Fe-(hydr)oxides by the laser ablation ICP-quadrupoleMS technique, using external calibration. The calibration curves were obtained from analyses of reference materials with different matrices, and the analytical conditions were checked on the NIST 614 glass. The linearity (R2 ≥ 0.98), limit of detection (0.002-0.044 µg g-1), limit of quantification (0.008-0.146 µg g-1), recovery (88.4-112.4%), and intraday (0.1-14.1%) and interday (1.6-17.8%) precision were systematically assessed. The results obtained showed that the method is fit for the purpose and showed evidence of a nonsignificant interference of the matrix. Thus, the developed procedure was applied in the analyses of magnetite, martite, hematite, and goethite grains from Cauê Iron Formation (Brazil). The REE + Y patterns of the minerals are consistent with the previous study of bulk analyses on whole rocks and highlight the postdepositional signature of these elements in banded iron formations.

Characterization of the physiology and cell-mineral interactions of the marine anoxygenic phototrophic Fe(II) oxidizer Rhodovulum iodosum--implications for Precambrian Fe(II) oxidation.

Anoxygenic phototrophic Fe(II)-oxidizing bacteria (photoferrotrophs) are suggested to have contributed to the deposition of banded iron formations (BIFs) from oxygen-poor seawater. However, most studies evaluating the contribution of photoferrotrophs to Precambrian Fe(II) oxidation have used freshwater and not marine strains. Therefore, we investigated the physiology and mineral products of Fe(II) oxidation by the marine photoferrotroph Rhodovulum iodosum. Poorly crystalline Fe(III) minerals formed initially and transformed to more crystalline goethite over time. During Fe(II) oxidation, cell surfaces were largely free of minerals. Instead, the minerals were co-localized with EPS suggesting that EPS plays a critical role in preventing cell encrustation, likely by binding Fe(III) and directing precipitation away from cell surfaces. Fe(II) oxidation rates increased with increasing initial Fe(II) concentration (0.43-4.07 mM) under a light intensity of 12 µmol quanta m(-2) s(-1). Rates also increased as light intensity increased (from 3 to 20 µmol quanta m(-2) s(-1)), while the addition of Si did not significantly change Fe(II) oxidation rates. These results elaborate on how the physical and chemical conditions present in the Precambrian ocean controlled the activity of marine photoferrotrophs and confirm the possibility that such microorganisms could have oxidized Fe(II), generating the primary Fe(III) minerals that were then deposited to some Precambrian BIFs.

Oxygenic photosynthesis as a protection mechanism for cyanobacteria against iron-encrustation in environments with high Fe(2+) concentrations.

If O2 is available at circumneutral pH, Fe(2+) is rapidly oxidized to Fe(3+), which precipitates as FeO(OH). Neutrophilic iron oxidizing bacteria have evolved mechanisms to prevent self-encrustation in iron. Hitherto, no mechanism has been proposed for cyanobacteria from Fe(2+)-rich environments; these produce O2 but are seldom found encrusted in iron. We used two sets of illuminated reactors connected to two groundwater aquifers with different Fe(2+) concentrations (0.9 µM vs. 26 µM) in the Äspö Hard Rock Laboratory (HRL), Sweden. Cyanobacterial biofilms developed in all reactors and were phylogenetically different between the reactors. Unexpectedly, cyanobacteria growing in the Fe(2+)-poor reactors were encrusted in iron, whereas those in the Fe(2+)-rich reactors were not. In-situ microsensor measurements showed that O2 concentrations and pH near the surface of the cyanobacterial biofilms from the Fe(2+)-rich reactors were much higher than in the overlying water. This was not the case for the biofilms growing at low Fe(2+) concentrations. Measurements with enrichment cultures showed that cyanobacteria from the Fe(2+)-rich environment increased their photosynthesis with increasing Fe(2+) concentrations, whereas those from the low Fe(2+) environment were inhibited at Fe(2+) > 5 µM. Modeling based on in-situ O2 and pH profiles showed that cyanobacteria from the Fe(2+)-rich reactor were not exposed to significant Fe(2+) concentrations. We propose that, due to limited mass transfer, high photosynthetic activity in Fe(2+)-rich environments forms a protective zone where Fe(2+) precipitates abiotically at a non-lethal distance from the cyanobacteria. This mechanism sheds new light on the possible role of cyanobacteria in precipitation of banded iron formations.