Iron Formations as Palaeoenvironmental Archives

Ancient iron formations - iron and silica-rich chemical sedimentary rocks that formed throughout the Precambrian eons - provide a significant part of the evidence for the modern scientific understanding of palaeoenvironmental conditions in Archaean (4.0–2.5 billion years ago) and Proterozoic (2.5–0.539 billion years ago) times. Despite controversies regarding their formation mechanisms, iron formations are a testament to the influence of the Precambrian biosphere on early ocean chemistry. As many iron formations are pure chemical sediments that reflect the composition of the waters from which they precipitated, they can also serve as nuanced geochemical archives for the study of ancient marine temperatures, redox states, and elemental cycling, if proper care is taken to understand their sedimentological context.

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 (FeIII2O3), (partially) reduced minerals such as magnetite (FeIIFeIII2O4) 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.

A CO2 greenhouse efficiently warmed the early Earth and decreased seawater 18O/16O before the onset of plate tectonics

The low 18O/16O stable isotope ratios (δ18O) of ancient chemical sediments imply ∼70 °C Archean oceans if the oxygen isotopic composition of seawater (sw) was similar to modern values. Models suggesting lower δ18Osw of Archean seawater due to intense continental weathering and/or low degrees of hydrothermal alteration are inconsistent with the triple oxygen isotope composition (Δ’17O) of Precambrian cherts. We show that high CO2 sequestration fluxes into the oceanic crust, associated with extensive silicification, lowered the δ18Osw of seawater on the early Earth without affecting the Δ’17O. Hence, the controversial long-term trend of increasing δ18O in chemical sediments over Earth’s history partly reflects increasing δ18Osw due to decreasing atmospheric pCO2. We suggest that δ18Osw increased from about −5‰ at 3.2 Ga to a new steady-state value close to −2‰ at 2.6 Ga, coinciding with a profound drop in pCO2 that has been suggested for this time interval. Using the moderately low δ18Osw values, a warm but not hot climate can be inferred from the δ18O of the most pristine chemical sediments. Our results are most consistent with a model in which the “faint young Sun” was efficiently counterbalanced by a high-pCO2 greenhouse atmosphere before 3 Ga.

A novel approach to investigate the deposition of (bio)chemical sediments: The sedimentation velocity of cyanobacteria–ferrihydrite aggregates

ABSTRACT Sedimentation velocities of various chemical sediments are typically calculated using Stokes's law. However, applying it to chemical sediments that form in situ in the water column is not ideal because the particle properties do not fulfill many of the assumptions underpinning the applicability of Stokes' law. As a consequence, it has been difficult to predict the sedimentation rate of ancient chemical sediments, such as Precambrian banded iron formations (BIF), because their primary sediments likely comprised aggregates of ferric hydroxides, such as ferrihydrite [Fe(OH)3], and marine bacterial biomass, including cyanobacteria. In this work we use a new experimental method to address the mechanisms by which primary BIF sediment, formed by the oxidation of dissolved Fe(II) by O2 and simultaneously incubated with cyanobacterium Synechococcus sp., were deposited to the Archean ocean. Specifically, we formed the aggregates in situ over a wide range of initial pH and Fe(II) concentrations, continuously recorded the entire settling processes of aggregates under each condition, and then processed the data in MATLAB according to different settling mechanisms. Our results demonstrate that ferrihydrite–cyanobacteria aggregates settled to the ocean floor either through the formation of uniformly descending concentration fronts or through convective plumes. The sedimentation mechanism depended on both initial Fe(II) concentration and the pH. Correspondingly, two algorithms were developed to characterize the sedimentation velocity. These algorithms tracked the alteration of light intensity from low to high as sediments descended from an initially homogeneous state through a water tank, and as well calculated the average light intensity over time, from which vertical time series were constructed allowing calculation of the sedimentation velocity. Our method not only provides an accurate estimation of the in situ sedimentation velocity of cell–mineral aggregates, but also provides new insights into the physical mechanisms by which the primary sediments composing BIF were deposited.

Predicting potential areas for the formation of Co-rich ferromanganese crusts in the Canary Islands Seamount Province using multi-criteria GIS analysis

<p>Marine ferromanganese crusts are metal-rich chemical sediments showing an increasing economic interest as potential mineral resources for strategic and critical metals. Formation of Fe-Mn crusts is linked to a series of different factors that favor or limit their genesis on the seabed. The objective of this work is the search of areas for potential formation of these deposits, using data obtained in the Canary Islands Seamount Province. The study has been carried out based on multi-criteria analysis, using a Geographic Information System (ArcGis 10.5, Spatial Analysis and Statistical tools). For this purpose, it has been created a cartographic model, which considers data related to depth, seabed substrate nature and age, slope and exposure to marine bottom currents. This model has been applied to non-sampled areas, contrasting them with data derived from the analysis of samples taken in different oceanographic surveys, in order to establish the correct conclusions. This work has been carried out using bathymetric and geological data shared by the Geological Survey of Spain (IGME) with the MINDeSEA [1] and EMODnet-Geology [2] European projects.</p><p>[1] This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 731166.</p><p>[2] EMODNET-Geology project (EASME/EMFF/2018/1.3.1.8-Lot 1/SI2.811048).</p>

Origin and significance of Si and O isotope heterogeneities in Phanerozoic, Archean, and Hadean zircon

Hydrosphere interactions and alteration of the terrestrial crust likely played a critical role in shaping Earth’s surface, and in promoting prebiotic reactions leading to life, before 4.03 Ga (the Hadean Eon). The identity of aqueously altered material strongly depends on lithospheric cycling of abundant and water-soluble elements such as Si and O. However, direct constraints that define the character of Hadean sedimentary material are absent because samples from this earliest eon are limited to detrital zircons (ZrSiO4). Here we show that concurrent measurements of Si and O isotope ratios in Phanerozoic and detrital pre-3.0 Ga zircon constrain the composition of aqueously altered precursors incorporated into their source melts. Phanerozoic zircon from (S)edimentary-type rocks contain heterogeneous δ18O and δ30Si values consistent with assimilation of metapelitic material, distinct from the isotopic character of zircon from (I)gneous- and (A)norogenic-type rocks. The δ18O values of detrital Archean zircons are heterogeneous, although yield Si isotope compositions like mantle-derived zircon. Hadean crystals yield elevated δ18O values (vs. mantle zircon) and δ30Si values span almost the entire range observed for Phanerozoic samples. Coupled Si and O isotope data represent a constraint on Hadean weathering and sedimentary input into felsic melts including remelting of amphibolites possibly of basaltic origin, and fractional addition of chemical sediments, such as cherts and/or banded iron formations (BIFs) into source melts. That such sedimentary deposits were extensive enough to change the chemical signature of intracrustal melts suggests they may have been a suitable niche for (pre)biotic chemistry as early as 4.1 Ga.

Hf-Nd Isotopes in Archean Marine Chemical Sediments: Implications for the Geodynamical History of Early Earth and Its Impact on Earliest Marine Habitats

The Hf-Nd isotope systems are coupled in magmatic systems, but incongruent Hf weathering (‘zircon effect’) of the continental crust leads to a decoupling of the Hf-Nd isotope systems in low-temperature environments during weathering and erosion processes. The Hf-Nd isotope record was recently dated back from the Cenozoic oceans until the Archean, showing that both isotope systems were already decoupled in seawater 2.7 Ga ago and potentially 3.4 Ga and 3.7 Ga ago. While there might have existed a hydrothermal pathway for Hf into Archean seawater, incongruent Hf weathering of more evolved, zircon-bearing uppermost continental crust that was emerged and available for subaerial weathering accounts for a significant decoupling of Hf-Nd isotopes in the dissolved (<0.2 µm) and suspended (>0.2 µm) fractions of Early Earth’s seawater. These findings contradict the consensus that uppermost Archean continental crust was (ultra)mafic in composition and predominantly submerged. Hence, Hf-Nd isotopes in Archean marine chemical sediments provide the unique potential for future research to trace the emergence of evolved continental crust, which in turn has major implications for the geodynamical evolution of Early Earth and the nutrient flux into the earliest marine habitats on Earth.