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.

Origin, tectonic environment and age of the Bibole banded iron formations, northwestern Congo Craton, Cameroon: geochemical and geochronological constraints

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

Inhibition of photoferrotrophy by nitric oxide in ferruginous environments

Anoxygenic phototrophic Fe(II)-oxidizers (photoferrotrophs) are thought to have thrived in Earth’s ancient ferruginous oceans and played a primary role in the precipitation of Archean and Paleoproterozoic (3.8-1.85 Ga) banded iron formations (BIF). The end of BIF deposition by photoferrotrophs has often been interpreted as being the result a deepening of water column oxygenation below the photic zone concomitant with the proliferation of cyanobacteria. We suggest here that a potentially overlooked aspect influencing BIF precipitation by photoferrotrophs is competition with another anaerobic Fe(II)-oxidizing metabolism. It is speculated that microorganisms capable of coupling Fe(II) oxidation to the reduction of nitrate were also present early in Earth history when BIF were being deposited, but the extent to which they could compete with photoferrotrophs when favourable geochemical conditions overlapped is unknown. Utilizing microbial incubations and numerical modelling, we show that nitrate-reducing Fe(II)-oxidizers metabolically outcompete photoferrotrophs for dissolved Fe(II). Moreover, the nitrate-reducing Fe(II)-oxidizers inhibit photoferrotrophy via the production of toxic nitric oxide (NO). Four different photoferrotrophs, representing both green sulfur and purple non-sulfur bacteria, are susceptible to this toxic effect despite having genomic capabilities for NO detoxification. Indeed, despite NO detoxification mechanisms being ubiquitous in some groups of phototrophs at the genomic level (e.g. Chlorobi and Cyanobacteria) it is likely they would still be influenced by NO stress. We suggest that the production of NO during nitrate-reducing Fe(II) oxidation in ferruginous environments represents an as yet unreported control on the activity of photoferrotrophs in the ancient oceans and thus the mechanisms driving precipitation of BIF.