Tag: Banded iron formation

Detecting oxygenic photosynthesis in the Archaean Earth System

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For life on Earth, one of the most fundamental shifts in ecosystems was the Great Oxygenation Event 2.5 to 2.3 billion years (Ga) ago. The first evidence for its occurrence was from the sedimentary record, particularly ancient soils (palaeosols) that mark exposure of the continental surface above sea level and rock weathering. Palaeosols older than 2.4 Ga have low iron contents that suggest iron was soluble in surface waters, i.e. in its reduced bivalent form Fe2+. Sediments formed by flowing water also contain rounded grains of minerals that in today’s oxygen-rich environments are soon broken down and dissolved through oxidising reactions, for instance pyrite (FeS2) and uraninite (UO2). After 2.4 Ga palaeosols are reddish to yellowish brown in colour and contain insoluble oxides and hydroxides of Fe3+ principally hematite (Fe2O3) and goethite (FeO.OH). After this time sediments deposited by wind action and rivers are similar in colour: so-called ‘redbeds’. Following the GOE the atmosphere initially contained only traces of free oxygen, but sufficient to make the surface environment oxidising. In fact such an atmosphere defies Le Chatelier’s Principle: free oxygen should react rapidly with the rest of the environment through oxidation. That it doesn’t shows that it is continually generated as a result of oxygenic photosynthesis. The CO2 + H2O = carbohydrate + oxygen equilibrium does not reach a balance because of continual burial of dead organic material.

Free oxygen is a prerequisite for all multicelled eukaryotes, and it is probably no coincidence that fossils of the earliest known ones occur in sediments in Gabon dated at 2.1 Ga: 300 Ma after the Great Oxygenation Event. However, the GOE relates to surface environments of that time. From 2.8 Ga – in the Mesoarchaean Era – to the late Palaeoproterozoic around 1.9 Ga, vast quantities of Fe3+ were locked in iron oxide-rich banded iron formations (BIFs): roughly 105 billion tons in the richest deposits alone (see: Banded iron formations (BIFs) reviewed; December 2017). Indeed, similar ironstones occur in Archaean sedimentary sequences as far back as 3.7 Ga, albeit in uneconomic amounts. Paradoxically, enormous amounts of oxygen must have been generated by marine photosynthesis to oxidise Fe2+ dissolved in the early oceans by hydrothermal alteration of basalt lava upwelling from the Archaean mantle. But none of that free oxygen made it into the atmosphere. Almost as soon as it was released it oxidised dissolved Fe2+ to be dumped as iron oxide on the ocean floor. Before the GOE that aspect of geochemistry did obey Le Chatelier!

A limestone made of stromatolites

The only likely means of generating oxygen on such a gargantuan scale from the earliest Archaean onwards is through teeming prokaryote organisms capable of oxygenic photosynthesis. Because modern cyanobacteria do that, the burden of the BIFs has fallen on them. One reason for that hypothesis stems from cyanobacteria in a variety of modern environments building dome-shaped bacterial mats. Their forms closely resemble those of Archaean stromatolites found as far back as 3.7 Ga. But these are merely peculiar carbonate bodies that could have been produced by bacterial mats which deploy a wide variety of metabolic chemistry. Laureline Patry of the Université de Bretagne Occidentale, Plouzané, France, and colleagues from France, the US, Canada and the UK have developed a novel way of addressing the opaque mechanism of Archaean oxygen production (Patry, L.A. and 12 others. Dating the evolution of oxygenic photosynthesis using La-Ce geochronology. Nature, v. 642, p. 99-104; DOI: 10.1038/s41586-025-09009-8).

They turned to the basic geochemistry of rare earth elements (REE) in Archaean stromatolitic limestones from the Superior Craton of northern Canada. Of the 17 REEs only cerium (Ce) is capable of being oxidised in the presence of oxygen. As a result Ce can be depleted relative to its neighbouring REEs in the Periodic Table, as it is in many Phanerozoic limestones. Five samples of the limestones show consistent depletion of Ce relative to all other REE. It is also possible to date when such fractionation occurred using 138La– 138Ce geochronology.  The samples were dated at 2.87 to 2.78 Ga (Mesoarchaean), making them the oldest limestones that show Ce anomalies and thus oxygenated seawater in which the microbial mats thrived. But that is only 300 Ma earlier than the start of the GOE. Stromatolites are abundant in the Archaean record as far back as 3.4 Ga, so it should be possible to chart the link between microbial carbonate mats and oxygenated seawater to a billion years before the GOE, although that does not tell us about the kind of microbes that were making stromatolites.

See also: Tracing oxygenic photosynthesis via La-Ce geochronology. Bioengineer.org, 29 May 2025; Allen, J.F. 2016. A proposal for formation of Archaean stromatolites before the advent of oxygenic photosynthesis. Frontiers in Microbiology, v. 7; DOI: 10.3389/fmicb.2016.01784.

A new explanation for banded iron formations (BIFs)

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The main source for iron and steel has for more than half a century been Precambrian rock characterised by intricate interlayering of silica- and iron oxide-rich sediments known as banded iron formations or BIFs. They always appear in what were shallow-water parts of Precambrian sedimentary basins. Although much the same kind of material turns up in sequences from 3.8 to 0.6 Ga, by far the largest accumulations date from 2.6 to 1.8 Ga, epitomised by the vast BIFs of the Palaeoproterozoic Hamersley Basin in Western Australia. This peak of iron-ore deposition brackets the time (~2.4 Ga) when world-wide evidence suggests that the Earth’s atmosphere first acquired tangible amounts of free oxygen: the so-called ‘Great Oxidation Event’. Yet the preservation of such enormous amounts of oxidised iron compounds in BIFs is paradoxical for two reasons: the amount of freely available atmospheric oxygen at their acme was far lower than today; had the oceans contained much oxygen, dissolved ions of reduced Fe-2 would not have been able to pervade seawater as they had to for BIFs to have accumulated in shallow water. Iron-rich ocean water demands that its chemical state was highly reducing.

Oblique view of an open pit mine in banded iron formation at Mount Tom Price, Hamersley region Western Australia (Credit Google earth)
Oblique view of an open pit mine in banded iron formation at Mount Tom Price, Hamersley region Western Australia (Credit Google earth)

The paradox of highly oxidised sediments being deposited when oceans were highly reduced was resolved, or seemed to have been, in the late 20th century. It involved a hypothesis that reduced, Fe-rich water entered shallow, restricted basins where photosynthetic organisms – probably cyanobacteria – produced localised enrichments in dissolved oxygen so that the iron precipitated to form BIFs. Later work revealed oddities that seemed to suggest some direct role for the organisms themselves, a contradictory role for the co-dominant silica-rich cherty layers and even that another kind of bacteria that does not produce oxygen directly may have deposited oxidised iron minerals. Much of the research focussed on the Hamersley BIF deposits, and it comes as no surprise that another twist in the BIF saga has recently emerged from the same, enormous repository of evidence (Rasmussen, B. et al. 2015. Precipitation of iron silicate nanoparticles in early Precambrian oceans marks Earth’s first iron age. Geology, v. 43, p. 303-306).

The cherty laminations have received a great deal less attention than the iron oxides. It turns out that they are heaving with minute particles of iron silicate. These are mainly the minerals stilpnomelane [K(Fe,Mg)8(Si, Al)12(O, OH)27] and greenalite [(Fe)2–3Si2O5(OH)4] that account for up to 10% of the chert. They suggest that ferruginous, silica-enriched seawater continually precipitated a mixture of iron silicate and silica, with cyclical increases in the amount of iron-silicate. Being such a tiny size the nanoparticles would have had a very high surface area relative to their mass and would therefore have been highly reactive. The authors suggest that the present mineralogy of BIFs, which includes iron carbonates and, in some cases, sulfides as well as oxides may have resulted from post-depositional mineral reactions. Much the same features occur in 3.46 Ga Archaean BIFs at Marble Bar in Western Australia that are almost a billion years older that the Hamersley deposits, suggesting that a direct biological role in BIF formation may not have been necessary.

More on BIFs and the Great Oxidation Event