Detecting oxygenic photosynthesis in the Archaean Earth System

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.

Earliest direct evidence of plate motions

There are two ways that we recognise the movement of tectonic plates. Since the latter half of the Mesozoic Era, following break up of the Pangaea supercontinent, it bests manifests itself in the magnetic ‘stripes’ on the ocean floor. They result from alternating polarisation of the geomagnetic field as new oceanic lithosphere is generated at constructive plate boundaries to drive sea-floor spreading. The oldest remaining stripes date back to the early Jurassic. For earlier times geologists have to turn to the continental crust.  Lavas and some sedimentary rocks undergo magnetisation at the time of their formation and retained that imprint. Such remanent, palaeomagnetism reveals the original latitude at which it was imprinted, together with the subsequent rotation of a drifting continent relative to an assumed N to S axis joining the opposed magnetic poles. The apparent ‘wandering’ of the pole through time when successive ancient pole positions of different ages are plotted in relation to the present position of a continent is a good guide to its history of drifting as a result of plate tectonics. Comparing the polar-wander paths of two continents allows the time when they were formerly united to be estimated. So palaeomagnetic pole data makes it possible to reconstruct not just Pangaea but a whole series of earlier supercontinents, ancient magnetic data being supplemented by other geological evidence such as reconnecting the trends on different continents of ancient mountain belts.

Apparent polar wander paths for two continents for a period when they were united then split and were separated by sea-floor spreading, eventually to collide and reunite

The further back in time the fewer palaeomagnetic pole positions have been estimated, and the more uncertain are the apparent polar wander paths and the more complex each continent’s accumulated geological history. One of the reasons for such uncertainty is that episodes of metamorphism can reset a rock’s remanent magnetisation, hundreds of million years after it originally formed. Thus, the harder it becomes to be certain about early supercontinents that have been suggested, of which there are quite a few. The earliest that has been proposed is Vaalbara, albeit on grounds of geological similarity, that supposedly united the Kaapvaal and Pilbara Cratons of southern Africa and Western Australia, respectively. Its duration is suggested to have been between 3.6 to 2.8 Ga (billion years ago). The oldest supercontinents with sound palaeomagnetic records date from the end of the Archaean Eon (2.5 Ga). It is the lack or uncertainty of earlier palaeomagnetic evidence that makes the start of plate tectonics the subject of so much debate.

However, geophysicists continually strive to improve the detection of ancient magnetisation, and advances have been made recently to unravel original magnetisation signals from those that have been superimposed later. The fruits of these developments are borne out by a study of a sequence of mafic lavas from the Pilbara Craton that formed about 3.2 Ga ago (Brenner, A.R. et al. 2020. Paleomagnetic evidence for modern-like plate motion velocities at 3.2 Ga. Science Advances, v. 6, article eaaz8670; DOI: 10.1126/sciadv.aaz8670). Alec Brenner and colleagues from several US universities measured palaeomagnetism in more than 200 diamond drill cores from two localities in this sequence and combined their data with others from the Pilbara to cover a roughly 600 Ma period between 3.35 to 2.77 Ga. The palaeopoles form a polar wander path that spans roughly 50 degrees of palaeolatitude. From this they have been able to estimate, in considerable detail, the rate at which the Pilbara Craton had moved in Mesoarchaean. In the first 170 Ma the average horizontal motion was about 2.5 cm per year, falling rapidly to 0.4 cm per year over the following 410 Ma. The earlier speed is comparable with the average of modern plate motions. Data from the later period suggests relative stagnation. Motions over the entire ~600 Ma could be due to episodic operation of plate tectonics on the global scale, or a local slowing in the rate of plate growth.