Tag: BIFs

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.

Did Precambrian BIFs ‘fall’ into the mantle to trigger mantle plumes?

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How the Earth has been shaped has depended to a large extent on a very simple variable among rocks: their density. Contrasts in density between vast rock masses are expressed when gravity attempts to maintain a balance of forces. The abrupt difference in elevation of the solid surface at the boundaries of oceans and continents – the Earth’s hypsometry – stems from the contrasted densities of continental and oceanic crust: the one dominated by granitic rocks (~2.8 t m-3) the other by those of basaltic composition (~ 3.0 t m-3). Astronomers have estimated that Earth’s overall density is about 5.5 t m-3 – it is the densest planet in the Solar System. The underlying mantle makes up 68% of Earth’s mass, with a density that increases with depth from 3.3 to 5.4 t m-3 in a stepwise fashion, at a number of discontinuities, because mantle minerals undergo changes induced by pressure. The remaining one third of Earth’s mass resides in the iron-nickel core at densities between 9.5 to 14.5 t m-3. Such density layering is by no means completely stable. Locally increased temperatures in mantle rocks reduce their density sufficiently for masses to rise convectively to be replaced by cooler ones, albeit slowly. By far the most important form of convection affecting the lithosphere involves the resorption of oceanic lithosphere plates at destructive margins, which results in subduction. This is thought to be due to old, cold oceanic basalts undergoing metamorphism as pressure increases during subduction. They are transformed at depth to a mineral assemblage (eclogite) that is denser (3.4 to 3.5 t m-3) than the enveloping upper mantle. That density contrast is sufficient for gravity to pull slabs of oceanic lithosphere downwards. This slab-pull force is transmitted through oceanic lithosphere that remains at the surface to become the dominant driver of modern plate tectonics. As a result, extension of the surface oceanic lithosphere at constructive margins draws mantle upwards to partially melt at reduced pressure, thus adding new basaltic crust at mid-ocean rift systems to maintain a form of mantle convection. Seismic tomography shows that active subducted slabs become ductile about 660 km beneath the surface and below that no earthquakes are detected. Quite possibly, the density of the reconstituted lithospheric slab becomes less than that of the mantle below the 660 km discontinuity. So the subducted slab continues by moving sideways and buckling in response to the ‘push’ from its rigid upper parts above. But it has been suggested that some subducted slabs do finally sink to the core-mantle boundary, but that is somewhat conjectural.

Typical banded iron formation

There are sedimentary rocks whose density at the surface exceeds that of the upper mantle: banded iron formations (BIFs) that contain up to 60% iron oxides (mainly Fe2O3) and have an average density at the surface of around 3.5 t m-3. BIFs formed mainly in the late Archaean and early Proterozoic Eons  (3.2 to 1.0 Ga) and none are known from the last 400 Ma. They formed when soluble iron-2 (Fe2+) – being added to ocean water by submarine hydrothermal activity –was precipitated as Fe3+ in the form of iron oxide (Fe2O3) where oxygen was present in ocean water. With little doubt this happened only in shallow marine basins where cyanobacteria that appeared about 3.5 Ga ago had sufficient sunlight to photosynthesise. Until about 2.4 Ga the atmosphere and thus the bulk of ocean water contained very little oxygen so the oceans were pervaded by soluble iron so that BIFs were able to form wherever such biological activity was going on. Conceivably (but not proven), that BIF-forming biochemical reaction may even have operated far from land in ocean surface water, slowly to deposit Fe2O3 on the deep ocean floor. After 2.4 Ga oxygen began to build in the atmosphere after the Great Oxidation Event had begon. That time was also when the greatest production of BIFs took place. Strangely, the amount of BIF in the geological record fell during the next 600 Ma to rise again to a very high peak at 1.8 Ga. Since there must have been sufficient soluble iron and an increasing amount of available oxygen for BIFs to form throughout that ‘lean’ period the drop in BIF formation is paradoxical. After 1.0 Ga BIFs more or less disappear. By then so much oxygen was present in the atmosphere and from top to bottom in ocean water that soluble iron was mostly precipitated at its hydrothermal source on the ocean floor. Incidentally, modern ocean surface water far from land contains so little dissolved iron that little microbiological activity goes on there: iron is an essential nutrient so the surface waters of remote oceans are effectively ‘wet deserts’.

Plots of probability of LIPs and BIFs forming at the Earth’s surface during Precambrian times, based on actual occurrences (Credit: Keller, et al., modified Fig 1A)

Spurred by the fact that if a sea-floor slab dominated by BIFs was subducted it wouldn’t need eclogite formation to sink into the mantle, Duncan Keller of Rice University in Texas and other US and Canadian colleagues have published a ‘thought experiment’ using time-series data on LIPs and BIFs compiled by other geoscientists (Keller, D.S. et al. 2023. Links between large igneous province volcanism and subducted iron formations. Nature Geoscience, v. 16, article; DOI: 10.1038/s41561-023-01188-1.). Their approach involves comparing the occurrences of 54 BIFs through time with signs of activity in the mantle during the Palaeo- and Mesoproterozoic Eras, as marked by large igneous provinces (LIPs) during that time span. To do this they calculated the degree of correlation in time between BIFs and LIPs. The authors chose a minimum area for LIPs of 400 thousand km2 – giving a total of 66 well-dated examples. Because the bulk of Precambrian flood-basalt provinces, such as occurred during the Phanerozoic, have been eroded away, most of their examples are huge, well-dated dyke swarms that almost certainly fed such plateau basalts. Rather than a direct time-correlation, what emerged was a match-up that covered 74% of the LIPs with BIFs that had formed about 241 Ma earlier. They also found a less precise correlation between LIPs associated with 241 Ma older BIFs and protracted periods of stable geomagnetic field, known as ‘superchrons’. These are thought by geophysicists to be influenced by heat flow through the core-mantle boundary (CMB).

The high bulk density of BIFs at the surface would be likely to remain about 15 % greater than that of peridotite as pressure increased with depth in the mantle. Such slabs could therefore penetrate the 660 mantle discontinuity. Their subduction would probably result in their eventually ‘piling up’ in the vicinity of the CMB. The high iron content of BIFs may also have changed the way that the core loses heat, thereby triggering mantle plumes. Certainly, there is a complex zone of ultra-low seismic velocities (ULVZ) that signifies hot, ductile material extending above the CMB. Because BIFs’ high iron-content makes them thermally highly conductive compared with basalts and other sediments, they may be responsible. Clearly, Keller et al’s hypothesis is likely to be controversial and they hope that other geoscientists will test it with new or re-analysed geophysical data. But the possibility of BIFs falling to the base of the mantle spectacularly extends the influence of surface biological processes to the entire planet. And, indeed, it may have shaped the later part of its tectonic history having changed the composition of the deep mantle. The interconnectedness of the Earth system also demands that the consequences – plumes and large igneous provinces – would have fed back to the Precambrian biosphere. See also: Iron-rich rocks unlock new insights into Earth’s planetary history, Science Daily, 2 June 2023

Signs of Milankovich Effect during Snowball Earth episodes

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The idea that the Earth was like a giant snowball during the Neoproterozoic Era arose from the discovery of rocks of that age that could only have formed as a result of glaciation. However, unlike the Pleistocene ice ages, evidence for these much older glacial conditions occurs on all continents. In some locations remanent magnetism in sedimentary rocks of that age is almost horizontal; i.e. they had been deposited at low magnetic latitudes, equivalent to the tropics of the present day. Frigid as it then was, the Earth still received solar heating and magmatic activity would have been slowly adding CO2 to the atmosphere so that less heat escaped – a greenhouse effect must have been functioning. Moreover, an iced-over world would not have been supporting much photosynthetic life to draw down the greenhouse gas into solid carbohydrates and carbonates to be buried on the ocean floor. As far as we know the Solar System’s geometry during the Neoproterozoic was much as it is today. So changes in the gravitational fields induced by the orbiting Giant Planets would have been affecting the shape (eccentricity) of Earth’s orbit, the tilt (obliquity) of its rotational axis and the precession (wobble) of its rotation as they do at present through the Milankovich effect. These astronomical forcings vary the amount of solar energy reaching the Earth’s surface. It has been suggested that a Snowball Earth’s climate system would have been just as sensitive to astronomical forcing as it has been during the last 2 million years or more. Proof of that hypothesis has recently been achieved, at least for one of the Snowball events (Mitchell, R.N. and 8 others 2021. Orbital forcing of ice sheets during snowball Earth. Nature Communications, v. 12, article 4187; DOI: 10.1038/s41467-021-24439-4).

Another of the enigmas of the Neoproterozoic is that after and absence of more than a billion years banded iron formations (see: Banded iron formations (BIFs) reviewed, December 2017) began to form again. BIFs are part of the suite of sedimentary rocks that characterise Snowball Earth events, often alternating with glaciogenic sediments. Throughout each cold cycle – the Sturtian (717 to 663 Ma) and Marinoan (650 to 632 Ma) glacial periods – conditions of sediment deposition varied a great deal from place to place and over time. Some sort of cyclicity is hinted at, but the pace of alternations has proved impossible to check, partly because the dominant rocks (glacial conglomerates or diamictites) show little stratification and others that are bedded (various non-glacial sandstones) vary from place to place and give no sign of rates of deposition, having been deposited under high-energy conditions. BIFs, on the other hand are made up of enormous numbers of parallel layers on scales from millimetres to centimetres. Bundles of bands can be traced over large areas, and they may represent repeated cycles of deposition.

Typical banded iron formation

How BIFs formed is crucial. They were precipitated from water rich in dissolved iron in its reduced Fe2+ (ferrous) form, which originated from sea-floor hydrothermal vents. Precipitation occurred when the amount of oxygen in the water increased the chance of electrons being removed from iron ions to transform them from ferrous to ferric (Fe3+). Their combination with oxygen yields insoluble iron oxides. Cyclical changes in the availability of oxygen and the balance between reducing and oxidising conditions result in the banding. In fact several rhythms of alternation are witnessed by repeated packages at deci-, centi- and millimetre scales within each BIF deposit. Overall the packages suggest a constant rate of deposition: a ‘must-have’ for precise time-analysis of the cycles. BIFs contain both weakly magnetic hematite (Fe2O3) and strongly magnetic magnetite (Fe3O4), their ratio depending on varying geochemical conditions during deposition. Ross Mitchell of Curtin University, Western Australia and his Chinese, Australian and Dutch colleagues measured magnetic susceptibility at closely spaced intervals (1 and 0.25 m) in two section of BIFs from the Sturtian glaciation in the Flinders Ranges of South Australia. Visually both sections show clear signs of two high-frequency and three lower frequency kinds of cycles, expressed in thickness.

The tricky step was converting the magneto-stratigraphic data to a time series. High-precision zircon U-Pb dating of volcanic rocks in the sequence suggested a mean BIF deposition rate of 3.7 to 4.4 cm per thousand years. This allowed the thickness of individual bands and packages to be expressed in years, the prerequisite for time-series analysis of the BIF magneto-stratigraphic sequence. This involves a mathematical process known as the Fast-Fourier Transform, which expresses the actual data as a spectral curve. Peaks in the curve represent specific frequencies expressed as cycles per metre. The rate of deposition of the BIF allows each peak to be assigned a frequency in years, which can then be compared with the hypothetical spectrum associated with the Milankovich effect. One of the BIF sequences yielded peaks corresponding to 23, 97 and 106 ka. These match the effects of variation in precession (23 ka) and ‘short’ orbital eccentricity (97 and 106 ka) found in Cenozoic sea-floor sediments and ice cores. The other showed peaks at 405, 754 and 1.2 Ma corresponding to ‘long’ orbital eccentricity and long-term features of both obliquity and precession. Quite a result! But how does this bear on Snowball Earth events? Cyclical changes in solar heating would have affected the extent of ice sheets and sea ice at all latitudes, forcing episodes of expansion and contraction and thus changes in sediment supply to the sea floor. That helps explain the many observed variations in sedimentation other than that of BIFs. Rather than supporting a ‘hard’ Snowball model of total marine ice cover for millions of years, it suggests that such an extreme was relieved by period of extensive open water, much as affected the modern Arctic Ocean for the last 2 million years or so. There could have been global equivalents of ice ages and interglacials during the Sturtian and Marinoan. ‘Hard’ conditions would have shut down much of the oceans’ biological productivity, periodically to have been reprieved by more open conditions: a mechanism that would have promoted both extinctions and evolutionary radiations. Snowball events may have driven the takeover of prokaryote (bacteria) dominance by that of the multicelled eukaryotes that is signalled by the Ediacaran faunas that swiftly followed glacial epochs and the explosion of multicelled life during the Cambrian. As eukaryotes, we may well owe our existence to Snowball.