During most of the last hundred years every car body, rebar rod in concrete, ship, bridge and skyscraper frame had its origins in vividly striped red rocks from vast open-pit mines. Comprising mainly iron oxides with some silica, these banded iron formations, or BIFs for short, occur in profitable tonnages on every continent.
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.
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.
The Earth’s earliest atmosphere undoubtedly had a chemistry dominated by carbon dioxide and nitrogen, together with transient water vapour, outgassed from volcanoes giving pervasive reducing conditions at the surface and in the oceans. Until the last couple of decades the only clear evidence of a switch to oxidising conditions and presumably significant atmospheric oxygen was direct, mineralogical evidence. The most obvious signs are ancient, reddened soils formed when soluble Fe2+ lost electrons to molecular oxygen to form the distinct red, orange and brown oxides and hydroxides of insoluble Fe3+ that impart a deep staining in even small quantities. Others include the disappearance from river-transported sediments of clearly transported grains of metal sulfides and uranium oxide that remain stable under reducing conditions but quickly break down in the presence of oxygen.
Widespread observations in Precambrian sediments, eventually linked with reliable radiometric ages, strongly suggested a fundamental environmental change at around 2.3 billion years ago: the Great Oxidation Event. A few such signs emerge from somewhat older rocks back to 2.7 Ga, but only the 2.3 Ga event created a permanent feature of our home world; at first toxic to many of the prokaryote life forms of earlier times but eventually a prime condition for the rise of the Eukarya and eventually metazoan animals. Isotopic analysis of sulfur from Precambrian sediments also gave hints of a more complex but much debated transition because of the way S-isotopes fractionate under different environmental conditions. Now other indirect, isotopic approaches to redox conditions have become feasible, with a surprising result: powerful evidence that about 3 billion years ago there was appreciable atmospheric oxygen (Crowe, S.A. et al. 2013. Atmospheric oxygenation three billion years ago. Nature, v. 501, p. 535-538).
The Danish-South African-German-Canadian group relied on a fractionation process among the isotopes of chromium, which can exist in several oxidation states. When minerals that contain Cr3+ are weathered under oxidising conditions to release soluble Cr6+ the loss in solution preferentially removes the 53Cr isotope from residual soil. If the isotope enters groundwater with reducing conditions to precipitate some Cr3+ -rich material yet more 53Cr remains in solution. Eventually such enriched water may enter the oceans, where along with iron and other transition-group metal ions chromium can end up in banded iron formations (BIFs) to preserve isotopic evidence for oxidising conditions along it route from land to sea.
The team analysed both a palaeosol and a BIF unit from a stratigraphic sequence in the Achaean of NE South Africa that is between 2980 and 2924 Ma old. A substantial proportion of the palaeosol is depleted in 53Cr whereas the lower part of the slightly younger BIF is significantly enriched. Changes in the concentration of redox sensitive elements, such as chromium itself, uranium and iron, in the two lithologies helps confirm the isotopic evidence for a major ~3 Ga oxidation event. It is possible to use the data to estimate what the atmospheric oxygen content might have been at that time: not enough to breathe, but significant at between 6 x 10-5 to 3 x 10-3 the atmospheric level at present. Oxygen can be produced abiogenically through irradiation of water vapour in the atmosphere as well as by organic photosynthesis. However, the first route seems incapable of yield more than a billionth of present atmospheric concentrations, so the spotlight inevitably falls on a ‘much deep history’ of the action of blue-green bacteria (cyanobacteria) than hitherto suspected.