Ocean chemistry at the time of the earliest animals

The Ediacaran fauna of the late Neoproterozoic (occurring between 575-543 Ma) marks the first clear sign of animal life, although the affinities of many of the taxa are obscure. ‘Molecular clocks’ based on differences between the DNA of living organisms seems to suggest a last common ancestor of all animals somewhat earlier than the Ediacaran period, perhaps as early as 1000 Ma. Whatever that first animal was, its emergence and that of the Ediacarans took place in climatically and chemically peculiar times. The Neoproterozoic was marked by at least three glacial epochs that left traces at palaeolatitudes as low as the tropics: so-called ‘Snowball Earth’ events. It also contains the most erratic swings in carbon isotopes that are known from the geological record, which have something to do with ups and downs of life at the time, probably variations in global biomass and/or the rate at which organic carbon was buried in seafloor sediments. Among Neoproterozoic sediments two are outstanding: graphitic and sulfidic mudrocks; banded iron formations (BIFs) which are sulfur-poor. BIFs of that age have been an enigma, the most massive and long-lived being those in the Palaeoproterozoic (before 1.8 Ga) and the Archaean. Neoproterozoic BIFs seem to mark the return after a billion years of most peculiar ocean chemistry, when soluble iron(II) ions were abundant at all depths in the ocean yet were oxidised to insoluble iron(III) at the sites where Fe2O3 was deposited in huge amounts. In the earlier BIF period that had to have been where oxygen was being locally emitted by primitive blue-green bacterial photosynthesisers, i.e. in shallow water. We must surmise that occurred again in the Neoproterozoic, although the source of oxygen would then have included more advanced oxygenic photosynthesisers. But that is not the puzzle. How did ocean-wide conditions return to allow the abundance of dissolved iron(II) ions and why did those conditions not prevail in the BIF-less billion years?

Donald Canfield of the University of Southern Denmark has long been immersed in issues of ocean-chemistry evolution in relation to atmospheric oxygen levels, and offered an answer to the second question that has largely replaced the once accepted wisdom that ocean water became oxygenated throughout after 1.8 Ga thereby allowing iron to enter oxidised minerals immediately it emerged in ocean-floor basalts magmas. Instead, he suggested that the deep ocean, at least, contained abundant hydrogen sulfide as witnessed by sulfur isotope patterns in marine sediments. In other words, oceanic Fe(II) was efficiently precipitated through the Mesoproterozoic in the form of sulfides. The H2S was probably generated by bacterial reduction of sulfate ions, themselves derived by oxidation of on-land exposures of sulfidic rocks because of low but increasing atmospheric oxygen. Canfield and a rich variety of international colleagues once again has an authoritative say, this time as regards the Neoproterozoic iron formations (Canfield, D.E. et al. 2008. Ferruginous conditions dominated later Neoproterozoic deep-water chemistry. Science, v. 321, p. 949-952).

If the supply of sulfate from the continents waned, then bacterial production of sulfides would follow suit in sulfur-poor oceans. Provided deep-ocean oxygen levels remained very low, iron(II) derived from continually generated ocean-floor basalts and their hydrothermal alteration could once again pervade the oceans. Oxygen in shallow water would again encourage precipitation of hematite and BIFs. This hypothesis does not need a special explanation for fully oxygenated Precambrian oceans reverting back to anoxia in the Neoproterozoic and then back and forth in their oxygen concentrations to explain short BIF episodes, merely variations in the supply of sulfate from weathered continental surfaces. Canfield et al. tested this hypothesis by examining the proportions of total iron in 800-530Ma sediments contained by minerals able to react easily with their environment, such as sulfides and carbonates, and the proportions of such reactive iron in sulfide minerals. In modern oxygenated waters the proportion of such reactive iron in sediments does not rise above about 40%, and is often lower. In the Neoproterozoic samples, shallow marine rocks obeyed the modern <40% rule, but those from intermediate to deep-water settings (below storm-wave base) sometimes show far higher values. That is a clear signature of anoxic waters, and it persists into the Cambrian. Interestingly, many deep-water sediments from the Ediacaran Period do show signs of oxygenation, while others were anoxic. Among the sediments deposited under anoxic conditions none have iron sulfide proportions as high as those produced in modern euxinic basins such as the Black Sea, thereby signalling a dearth of bacterially generated H2S and low sulfate supply to the oceans as predicted. But why did the supply dry up? One possibility is that chemical weathering on the continents plummeted during ‘Snowball Earth’ episodes. Yet the evidence for anoxic, high iron(II) conditions in the oceans persisted well beyond the times of the known glacial epochs. Another plausible explanation is pyrite burial, analogous to that of carbon, and subduction of sulfide-rich sediments that progressively completely stripped the oceans of sulfate. What of the effect on early animal life? Iron is an essential micronutrient, much touted today as a means of encouraging phytoplankton blooms in ocean surface water. Together with rising shallow-water oxygen levels, perhaps an explosion in food supply enabled large early animals, such as the Ediacarans, to develop and thrive, instead of much smaller precursors whose survival as fossils would be less likely.

The next big step was also one of geochemistry, when animals became able to secrete calcium-rich skeletons by extracting that element from seawater. It took place around 543 Ma at the start of the Cambrian, while iron-rich deep waters were also common. Was there somehow a connection between the two chemical highlights of the late Precambrian? Calcium is very interesting metabolically: too little and cells do not function properly; too much and they die. The ‘window’ of metabolically tolerable calcium concentrations is narrow. One possible means whereby calcium-rich hard parts may have developed among animals is that their outer cells were harnessed by evolution to rid the body of excess calcium in an organised way, creating the opportunity for both armour and armaments. Would elevated iron enhance the solubility of calcium in ocean water?

See also: Lyons, T.W 2008. Ironing out ocean chemistry at the dawn of animal life. Science, v. 321, p.923-924.

The Great Ordovician Diversification

Geologists in general learn that the tangible fossils first appeared at the start of the Cambrian Period. So they did, but we refer to that event as the Cambrian Explosion, but it was hardly explosive as there were very few fossil taxa of Lower Cambrian age. Indeed, by the end of the Cambrian only 500 or so genera are known. Fossils truly exploded in the later Ordovician, reaching 1600 genera, which number wasn’t exceeded until the start of the Cretaceous, 300 Ma later. Sudden rises in diversity, like mass extinctions, demand an explanation, but few have been offered for the late Ordovician explosive diversification, unlike the mass extinction at its close, which halved the number of genera living at the time. That has been attributed to the widespread glaciation of Gondwanaland, the fall in sea levels drastically reducing ecological niches (a wilder scenario is that the extinction was caused instantaneously by a gamma-ray burst from a nearby supernova, but there is little evidence for such an event).

The Ordovician has been assumed to have been a period that experienced ‘supergreenhouse’ conditions because of a far greater proportion of CO2 in the atmosphere in the early Palaeozoic. Advances in stable-isotope analyses of small samples allow that idea to be tested (Trotter, J.A. et al. 2008. Did cooling oceans trigger Ordovician biodiversification? Evidence from conodont thermometry. Science, v. 321, p. 550-554). Julie Trotter of the Australian National University and her French and Canadian colleagues show that oxygen isotopes in conodonts that range in age from Lower Ordovician to Lower Silurian changed steadily with time. Assuming the conodont animals were planktonic, the increase in the proportion of 18O represents decreasing sea-surface temperatures, from around 40ºC (truly supergreenhouse) to levels very similar to those that prevail in today’s tropical ocean, around 30ºC, to even more temperate levels (24ºC) by the close of the Ordovician. So it seems as if cooling encouraged rapid evolution of new organisms at that time.

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