Fossil fuel, mercury and the end-Palaeozoic catastrophe

Siberian flood-basalt flows in the Putorana Plateau, Taymyr Peninsula, Russia. (Credit: Paul Wignall)

The end of the Permian Period (~252 Ma ago) saw the loss of 90% of marine fossil species and 70% of those known from terrestrial sediments: the greatest known extinction in Earth’s history. In their naming of newly discovered life forms, palaeontologists can become quite lyrical. Extinctions, however, really stretch their imagination. They call the Permo-Triassic boundary event ‘The Great Dying’. Why not ‘Permageddon’? Sadly, that was snaffled in the 1980s by an astonishingly short-haired heavy-metal tribute band. Enough bathos … The close of the Palaeozoic left a great many ecological niches to be filled by adaptive radiation during the Triassic and later Mesozoic times. Coinciding with the largest known flood-basalt outpouring – the three million cubic kilometres of Siberian Traps – the P-Tr event seemed to be ‘done and dusted’ after that possible connection was discovered in the mid 1990s. Notwithstanding, the quest for a gigantic, causative impact crater continues (see: Palaeobiology Earth-logs, May, September and October 2004), albeit among a dwindling circle of enthusiasts. The Siberian Traps are suitably vast to snuff the fossil record, for their eruption must have belched all manner of climate-changing gases and dusts into the atmosphere; CO2 to encourage global warming; SO2 and dusts as cooling agents. There is also evidence of a role for geochemical toxicity (see: Nickel, life and the end-Permian extinction, June 2014). The extinctions accompanied not only climate change but also a catastrophic fall in atmospheric oxygen content (see: Homing in on the great end-Permian extinction, April 2003; When rain kick-started evolution, December 2019). Recovery of the biosphere during the early Triassic was exceedingly slow.

Research focussed on the P-Tr boundary eventually uncovered an element of pure chance. Shales in Canada that span the boundary show major, negative δ13C excursions in the carbon-isotope record that coincide with fly ash in the analysed layers. This material is similar in all respects to that emitted from coal-fired power stations (see: Coal and the end-Permian mass extinction, March 2011). The part of Siberia onto which the flood basalts were erupted is rich in Permian coal measures and oil shales that lay close to the surface 252 Ma ago. The coal ash and massive emissions of CO2 may have resulted from their burning by the flood basalt event. Now evidence has emerged that this did indeed happen (Elkins-Tanton, L.T. et al. 2020. Field evidence for coal combustion links the 252 Ma Siberian Traps with global carbon disruption. Geology, v. 48, early publication; DOI: 10.1130/G47365.1).

The US, Canadian and Russian team found large quantities of burnt coal and woody material, and bituminous blobs in 600 m thick volcanic ashes at the base of the Siberian traps themselves. They concluded that the magma chamber from which the flood basalts emerged had incorporated sizeable volumes of the coal measures, leading to their combustion and distillation. This would have released CO2 enriched in light 12C due to isotopic fractionation by biological means, i.e. its δ13C would have been sufficiently negative to affect the carbon locked up in the Canadian P-Tr boundary-layer shales that show the sharp isotopic anomalies. The magnitude of the anomalies suggest that between six to ten thousand billion tons of carbon released as CO2 or methane by interaction of the Siberian Traps with sediments through which their magma passed could have created the global δ13C anomalies. That is about one tenth of the organic carbon originally locked in the Permian coal measures beneath the flood basalts

Another paper whose publication coincided with that by Elkins-Tanton et al. suggests that environmental mercury appears to have followed the same geochemical course as did carbon at the end of the Palaeozoic Era (Dal Corso, J. and 9 others 2020. Permo–Triassic boundary carbon and mercury cycling linked to terrestrial ecosystem collapse. Nature Communications, v. 11, paper 2962; DOI: 10.1038/s41467-020-16725-4). This group, based at Leeds and Oxford Universities, UK and the University of Geosciences in Wuhan, China, base their findings on biogeochemical modelling of the global carbon and mercury cycles at the end of the Permian. Their view is that the coincidence in marine sediments at the P-Tr boundary of a short-lived spike in mercury and an anomaly in its isotopic composition with the depletion in 13C, described earlier, shows an intimate link between mercury and the biological carbon cycle in the oceans at the time. They suggest that this synergy marks ecosystem collapse and derives ‘from a massive oxidation of terrestrial biomass’; i.e. burning of organic material on the land surface. Their modelling hints at huge wildfires in equatorial peatlands but also a role for the Siberian flood-basalt volcanism and the incorporation of coal measures into the Siberian Trap magma chamber.

Earliest plate tectonics tied down?

Papers that ponder the question of when plate tectonics first powered the engine of internal geological processes are sure to get read: tectonics lies at the heart of Earth science. Opinion has swung back and forth from ‘sometime in the Proterozoic’ to ‘since the very birth of the Earth’, which is no surprise. There are simply no rocks that formed during the Hadean Eon of any greater extent than 20 km2. Those occur in the 4.2 billion year (Ga) old Nuvvuagittuq greenstone belt on Hudson Bay, which have been grossly mangled by later events. But there are grains of the sturdy mineral zircon ZrSiO4)  that occur in much younger sedimentary rocks, famously from the Jack Hills of Western Australia, whose ages range back to 4.4 Ga, based on uranium-lead radiometric dating. You can buy zircons from Jack Hills on eBay as a result of a cottage industry that sprang up following news of their great antiquity: that is, if you do a lot of mineral separation from the dust and rock chips that are on offer, and they are very small. Given a laser-fuelled SHRIMP mass spectrometer and a lot of other preparation kit, you could date them. Having gone to that expense, you might as well analyse them chemically using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to check out their trace-element contents. Geochemist Simon Turner of Macquarie University in Sydney, Australia, and colleagues from Curtin University in Western Australia and Geowissenschaftliches Zentrum Göttingen in Germany, have done all this for 32 newly extracted Jack Hills zircons, whose ages range from 4.3 to 3.3 Ga (Turner, S. et al. 2020. An andesitic source for Jack Hills zircon supports onset of plate tectonics in the HadeanNature Communications, v. 11, article 1241; DOI: 10.1038/s41467-020-14857-1). Then they applied sophisticated geochemical modelling to tease out what kinds of Hadean rock once hosted these grains that were eventually eroded out and transported to come to rest in a much younger sedimentary rock.

Artist’s impression of the old-style hellish Hadean (Credit : Dan Durday, Southwest Research Institute)

Zircons only form duuring the crystallisation of igneous magmas, at around 700°C, the original magma having formed under somewhat hotter conditions – up to 1200°C for mafic compositions. In the course of their crystallising, minerals take in not only the elements of which they are mainly composed, zirconium, silicon and oxygen in the case of zircon , but many other elements that the magma contains in low concentrations. The relative proportions of these trace elements that are partitioned from the magma into the growing mineral grains are more or less constant and unique to that mineral, depending on the particular composition of the magma itself. Using the proportions of these trace elements in the mineral gives a clue to the original bulk composition of the parent magma. The Jack Hills zircons  mainly  reflect an origin in magmas of andesitic composition, intermediate in composition between high-silica granites and basalts that have lower silica contents. Andesitic magmas only form today by partial melting of more mafic rocks under the influence of water-rich fluid driven upwards from subducting oceanic lithosphere. The proportions of trace elements in the zircons could only have formed in this way, according to the authors.

Interestingly, the 4.2 Ga Nuvvuagittuq greenstone belt contains metamorphosed mafic andesites, though any zircons in them have yet to be analysed in the manner used by Turner et al., although they were used to date those late-Hadean rocks. The deep post-Archaean continental crust, broadly speaking, has an andesitic composition, strongly suggesting its generation above subduction zones. Yet that portion of Archaean age is not andesitic on average, but a mixture of three geochemically different rocks. It is referred to as TTG crust from those three rock types (trondhjemite, tonalite and granodiorite). That TTG nature of the most ancient continental crust has encouraged most geochemists to reject the idea of magmatic activity controlled by plate tectonics during the Archaean and, by extension, during the preceding Hadean. What is truly remarkable is that if mafic andesites – such as those implied by the Jack Hills zircons and found in the Nuvvuagittuq greenstone belt – partially melted under high pressures that formed garnet in them, they would have yielded magmas of TTG composition. This, it seems, puts plate tectonics in the frame for the whole of Earth’s evolution since it stabilised several million years after the catastrophic collision that flung off the Moon and completely melted the outer layers of our planet. Up to now, controversy about what kind of planet-wide processes operated then have swung this way and that, often into quite strange scenarios. Turner and colleagues may have opened a new, hopefully more unified, episode of geochemical studies that revisit the early Earth . It could complement the work described in An Early Archaean Waterworld published on Earth-logs earlier in March 2020.

Better dating of Deccan Traps, and the K-Pg event

Predictably, the dialogue between the supporters of the Deccan Trap flood basalts and the Chicxulub impact as triggers that were responsible for the mass extinction at the end of the Mesozoic Era (the K-Pg event) continues. A recent issue of Science contains two new approaches focussing on the timing of flood basalt eruptions in western India relative to the age of the Chicxulub impact. One is based on dating the lavas using zircon U-Pb geochronology (Schoene, B. et al. 2019. U-Pb constraints on pulsed eruption of the Deccan Traps across the end-Cretaceous mass extinction. Science, v. 363, p. 862-866; DOI: 10.1126/science.aau2422), the other using 40Ar/39Ar dating of plagioclase feldspars (Sprain, C.G. et al. 2019. The eruptive tempo of Deccan volcanism in relation to the Cretaceous-Paleogene boundary. Science, v. 363, p. 866-870; DOI: 10.1126/science.aav1446). Both studies were initiated for the same reason: previous dating of the sequence of flows in the Deccan Traps was limited by inadequate sampling of the flow sequence and/or high analytical uncertainties. All that could be said with confidence was that the outpouring of more than a million cubic kilometres of plume-related basaltic magma lasted around a million years (65.5 to 66.5 Ma) that encompassed the sudden extinction event and the possibly implicated Chicxulub impact. The age of the impact, as recorded by its iridium-rich ejecta found in sediments of the Denver Basin in Colorado, has been estimated from zircon U-Pb data at 66.016 ± 0.050 Ma; i.e. with a precision of around 50 thousand years.

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The Deccan Traps in the Western Ghats of India (Credit: Wikipedia)

Because basalts rarely contain sufficient zircons to estimate a U-Pb age of their eruption, Blair Schoene and colleagues collected them from palaeosols or boles that commonly occur between flows and sometimes incorporate volcanic ash. Their data cover 23 boles and a single zircon-bearing basalt. Sprain et al. obtained 40Ar/39Ar ages from 19 flows, which they used to supplement 5 ages obtained by their team in previous studies that used the same analytical methods and 4 palaeosol ages from an earlier paper by Schoene’s group.

The zircon U-Pb data from palaeosols, combined with estimates of magma volumes that contributed to the lava sequence between each dated stratigraphic level, provide a record of the varying rates at which lavas accumulated. The results suggest four distinct periods of high-volume eruption separated by long. periods of relative quiescence. The second such pulse precedes the K-Pg event by up to 100 ka, the extinction and impact occurring in a period of quiescence. A few tens of thousand years after the event Deccan magmatism rose to its maximum intensity. Schoene’s group consider that this supports the notion that both magmatism and bolide impact drove environmental deterioration that culminated in mass extinction.

The Ar-Ar data derived from the basalt flows themselves, seem to tell a significantly different story. A plot of basalt accumulation, similarly derived from dating and stratigraphy, shows little if any sign of major magmatic pulses and periods of quiescence. Instead, Courtney Sprain’s team distinguish an average eruption rate of around 0.4 km3 per year before the K-Pg event and 0.6 km3 per year following it. Yet they observe from climate proxy data that there seems to have been only minor climatic change (about 2 to 3 °C warming) during the period around and after the K-Pg event when some 75% of the lavas flooded out. Yet during the pre-extinction period of slower effusion global temperature rose by 4°C then fell back to pre-eruption levels immediately before the K-Pg event. This odd mismatch between magma production and climate, based on their data, prompts Sprain et al. to speculate on possible shifts in the emission of climate-changing gases during the period Deccan volcanism: warming by carbon dioxide – either from the magma or older carbon-rich sediments heated by it; cooling induced by stratospheric sulfate aerosols formed by volcanogenic SO2 emissions. That would imply a complex scenario of changes in the composition of gas emissions of either type. They suggest that one conceivable trigger for the post-extinction climate shift may have been exhaustion of the magma source’s sulfur-rich volatile content before the Chicxulub impact added enough energy to the Earth system to generate the massive extrusions that followed it. But their view peters out in a demand for ‘better understanding of [the Deccan Traps’] volatile release’.

A curious case of empiricism seeming to resolve the K-Pg conundrum, on the one hand, yet pushing the resolution further off, on the other …

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