Category Archives: Geochemistry, mineralogy, petrology and volcanology

Earth’s water and the Moon

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Where did all our water come from? The Earth’s large complement of H2O, at the surface, in its crust and even in the mantle, is what sets it apart in many ways from the rest of the rocky Inner Planets. They are largely dry, tectonically torpid and devoid of signs of life. For a long while the standard answer has been that it was delivered by wave after wave of comet impacts during the Hadean, based on the fact that most volatiles were driven to the outermost Solar System, eventually to accrete as the giant planets and the icy worlds and comets of the Kuiper Belt and Oort Cloud, once the Sun sparked its fusion reactions That left its immediate surroundings depleted in them and enriched in more refractory elements and compounds from which the Inner Planets accreted. But that begs another question: how come an early comet ‘storm’ failed to ‘irrigate’ Mercury, Venus and Mars? New geochemical data offer a different scenario, albeit with a link to the early comet-storms paradigm.

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Simulated view of the Earth from lunar orbit: the ‘wet’ and the ‘dry’. (credit: Adobe Stock)

Three geochemists from the Institut für Planetologie, University of Münster, Germany, led by Gerrit Budde have been studying the isotopes of the element molybdenum (Mo) in terrestrial rocks and meteorite collections. Molybdenum is a strongly siderophile (‘iron loving’) metal that, along with other transition-group metals, easily dissolves in molten iron. Consequently, when the Earth’s core began to form very early in Earth’s history, available molybdenum was mostly incorporated into it. Yet Mo is not that uncommon in younger rocks that formed by partial melting of the mantle, which implies that there is still plenty of it mantle peridotites. That surprising abundance may be explained by its addition along with other interplanetary material after the core had formed. Using Mo isotopes to investigate pre- and post-core formation events is similar to the use of isotopes of other transition metals, such as tungsten (seePlanetary science, May 2016).

Budde and colleagues showed that the 95Mo and 94Mo abundances in water- and carbon-poor meteorites that come from the Asteroid Belt and formed in the inner Solar System differ consistently from those in volatile-rich carbonaceous chondrites that formed much further away from the Sun. The average abundances of the two molybdenum isotopes in the Earth’s silicate rocks, which ultimately had their origin in the mantle, fall between those of the two classes of meteorites (Budde, G. et al.  2019. Molybdenum isotopic evidence for the late accretion of outer Solar System material to Earth. Nature Astronomy, v. 3, online ; DOI: 10.1038/s41550-019-0779-y). They must reflect the materials that accreted after core formation. If the 95Mo and 94Mo abundances resembled those in non-carbonaceous, dry meteorites that would suggest late accretion with much the same composition as expected from Earth’s position in the Inner Solar System. Alternatively, some molybdenum from Earth’s original formative materials failed to unite with iron in the core. The Mo ‘signature’ of volatile-rich carbonaceous meteorites in the mantle’s make-up points to a large amount of accreting material from the Outer Solar System. In contrast, lunar rocks show no carbonaceous meteorite component of Mo isotopes, which helps to explain its overall dryness compared with the Earth. Yet, the Moon is strongly believed to have formed from material blasted away by an impact between the proto-Earth and an errant, Mars-sized body (Theia).

The authors suggest a high probability that Theia was a carbon- and volatile-rich body from the outer Solar System flung inwards by gravitational perturbation associated with the then unstable orbits of the giant planets Jupiter and Saturn. In that case Theia could have delivered not only the anomalous molybdenum, but most of Earth’s water and other volatile compounds.   If the theory is correct, then the cataclysmic event that formed the Moon laid the basis for Earth’s continual tectonic activity and its eventually sparking up life; without the Moon, there would be no life on Earth. That kind of chance event isn’t a factor considered in either the Drake Equation or the Goldilocks Zone. Life, natural selection and sentient beings that might spring from them may be a great deal more elusive than commonly believed by exobiologists.

See also: Formation of the moon brought water to Earth (Science Daily, 21 May 2019)

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

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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 …

Read more on Palaeobiology and Magmatism

Volcanism and the Justinian Plague

Between 541 and 543 CE, during the reign of the Roman Emperor Justinian, bubonic plague spread through countries bordering the Mediterranean Sea. This was a decade after Justinian’s forces had had begun to restore the Roman Empire’s lost territory in North Africa, Spain, Italy and the present-day Balkans by expeditions out of Byzantium (the Eastern Empire). At its height, the Plague of Justinian, was killing 5000 people each day in Constantinople, eventually to consume 20 to 40% of its population and between 25 to 50 million people across the empire. Like the European Black Death of the middle 14th century. The bacterium Yersinia pestis originated in Central Asia and is carried in the gut of fleas that live on rats. The ‘traditional’ explanation of both plagues was that plague spread westwards along the Silk Road and then with black rats that infested ship-borne grain cargoes. Plausible as that might seem, Yersinia pestis, fleas and rats have always existed and remain present to this day. Trade along the same routes continued unbroken for more than two millennia. Although plagues with the same agents recurred regularly, only the Plague of Justinian and the Black Death resulted in tens of million deaths over short periods. Some other factor seems likely to have boosted fatalities to such levels.

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Monk administering the last rites to victims of the Plague of Justinian

Five years before plague struck the Byzantine historian Procopius recorded a long period of fog and haze that continually reduced sunlight; typical features of volcanic aerosol veils. Following this was the coldest decade in the past 2300 years, as recorded by tree-ring studies. It coincides with documentary evidence of famine in China, Ireland, the Middle East and Scandinavia.. A 72 m long ice core extracted from the Colle Gnifetti glacier in the Swiss Alps in 2013 records the last two millennia of local climatic change and global atmospheric dust levels. Sampled by laser slicing, the core has yielded a time series of data at a resolution of months or better. In 536 an Icelandic volcano emitted ash and probably sulfur dioxide over 18 months during which summer temperature fell by about 2°C. A second eruption followed in 540 to 541. ‘Volcanic winter’ conditions lasted from 536 to 545, amplifying the evidence from tree-ring data from the 1990’s.

The Plague of Justinian coincided with the second ‘volcanic winter’ after several years of regional famine. This scenario is paralleled by the better documented Great Famine of 1315-17 that ended the two centuries of economic prosperity during the 11th to 13th centuries. The period was marked by extreme levels of crime, disease, mass death, and even cannibalism and infanticide. In a population weakened through malnutrition to an extent that we can barely imagine in modern Europe, any pandemic disease would have resulted in the most affected dying in millions. Another parallel with the Plague of Justinian is that it followed the ending of four centuries of the Medieval Warm Period, during which vast quantities of land were successfully brought under the plough and the European population had tripled. That ended with a succession of major, sulfur-rich volcanic eruption in Indonesia at the end of the 13th century that heralded the Little Ice Age. Although geologists generally concern themselves with the social and economic consequences of a volcano’s lava and ash in its immediate vicinity– the ‘Pompeii view’ – its potential for global catastrophe is far greater in the case of really large (and often remote) events.

Chemical data from the same ice core reveals the broad economic consequences of the mid-sixth century plague. Lead concentrations in the ice, deposited as airborne pollution from smelting of lead sulfide ore to obtain silver bullion, fell and remained at low levels for a century. The recovery of silver production for coinage is marked by a spike in glacial lead concentration in 640; another parallel with the Black Death, which was followed by a collapse in silver production, albeit only for 4 to 5 years.

Related article: Gibbons, A. 2018. Why 536 was ‘the worst year to be alive’. Science, v. 362,p. 733-734; DOI:10.1126/science.aaw0632

Read more on Geohazards, Magmatism and Palaeoclimatology

Oceanic hydrothermal vents and the origin of life

A range of indirect evidence has been used to suggest that life originated deep in the oceans around hydrothermal vents, such as signs of early organic matter in association with Archaean pillow lavas. One particularly persuasive observation is that a number of proteins and other cell chemicals are constructed around metal sulfide groups. Such sulfides are common around hydrothermal ‘smokers’ associated with oceanic rift systems. Moreover, Fischer-Tropsch reactions between carbon monoxide and hydrogen produce quite complex hydrocarbon molecules under laboratory conditions. Such hydrogenation of a carbon-bearing gas requires a catalyst, a commonly used one being chromium oxide (see Abiotic formation of hydrocarbons by oceanic hydrothermal circulation May 2004). It also turns out that fluids emitted by sea-floor hydrothermal systems are sometimes rich in free hydrogen, formed by the breakdown of olivine in ultramafic rocks to form hydroxylated minerals such as serpentine and talc. The fact that chromium is abundant in ultramafic rocks, in the form of its oxide chromite, elevates the possibility that Fischer-Tropsch reactions may have been a crucial part of the life-forming process on the early Earth. What is needed is evidence that such reactions do occur in natural settings.

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A white carbonate mound forming at the Lost City hydrothermal vent field on the Mid-Atlantic Ridge (Credit: Baross 2018)

One site on the mid-Atlantic ridge spreading centre, the Lost City vent field, operates because of serpentinisation of peridotites exposed on the ocean floor, to form carbonate-rich plumes and rocky towers; ‘white smokers’. So that is an obvious place to test the abiotic theory for the origin of life. Past analyses of the vents have yielded a whole range of organic molecules, including alkanes, formates, acetates and pyruvates, that are possible precursors for such a natural process. Revisiting Lost City with advanced analytical techniques has taken the quest a major step forward (Ménez, B. et al. 2018. Abiotic synthesis of amino acids in the recesses of the oceanic lithosphere. Nature, advance online publication; DOI: 10.1038/s41586-018-0684-z). The researchers from France and Kazakhstan focused on rock drilled from 170 m below the vent system, probably beyond the influence of surface contamination from living organisms. Using several methods they detected the nitrogen-containing amino acid tryptophan, and that alone. Had they detected other amino acids their exciting result would have been severely tempered by the possibility of surface organic contamination. The formation of tryptophan implies that its abiotic formation had to involve the reduction of elemental nitrogen (N2) to ammonia (NH3). Bénédicte Ménez and colleagues suggest that the iron-rich clay saponite, which is a common product of serpentine alteration at low temperatures, may have catalysed such reduction and amino-acid synthesis through Friedel–Crafts reactions. Fascinating as this discovery may be, it is just a step towards confirming life’s abiogenesis. It also permits speculation that similar evidence may be found elsewhere in the Solar System on rocky bodies, such as the moons Enceladus and Europa that orbit Saturn and Jupiter respectively. That is, if the rock base of hydrothermal systems thought to occur there can be reached.

Related article: Baross, J.A. 2018. The rocky road to biomolecules. Nature, v. 564, p. 42-43; DOI: 10.1038/d41586-018-07262-8.

Hot-spot track beneath the Greenland ice cap

Around 63 Ma ago, during the Palaeocene Epoch, major igneous activity broke out in what are now both sides of the North Atlantic Ocean. After initial sputtering it culminated massively between 57 and 53 Ma. Relics are to be seen in Baffin Island, West and East Greenland, the Faeroes and north-western parts of the British Islands, in the form of flood basalts, dyke swarms and scattered remnants of central volcanoes. Offshore drilling on the North Atlantic’s continental shelves suggests that the volcanism extended over 1.3 million km2 and blurted out around 6.6 million km3 of magma. Not for nothing have the products of this event been categorised as a Large Igneous Province. Its formation took place before the North Atlantic existed. It began to form as this precursor magmatic paroxysm waned.  Continued basaltic magma production created the ocean floor each side of the mid-Atlantic Ridge system to divide North America and Greenland from northern Europe. Sea floor spreading continues, rising above sea level in Iceland, which is underlain by a large mantle plume.

The plume beneath Iceland may have been present at a fixed position in the mantle for tens of million years. A hot spot over which plate movements have shifted lithosphere to be heated in a similar way to a sheet of paper dragged slowly over a candle flame. The Iceland plume may have left a hot-spot track similar to that involved in the Hawaiian island chain. The ocean floor to the east and west of Iceland is shallower and forms broad rides at right angles to the trend of the Mid-Atlantic Ridge system, judged to be such tracks that are still warm and buoyant after formation over the plume. But are there traces of earlier passage of drifting lithosphere over the plume. A way to detect older hot-spot tracks is through variations in geothermal heat flow through the continental surface, a linear pattern raising suspicions of such trace of passage. There is no sign to the east beneath Europe, so what about to the west. Greenland, being mainly blanketed in ice, is not a good place to conduct such a search as it would involve deep drilling through the ice at huge cost for each hole. But there is a roundabout way of obtaining geothermal information without even setting foot on Greenland’s icy wastes.

The geomagnetic field measured at the surface records anomalies in rock magnetisation in the solid Earth beneath. Near-surface variations due to large variations in rock types that comprise the continental crust appear as sharp, high frequency signals. Aeromagnetic surveys over Greenland are characterised by such noisy patterns because the subsurface geology is extremely complicated. However, the underlying upper mantle beneath all continents is geologically quite bland, but being uniformly rich in iron it contains a high proportion of magnetic minerals such as magnetite (Fe3O4). The upper mantle should therefore leave a signal in the surface geomagnetic field, albeit a commensurately bland one. Like radio signals that span a large range of wavelengths, Earth properties that vary spatially, such as the geomagnetic field, may be analysed using filters. Once the high-frequency geomagnetic features of the crust are filtered out what should remain is a signal that reflects the magnetic structure of the upper mantle. It should be more or less featureless, yet beneath Greenland it isn’t.

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Estimated Curie depth variation below Greenland (left) converted to geothermal heat flow variation (right). (Credit: Martos et al. 2018; Figures 1b and 1c)

Magnetic anomalies are created by magnetisation induced in magnetic minerals in rocks by the Earth’s magnetic field. Yet minerals lose their ability to be magnetised at temperatures above a threshold known as the Curie point, which is 580 °C for magnetite, the most abundant magnetic mineral. Depending on the geothermal heat flow the Curie point is exceeded at some depth in the lithosphere. So magnetic anomalies can safely be assumed to be produced only by rocks above the so-called Curie depth. Yasmina Martos of the British Antarctic Survey (now at the University of Maryland) and scientists from Britain, the US and Spain used a complex procedure, including gravity data and a few direct measurements of heat flow below Greenland as well as filtered aeromagnetic data, to estimate the variation in Curie depth beneath the ice cap. (Martos, Y.M. et al. 2018. Geothermal heat flux reveals the Iceland hotspot track underneath Greenland. Geophysical Research Letters, v. 45, online publication; doi: 10.1029/2018GL078289). Using that as an inverse proxy for heat flow they were able to map the likely geothermal variation beneath the island. Rather than a random and narrow variation in depth, as would be expected for roughly uniform heat flow, the Curie depth varied in a non-random way by over 20 km, equivalent to roughly 20 mW m-2.

The shallowest Curie depth and highest estimated heat flow occurs in East Greenland around Scoresby Sund where the largest sequence of Palaeocene flood basalts occur. It is also on a line perpendicular to the mid-Atlantic Rift system that meets the active Iceland plume. Running north-west from Scoresby Sund is a zone of locally high estimated heat flow. Martos et al. suggest that this is the track of Greenland’s motion over the Iceland hot spot from about 80 Ma to the period of maximum on-shore volcanism and the start of sea-floor spreading at around 50 Ma.

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Volcano heading for the sea

John Murray of The Open University, UK has been studying Europe’s largest active volcano Mount Etna on Sicily for most of his career. With a group of colleagues he installed high-precision GPS receivers at over 100 stations on the flanks of the mountain. This was to monitor any shifts in elevation and geographic position, which might be related to magmatic events within the volcano, such as inflation and contraction of the magma chamber. Measurements of position gathered annually since 2001 reveal a somewhat alarming picture (Murray, J.B. et al. 2018. Gravitational sliding of the Mt. Etna massif along a sloping basement. Bulletin of Volcanology, v. 80 online, open access; doi /10.1007/s00445-018-1209-1). The edifice is moving relentlessly ESE at 14 mm yr-1, on average, towards the Mediterranean Sea. Research by one of Murray’s co-authors, Benjamin van Wyk de Vries of the Université Clermont Auvergne, established that many volcanoes have associated signs of deformation due to their huge masses. Often, this is a matter of radial spreading that produces thrust-like faults at their base and in the basement on which they grew. In the case of Etna all the annual displacements on its flanks are skewed to the ESE. The researchers are able to show that this is not a case of flank instability that ultimately may result in lateral collapse but the entire volcano is slowly slipping sideways.

English: Mount Etna, Sicily, topped in snow It...

Mount Etna, Sicily, topped in snow (credit: Wikipedia)

An experimental mock up of the volcano– a cone and flanking layers of lava and pyroclastic rocks made of sand on a substrate of putty to represent underlying sedimentary strata – began to slide once it was tilted at a shallow angle. This suggests that the base of the volcano and igneous debris that it has emitted dips gently to the ESE. The underlying materials are poorly consolidated Quaternary sediments, which are likely to be rheologically weak. Geophysics shows that the NW side of the volcano rests on an almost horizontal plateau, the cone itself being above a spoon-like depression, probably produced by the cone’s mass, and the base dips seawards  in the SE sector. It is through this basement that magma makes its way to Etna’s summit vent system, probably along fractures.

The authors warn that such sliding volcanoes are prone to devastating sector collapse on the downslope side, although there are no signs that might be imminent. Yet it will almost certainly have an effect on eruptive activity as the magma conduits are continually changing. Future research needs to focus on periods when there is horizontal contraction on the volcano, as happens during lengthy periods of dormancy – the period for which there are data has been one of expansion.

Volcanism and sea level fall

Most volcanic activity stems from the rise of hot, deep rock, usually within the mantle. Pressure suppresses partial melting, so as hot rock rises the greater the chance that it will begin to melt without any rise in its temperature. That is the reason why mantle plumes are associated with many volcanic centres within plates. Extension at oceanic ridges allows upper mantle to rise in linear belts below rift systems giving rise to shallow partial melting, mid-ocean ridge basalts and sea-floor spreading. These aren’t the only processes that can reduce pressure to induce such decompression melting; any means of uplift will do, provided the rate of uplift exceeds the rate of cooling at depth. As well as tectonic uplift and erosion, melting of thick ice sheets and major falls in sea level may result in unloading of the lithosphere.

During Messinian Stage of the late Miocene up to 3 km of evaporitic salt was deposited in the deepest parts of the Mediterranean Basin. One mechanism might have been faster evaporation of seawater than its resupply from the Atlantic through the Straits of Gibraltar, similar to the way in which salts is deposited below the Dead Sea. But the salt layer beneath the modern Mediterranean Sea bed has interleaved riverine sediments containing fossils of land plants. The Straits had closed and the Mediterranean Sea evaporated away. From about 6 to 5.3 Ma ago sea level fell by 3 to 5 km, only returning to normal when the Straits reopened to launch the huge Zanclean flood, with which the Pliocene of southern Europe and North Africa commenced. A team from the Universities of Geneva, Orleans and Paris and the Instituto de Ciencias de la Tierra Jaume Almera in Barcelona has tested the hypothesis that the Messinian Crisis affected volcanic activity in the area (Sternai, P. et al. 2017. Magmatic pulse driven by sea-level changes associated with the Messinian salinity crisis. Nature Geoscience, v. 10 online; doi:10.1038/ngeo3032).

From the record of salt precipitation, Pietro Sternai and colleagues, reckon that the main phase of unloading of the Mediterranean Basin began at around 5.6 Ma. Allowing for loading by the thick evaporites they calculated that the effect of the loss of water mass was equivalent to an unloading of 15 MPa in the deeper Eastern Mediterranean and 10 MPa in the west. Using standard pressure-temperature melting curves for the upper mantle, they then estimated that any magma chambers affected by the decrease in pressure could yield up to 17% more melt. Radiometrically dated lavas and igneous dykes within the Mediterranean region became more frequent and the number of events more than doubled during the time of main salt deposition.

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Stromboli, one of the most active volcanoes in the Mediterranean Basin (credit: Wikipedia)

In May 2017 a study of subglacial volcanoes in West Antarctica based on radar mapping of the solid surface identified 138, 91 of them previously unknown (van Wyk de Vries et al. 2017. A new volcanic province: an inventory of subglacial volcanoes in West Antarctica.  Geological Society, London, Special Publication 461) They lie within a buried rift system and are covered by thick ice. Only one volcano in Antarctica is known to be active, Erebus, which is part of the cluster. Most of the news items stemming from the publication mentioned the possibility that the buried volcanic tract could be adding to the instability of the West Antarctic Ice Sheet through heating up its base. The WAIS is the ice sheet most feared to collapse seawards leading to a rise of about 3 m in global sea level. If the 2 km thick WAIS did slide off its underlying crust it might possibly trigger reactivation of the volcanic cluster.

Wildfires and climate at the K-Pg boundary

It is now certain that the Cretaceous-Palaeogene boundary 66 Ma ago coincided with the impact of a ~10 km diameter asteroid that produced the infamous Chicxulub crater north of Mexico’s Yucatán peninsula. Whether or not this was the trigger for the mass extinction of marine and terrestrial fauna and flora – the flood basalts of the Deccan Traps are still very much in the frame – the worldwide ejecta layer from Chicxulub coincides exactly with the boundary that separates the Mesozoic and Cenozoic Eras. As well as shocked quartz grains, anomalously high iridium concentrations and glass spherules the boundary layer contains abundant elemental carbon, which has been widely ascribed to soot released by vegetation that went up in flames on a massive scale. Atmospheric oxygen levels in the late Cretaceous were a little lower than those at present, or so recent estimates from carbon isotopes in Mesozoic to Recent ambers suggest (Tappert, R. et al. 2013. Stable carbon isotopes of C3 plant resins and ambers record changes in atmospheric oxygen since the Triassic. Geochimica et Cosmochimica Acta, v. 121, p. 240-262,) – other estimates put the level substantially above that in modern air. Whatever, global wildfires occurred within the time taken for the Chicxulub ejecta to settle from the atmosphere; probably a few years. It has been estimated that about 700 billion tonnes of soot were laid down, suggesting that most of the Cretaceous terrestrial biomass and even a high proportion of that in soils literally went up in smoke.

Charles Bardeen and colleagues at the University of Colorado, Boulder, have modelled the climatic and chemical effects of this aspect of the catastrophe (Bardeen, C.G. et al. 2017. On transient climate change at the Cretaceous−Paleogene boundary due to atmospheric soot injections. Proceedings of the National Academy of Sciences; doi:10.1073/pnas.1708980114). Despite the associated release of massive amounts of CO2 and water vapour by both the burning and the impact into seawater, giving increased impetus to the greenhouse effect, the study suggests that fine-grained soot would have lingered as an all enveloping pall in the stratosphere. Sunlight would have been blocked for over a year so that no photosynthesis would have been possible on land or in the upper ocean, the temperatures of the continent and ocean surfaces would have dropped by as much as 28 and 11 °C respectively to cause freezing temperatures at mid-latitudes. Moreover, absorption of solar radiation by the stratospheric soot layer would have increased the temperature of the upper atmosphere by several hundred degrees to destroy the ozone layer. Consequently, once the soot cleared the surface would have had a high ultraviolet irradiation for around a year.

The main implication of the modelling is a collapse in both green terrestrial vegetation and oceanic phytoplankton; most of the food chain would have been absent for long enough to wipe out those animals that depended on it entirely. While an enhanced greenhouse effect and increased acidification of the upper ocean through CO2 emissions by the Deccan flood volcanism would have placed gradually increasing and perhaps episodic stresses on the biosphere, the outcome of the Chicxulub impact would have been immediate and terrible.

More on mass extinctions and impacts here and here

The late-Ordovician mass extinction: volcanic connections

The dominant feature of Phanerozoic stratigraphy is surely the way that many of the formally named major time boundaries in the Stratigraphic Column coincide with sudden shifts in the abundance and diversity of fossil organisms. That is hardly surprising since all the globally recognised boundaries between Eras, Periods and lesser divisions in relative time were, and remain, based on palaeontology. Two boundaries between Eras – the Palaeozoic-Mesozoic (Permian-Triassic) at 252 Ma and Mesozoic-Cenozoic (Cretaceous-Palaeogene) at 66 Ma – and a boundary between Periods – Triassic-Jurassic at 201 Ma – coincide with enormous declines in biological diversity. They are defined by mass extinctions involving the loss of up to 95 % of all species living immediately before the events. Two other extinction events that match up to such awesome statistics do not define commensurately important stratigraphic boundaries. The Frasnian Stage of the late-Devonian closed at 372 Ma with a prolonged series of extinctions (~20 Ma) that eliminated  at least 70% of all species that were alive before it happened. The last 10 Ma of the Ordovician period witnessed two extinction events that snuffed out about the same number of species. The Cambrian Period is marked by 3 separate events that in percentage terms look even more extreme than those at the end of the Ordovician, but there are a great many less genera known from Cambrian times than formed fossils during the Ordovician.

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Faunal extinctions during the Phanerozoic in relation to the Stratigraphic Column.

Empirical coincidences between the precise timing of several mass extinctions with that of large igneous events – mainly flood basalts – suggest a repeated volcanic connection with deterioration of conditions for life. That is the case for four of the Famous Five, the end-Ordovician die-off having been ascribed to other causes; global cooling that resulted in south-polar glaciation of the Gondwana supercontinent and/or an extra-solar gamma-ray burst (predicated on the preferential extinction of Ordovician near-surface, planktonic fauna such as some trilobite families). Neither explanation is entirely satisfactory, but new evidence has emerged that may support a volcanic trigger (Jones, D.S. et al. 2017. A volcanic trigger for the Late Ordovician mass extinction? Mercury data from south China and Laurentia. Geology, v. 45, p. 631-634; doi:10.1130/G38940.1). David Jones and his US-Japan colleagues base their hypothesis on several very strong mercury concentrations in thin sequences in the western US and southern China of late Ordovician marine sediments that precede, but do not exactly coincide with, extinction pulses. They ascribe these to large igneous events that had global effects, on the basis of similar Hg anomalies associated with extinction-related LIPs. Yet no such volcanic provinces have been recorded from that time-range of the Ordovician, although rift-related volcanism of roughly that age has been reported from Korea. That does not rule out the possibility as LIPs, such as the Ontong Java Plateau, are known from parts of the modern ocean floor that formed in the Mesozoic and Cenozoic. Ordovician ocean floor was subducted long ago.

The earlier Hg pulses coincide with evidence for late Ordovician glaciations over what is now Africa and eastern South America. The authors suggest that massive volcanism may then have increased the Earth’s albedo by blasting sulfates into the stratosphere. A similar effect may have resulted from chemical weathering of widely exposed flood basalts which draws down atmospheric CO2. The later pulses coincide with the end of Gondwanan glaciation, which may signify massive emanation of volcanic CO2 into the atmosphere and global warming. Despite being somewhat speculative, in the absence of evidence, a common link between the Big Five plus several other major extinctions and LIP volcanism would quieten their popular association with major asteroid and/or comet impacts currently being reinvigorated by drilling results from the K-Pg Chicxulub crater offshore of Mexico’s Yucatan Peninsula.

Steam-bath Earth

The Earth’s mantle probably contained a significant amount of water from the start. Its earliest history was one of intense bombardment, including the impact that formed the Moon. Together with the conversion of gravitational potential energy to heat while the core was settling out from the mantle, impacts would have kept its overall temperature high enough to prevent water vapour from condensing on the surface until such heat input ceased and heat loss by radiation allowed the surface rapidly to cool. The atmosphere would have been rich in water vapour. Evidence from zircons that are the earliest tangible materials yet recovered hint at the formation of Zr-rich magmas – probably granitic in the broad sense – about 100 Ma after the Moon-forming event (see EPN July 2001: Zircons’ window on the Hadean). Yet no trace of substantial granitic rocks that old have ever been found.

Don Baker and Kassandra Sofonio of McGill University in Montreal, Canada have considered processes other than partial melting or fractional crystallisation that may have been possible during the earliest Hadean. In particular they have looked at one thought once to be a contender in the genesis of granite and latterly sidelined (Baker, D.R. & Sofonio, K. 2017. A metasomatic mechanism for the formation of Earth’s earliest evolved crust. Earth and Planetary Science Letters, v. 463, p. 48-55; http://dx.doi.org/10.1016/j.epsl.2017.01.022 ). They heated powdered artificial samples that chemically resembled the Earth’s original silicate mantle in sealed double capsules – an inner part containing the silicate powder and an outer one containing water. The capsules were held at around 727°C for a time and then quenched. The outer part of each capsule was found to be a glass of roughly granite composition. The experimental design ensured that superheated water diffused across the inner-outer capsule wall. So the ‘granite’ must have formed by a metasomatic process – essentially preferential solution of its component elements in supercritical water – the experimental temperature being insufficient to partially melt the ultramafic charge in the inner capsule.

Baker and Sofonio conclude that degassing of this metasomatic fluid – silicate-rich ‘steam’ – may have produced substantial masses of sialic crust on the Earth’s surface. Removal of material produced in such a manner would also have extracted trace elements with an affinity for granite from the early mantle – so-called incompatible elements. The subsequent recycling of such granitic blobs back into the mantle may explain geochemical signs in >500 Ma younger Archaean crust – produced by ‘normal’ igneous processes – of incompatible-element enriched reservoirs in the Early mantle.