Source: https://wileyearthpages.wordpress.com/category/geochemistry-mineralogy-petrology-and-volcanology/page/2/
Timestamp: 2019-04-23 10:17:35+00:00

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Geochemistry is a complex business(!), bearing in mind that rocks that can be analysed today predominantly come from the tiny proportion of Earth that constitutes the crust. The igneous rocks at the centre of wrangling how the whole Earth has evolved formed through a host of processes in the mantle and deep crust, which have operated since the Earth formed as a chemical system. To work out the composition of the primary source of crustal igneous rocks, the mantle, involves complex back calculations and modelling. It turns out that there may be several different kinds of mantle. To make matters worse, those mantle processes have probably changed considerably from time to time. To work back to the original formative processes for the planet itself faces the more recent discovery that different meteorite classes formed in different ways, different distances from the Sun and at different times in the early evolution of the pre-Solar nebula. Thankfully, some generalities about chemical evolution and the origin of the Earth can be traced using different isotopes of a growing suite of elements. For instance, lead isotopes have revealed when the Moon formed from Earth by a giant impact, and tungsten isotopes narrow-down the period when the Earth first accreted. Incidentally, the latest ideas on accretion involve a series of ‘embryo’ planets between the Moon and Mars in size.
Calculating from a compendium of isotopic data from various types of meteorite and terrestrial materials, Nicolas Dauphas of the University of Chicago has convincingly returned attention to a model of heterogeneous accretion of protoplanetary materials from different regions of the pre-Solar nebula (Dauphas, N. 2017. The isotopic nature of the Earth’s accreting material through time. Nature, v. 541, p. 521-524; doi:10.1038/nature20830). His work suggests that the first 60% of Earth’s accretion involved materials that were a mixture of meteorite types, half being a type known as enstatite chondrites. These meteorites are dry and contain grains of metallic iron-nickel alloy and iron sulfides set in predominant MgSiO3 the pyroxene enstatite. The Earth’s remaining bulk accumulated almost purely from enstatite-chondrite material. A second paper in the same issue of Nature (Fischer-Gödde, M. & Kleine, T. 2017. Ruthenium isotopic evidence for an inner Solar System origin of the late veneer. Nature, v. 541, p. 525-527; doi:10.1038/nature21045) reinforces the notion that the final addition was purely enstatite chondrite.
This is likely to cause quite a stir: surface rocks are nothing like enstatite chondrite and nor are rocks brought up from the upper mantle by volcanic activity or whose composition has been back-calculated from that of surface lavas; and where did the Earth’s water at the surface and in the mantle come from? It is difficult to escape the implication of a mantle dominated by enstatite chondrite From Dauphas’s analysis, for lots of other evidence from Earth materials seem to rule it out. One ‘escape route’ is that the enstatite chondrites that survived planetary accretion, which only make up 2% of museum collections, have somehow been changed during later times. The dryness of enstatite chondrites and the lack of evidence for a late veneer of ‘moist’ carbonaceous chondrite in these analyses cuts down the options for delivery of water, the most vital component of the bulk Earth and its surface. Could moister meteorites have contributed to the first 60% of accretion, or was post-accretion cometary delivery to the surface able to be mixed in to the deep mantle? Nature’s News & Views reviewer, Richard Carlson of the Carnegie Institution for Science in Washington DC, offers what may be a grim outlook for professional meteoriticists: that perhaps “the meteorites in our collection are not particularly good examples of Earth’s building blocks” (Carlson, R.W. 2017. Earth’s building blocks. Nature, v. 541, p. 468-470; doi:10.1038/541468a).
Animation of how the Solar System may have formed.
That the Moon formed and Earth’s geochemistry was reset by our planet’s collision with another, now vanished world, has become pretty much part of the geoscientific canon. It was but one of some unimaginably catastrophic events that possibly characterised the early Solar System and those around other stars. Since the mantle geochemistry of the Earth’s precursor was fundamentally transformed to that which underpinned all later geological events, notwithstanding the formation of the protoEarth about 4.57 Ga ago, I now think of the Moon-forming event as our homeworld’s ‘Year Zero’. It was the ‘beginning’ of which James Hutton reckoned there was ‘no vestige’. Any modern geochemist might comment, ‘Well, there must be some kind of signature!’, but what that might be and when it happened are elusive, to say the least. One way of looking for answers is, as with so many thorny issues these days, to make a mathematical model. James Connelly and Martin Bizzarro of the University of Copenhagen, Denmark, have designed one based on the fact that one of the volatile elements that must have been partially ‘blown off’ by such a collision is lead and, of course, that is an element with several isotopes that are daughters of long-term decay of radioactive uranium and thorium (Connelly, J.N. & Bizzarro, M. 2016. Lead isotope evidence for a young formation age of the Earth–Moon system. Earth and Planetary Science Letters, v. 452, p. 36-43. doi:10.1016/j.epsl.2016.07.010).
Artist’s impression of the impact of a roughly Mars-size planet with the proto-Earth to form an incandescent cloud, from part of which the Moon formed. A NASA animation of lunar history can be viewed here.
Global warming cannot simply be reversed by turning off the tap of fossil fuel burning. Two centuries’ worth of accumulated anthropogenic carbon dioxide would continue to trap solar energy, even supposing that an immediate shutdown of emissions was feasible; a pure fantasy for any kind of society hooked on coal, oil and gas. It takes too long for natural processes to download CO2 from the atmosphere into oceans, living organic matter or, ultimately, back once more into geological storage. In the carbon cycle, it has been estimated that an individual molecule of the gas returns to one of these ‘sinks’ in about 30 to 95 years. But that is going on all the time for both natural and anthropogenic emissions. Despite the fact that annual human emissions are at present only about 4.5 % of the amount emitted by natural processes, clearly the drawdown processes in the carbon cycle are incapable of balancing them, at present. Currently the anthropogenic excess of CO2 over that in the pre-industrial atmosphere is more than 100 parts per million achieved in only 250 years or so. The record of natural CO2 levels measured in cores through polar ice caps suggests that natural processes would take between 5 to 20 thousand years to achieve a reduction of that amount.
Whatever happens as regards international pledges to reduce emissions, such as those reported by the Paris Agreement, so called ‘net-zero emissions’ leave the planet still a lot warmer than it would be in the ‘natural course of things’. This is why actively attempting to reduce atmospheric carbon dioxide may be the most important thing on the real agenda. The means of carbon sequestration that is most widely touted is pumping emissions from fossil fuel burning into deep geological storage (carbon capture and storage or CCS), but oddly that did not figure in the Paris Agreement, as I mentioned in EPN December 2015. In that post I noted that CCS promised by the actual emitters was not making much progress: a cost of US$50 to 100 per tonne sequestered makes most fossil fuel power stations unprofitable. Last week CCS hit the worlds headlines through reports that an Icelandic initiative to explore a permanent, leak-proof approach had made what appears to be a major breakthrough (Matter, J.M. and 17 others, 2016. Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions. Science, v. 352, p. 1312-1314). EPN January 2009 discussed the method that has now been tested in Iceland. It stems from the common observation that some of the minerals in mafic and ultramafic igneous rocks tend to breakdown in the presence of carbon dioxide dissolved in slightly acid water. The minerals are olivine ([Fe,Mg]2SiO4)] and pyroxene ([Fe,Mg]CaSi2O6), from whose breakdown the elements calcium and magnesium combine with CO2 to form carbonates.
Iceland is not short of basalts, being on the axial ridge of the North Atlantic. Surprisingly for a country that uses geothermal power to generate electricity it is not short of carbon dioxide either, as the hot steam contains large quantities of it. In 2012 the CarbFix experiment began to inject a 2 km deep basalt flow with 220 t of geothermal CO2 ‘spiked’ with 14C to check where the gas had ended up This was in two phases, each about 3 months long. After 18 months the pump that extracted groundwater directly from the lave flow for continuous monitoring of changes in the tracer and pH broke down. The fault was due to a build up of carbonate – a cause for astonishment and rapid evaluation of the data gathered. In just 18 months 95% of the 14C in the injected CO2 had been taken up by carbonation reactions. A similar injection experiment into the Snake River flood basalts in Washington State, USA, is said to have achieved similar results (not yet published). A test would be to drill core from the target flow to see if any carbonates containing the radioactive tracer filled either vesicles of cracks in the rock – some press reports have shown Icelandic basalt cores that contain carbonates, but no evidence that they contain the tracer .
Kintisch, E., 2016. Underground injections turn carbon dioxide to stone. Science, v. 352, p. 1262-1263.
Apart from ancient detrital zircons no dated materials from the Earth’s crust come anywhere near the age when our home world formed, which incidentally was derived by indirect means. Hutton’s famous saying towards the close of the 18th century, ‘The result, therefore, of our present enquiry is, that we find no vestige of a beginning, – no prospect of an end’ seems irrefutable. Hardly surprising, you might think, considering the frantic pace of events that have reworked the geological record for four billion years and convincing evidence that not long after accretion the Moon-forming collision may have melted most of the early mantle. But there is a way of peering beyond even that definitive catastrophe. The metal tungsten, as anyone from the steel town of Rotherham will tell you, alloys very nicely with iron and makes it harder, stronger and more temperature resistant. Most of the Earth’s original complement of tungsten probably ended up in the core; it is a siderophile element. But traces can be detected in virtually any rock and, of course, in W-rich ore bodies. Its interest to modern-day geochemists lies in its naturally occurring isotopes, particularly 182W, a proportion of which forms by decay of a radioactive isotope of hafnium (182Hf). Or rather it did, for 182Hf has a half-life of about 9 million years. Only a vanishingly small amount from a nearby supernova that may have triggered formation of the solar system remains undecayed.
A sign of the former presence of 182Hf in the early Earth comes from higher amounts of its daughter isotope 182W in some Archaean rocks (3.96 Ga) than in younger rocks. That excess is probably from undecayed 182Hf in asteroidal masses that bombarded the Earth between 4.1 and 3.8 Ga. Now it turns out that some much younger flood basalts from the Ontong Java Plateau on the floor of the West Pacific Ocean (~120 Ma) and Baffin Island in northern Canada (~60 Ma) also contain anomalously high 182W/184W ratios (Rizo, H. et al. 2016. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts. Science, v. 352, p. 809-812; see also: Dahl, T.W. 2016. Identifying remnants of early Earth. Science, v. 352, p. 768-769). A different explanation is required for these occurrences. The flood basalts must have melted from chemically anomalous mantle, which originally contained undecayed 182Hf. The researchers have worked out that this heterogeneity stems from a silicate-rich planetesimal that had formed in the first 50 Ma of the solar system’s history, and was accreted to the Earth before the Moon-forming event – lunar rocks formed after 182Hf became extinct. That catastrophe and the succeeding 4.51 Ga of mantle convection failed to mix the ancient anomaly with the rest of the Earth.
It is sometimes forgotten that not only oceanic lithosphere provides evidence for hot spot tracks, probably because they are so obvious as island and seamount chains on bathymetric maps. They are not so clear on continents, either because of erosion of volcanoes or topography dominated by features that predate volcanism, but they account for about 20% of proposed tracks. Eastern Australia seems well endowed; four of them marked by a variety of volcanic structures that trend parallel to the Indo-Australian Plate’s NNE Cenozoic drift powered by the Southeast Indian Ridge that separates it from the Antarctic Plate. The timing of the volcanism along the proposed tracks is also highly persuasive. The longest of the tracks, extending about 2000 km SSW from Cape Hillsborough on the coast of central Queensland through New South Wales to Cosgrove in Victoria, is marked by sporadic volcanoes whose age decreases from Late Eocene in the north to Late Miocene in Victoria.
Unlike oceanic hot-spot tracks, those on continents are not continuous lines of volcanic occurrences. The Cosgrove track has several volcanic gaps, up to 650 km wide. This kind of patchy feature once encouraged hot-spot sceptics to question the tectonic affinities of what they regarded as fortuitous alignments. Where volcanic age trends consistent with the hypothesis emerged such doubts have faded into the background academic ‘noise’. In the case of the Cosgrove track all but one of the dates of volcanism tally quite well with the Cenozoic absolute motion of the Indo-Australian Plate and their position along the track (Davies, D.R. et al 2015. Lithospheric controls on magma composition along Earth’s longest continental hotspot track. Nature, v. 525, p. 511-514). Yet the objective of the authors, from the Australian National University and the University of Aberdeen in Britain, was not merely to establish the alignment as a hot-spot track, but to suggest what may have resulted in its marked patchiness.
The geochemistry of lavas from the volcanoes turns out to be of two fundamentally different types: ‘common-or-garden’ basalts in the case of Queensland and peculiar potassium-rich basalts containing the K-feldspathoid leucite in New South Wales and Victoria. Why these compositional differences occur where they do emerged very clearly when their positions were plotted on a new map of the thickness variations of the eastern Australian continental lithosphere. The ordinary basalts rest on the thinnest lithosphere (£110 km), whereas the leucitites are underlain by considerably thicker lithosphere (~135 km). This suggests that the rising mantle whose partial melting produced the magmas was halted at different depths, different geochemical ‘signatures’ of basalts depending on the pressure of melting. The most interesting outcome, albeit one based on an absence of evidence, is that the very large volcanic gaps along the track are each above much thicker lithosphere (>150 km). At those depths a rising mantle plume would be much less likely to begin melting.
Four million people in and around the Italian city of Naples on the shore of the Tyrrhenian Sea have always lived under a double threat of natural disaster. The one that immediately springs to most people’s mind is the huge volcano Vesuvius that looms over its eastern suburbs, for this was the source of the incandescent pyroclastic flow that overwhelmed Pompeii and Herculaneum in 79 CE. Less familiar outside Italy is a cluster of elliptical volcanic features directly to the west of the city: Campi Flegrei or the Phlegraean Fields. In fact the cluster is part of a vast, dormant caldera, half of which lies beneath the sea centred on the ancient Roman port of Puteoli (modern Pozzuoli). This volcanic collapse structure is about 10 km across; about as large as Vesuvius. Campi Flegrei is famous for its sulfur-rich fumaroles including the mythical crater home of Vulcan the god of fire, Solfatara.
Between 1970 and 1984 the ground around Pozzuoli rose more than 2 metres, which may be evidence that the deep seated magma chamber is inflating. Fears that this might presage an eruption in the near future stems from a curious feature affecting archaeological remains, such as upright pillars in the harbour area of Pozzuoli. At many different levels the stonework is pockmarked by curious holes that are the fossil borings of marine molluscs: at some stage the feet of the pillars descended below sea level. Together with historic records since the Roman era these borings help to establish the local ups and downs of the surface over the last two millennia in considerable detail. From a high of 4 m above sea level when the pillars were erected 194 BCE they slowly subsided to reach sea level around 300 CE when Puteoli ceased to be an important harbour and 4 metres below that around 900 CE. For the last millennium they have slowly risen until in 1538 more than 4 metres of inflation took place very rapidly. That was immediately followed by a small eruption of about 0.02 km3 of magma at Mount Nuovo, to the northeast of another recent crater now occupied by a lake: hence the fear surrounding the uplift in 1970-84. Campi Flegrei has a history of eruptions going back 40 thousand years, including two in the ‘super volcano’ category of 200 and 40 km3 that blanketed vast areas in pyroclastic ash.
One tantalising aspect of the ground inflation and deflation is that each cycle lasts of the order of a thousand years. Another seems to be that magma breaks to the surface very rapidly after a long period of inflation, as if whatever was keeping the magma chamber in a metastable state failed in a brittle fashion. Tiziana Vanorio and Waruntorn Kanitpanyacharoen of Stanford and Chulalonkorn universities in the US and Thailand have come up with a possible reason for such gradual crustal warping in volcanic areas and long-delayed eruption, for which Campi Flegrei is a model case (in fact the oscillations there are unsurpassed). Such long-term bending of the crust suggests abnormally strong rock near the surface. The co-workers analysed borehole cores that penetrated to the depth of small shallow earthquakes – in the metamorphic basement of the area – and found that the zone above the seismically active layer is not only stronger than the basement, but closely resembles a construction material to which Roman architecture owes its longevity (Vanorio, T. & Kanitpanyacharoen, W. 2015. Rock physics of fibrous rocks akin to Roman concrete explains uplifts at Campi Flegrei Caldera. Science, v. 349, p. 617-621).
Roman masons discovered that by mixing young, loose volcanic ash with lime mortar (calcium hydroxide) produced a strong concrete when cured. Specifically, the invention of concrete took place at Pozzuoli itself, using volcanic ash from Campi Flegrei and the product was known as pozzolana. Young ash from an explosive volcano is mainly shards of anhydrous silicate glass, which quickly react with water and calcium hydroxide to produce fibres of hydrous calc-silicate minerals, almost as in conventional cement curing, but without the need for heating limestone and clay to very high temperatures. The strength of pozzolano enabled Roman architects to build the great dome of the Pantheon in Rome, still the world’s largest unreinforced concrete dome. Moreover, the speed with which it sets by exothermic reactions enables its use below sea level. Vanorio and Kanitpanyacharoen found that the strong upper zone beneath Campi Flegrei is almost identical to pozzolano, and suggest that it formed as a result of calcium-rich hydrothermal fluids percolating through young pyroclastic rocks. The calcium derives from metamorphic basement rich in calc-silicate layers through which hot groundwater is driven as a result of heat from the underlying magma chamber. It seems the Campi Flegrei caldera has built its own containing dome. But that is perhaps a mixed blessing: the 1970-84 inflation seems now to be deflating and the flexible carapace may make using ground movements as means of predicting eruptions unreliable.
Is Secret to Roman Concrete in Volcanic Rock?

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