Category Archives: Geochemistry, mineralogy, petrology and volcanology

A ‘recipe’ for Earth’s accretion, without water

The Earth continues to collect meteorites, the vast majority of which are about as old as our planet; indeed many are slightly older. So it has long been thought that Earth originally formed by gravitational accretion when the parental bodies of meteorites were much more abundant and evenly distributed. Meteorites fall in several classes, metallic (irons) and several kinds that contain silicate minerals, some with a metallic component (stony irons) others without, some with blebs or chondrules of once molten material (chondrites) and others that do not (achondrites), and more subtle divisions among these general groups. In the latter half of the 20th century geochemists and cosmochemists became able to compare the chemical characteristics of different meteorite classes with that of the Sun –from its radiation spectrum – and those of different terrestrial rocks – from direct analysis. The relative proportions of elements in chondrites turned out to match those in the Sun – inherited from the gas nebula from which it formed – better than did other classes. The best match with this primitive composition turned out to be the chemistry of carbonaceous chondrites that contain volatile organic molecules and water as well as silicates and sulfides. The average chemistry of one sub-class of carbonaceous chondrites (C1) has been chosen as a ‘standard of standards’ against which the composition of terrestrial rocks are compared in order that they can be assessed in terms of their formative processes relative to one another. For a while carbonaceous chondrites were reckoned to have formed the bulk of the Earth through homogeneous accretion: that is until analyses became more precise at increasingly lower concentrations. This view has shifted …

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.

An example of an E-type Chondrite (from the Ab...

An example of an enstatite chondrite (from the Abee fall) in the Gallery of Minerals at the Royal Ontario Museum. (Photo credit: Wikipedia)

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.

Oceans of magma, Moon formation and Earth’s ‘Year Zero’

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.

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.

Loss of volatile daughter isotopes of Pb produced by the decay schemes of highly refractory isotopes of U and Th would have reset the U-Pb and Th-Pb isotopic systems and therefore the radiogenic ‘clocks’ that depend on them in the same way as melting or high-temperature metamorphism resets the simpler 87Rb-87Sr decay scheme. Each radioactive U isotope has a different decay rate that produces a different Pb isotope daughter (235U Þ 207Pb; 238U Þ 206Pb, so it is possible to devise means of using present-day values of ratios between Pb isotopes, such as 207Pb/206Pb, 206Pb/204Pb and 207Pb/204Pb, to work back to such a ‘closure’ time. In short, that is the approach used by Connelly and Bizzarro. The most complicated bit of that geochemical ruse is estimating values of the ratios for the Earth’s modern mantle and for the Solar system in general – a procedure based on what we can actually measure: lots of mantle-derived basalts and lots of meteorites. Cutting out some important caveats, the result of their model is quite a surprise: ‘Year Zero’ on their account was between 4426 and 4417 Ma years ago, which is astonishingly precise. And it is pretty close to the measured age of the of lunar Highland anorthosites – products of fractional crystallisation of the Moon’s early magma ocean – and also to that of the oldest zircons on Earth. But is also about 60 Ma later than previous estimates

The Connelly and Bizzarro paper follows hard on the heels of another with much the same objective  (Snape, J.F. and 8 others 2016. Lunar basalt chronology, mantle differentiation and implications for  determining the age of the Moon. Earth and Planetary Science Letters, v. 451, p. 149-158. doi.org/10.1016/j.epsl.2016.07.026). Once again omitting a great deal of argument, Snape and colleagues end up with an age for the isotopic resetting of the lunar mantle of 4376 Ma to the nearest 18 Ma; i.e. an age significantly different from that arrived at by Connelly and Bizzarro. So the answer to the question, ‘When was there a vestige of a beginning?’ is, ‘It depends on the model’… Thankfully, neither estimate for ‘Year Zero’ has much bearing on the big, practical questions, such as, ‘When did life form?’, ‘Has there always been plate tectonics?’

More on the origin of the early Solar System and formation of the Earth-Moon system

Salt and Earth’s atmosphere

It is widely known that glacial ice contains a record of Earth’s changing atmospheric composition in the form of bubbles trapped when the ice formed. That is fine for investigations going back about a million years, in particular those that deal with past climate change. Obviously going back to the composition of air tens or hundreds of million years ago cannot use such a handy, direct source of data, but has relied on a range of indirect proxies. These include the number of pores or stomata on fossil plant leaves for CO2, variations in sulfur isotopes for oxygen content and so on. Variation over time of the atmosphere’s content of oxygen has vexed geoscientists a great deal, partly because it has probably been tied to biological evolution: forming by some kind of oxygenic photosynthesis and being essential for the rise to dominance of eukaryotic animals such as ourselves. Its presence or absence also has had a large bearing on weathering and the associated dissolution or precipitation of a variety of elements, predominantly iron. Despite progressively more clever proxies to indicate the presence of oxygen, and intricate geochemical theory through which its former concentration can be modelled, the lack of an opportunity to calibrate any of the models has been a source of deep frustration and acrimony among researchers.

Yet as is often said, there are more ways of getting rid of cats than drowning them in butter. The search has been on for materials that trap air in much the same way as does ice, and one popular, if elusive target has been the bubbles in crystals of evaporite minerals. The trouble is that most halite deposits formed by precipitation of NaCl from highly concentrated brines in evaporating lakes or restricted marine inlets. As a result the bubbles contain liquids that do a grand job of preserving aqueous geochemistry but leave a lot of doubt as regards the provenance of gases trapped within them. For that to be a sample of air rather than gases once dissolved in trapped liquid, the salt needs to have crystallized above the water surface. That may be possible if salt forms from brines so dense that crystals are able to float, or perhaps where minerals such as gypsum form as soil moisture is drawn upwards by capillary action to form ‘desert roses’. A multinational team, led by Nigel Blamey of Brock University in Canada, has published results from Neoproterozoic halite whose chevron-like crystals suggest subaerial formation (Blamey, N.J.F. and 7 others, 2016. Paradigm shift in determining Neoproterozoic atmospheric oxygen. Geology, v. 44, p. 651-654). Multiple analyses of five halite samples from an ~815 Ma-old horizon in a drill core from the Neoproterozoic Canning Basin of Western Australia contained about 11% by volume of oxygen, compared with 25% from Cretaceous salt from China, 20% of late-Miocene age from Italy, and 19 to 22% from samples modern salt of the same type.

Salar de Atacama salt flat in the Chilean puna

Evaporite salts in the Salar de Atacama Chile (credit: Wikipedia)

Although the Neoproterozoic result is only about half that present in modern air, it contradicts results that stem from proxy approaches, which suggest a significant rise in atmospheric oxygenation from 2 to about 18% during the younger Cryogenian and Ediacaran Periods of the Neoproterozoic, when marine animal life made explosive developments at the time of repeated Snowball Earth events. Whether or not this approach can be extended back to the Great Oxygenation Event at around 2.3 Ga ago and before depends on finding evaporite minerals that fit stringent criteria for having formed at the surface: older deposits are known even from the Archaean.

Bury the beast in basalt

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 .
Although this seems a much more beneficial use of well-injection than fracking, the problem is essentially the same as reinjection of carbon dioxide into old oil and gas fields; the high cost. Alternatives might be to spread basaltic or ultramafic gravel over large areas so that it reacts with CO2 dissolved in rainwater or to lay bear fresh rocks of that kind by removal of soil cover.

Kintisch, E., 2016. Underground injections turn carbon dioxide to stone. Science, v. 352, p. 1262-1263.

In a first, Iceland power plant turns carbon emissions to stone. Phys.org

Tungsten isotopes provide a ‘vestige of a beginning’

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.

Artistic impression of the early Earth before Moon formation. (Source: Creative Commons)

Artistic impression of the early Earth before Moon formation. (Source: Creative Commons)

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.

So, when did plate tectonics start up?

Tiny, 4.4 billion year old zircon grains extracted from much younger sandstones in Western Australia are the oldest known relics of the Earth system. But they don’t say much about early tectonic processes. For that, substantial exposures of rock are needed, of which the undisputedly oldest are the Acasta gneisses 300 km north of Yellowknife in Canada’s North West Territories, which have an age of slightly more than 4 Ga. The ‘world’s oldest rock’ has been something of a grail for geologists and isotope geochemists who have combed the ancient Archaean cratons for 5 decades. But since the discovery of metasediments with an age of 3.8 Ga in West Greenland during the 1970s they haven’t made much headway into the huge time gap between Earth’s accretion at 4.54 Ga and the oldest known rocks (the Hadean Eon).

The Deccan Traps shown as dark purple spot on ...

Continental cratons (orange) where very-old rocks are likely to lurk. (credit: Wikipedia)

There have been more vibrant research themes about the Archaean Earth system, specifically the issue of when our planet settled into its modern plate tectonic phase A sprinkling of work on reconstructing the deep structural framework of Archaean relics has convinced some that opposed motion of rigid, brittle plates was responsible for their geological architecture, whereas others have claimed signs of a more plastic and chaotic kind of deformation of the outer Earth. More effort has been devoted to using the geochemistry of all the dominant rocks found in the ancient cratons, seeking similarities with and differences from those of more recent vintage. There can be little doubt that the earliest processes did form crust whose density prevented or delayed it from being absorbed into the mantle. Even the 4.4 Ga zircons probably crystallized from magma that was felsic in composition. Once trapped by buoyancy at the surface and subsequently wrapped around by similarly low density materials continental crust formed as a more or less permanent rider on the Earth’s deeper dynamics. But did it all form by the same kinds of process that we know to be operating today?

Plate tectonics involves the perpetual creation of rigid slabs of basalt-capped oceanic lithosphere at oceanic rift systems and their motions and interactions, including those with continental crust. Ocean floor cools as it ages and becomes hydrated by seawater that enters it. The bulk of it is destined eventually to oppose, head-to-head, the motions of other such plates and to deform in some way. The main driving force for global tectonics begins when an old, cold plate does deform, breaks, bends and drives downwards. Increasing pressure on its cold, wet basaltic top transforms it into a denser form: from a wet basaltic mineralogy (feldspar+pyroxene+amphibole) to one consisting of anhydrous pyroxene and garnet (eclogite) from which watery fluid is expelled upwards. Eclogite’s density exceeds that of mantle peridotite and compels the whole slab of oceanic lithosphere to sink or subduct into the mantle, dragging the younger parts with it. This gravity-induced ‘slab pull’ sustains the sum total of all tectonic motion. The water rising from it induces the wedge of upper mantle above to melt partially, the resulting magma evolves to produce new felsic crust in island arcs whose destiny is to be plastered on to and enlarge older continental masses.

Relics of eclogites and other high-pressure, low-temperature versions of hydrated basalts incorporated into continents bear direct and unchallengeable witness to plate tectonics having operated back to about 800 Ma ago. Before that, evidence for plate tectonics is circumstantial and in need of special pleading. Adversarial to-ing and fro-ing seems to be perpetual, between geoscientists who see no reason to doubt that Earth has always behaved in this general fashion and others who see room for very different scenarios in the distant past. The non-Huttonian tendency suggests an early, more ductile phase when greater radioactive heat production in the mantle produced oceanic crust so fast that when it interacted with other slabs it was hot enough to resist metamorphic densification wherever it was forced down. Faster production of magma by the mantle without slab-pull could have produced a variety of ‘recycling’ turnover mechanisms that were not plate-tectonic.

One thing that geochemists have discovered is that the composition of Archaean continental crust is very different from that produced in later times. In 1985 Ross Taylor and Scott McLennan, then of the Australian National University, hit on the idea of using shales of different ages as proxies for the preceding continental crust from which they had been derived by long erosion. Archaean and younger shales differed in such a way that suggests that after 2.5 Ga (the end of the Archaean) vast amounts of feldspar were extracted from the continent-forming magmas. This left the later Precambrian and Phanerozoic upper crust depleted in the rare-earth element europium, which ended up in a mafic, feldspar-rich lower crust. On the other hand, no such mass fractionation had left such a signature before 2.5 Ga. Another ANU geochemist, now at the University of Maryland, Roberta Rudnick has subsequently carried this approach further, culminating in a recent paper (Tang, M., Chen, K and Rudnick, R.L. 2016. Archean upper crust transition from mafic to felsic marks the onset of plate tectonics. Science, v. 351, p. 372-375). This uses nickel, chromium and zinc concentrations in ancient igneous and sedimentary rocks to track the contribution of magnesium (the ‘ma’ in ‘mafic’) to the early continents. The authors found that between 3.0 to 2.5 Ga continental additions shifted from a dominant more mafic composition to one similar to that of later times by the end of the Archaean. Moreover, this accompanied a fivefold increase in the pace of continental growth. Such a spurt has long been suspected and widely suggested to mark to start of true plate tectonics: but an hypothesis bereft of evidence.

A better clue, in my opinion, came 30 years ago from a study of the geochemistry of actual crustal rocks that formed before and after 2.5 Ga (Martin, H. 1986. Effect of steeper Archean geothermal gradient on geochemistry of subduction-zone magmas. Geology, v. 14, p. 753-756). Martin showed that plutonic Archaean and post-Archaean felsic rocks of the continental crust lie in distinctly different fields on plots of their rare-earth element (REE) abundances. Archaean felsic plutonic rocks show a distinct trend of enrichment in light REE relative to heavy REE as measures of the degree of partial melting decreases, whereas the younger crustal rocks show almost constant, low values of heavy REE/light REE whatever the degree of melting. The conclusion he reached was that while in the post Archaean the source was consistent with modern subduction processes – i.e. partial melting of hydrated peridotite in the mantle wedge above subduction zones – but during the Archaean the source was hydrated, garnet-bearing amphibolite of basaltic composition, in the descending slab of subducted oceanic crust. Together with Taylor and McLennan’s lack of evidence for any fractional crystallization in Archaean continental growth, in contrast to that implicated in Post-Archaean times.

The geochemistry forces geologists to accept that a fundamental change took place in the generation and speed of continental growth at the end of the Archaean, marking a shift from a dominance of melting of oceanic, mafic crust to one where the upper mantle was the main source of felsic, low-density magmas. Yet, no matter how much we might speculate on indirect evidence, whether or not subduction, slab-pull and therefore plate tectonics dominated the Archaean remains an open question.

More on continental growth and plate tectonics

Deccan Trap sprung by bolide?

English: Alvarez and K-T Boundary

Luis and Walter Alvarez at the end-Mesozoic Boundary (credit: Wikipedia)

It was 35 years back that father and son team Luis and Walter Alvarez upset a great many geoscientists by suggesting that a very thin layer of iridium-rich mud that contained glass spherules and shocked mineral grains was evidence for a large meteorite having struck Earth. They especially annoyed palaeontologists because of their claim that it occurred at the very top of the youngest Cretaceous and that the mud was spread far and wide in deep- and shallow-marine stratigraphic sequences and also in those of continental rocks. It marked the boundary between the Mesozoic and Cenozoic Eras and, of course, the demise of the dinosaurs and a great many more, less ‘sexy’ beasts. Luis was a physicist, his son a proper geologist and their co-researchers were chemists. It can hardly be said that they stole anyone’s thunder since the issue of mass extinctions was quiescent, yet their discovery ranks with that of Alfred Wegener; another interloper into the closed-shop geoscientific community. They got the same cold-shoulder treatment, but massive popular acclaim as well, even from a minority of geologists who welcomed their having shaken up their colleagues, 15 years after the last ‘big thing’: plate tectonics. And then the actual site of the impact was found by geophysicists in a sedimentary basin in the Gulf of Mexico off the small town of Chicxulub on the Yucatan peninsula.

Chicxulub impact - artist impression

Chicxulub impact – artist impression (credit: Wikipedia)

As they say, ‘the rest is history’ and a great many geoscientists didn’t just jump but pounced on this potential bandwagon. Central to this activity was the fact that, within error, the ages of the impact, the mass extinction and a vast pile of continental lavas in western India, the Deccan Traps, were more or less the same (around 66 Ma). Flood basalt events are just about as dramatic as mega-impacts because of their sheer scale, of the order of a million cubic kilometres; that they were exuded in a mere million years or so, but in only a few tens of stupendous lava flows; and they are far beyond the direct experience of humans, blurting out only every 30 Ma or so. This periodicity roughly tallies with mass extinctions, great and small, through the Mesozoic. There have been two large bands of enthusiasts engaged in the causality of the end-Mesozoic die-off – the extraterrestrials and the parochialists who favoured a more mundane, albeit cataclysmic snuffing-out. Mass extinctions in general have been repeatedly examined, and in recent years it has become clear that most of those since 250 Ma ago seem to be associated with basalt-flood events and are purely terrestrial in origin. As regards the event that ended the Mesozoic, it has proved difficult to resolve whether to point the finger at the Deccan Traps or the Chicxulub impact. Both might have severely damaged the biosphere in perhaps different ways, so a ‘double whammy’ has become a compromise solution.

The Western Ghat hills at Matheran in Maharash...

Deccan flood basalts forming the Western Ghats in Maharashtra, India (credit: Wikipedia)

Unsurprisingly, a lot of effort from different quarters has gone into charting the progress of the Deccan volcanism. Some dating seemed at one stage to place the bulk of the volcanism significantly before the mass extinction and impact, others had them spot on and there were even signs of an hiatus in eruptions at the critical juncture. The problem was geochronological precision of the argon-argon method of radiometric dating that is most used for rocks of basaltic composition: many labs cannot do better than an uncertainty of 1%, which is ±0.7 Ma for ages around the end of the Mesozoic, not far short of the entire duration of these huge events. Some Deccan samples have now been dated to a standard of ±0.1 Ma by the Ar-Ar lab at the Department of Earth and Planetary Sciences, University of California-Berkeley (Renne, P.R. et al. 2010. State shift in Deccan volcanism at the Cretaceous-Paleogene boundary, possibly induced by impact. Science, v. 350, p. 76-78). The results, between 65.5 to 66.5 Ma, nicely bracket the K/T (now K/Pg) boundary age of 66.04±0.04 Ma. It looks like the double whammy compromise is the hypothesis of choice. But there is more to mere dating.

Renne and colleagues plot the ages against their position in the volcanic stratigraphy of the Deccan Traps in two ways: against the estimated height from base in the pile and against the estimated volume of the erupted materials as it built up – the extent and thickness of successive flows varies quite a lot. The second plot provided a surprise. After the K/Pg event the mean rate of effusion – the limited number of individual flows capped by well-developed soils shows that the build-up was episodic – doubled from 0.4±0.2 to 0.9±0.3 km3 yr-1. Despite the much larger uncertainty in the extent and volume of individual lava Formations than that of their ages, this is clearly significant. Does it imply that the Chicxulub impact somehow affected the magma production from, the mantle plume beneath the Deccan? It had been suggested early in the debate that the antipodean position of the lava field relative to that of Chicxulub may indicate that the huge seismicity from the impact triggered the Deccan magma production. Few accepted that possibility when it first appeared. However, Renne and co. do think it deserves another look, at least at the possibility of some linked effect on the magmatism. Perhaps the magma chamber was somehow enlarged by increased global seismicity; other chambers could have been added; magma might have been ‘pumped’ out more efficiently, or a combination of such effects. The ‘plumbing’ of flood basalt piles is generally hidden, but huge dyke swarms in Precambrian times have been suggested as feeders to long-eroded flood basalts. Seismicity of the scale produced by asteroid impacts can do a lot of damage. The Chicxulub impactor at around 10 km diameter would have carried energy a million times greater than that of the largest thermonuclear bomb, equivalent to an earthquake of Magnitude 12.4 that would have been a thousand times more powerful than the largest recorded earthquake with tectonic causes. Extensional faulting sourced in this fashion in the Deccan area may have increased the pathways along which magma might blurt out.

Duncan, R. 2015. Deadly combination. Nature, v. 527, p. 172-173.

Continental hot-spot track in eastern Australia

cosgrove volcano track shown on map of australia

The Cosgrove volcanic track on a natural-colour image mosaic of Australia (credit: Drew Whitehouse, NCI National Facility VizLab)

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.

Roman concrete restrains magma

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.

The Bay of Naples with Vesuvius to the east of the city and Campi Flegrei to the west. (credit: Google Earth)

The Bay of Naples with Vesuvius to the east of the city and Campi Flegrei to the west. (credit: Google Earth)

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).

Deutsch: Pozzuoli, Macellum

Mollusc-bored pillars in the Macellum (indoor market) of Pozzuoli (credit: Wikipedia)

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.

Intérieur du panteon à Rome

Interior view of the dome of the Pantheon in Rome (credit: Wikipedia)

How far has geochemistry led geology?

 

Granite pmg ss 2006

Thin section of a typical granite: clear white and grey grains are quarts (silica); striped black and white is feldspar; coloured minerals are micas (credit: Wikipedia)

In the Solar System the Earth is unique in having a surface split into two distinct categories according to their relative elevation; one covered by water, the other not. More than 60% of its surface – the ocean basins – falls between 2 to 11 km below sea level with a mean around 4 to 5 km deep. A bit less than 40% – land and the continental shelves – stands higher than 1 km below sea level up to almost 9 km above, with a mean around 1 km high. Between 1 and 2 km below sea level is represented by only around 3 % of the surface area. This combined hypsography and wetness is reckoned to have had a massive bearing on the course of climate and biological evolution, as far as allowing our own emergence. The Earth’s bimodal elevation stems from the near-surface rock beneath each division having different densities: continental crust is less dense than its oceanic counterpart, and there is very little crustal rock with an intermediate density. Gravitational equilibrium ensures that continents rise higher than oceans. That continents were underpinned mainly by rocks of granitic composition and density, roughly speaking, was well known by geologists at the close of the 19th century. What lay beneath the oceans didn’t fully emerge until after the advent of plate tectonics and the notion of simple basaltic magmas pouring out as plates became detached.

In 1915 Canadian geologist Norman Levi Bowen resolved previously acquired knowledge of the field relations, mineralogy and, to a much lesser extent, the chemistry of igneous rocks, predominantly those on the continents in a theory to account for the origin of continents. This involved a process of distillation or fractionation in which the high-temperature crystallisation of mafic (magnesium- and iron-rich) minerals from basaltic magma left a residual melt with lower Mg and Fe, higher amounts of alkalis and alkaline earth elements and especially enriched in SiO2 (silica). A basalt with ~50% silica could give rise to rocks of roughly granitic composition (~60% SiO2) – the ‘light’ rocks that buoy-up the continental surface – through Bowen’s hypothetical fractional crystallisation. Later authors in the 1930s, including Bowen’s teacher Reginald Aldworth Daly, came up with the idea that granites may form by basalt magma digesting older SiO2-rich rocks or by partially melting older crustal rocks as suggested by British geologist Herbert Harold Read. But, of course, this merely shifted the formation of silica-rich crust further back in time

A great deal of field, microscope and, more recently, geochemical lab time has been spent since on to-ing and fro-ing between these hypotheses, as well as on the petrology of basaltic magmas since the arrival of plate theory and the discovery of the predominance of basalt beneath ocean floors. By the 1990s one of the main flaws seen in Bowen’s hypothesis was removed, seemingly at a stroke. Surely, if a basalt magma split into a dense Fe- Mg-rich cumulate in the lower crust and a less dense, SiO2-rich residual magma in the upper continental crust the bulk density of that crust ought to remain the same as the original basalt. But if the dense part somehow fell back into the mantle what remained would be more able to float proud. Although a neat idea, outside of proxy indications that such delamination had taken place, it could not be proved.

Since the 1960s geochemical analysis has became steadily easier, quicker and cheaper, using predominantly X-ray fluorescence and mass-spectrometric techniques. So geochemical data steadily caught up with traditional analysis of thin sections of rock using petrological microscopes. Beginning in the late 1960s igneous geochemistry became almost a cottage industry and millions of rocks have been analysed. Recently, about 850 thousand multi-element analyses of igneous rocks have been archived with US NSF funding in the EarthChem library. A group from the US universities of Princeton, California – Los Angeles and Wisconsin – Madison extracted 123 thousand plutonic and 172 thousand volcanic igneous rocks of continental affinities from EarthChem to ‘sledgehammer’ the issue of continent formation into a unified theory (Keller, C.B. et al. 2015. Volcanic-plutonic parity and the differentiation of the continental crust. Nature, v. 523, p. 301-307).

In a nutshell, the authors compared the two divisions in this vast data bank; the superficial volcanic with the deep-crustal plutonic kinds of continental igneous rock. The gist of their approach is a means of comparative igneous geochemistry with an even longer pedigree, which was devised in 1909 by British geologist Alfred Harker. The Harker Diagram plots all other elements against the proportionally most variable major component of igneous rocks, SiO2. If the dominant process involved mixing of basalt magma with or partial melting of older silica-rich rocks such simple plots should approximate straight lines. It turns out – and this is not news to most igneous geochemists with far smaller data sets – that the plots deviate considerably from straight lines. So it seems that old Bowen was right all along, the differing deviations from linearity stemming from subtleties in the process of initial melting of mantle to form basalt and then its fractionation at crustal depths. Keller and colleagues found an unexpected similarity between the plutonic rocks of subduction-related volcanic arcs and those in zones of continental rifting. Both record the influence of water in the process, which lowers the crystallisation temperature of granitic magma so that it freezes before the bulk can migrate to the surface and extrude as lava. Previously. rift-related magmas had been thought to be drier than those formed in arcs so that silica-rich magma should tend to be extruded.

But there is a snag, the EarthChem archive hosts only data from igneous rocks formed in the Phanerozoic, most being less than 100 Ma old. It has long been known that continental crust had formed as far back as 4 billion years ago, and many geologists believe that most of the continental crust was in place by the end of the Precambrian about half a billion years ago. Some even reckon that igneous process may have been fundamentally different before 3 billion years ago(see: Dhuime, B., Wuestefeld, A. & Hawkesworth, C. J. 2015. Emergence of modern continental crust about 3 billion years ago.  Nature Geoscience, v. 8, p.552–555). So big-science data mining may flatter to deceive and leave some novel questions unanswered .