Month: June 2014

Nickel, life and the end-Permian extinction

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The greatest mass extinction of the Phanerozoic closed the Palaeozoic Era at the end of the Permian, with the loss of perhaps as much as 90% of eukaryote diversity on land and at sea. It was also over very quickly by geological standards, taking a mere 20 thousand years from about 252.18 Ma ago. There is no plausible evidence for an extraterrestrial cause, unlike that for the mass extinction that closed the Mesozoic Era and the age of dinosaurs. Almost all researchers blame one of the largest-ever magmatic events that spilled out the Siberian Traps either through direct means, such as climate change related to CO2, sulfur oxides or atmospheric ash clouds produced by the flood volcanism or indirectly through combustion of coal in strata beneath the thick basalt pile. So far, no proposal has received universal acclaim. The latest proposal relies on two vital and apparently related geochemical observations in rocks around the age of the extinctions (Rothman, D.H. et al. 2014. Methanogenic burst in the end-Permian carbon cycle. Proceedings of the National Academy of the United States, v. 111, p. 5462-5467).

Siberian flood-basalt flows in Putorana, Taymyr Peninsula. (Credit: Paul Wignall; Nature http://www.nature.com/nature/journal/v477/n7364/fig_tab/477285a_F1.html)
Siberian flood-basalt flows in Putorana, Taymyr Peninsula. (Credit: Paul Wignall; Nature http://www.nature.com/nature/journal/v477/n7364/fig_tab/477285a_F1.html)

In the run-up to the extinction carbon isotopes in marine Permian sediments from Meishan, China suggest a runaway growth in the amount of inorganic carbon (in carbonate) in the oceans. The C-isotope record from Meishan shows episodes of sudden major change (over ~20 ka) in both the inorganic and organic carbon parts of the oceanic carbon cycle. The timing of both ‘excursions’ from the long-term trend immediately follows a ‘spike’ in the concentration of the element nickel in the Meishan sediments. The Ni almost certainly was contributed by the massive outflow of basalt lavas in Siberia. So, what is the connection?

Some modern members of the prokaryote Archaea that decompose organic matter to produce methane have a metabolism that depends on Ni, one genus being Methanosarcina that converts acetate to methane by a process known as acetoclastic methanogenesis. Methanosarcina acquired this highly efficient metabolic pathway probably though a sideways gene transfer from Bacteria of the class Clostridia; a process now acknowledged as playing a major role in the evolution of many aspects of prokaryote biology, including resistance to drugs among pathogens. Molecular-clock studies of the Methanosarcina genome are consistent with this Archaea appearing at about the time of the Late Permian. A burst of nickel ‘fertilisation’ of the oceans may have resulted in huge production of atmospheric methane. Being a greenhouse gas much more powerful than CO2, methane in such volumes would very rapidly have led to global warming. Before the Siberian Traps began to be erupted nickel would only have been sufficiently abundant to support this kind of methanogen around ocean-floor hydrothermal springs. Spread globally by eruption plumes, nickel throughout the oceans would have allowed Methanosarcina or its like to thrive everywhere with disastrous consequences. Other geochemical processes, such as the oxidation of methane in seawater, would have spread the influence of the biosphere-lithosphere ‘conspiracy’. Methane oxidation would have removed oxygen from the oceans to create anoxia that, in turn, would have encouraged other microorganisms that reduce sulfate ions to sulfide and thereby produce toxic hydrogen sulfide. That gas once in the atmosphere would have parlayed an oceanic ‘kill mechanism’’ into one fatal for land animals.

There is one aspect that puzzles me: the Siberian Traps probably involved many huge lava outpourings every 10 to 100 ka while the magma lasted, as did all other flood basalt events. Why then is the nickel from only such eruption preserved in the Meishan sediments, and if others are known from marine sediments is there evidence for other such methanogen ‘blooms’ in the oceans?

What’s happening at the core-mantle boundary?

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The lithosphere that falls into the mantle at subduction zones must end up somewhere in the deep Earth; the question is, where and what happens to it. There are hints from seismic tomography of the mantle that such slabs penetrate as deep as the boundary between the lowermost mantle and the molten outer core. The lithosphere’s two components, depleted mantle and oceanic crust, are compositionally quite different, being peridotitic and basaltic, so each is likely to be involved different petrological processes. As regards the physics, since seismic activity ceases below a depth of about 700 km neither entity behaves in a brittle fashion in the lower mantle. Such ductile materials might even pile up in the manner of intestines on the lithological equivalent of the abattoir floor; Bowels of the Earth as John Elder had it in his book of the same name.

Sketch of the lower 1000 km of the Earth’s mantle (credit: Williams, Q. 2014. Deep mantle matters. Science, v. 344, p. 800-801)

Pressure would make these recycled components mineralogically different, as indeed a relative light squeeze does in the upper mantle, where cold wet basalts become dry and denser eclogites thereby pulling more lithosphere down Wadati and Benioff’s eponymous zones to drive plate tectonics. Decades old experiments at lower-mantle pressures suggest that mantle minerals recompose from olivine with a dash of pyroxene to a mixture of more pressure-resistant iron-magnesium oxide and perovskite ((Mg,Fe)SiO3). Experiments in the early 21st century, under conditions at depths below 2600 km, revealed that perovskite transforms at the very bottom of the mantle (the D” zone) into layers of magnesium plus iron, silicon and oxygen. This is provisionally known as ‘post-perovskite’. The experiments showed that the transition releases heat. So, should oceanic lithosphere descend to the D” zone, it would receive an energy ‘kick’ and its temperature would increase. Conversely, if D”-zone materials rose to the depth of the perovskite to post-perovskite transition they would become less dense: a possible driver for deep-mantle plumes.

Now a new iron-rich phase stable in the bottom 1000 km of the mantle has emerged from experiments, seeming to result from perovskite undergoing a disproportionation reaction (Zhang, L. And 11 others 2014. Disproportionation of (Mg,Fe)SiO3 perovskite in Earth’s deep mantle. Science, v. 344, p. 877-882). In the same issue of Science other workers using laser-heated diamond anvils have revealed that, despite the huge pressures, basaltic rock may melt at temperatures considerably below the solid mantle’s ambient temperature (Andrault, D. et al. 2014. Melting of subducted basalt at the core-mantle boundary. Science, v. 344, p. 892-895). Both studies help better understand the peculiarities of the deepest mantle that emerge from seismic tomography (Williams, Q. 2014. Deep mantle matters. Science, v. 344, p. 800-801).

Huge blocks with reduced S-wave velocities that rise above the D” zone sit beneath Africa and the Pacific Ocean. There are also smaller zones at the core-mantle boundary (CMB) with shear-wave velocities up to 45% lower than expected. These ultralow-velocity zones (ULVZs) probably coincide with melting of subducted oceanic basalts, but the magma cannot escape by rising as it would soon revert to perovskite. Yet, since ultramafic compositions cannot melt under such high pressures the ULVSs indirectly show that subduction does descend to the CMB. Seismically defined horizontal layering in the D” zone thus may result from basaltic slabs whose ductility has enabled them to fold like sheets of lasagne as the reach the base of the mantle. Development of variants of the laser-heated diamond anvil set-up seem likely to offer insights into our own world’s ‘digestive’ system at a far lower cost and with vastly more relevance than the growing fad for speculating on Earth-like planets that the current ‘laws’ of physics show can never be visited and on ‘exobiology’ that cannot proceed further than the extremes of the Earth’s near-surface environment and the DNA double helix.

Year Zero: the giant-impact hypothesis

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On close examination, the light-coloured Highlands of the Moon look remarkably like an old sign by a North American road through hunting country: they are pocked by impact craters of every size. More than that, a lengthy period of bombardment is signified by signs that the craters themselves are cratered to form a chaotic landscape dominated by interlocking and overlapping circular feature. In contrast the dark basaltic plains, called maria (seas), are pretty smooth albeit with some craters. They are clearly much younger than the Highlands. The discovery by Apollo astronauts that the older lunar Highlands are made almost exclusively of calcic plagioclase feldspar was a major surprise, requiring an astonishing event to explain them. Such anorthosites may form by flotation of low-density feldspar from a cooling and crystallising basaltic magma. Yet to form the bulk of the Moon’s early crust from such materials requires not simply a deep magma chamber, but literally an ocean of molten material at least 200 km deep. The anorthosites also turned out to be far older than the oldest rocks on Earth, close to 4.5 billion years. The most likely explanation seemed to be that the melting resulted from a gargantuan collision between two protoplanets, the Earth’s forebear and another now vanished. This would have melted and partially vaporised both bodies. After this discovery the Moon was widely believed to have formed from liquid and vaporised rock flung into orbit around what became the Earth.

Artist’s depiction of a collision between two planetary bodies likely to have formed the Moon (Credit: Wikipedia)

Such a catastrophic model for joint formation of the Earth and Moon shortly after planets of the Solar System had formed is hard to escape, but it carries two major puzzles. First, Earth and Moon seem to have very similar, indeed almost the same chemistry: So what happened to the colliding planet? If it had been identical in composition to the proto Earth there is no problem, but a different composition would surely have left some detectable trace in a Moon-Earth geochemical comparison. Initial models of the collision suggested that the other planet (dubbed Theia) was about the size of Mars and should have contributed 70 to 90% of the lunar mass: the Moon-Earth geochemical difference should have been substantial The second issue raised in the early days of the hypothesis was that since the Moon seemed to be almost totally dry (at least, the first rock analyses suggested that), then how come the Earth had retained so much water?

For decades, after an initial flurry of analyses, the Apollo samples remained in storage. Only in the last 10 years or so, when the need to gee-up space exploration required some prospect of astronauts one more to be sent beyond Earth orbit, have the samples been re-examined. With better analytical tools, the first puzzle was resolved: lunar rocks do contain measurable amounts of water, so the impact had not entirely driven off volatiles from the Moon. The bulk geochemical similarity was especially puzzling for the isotopes of oxygen. Meteorites of different types are significantly ear-marked by their relative proportions of different oxygen isotopes, signifying to planetary scientists that each type formed in different parts of the early Solar System; a suggestion confirmed by the difference between those in meteorites supposedly flung from Mars and terrestrial oxygen isotope proportions. A clear target for more precise re-examination of the lunar samples, plus meteorites reckoned to have come from the Moon, is therefore using vastly improved mass spectrometry to seek significant isotopic differences (Harwartz, D. et al. 2014. Identification of the giant impactor Theia in lunar rocks. Science, v. 344, p. 1146-1150). It turns out that there is a 12 ppm difference in the proportion of 17Oin lunar oxygen, sufficient to liken Theia’s geochemistry to that of enstatite chondrites. However, that difference may have arisen by the Earth, once the Moon had formed, having attracted a greater proportion of carbonaceous-chrondrite material during the later stages of planetary accretion by virtue of its much greater gravitational attraction. That would also account for the much higher volatile content of the Earth.

The new data do help to support the giant-impact hypothesis, but still leave a great deal of slack in the big questions: Did Theia form in a similar orbit around the Sun to that of Earth; was the impact head-on or glancing; how fast was the closure speed; how big was Theia and more besides? If Theia had roughly the same mass as the proto-Earth then modelling suggests that about half the mass of both Moon and Earth would be made of Theia stuff, giving the Moon and post-impact Earth much the same chemistry, irrespective of where Theia came from. Were William of Ockham’s ideas still major arbiters in science, then his Razor would suggest that we stop fretting about such details. But continuing the intellectual quest would constitute powerful support for a return to the Moon and more samples…

Fracking in the UK; will it happen?

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Whether or not one has read the Tractatus Logico-Philosophicus of Ludwig Wittgenstein, there can be little doubt that one of his most famous quotations can be applied to much of the furore over hydraulic fracturing (fracking) of hydrocarbon-rich shale in south-eastern Britain: ‘Whereof one cannot speak, one must remain silent’ (more pithily expressed by Mark Twain as ‘Better to remain silent and be thought a fool than to speak and remove all doubt’). A press release by the British Geological Survey  in late May 2014 caused egg to appear on the shirts of both erstwhile ‘frackmeister’ David Cameron (British Prime Minister) and anti-fracking protestors in Sussex. While there are oil shales beneath the Weald, these Jurassic rocks have never reached temperatures sufficient to generate any significant gas reserves (see: Upfront, New Scientist, 31 May 2014 issue, p. 6). Yet BGS estimate the oil shales to contain a total of 4.4 billion barrels of oil. That might sound a lot, but the experience of shale fracking companies in the US is that, at best, only about 5% can be recovered and, in cases that are geologically similar to the Weald, as little as 1% might be expected. Between 44 and 220 million barrels is between two and six months’ worth of British oil consumption; and that is only if the entire Wealden shales are fracked.

Areas where petroleum-rich shales occur at the surface in Britain. (credit: British Geological Survey)
Areas where petroleum-rich shales occur at the surface in Britain. (credit: British Geological Survey)

Why would any commercial exploration company, such as Cuadrilla, go to the trouble of drilling wells, even of an ‘exploratory nature’, for such meager potential returns? Well, when there is sufficient hype, and the British Government has gushed in this context for a few years, bigger fish tend to bite and cash flows improve. For instance, Centrica the owner of British Gas forked out $160 million to Cuadrilla in June 2013 for a quarter share in the well-publicised licence area near Blackpool in Lancashire; the grub stake to allow Cuadrilla to continue exploration in exchange for 25% of any profit should commercial quantities of shale-gas be produced.

Sedimentary rock sequences further north in Britain whose geological evolution buried oil shales more deeply are potential gas producers through fracking; an example is the Carboniferous Bowland Shale beneath the Elswick gasfield in west Lancashire, targeted by Cuadrilla. Far greater potential may be present in a large tract of the Pennine hills and lowlands that flank them where the Bowland Shale occurs at depth.

Few people realize just how much detail is known about what lies beneath their homes apart from maps of surface geology. That is partly thanks to BGS being the world’s oldest geological survey (founded in 1835) and partly the sheer number of non-survey geologists who have prowled over Britain for 200 years or more and published their findings. Legally, any excavation, be it an underground mine, a borehole or even the footings for a building, must be reported to BGS along with whatever geological information came to light as a result. The sheer rarity of outcropping rock in Britain is obvious to everyone: a legacy of repeated glaciation that left a veneer of jumbled debris over much of the land below 500m that lies north of the northern outskirts of the London megalopolis. Only highland areas where glacial erosion shifted mullock to lower terrains have more than about 5% of the surface occupied by bare rock. Of all the data lodged with BGS by far the most important for rock type and structure at depth are surveys that used seismic waves generated by vibrating plates deployed on specialized trucks. These and the cables that connected hundreds of detectors were seen along major and minor roads in many parts of Britain during the 1980s during several rounds of licenced onshore exploration for conventional petroleum resources. That the strange vehicles carried signs saying Highway Maintenance lulled most people apart from professional geologists as regards their actual purpose. Over 75 thousand kilometers of seismic sections that penetrated thousands of metres into the Earth now reside in the UK Onshore Geophysical Library (an Interactive Map at UKOGL allows you to see details of these surveys, current areas licenced for exploration and the locations of various petroleum wells).

Seismic survey lines in northern England (green lines) from the interactive map at the UK Onshore Geophysical Library
Seismic survey lines in northern England (green lines) from the interactive map at the UK Onshore Geophysical Library

Such is the detail of geological knowledge that estimates of any oil and gas, conventional or otherwise, residing beneath many areas of Britain are a lot more reliable than in other parts of the world which do not already have or once had a vibrant petroleum industry. So you can take it that when the BGS says there is such and such a potential for oil or gas beneath this or that stretch of rural Britain they are pretty close to the truth. Yet it is their raw estimates that are most often publicized; that is, the total possible volumes. Any caveats are often ignored in the publicity and hype that follows such an announcement. BGS recently announced that as much as 38 trillion cubic metres of gas may reside in British shales, much in the north of England. There followed a frenzy of optimism from Government sources that this 40 years’ worth of shale gas would remove at a stroke Britain’s exposure to the world market of natural gas, currently dominated by Russia, and herald a rosy economic future to follow the present austerity similar to the successes of shale-gas in North America. Equally, there has been fear of all kinds of catastrophe from fracking on our ‘tight little island’ especially amongst those lucky enough not to live in urban wastelands. What was ignored by both tendencies was reality. In the US, fracking experience shows that only 10% at most of the gas in a fractured shale can be got out; even the mighty Marcellus Shale of the NE US underlying an area as big as Britain can only supply 6 years of total US gas demand. Britain’s entire shale-gas endowment would serve only 4 years of British gas demand.

To tap just the gas in the upper part of the Bowland basin would require 33 thousand fracking wells in northern Britain. Between 1902 and 2013 only 19 onshore petroleum wells were drilled here in an average year. To make any significant contribution to British energy markets would require 100 per annum at a minimum. Yet, in the US, the flow rate from fracked wells drops to a mere zephyr within 3 years. Fracking on a large scale may well never happen in Britain, such are the largely unstated caveats. But the current hype is fruitful for speculation that it will, and that can make a lot of cash sucked in by the prospect – without any production whatsoever.

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