Geochemistry – Earth-logs

Early land plants and oceanic extinctions

Published on November 16, 2022 by zooks777Leave a comment

In September 2022 Earth-logs highlighted how greening of the continents affected the composition of the continental crust. It now seems that was not the only profound change that the first land plants wrought on the Earth system. Beginning in the Silurian, the spread of vegetation swept across the continents during the Devonian Period. From a height of less than 30 cm among the earliest species by the Late Devonian the stature of plants went through a large increase with extensive forests of primitive tree-sized conifers, cycads, horsetails and sporiferous lycopods up to 10 m tall. Their rapid evolution and spread was not hampered by any herbivores. It was during the Devonian that tetrapod amphibians emerged from the seas, probably feeding on burgeoning terrestrial invertebrates. The Late Devonian was marked by five distinct episodes of extinction, two of which comprise the Devonian mass extinction: one of the ‘Big Five’. This affected both marine and terrestrial organisms. Neither flood volcanism nor extraterrestrial impact can be linked to the extinction episodes. Rather they marked a long drawn-out period of repeated environmental stress.

Phytoplankton bloom off the east coast of Scotland ‘fertilised’ by effluents carried by the Tay and Forth estuaries.

One possibility is that a side effect of the greening of the land was the release of massive amounts of nutrients to the seas that would have resulted in large-scale blooms of phytoplankton whose death and decay depleted oxygen levels in the water column. That is a process seen today where large amounts of commercial fertilisers end up in water bodies to result in their eutrophication. Matthew Smart and others from Indiana University-Purdue University, USA and the University of Southampton, UK, geochemically analysed Devonian lake deposits from Greenland and Scotland to test this hypothesis (Smart, M.S. et al. 2022. Enhanced terrestrial nutrient release during the Devonian emergence and expansion of forests: Evidence from lacustrine phosphorus and geochemical records. Geological Society of America Bulletin, v. 134, early release article; DOI: 10.1130/B36384.1).

Smart et al. show that in the Middle and Late Devonian the lacustrine strata show cycles in their abundance of phosphorus (P an important plant nutrient) that parallel evidence for wet and dry cycles in the lacustrine basins. The cycles show that the same phosphorus abundance patterns occurred at roughly the same times at five separate sites. This may suggest a climatic control forced by changes in Earth’s orbital behaviour, similar to the Milankovich Effect on the Pleistocene climate and at other times in Phanerozoic history. The wet and dry intervals show up in the changing ratio between strontium and copper abundances (Sr/Cu): high values signify wet conditions, low suggesting dry. The wet periods show high ratios of rubidium to strontium (Rb/Sr) that suggest enhanced weathering, while dry periods show the reverse – decreased weathering.

When conditions were dry and weathering low, P built up in the lake sediments, whereas during wet conditions P decreases; i.e. it was exported from the lakes, presumably to the oceans. The authors interpret the changes in relation to the fate of plants under the different conditions. Dry periods would result in widespread death of plants and their rotting, which would release their P content to the shallowing, more stagnant lakes. When conditions were wetter root growth would have increased weathering and more rainfall would flush P from the now deeper and more active lake basins. The ultimate repository of the sediments and freshwater, the oceans, would therefore be subject to boom and bust (wet and dry) as regards nutrition and phytoplankton blooms. Dead phytoplankton, in turn, would use up dissolved oxygen during their decay. That would lead to oceanic anoxia, which also occurred in pulses during the Devonian, that may have contributed to animal extinction.

See also: Linking mass extinctions to the expansion and radiation of land plants, EurekaAlert 10 November 2022; Mass Extinctions May Have Been Driven by the Evolution of Tree Roots, SciTechDaily, 14 November 2022.

Earliest plate tectonics tied down?

Published on March 15, 2020March 12, 2020 by zooks7771 Comment

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

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

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

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

Closure for the K-Pg extinction event?

Published on January 28, 2020February 10, 2020 by zooks777Leave a comment

Anyone who has followed the saga concerning the mass extinction at the end of the Cretaceous Period (~66 Ma ago) , which famously wiped out all dinosaurs except for the birds, will know that its cause has been debated fiercely over four decades. On the one hand is the Chicxulub asteroid impact event, on the other the few million years when the Deccan flood basalts of western India belched out gases that would have induced major environmental change across the planet. Support has swung one way or the other, some authorities reckon the extinction was set in motion by volcanism and then ‘polished-off’ by the impact, and a very few have appealed to entirely different mechanism lumped under ‘multiple causes’. One factor behind the continuing disputes is that at the time of the Chicxulub impact the Deccan Traps were merrily pouring out Disentanglement hangs on issues such as what actual processes directly caused the mass killing. Could it have been starvation as dust or fumes shut down photosynthesis at the base of the food chain? What about toxic gases and acidification of ocean water, or being seared by an expanding impact fireball and re-entering incandescent ejecta? Since various lines of evidence show that the late-Cretaceous atmosphere had more oxygen that today’s the last two may even have set the continents’ vegetation ablaze: there is evidence for soots in the thin sediments that mark the K-Pg boundary. The other unresolved issue is timing: of volcanogenic outgassing; of the impact, and of the extinction itself. A new multi-author, paper may settle the whole issue (Hull, P.M and 35 others 2020. On impact and volcanism across the Cretaceous-Paleogene boundary. Science, v. 367, p. 266-272; DOI: 10.1126/science.aay5055).

K-Pg oxygen — Marine temperature record derived from δ18O and Mg/Ca ratios spanning 1.5 Ma that includes the K-Pg boundary: the bold brown line shows the general trend derived from the data points (Credit: Hull et al. 2020; Fig 1)

The multinational team approached the issue first by using oxygen isotopes and the proportion of magnesium relative to calcium (Mg/Ca ratio) in fossil marine shells (foraminifera and molluscs) in several ocean-floor sediment cores, through a short interval spanning the last 500 thousand years of the Cretaceous and the first million years of the Palaeocene. The first measures are proxies for seawater temperature. The results show that close to the end of the Cretaceous temperature rose to about 2°C above the average for the youngest Cretaceous (the Maastrichtian Age; 72 to 66 Ma) and then declined. By the time of the mass extinction (66 Ma) sea temperature was back at the average and then rose slightly in the first 200 ka of Palaeocene to fall back to the average at 350 ka and then rose slowly again.

Changes in carbon isotopes (δ13C) of bulk carbonate samples from the sediment cores (points) and in deep-water foraminifera (shaded areas) across the K-Pg boundary. (Credit: Hull et al. 2020; Fig 2A)

The second approach was to look in detail at carbon isotopes (δ¹³C) – a measure of changes in the marine carbon cycle – and oxygen isotopes (δ¹⁸O) in deep water foraminifera and bulk carbonate from the sediment cores, in comparison to the duration of Deccan volcanism (66.3 to 65.4 Ma). The δ¹³C measure from bulk carbonate stays roughly constant in the Maastrichtian, then falls sharply at 66 Ma. The δ¹³C of the deep water forams rises to a peak at 66 Ma. The δ¹⁸O measure of temperature peaks and declines at the same times as it does for the mixed fossils. Also examined was the percentage of coarse sediment grains in the muds from the cores. That measure is low during the Maastrichtian and then rises sharply at the K-Pg boundary.

Since warming seems almost certainly to be a reflection of CO₂ from the Deccan (50 % of total Deccan outgassing), the data suggest not only a break in emissions at the time of the mass extinction but also that by then the marine carbon system was drawing-down its level in air. The δ¹³C data clearly indicate that the ocean was able to absorb massive amounts of CO₂ at the very time of the Chicxulub impact and the K-Pg boundary. Flood-basalt eruption may have contributed to the biotic aftermath of the extinction for as much as half a million years. The collapse in the marine fossil record seems most likely to have been due to the effects of the Chicxulub impact. A third study – of the marine fossil record in the cores – undertaken by, presumably, part of the research team found no sign of increased extinction rates in the latest Cretaceous, but considerable changes to the marine ecosystem after the impact. It therefore seems that the K-Pg boundary impact ‘had an outsized effect on the marine carbon cycle’. End of story? As with earlier ‘breaks through’; we shall see.

See also: Morris, A. 2020 Earth was stressed before dinosaur extinction (Northwestern University)

How far has geochemistry led geology?

Published on July 16, 2015 by zooks7774 Comments

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 19^th 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 .

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