A Lower Jurassic environmental crisis

Curiously, one of the largest environmental disruptions during the Phanerozoic Eon (i.e. since 541 Ma ago) does not stand out in the way that the ‘Big Five’ mass extinctions do. Each of them killed off between 70 and 95% of all marine species. The Jurassic was a period of biological recovery from the End-Triassic extinction 201 Ma ago. Throughout its ~50 Ma duration extinction rates were below the average for the Phanerozoic, and they remained relatively low until the K-Pg mass extinction that drew the Mesozoic Era to a close at 66 Ma. Nevertheless, there were significant extinctions, such as the demise of several lineages of herbivorous dinosaurs towards the end of the Early Jurassic followed by the rise of the familiar, long-necked variety of eusauropods. Marine organisms that secreted hard parts made of calcium carbonate also experienced a collapse then. From time to time during the Jurassic and Cretaceous Periods the oceans lost a great deal of dissolved oxygen, increasing the chances of organic carbon being buried in marine sediments. Such oceanic anoxia resulted in the widespread deposition of hydrocarbon source rocks in the form of black bituminous muds. Overall, both the Jurassic and Cretaceous experienced  greenhouse climatic conditions, with  atmospheric CO2 levels rising to almost 3000 ppm and oxygen levels significantly lower than the modern 21%. Sea levels rose by up to 200 metres, thought to be due to fast sea-floor spreading and large areas of warm, buoyant oceanic lithosphere.

A notable ocean-anoxia event took place during the Lower Jurassic, around 183 Ma ago at the start of the Toarcian Age. This stratigraphic level was penetrated by a 1.5 km borehole sunk in 2015-2016 at Mochras in North Wales, UK, on the shore of Cardigan Bay. The core provided the thickest and most complete record ever recovered for this event, and has been analysed in exquisite detail using many techniques. The most revealing data have been published by a multinational team led by scientists from Trinity College, Dublin (Ruhl, M. et al. 2022. Reduced plate motion controlled timing of Early Jurassic Karoo-Ferrar large igneous province volcanism. Science Advances, v. 8, article eabo0866; DOI: 10.1126/sciadv.abo0866).

Plate boundaries around Gondwanaland and the Karoo-Ferrar large igneous province in the Early Jurassic (small yellow dots show dated localities) . Large pink dots: positions of Tristan de Cunha and Bouvet hotspots at the time (Credit: Ruhl et al. Fig 1A)

At the start of the Toarcian (183.7 Ma) the 187Os/186Os ratio of the samples begins to rise from 0.3 to almost 0.8 to fall back to 0.3 by 180.8 Ma. Osmium isotopes are a measure of continental weathering, and this ‘excursion’ surely signifies significant global warming and increases in atmospheric humidity and acidity that broke down rocks at the continental surface. Over the same period δ13C rises, decreases to by far the lowest value in the Lower Jurassic, rises again to gradually fall back. The start of the Toarcian seems to have experienced a major release of carbon then a profound sequestration of organic carbon, presumably through burial of dead organisms in the black mudstones that signify anoxic conditions. Remarkably, the 95 m thick Toarcian black-mudstone sequence also reveals a tenfold increase in its content of the element mercury, from 20 to 200 parts per billion (ppb), peaking at the same time (~182.8 Ma) as the most negative δ13C value was reached: the acme of carbon sequestration. A coincidence of massive organic carbon burial and increased mercury in marine sediments also happened at the time of the end-Permian mass extinction, although that does not necessarily imply exactly the same mechanism.

The early Toarcian geochemical trends, however, coincide with the initiation and duration of the Karoo-Ferrar large igneous province, which formed flood basalts, igneous dyke swarms and large volcanic centres in South Africa and Antarctica. That LIP may have emitted mercury, but so too may have increased chemical weathering of the land surface. Whichever, mercury forms an organic compound (methyl mercury) in water bodies. Readily incorporated into living organisms, that could explain the close parallel between the δ13C and Hg records in the Jurassic sediment core from Wales. The Karoo-Ferrar igneous activity itself presents a bit of a conundrum, as suggested by Ruhl et al. It happened at the very time that there was a 120° change in the direction of motion of the tectonic plate carrying along Africa and, indeed, the Gondwanaland supercontinent during the Jurassic. The directional change also involved local plate movement stopping for a while. According to the authors, it wasn’t a fortuitous coincidence of two mantle plumes from the core-mantle boundary hitting the bottom of the continental lithosphere below Africa and Antarctica at this tectonic ‘U-turn’. It is more likely that the pause gave existing plumes the opportunity and time to ‘erode’ the base of the continental lithosphere and rise. Decompression melting would then have produced the voluminous magmas. The two plumes were in place for a very long time and created seamount chains as plates moved over them. Both are still volcanically active: Tristan de Cunha on the mid-Atlantic Ridge, and Bouvet Island at a triple junction between South Africa and Antarctica.

So, a venture to unravel a period of profound environmental change during the Early Jurassic, which didn’t result in mass extinction, may well have spawned a new model for massive igneous events that did. Ruhl et al. suggest that the short-lived Siberian, North Atlantic and East African Rift LIPs each seem to have coincided with short episodes of tectonic slowing-down: LIPs may result in dramatic environmental change, but at the whim of plate tectonics.

See also: https://scitechdaily.com/surprising-discovery-shows-how-slowing-of-continental-plate-movement-controlled-earths-largest-volcanic-events/

The Earth System in action: land plants affected composition of continental crust

The essence of the Earth System is that all processes upon, above and beneath the surface interact in a bewildering set of connections. Matter and energy in all their forms are continually being exchanged, deployed and moved through complex cycles: involving rocks and sediments; water in its various forms; gases in the atmosphere; magmas; moving tectonic plates and much else besides. The central and massively dominant role of plate tectonics connects surface processes with those of our planet’s interior: the lithosphere, mantle and, arguably, the core. Interactions between the Earth System’s components impose changes in the dynamics and chemical processes through which it operates. Living processes have been a part of this for at least 3.5 billion years ago, in part through their role in the carbon cycle and thus the Earth’s climatic evolution. During the Silurian Period life became a pervasive component of the continental surface, first in the form of plants, to be followed by animals during the Devonian Period. Those novel changes have remained in place since about 430 Ma ago, plants being the dominant base of continental ecosystems and food chains.

Schematic diagram showing changes in river systems and their alluvium before and after the development of land plants. (Credit: Based on Spencer et al. 2022, Fig 4)

Land plants exude a variety of chemicals from their roots that break down rock to yield nutrient elements. So they play a dominant role in the formation of soil and are an important means of rock weathering and the production of clay minerals from igneous and metamorphic minerals. Plant root systems bind near-surface sediments thus increasing their resistance to erosion by wind and water, and to mass movement under gravity. This binding and plant canopies efficiently reduce dust transport, slow water flow on slopes and decrease the sediment load of flowing water. Plants and their roots also stabilise channels systems. There is much evidence that before the Devonian most rivers comprised continually migrating braided channels in which mainly coarse sands and gravels were rapidly deposited while silts and muds in suspension were shifted to the sea. Thereafter flow became dominated by larger and fewer channels meandering across wide tracts on which fine sediment could accumulate as alluvium on flood plains when channels broke their banks. Land plants more efficiently extract CO2 from the atmosphere through photosynthesis and the new regime of floodplains could store dead plant debris in the muds and also in thick peat deposits. As a result, greenhouse warming had dwindled by the Carboniferous, encouraging global cooling and glaciation. 

Judging the wider influence of the ‘greening of the land’ on other parts of the Earth system, particularly those that depend on internal  magmatic processes, relies on detecting geochemical changes in minerals formed as direct outcomes of plate tectonics. Christopher Spencer of Queen’s University in Kingston, Canada and co-workers at the Universities of Southampton, Cambridge and Aberdeen in the UK, and the China University of Geosciences in Wuhan set out to find and assess such a geochemical signal (Spencer, C., Davies, N., Gernon, T. et al. 2022. Composition of continental crust altered by the emergence of land plants. Nature Geoscience, v. 15 online publication; DOI: 10.1038/s41561-022-00995-2). Achieving that required analyses of a common mineral formed when magmas crystallise: one that can be precisely dated, contains diverse trace elements and whose chemistry remains little changed by later geological events. Readers of Earth-logs might have guessed that would be zircon (ZrSiO). Being chemically unreactive and hard, small zircon grains resist weathering and the abrasion of transport to become common minor minerals in sediments. Thousands of detrital zircon grains teased out from sediments have been dated and analysed in the last few decades. They span almost the entirety of geological history. Spencer et al. compiled a database of over 5,000 zircon analyses from igneous rocks formed at subduction zones over the last 720 Ma, from 183 publications by a variety of laboratories.

The approach considered two measures: the varying percentages of mudrocks in continental sedimentary sequences since 600 Ma ago; aspects of the hafnium- (Hf) and oxygen-isotope proportions measured in the zircons using mass spectrometry and their changes over the same time. Before ~430 Ma the proportion of mudrocks in continental sedimentary sequences is consistently much lower than it is in post post-Silurian, suggesting a link with the rise of continental plant cover (see second paragraph). The deviation of the 176Hf/177Hf ratio in an igneous mineral from that of chondritic meteorites (the mineral’s εHf value) is a guide to the source of the magma, negative values indicating a crustal source, whereas positive values suggest a mantle origin. The relative proportions of two oxygen isotopes 18O and 16O  in zircons, expressed as δ18O, indicates the proportion of products of weathering, such as clay minerals, involved in magma production – 18O selectively moves from groundwater to clay minerals when they form, increasing their δ18O.

While the two geochemical parameters express very different geological processes, the authors noticed that before ~430 Ma the two showed low correlation between their values in zircons. Yet, surprisingly, the parameters showed a considerable and consistent increase in their correlation in younger zircons, directly paralleling the ‘step change’ in the proportions of mudstones after the Silurian. Complex as their arguments are, based on several statistical tests, Spencer et al. conclude that the geologically sudden change in zircon geochemistry ultimately stems from land plants’ stabilisation of river systems. As a result more clay minerals formed by protracted weathering, increasing the δ18O in soils when they were eroded and transported. When the resulting marine mudrocks were subducted they transferred their oxygen-isotope proportions to magmas when they were partially melted.

That bolsters the case for dramatic geological consequences of the ‘greening of the land’. But did its effect on arc magmatism fundamentally change the bulk composition of post-Silurian additions to the continental crust? To be convinced of that I would like to see if other geochemical parameters in subduction-related magmas changed after 430 Ma. Many other elements and isotopes in broadly granitic rocks have been monitored since the emergence of high-precision rock-analysing technologies around 50 years ago. There has been no mention, to my knowledge, that the late-Silurian involved a magmatic game-changer to match that which occurred in the Archaean, also revealed by hafnium and oxygen isotopes in much more ancient zircons.   

See also: https://www.sci.news/othersciences/geoscience/land-plants-continental-crust-composition-11151.htmlhttps://www.eurekalert.org/news-releases/963296

Climate out of control after the Permian-Triassic mass extinction

The snuffing out of up to 90 percent of all terrestrial and marine species at the end of the Permian (252 Ma) was the outcome of lethal climatic warming. It probably stemmed from a stupendous episode of flood basalt volcanism and intrusions in what is now Siberia that burned vast amounts of peat or coal in the basin that the flows filled (see: Coal and the end-Permian mass extinction; March 2011). The carbon dioxide so released created planetary hyperthermia and toxic acid rain. For at least five million years Earth was an almost sterile world, a notable absence being dense vegetation on the land surface – the Early Triassic is devoid of coal, whereas there is plenty of Late Permian age. Much the same slow recovery of life is found in meagre collections of land and marine animal fossils of that age. Yet, other mass extinctions were followed by recovery and species diversification at a much faster pace.

One conceivable explanation could be the near absence of vegetation whose photosynthesis and burial would otherwise draw down CO2 and the same goes for its marine equivalent phytoplankton. But there is a powerful inorganic means of carbon sequestration: silicate weathering. The chemistry depends on carbon dioxide dissolved in water. For simple silicates it can be expressed as:

2CO2 + H2O + CaSiO3 → Ca2+ + 2HCO3 + SiO2.

The higher the ambient temperature, the faster such reactions proceed. Most silicates are more complex and many common ones, such as feldspars, include aluminium, so that another product of weathering is insoluble, fine-grained clay minerals. So various soluble metal ions (Ca, Mg, K, Na etc), dissolved bicarbonate ions, silica in various guises and clays eventually end up in the sea. Once there, it is possible for them to recombine, as for instance calcium and bicarbonate ions:

Ca2+ + 2HCO3→ CaCO3 + CO2 + H2O

Despite some CO2 gas being released, this reaction results in a net sequestration of carbon in calcium carbonate. Incidentally, the same kind of chemical reaction occurs in the soils produced by weathering. The carbonate may cement soils to form a hard crust of caliche or ‘calcrete’. Chemical weathering enhanced by a hot climate, it might seem, should reduce the greenhouse effect quickly: a feedback mechanism that normally stabilises climate. But that did not happen after the P-Tr extinction event, thereby stressing all remaining life forms. A group of scientists at the University of Waikato in New Zealand have developed a possible explanation for this potentially fatal hazard for life on Earth (Isson, T.T. et al. 2022. Marine siliceous ecosystem decline led to sustained anomalous Early Triassic warmth. Nature Communications, v. 13, article 3509; DOI: 10.1038/s41467-022-31128-3). It focuses on the silica (SiO2) released by chemical weathering, which enters the ocean in the form of a colloid: Si(OH)4, a form of silicic acid known as ‘reactive silica’. Under ‘normal’ conditions, this is removed by organisms, such as diatoms and radiolaria, and is constantly recycled on a time scale of about 400 years, some contributing to deep-ocean oozes in the form of chert. But, like all other marine organisms, they too were victims of the P-Tr mass extinction.

Examples of marine radiolaria (top)

Reactive silica colloids in seawater also participate in inorganic chemical reactions, combining with dissolved metal ions to form complex hydrated aluminosilicates, i.e. more clay minerals. The reactions change the alkalinity of seawater. As a result dissolved HCO3ions transform to CO2 gas and water. Despite the complexity of the chemistry that interweaves the carbon and silicon cycles, there is a simple conclusion. If the abundance of silica-secreting marine organisms falls drastically while continental weathering continues to deliver silica, clay-mineral formation on the ocean floor results in release of CO2 that reverses the effect of enhanced weathering and thus maintains hyperthermal conditions. The other outcome is that less chert and flint granules form Terry Isson and colleagues examined the varying proportion of chert in cores through Lower Triassic marine sediments. A ‘chert gap’characterises the 4 to 6 Ma following the P-Tr boundary event. This can be explained in part by extinction of silica-secreting organisms and by inorganic reactions converting the reactive silica that enhanced weathering delivered to the oceans to clay minerals. This supports the idea that the inorganic part of the silica cycle maintained greenhouse conditions in the absence of organic ‘competition’ for reactive silica. Many other biogeochemical cycles link biological and chemical processes that combine to affect climate: involving phosphorus, nitrogen and iron, to name but three.

Conditions that may have underpinned the ‘Cambrian Explosion’

Geologists of my generation leaned that the earliest signs of abundant and diverse animal life were displayed by an extraordinary assemblage of fossils in a mudstone exposure high on a ridge in the Rocky Mountains of British Columbia. The Burgess Shale lagerstätte, or ‘site of exceptional preservation’, was discovered by Charles Walcott in 1909. It contained exquisite remains, some showing signs of soft tissue, of a great range of animals, many having never before been seen. Though dated at 509 Ma (Middle Cambrian) it was regarded for much of the 20th century as the sign of a sudden burgeoning from which all subsequent life had evolved: the Cambrian Explosion. Walcott only scratched the surface of its riches, its true wonders only being excavated and analysed later by Harry Whittington and his protégé Simon Conway Morris of Cambridge University. Their results were summarised and promoted in one of the great books on palaeontology and evolutionary biology, Wonderful Life (1989) by Steven Jay Gould.

Harbingers of animal profusion first appear around 635 Ma in the Late Neoproterozoic as the Ediacaran Fauna, with the oldest precursors turning up around a billion years ago in the Torridonian Sandstone Formation of northern Scotland. The evolutionary links between them and the Cambrian Explosion are yet to be documented, as creatures of the Ediacaran remain elusive in the earliest Phanerozoic rocks. As regards the conditions that promoted the explosion of animal faunas, the Burgess Shale is a blank canvas, for its riches were not preserved in situ, but had drifted onto deep, stagnant ocean floor to be preserved in oxygen-poor muds that enabled their intricate preservation. The animals could not have lived and evolved without abundant oxygen: what that environment was is not recorded by Walcott’s famous stratigraphic site.

Artistic impression of the Chengjian Biota

China, it has emerged, offers a major clue from around 40 lagerstätten in Chengjian County, Yunnan. They are not only older (518 Ma) than the Burgess Shale but contain 27 percent more faunal diversity: 17 phylums and more than 250 species. Since the discovery of the Chengjian Biota in the first decade of the 21st century palaeontologists have, understandably, been preoccupied by describing its riches in hundreds of scientific papers. The nature of the ecosystem has remained as obscure as that of the Burgess Shale, largely due to the exposed host rocks (laminated siltstones and mudstones) having been weathered. They are superficially similar to the Burgess Shale. In March 2022, 10 scientists working at laboratories in China, Canada, Switzerland and the UK published the results of their painstaking sedimentological investigation of a core dilled through through the entire fossiliferous sequence (Salih, F. and 9 others 2022. The Chengjiang Biota inhabited a deltaic environment. Nature Communications, v. 13, article 1569; DOI: 10.1038/s41467-022-29246-z).

Reconstruction of the near-shore deltaic environment in which the Chengjian Biota lived and evolved. Several rock types and the sedimentary processes that probably formed them shown in ‘cores’ (Credit: Salih et al. Figure 3)

The unweathered core displays a variety of tiny sedimentary structures. These include cross laminations formed by migrating ripples, occasional fine sandstones that include signs of burrowing, graded bedding formed by minor turbidity currents, hummocks formed by back and forth water flow, ripples formed by flow in a single direction and small channels. Unlike the Burgess Shale, the fine-grained Chengjian sediments seem to have been deposited in environments that were far from stagnant and deep. They most closely resemble the offshore parts of the delta of a predominantly muddy river, subject to occasional floods and storms and characterised by large and rapid accumulation of mud and silt by dense sediment-loaded river water flowing down a gently sloping seabed into clearer seawater. That the sediment supply was full of nutrients and oxygen is reflected by small organisms living in burrows. The high-quality preservation of fossils in some layers can be attributed to sudden influxes of freshwater into their marine habitat during storms, so that they were killed in place. Such a near-shore environment, full of nutrients and oxygen but subjected to repeated geochemical and physical stresses, can explain adaptive radiation and evolution at a fast pace. Clearly, that is by no means a full explanation of the Cambrian Explosion, but offers sufficient insight for research to proceed fruitfully.

See also: Modern Animal Life Could Have Origins in a Shallow, Nutrient-Rich Delta, SciTechDaily, 23 March 2022.

Multiple impacts set back oxygen build-up in the Archaean

Earth’s present atmosphere contains oxygen because of one form of photosynthesis that processes water and carbon dioxide to make plant carbohydrates, leaving oxygen at a waste product. The photochemical trick that underpins oxygenic photosynthesis seems only to have evolved once. It was incorporated in a simple, single-celled organism or prokaryote, which lacks a cell nucleus but contains the necessary catalyst chlorophyll. Such an organism gave rise to cyanobacteria or blue-green bacteria, which still make a major contribution to replenishing atmospheric oxygen. Chloroplasts that perform the same function in plant cells are so like cyanobacteria that they were almost certainly co-opted during the evolution of a section of nucleus-bearing eukaryotes that became the ancestors of plants. A range of evidence suggests that oxygenic photosynthesis appeared during the Archaean Eon, the most tangible being the presence of stromatolites, which cyanobacteria mats or biofilms form today. These knobbly structures in carbonate sediments extend as far back as 3.5 billion years ago (see: Signs of life in some of the oldest rocks; September 2016). Yet it took a billion years before the first inklings of biogenic oxygen production culminated in the Great Oxygenation Event or GOE (see: Massive event in the Precambrian carbon cycle; January, 2012) at around 2400 Ma. Then, for the first time, oxidised iron in ancient soils turned them red. If oxygen was being produced, albeit in small amounts, in shallow, sunlit Archaean seas, why didn’t it build up in the atmosphere of those times? Geochemical analyses of Archaean sediments do point to trace amounts, with a few ‘whiffs’ of more substantial amounts. But they fall well below those of Meso- and Neoproterozoic and Phanerozoic times. One hypothesis is that Archaean oceans contained dissolved, ferrous iron (Fe2+) – a powerful reducing agent – with which available oxygen reacted to form insoluble ferric iron (Fe3+) oxides and hydroxides that formed banded iron formations (BIFS). The Fe2+ in this hypothesis is attributed to hydrothermal activity in basaltic oceanic crust. There is, however, another possibility for suppression of atmospheric oxygen accumulation in the Archaean and early-Palaeoproterozoic.

Summary of the evolution of atmospheric oxygen and related geological features. The percentage scale is logarithmic with the modern level being100%. Credit Alex Glass, Duke University

Simone Marchi of the Southwest Research Institute of Boulder, CO, USA and colleagues from the US, Austria and Germany suggest that planetary bombardment offers a plausible explanation (Marchi, S. et al 2021. Delayed and variable late Archaean atmospheric oxidation due to high collision rates on Earth. Nature Geoscience, v. 14 advance publication; DOI: 10.1038/s41561-021-00835-9). Over the last 20 years evidence of extraterrestrial impacts has emerged, in the form of thin spherule-bearing layers in Archaean sedimentary strata, probably formed by impacts of objects around 10 km across. So far 35 such layers have been identified from several locations in South Africa and Western Australia. They span the last billion years of the Archaean and the earliest Palaeoproterozoic, although they are not evenly spaced in time. The spherules represent droplets of mainly crustal but some meteoritic rocks that were vaporised by impacts and then condensed as liquid. Meteorites in particular contain reduced elements and compounds, including iron, whose oxidation by would remove free oxygen.

The evidence from spherule beds is supplemented by the team’s new calculations of the likely flux of impactors during the Archaean. These stem from re-evaluation of the lunar cratering record that is used to estimate the number and size of impacts on Earth up to 2.5 Ga ago. This flux amounts to the ‘leftovers’ of the catastrophic period around 4.1 Ga when the giant planets Jupiter and Saturn ran amok before they settled into their present orbits. Their perturbation of gravitational fields in the solar system injected a long-lived supply of potential impactors into the inner solar system, which is recorded by craters on the post-4.1 Ga lunar maria. The calculations suggest that the known spherule layers underestimate the true number of such collisions on Earth. Modelling by Marchi et al., based on the meteorite flux and the oxidation of vaporised materials produced by impacts, plausibly accounts for the delay in atmospheric oxygen build-up.

It is worth bearing in mind, however, that large impacts and their geochemical aftermath are, in a geological sense, instantaneous events widely spaced in time. They may have chemically ‘sucked’ oxygen out of the Archaean and early-Palaeoproterozoic atmosphere. Yet photosynthesising bacteria would have been generating oxygen continuously between such sudden events. The same goes for the supply of reduced ferrous iron and its circulation in the oceans of those times, capable of scavenging available oxygen through simple chemical reactions. In fact we can still observe that in action around ocean-floor hydrothermal vents where a host of reduced elements and compounds are oxidised by dissolved oxygen. The difference is that oxygen is now produced more efficiently on land and in the upper oceans and a less vigorous mantle is adding less iron-rich basalt magma to the crust: the balance has changed. Another issue is that the Great Oxygenation Event terminated the oxygen-starved conditions of the Archaean and Palaeoproterozoic in about 200 million years, despite the vast production of BIFs before and after it happened. The Wikipedia entry for the GOE provides a number of hypotheses for how that termination came about. Interestingly, one idea looks to a shortage of dissolved nickel that is vital for methane generating bacteria: a nickel ‘famine’. A geochemical setback for methanogens would have been a boost for oxygenic photosynthesisers and especially their waste product oxygen: methane quickly reacts with oxygen in the atmosphere to produce CO2 and water. Anomalously high nickel is a ‘signature element’ for meteorite bombardment, though it can be released by hydrothermal alteration of basalt. Had meteoritic nickel been fertilising methane-generating bacteria in the oceans prior to the GOE?

See also: A new Earth bombardment model. Science Daily, 21 October 2021.

Human impact on surface geological processes

I last wrote about sedimentation during the ‘Anthropocene’ a year ago (See: Sedimentary deposits of the ‘Anthropocene’, November 2019). Human impact in that context is staggeringly huge: annually we shift 57 billion tonnes of rock and soil, equivalent to six times the mass of the UKs largest mountain, Ben Nevis. All the world’s rivers combined move about 35 billion tonnes less. I don’t particularly care for erecting a new Epoch in the Stratigraphic Column, and even less about when the ‘Anthropocene’ is supposed to have started. The proposal continues to be debated 12 years after it was first suggested to the IUGS International Commission on Stratigraphy. I suppose I am a bit ‘old fashioned’, but the proposals is for a stratigraphic entity that is vastly shorter than the smallest globally significant subdivision of geological time (an Age) and the duration of most of the recorded mass extinctions, which are signified by horizontal lines in the Column. By way of illustration, the thick, extensive bed of Carboniferous sandstone on which I live is one of many deposited in the early part of the Namurian Age (between 328 and 318 Ma). Nonetheless, anthropogenic sediments of, say, the last 200 years are definitely substantial. A measure of just how substantial is provided by a paper published online this week (Kemp, S.B. et al. 2020. The human impact on North American erosion, sediment transfer, and storage in a geologic context. Nature Communications, v. 11, article 6012; DOI: 10.1038/s41467-020-19744-3).

‘Badlands’ formed by accelerated soil erosion.

Anthropogenic erosion, sediment transfer and deposition in North America kicked off with its colonisation by European immigrants since the early 16th century. First Americans were hunter-gatherers and subsistence farmers and left virtually no traces in the landscape, other than their artefacts and, in the case of farmers, their dwellings. Kemp and colleagues have focussed on late-Pleistocene alluvial sediment, accumulation of which seems to have been pretty stable for 40 ka. Since colonisation began the rate has increased to, at present, ten times that previously stable rate, mainly during the last 200 years of accelerated spread of farmland. This is dominated by outcomes of two agricultural practices – ploughing and deforestation. Breaking of the complex and ancient prairie soils, formerly held together by deep, dense mats of grass root systems, made even flat surfaces highly prone to soil erosion, demonstrated by the ‘dust bowl’ conditions of the Great Depression during the 1930s. In more rugged relief, deforestation made slopes more likely to fail through landslides and other mass movements. Damming of streams and rivers for irrigation or, its opposite, to drain wetlands resulted in alterations to the channels themselves and their flow regimes. Consequently, older alluvium succumbed to bank erosion. Increased deposition behind an explosion of mill dams and changed flow regimes in the reaches of streams below them had effects disproportionate to the size of the dams (see: Watermills and meanders, March 2008). Stream flow beforehand was slower and flooding more balanced than it has been over the last few hundred years. Increased flooding, the building of ever larger flood defences and an increase in flood magnitude, duration and extent when defences were breached form a vicious circle that quickly transformed the lower reaches of the largest American river basins.

North American rates of alluvium deposition since 40 Ka ago – the time axis is logarithmic. (Credit: Kemp et al., 2020; Fig. 2)

All this deserves documentation and quantification, which Kemp et al. have attempted at 400 alluvial study sites across the continent, measuring >4700 rates of sediment accumulation at various times during the past 40 thousand years. Such deposition serves roughly as a proxy for erosion rate, but that is a function of multiple factors, such as run-off of rain- and snow-melt water, anthropogenic changes to drainage courses and to slope stability. The scale of post-settlement sedimentation is not the same across the whole continent. In some areas, such as southern California, the rate over the last 200 years is lower than the estimated natural, pre-settlement rate: this example may be due to increased capture of surface water for irrigation of a semi-arid area so that erosion and transport were retarded. In others it seems to be unchanged, probably for a whole variety of reason. The highest rates are in the main areas of rain-fed agriculture of the mid-west of the US and western Canada.

In a nutshell, during the last century the North American capitalism shifted as much sediment as would be moved naturally in between 700 to 3000 years. No such investigation has been attempted in other parts of the world that have histories of intense agriculture going back several thousand years, such as the plains of China, northern India and Mesopotamia, the lower Nile valley, the great plateau of the Ethiopian Highlands, and Europe. This is a global problem and despite its continent-wide scope the study by Kemp et al. barely scratches the surface. Despite earnest endeavours to reduce soil erosion in the US and a few other areas, it does seem as if the damage has been done and is irreversible.

Photosynthesis, arsenic and a window on the Archaean world

At the very base of the biological pyramid life is far simpler than that which we can see.  It takes the form of single cells that lack a nucleus and propagate only by cloning: the prokaryotes as opposed to eukaryote life such as ourselves. It is almost certain that the first viable life on Earth was prokaryotic, though which of its two fundamental divisions – Archaea or Bacteria – came first is still debated. At present, most prokaryotes metabolise other organisms’ waste or dead remains: they are heterotrophs (from the Greek for ‘other nutrition’). But there are others that are primary producers getting their nutrition by themselves, exploiting the inorganic world in a variety of ways: the autotrophs. Biogeochemical evidence from the earliest sedimentary rocks suggests that, in the Archaean prokaryotic autotrophs were dominant, mainly exploiting chemical reactions to gain energy necessary for building carbohydrates. Some reduced sulfate ions to those of sulphide, others combined hydrogen with carbon dioxide to generate methane as a by-product. Sunlight being an abundant energy resource in near-surface water, a whole range of prokaryotes exploit its potential through photosynthesis. Under reducing conditions some photosynthesisers convert sulfur to sulfuric acid , yet others combine photosynthesis with chemo-autotrophy. Dissolved material capable of donating electrons – i.e. reducing agents – are exploited in photosynthesis: hydrogen, ferrous iron (Fe2+), reduced sulfur, nitrite, or some organic molecules. Without one group, which uses photosynthesis to convert CO2 and water to carbohydrates and oxygen, eukaryotes would never have arisen, for they depend on free oxygen. A transformation 2400 Ma ago marked a point in Earth history when oxygen first entered the atmosphere and shallow water (see: Massive event in the Precambrian carbon cycle; January, 2012), known as Great Oxygenation Event (GOE). It has been shown that the most likely sources of that excess oxygen were extensive bacterial mats in shallow water made of photosynthesising blue-green bacteria that produced the distinctive carbonate structures known as stromatolites. These had formed in Archaean sedimentary basins for 1.9 billion years. It has been generally assumed that blue-green bacteria had formed them too, before the oxygen that they produced overcame the reducing conditions that had generally prevailed before the GOE. But that may not have been the case …

Microbial mats made by purple sulfur bacteria in highly toxic spring water flowing into a salt-lake in northern Chile. (credit: Visscher et al. 2020; Fig 1c)

Prokaryotes are a versatile group and new types keep turning up as researchers explore all kinds of strange and extreme environments, for instance: hot springs; groundwater from kilometres below the surface and highly toxic waters. A recent surprise arose from the study of anoxic springs laden with dissolved salts, sulfide ions and arsenic that feed parts of hypersaline lakes in northern Chile (Visscher, P.T. and 14 others 2020. Modern arsenotrophic microbial mats provide an analogue for life in the anoxic ArcheanCommunications Earth & Environment, v. 1, article 24; DOI: 10.1038/s43247-020-00025-2). This is a decidedly extreme environment for life, as we know it, made more challenging by its high altitude exposure to high UV radiation. The springs’ beds are covered with bright-purple microbial mats. Interestingly the water’s arsenic concentration varies from high in winter to low in summer, suggesting that some process removes it, along with sulfur, according to light levels: almost certainly the growth and dormancy of mat-forming bacteria. Arsenic is an electron donor capable of participating in photosynthesis that doesn’t produce oxygen. The microbial mats do produce no oxygen whatever – uniquely for the modern Earth – but they do form carbonate crusts that look like stromatolites. The mats contain purple sulfur bacteria (PSBs) that are anaerobic photosynthesisers, which use sulfur, hydrogen and Fe2+ as electron donors. The seasonal changes in arsenic concentration match similar shifts in sulfur, suggesting that arsenic is also being used by the PSBs. Indeed they can, as the aio gene, which encodes for such an eventuality, is present in the genome of PSBs.

Pieter Visscher and his multinational co-authors argue for prokaryotes similar to modern PSBs having played a role in creating the stromatolites found in Archaean sedimentary rocks. Oxygen-poor, the Archaean atmosphere would have contained no ozone so that high-energy UV would have bathed the Earth’s surface and its oceans to a considerable depth. Moreover, arsenic is today removed from most surface water by adsorption on iron hydroxides, a product of modern oxidising conditions (see: Arsenic hazard on a global scale; May 2020): it would have been more abundant before the GOE. So the Atacama springs may be an appropriate micro-analogue for Archaean conditions, a hypothesis that the authors address with reference to the geochemistry of sedimentary rocks in Western Australia deposited in a late-Archaean evaporating lake. Stromatolites in the Tumbiana Formation show, according to the authors, definite evidence for sulfur and arsenic cycling similar to that in that Atacama springs. They also suggest that photosynthesising blue-green bacteria (cyanobacteria) may not have viable under such Archaean conditions while microbes with similar metabolism to PSBs probably were. The eventual appearance and rise of oxygen once cyanobacteria did evolve, perhaps in the late-Archaean, left PSBs and most other anaerobic microbes, to which oxygen spells death, as a minority faction trapped in what are became ‘extreme’ environments when long before they ‘ruled the roost’. It raises the question, ‘What if cyanobacteria had not evolved?’. A trite answer would be, ‘I would not be writing this and nor would you be reading it!’. But it is a question that can be properly applied to the issue of alien life beyond Earth, perhaps on Mars. Currently, attempts are being made to detect oxygen in the atmospheres of exoplanets orbiting other stars, as a ‘sure sign’ that life evolved and thrived there too. That may be a fruitless venture, because life happily thrived during Earth’s Archaean Eon until its closing episodes without producing a whiff of oxygen.

See also: Living in an anoxic world: Microbes using arsenic are a link to early life. (Science Daily, 22 September 2020)

End-Triassic mass extinction: evidence for oxygen depletion on the ocean floor

For British geologists of my generation the Triassic didn’t raise our spirits to any great extent. There’s quite a lot of it on the British Geological Survey 10-miles-to-the-inch geological map (South Sheet) but it is mainly muds, sandstones or pebble beds, generally red and largely bereft of fossils. For the Triassic’s 50 Ma duration following the end-Permian extinction at 252 Ma Britain was pretty much a desert in the middle of the Pangaea supercontinent. Far beyond our travel grants’ reach, the Triassic is a riot, as in the Dolomites of Northern Italy. Apart from a day trip to look at the Bunter Pebble Beds in a quarry near Birmingham and several weeks testing the load-bearing strength of the Keuper mudstones in the West Midlands (not far off zero) in a soil-mechanics lab, we did glimpse the then evocatively named Tea Green Marl (all these stratigraphic names have vanished). Conveniently they outcrop by the River Severn estuary, below its once-famous suspension bridge and close-by the M5 motorway. Despite the Tea Green Marl containing a bone bed with marine reptiles, time didn’t permit us to fossick, and, anyway, there was a nearby pub … The formation was said to mark a marine transgression leading on to the ‘far more interesting Jurassic’ – the reason we were in the area. We were never given even a hint that the end of the Triassic was marked by one of the ‘Big Five’ mass extinctions: such whopping events were not part of the geoscientific canon in the 1960s.

Pangaea just before the start of Atlantic opening at the end of the Triassic, showing the estimated extend of the CAMP large igneous province. The pink triangles show the sites investigated by He and colleagues.

At 201.3 Ma ago around 34 % of marine genera disappeared, comparable with the effect of the K-Pg extinction that ended the Mesozoic Era. Extinction of Triassic terrestrial animals is less quantifiable. Early dinosaurs made it through to diversify hugely during the succeeding Jurassic and Cretaceous Periods. Probably because nothing famous ceased to be or made its first appearance, the Tr-J mass extinction hasn’t captured public attention in the same way as those with the K-Pg or the P-Tr acronyms.  But it did dramatically alter the course of biological evolution. The extinctions coincided with a major eruption of flood basalts known as the Central Atlantic Magmatic Province (CAMP), whose relics occur on either side of the eponymous ocean, which began to open definitively at about the same time. So, chances are, volcanic emissions are implicated in the extinction event, somehow (see: Is end-Triassic mass extinction linked to CAMP flood basalts? June 2013). Tianchen He  of Leeds University, UK and the China University of Geosciences and British and Italian colleagues have studied three Tr-J marine sections on either side of Pangaea: in Sicily, Northern Ireland and British Columbia (He, T. and 12 others 2020. An enormous sulfur isotope excursion indicates marine anoxia during the end-Triassic mass extinction. Science Advances, v. 6, article eabb6704; DOI: 10.1126/sciadv.abb6704). Their objective was to test the hypothesis that CAMP resulted in an episode of oceanic anoxia that caused the many submarine organisms to become extinct. Since eukaryote life depends on oxygen, a deficit would put marine animals of the time under great stress. Such events in the later Mesozoic account for global occurrences of hydrocarbon-rich, black marine shales – petroleum source rocks – in which hypoxia thwarted complete decay of dead organisms over long periods. However there is scant evidence for such rocks having formed ~201 Ma ago. Such as there is dates to about 150 ka younger than the Tr-J boundary in an Italian shallow marine basin. The issue of evidence is compounded by the fact that there are no ocean-floor sediments as old as that, thanks to their complete subduction as Pangaea broke apart in later times and its continental fragments drifted to their present configuration.

But there is an indirect way of detecting deep-ocean anoxia, in the inevitable absence of any Triassic and early Jurassic oceanic crust. It emerges from what happens to the stable isotopes of sulfur when there are abundant bacteria that use the reduction of sulfate (SO42-) to sulfide (S2-) ions. Such microorganisms thrive in anoxic conditions and produce abundant hydrogen sulfide, which in turn leads to the precipitation of dissolved iron as minute grains of pyrite (FeS2). This biogenic process selectively excludes 34S from the precipitated pyrite. As a result, at times of widespread marine reducing conditions seawater as a whole becomes enriched in 34S relative to sulfur’s other isotopes. The enrichment is actually expressed in the unreacted sulfate ions, and they may be precipitated as calcium sulfate or gypsum (CaSO4) in marine sediments deposited anywhere: He et al. focussed on such fractionation. They discovered large ‘spikes’ in the relative enrichment of 34S at the Tr-J boundary in shallow-marine sedimentary sequences exposed at the three sites. Moreover, they were able to estimate that the conditions on the now vanished bed of the Triassic ocean that gave rise to the spikes lasted for about 50 thousand years. The lack of dissolved oxygen resulted in a five-fold increase in pyrite burial in the now subducted ocean-floor sediments of that time. The authors suggest that the oxygen depletion stemmed from extreme global warming, which, in turn, encouraged methane production by other ocean-floor bacteria and, in a roundabout way, other chemical reactions that consumed free dissolved oxygen. Quite a saga of a network of interactions in the whole Earth system that may hold a dreadful warning for the modern Earth and ourselves.

‘Mud, mud, glorious mud’

Earth is a water world, which is one reason why we are here. But when it comes to sedimentary rocks, mud is Number 1. Earth’s oceans and seas hide vast amounts of mud that have accumulated on their floors since Pangaea began to split apart about 200 Ma ago during the Early Jurassic. Half the sedimentary record on the continents since 4 billion years ago is made of mudstones. They are the ultimate products of the weathering of crystalline igneous rocks, whose main minerals – feldspars, pyroxenes, amphiboles, olivines and micas, with the exception of quartz – are all prone to breakdown by the action of the weakly acidic properties of rainwater and the CO2 dissolved in it. Aside from more resistant quartz grains, the main solid products of weathering are clay minerals (hydrated aluminosilicates) and iron oxides and hydroxides. Except for silicon, aluminium and ferric iron, most metals end up in solution and ultimately the oceans.  As well as being a natural product of weathering, mud is today generated by several large industries, and humans have been dabbling in natural muds since the invention of pottery some 25 thousand years ago.  On 21 August 2020 the journal Science devoted 18 pages to a Special Issue on mud, with seven reviews (Malakoff, D. 2020. Mud. Science, v. 369, p. 894-895; DOI: 10.1126/science.369.6506.894).

Mud carnival in Brazil (Credit: africanews.com)

The rate at which mud accumulates as sediment depends on the rate at which erosion takes place, as well as on weathering. Once arable farming had spread widely, deforestation and tilling the soil sparked an increase in soil erosion and therefore in the transportation and deposition of muddy sediment. The spurt becomes noticeable in the sedimentary record of river deltas, such as that of the Nile, about 5000 years ago. But human influences have also had negative effects, particularly through dams. Harnessing stream flow to power mills and forges generally required dams and leats. During medieval times water power exploded in Europe and has since spread exponentially through every continent except Antarctica, with a similar growth in the capacity of reservoirs. As well as damming drainage these efforts also capture mud and other sediments. A study of drainage basins in north-east USA, along which mill dams quickly spread following European colonisation in the 17th century, revealed their major effects on valley geomorphology and hydrology (see: Watermills and meanders; March 2008). Up to 5 metres of sediment build-up changed stream flow to an extent that this now almost vanished industry has stoked-up the chances of major flooding downstream and a host of other environmental changes. The authors of the study are acknowledged in one Mud article (Voosen, P. 2020. A muddy legacy. Science, v. 369, p. 898-901; DOI: 10.1126/science.369.6506.898) because they have since demonstrated that the effects in Pennsylania are reversible if the ‘legacy’ sediment is removed. The same cannot be expected for truly vast reservoirs once they eventually fill with muds to become useless. While big dams continue to function, alluvium downstream is being starved of fresh mud that over millennia made it highly and continuously productive for arable farming, as in the case of Egypt, the lower Colorado River delta and the lower Yangtze flood plain below China’s Three Gorges Dam.

Mud poses extreme risk when set in motion. Unlike sand, clay deposits saturated with water are thixotropic – when static they appear solid and stable but as soon as they begin to move en masse they behave as a viscous fluid. Once mudflows slow they solidify again, burying and trapping whatever and whomever they have carried off. This is a major threat from the storage of industrially created muds in tailings ponds, exemplified by a disaster at a Brazilian mine in 2019, first at the site itself and then as the mud entered a river system and eventually reached the sea. Warren Cornwall explains how these failures happen and may be prevented (Cornwall, W. 2020. A dam big problem.  Science, v. 369, p. 906-909; DOI: 10.1126/science.369.6506.906). Another article in the Mud special issue considers waste from aluminium plants (Service, R.F. 2020. Red alert. Science, v. 369, p. 910-911; DOI: 10.1126/science.369.6506.910). The main ore for aluminium is bauxite, which is the product of extreme chemical weathering in the tropics. The metal is smelted from aluminium hydroxides formed when silica is leached out of clay minerals, but this has to be separated from clay minerals and iron oxides that form a high proportion of commercial bauxites, and which are disposed of in tailings dams. The retaining dam of such a waste pond in Hungary gave way in 2010, the thixotropic red clay burying a town downstream to kill 10 people. This mud was highly alkaline and inflicted severe burns on 150 survivors. Service also points out a more positive aspect of clay-rich mud: it can absorb CO2 bubbled through it to form various, non-toxic carbonates and help draw down the greenhouse gas.

Muddy sediments are chemically complex, partly because their very low permeability hinders oxygenated water from entering them: they maintain highly reducing conditions. Because of this, oxidising bacteria are excluded, so that much of the organic matter deposited in the muds remains as carbonaceous particles. They store carbon extracted from the atmosphere by surface plankton whose remains sink to the ocean floor. Consequently, many mudrocks are potential source rocks for petroleum. Although they do not support oxygen-demanding animals, they are colonised by bacteria of many different kinds. Some – methanogens – break down organic molecules to produce methane. The metabolism of others depends on sulfate ions in the trapped water, which they reduce to sulfide ions and thus hydrogen sulfide gas: most muds stink. Some of the H2S reacts with metal ions, to precipitate sulfide minerals, the most common being pyrite (FeS2). In fact a significant proportion of the world’s copper, zinc and lead resources reside in sulfide-rich mudstones: essential to the economies of Zambia and the Democratic Republic of Congo. But there are some strange features of mud-loving bacteria that are only just emerging. The latest is the discovery of bacteria that build chains up to 5 cm long that conduct electricity (Pennisi, E. 2020. The mud is electric. Science, v. 369, p. 902-905; DOI: 10.1126/science.369.6506.902). The bacterial ‘nanowires’ sprout from minute pyrite grains, and transfer electrons released by oxidation of organic compounds, effectively to catalyse sulfide-producing reduction reactions. NB Oxygen is not necessary for oxidation as its chemistry involves the loss of electrons, while reduction involves a gain of electrons, expressed by the acronym OILRIG (oxidation is loss, reduction is gain). It seems such electrical bacteria are part of a hitherto unsuspected chemical ecosystem that helps hold the mud together as well as participating in a host of geochemical cycles. They may spur an entirely new field of nano-technology, extending, bizarrely, to an ability to generate electricity from moisture in the air.

If you wish to read these reviews in full, you might try using their DOIs at Sci Hub.

How marine animal life survived (just) Snowball Earth events

diamict3
A Cryogenian glacial diamictite containing boulders of many different provenances from the Garvellach Islands off the west coast of Scotland. (Credit: Steve Drury)

Glacial conditions during the latter part of the Neoproterozoic Era extended to tropical latitudes, probably as far as the Equator, thereby giving rise to the concept of Snowball Earth events. They left evidence in the form of sedimentary strata known as diamictites, whose large range of particle size from clay to boulders has a range of environmental explanations, the most widely assumed being glacial conditions. Many of those from the Cryogenian Period are littered with dropstones that puncture bedding, which suggest that they were deposited from floating ice similar to that forming present-day Antarctic ice shelves or extensions of onshore glaciers. Oceans on which vast shelves of glacial ice floated would have posed major threats to marine life by cutting off photosynthesis and reducing the oxygen content of seawater. That marine life was severely set back is signalled by a series of perturbations in the carbon-isotope composition of seawater. Its relative proportion of 13C to 12C (δ13C) fell sharply during the two main Snowball events and at other times between 850 to 550 Ma. The Cryogenian was a time of repeated major stress to Precambrian life, which may well have speeded up evolution, sediments of the succeeding Ediacaran Period famously containing the first large, abundant and diverse eukaryote fossils.

For eukaryotes to survive each prolonged cryogenic stress required that oxygen was indeed present in the oceans. But evidence for oxygenated marine habitats during Snowball Earth events has been elusive since these global phenomena were discovered. Geoscientists from Australia, Canada, China and the US have applied novel geochemical approaches to occasional iron-rich strata within Cryogenian diamictite sequences from Namibia, Australia and the south-western US in an attempt to resolve the paradox (Lechte, M.A. and 8 others 2019. Subglacial meltwater supported aerobic marine habitats during Snowball Earth. Proceedings of the National Academy of Sciences, 2019; 201909165 DOI: 10.1073/pnas.1909165116). Iron isotopes in iron-rich minerals, specifically the proportion of 56Fe relative to that of 54Fe (δ56Fe), help to assess the redox conditions when they formed. This is backed up by cerium geochemistry and the manganese to iron ratio in ironstones.

In the geological settings that the researchers chose to study there are sedimentological features that reveal where ice shelves were in direct contact with the sea bed, i.e. where  they were ‘grounded’. Grounding is signified by a much greater proportion of large fragments in diamictites, many of which are striated through being dragged over underlying rock. Far beyond the grounding line diamictites tend to be mainly fine grained with only a few dropstones. The redox indicators show clear changes from the grounding lines through nearby environments to those of deep water beneath the ice. Each of them shows evidence of greater oxidation of seawater at the grounding line and a falling off further into deep water. The explanation given by the authors is fresh meltwater flowing through sub-glacial channels at the base of the grounded ice fed by melting at the glacier surface, as occurs today during summer on the Greenland ice cap and close to the edge of Antarctica. Since cold water is able to dissolve gas efficiently the sub-glacial channels were also transporting atmospheric oxygen to enrich the near shore sub-glacial environment of the sea bed. In iron-rich water this may have sustained bacterial chemo-autotrophic life to set up a fringing food chain that, together with oxygen, sustained eukaryotic heterotrophs. In such a case, photosynthesis would have been impossible, yet unnecessary. Moreover, bacteria that use the oxidation of dissolved iron as an energy source would have caused Fe-3 oxides to precipitate, thereby forming the ironstones on which the study centred. Interestingly, the hypothesis resembles the recently discovered ecosystems beneath Antarctic ice shelves.

Small and probably unconnected ecosystems of this kind would have been conducive to accelerated evolution among isolated eukaryote communities. That is a prerequisite for the sudden appearance of the rich Ediacaran faunas that colonised sea floors globally once the Cryogenian ended. Perhaps these ironstone-bearing diamictite occurrences where the biological action seems to have taken place might, one day, reveal evidence of the precursors to the largely bag-like Ediacaran animals