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.

Influence of massive igneous intrusions on end-Triassic mass extinction

About 200 Ma ago, the break-up of the Pangaea supercontinent was imminent. The signs of impending events are spread through the eastern seaboard of North America, West Africa and central and northern South America. Today, they take the form of isolated patches of continental flood basalts, dyke swarms – probably the feeders for much more extensive flood volcanism – and large intrusive sills. Break-up began with the separation of North America from Africa and the start of sea-floor spreading that began to form the Central Atlantic Ocean: hence the name Central Atlantic Magmatic Province (CAMP) for the igneous activity. It all kicked off at the time of the Triassic-Jurassic stratigraphic boundary, and a mass extinction with a similar magnitude to that at the end of the Cretaceous. Disappearances of animals in the oceans and on continents were selective rather than general, as were extinctions of land plants. The mass extinction is estimated to have taken about ten thousand years. It left a great variety of ecological niches ready for re-occupation. On land a small group of reptiles with a substantial destiny entered some of these vacant niches. They evolved explosively to the plethora of later dinosaurs as their descendants became separated as a result of continental drift and adaptive radiation.

Flood basalts of the Central Atlantic Magmatic Province in Morocco (Credit: Andrea Marzoli)

The end-Triassic mass extinction, like three others of the Big Five, was thus closely associated in time with massive continental flood volcanism: indeed one of the largest such events. Within at most 10 ka large theropod dinosaurs entered the early Jurassic scene of eastern North America. The Jurassic was a greenhouse world whose atmosphere had about five times more CO2, a mean global surface temperature between 5 and 10°C higher and deep ocean temperatures 8°C above those at present. Was mantle carbon transported by CAMP magmas the main source (widely assumed until recently) or, as during the end-Permian mass extinction, was buried organic carbon responsible? A multinational group of geoscientists have closely examined samples from a one million cubic kilometre stack of intrusive basaltic sills, dated at 201 Ma, in the Amazon basin of Brazil that amount to about a third of all CAMP magmatism (Capriolo, M. and 11 others 2021. Massive methane fluxing from magma–sediment interaction in the end-Triassic Central Atlantic Magmatic ProvinceNature Communications, v. 12, article 5534; DOI: 10.1038/s41467-021-25510-w).

The team focussed on fluid inclusions in quartz within the basaltic sills that formed during the late stages of their crystallisation. The tiny inclusions contain methane gas and tiny crystals of halite (NaCl) as well as liquid water. Such was the bulk composition of the intrusive magma that the presence of around 5% of quartz in the basalts would be impossible without their magma having assimilated large volumes of silica-rich sedimentary rocks such as shales. The host rocks for the huge slab of igneous sills are sediments of Palaeozoic age: a ready source for contamination by both organic carbon and salt. The presence of methane in the inclusions suggests that more complex hydrocarbons had been ‘cracked’ by thermal metamorphism. Moreover, it is highly unlikely to have been derived from the mantle, partly because methane has been experimentally shown not to be soluble in basaltic magmas whereas CO2 is. The authors conclude that both quartz and methane entered the sills in hydrothermal fluids generated in adjacent sediments. Thermal metamorphism of the sediments would also have driven such fluids to the surface to inject methane directly to the atmosphere. Methane is 25 times as potent as carbon dioxide at trapping heat in the atmosphere, yet it combines with the hydroxyl (OH) radical to form CO2 and water vapour within about 12 years. Nevertheless during continuous emission methane traps 84 times more heat in the atmosphere than would an equivalent mass of carbon dioxide.

Calculations suggest about seven trillion tonnes of methane were generated by the CAMP intrusions in Brazil. Had the magmas mainly been extruded as flood basalts then perhaps global warming at the close of the Triassic would have been far less. Extinctions and subsequent biological evolution would have taken very different paths; dinosaurs may not have exploded onto the terrestrial scene so dramatically during the remaining 185 Ma of the Mesozoic. So it seems important to attempt an explanation of why CAMP magmas in Brazil did not rise to the surface but stayed buried as such stupendous igneous intrusions. Work on smaller intrusive sills suggests that magmas that are denser than the rocks that they pass through – as in a large, thick sedimentary basin – are forced by gravity to take a lateral ‘line of least resistance’ to intrude along sedimentary bedding. That would be aided by the enormous pressure of steam boiled from wet sedimentary rocks forcing beds apart. In areas where only thin sedimentary cover rests on crystalline, more dense igneous and metamorphic rocks, basaltic magma has a greater likelihood of rising through vertical dyke swarms to reach the surface and form lava floods.

Anthropocene more an Event than an Epoch.

The Vattenfall lignite mine in Germany; the Anthropocene personified

The issue of whether or not to assign the time span during which human activities have been significantly affecting the planet and its interwoven Earth Systems has been dragging on since the term ‘Anthropocene’ was first proposed more than two decades ago. A suggestion that may resolve matters, both amicably and with a degree of scientific sense, has emerged in a short letter to the major scientific journal Nature, written by six eminent scientists (Bauer, A.M. et al. 2021. Anthropocene: event or epoch? Nature, v. 597, p. 332; DOI: 10.1038/d41586-021-02448-z). The full text is below

The concept of the Anthropocene has inspired more than two decades of constructive scholarship and public discussion. Yet much of this work seems to us incompatible with the proposal to define the Anthropocene as an epoch or series in the geological timescale, with a precise start date and stratigraphic boundary in the mid-twentieth century. As geologists, archaeologists, environmental scientists and geographers, we have another approach to suggest: recognize the Anthropocene as an ongoing geological event.

The problems with demarcating the Anthropocene as a globally synchronous change in human–environment relations, occurring in 1950 or otherwise, have long been evident (P. J. Crutzen and E. F. Stoermer IGBP Newsletter 41, 17–18; 2000). As an ongoing geological event, it would be analogous to other major transformative events, such as the Great Oxidation Event (starting around 2.4 billion years ago) or the Great Ordovician Biodiversification Event (around 500 million years ago).

Unlike formally defined epochs or series, geological events can encompass spatial and temporal heterogeneity and the diverse processes — environmental and now social — that interact to produce global environmental changes. Defining the Anthropocene in this way would, in our view, better engage with how the term has been used and criticized across the scholarly world.”

AUTHORS: Andrew M. Bauer, Stanford University, Stanford, California, USA; Matthew Edgeworth, University of Leicester, Leicester, UK;  Lucy E. Edwards, Florence Bascom Geoscience Center, Reston, Virginia, USAErle C. Ellis, University of Maryland, Baltimore County, Maryland, USA ; Philip Gibbard, Scott Polar Research Institute, University of Cambridge, Cambridge, UK;  Dorothy J. Merritts, Franklin and Marshall College, Lancaster, Pennsylvania, USA.

I have been grousing about the attempt to assign Epoch/Series status to the Anthropocene for quite a while (you can follow the development of my personal opinions by entering ‘Anthropocene’ in the Search Earth-logs box). In general I believe that the proposal being debated is scientifically absurd, and a mere justification for getting a political banner to wave. What the six authors of this letter propose seems eminently sensible. I hope it is accepted by International Commission on Stratigraphy as a solution to the increasingly sterile discussions that continue to wash to and fro in our community. Then perhaps the focus can be on action rather than propaganda.

As things have stood since 21 May 2019, a proposal to accept the Anthropocene as a formal chrono-stratigraphic unit defined by a GSSP at its base around the middle of the 20th century is before the ICS and the International Union of Geological Sciences (IUGS) for ratification. It was accepted by 88% of the 34-strong Anthropocene Working Group of the ICS Subcommission on Quaternary Stratigraphy. But that proposal has yet to be ratified by either the ICS or IUGS. Interestingly, one of the main Anthropocene proponents was recently replaced as chair of the Working Group.

When Greenland was a warm place

On 14-15 August 2021 it rained for the first time since records began at the highest point on the Greenland ice cap. Summit Camp at 3.216 m is run by the US National Science Foundation, which set it up in 1989, and is famous for climate data gleaned from two deep ice cores there. This odd event came at a time when surface melting of the ice cap covered 870 thousand km2: over half of its total 1.7 million km2 extent: a sure sign of global warming. The average maximum temperature in August at Summit is -14°C, but since the mid 20th century the Arctic has been warming at about twice the global rate. Under naturally fluctuating climatic conditions during the Pleistocene, associated with glacial-interglacial cycles, Greenland may have been ice-free for extended periods, perhaps as long as a quarter of a million years around 1.1 Ma ago. If 75% of the up to 3 km thick ice on Greenland melted that would add 5 to 6 m to global sea level, perhaps as early as 2100 if current rates of climate warming persist.

The edge of the ice cap in NE Greenland (credit: Wikipedia)

The worst scenario is runaway warming on the scale of that which took place 56 Ma ago during the Palaeocene-Eocene Thermal Maximum (PETM) when global mean temperature rose by between 5 to 8°C at a rate comparable with what the planet is experiencing now as a result of growth in the world economy. In fact, the CO2 released during the PETM emerged at a rate that was only about tenth of modern anthropogenic emissions  Sediments that span the Palaeocene-Eocene boundary occur in NE Greenland, a study of which was recently published by scientists from Denmark, Greenland, the UK, Australia and Poland (Hovikoski, J. and 13 others 2021. Paleocene-Eocene volcanic segmentation of the Norwegian-Greenland seaway reorganized high-latitude ocean circulation. Communications Earth & Environment, v. 2, article 172; DOI: 10.1038/s43247-021-00249-w). The greenhouse world of NE Greenland that lay between 70 and 80°N then, as it still does, was an area alternating between shallow marine and terrestrial conditions, the latter characterised by coastal plain and floodplain sediments deposited in estuaries, deltas and lakes. They include coals derived from lush, wooded swamps, inhabited by hippo-like ungulates, primates and reptiles.

At that time the opening of the northern part of the North Atlantic had barely begun, with little chance for an equivalent of the Gulf Stream to have had a warming influence on the Arctic. Shortly after the PETM volcanism began in earnest, to form the flood basalts of the North Atlantic Igneous Province. Each lava flow is capped by red soil or bole: further evidence for a warm, humid climate and rapid chemical weathering. As well as lava build-up, tectonic forces resulted in uplift, effectively opening migration routes for animals and land plants to colonise the benign – for such high latitudes – conditions and perhaps escape the far hotter conditions further south.

The situation now is much different, with the potential for even more rapid melting of the Greenland ice cap to flood freshwater into the North Atlantic, as is currently beginning. Diluting surface seawater reduces its density and thus its tendency to sink, which is the main driving force that pulls warmer water towards high-latitudes in the form of the Gulf Stream. Slowing and even shutting down its influence may have an effect that contradicts the general tendency for global warming – a cooling trend at mid- to high latitudes with chaotic effects on atmospheric pressure systems, the jet stream and weather in general.

See also: Barham, M. et al. 2021. When Greenland was green: rapid global warming 55 million years ago shows us what the future may hold. The Conversation, 23 August 2021.

Apocalypse Soon: Will current global warming trigger a mass extinction?

Since the start of 2020 I doubt there has been much field research. But such a vast amount of data has been amassed over the years that there must be opportunities to keep the academic pot boiling. One way is to look for new correlations between different kinds of data. For instance matching the decades-old time series of extinctions with those of other parameters that have changed over geological time. At a time of growing concern about anthropogenic climate change a group based at the State Key Laboratory of Biogeology and Environmental Geology, at China University of Geosciences, Wuhan have checked the extinction rates of marine fossils over the last 450 Ma against variations in sea-surface temperature (Song, H. et al 2021. Thresholds of temperature change for mass extinctions. Nature Communications, v. 12, Article number 4694; DOI: 0.1038/s41467-021-25019-2).

Extinction data are usually presented in time ‘bins’ based on the number of disappearances of fossil genera in one or a number of geological Stages – the finest divisions of the stratigraphic column. The growing data set for sea-surface temperatures derived using oxygen isotopes from marine fossil shells is more continuous, being derived from many different layers of suitable sedimentary rock within a Stage. Clearly, the two kinds of data have to be expressed in a similar way to check for correlations. Haijun Song and co-workers converted both the extinction and temperature time series to 45 time ‘bins’, each around 10 Ma long. They express the binned climatic data in two ways: as the largest temperature change (°C) and the highest rate of temperature change (°C Ma-1) within each bin. That is, they expressed to some extent the greater continuity of seawater temperature data as well as matching them to those for extinctions.

Changes since the end of the Ordovician: red = extinction rate in time bins; green = the greatest magnitude of change in temperature in each bin; blue- the greatest rate of temperature change in each bin. Grey bars show mass extinctions (Credit: Song et al., Fig 1)

There are good correlations between the climatic and extinction data, particularly for mass extinctions. Bearing in mind that mass extinctions take place far more rapidly than can be expressed with 10 Ma time bins, the authors were concerned that bias could creep into the binned extinction data. They were able to discount this by examining both data sets in finer detail at the times of the ‘Big 5’ extinctions. Earlier research had identified warming episodes around the times of each mass extinction, often implicating greenhouse-gas emissions from Large Igneous Provinces. Yet there are other factors that may have influenced the 7 ‘lesser’ mass extinctions in the fossil record. The authors are sufficiently confident in the correlations they have revealed to suggest thresholds that seem to have launched major mass extinctions: greater than 5.2 °C and 10 °C Ma-1 for magnitudes and rates of sea-surface temperature change, respectively.

In the context of the modern climate, the data analysis predicts that a rise of 5.2 °C above the preindustrial mean global temperature spells extinctions of ‘Big Five’ magnitude. The rate of temperature increase since 1880 – 0.08 ° per decade – is hugely faster than that expressed by the data that span the last 450 Ma. This is more alarming than the stark Sixth Report of the Intergovernmental Panel on Climate Change IPCC released on 9 August 2021.

Signs of Milankovich Effect during Snowball Earth episodes

The idea that the Earth was like a giant snowball during the Neoproterozoic Era arose from the discovery of rocks of that age that could only have formed as a result of glaciation. However, unlike the Pleistocene ice ages, evidence for these much older glacial conditions occurs on all continents. In some locations remanent magnetism in sedimentary rocks of that age is almost horizontal; i.e. they had been deposited at low magnetic latitudes, equivalent to the tropics of the present day. Frigid as it then was, the Earth still received solar heating and magmatic activity would have been slowly adding CO2 to the atmosphere so that less heat escaped – a greenhouse effect must have been functioning. Moreover, an iced-over world would not have been supporting much photosynthetic life to draw down the greenhouse gas into solid carbohydrates and carbonates to be buried on the ocean floor. As far as we know the Solar System’s geometry during the Neoproterozoic was much as it is today. So changes in the gravitational fields induced by the orbiting Giant Planets would have been affecting the shape (eccentricity) of Earth’s orbit, the tilt (obliquity) of its rotational axis and the precession (wobble) of its rotation as they do at present through the Milankovich effect. These astronomical forcings vary the amount of solar energy reaching the Earth’s surface. It has been suggested that a Snowball Earth’s climate system would have been just as sensitive to astronomical forcing as it has been during the last 2 million years or more. Proof of that hypothesis has recently been achieved, at least for one of the Snowball events (Mitchell, R.N. and 8 others 2021. Orbital forcing of ice sheets during snowball Earth. Nature Communications, v. 12, article 4187; DOI: 10.1038/s41467-021-24439-4).

Another of the enigmas of the Neoproterozoic is that after and absence of more than a billion years banded iron formations (see: Banded iron formations (BIFs) reviewed, December 2017) began to form again. BIFs are part of the suite of sedimentary rocks that characterise Snowball Earth events, often alternating with glaciogenic sediments. Throughout each cold cycle – the Sturtian (717 to 663 Ma) and Marinoan (650 to 632 Ma) glacial periods – conditions of sediment deposition varied a great deal from place to place and over time. Some sort of cyclicity is hinted at, but the pace of alternations has proved impossible to check, partly because the dominant rocks (glacial conglomerates or diamictites) show little stratification and others that are bedded (various non-glacial sandstones) vary from place to place and give no sign of rates of deposition, having been deposited under high-energy conditions. BIFs, on the other hand are made up of enormous numbers of parallel layers on scales from millimetres to centimetres. Bundles of bands can be traced over large areas, and they may represent repeated cycles of deposition.

Typical banded iron formation

How BIFs formed is crucial. They were precipitated from water rich in dissolved iron in its reduced Fe2+ (ferrous) form, which originated from sea-floor hydrothermal vents. Precipitation occurred when the amount of oxygen in the water increased the chance of electrons being removed from iron ions to transform them from ferrous to ferric (Fe3+). Their combination with oxygen yields insoluble iron oxides. Cyclical changes in the availability of oxygen and the balance between reducing and oxidising conditions result in the banding. In fact several rhythms of alternation are witnessed by repeated packages at deci-, centi- and millimetre scales within each BIF deposit. Overall the packages suggest a constant rate of deposition: a ‘must-have’ for precise time-analysis of the cycles. BIFs contain both weakly magnetic hematite (Fe2O3) and strongly magnetic magnetite (Fe3O4), their ratio depending on varying geochemical conditions during deposition. Ross Mitchell of Curtin University, Western Australia and his Chinese, Australian and Dutch colleagues measured magnetic susceptibility at closely spaced intervals (1 and 0.25 m) in two section of BIFs from the Sturtian glaciation in the Flinders Ranges of South Australia. Visually both sections show clear signs of two high-frequency and three lower frequency kinds of cycles, expressed in thickness.

The tricky step was converting the magneto-stratigraphic data to a time series. High-precision zircon U-Pb dating of volcanic rocks in the sequence suggested a mean BIF deposition rate of 3.7 to 4.4 cm per thousand years. This allowed the thickness of individual bands and packages to be expressed in years, the prerequisite for time-series analysis of the BIF magneto-stratigraphic sequence. This involves a mathematical process known as the Fast-Fourier Transform, which expresses the actual data as a spectral curve. Peaks in the curve represent specific frequencies expressed as cycles per metre. The rate of deposition of the BIF allows each peak to be assigned a frequency in years, which can then be compared with the hypothetical spectrum associated with the Milankovich effect. One of the BIF sequences yielded peaks corresponding to 23, 97 and 106 ka. These match the effects of variation in precession (23 ka) and ‘short’ orbital eccentricity (97 and 106 ka) found in Cenozoic sea-floor sediments and ice cores. The other showed peaks at 405, 754 and 1.2 Ma corresponding to ‘long’ orbital eccentricity and long-term features of both obliquity and precession. Quite a result! But how does this bear on Snowball Earth events? Cyclical changes in solar heating would have affected the extent of ice sheets and sea ice at all latitudes, forcing episodes of expansion and contraction and thus changes in sediment supply to the sea floor. That helps explain the many observed variations in sedimentation other than that of BIFs. Rather than supporting a ‘hard’ Snowball model of total marine ice cover for millions of years, it suggests that such an extreme was relieved by period of extensive open water, much as affected the modern Arctic Ocean for the last 2 million years or so. There could have been global equivalents of ice ages and interglacials during the Sturtian and Marinoan. ‘Hard’ conditions would have shut down much of the oceans’ biological productivity, periodically to have been reprieved by more open conditions: a mechanism that would have promoted both extinctions and evolutionary radiations. Snowball events may have driven the takeover of prokaryote (bacteria) dominance by that of the multicelled eukaryotes that is signalled by the Ediacaran faunas that swiftly followed glacial epochs and the explosion of multicelled life during the Cambrian. As eukaryotes, we may well owe our existence to Snowball.

Global warming: Can mantle rocks reduce the greenhouse effect?

Three weeks ago I commented on a novel and progressive use for coal seams as stores for large quantities of hydrogen gas. That would be analogous to batteries for solar- and wind power plants by using electricity generated outside times of peak demand to electrolyse water to hydrogen and oxygen. There are other abundant rocks that naturally react with the atmosphere to permanently sequester carbon dioxide in alteration products, and form possible solutions to global warming. The most promising of these contain minerals that are inherently unstable under surface conditions; i.e. when they come into contact with rainwater that contains dissolved CO2. The most common are anhydrous minerals containing calcium and magnesium that occur in igneous rocks. Basalts contain the minerals plagioclase feldspar (CaAl2Si2O8), olivine ([Fe,Mg]2SiO4)] and pyroxene ([Fe,Mg]CaSi2O6)] that weather to yield the minerals calcium and magnesium carbonate. My piece Bury the beast in basalt, written in June 2016, mentions experiments in the basalts of Iceland and Washington State, USA to check their potential for drawing down atmospheric CO2. News of an even more promising prospect for CO2 sequestration in igneous rock emerged in the latest issue of Scientific American (Fox, D. 2021. Rare Mantle Rocks in Oman Could Sequester Massive Amounts of CO2. Scientific American, July 2021 issue).

Distribution of ophiolites around the Eastern Mediterranean and Black Seas. Most orogenic belts carry comparable volumes of ophiolites. (Credit: Gültekin Topuz, Istanbul Technical University)

The most abundant magnesium-rich material in our planet is the peridotite of the mantle, which consists of more than 60% olivine with lesser amounts of pyroxene and almost no feldspar. Being so rich in Mg and Fe, it is said to have an ultramafic composition and is extremely prone to weathering. The rock dunite is the ultimate ultramafic rock being made of more than 90% olivine. All ultramafic rocks are denser than 3,000 kg m-3, so might be expected to be rare in lower density continental crust (2,600 kg m-3). But they are present at the base of sections of oceanic lithosphere that plate tectonics has thrust up and onto the continents, known as ophiolite bodies. They often occur in orogenic belts at former destructive plate margins and are more common than one might expect. One of the largest and certainly the best-exposed occurs in the Semail Mountains of Oman, where scientists from the Lamont-Doherty Earth Observatory, New York State, USA, and other collaborators have been investigating its potential for absorbing CO2, since 2008.

Olivine-rich rocks react with naturally carbonated groundwater or hydrothermal fluids to form soft, often highly coloured material known as serpentine, well-known for the ease with which it can be carved and polished. As well as the mineral serpentinite [Mg3Si2O5(OH)4], the hydration reactions yield magnetite (Fe3O4), magnesium carbonate (magnesite) and silica (SiO2). If reaction takes place in the absence of oxygen gaseous hydrogen also forms. All these have been noted in the Oman ophiolite: fractures in serpentinites are filled with carbonates, and springs associated with them emit copious amounts of hydrogen and, in some cases, methane. Interestingly, the reactions – like those that involve anhydrous calcium-aluminium silicates when cement is wetted and then cures – release large amounts of heat. This makes the reactions self-sustaining once they begin in peridotite or dunite. However, at the Earth’s surface they are somewhat sluggish as the heat of reaction is lost to the air.  

Mantle rock in the Oman ophiolite, showing cores of fresh peridotite, brownish serpentinite and white carbonate veins (credit: Juerg Matter, Oman Drilling Project, Southampton University, UK)

The capacity for CO2 sequestration by ultramafic igneous rocks is high: a ton of olivine when completely hydrated takes in 0.62 tons of CO2. The Lamont-Doherty team has estimated that they speed up in crushed peridotite, for instance after milling during industrial-scale mining – peridotites are host rocks for platinum-group metals, nickel and chromium. (Kelemen, P.B. et al. 2020. Engineered carbon mineralization in ultramafic rocks for CO2 removal from air. Chemical Geology, v. 550, article 119628; DOI: 10.1016/j.chemgeo.2020.119628). Spreading mine waste over large areas of desert surfaces  would be one way of capturing CO2. However, using the age of emplacement of the Oman ophiolite (96-70 Ma) and the amount of carbonate found in fractured serpentinite there, the team estimates that each ton of the 15 m deep zone of active weathering has naturally absorbed CO2 at a rate of about 1 g m-3 year-1 equivalent to 1000 tons per cubic km per year. But parts of the ophiolite have been fully altered to serpentinite plus carbonates since the Cretaceous, probably at depth. Dating some of the near-surface carbonate veins revealed that they had formed in only a few thousand years rather than the tens of million years expected. Natural sequestration could therefore be happening at depth about 10,000 times faster than theory predicts. Also natural springs emerging from the peridotite are highly alkaline and by combining with atmospheric carbon dioxide precipitate carbonate to form travertine deposits at the surface. This is so rapid that if the carbonate is scraped off the exposed rock, within a year it has recoated the surface.

This year, deep drilling into the Oman ophiolite has begun. To the surprise of members of the team, carbonate minerals are not present in the bedrock below 100 m depth: CO2 is not penetrating naturally beyond that depth. If it becomes possible to inject CO2 deep beneath the surface the exothermic reactions could be kick-started. This would involve sinking pairs of boreholes to set up a flow of carbon-charged water from the ‘injection’ hole to the other that would return decarbonised water to the surface for re-use. The carbon-capture experiment in Iceland (Carbfix) has been running since 2012. Carbon dioxideseparated from hot water passing through a geothermal power plant is re-injected into basalt at a depth of half a kilometre. This small pilot runs at a cost of US$25 per ton of sequestered gas. But it uses already concentrated CO2, whereas global-scale sequestration would require capturing, compressing and dissolving it directly from the atmosphere, probably costing about $120 to $220 per ton injected into mantle rock. The engineering required – about 5,000 boreholes – to capture a billion tons of CO2 deep in the Oman ophiolites is achievable with current technology. Since 2005 almost 140 thousand fracking wells have been sunk in the US alone; they are analogous to the paired holes needed for sequestration. Worldwide, the petroleum industry has driven tens of million wells for conventional oil and gas extraction.

The energy needed to run carbon capture in mantle rocks in an arid country like Oman could be solar derived. Moreover, there are possible by-products such as hydrogen released by the chemical reactions. The alternative, more conventional approach of pumping CO2 into deep, permeable sedimentary reservoirs also carries substantial costs but has the disadvantage of possible leakage. Ophiolites are not rare, occurring as they do in areas of ancient destructive plate margins. So permanently locking away excess atmospheric greenhouse gases currently driving global warming would require only a tiny proportion of the volume of peridotite that is easily accessible by drilling. It would clearly cost an eye-watering sum, but bear in mind that the four biggest petroleum companies – BP, Shell, Chevron and Exxon – have harvested profits of around US$ 2 trillion since 1990. Along with the global coal industries, they are the source of the present climate emergency.

Climate change has shifted Earth’s poles

The shifting position of the Tropic of Cancer in Mexico due to nutation from 2005 to 2010 (Credit: Roberto González, Wikimedia Commons)

First suggested by Isaac Newton and confirmed from observations by Seth Chandler in 1891, the Earth’s axis of rotation and thus its geographic poles wander in much the same manner as does the axis of a gyroscope, through a process known as nutation. The best-known movement of the poles – Chandler wobble – results in a change of about 9 metres in the poles’ positions every 433 days, which describes a rough circle around the mean position of each pole. Every 18.6 years the orbital behaviour of the Moon results in a substantially larger shift, illustrated by a shift in the position of the circles of latitude, as above. Essentially, nutation results from the combined effects of gravitational forces imposed by other bodies. The axial precession cycle of 26 thousand years that is part of the Milankovich effect on long-term climate forcing is a result of nutation. But the Earth’s own gravitational field changes too, as mass within and upon it shifts from place to place. So mantle convection and plate tectonics inevitably change Earth’s mode of rotation, as do changes in the Earth’s molten iron core.

The most sensitive instrument devoted to measuring changes in Earth’s gravity is the tandem of two satellites known as the Gravity Recovery and Climate Experiment or GRACE. Among much else, GRACE has revealed the rate of withdrawal of groundwater from aquifers in Northern India and areas of mass deficit over the Canadian Shield that resulted from melting of its vast ice sheet since 18 ka ago (see: Ice age mass deficit over Canada deduced from gravity data, July 2007). Further GRACE data have now confirmed that more recent melting of polar glaciers due to global warming underlie an unusual reversal and acceleration of polar wandering since the 1990s (Deng, S. et al. 2021. Polar drift in the 1990s explained by terrestrial water storage changes. Geophysical Research Letters, v. 48, online article e2020GL092114; DOI: 10.1029/2020GL092114). In 1995 polar drift changed from southwards to eastwards, and increased by 17 times from its mean speed from 1981 to 1995. That tallies with an increase in the flow of glacial meltwater from polar regions and also with changes in the mass balance of surface and subsurface water at lower latitudes, especially in India, the USA and China where groundwater pumping for irrigation is on a massive scale.

Clearly, human activity is not only changing climate, but also our planet’s astronomical behaviour. That connection, in itself, is enough to set alarm bells ringing, even though the axial shift’s main tangible effect is to change the length of the day by a few milliseconds. Polar wandering has been documented for the last 176 years. Conceivably, data on shifts in past direction and speed may allow climatic changes throughout the industrial revolution to be assessed independently of meteorological data and on a whole-planet basis.

Ses also: Climate has shifted the axis of the Earth (EurekaAlert, 22 April 2021)

Arctic warmer than now half a million years ago

Just over a month since evidence emerged that the Arctic Ocean was probably filled with fresh water from 150 to 131 and 70 to 62 thousand years ago (When the Arctic Ocean was filled with fresh water, February 2021), another study has shaken ‘received wisdom’ about Arctic conditions. This time it is about the climate in polar regions, and comes not from an ice core but speleothem or calcium carbonate flowstone that was precipitated on a cave wall in north-eastern Greenland. The existence of caves at about 80°N between 350 to 670 m above sea level in a very cold, arid area is a surprise in itself, for they require flowing water to form. The speleothem is up to 12 cm thick, but none is growing under modern, relatively warm conditions, cave air being below freezing all year. For speleothem to form to such an extent suggests a long period when air temperature was above 0°C. So was it precipitated before glacial conditions were established in pre-Pleistocene times?

Limestone caves in the arid Grottedal region of north-eastern Greenland (Credit: Moseley et al. 2021; Fig 2D)

A standard means of discovering the age of cave deposits, such as speleothem or stalagmites, is uranium-series dating (see: Irish stalagmite reveals high-frequency climate changes, December 2001). In this case the sheet of flowstone turned out to have been deposited between 588 to 537 thousand years ago; a 50 ka ‘window’ into conditions that prevailed during the middle part of 100 ka climatic cycling – about 6 glacial-interglacial stages before present. (Moseley, G.E. et al. 2021. Speleothem record of mild and wet mid-Pleistocene climate in northeast Greenland. Science Advances, v. 7, online article  eabe1260; DOI: 10.1126/sciadv.abe1260). Roughly half the layer formed during an interglacial, the rest under glacial conditions that followed. Detailed oxygen-isotope studies revealed that air temperatures during which calcium carbonate was precipitated were at least 3.5°C above those prevailing in the area at present; warm enough to melt local permafrost and to increase the summer extent of ice-free conditions in the Arctic Ocean, thereby encouraging greater rainfall. These warm and wet conditions correlate with increased solar heating over the North Atlantic region at that time, as suggested by modelling based on Milankovich astronomical forcing.

Unfortunately, the climate record derived from cores through the Greenland ice sheet only reaches back to about 120 ka, during the last interglacial period. So it is not possible to match the speleothem results to an alternative data set. Yet, thanks to the rediscovery of dirt cored from the very base of the deepest part of the ice sheet (beneath Camp Century) in a freezer in Denmark – it was discarded as interest focused on the record preserved in the ice itself – there is now evidence for complete melting of the ice sheet at some time in the past. The dirt contains abundant fossil plants. Analysing radioactive isotopes of aluminium and beryllium that formed in associated quartz grains as a result of cosmic ray bombardment when the area was ice-free suggests two periods of complete melting followed by glaciation , the second  being within the last million years.

The onshore Arctic climate is clearly more unstable than previously believed.

See also:  Geologists Find Million-Year-Old Plant Fossils Deep Beneath Greenland Ice Sheet. Sci News, 16 March 2021.

Magnetic reversal and demise of the Neanderthals?

A rumour emerged last week that the Neanderthals met their end as one consequence of an extraterrestrial, possibly even extragalactic influence. Curiously, it stems from a recent discovery in New Zealand, where of course Neanderthals never set foot and nor did anatomically modern humans, the ancestors of Maori people, until a mere 800 years ago. It started with an ancient log from a kauri tree (Agathis australis), a species that Maoris revere. Found in excavations of boggy ground, the log weighed about 60 tons, so it was a valuable commodity, especially as it is illegal to fell living kauri trees. The wood is unaffected by burial and insect attack, has a regular grain and colour throughout, so is ideal for monumental Maori sculpture. Such swamp kauri also preserves their own life history in annual growth rings, and the log in question has 1700 of them. Using growth rings to chart climate variation gives the most detailed records of the recent past, provided the wood can be dated. Matching growth ring records from several trees of different ages is key to charting local climate with annual precision over several millennia.

An ancient kauri tree log recovered by swampland excavations in New Zealand. (Credit: Jonathan Palmer, in Voosen 2021)

Radiocarbon dating indicates that this particular kauri tree was growing around 42 thousand years ago. That is close to the upper limit for using 14C concentration in organic matter to determine age because the isotope has a short half-life (5730 years). In this case samples of the log would contain only about 0.7 % of its original complement of radioactive carbon. Cosmic rays generate 14C when they hit nitrogen atoms in the atmosphere and it enters COand thus the carbon cycle. Carbon dioxide taken up by photosynthesis to contribute carbon to plants contains only about one part per trillion of 14C. Consequently wood as ancient as that in the kauri log contains almost vanishingly small amounts, yet it can still be measured using mass spectrometry to yield an accurate radiometric age.

The particularly interesting thing about the 42 ka date is that it coincides with the timing of the last reversal of the Earth’s magnetic field, known as the Laschamps event. The kauri tree bears detailed witness through its growth rings to the environmental effects of a decrease in that field to almost zero as the poles flipped. The bulk of cosmic rays are normally deflected away from the Earth by the geomagnetic field, but during a reversal a great many more pass through the atmosphere, the most energetic reaching the surface and the biosphere. The kauri growth rings record fluctuations in the generation of 14C by their passage and thereby the geomagnetic field strength, which was only 6% of normal levels from 42.3 to 41.6 ka (Cooper, A. and 32 others  2021. A global environmental crisis 42,000 years ago. Science, v. 371, p. 811-818; DOI: 10.1126/science.abb8677). This coincided with an unrelated succession of periods of low solar activity and a reduced solar ‘wind’, which also provides some cosmic-rayprotection when activity is at normal levels; a ‘double whammy’. One consequence would have been destruction of stratospheric ozone by cosmic rays and thus increased ultraviolet exposure at ground level.

Combined with the highly precise growth-ring dating, the climatic changes over the 1700 year lifetime of the kauri tree can be linked to other records of environmental change. These include glacial ice- and lake-bed cores together with stalactite layers. Apparently, the Laschamps geomagnetic reversal coincided with abrupt shifts in wind belts and precipitation, perhaps triggering major droughts in the southern continents. Highly plausible, but some of the other speculations are less certain. For instance, some time around 42 ka, but far from well-established, Australia’s marsupial megafauna experienced major extinctions, the Neanderthals disappear from the fossil record and modern humans started decorating caves in Europe (20 ka after they did in Indonesia). In fact, speculation becomes somewhat silly, with suggestions that early Europeans went to live in caves because of increased exposure to UV (they knew, did they, while Neanderthals didn’t?), their painting and, by implication, their entire culture shifting through the shock and awe of mighty displays of the aurora borealis. Just because the number 42 is (or was), according to the late Douglas Adams’s Hitchhiker’s Guide to the Galaxy, ‘the answer to life, the universe and everything’, the authors tag the episode as the ‘Adams Event’. In their summary for The Conversation they include an animation with a quintessential Stephen Fry narrative, which Earth-logs readers can judge for themselves. Perhaps ‘Lockdown Trauma’ has a lot more to answer for, other than upsurges in Zoom conferences, knitting and gourmet experimentation …

See also: Voosen, P. 2021. Kauri trees mark magnetic flip 42,000 years ago. Science, v. 371, p. 766; DOI: 10.1126/science.371.6531.766