Can rock weathering halt global warming?

The Lockdown has hardly been a subject for celebration, but there have been two aspects that are, to some extent, a comfort: the trickle of road traffic and the absence of convection trails. As a result the air is less polluted and much clearer, and the quietness, even in cities, has been almost palpable. Wildlife seems to have benefitted and far less CO2 has been emitted. Apart from the universal tension of waiting for one of a host of potential Covid-19 symptoms to strike and the fact that the world economy is on the brink of the greatest collapse in a century, it is tempting to hope that somehow business-as-usual will remain this way. B*gger the gabardine rush to work and the Great Annual Exodus to ‘abroad’. The crisis in the fossil fuel industry can continue, as far as I am concerned, But then, of course, I am retired, lucky to have a decent pension and live rurally. Despite the health risks, however, global capital demands that business-as-it-was must return now. A planet left to that hegemonic force has little hope of staving off anthropogenic ecological decline. But is there a way for capital to ‘have its cake and eat it’? Some would argue that there are indeed technological fixes. Among them is sweeping excess of the main greenhouse gas ‘under the carpet’ by burying it. There are three main suggestions: physically extracting CO2 where it is emitted and pumping it underground into porous rocks; using engineered biological processes in the oceans to take carbon into planktonic carbohydrate or carbonate shells and disposing the dead remains in soil or ocean-floor sediments; enhancing and exploiting the natural weathering of rock. The last is the subject of a recent cost-benefit analysis (Beerling, D.J. and 20 others 2020. Potential for large-scale CO2 removal via enhanced rock weathering with croplands. Nature, v. 583, p. 242–248; DOI: 10.1038/s41586-020-2448-9).

Carbon dioxide in the rock cycle (Credit: Skeptical Science, in Wikipedia)

Research into the climatic effects of rock weathering has a long history, for it represents one of the major components of the global carbon cycle, as well as the rock cycle. Natural chemical weathering is estimated to remove about a billion metric tons of atmospheric carbon annually. That is because the main agent of weathering is the slightly acid nature of rainwater, which contains dissolved CO2 in the form of carbonic acid (H2CO3). This weak acid comprises hydrogen ions (H+), which confer acidity, that are released by the dissolution of CO2 in water, together with HCO3ions (bicarbonate, now termed hydrogen carbonate). During weathering the hydrogen ions break down minerals in rock. This liberates metals that are abundant in the silicate minerals that make up igneous rocks – predominantly Na, Ca, K, and Mg – as their dissolved ions, leaving hydrated aluminium silicates (clay minerals) and iron oxides as the main residues, which are the inorganic basis of soils. The dissolved metals and bicarbonate ions may ultimately reach the oceans. However, calcium and magnesium ions in soil moisture readily combine with bicarbonate ions to precipitate carbonate minerals in the soil itself, a process that locks-in atmospheric carbon. Another important consequence of such sequestration is that it may make the important plant nutrient magnesium – at the heart of chlorophyll – more easily available and it neutralises any soil acidity built-up by continuous agriculture.  But carbon sequestration naturally achieved by weathering amounts to only about a thirtieth of that emitted by the burning of fossil fuels, and we know that is incapable of coping with the build-up of anthropogenic CO2 in the atmosphere: it certainly has not since the start of the Industrial Revolution.

What could chemical weathering do if it was deliberately enhanced?  One of the most common rocks, basalt, is made up of calcium-rich feldspar and magnesium-rich pyroxene and olivine. In finely granulated form this mix is particularly prone to weathering, and the magnesium released would enrich existing soil as well as drawing down CO2. Hence the focus by David Beerling and his British, US and Belgian colleagues on systematic spreading of ground-up basalt on cropland soils, in much the same way as crushed limestone is currently applied to reverse soil acidification. It is almost as cheap as conventional liming, with the additional benefit of fertilising: it would boost to crop yields. The authors estimate that removal of a metric ton of CO2 from the atmosphere by this means would cost between US$ 55 to 190, depending on where it was done. One of their findings is that the three largest emitters of carbon dioxide – China, the US and India – happen to have the greatest potential for carbon sequestration by enhanced weathering. Incidentally, increased fertility also yields more organic waste that itself could be used to increase the actual carbon content of soils, if converted through pyrolysis to ‘biochar’ .

It all sounds promising, almost ‘too good to be true’. The logistics that would be needed and the carbon emissions that the sheer mass of rock to be finely ground and then distributed would entail, for as long as global capital continues to burn fossil fuels, are substantial, as the authors admit. The grinding would have to be far more extreme than the production of igneous-rock road aggregate. Basalt or related rock is commonly used for resurfacing motorways, not especially well known for degrading quickly to a clay-rich mush. It would probably have to be around the grain size achieved by milling to liberate ore minerals in metal mines, or to produce the feedstock for cement manufacture: small particles create a greater surface area for chemical reactions. But there remains the issue of how long this augmented weathering would take to do the job: its efficiency. Experimental weathering to test this great-escape hypothesis is being conducted by a former colleague of mine, using dust from an Irish basalt quarry to coat experimental plots of a variety of soil types. After two months Mg and Ca ions were indeed being released from the dust, and tiny fragments of olivine, feldspar and pyroxene do show signs of dissolution. Whether this stems from rainwater – the main objective – or from organic acids and bacteria in the soils is yet to be determined. No doubt NASA is doing much the same to see if dusts that coat much of Mars can be converted into soils  Beerling et al. acknowledge that the speed of weathering is a major uncertainty. Large-scale field trials seem some way off, and are likely to be plagued by cussedness! Will farmers willingly change their practices so dramatically?

See also: Lehmann, J & Possinger, A. 2020. Removal of atmospheric CO2 by rock weathering holds promise for mitigating climate change. Nature, v. 583, p. 204-205; DOI: 10.1038/d41586-020-01965-7

Note (added 15 July 2020): Follower Walter Pohl has alerted me to an interesting paper on using ultramafic rocks in the same way (Kelemen, P.B. et al. 2020. Engineered carbon mineralization in ultramafic rocks for COremoval from air: Review and new insights. Chemical Geology, v.  550, Article 119628; DOI:10.1016/j.chemgeo.2020.119628). Walter’s own blog contains comments on the climatic efficacy of MgCO3 (magnesite) formed when olivine is weathered.

Turmoil in Roman Republic followed Alaskan volcanic eruption

That activities in the global political-economic system are now dramatically forcing change in natural systems is clear to all but the most obdurate. In turn, those changes increase the likelihood of a negative rebound on humanity from the natural world. In the first case, data from ice cores suggests that an anthropogenic influence on climate may have started with the spread of farming in Neolithic times. Metal pollution of soils had an even earlier start, first locally in Neanderthal hearths whose remains meet the present-day standards for contaminated soil, and more extensively once Bronze Age smelting of copper began. Global spread of anomalously high metal concentrations in atmospheric dusts shows up as ‘spikes’ in lead within Greenland ice cores during the period from 1100 BCE to 800 CE. This would have resulted mainly from ‘booms and busts’ in silver extraction from lead ores and the smelting of lead itself. In turn, that may reflect vagaries in the world economy of those times

Precise dating by counting annual ice layers reveals connections of Pb peaks and troughs with major historic events, beginning with the spread of Phoenician mining and then by Carthaginians and Romans, especially in the Iberian Peninsula. Lead reaches a sustained peak during the acme of the Roman Republic from 400 to 125 BC to collapse during widespread internal conflict during the Crisis of the Republic. That was resolved by the accession of Octavian/Augustus as Emperor in 31 BCE and his establishment of Pax Romana across an expanded empire. Lead levels rose to the highest of Classical Antiquity during the 1st and early 2nd centuries CE. Collapse following the devastating Antonine smallpox pandemic (165 to 193 CE) saw the ice-core records’ reflecting stagnation of coinage activity at low levels for some 400 years, during which the Empire contracted and changed focus from Rome to Constantinople. Only during the Early Medieval period did levels rise slowly to the previous peak.

The Okmok caldera on the Aleutian island of Umnak (Credit: Desert Research Institute, Reno, Nevada USA)

Earth-logs has previously summarised how natural events, mainly volcanic eruptions, had a profound influence in prehistory. The gigantic eruption of Toba in Sumatra (~73 ka ago) may have had a major influence on modern-humans migrating from Africa to Eurasia. The beginning of the end for Roman hegemony in the Eastern Mediterranean was the Plague of Justinian (541–549 CE), during which between 25 to 50 million people died of bubonic plague across the Eastern Empire. This dreadful event followed the onset of famine from Ireland to China, which was preceded by signs of climatic cooling from tree-ring records, and also with a peak of volcanogenic sulfate ions in the Greenland and Antarctic ice caps around 534 CE. Regional weakening of the populace by cold winters and food shortages, also preceded the Black Death of the mid-14th century. In the case of the Plague of Justinian, it seems massive volcanism resulted in global cooling over a protracted period, although the actual volcanoes have yet to be tracked down. Cooling marked the start of a century of further economic turmoil reflected by lead levels in ice cores (see above). Its historical context is the Early Medieval equivalent of world war between the Eastern Roman Empire, the Sassanid Empire of Persia and, eventually, the dramatic appearance on the scene of Islam and the Arabian, Syrian and Iraqi forces that it inspired (see: Holland, T. 2013. In the Shadow of the Sword: The battle for Global Empire and the End of the Ancient World. Abacus, London)

An equally instructive case of massive volcanism underlying social, political and economic turmoil has emerged from the geochemical records in five Greenlandic ice cores and one from the Siberian island of Severnaya Zemlya (McConnell, J.R. and 19 others 2020. Extreme climate after massive eruption of Alaska’s Okmok volcano in 43 BCE and effects on the late Roman Republic and Ptolemaic Kingdom. Proceedings of the National Academy of Sciences, recent article (22 June 2020); DOI: 10.1073/pnas.2002722117). In this case the focus was on ice layers in all six cores that contain sulfate spikes and, more importantly, abundant volcanic dust, specifically shards of igneous glass. Using layer counting, all six show major volcanism in the years 45 to 43 BCE. The Ides (15th) of March 44 BCE famously marked the assassination of Julius Caesar, two years after the Roman Republic’s Senate appointed him Dictator, following four years of civil war. This was in the later stages of the period of economic decline signified by the fall in ice-core levels of Pb (see above). The Roman commentator Servius reported “…after Caesar had been killed in the Senate on the day before, the sun’s light failed from the sixth hour until nightfall.” Other sources report similar daytime dimming, and unusually cold weather and famine in 43 and 42 BCE.

As well as pinning down the date and duration of the volcanic dust layers precisely (to the nearest month using laser scanning of the ice cores’ opacity), Joseph McConnell and the team members from the US, UK, Switzerland, Germany and Denmark also chemically analysed the minute glass shards from one of the Greenlandic ice cores. This has enabled them to identify a single volcano from 6 possible candidates for the eruption responsible for the cold snap: Okmok, an active, 8 km wide caldera in the Aleutian Islands of Alaska. Previous data suggest that its last major eruption was 2050 years ago and blasted out between 10 to 100 km3 of debris, including ash. Okmok is an appropriate candidate for a natural contributor to profound historic change in the Roman hegemony. The authors also use their ice-core data to model Okmok’s potential for climate change: it had a global reach in terms of temperature and precipitation anomalies. Historians may yet find further correlations of Okmok with events in other polities that kept annual records, such as China.

See also: Eruption of Alaska’s Okmok volcano linked to period of extreme cold in ancient Rome (Science Daily, 22 June 2020); Kornei, K. 2020. Ancient Rome was teetering. Then a volcano erupted 6,000 miles away. (New York Times, 22 June 2020)

Did an impact affect hunter gatherers at the start of the Younger Dryas?

Whether or not the return to a glacial climate between 12.8 and 11.7 thousand years (ka) ago, known as the Younger Dryas (YD), was triggered by some kind of extraterrestrial impact has been a hot and sometimes fractious issue since 2007 (see: Whizz-bang view of Younger Dryas; Earth-logs, July 2007). Before then the most favoured causal mechanism was a shutdown of the Gulf Stream’s Arctic warming influence as a result of some kind of catastrophic flooding of fresh water into the North Atlantic. That would have lowered the density of surface waters, thereby preventing them from sinking to drive the deep circulation that draws surface water from the tropics into high northern latitudes (see: The Younger Dryas flood; May 2010). In 2008 the melt-water flood supporters were sufficiently piqued by the suggestion of a hitherto unsuspected impact event to mount a powerful rejoinder (see: Impact cause for Younger Dryas draws flak; May 2008), casting doubt on the validity of the data that had been presented. It seemed like a repeat of the initial furore over claims for a ‘mountain falling out of the sky’ wiping out the dinosaurs and much else. Yet, like the claims by Alvarez pere et fils for the K-T impact, accumulated weight of evidence published by its protagonists eventually has given the idea of an impact trigger for the YD a measure of respectability. This began with evidence of an impact crater beneath the Greenland icecap (see: Subglacial impact structure in Greenland: trigger for Younger Dryas?; November 2018), then signs of a 12.8 ka fire storm in Chile followed by geochemical evidence from South Carolina, USA for a coinciding impact (see: More on the Younger Dryas causal mechanism; November 2019).

Colour-coded subglacial topography from radar sounding over the Hiawatha Glacier of NW Greenland, showing a possible impact crater (Credit: Kjaer et al. 2018; Fig. 1D)

The YD played havoc with humans who had begun to repopulate northern Europe from their Ice Age refuges in the south and those who had first ventured into the Americas  across the Beringia land bridge between Siberia and Alaska. The climate decline was extremely rapid, spanning a mere decade or so, and many would have been trapped to perish in what again became frigid steppe land. There is now evidence that late-Palaeolithic to Mesolithic hunter gatherers living far south of the reglaciated zone also suffered devastation at the start of the YD (Moore, A.M.T. and 13 others 2020. Evidence of Cosmic Impact at Abu Hureyra, Syria at the Younger Dryas Onset (~12.8 ka): High-temperature melting at > 2,200 °C. Nature Science Reports, v. 10, p. 1-22; doi: 10.1038/s41598-020-60867-w). Abu Hureyra is a tell – a mound settlement – originally on the banks of the Euphrates in northern Syria. It now lies beneath Lake Assad, but was excavated in the early 1970s to reveal a charcoal-littered habitation surface with signs of a settlement and some cultivation. Charcoal from archived samples yielded a precise radiocarbon age of 12825 ± 55 ka, coinciding with the start of the YD. The sediment from the habitation floor also contained signs compatible with ejecta from a high-energy impact: tiny diamonds and glass spherules. Analyses of the glass by the authors suggests that it formed at a temperature up to 2200°C, far greater than that of magma associated with a volcanic eruption or in hearths used by the inhabitants. However, others have analysed the glass and suggest more mundane temperatures that could be explained more simply by accidental burning of thatched huts. That possibility might explain the lack of other impact indicators, such as shocked mineral grains and anomalous geochemistry, particularly the platinum-group metals that were the original ‘smoking gun’ for the K-T boundary event and other major impacts. Incidentally, these crucial indicators have been reported from other YD sites investigated by several members of the team behind this paper. My view is that what seems to be a remarkable coincidence will not settle the matter, but will probably draw the same kind of ‘flak’ as did others on this topic. It is hardly likely that new samples will be collected from the now submerged Abu Hureyra site.

See also: Cometary Debris may have destroyed Paleolithic settlement 12,800 years ago (Science News. 2 July 2020)

Update on climate and sea-level change during the Cenozoic

The Cenozoic Era was a period of fundamental change in the outer part of the Earth system. It culminated in the greatest climatic cooling since the Permian Period, during which upright apes emerged between 6 to 10 Ma ago.  The most decisive part of hominin evolution – the appearance of our own genus Homo – took place in the last 2.5 Ma that saw icecaps plastered over both polar regions and repeated pulses of major climate upheaval that dramatically affected all parts of the continents. Whereas the Mesozoic was dominated by reptiles, most famously the dinosaurs, the Cenozoic is rightly known as the age of mammals and of birds. The flowering plants, especially grasses, also transformed terrestrial ecosystems. The background to what has become ‘our time’ is not only climate change, but massive shifts in sea level and the outlines of the continents. For more than two decades many palaeoclimatologists have focused on the Cenozoic, gathering data using a variety of rapidly advancing technologies from a growing number of sites, in sediments from the continents and the ocean floor. One problem has been correlating all this global data precisely, coming as it does from many incomplete sedimentary sequences dotted around the planet. A great deal of basic information has come from the petroleum industry, which, of course, has continually eyed sedimentary rocks as the source of hydrocarbons through the 20th century. It was seismic reflection surveying that first gave clues to global ups and downs of sea level from onlaps and offlaps of strata that are visible on seismic sections, amplified by sequence stratigraphy. Six geoscientists from Rutgers University in New Jersey, USA have blended oil-industry archives with academic research to produce the first fully calibrated, comprehensive record of the Cenozoic (Miller, K.G. et al. 2020. Cenozoic sea-level and cryospheric evolution from deep-sea geochemical and continental margin records. Science Advances, v. 6, article eaaz1346; DOI: 10.1126/sciadv.aaz1346).

Latest palaeoclimate data for the Cenozoic Era. A oxygen-isotope data from benthic foraminifera (pale blue = polar icecaps, green = ice-free, pink – hothouse); B estimated mean sea-surface temperature from the calcium/magnesium ratio in Pacific Ocean cores; C variation in global mean sea level estimated from A and corrected for changes in the density of seawater due to water temperature (B); D atmospheric CO2 variations estimated using various proxies – see top right box. Click on the image to show a full-size version in a new browser tab. (Credit: Miller et al. 2020; Fig. 1)

Fluctuations in the proportion of 18O (δ18O) in the tests of foraminifera that lived in deep water are the key to global changes in sea level  and point to the influence of glacial ice accumulating on land (see Cooling sets in: Stepping Stones, Chapter 17). This is because glaciers are made from water that has evaporated from the oceans. When this happens, water that incorporates the lighter 16O isotope evaporates more easily and becomes enriched in atmospheric water vapour. When this water falls as snow that accumulates on land to form ice, the oceans are slightly enriched in the heavier 18O: δ18O incorporated into the shelly material of organism dwelling in the deep ocean increases at levels of a few parts per thousand. Conversely, their δ18O decreases when huge ice caps melt (A on the figure). The oxygen isotope records from fossils in ocean floor sediments give a far more precise impression of fluctuating sea level than do seismic sections and sequence stratigraphy of sedimentary rocks that interest the oil industry. But it is an ‘impression’, because other factors affect sea level.

Not only the global volume of ocean water is involved: the volume of the ocean basins changes too. This can occur because of changes in the rate of sea-floor spreading: when that is fast the hot new oceanic lithosphere is less dense and so buoys-up part of the ocean floor to drive sea level upwards. Slow spreading does the converse, as more lithosphere cools and sinks slightly. Another factor is the changing rate of marine sedimentation of material eroded from the continents. That fills ocean basins to some extent, again displacing the water upwards. When sediments are compacted as they become more deeply buried that has an effect too, to increase basin volume and result in sea-level fall. Oil industry geoscientists have attempted to allow for these long-term, slow mechanisms, to give a more accurate sea-level record.

Yet there is another important factor: the density and thus volume of ocean water changes with temperature. The warmer it is the greater the volume of ocean water and the higher is sea level. This is where academic work comes in handy. Two common elements that are dissolved in ocean water are magnesium and calcium. They also occur in the carbonate tests of the same deep-water forams that are used for oxygen-isotope measurements. It turns out that the warmer the water is the more magnesium enters the foram tests, and vice versa: their Mg/Ca ratio is a reliable proxy for mean ocean temperature and can be measured easily, centimetre-by-centimetre through cores. Kenneth Miller and colleagues have used this with the oxygen isotope proxy for land-ice volume to correct the sea-level record.

The Cenozoic ocean temperature record (B on the figure) is, in itself, interesting. It reveals far more large fluctuations than previously thought, especially in the Palaeocene and early Eocene. Yet, overall, the trend is one of steady cooling compared with the sudden shifts in δ18O that mark the onset of the Antarctic ice cap at the Eocene-Oligocene boundary around 34 Ma ago, and the apparent, temporary emergence from ‘ice-house conditions in the Middle Miocene. Also, sea level corrected for ocean temperature effects (C on the figure) suggests that for much of the Cenozoic sea level was lower than expected; i.e. it rarely exceeded 60 m above the current level, which is that expected when no substantial mass of  land ice exists.

The other important compilation made by Miller et al. is that of the CO2 content of the atmosphere estimated using six different proxies. It is a lot more fuzzy than the oceanic records because the proxies are not precise. Nevertheless, it is interesting. The current, partly anthropogenic level of around 400 parts per million (ppm) is not unique. In fact from 55 to 23 Ma it was consistently above this ‘Anthropocene’ level, peaking at twice that level at the end of the Eocene. That’s odd, because it doesn’t tally with the oxygen isotopes that indicate the onset of large scale Antarctic glaciation shortly afterwards. In fact most of the climatic highlights shown by A on the figure are not reflected in the Cenozoic history of the most influential greenhouse gas. In the short term of glacial-interglacial cycles during the late Pleistocene, atmospheric CO2 levels are very closely related to fluctuations of land-ice volume. In the 65 Ma of the Cenozoic such a link is hard to argue for. There are more puzzles than revelations in this otherwise major addition to palaeoclimatology.

Alternative explanation for interglacial climate instabilities; and a warning

For the past two and a half million years there has been no such thing as a stable climate on our home world. The major fluctuations that have given rise to glacial and interglacial episodes and the times that separate them are most familiar, as is their connection with the periodicity of gravitational effects on the Earth’s orbital and rotational behaviour. There are mysteries, such as the dominance of a ~100 ka cyclicity with the least effect on solar heating since a million years ago and the shift that took place then from dominant ~40 ka cycles that preceded it. But over shorter time scales there are more irregular climatic perturbations that can not be attributed to gravity variations in the Inner Solar System. In the run-up to maximal glacial conditions in the Northern Hemisphere are changes in the isotopic records that reveal increases and decreases in the mass of ice on continental masses. Known as Dansgaard-Oeschger events they occurred on a (very) roughly 10 ka basis and lasted between 1000 and 2000 years. They resulted in rapid temperature changes spanning up to 15°C over the Greenland ice cap and have been explained by changes in surface- and deep-water circulation within the North Atlantic. Effectively, the Gulf Stream and the thermohaline circulation that drives it were periodically shut down and turned on. Even more irregular in occurrence are sudden global coolings in the midst of general warming into interglacial episodes. The most spectacular of these was the Younger Dryas cooling to almost full-glacial conditions between 12.8 and 11.5 ka, at a time when the Earth had achieved a mean surface temperature almost as high as that which has prevailed over the last 11,000 years.  There have been lesser cold ‘snaps’ during the Holocene, and in every one of the earlier interglacials for which there are data. Their occurrence seems unpredictable, even chaotic.

In 2006 the Younger Dryas was explained as the result of massive amounts of freshwater flooding into the Arctic Ocean from huge, ice-dammed lakes in North America. Decreased density of the high-latitude surface water resulted in its failure to sink and thus drive thermohaline circulation (see The Younger Dryas and the Flood June 2006). This hypothesis has subsequently been applied to other such sudden climatic events, such as the cooling episode around 8.2 ka during the Holocene. A recent study set out to test this notion from ocean-floor records of the last half-million years (Galaasen, E.V. and 9 others 2020. Interglacial instability of North Atlantic Deep Water ventilation. Science, v. 367, p. 1485-1489; DOI: 10.1126/science.aay6381). The data are from a seafloor sediment core in a trough south of Greenland, where cold, salty and dense bottom water flows southward from the Arctic to drag warmer surface water northwards in the Gulf Stream to replace it. That warm surface water has a high salinity because of evaporation in the tropics, so once it cools it sinks, thereby maintaining thermohaline circulation.

Modelled circulation rate of Atlantic circulation during 10 ka of the last interglacial before the Holocene (credit: Thomas Stocker, 2020 Science)

Eirik Galaasen of the University of Bergen and colleagues from several countries flanking the North Atlantic found large, abrupt changes in the mass flow of water through the trough – based on studies of carbon isotopes in bottom-living foraminifera – during each of the four interglacials that preceded the current one. The higher the δ13C in the forams the more vigorous the deep flow, whereas low values suggest weak flow or stagnation, due to waning of thermohaline circulation. Transition between the two states is rapid and each state lingered for several centuries. While the Holocene records only one such perturbation of note, that at 8.2 ka, previous interglacials reveal dozens of them. One possibility is that the thermohaline circulation system of the North Atlantic behaved in a chaotic fashion during previous interglacial episodes, producing similarly erratic shifts in climate. Seemingly, the Holocene bucks the trend, which may have added an element of luck to the establishment of human agricultural economies throughout that Epoch. All the signs are that current, anthropogenic global warming will slow down the water circulation in the North Atlantic. Might that set-off what seems to have been the norm of chaotic interglacial climate shifts for the best part of that half-million years? Hard to tell, without more studies …

See also: Stocker, T.F. 2020. Surprises for climate stability. Science, v. 367, p. 1425-1426; DOI: 10.1126/science.abb3569; How stable is deep ocean circulation in warmer climate? (Science Daily)

Soluble iron and global climate

The environment that humans inhabit is better described as the Earth System, for a good reason. Every part of our planet, the living and the seemingly inert, from the core to the outermost atmosphere, is and always has been interacting with all the others in one way or another. Earth-logs aims to express that, as does my recently revised and now free book Stepping Stones. The vagaries of the Earth’s climate present good examples, the most obvious being the role of chemistry in the form of atmospheric greenhouse gases, especially carbon dioxide, and their interaction with other parts of the Earth System.

Carbon and oxygen atoms that make up CO2 are also present in dissolved form in rain, freshwater and the oceans as the dissolved gas itself, carbonic acid (H2CO­3­) and the soluble bicarbonate ion HCO3, in proportions that depend on water temperature and acidity (pH). Those forms make the oceans an extremely large ‘sink’ for carbon; i.e. CO2 in dissolved form is removed from the atmospheric greenhouse effect. In the short term, there is a rough balance because water bodies also emit CO2, particularly when they heat up.

Phytoplankton bloom in the Channel off SW England (Landsat image)

Carbon dioxide enters more resilient forms through the marine part of the biosphere, at the base of which is photosynthesising phytoplankton. Photosynthesisers ‘sequester’ CO2 from the oceans as various carbohydrates in their soft tissue. Some of them use bicarbonate ions to form calcium carbonate in shells or tests. Once the organisms die both their soft and hard parts may end up buried in ocean-floor sediments: a longer-term sink. How much carbon is buried in these two forms depends on whether bacteria break down the soft tissues by oxidation and on the acidity of water that tends to dissolve the carbonate. Both processes ultimately yield dissolved CO2 that returns to the atmosphere.

Even the simplest phytoplankton cannot live on carbon dioxide and water alone: they need nutrients. The most familiar to any gardener are nitrogen, phosphorus and potassium. These are mainly supplied in runoff from the continents; although marine upwellings supply large amounts where deep ocean water is forced to the surface. Large tracts in the central parts of the oceans are, in effect, marine deserts whose biological productivity is very low. Surprisingly this is not because of severe shortages of N, P and K. This is because a key nutrient, albeit a minor one, is missing; dissolved iron that phytoplankton and ocean fertility in general depend on. This was discovered in the 1970s by US oceanographer John Martin. Just how important iron is to fertility of the oceans and to global climate emerged from studies of ice cores from the Antarctic ice sheet. Air bubbles in the myriad annual layers reveal that their CO2 content falls with each change in oxygen isotopes related to the periodic build up of polar ice caps during cold periods. The greenhouse effect diminished as a result during each stadial, for the simple reason that up to a third of all atmospheric carbon dioxide – about 200 billion tonnes – was withdrawn. The clearest of these are at the last glacial maximum and during the rapid build up glacial ice between 70 and 60 thousand years ago; a time of low sea level when a major ‘out-of-Africa’ human migration took place. A possible candidate for achieving this could have been massively increased ocean fertility and the burial of dead phytoplankton and their shells.

Analyses of Antarctic ice cores record fluctuations in atmospheric CO2 trapped in bubbles during the last ice age (top) and how iron-rich dust deposition onto the ice increased hugely during two major cold periods (bottom) – the last glacial maximum (35 to 18 ka) and between 70 and 60 ka. (Credit, Stoll; Fig. 1)

During stadials the ice cores also reveal that a great deal more dust found its way from the continents to the polar ice sheets. Analysing the dusty layers showed that to have included lots of iron. Falling into the cold ocean-surface waters around the polar regions would have added this crucial nutrient to a medium already rich in CO2 – the colder water is the more gas it will dissolve. These distant oceans bloomed with phytoplankton, speeding up the sequestration of carbon into ocean-floor sediments. Iron may have triggered a biological pump of gargantuan proportions that amplified ice-age cooling. Today the remotest parts of the world’s oceans are starved of iron so the pump only functions in a few places where iron is supplied by rivers or upwellings of deep ocean water

The marine biosphere is clearly a very important active component in the Earth’s climate subsystem. Climate’s continually changing interactions with the rest of the Earth System make climate change hugely complex. It is difficult to predict but growing understanding of its past behaviour is helpful. The late John Martin’s hypothesis of the effects on climate of changing iron concentrations in surface ocean water has a corollary: the stronger the biological pump the more oxygen in deep water must be used up in bacterial decay of descending organic matter. Indeed it was as recent estimates of the degree of oxygenation in ocean-sediment layers correlate with changes in climate that they also reveal.

So, would deliberate iron-fertilisation of polar oceans help draw down greenhouse warming? When several small patches of the Southern Ocean were injected with a few tonnes of dissolved iron they did indeed respond with phytoplankton blooms. However, it is impossible to tell if that had any effect on the atmosphere. ‘Going for broke’ with a massive fertilisation of this kind has been proposed, but this ventures dp into the political swamp that currently surrounds global warming and the wider environment. It is becoming possible to model such a strategy by using the data from the experiments and from ice cores, and early results seem to confirm the role of iron and the biological pump in CO2 sequestration by suggesting that half the known draw-down during ice ages can be explained in this way.

Based on a review by: Heather Stoll in February 2020. (30 years of the iron hypothesis of ice ages. Nature, v. 578, p. 370-371; DOI: 10.1038/d41586-020-00393-x}

Finding Archaean atmospheric composition using micrometeorites

Modern micrometeorites (about 20 μm in diameter) from deep-sea sediments, with shiny magnetite-rich veneers (Credit: D. E. Brownlee)

The gases making up the Earth’s atmosphere and their relative proportions before 2.5 billion years (Ga) ago are known with very little certainty. Carbonate rocks are rare, indicating that the oceans were more acidic, which implies that they had dissolved more CO2 from the atmosphere, which, in turn implies that there was much more of that gas than in present air. There are few signs of widespread glaciogenic sediments of Archaean age, at a time when the Sun’s energy output is estimated to have been at 70 to 75% of its present level. Without an enhanced greenhouse effect oceans would have been frozen over; so that supports high CO2 concentrations too. The fact that water worn grains of minerals such as uraninite (UO2) and pyrite (FeS2), which are stable only in reducing conditions, occur in Archaean conglomerates is a good indicator that there were only vanishingly small amounts of oxygen in the air. That was not to change until marine photosynthesisers produced enough to overcome the general reducing conditions at the Earth’s surface, marked by the Great Oxidation Event at around 2.4 Ga (see: Massive event in the Precambrian carbon cycle; Earth-logs, January 2012. Search for more articles in sidebar at Earth-logs home page). It was then that ancient soils (palaeosols) became the now familiar red colour because of their content of ferric iron oxides and hydroxides The problem is that reliable numbers cannot be attached to these kinds of observation. A common means of estimating CO2 levels comes from the way in which the gas reacts with silicates as soils form at the land surface, estimated from carbon isotopes in soil carbonate nodules. Since the rise of land plants around 400 Ma ago the distribution of pores (stomata) in fossil leaves provides a more precise estimate: the more CO2 in air the less densely packed are leaf stomata. For the Precambrian we are stuck with estimates based on chemical reactions of minerals with the atmosphere. Until recently, one reaction that must always have been extremely common was overlooked.

When meteorite pass through the atmosphere at very high speed friction heats them to incandescence. Their surfaces not only melt but the minerals from which they are composed react very strongly with air. The reaction products should therefore provide chemical clues to the relative proportions of atmospheric gases. Both oxygen and carbon dioxide are reactive at such temperatures, although nitrogen is virtually inert, yet it tends to buffer oxidation reactions. The rest of the atmosphere comprises noble gases – mainly argon – and by definition they are completely unreactive. Pure-iron micrometeorites collected from 2.7 Ga old sediments in the Pilbara Province of Western Australia are veneered with magnetite (Fe3O4) and wüstite (FeO), thus preserving a record of their passage through the Neoarchaean atmosphere. If the oxidant had been oxygen, for these minerals to form from elemental iron suggests oxygen levels around those prevailing today: clearly defying the abundant evidence for its near-absence during the Archaean. Carbon dioxide is the only candidate. Two studies have produced similar results (Lehmer, O. R. et al. 2020. Atmospheric CO2 levels from 2.7 billion years ago inferred from micrometeorite oxidationScience Advances, v. 6, article aay4644;  DOI: 10.1126/sciadv.aay4644 and Payne, R.C. et al. 2020. Oxidized micrometeorites suggest either high pCO2 or low pN2 during the Neoarchean. Proceedings of the National Academy of Sciences, v. 117 1360 DOI:10.1073/pnas.1910698117). Both use complex modelling of the chemical effects of meteorite entry. Lehmer and colleagues estimated that the Neoarchaean atmosphere contained about 64% CO2, with a surface atmospheric pressure about half that at present. This would be sufficient for a surface temperature of about 30°C achieved by the greenhouse effect, taking into account lower solar heating. The team led by Payne concluded a lower concentration (25 to 50%) and a somewhat cooler planet at that time. Both results suggest ocean water considerably more acid than are today’s. The combined warmth and acidity would have had a fundamental bearing on both the origin, survival and evolution of early life.

See also: Carroll, M. 2020. Meteorites reveal high carbon dioxide levels on early Earth; Yirka, R. Computer model shows ancient Earth with an atmosphere 70 percent carbon dioxide. (both from

Closure for the K-Pg extinction event?

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

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

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

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

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

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

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

How marine animal life survived (just) Snowball Earth events

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

Risks of sudden changes linked to climate

The Earth system comprises a host of dynamic, interwoven components or subsystems. They involve processes deep within Earth’s interior, at its surface and in the atmosphere. Such processes combine inorganic chemistry, biology and physics. To describe them properly would require a multi-volume book; indeed an entire library, but even that would be even more incomplete than our understanding of human history and all the other social sciences. Cut to its fundamentals, Earth system science deals with – or tries to – a planetary engine. In it, the available energy from inside and from the Sun is continually shifted around to drive the bewildering variety, multiplicity of scales and variable paces of every process that makes our planet the most interesting thing in the entire universe. It has done so, with a variety of hiccups and monumental transformations, for some four and half billion years and looks likely to continue on its roiling way for about five billion more – with or without humanity. Though we occupy a tiny fraction of its history we have introduced a totally new subsystem that in several ways outpaces the speed and the magnitude of some chemical, physical and organic processes. For example: shifting mass (see the previous item, Sedimentary deposits of the ‘Anthropocene’); removing and modifying vegetation cover; emitting vast amounts of various compounds as a result of economic activity – the full list is huge. In such a complex natural system it is hardly surprising that rapidly increasing human activities in the last few centuries of our history have hitherto unforeseen effects on all the other components. The most rapidly fluctuating of the natural subsystems is that of climate, and it has been extraordinarily sensitive for the whole of Earth history.

Cartoon metaphor for a ‘tipping point’ as water is added to a bucket pivoted on a horizontal axis. As water level rises to below the axis the bucket becomes increasingly stable. Once the level rises above this pivot instability sets in until the syetem suddenly collapses

Within any dynamic, multifaceted system-component each contributing process may change, and in doing so throw the others out of kilter: there are ‘tipping points’. Such phenomena can be crudely visualised as a pivoted bucket into which water drips and escapes. While the water level remains below the pivot, the system is stable. Once it rises above that axis instability sets in; an external push can, if strong enough, tip the bucket and drain it rapidly. The higher the level rises the less of a push is needed. If no powerful push upsets the system the bucket continues filling. Eventually a state is reached when even a tiny force is able to result in catastrophe. One much cited hypothesis invokes a tipping point in the global climate system that began to allow the minuscule effect on insolation from changes in the eccentricity of Earth’s orbit to impose its roughly 100 ka frequency on the ups and downs of continental ice volume during the last 800 ka. In a recent issue of Nature a group of climate scientists based in the UK, Sweden, Germany, Denmark, Australia and China published a Comment on several potential tipping points in the climate system (Lenton, T.M. et al. 2019. Climate tipping points — too risky to bet against. Nature, v. 575, p. 592-595; DO!: 10.1038/d41586-019-03595-0). They list what they consider to be the most vulnerable to catastrophic change: loss of ice from the Greenland and Antarctic ice sheets; melting of sea ice in the Arctic Ocean; loss of tropical and boreal forest; melting of permanently frozen ground at high northern latitudes; collapse of tropical coral reefs; ocean circulation in the North and South Atlantic.

The situation they describe makes dismal reading. The only certain aspect is the steadily mounting level of carbon dioxide in the atmosphere, which boosts the retention of solar heat by delaying the escape of long-wave, thermal radiation from the Earth’s surface to outer space through the greenhouse effect. An ‘emergency’ – and there can be little doubt that one of more are just around the corner – is the product of ‘risk’ and ‘urgency’. Risk is the probability of an event times the damage it may cause. Urgency is the product of reaction time following an alert divided by the time left to intervene before catastrophe strikes. Not a formula designed to make us confident of the ‘powers’ of science! As the commentary points out, whereas scientists are aware of and have some data on a whole series of tipping points, their understanding is insufficient to ‘put numbers on’ These vital parameters. And there may be other tipping points that they are yet to recognise.  Another complicating factor is that in a complex system catastrophe in one component can cascade through all the others: a tipping may set off a ‘domino effect’ on all the others. An example is the steady and rapid melting of boreal permafrost. Frozen ground contains methane in the solid form of gas hydrate, which will release this ‘super-greenhouse’ gas as melting progresses.   Science ‘knows of’ such potential feedback loops in a largely untried, theoretical sense, which is simply not enough.

A tipping point that has a direct bearing on those of us who live around the North Atlantic resides in the way that water circulates in that vast basin. ‘Everyone knows about’ the Gulf Stream that ships warm surface water from equatorial latitudes to beyond the North Cape of Norway. It keeps NW Europe, otherwise subject to extremely cold winter temperatures, in a more equable state. In fact this northward flow of surface water and heat exerts controls on aspects of climate of the whole basin, such as the tracking of tropical storms and hurricanes, and the distribution of available moisture and thus rain- and snowfall. But the Gulf Steam also transports extra salt into the Arctic Ocean in the form of warm, more briny surface water. Its relatively high temperature prevents it from sinking, by reducing its density. Once at high latitudes, cooling allows Gulf-Steam water to sink to the bottom of the ocean, there to flow slowly southwards. This thermohaline circulation effectively ‘drags’ the Gulf Stream into its well-known course. Should it stop then so would the warming influence and the control it exerts on storm tracks. It has stopped in the past; many times. The general global cooling during the 100 ka that preceded the last ice age witnessed a series of lesser climate events. Each began with a sudden global warming followed by slow but intense cooling, then another warming to terminate these stadials or Dansgaard-Oeschger cycles (see: Review of thermohaline circulation, Earth-logs February 2002). The warming into the Holocene interglacial since about 20 ka was interrupted by a millennium of glacial cold between 12.9 and 11.7 ka, known as the Younger Dryas (see: On the edge of chaos in the Younger Dryas, Earth-logs May 2009). A widely supported hypothesis is that both kinds of major hiccup reflected shuts-down of the Gulf Stream due to sudden influxes of fresh water into North Atlantic surface water that reduced its density and ability to sink. Masses of fresh water are now flowing into the Arctic Ocean from melting of the Greenland ice sheet and thinning of Arctic sea ice (also a source of fresh water). Should the Greenland ice sheet collapse then similar conditions for shut-down may arise – rapid regional cooling amidst global warming – and similar consequences in the Southern Hemisphere from the collapse of parts of the Antarctic ice sheets and ice shelves.  Lenton et al. note that North Atlantic thermohaline circulation has undergone a 15% slowdown since the mid-twentieth century…

See also: Carrington, D. 2019. Climate emergency: world ‘may have crossed tipping points’ (Guardian, 27 November 2019)