Thawing permafrost, release of carbon and the role of iron

Projected shrinkage of permanently frozen ground i around the Arctic Ocean over the next 60 years

Global warming is clearly happening. The crucial question is ‘How bad can it get?’ Most pundits focus on the capacity of the globalised economy to cut carbon emissions – mainly CO2 from fossil fuel burning and methane emissions by commercial livestock herds. Can they be reduced in time to reverse the increase in global mean surface temperature that has already taken place and those that lie ahead? Every now and then there is mention of the importance of natural means of drawing down greenhouse gases: plant more trees; preserve and encourage wetlands and their accumulation of peat and so on. For several months of the Northern Hemisphere summer the planet’s largest bogs actively sequester carbon in the form of dead vegetation. For the rest of the year they are frozen stiff. Muskeg and tundra form a band across the alluvial plains of great rivers that drain North America and Eurasia towards the Arctic Ocean. The seasonal bogs lie above sediments deposited in earlier river basins and swamps that have remained permanently frozen since the last glacial period. Such permafrost begins at just a few metres below the surface at high latitudes down to as much as a kilometre, becoming deeper, thinner and more patchy until it disappears south of about 60°N except in mountainous areas. Permafrost is melting relentlessly, sometimes with spectacular results broadly known as thermokarst that involves surface collapse, mudslides and erosion by summer meltwater.

Thawing permafrost in Siberia and associated collapse structures

Permafrost is a good preserver of organic material, as shown by the almost perfect remains of mammoths and other animals that have been found where rivers have eroded their frozen banks. The latest spectacular find is a mummified wolf pup unearthed by a gold prospector from 57 ka-old permafrost in the Yukon, Canada. She was probably buried when a wolf den collapsed. Thawing exposes buried carbonaceous material to processes that release CO, as does the drying-out of peat in more temperate climes. It has long been known that the vast reserves of carbon preserved in frozen ground and in gas hydrate in sea-floor sediments present an immense danger of accelerated greenhouse conditions should permafrost thaw quickly and deep seawater heats up; the first is certainly starting to happen in boreal North America and Eurasia. Research into Arctic soils had suggested that there is a potential mitigating factor. Iron-3 oxides and hydroxides, the colorants of soils that overlie permafrost, have chemical properties that allow them to trap carbon, in much the same way that they trap arsenic by adsorption on the surface of their molecular structure (see: Screening for arsenic contamination, September 2008).

But, as in the case of arsenic, mineralogical trapping of carbon and its protection from oxidation to CO2 can be thwarted by bacterial action (Patzner, M.S. and 10 others 2020. Iron mineral dissolution releases iron and associated organic carbon during permafrost thaw. Nature Communications, v. 11, article 6329; DOI: 10.1038/s41467-020-20102-6). Monique Patzner of the University of Tuebingen, Germany, and her colleagues from Germany, Denmark, the UK and the US have studied peaty soils overlying permafrost in Sweden that occurs north of the Arctic Circle. Their mineralogical and biological findings came from cores driven through the different layers above deep permafrost. In the layer immediately above permanently frozen ground the binding of carbon to iron-3 minerals certainly does occur. However, at higher levels that show evidence of longer periods of thawing there is an increase of reduced iron-2 dissolved in the soil water along with more dissolved organic carbon – i.e. carbon prone to oxidation to carbon dioxide. Also, biogenic methane – a more powerful greenhouse gas – increases in the more waterlogged upper sediments. Among the active bacteria are varieties whose metabolism involves the reduction of insoluble iron in ferric oxyhdroxide minerals to the soluble ferrous form (iron-2). As in the case of arsenic contamination of groundwater, the adsorbed contents of iron oxyhydroxides are being released as a result of powerful reducing conditions.

Applying their results to the entire permafrost inventory at high northern latitudes, the team predicts a worrying scenario. Initial thawing can indeed lock-in up to tens of billion tonnes of carbon once preserved in permafrost, yet this amounts to only a fifth of the carbon present in the surface-to-permafrost layer of thawing, at best. In itself, the trapped carbon is equivalent to between 2 to 5 times the annual anthropogenic release of carbon by burning fossil fuels. Nevertheless, it is destined by reductive dissolution of its host minerals to be emitted eventually, if thawing continues. This adds to the even vaster potential releases of greenhouse gases in the form of biogenic methane from waterlogged ground. However, there is some evidence to the contrary. During the deglaciation between 15 to 8 thousand years ago – except for the thousand years of the Younger Dryas cold episode – land-surface temperatures rose far more rapidly than happening at present. A study of carbon isotopes in air trapped as bubbles in Antarctic ice suggests that methane emissions from organic carbon exposed to bacterial action by thawing permafrost were much lower than claimed by Patzner et al. for present-day, slower thawing (see: Old carbon reservoirs unlikely to cause massive greenhouse gas release, study finds. Science Daily, 20 February 2020) – as were those released by breakdown of submarine gas hydrates.

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.

How permanent is the Greenland ice sheet?

80% of the world’s largest island is sheathed in glacial ice up to 3 km thick, amounting to 2.85 million km3. A tenth as large as the Antarctic ice sheet, if melted it could still add over 7 m to global sea level if it melted completely; compared with 58 m should Antarctica suffer the same fate. Antarctica accumulated glacial ice from about 34 to 24 million years ago during the Oligocene Epoch, deglaciated to became largely ice free until about 12 Ma and then assumed a permanent, albeit fluctuating, ice cap until today. In contrast, Greenland only became cold enough to support semi-permanent ice cover from about 2.4 Ma during the late-Pliocene to present episode of ice-age and interglacial cycles. The base of the GRIP ice core from central Greenland has been dated at 1 Ma old, but such is the speed of ice movement driven by far higher snow precipitation than in Antarctica that it is possible that basal ice is shifted seawards. The deepest layers recovered by drilling have lost their annual layering as a result of ice’s tendency to deform in a plastic fashion so do not preserve detailed glacial history before about 110 ka. In contrast, the more slowly accumulating and more sluggishly moving Antarctic ice records over 800 ka of climatic cyclicity in continuous cores and has yielded 2.7 Ma old blue ice exposed at the surface with another 2 km lying beneath it.

However, sediments at the base of two ice cores from Greenland have raised the possibility of periods when the island was free of ice. One such example is from an early core drilled to a depth of 1390 m beneath the 1960’s US military’s nuclear weapons base, Camp Century. It helped launch the use of continental ice as a repository of Earth recent climatic history at a far better resolution than do sediment cores from the ocean floors. It languished in cold storage after it was transferred from the US to the University of Copenhagen. Recently, samples from the bottom 3 m of sediment-rich ice were rediscovered in glass jars. A workshop centring on this seemingly unprepossessing material took place in the last week of October 2019 at the University of Vermont, USA (Voosen, P. 2019. Mud in stored ice core hints at thawed Greenland. Science, v. 366, p. 556-557; DOI: 10.1126/science.366.6465.556.

Sediment recovered from the base of the Camp Century core through the Greenland ice sheet (credit Jean-Louis Tison, Free University of Brussels)

To the participants’ astonishment, among the pebbles and sand were fragments of moss and woody material. It was not till, but a soil; Greenland had once lost its ice cover. Measurement of radioactive isotopes 26Al and 10Be, that form when cosmic rays pass through exposed sand grains, revealed that the once vegetated soil had formed at about 400 ka. Preliminary DNA analyses of preserved plant material indicates species that would have thrived at around 10°C. Samples have been shared widely for comprehensive analysis  to reconstruct the kind of surface environment that developed during the 400 ka interglacial. Also, Greenland may have been bare of ice during several such relatively warm intervals. So other cores to the base of the ice may be in the funding pipeline. But most interest centres on the implications of a period of rapid anthropogenic climatic warming that may take Arctic temperatures above those that melted the Greenland ice sheet 400 ka ago.

See also: UVM Today 2019. Secrets under the ice.

The mid-Pleistocene transition

As shown by oxygen-isotope records from marine sediments, before about 1.25 Ma global climate cycled between cold and warm episodes roughly every 41 ka. Between 1.25 to 0.7 Ma these glacial-interglacial pulses lengthened to the ~100 ka periods that have characterised the last seven cycles that were also marked by larger volume of Northern Hemisphere ice-sheet cover during glacial maxima. Both periodicities have been empirically linked to regular changes in the Earth’s astronomical behaviour and their effects on the annual amount of energy received from the Sun, as predicted by Milutin Milankovich. As long ago as 1976 early investigation of changes of oxygen isotopes with depth in deep-sea sediments had revealed that their patterns closely matched Milankovich’s  hypothesis. The 41 ka periodicity matches the rate at which the Earth’s axial tilt changes, while the ~100 ka signal matches that for variation in the eccentricity of Earth’s orbit. 19 and 24 ka cycles were also found in the analysis that reflect those involved in the gyroscope-like precession of the axis of rotation. Surprisingly, the 100 ka cycling follows by far the weakest astronomical effect on solar warming yet the climate fluctuations of the last 700 ka are by far the largest of the last 2.5 million years. In fact the 2 to 8 % changes in solar heat input implicated in the climate cycles are 10 times greater than those predicted even for times when all the astronomical influences act in concert. That and other deviations from Milankovich’s hypothesis suggest that some of Earth’s surface processes act to amplify the astronomical drivers. Moreover, they probably lie behind the mid-Pleistocene transition from 41 to 100 ka cyclicity. What are they? Changes in albedo related to ice- and cloud cover, and shifts in the release and absorption of carbon dioxide and other greenhouse gases are among many suggested factors. As with many geoscientific conundrums, only more and better quality data about changes recorded in sediments that may be proxies for climatic variations are likely to resolve this one.

Adam Hazenfratz of ETH in Zurich and colleagues from several other European countries and the US have compiled details about changing surface- and deep-ocean temperatures and salinity – from δ18O and Mg/Ca ratios in foraminifera shells from a core into Southern Ocean-floor sediments – that go back 1.5 Ma (Hazenfratz, A.P. and 9 others 2019. The residence time of Southern Ocean surface waters and the 100,000-year ice age cycle. Science, v. 363, p. 1080-1084; DOI: 10.1126/science.aat7067). Differences in temperature and salinity (and thus density) gradients show up at different times in this critical sediment record. In turn, they record gross shifts in ocean circulation at high southern latitudes that may have affected the CO2 released from and absorbed by sea water. Specifically, Hazenfratz et al. teased out fluctuations in the rate of  mixing of dense, cold and salty water supplied to the Southern Ocean by deep currents with less dense surface water. Cold, dense water is able to dissolve more CO2 than does warmer surface water so that when it forms near the surface at high latitudes it draws down this greenhouse gas from the atmosphere and carries it into long-term storage in the deep ocean when it sinks. Deep-water formation therefore tends to force down mean global surface temperature, the more so the longer it resides at depth. When deep water wells to the surface and warms up it releases some of its CO2 content to produce an opposite, warming influence on global climate. So, when mixing of deep and surface waters is enhanced the net result is global warming, whereas if mixing is hindered global climate undergoes cooling.

The Southern Ocean, where most dissolved and gaseous carbon dioxide are emitted and absorbed by seawater (Credit: British Antarctic Survey)

The critical factor in the rate of mixing deep with surface water is the density of that at the surface. When its salinity and density are low the surface water layer acts as a lid on what lies beneath, thereby increasing the residence time of deep water and the CO2 that it contains. This surface ‘freshening’ in the Southern Ocean seems to have begun at around 1.25 Ma and became well established 700 ka ago; that is, during the mid-Pleistocene climate transition. The phenomenon helped to lessen the greenhouse effect after 700 ka so that frigid conditions lasted longer and more glacial ice was able to accumulate, especially on the northern continents. This would have made it more difficult for the 41 ka astronomically paced changes in solar heating to have restored the rate of deep-water mixing to release sufficient CO2 to return the climate to interglacial conditions That would lengthen the glacial-interglacial cycles. The link between the new 100 ka cyclicity and very weak forcing by the varying eccentricity of Earth’s orbit may be fortuitous. So how might anthropogenic global warming affect this process? Increased melting of the Antarctic ice sheet may further freshen surface waters of the Southern Ocean, thereby slowing its mixing with deep, CO2-rich deep water and the release of stored greenhouse gases. As yet, no process leading to the decreased density of surface waters between 1.25 and 0.7 Ma has been suggested, but it seems that something similar may attend global warming.

Related articles: Menviel, L. 2019. The southern amplifier. Science, v. 363, p. 1040-1041; DOI: 10.1126/science.aaw7196; The deep Southern Ocean is key to more intense ice ages (

Read more on Palaeoclimatology

Gas hydrates: a warning from the past

Detailed acoustic imaging above the Troll gas field in the northern North Sea off western Norway has revealed  tens of thousands of elliptical pits on the seabed. At around 10 to 20 per square kilometre over an area of about 15,000 km2 there are probably between 150 to 300 thousand of them. They range between 10 to 100 m across and are about 6 m deep on average, although some are as deep as 20 m. They are pretty much randomly distributed but show alignment roughly parallel to regional N-S sea-floor currents. Many of the world’s continental shelves display such pockmark fields, but the Troll example is among the most extensive. Almost certainly the pockmarks formed by seepage of gas or water to the surface. However, detailed observations suggest they are inactive structures with no sign of bubbles or fluid seepage. Yet the pits cut though glacial diamictites deposited by the most recent Norwegian Channel Ice Stream through which icebergs once ploughed and which is overlain by thin Holocene marine sediments. One possibility is that they record gas loss from the Troll field, another being destabilisation of shallow gas hydrate deposits.

Troll pockmarks
Parts of the Troll pockmark field off Norway. A: density of pockmarks in an area of 169 square km. B: details of a cluster of pockmarks. (Credit: Adriano Mazzini, Centre for Earth Evolution and Dynamics (CEED) University of Oslo)

Norwegian geoscientists have studied part of the field in considerable detail, analysing carbonate-rich blocks and foraminifera in the pits (Mazzini, A. and 8 others 2017. A climatic trigger for the giant Troll pockmark field in the northern North Sea. Earth and Planetary Science Letters, v. 464, p. 24-34; The carbonates show very negative δ13C values that suggest the carbon in them came from methane, which could indicate either of the two possible means of formation. However, U-Th dating of the carbonates and radiocarbon ages of forams in the marine sediment infill suggest that they formed at around 10 ka ago; 1500 years after the end of the Younger Dryas cold episode and the beginning of the Holocene interglacial. Most likely they represent destabilisation of a once-extensive, shallow layer of methane hydrates in the underlying sediments, conditions during the Younger Dryas having been well within the stability field of gas hydrates. Sporadic leaks from the deeper Troll gas field hosted by Jurassic sandstones is unlikely to have created such a uniform distribution of gas-release pockmarks. Adriano Mazzini and colleagues conclude that rapid early Holocene warming led to sea-floor temperatures and pressures outside the stability field of gas hydrates. There are few signs that hydrates linger in the area, explaining the present inactivity of the pockmarks – all the methane and CO2 escaped before 10 ka.

Gas hydrates are thought to be present beneath shallow seas today, wherever sea-floor sediments have a significant organic carbon content and within the pressure-temperature window of stability of these strange ice-like materials. Mazzini et al.’s analysis of the Troll pockmark field clearly has profound implications for the possible behaviour of gas hydrates at a time of global climatic warming. As well as their destabilisation adding to methane release from onshore peat deposits currently locked by permafrost and a surge in global warming, there is an even more catastrophic possibility. The whole of the seaboard of the southern North Sea was swept by a huge tsunami about 8000 years ago, which possibly wiped out Mesolithic human occupancy of lowland Britain, the former land mass of Doggerland, and the ‘Low Countries’ of western Europe. This was created by a massive submarine landslide – the Storegga Slide just to the north of the Troll field – which may have been triggered by destabilisation of submarine gas hydrates during early Holocene warming of the oceans.

Ancient CO2 estimates worry climatologists

Concerns about impending, indeed actual, anthropogenic climate change brought on by rapidly rising levels of the greenhouse gas carbon dioxide have spurred efforts to quantify climates of the distant past. Beyond the CO2 record of the last 800 ka established from air bubbles trapped in glacial ice palaeoclimate researchers have had to depend on a range of proxies for the greenhouse effect. Those based on models linking plate tectonic and volcanic CO2 emissions with geological records of the burial of organic matter, weathering and limestone accumulation are imprecise in the extreme, although they hint at considerable variation during the Phanerozoic. Other proxies give a better idea of the past abundance of the main greenhouse gas, one using the curious openings or stomata in leaves that allow gases to pass to and fro between plant cells and the atmosphere. Well preserved fossil leaves show stomata nicely back to about 400 Ma ago when plants first colonised the land.

Embed from Getty Images
Stomata on a rice leaf (credit: Getty images)

Stomata draw in CO2 so that it can be combined with water during photosynthesis to form carbohydrate. So the number of stomata per unit area of a leaf surface is expected to increase with lowering of atmospheric CO2 and vice versa. This has been observed in plants grown in different air compositions. By comparing stomatal density in fossilised leaves of modern plants back to 800 ka allows the change to be calibrated against the ice-core record. Extending this method through the Cenozoic, the Mesozoic and into the Upper Palaeozoic faces the problems of using fossils of long-extinct plant leaves. This is compounded by plants’ exhalation of gases to the atmosphere – some CO2 together with other products of photosynthesis, oxygen and water vapour. Increasing stomatal density when carbon dioxide is at low concentration risks dehydration. How extinct plant groups coped with this problem is, unsurprisingly, unknown. So past estimates of the composition of the air become increasingly reliant on informed guesswork rather than proper calibration. The outcome is that results from the distant past tend to show very large ranges of CO2 values at any particular time.

An improvement was suggested some years back by Peter Franks of the University of Sydney with Australian, US and British co-workers (Franks, P.J. et al. 2014. New constraints on atmospheric CO2 concentration for the Phanerozoic. Geophysical Research Letters, v. 41, p. 4685-4694; doi:10.1002/2014GL060457). Their method included a means of assessing the back and forth exchange of leaf gases with the atmosphere from measurements of the carbon isotopes in preserved organic carbon in the fossil leaves, and combined this with stomatal density and the actual shape of stomata. Not only did this narrow the range of variation in atmospheric CO2 results for times past, but the mean values were dramatically lessened. Rather than values ranging up to 2000 to 3000 parts per million (~ 10 times the pre-industrial value) in the Devonian and the late-Triassic and early-Jurassic, the gas-exchange method does not rise above 1000 ppm in the Phanerozoic.

The upshot of these findings strongly suggests that the Earth’s climate sensitivity to atmospheric CO2 (the amount of global climatic warming for a doubling of pre-industrial CO2 concentration) may be greater than previously thought; around 4° rather than the currently accepted 3°C. If this proves to be correct it forebodes a much higher global temperature than present estimates by the Intergovernmental Panel on Climate Change (IPCC) for various emission scenarios through the 21st century.

See also: Hand, E. 2017. Fossil leaves bear witness to ancient carbon dioxide levels. Science, v. 355, p. 14-15; DOI: 10.1126/science.355.6320.14.

Kelly, H. 2017. How did plants evolve stomata.

Impact linked to the Palaeocene-Eocene boundary event

The PalaeoceneEocene (P-E) boundary at 55.8 Ma marks the most dramatic biological changes since the mass extinction at the Cretaceous-Palaeogene boundary 10 million years earlier. They included the rapid expansions of mammals and land plants and major extinction of deep-water foraminifera.  It was a time of sudden global warming (5-10°C in 10-20 ka) superimposed on the general Cenozoic cooling from the ‘hothouse’ of the Cretaceous Period. It coincided with a decrease in the proportion of 13C in marine carbonates.  Because photosynthesis, the source of organic carbon, favours light 12C, such a negative δ13C “spike” is generally ascribed to an unusually high release of organic carbon to the atmosphere.  The end-Palaeocene warming may have resulted from a massive release of methane from gas-hydrate buried in shallow seafloor sediments. But another process may yield such a signature; massive burning of organic material at the land surface. Since its discovery, the P-E thermal maximum has been likened to the situation that we may face should CO2 emissions from fossil-fuel burning continue to rise without control. Unsurprisingly, funds are more easily available for research on this topic than, say, ‘Snowball Earth’ events.

Climate change during the last 65 million year...
Climate change during the last 65 million years. The Paleocene–Eocene Thermal Maximum is labelled PETM. (Photo credit: Wikipedia)

Three seafloor sediment cores off the east coast of the US that include the P-E boundary have been found to contain evidence for an impact that occurred at the time of the δ13C “spike” (Schaller, M.F. et al. 2016. Impact ejecta at the Paleocene-Eocene boundary. Science, v. 354, p. 225-229). The evidence is dominated by tiny spherules and tear-shaped blobs of glass, some of which contain tiny crystals of shocked and high-temperature forms of silica (SiO2). These form part of the suite of features that have been used to prove the influence of asteroid impacts. Two other onshore sites have yielded iridium anomalies at the boundary, so it does look like there was an impact at the time. The question is, was it large enough either to cause vast amounts of methane to blurt out from shall-water gas hydrates or set the biosphere in fire? Two craters whose age approximates that of the P-E boundary are known, one in Texas the other in Jordan, with diameters of 12 and 5 km respectively; far too small to have had any global effect. So either a suitably substantial crater of the right age is hidden somewhere by younger sediments or the association is coincidental – the impact that created the Texan crater could conceivably have flung glassy ejecta to the area of the three seafloor drilling sites.

Almost coinciding with the spherule-based paper’s publication another stole its potential thunder. Researchers at Southampton University used a mathematical model to investigate how a methane release event might have unfolded (Minshull, T.A. et al. 2016. Mechanistic insights into a hydrate contribution to the Paleocene-Eocene carbon cycle perturbation from coupled thermohydraulic simulations. Geophysical Research Letters, v. 43, p. 8637-8644, DOI: 10.1002/2016GL069676). Their findings challenge the hypothesized role of methane hydrates in causing the sudden warming at the P-E boundary. But that leaves out the biosphere burning, which probably would have neded a truly spectacular impact.

More on mechanisms for ancient climate change

Bury the beast in basalt

Global warming cannot simply be reversed by turning off the tap of fossil fuel burning. Two centuries’ worth of accumulated anthropogenic carbon dioxide would continue to trap solar energy, even supposing that an immediate shutdown of emissions was feasible; a pure fantasy for any kind of society hooked on coal, oil and gas. It takes too long for natural processes to download CO2 from the atmosphere into oceans, living organic matter or, ultimately, back once more into geological storage. In the carbon cycle, it has been estimated that an individual molecule of the gas returns to one of these ‘sinks’ in about 30 to 95 years. But that is going on all the time for both natural and anthropogenic emissions. Despite the fact that annual human emissions are at present only about 4.5 % of the amount emitted by natural processes, clearly the drawdown processes in the carbon cycle are incapable of balancing them, at present. Currently the anthropogenic excess of CO2 over that in the pre-industrial atmosphere is more than 100 parts per million achieved in only 250 years or so. The record of natural CO2 levels measured in cores through polar ice caps suggests that natural processes would take between 5 to 20 thousand years to achieve a reduction of that amount.
Whatever happens as regards international pledges to reduce emissions, such as those reported by the Paris Agreement, so called ‘net-zero emissions’ leave the planet still a lot warmer than it would be in the ‘natural course of things’. This is why actively attempting to reduce atmospheric carbon dioxide may be the most important thing on the real agenda. The means of carbon sequestration that is most widely touted is pumping emissions from fossil fuel burning into deep geological storage (carbon capture and storage or CCS), but oddly that did not figure in the Paris Agreement, as I mentioned in EPN December 2015. In that post I noted that CCS promised by the actual emitters was not making much progress: a cost of US$50 to 100 per tonne sequestered makes most fossil fuel power stations unprofitable. Last week CCS hit the worlds headlines through reports that an Icelandic initiative to explore a permanent, leak-proof approach had made what appears to be a major breakthrough (Matter, J.M. and 17 others, 2016. Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions. Science, v. 352, p. 1312-1314). EPN January 2009 discussed the method that has now been tested in Iceland. It stems from the common observation that some of the minerals in mafic and ultramafic igneous rocks tend to breakdown in the presence of carbon dioxide dissolved in slightly acid water. The minerals are olivine ([Fe,Mg]2SiO4)] and pyroxene ([Fe,Mg]CaSi2O6), from whose breakdown the elements calcium and magnesium combine with CO2 to form carbonates.
Iceland is not short of basalts, being on the axial ridge of the North Atlantic. Surprisingly for a country that uses geothermal power to generate electricity it is not short of carbon dioxide either, as the hot steam contains large quantities of it. In 2012 the CarbFix experiment began to inject a 2 km deep basalt flow with 220 t of geothermal CO2 ‘spiked’ with 14C to check where the gas had ended up This was in two phases, each about 3 months long. After 18 months the pump that extracted groundwater directly from the lave flow for continuous monitoring of changes in the tracer and pH broke down. The fault was due to a build up of carbonate – a cause for astonishment and rapid evaluation of the data gathered. In just 18 months 95% of the 14C in the injected CO2 had been taken up by carbonation reactions. A similar injection experiment into the Snake River flood basalts in Washington State, USA, is said to have achieved similar results (not yet published). A test would be to drill core from the target flow to see if any carbonates containing the radioactive tracer filled either vesicles of cracks in the rock – some press reports have shown Icelandic basalt cores that contain carbonates, but no evidence that they contain the tracer .
Although this seems a much more beneficial use of well-injection than fracking, the problem is essentially the same as reinjection of carbon dioxide into old oil and gas fields; the high cost. Alternatives might be to spread basaltic or ultramafic gravel over large areas so that it reacts with CO2 dissolved in rainwater or to lay bear fresh rocks of that kind by removal of soil cover.

Kintisch, E., 2016. Underground injections turn carbon dioxide to stone. Science, v. 352, p. 1262-1263.

In a first, Iceland power plant turns carbon emissions to stone.

Paris Agreement 2015: Carbon Capture and Storage

Anyone viewing news that covered the adoption of the Paris Agreement on climate change on 11 December 2015 would have seen clear evidence of the reality of the old saw, ‘There was dancing in the streets’. Not since the premature celebration of the landing of the Philae spacecraft on comet 67P/Churyumov–Gerasimenko 11 months before has there been such public abandonment of normal human restraint. In the case of ‘little Philae’ the object of celebration sputtered out three days after landing, albeit with the collection of some data. Paris 2015 is a great deal more important: the very health of our planet and its biosphere hangs on its successful implementation. At 32 pages long, by UN standards the document agreed to by all 196 UN Member States is pretty succinct considering everything it is supposed to convey to its signatories and the human race at large.

The Bagger 288 bucket wheel reclaimer moves from one lignite mine to another in Germany.
The Bagger 288 bucket wheel reclaimer moves from one lignite mine to another in Germany.

One central and, by most scientific criteria, the most important technology needed as a stopgap before the longed-for adoption of carbon-free energy generation does not figure in the diplomatic screed: carbon capture and storage (CCS) is not mentioned once. Indeed, only 10 Member States have included it in their pledge or ‘intended nationally determined contribution’ (INDC) – Bahrain, Canada, China, Egypt, Iran, Malawi, Norway, Saudi Arabia, South Africa and the United Arab Emirates. Only three of them are notable users of coal-fired power stations for which CCS is most urgent. An article in the January 2016 issue of Scientific American offers an explanation of what seems to be a certain diplomatic timidity about this highly publicized stop-gap measure (Biello, D. 2016. The carbon capture fallacy. Scientific American, v. 314(1) 55-61). David Biello emphasizes the urgency of CCS from more industries than fossil fuel power plants, cement manufacture being a an example. He focuses on the economics and logistics of one of very few CCS facilities that may be on track for commissioning (33 have been shut down or cancelled worldwide since 2010).

The Kemper power station in Mississippi, USA is the most advanced in the US, as it has to be to burn the strip-mined, wet, brown coal or lignite that is its sole fuel. The chemistry it deploys is quite simple but technologically complex and expensive. So Kemper survives only because it aims to sell the captured CO2 to a petroleum company so that it can be pumped into oil fields to increase dwindling production. However, its extraction costs US$1.50 per tonne, while naturally occurring, underground CO2 costs US$0.50 to pump out. Moreover, Kemper’s power output at US$11 000 per kW of generating capacity is three times more expensive than that for a typical coal-fired boiler. Mississippi Power is lucky, in that it only needs to pipe the gas 100 km to its ‘partner’ oil field; a pretty small one producing about 5 000 barrels per day. Some coal plants are near oil fields, but the majority are not. To cap it all, only about a third of the CO2 production is likely to remain in long-term underground storage.

Because Kemper has, predictably, hit the financial buffers (almost US$4 billion over budget) to avoid bankruptcy it has raised electricity prices to its customers by 18%. Without the projected revenue from its partnered oil field it would go belly up. Even in the happy event of financial break-even, in carbon terms it would be subsidising the oilfield to produce…CO2! But the sting in the tail of Biello’s account of this ‘flagship’ project is that the plant is currently neither burning coal nor capturing carbon: it uses natural gas…

Ants and carbon sequestration

Aside from a swift but highly unlikely abandonment of fossil fuels, reduction of greenhouse warming depends to a large extent, possibly entirely, on somehow removing CO2 from the atmosphere. Currently the most researched approach is simply pumping emissions into underground storage in gas permeable rock, but an important target is incorporating anthropogenic carbon in carbonate minerals through chemical interaction with potentially reactive rocks. In a sense this is a quest to exploit equilibria involving carbon compounds that dominate natural chemical weathering and to sequester CO2 in solid, stable minerals.

The two most likely minerals to participate readily in weathering that involves CO2 dissolved in water are plagioclase feldspar, a calcium-rich aluminosilicate and olivine, a magnesium silicate. Both are abundant in mafic and ultramafic rocks, such as basalt and peridotite, which themselves are among the most common rocks exposed at the Earth’s surface. The two minerals, being anhydrous, are especially prone to weathering reactions involving acid waters that contain hydrogen ions, and in the presence of CO2 they yield stable carbonates of calcium and magnesium respectively. Despite lots of exposed basalts and ultramafic rocks, clearly such natural sequestration is incapable of absorbing emissions as fast as they are produced.

One means of speeding up weathering is to grind up plagioclase- and olivine-bearing rocks and spread the resulting gravel over large areas; as particles become smaller their surface area exposed to weathering increases. Yet it doesn’t take much pondering to realise that a great deal of energy would be needed to produce sufficient Ca- and Mg-rich gravel to take up the approximately 10 billion tonnes of CO2 being released each year by burning fossil fuels: though quick by geological standards the reaction rates involved are painfully slow in the sense of what the climatic future threatens to do. So is there any way in which these reactions might be speeded up?

Two biological agencies are known to accelerate chemical weathering, or are suspected to do so: plant roots and animals that live in soil. Ronald Dorn of Arizona State University set out to investigate the extent to which such agencies do sequester carbon dioxide, under the semi-arid conditions that prevail in Arizona and Texas (Dorn, R.I. 2014. Ants as a powerful biotic agent of olivine and plagioclase dissolution. Geology, v. 42, p. 771-774). His was such a simple experiment that it is a wonder it had not been conducted long ago; but it actually took more than half his working life. Spaced over a range of topographic elevations, Dorn used an augur at each site to drill five half-metre holes into the root mats of native trees, established ant and termite colonies and bare soil surfaces free of vegetation or animal colonies, filling each with sand-sized crushed basalt.

Empire of the Ants (film)
Film poster for Empire of the Ants (starring Joan Collins) (credit: Wikipedia)

Every five years thereafter he extracted the basalt sand from one of the holes at each site and each soil environment. To assess how much dissolution had occurred he checked for changes in porosity, and heated the samples to temperatures where carbonates break down to discover how much carbonate had been deposited. That way he was able to assess the cumulative changes over a 25 year period relative to the bare-ground control sites. The results are startling: root mats achieved 11 to 49 times more dissolution than the control; termites somewhat less, at 10 to 19 times; while ants achieved 53 to 177 times more dissolution. While it was certain that the samples had been continuously exposed to root mats throughout, the degree of exposure to termites and ants is unknown, so the animal enhancements of dissolution are probably minima.

Microscopic examination of mineral grains exposed to ant activity shows clear signs of surface pitting and other kinds of decay. Chemically, the samples showed that exposure to ants consistently increased levels of carbonate in the crushed basalt sand compared with controls, with levels rising by 2 to 4% by mass, with some variation according to ant species. Clearly, there is some scope for a role for ants in carbon sequestration and storage; after all, there are estimated to be around 1013 to 1016 individual ants living in the world’s soils. In the humid tropics the total mass of ants may be up to 4 times greater than all mammals, reptiles and amphibians combined. There is more to learn, but probably a mix of acid secretions and bioturbation by ants and termites is involved in their dramatic effect on weathering. One interesting speculation is that ants may even have played a role in global cooling through the Cenozoic, having evolved around 100 Ma ago.