Climate out of control after the Permian-Triassic mass extinction

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

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

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

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

Ca2+ + 2HCO3→ CaCO3 + CO2 + H2O

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

Examples of marine radiolaria (top)

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

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.

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…