Tag: Carbon dioxide

Finding Archaean atmospheric composition using micrometeorites

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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 oxidation. Science 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 Phys.org)

Ancient CO2 estimates worry climatologists

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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.


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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.

Ants and carbon sequestration

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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.

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Carbon dioxide burial: an analogy of some pitfalls

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Schematic showing both terrestrial and geologi...
geological sequestration of carbon dioxide emissions from a coal-fired power plant.  (Photo credit: LeJean Hardin and Jamie Payne Wikipedia)

Of all the ‘geoengineering’ approaches that may offer some relief from global warming pumping CO2 into deep sedimentary rocks, through carbon capture and storage (CCS) is one that most directly intervenes in the natural carbon cycle. In fact it adds an almost wholly  anthropogenic route to the movement of carbon. It is difficult if not impossible for natural processes to ‘pump’ gases downwards except when they are dissolved in water and most often through the conversion of CO2 to solid carbonates or carbohydrates that are simply buried on the ocean floor. Artificially producing carbonate or organic matter on a sufficient scale to send meaningful amounts of anthropogenic carbon dioxide to long-term rock storage is pretty much beyond current technology, but gas sequestration seems feasible, if costly. The main issues concern making sure geological traps are ‘tight’ enough to prevent sufficient leakage to render the exercise of little use and to understand the geochemical effects of large amounts of buried gas that would inevitably move around to some extent.

The geochemistry is interesting as reactions of CO2 with rock and subsurface water are inevitable. The most obvious is that solution in water releases hydrogen ions to create weakly acidic fluids: on the one hand that might be a route for precipitation of carbonate and more secure carbon storage, through reaction with minerals (see http://earth-pages.co.uk/2012/04/10/possible-snags-and-boons-for-co2-disposal/), but another possibility is increasing solution of minerals that might eventually cause a trap to leak. A counterpart of pH change is the release of electrons, whose acceptance in chemical reactions creates reducing conditions. The most common minerals to be affected by reducing reactions are the iron oxides, hydroxides and sulfates that often coat sand-sized grains in sedimentary rocks, or occur as accessory minerals in igneous and metamorphic rocks. Iron in such minerals is in the Fe-3 valence state (ferric iron from which an electron has been lost through oxidation) which makes them among the least soluble common materials, provided conditions remain oxidising. Flooding sedimentary rocks with CO2 inevitably produces a commensurate flow of electrons that readily interact with Fe-3. The oxidised product Fe-2 (ferrousiron) is soluble in water, and so reduction breaks down iron-rich grain coatings. Much the same happens with less abundant manganese oxides and hydroxides. One important concern is that iron hydroxide (FeO.OH or goethite) has a molecular structure so open that it becomes a kind of geochemical sponge. Goethite may lock up a large range of otherwise soluble ions, including those of arsenic and some toxic metals. Should goethite be dissolved by reduction that toxic load moves into solution and can migrate.

Bleached zone with carbonate-oxide core in Jurassic Entrada Sandstone, Green River, Utah. (Image: Max Wigley, University of Cambridge)

Except where deep, carbonated groundwater leaks to the surface in springs – the famous Perrier brand of mineral water is an example – it is difficult to judge what is happing to gases and fluids at depth. But their long-past activity can leave signatures in sedimentary rocks exhumed to the surface. Most continental sandstones, formed either through river or wind action, are strongly coloured by iron minerals simply because of strongly oxidising conditions at the Earth’s surface for the past two billion years or more. Should reducing fluids move through the, the iron is dissolved and leached away to leave streaks and patches of bleached sandstone in otherwise red rocks. In a few cases an altogether more pervasive bleaching of hundreds of metres of rock marks the site of massive fluid-leakage zones. Terrestrial Mesozoic sedimentary sequences in the Green River area of Utah, USA exhibit spectacular examples, easily amenable to field and lab study (Wigley, M. et al. 2012. Fluid-mineral reactions and trace metal mobilization in an exhumed natural CO2 reservoir, Green River, Utah. Geology, v. 40, p. 555-558). There the bleaching rises up through the otherwise brown and yellow sandstones, cutting across the bedding. In the bleached zone, secondary calcite fills pore spaces. At the contact with unbleached sandstone there are layers of carbonate and metal oxides, enriched in cobalt, copper, zinc, nickel, lead, tin, molybdenum and chromium: not ores but clear signs confirming the general model of reductive dissolution of iron minerals and movement of metal-rich fluid. Carbon isotopes from the junction are richer in 13C than could be explained by the gas phase having been methane, and confirm naturally CO2 – rich fluids.

So, Green River provides a natural analogue for a carbon capture and storage system, albeit one that leaked so profusely it would be a latter day disaster zone. In that sense the site will help in deciding where not to construct CCS facilities.

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