Tag: Carbon capture and storage

Bury the beast in basalt

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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.

Related articles:

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. Phys.org

Paris Agreement 2015: Carbon Capture and Storage

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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…

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Carbon capture and storage: dissolving it

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Amassador Jacobson, centre, visits the carbon ...
A Canadian carbon capture and storage project in Saskatchewan (credit: US Mission to Canada via Flickr)

Tucking away vast amounts of atmospheric carbon dioxide (carbon capture and storage or CCS), or at least that emitted by fossil-fuel power stations, is a widely suggested and well supported approach to slowing down global warming. It has two main downsides: if successful it helps maintain the dominance of fossil fuels and vast amounts of buried greenhouse gas might simply leak out some time. Ideally, the storage part of CCS would involve CO2 being taken up by an inert solid. Carbonates may be stable enough but arranging the chemical reactions to make them seem difficult, the most widely considered being by encouraging weathering of ultramafic rocks to form magnesium carbonates as a by-product: huge areas would have be coated with finely-ground peridotite. A less satisfactory approach would to dissolve the gas in water held at great depths in sedimentary aquifers, but if that water doesn’t move and doesn’t get warmed it might do the trick.

Unsurprisingly, a lot of funds are available to research CCS  and ideas are pouring forth, a recent, sober assessment focussing on the solubility option (Steele-MacInnis, M. et al. 2012. Volumetrics of CO2 storage in deep saline formations. Environmental Science and Technology (August 2012 online) DOI: 10.1021/es301598t). The team from Virginia Tech and the US Department of Energy conclude that solution in brines trapped in deep aquifers may help, although solution is an equilibrium between gas and dissolved CO2, so that a gas layer in the aquifer is always likely to be present, even at high pressures. The only way of avoiding that is if the dissolved gas reacted with carbonate in the aquifer so that calcium and hydrogen-carbonate (HCO3–) ions entered solution. That ‘enhanced’ solution is not so easy since, although it mimics the calcite-weathering effect by acid rain that naturally takes CO2 from the atmosphere, calcite dissolves very sluggishly. But solution adds to the density of already dense brine so that it is less likely to leak upwards into more shallow aquifers. Their preferred technology is to liquefy the gas under pressure and pump that to deep aquifers where eventually the supercritical CO2 liquid will dissolve. The problem is this: while experiment and theory suggest the approach will work, nobody knows how long CO2 solution in brine will take. There needs to be a sizeable pilot study…

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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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Possible snags and boons for CO2 disposal

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Partial panorama of a colossal mountain of asb...
Asbestos mine tailingsat Thetford in Quebec, Canada.(Photo credit: Wikipedia)

Not many people would like to visit a waste heap at an asbestos mine. That is not because waste heaps are generally boring but all forms of asbestos are carcinogens when inhaled. Encountering pits in the tailings that emits puffs of warm air would cause health and safety alarm bells to ring. Yet that is exactly what has attracted researchers to the huge asbestos mining complex at Thetford in Quebec, Canada: the air leaving the vents can be extremely depleted in carbon dioxide (Pronost, J. and 10 others 2012. CO3-depleted warm air venting from chrysotile milling waste (Thetford Mines, Canada): Evidence for in-situ carbon capture and storage. Geology, v. 40, p. 275-278). More precisely, the depletion – down to less than 10 parts per million (ppm) compared with normal atmospheric levels of 385 ppm – occurs in winter, when the puffing pits emit warm air far above the frigid air temperatures encountered in winter Quebec. The chrysotile must be reacting with groundwater and CO2, and is therefore a potential means of using near-surface natural materials for carbon capture and storage (CCS). The end product is an innocuous carbonate – Mg5(OH)2(CO3)4·4H2O – and dissolved silica. Quite a find, it might seem, as the reaction is exothermic too: CCS plus geothermal energy plus safe decomposition of a major environmental hazard. In fact any magnesium-rich silicates are likely to undergo the same carbonation reaction, especially if ground-up to increase the net surface area exposed to moist air.

Schematic showing both terrestrial and geologi...
scheme for carbon sequestration and storage at a coal-fired power plant. Rendering by LeJean Hardin and Jamie Payne. Source: http://www.ornl.gov/info/ornlreview/v33_2_00/research.htm

The parent asbestos rock at Thetford is a metamorphic derivative from mantle ultramafic rocks in an ophiolite, and the asbestos insulation business, both for extremely hazardous blue (crocidolite) and less dangerous white (chrysotile) asbestos has been hugely profitable since the 19th century. Consequently, wherever there are altered ophiolites, generally in collision-zone orogenic belts, asbestos has been exposed either naturally or through mining and processing. There are many related cancer ‘hot spots’ in populous mining areas of Canada, India, the Alps and southern Africa, and in dry climates even natural exposures pose considerable risk. Could these blighted areas take on a new role in lessening the chance of global warming? About 30 billion tonnes of CO2 are emitted by burning fossil fuels each year. To keep pace, at the current atmospheric concentration of CO2­, some 75 trillion tonnes of air would have to react annually with about 100 billion tonnes of magnesian silicate, making this form of CCS the largest industry on the planet (http://www.newscientist.com/article/mg21428593.800-stripping-co2-from-air-requires-largest-industry-ever.html).

Another factor tempering somewhat forced optimism for CCS as a way of having our fossil fuel cake and eating it is that direct injection of greenhouse gases into deep storage may have an unforeseen down-side. Deep drilling and injection of fluids may trigger earthquakes. The alarm raised by small yet disturbing seismicity accompanying sites for shale-gas development by ‘fracking’ (http://earth-pages.co.uk/2011/11/04/fracking-check-list/ and http://earth-pages.co.uk/2011/10/14/britain-to-be-comprehensively-fracked/) has died down to some extent following detailed analysis of small earthquakes around drilling sites. It turns out that they are triggered not by the drilling itself but the subsurface disposal of the large amounts of fluids that have to be passed through the oil shales to make the tight rock permeable to gas (Kerr, R.A. 2012 Learning how to NOT make earthquakes. Science, v. 23 p. 1436-1437). Safe subsurface disposal requires injection wells penetrating 1 to 3 km below the surface, often below the cover of sedimentary strata and into crystalline basement. Such hard rocks store elastic strain induced by burial and tectonics, and release it when lubricated by fluids, especially if they contain dormant faults. Once impermeable rock can thus be hydrofractured in the same manner as ‘fracked’ gas-prone shales and old, often unsuspected faults reactivate: a catastrophic prospect for injected CO2. In sedimentary sequences, drilling CCS wells into porous rocks capped by impermeable ones – the scenario for ‘safe’ gas storage – could also induce ‘fracking’ of the sealing rocks and thereby causing leakage (see also http://www.newscientist.com/article/dn21633-fracking-could-foil-carbon-capture-plans.html).

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