Tag: Olivine

Naturally occurring hydrogen: an abundant green fuel?

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Burning hydrogen produces only water vapour, so it is not surprising that it has been touted as the ultimate ‘green’ energy source, and increasingly attracts the view that the ‘Hydrogen Economy’ may replace that based on fossil fuels. It is currently produced from natural gas by ‘steam reforming’ of methane that transforms water vapour and CH4 to hydrogen and carbon monoxide. That clearly doesn’t make use of the hydrogen ‘green’ as the CO becomes carbon dioxide because it reacts with atmospheric oxygen; it is termed ‘grey hydrogen’. But should it prove possible to capture CO and store it permanently underground in some way then that can be touted as ‘blue hydrogen’ thereby covering up the carbon footprint of all the rigmarole in getting the waste CO into a safe reservoir. However, if carbon-free electricity from renewables is used to electrolyse water into H and O the hydrogen aficionados can safely call it ‘green hydrogen’.   It seem there is a bewildering colour coding for hydrogen that depends on the various options for its production: ‘yellow’ if produced using solar energy; ‘red’ if made chemically from biowaste; ‘black’ by coking coal using steam; ‘pink’ is electrolysis using nuclear power; and even ‘turquoise’ hydrogen if methane is somehow turned into hydrogen and solid carbon using renewables – a yet-to-be-developed technology! Very jolly but confusing: almost suspiciously so!

But not to be forgotten is the ‘white’ variety, applied to hydrogen that is emitted by natural processes within the Earth. Eric Hand, the European news editor for the major journal Science has written an excellent Feature article about ‘white’ hydrogen in a recent issue (Hand, E. 2023. Hidden hydrogen. Science, v. 379, article adh1460; DOI: 10.1126/science.adh1460). Hand’s feature is quirky, but well-worth a read. It is based on the proceedings of a Geological Society of America mini-conference about non-petroleum, geological energy resources  held in October 2022. He opens with a bizarre anecdote related by a farmer who lives in rural Mali. The only drilling that ever went on in his village was for water, and many holes were dry. But one attempt resulted in ‘wind coming out of the hole’. When a driller looked in the hole, the ‘wind’ burst into flame – he had a cigarette in his mouth. The fire burned for months. Some 20 years later the story reached a Malian company executive who began prospecting the area’s petroleum potential, believing the drilling had hit natural gas. Analysis of the gas revealed that it was 98% hydrogen – now the village has electricity generated by ‘white’ hydrogen.

Mantle rock in the Oman ophiolite, showing cores of fresh peridotite, surrounded by brownish serpentinite and white magnesium carbonate veins (credit: Juerg Matter, Oman Drilling Project, Southampton University, UK)

So how is hydrogen produced by geological processes? Some springs in the mountains of Oman also release copious amounts of the gas. The springs emerge from ultramafic rocks of the vast ophiolite that was emplaced onto the Arabian continental crust towards the end of the Cretaceous. The lower part of this obducted mass of oceanic lithosphere is mantle rock dominated by iron- and magnesium-rich silicates, mainly olivine [(Mg,Fe)2SiO4 – a solid solution of magnesium and iron end members]. When saturated with groundwater in which CO2 is dissolved olivine breaks down slowly but relentlessly. The hydration reaction is exothermic and generates heat, so is self-sustaining. Olivine’s magnesium end member is hydrated to form the soft ornamental mineral serpentine (Mg3Si2O5(OH)4) and magnesium carbonate. Under reducing conditions the iron end member reacts with water to produce an iron oxide, silica and hydrogen:

3Fe2SiO4 + 2H2O → 2 Fe3O4 + 3SiO­2 +3H2

Gases emanating from mid-ocean ridges contain high amounts of hydrogen produced in this way, for example from Icelandic geothermal wells. But Mali is part of an ancient craton, so similar reactions involving iron-rich ultramafic rocks deep in the continental crust are probably sourcing hydrogen in this way too. Hydrogen production on the scale of that discovered in Mali seems to be widespread, with discoveries in Australia, the US, Brazil and the Spanish Pyrenees that have pilot-scale production plants. The US Geological Survey has estimated that around 1 trillion tonnes of ‘white’ hydrogen may be available for extraction and use

Hydrogen, like other natural gases, may be trapped below the surface in the same ways as in commercial petroleum fields. But petroleum-gas wells emit little if any hydrogen mixed in with methane. That absence is probably because petroleum fields occur in deep sedimentary basins well above any crystalline basement. The geophysical exploration that discovers and defines the traps in petroleum fields has never been deployed over areas of crystalline continental crust because as far as the oil companies are concerned they are barren. That may be about to change. There is another exploration approach: known hydrogen seepage seems to deter vegetation so that the sites are in areas of bare ground, which have been called ‘fairy circles’. These could be detected easily using remote sensing techniques.

Artificially increasing serpentine formation by pumping water into the mantle part of ophiolites, such as that in Oman, and other near-surface ultramafic rocks is also a means of carbon sequestration, which should produce hydrogen as a by-product (see: Global warming: Can mantle rocks reduce the greenhouse effect?, July 2021). A ‘two-for-the-price-of-one’ opportunity?

In the mantle wet may not imply soft

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For half a century the Earth’s planetary dynamism – plate movements, mantle convection and so on – has been ascribed to its abundance of water. Experiments on the ductility of quartz seemed to show that it became much weaker under hydrous conditions, and that was assumed to hold for all common silicates, a view backed up by experiments that deformed minerals under varying conditions. It was widely believed that even a few parts per million in a rock at depth would weaken it by orders of magnitude, a view that increasingly dominated theoretical tectonics on scales up to the whole lithosphere and at different mantle depths. Strangely, the founding assertion was not followed up with more detailed and sophisticated work until the last year or so. Though rarely seen in bulk, the dominant mineral in the mantle is olivine and that is likely to be a major control over ductility at depth, in plumes and other kinds of convection.

Peridotite xenoliths in basalt—olivines are li...
Peridotite xenoliths —olivines are light green crystals, pyroxenes are darker. (credit: Wikipedia)

Experimental work at the temperatures and pressures of the mantle has never been easy, and that becomes worse the more realistic the mineral composition of the materials being investigated. High-T, high-P research tends to focus on as few variables as possible: one mineral and one variable other than P and T is the norm. This applies to the latest research (Fei, H. et al. 2013. Small effect of water on upper mantle rheology based on silicon self-diffusion coefficients. Nature, v. 498, p. 213-215) but the measurements are of the rate at which silicon atoms diffuse through olivine molecules rather than direct measurements of strain. The justification for this approach is that one of the dominant processes involved in plastic deformation is a form of structural creep in which atoms diffuse through molecules in response to stress – the other is ‘dislocation creep’ achieved by the migration of structural defects in the atomic lattice.

Contrary to all expectations, changing the availability of water by 4 to 5 orders of magnitude changed silicon diffusion by no more than one order. If confirmed this presents major puzzles concerning Earth’s mantle and lithosphere dynamics. For instance, the weak zone of the asthenosphere cannot be a response to water and nor can the relative immobility of hotspots. Confirmation is absolutely central, in the sense of repeating Fei et al.’s experiments and also extending the methods to other olivine compositions – magnesium-rich forsterite was used, whereas natural olivines are solid solutions of Mg- and Fe-rich end members – and to materials more representative of the mantle, e.g.  olivine plus pyroxene as a minimum (Brodholt, J. 2013. Water may be a damp squib. Nature, v. 498, p. 18-182)

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