Category: Physical resources

The Moon may have water resources in its soil

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Apart from signs of water ice in permanently shadowed areas of some polar craters, the Moon’s surface has generally been considered to be very dry. Rocks returned by the various Apollo missions contain minute traces of water by comparison with similar rocks on Earth. They consist only of anhydrous minerals such as feldspars, pyroxenes and olivines. But much of the lunar surface is coated by regolith: a jumble of rock fragments and dust ejected from a vast number of impact craters over billions of years. It is estimated to be between 3 and 12 m deep. Much of the finer grained regolith is made up of silicate-glass spherules created by the most powerful impacts.

The lunar regolith at Tranquillity Base bearing an astronaut’s bootprint (Credit: Buzz Aldrin, NASA Apollo 11, Photo ID AS11-40-5877)

The scientific and economic (i.e. mining) impetus for the establishment of long term human habitation on the lunar surface hangs on the possibility of extracting water from the Moon itself. It is needed for human consumption and as a source through electrolysis of both oxygen and hydrogen for breathing and also for rocket fuel. The stupendous cost, in both monetary and energy terms, of shifting mass from Earth to the Moon clearly demands self-sufficiency in water for a lunar base occupied for more than a few weeks.

Remote sensing that focussed on the ability of water molecules and hydroxyl (OH–) ions to absorb solar radiation with a wavelength of 2.8 to 3.0 micrometres was deployed by the Indian lunar orbiter Chandrayaan-1 that collected data for several months in 2008-9. The results suggested that OH– and H2O were detectable over a large proportion of the lunar surface at concentrations estimated at between 10 parts per million (ppm) up to about 0.1%. Where did these hydroxyl ions and water molecules come from and what had locked them up? There are several possibilities for their origin: volcanic activity that tapped the Moon’s mantle (magma could not have formed had some water not been present at great depths); impacts of icy bodies such as comets; even the solar wind that carries protons, i.e. hydrogen atoms stripped of their electrons. Conceivably, protons could react with oxygen in silicate material at the surface to produce both OH– and H2O to be locked within solid particles. To assess the possibilities a group of researchers at Chinese and British institutions have examined in detail the 1.7 kg of lunar-surface materials collected and returned to Earth by the 2020 Chinese Chang’e 5 lunar sample return mission (He, H. and 27 others 2023. A solar wind-derived water reservoir on the Moon hosted by impact glass beads. Nature Geoscience, online article; DOI: 10.1038/s41561-023-01159-6)

He et al. focussed on glass spherules formed by impact melting of lunar basalts, whose bulk composition they retain. The glass ‘beads’ contain up to 0.2 % water, mainly concentrated in their outermost parts. This alone suggests that the water and hydroxyl ions were formed by spherules being bathed in the solar wind rather than being of volcanic or cometary origin and trapped in the glass. An abnormally low proportion of deuterium (2H) relative to the more abundant 1H isotope of hydrogen in the spherules is consistent with that hypothesis. Indeed, the high temperatures involved in impact melting would be expected to have driven out any ‘indigenous’ water in the source rocks. The water and OH– ions seem to have built up over time, diffusing into the glass from their surfaces rather than gradually escaping from within.

An awful lot of regolith coats the lunar surface, as many of the images taken by the Apollo astronauts amply show. So how much water might be available from the lunar regolith? The Chinese-British team reckon between 3.0 × 108 to 3.0 × 1011 metric tons. But how much can feasibly be extracted at a lunar base camp? The data suggest that a cubic metre (~2 t) of regolith could yield enough to fill 4 shot glasses (~0.13 litres). Using a solar furnace and a condenser – the one in full sunlight the other in the shade – is not, as they say, ‘rocket science’. But for a minimum 3 litres per day intake of fluids per person, a team of 4 astronauts would need to shift and process roughly 100 m3 of regolith every day. Over a year, this would produce a substantial pit. But that assumes all the regolith contains some water, yet the data are derived from the surface alone …See also:Glass beads on moon’s surface may hold billions of tonnes of water, scientists say. The Guardian, 27 March 2023.

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?

British government fracking fan fracked

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In November 2019 the Conservative government of Boris Johnson declared a moratorium on development of shale gas by hydraulic fracturing (‘fracking’) in England. This followed determined public protests at a number of potential fracking sites, the most intransigent being residents of Lancashire’s Fylde peninsula. They had been repeatedly disturbed since mid 2017 by low-magnitude earthquakes following drilling and hydraulic-fluid injection tests by Cuadrilla Resources near Little Plumpton village. Their views were confirmed in a scientific study by the British Geological Survey for the Oil and Gas Authority that warned of the impossibility of predicting the magnitude of future earthquakes that future fracking might trigger. The shale-gas industry of North America, largely in areas of low population and simple geology, confirmed the substantial seismic hazard of this technology by regular occurrences of earthquakes up to destructive magnitudes greater than 5.0. The Little Plumpton site was abandoned and sealed in February 2022.

Cuadrilla’s exploratory fracking site near Little Plumpton in Fylde, Lancashire. (Credit: BBC)

On 22 September 2022 the moratorium was rescinded by Jacob Rees-Mogg, Secretary of State for Business, Energy and Industrial Strategy in the new government of Liz Truss, two weeks after his appointment. This was despite the 2019 Conservative manifesto pledging not to lift the moratorium unless fracking was scientifically proven to be safe. His decision involved suggesting that the seismicity threshold for pausing fracking operations be lifted from magnitude 0.5 to 2.5, which Rees-Mogg claimed without any scientific justification to be ‘a perfectly routine natural phenomenon’.  He further asserted that opposition to fracking was based around ‘hysteria’ and public ignorance of seismological science, and that some protestors had been funded by Vladimir Putin. In reality the Secretary of State’s decision was fuelled by the Russian Federation’s reducing gas supplies to Europe following its invasion of Ukraine, the soaring world price of natural gas and an attendant financial crisis. There was also a political need to be seen to be ‘doing something’, for which he has a meagre track record in the House of Commons. Rees Mogg claimed that lifting the moratorium would bolster British energy security. That view ignored the probable lead time of around 10 years before shale gas can become an established physical resource in England. Furthermore, an August 2018 assessment of the potential of UK shale-gas, by a team of geoscientists, including one from the British Geological Survey, suggested that shale-gas potential would amount to less than 10 years supply of UK needs: contrary to Rees-Mogg’s claim that England has ‘huge reserves of shale’. Indeed it does, but the vast bulk of these shales have no commercial gas potential.

Ironically, the former founder of Cuadrilla Resources, exploration geologist Chris Cornelius, and its former public affairs director, Mark Linder, questioned the move to unleash fracking in England, despite supporting shale-gas operations where geologically and economically appropriate. Their view is largely based on Britain’s highly complex geology that poses major technical and economic challenges to hydraulic fracturing. Globally, fracking has mainly been in vast areas of simple, ‘layer-cake’ geology. A glance at large-scale geological maps of British areas claimed to host shale-gas reserves reveals the dominance of hundreds of faults, large and small, formed since the hydrocarbon-rich shales were laid down. Despite being ancient, such faults are capable of being reactivated, especially when lubricated by introduction of fluids. Exactly where they go beneath the surface is unpredictable on the scales needed for precision drilling.  Many of the problems encountered by Cuadrilla’s Fylde programme stemmed from such complexity. Over their 7 years of operation, hundreds of millions of pounds were expended without any commercial gas production. Each prospective site in Britain is similarly compartmentalised by faulting so that much the same problems would be encountered during attempts to develop them. By contrast the shales fracked profitably in the USA occur as horizontal sheets deep beneath entire states: entirely predictable for the drillers. In Britain, tens of thousands of wells would need to be drilled on a ‘compartment-by-compartment’ basis at a rate of hundreds each year to yield useful gas supplies. Fracking in England would therefore present unacceptable economic risks to potential investors. Cornelius and Linder have moved on to more achievable ventures in renewables such as geothermal heating in areas of simple British geology.

Jacob Rees-Mogg’s second-class degree in history from Oxford and his long connection with hedge-fund management seem not to be appropriate qualifications for making complex geoscientific decisions. Such a view is apparently held by several fellow Conservative MPs, one of whom suggested that Rees-Mogg should lead by example and make his North East Somerset constituency the ‘first to be fracked’, because it is underlain by potentially gas-yielding shales. The adjoining constituency, Wells, has several sites with shale-gas licences but none have been sought within North East Somerset. Interestingly, successive Conservative governments since 2015, mindful of a ‘not-in-my-backyard’ attitude in the party’s many rural constituencies, have placed a de-facto ban on development of onshore wind power.

Ancient deep groundwater

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Worldwide, billions of people depend on groundwater for their water needs from wells, deep boreholes and natural springs. Even surface water in rivers and lakes is directly connected to that moving sluggishly below the surface. In fact the surface water level marks where the water table coincides with the land surface. From season to season the water table rises and falls and so too do river and lake levels, depending on fluctuations in rainfall, snow melt, evaporation and extraction. Where it is present, vegetation plays a role in the hydrological cycle, through transpiration from roots through stems and leaves, from which it is exhaled by minute pores or stomata; effectively plants are able to pump water through their tissues to a height of up to a hundred metres.  Groundwater, like that at the surface, moves under gravity roughly parallel to the slope of the land surface from the place where precipitation infiltrates soil and rock. But the deeper it is the slower the flow and the less it is in direct contact with surface processes to be replenished by infiltration. Wells and boreholes rarely penetrate deeper than a few hundred metres, so that the vast bulk of groundwater is never used. Indeed most deep groundwater would not be drinkable or suitable for irrigation since over millennia or longer it dissolves material from the rock that contains it to become saline. In some deep sedimentary aquifers it may actually be composed of seawater trapped at the time of sedimentation.

Damp conditions in the Mponeng gold mine near Johannesburg, South Africa, the world’s deepest at 3.8 km below the surface with planned expansion to 4.3 km (Credit: AngloGold Ashanti)

The pore spaces in sandstones and fractures in limestones, the most common aquifers, are not the only conduits for groundwater. Crystalline igneous and metamorphic rocks are generally full of minute fractures resulting from their tectonic history. The deepest mines in crystalline basement, such as the gold mines of the Johannesburg area in South Africa, penetrate almost 4 km below the surface, yet are by no means dry and have to be pumped to stave off flooding. The water is a brine containing sodium and calcium chloride with high concentrations of dissolved, reduced gases such as hydrogen, methane and ethane (C2H6). Studies of the proportions of oxygen isotopes in the water reveal that the water in the fractures is very different from that in modern rainwater: this fluid is completely isolated from the modern hydrological cycle and is very old indeed. Just how old has now been determined (Warr, O. et al. 2022. 86Kr excess and other noble gases identify a billion-year-old radiogenically-enriched groundwater system. Nature Communications v. 13, Article number 3768; DOI: 10.1038/s41467-022-31412-2).

Brine extracted from a borehole in the floor of the Moab Khotsong gold/uranium mine also contains the noble gases helium, neon, argon, krypton and xenon. Noble gases are present in today’s atmosphere, so conceivably they may have originally entered the brine in rain water that seeped along fractures. However, when their isotopes are measured their proportions are very different from those in air. There are excesses of 4He, 21Ne, 22Ne, 40Ar, 86Kr and several isotopes of Xe. These isotopes are emitted during the radioactive decay of uranium, thorium and 40K, the main heat producing isotopes in the crust and mantle. Oliver Warr of the University of Toronto Canada and geochemists from Oxford University UK, Princeton University and the New Mexico Institute of Mining and Technology US, and the Sorbonne France show that originally atmospheric noble gases have been enriched in these radiogenic isotopes. Their present isotopic proportions therefore give clues to the time when air dissolved in groundwater was trapped in the host rock more than a billion years ago. A complicating factor is that the host rocks themselves are dated at about three times that age. They suggest that the fractures systems were initiated by the Vredfort asteroid impact at 2.0 Ga to form aquifers, but they became isolated from hydrological circulation around 1.2 Ga and now now contain the world’s oldest groundwater.

One of the implications of the study is that such trapped water may be present at depth in the crust of Mars, despite its current aridity. Another is that, because the fluid contains hydrogen, sulfate ions and hydrocarbon gases, it can potentially support organisms that use them to power their metabolism and reproduce. In 2008 microbes were found living in similar ancient groundwater 2.4 km below the surface in the Kidd Creek Mine, Canada, at a level of around 5 thousand cells per millilitre (50 times less than in surface water). They are powered by reduction of sulfate ions to sulfide. In 2008 another peculiar discovery in the deep biosphere emerged from the Mponeng gold mine near Johannesburg, South African (the world’s deepest) in the form of a living sulfate reducing bacterium Desulforudis audaxviator. DNA  analysis of the ancient water revealed that it was the sole inhabitant, a biological mystery confirmed by later deep-biosphere studies in Death Valley, USA, and Siberia.

See also: Researchers uncover life’s power generators in the Earth’s oldest groundwaters, EurekaAlert, 5 July 2022; Mantle link with biosphere, July 2009

Geothermal heat from coalfields: a ‘green’ revolution?

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Sooner rather than later all energy users will be forced to change their source of energy to ones that do not involve fossil fuels. On average, 84% of household energy consumption is for space heating and hot water. Reducing domestic greenhouse gas emissions must replace the current dominance of coal, natural gas and oil in keeping ourselves warm and clean. One widely suggested solution is the use of heat pumps to ‘concentrate’ the solar energy that is temporarily stored in air or in the soil and rock just beneath our homes and gardens: air- and ground-source heating systems. Heat pumps rely on overcoming the Second Law of Thermodynamics, as do refrigerators and air conditioners. The Law implies that hot things always cool down; that is, energy cannot move ‘of its own accord’ from a cooler source to a warmer destination. But reversing the natural flow of heat energy is possible. To achieve this involves work in some form. There are several kinds of heat pumps powered by electricity, the simplest using a vapour compression cycle, as in refrigeration, which ‘pumps’ heat out of a fridge interior or a room. So, warm air is emitted to the outside world. Reverse the flow and the pump becomes a device that captures heat from a cold source – either a gas or a fluid – and delivers it for a domestic or industrial use.

In the case of a ground-source heat pump, the energy delivered also includes geothermal heat flowing from deep in the Earth: ultimately from radioactive decay of unstable isotopes bound up in rocks and the minerals they contain. At the surface, this supply is far less than solar heating. Yet, because of the Second Law of Thermodynamics it flows from a much hotter source: the Earth’s mantle. The deeper down, the hotter it gets. Beneath most of the continental surface temperature increases at between 15 to 35°C per kilometre. Without surface air being circulated to the deepest parts of mines it would be impossible to work in them. I remember as a school student visiting the deepest level of Maltby Main coal mine in South Yorkshire. Because my school was co-educational, our guide shouted ahead to the miners that women were coming – these miners normally worked in just helmet, boots and a jock strap! Dozens of them rushed frantically to find their trousers. Maltby Main’s shafts reached almost a kilometre below the surface and without ventilation the air temperature would have been more than 50°C. As it was, it was well above 30 degrees

As well as methane (‘fire damp’), CO2 (‘choke damp’) and roof collapse, one of the main hazards of coal mining is flooding by groundwater. When operational, before the Conservative governments of the 1980s and early 90s set about destroying deep-coal mining in Britain, all mines had massive pumps to remove water from their deepest levels or ‘sumps’. It is hazardous stuff, being highly acidic and rich in dissolved metals – including arsenic in some areas – as well as being warm: a low-temperature hydrothermal fluid. In many cases such water seeps to the surface from the now flooded mine workings, and precipitates brightly coloured iron hydroxides. Most of the abandoned British coalfields are plagued by such minewater escaping to the surface. Untreated it contaminates surface water, soils and sediments, posing threats to vegetation, wild life and people. Yet, it has considerable potential as a heat source, especially for community heating systems based on large-scale heat pumps (Farr, G. et al. 2020. The temperature of Britain’s coalfields. Quarterly Journal of Engineering Geology and Hydrogeology, v. 54, article qjegh2020-109; DOI: 10.1144/qjegh2020-109).

Pollution of South Esk river near Edinburgh by water from old coal-mine workings (Credit: EdinburghLive, 11 June 2020)

For decades, geothermal energy has been touted as a near-ideal renewable, carbon-free resource, using natural hot-spring systems in volcanically active areas, such as Iceland and New Zealand, from areas of unusually high heat flow over highly radioactive granite intrusions or from very deep sedimentary aquifers as exploited in parts of the Paris Basin. But in Britain various optimistic projects have arisen and then faded away. All relied on pumping surface water down boreholes to depths that achieve high temperatures, returning it to the surface at around 60°C to the surface and then piping it to users: very expensive. About a quarter of the population live above the former coalfields of Britain. Around 2.2 million gigawatt hours of geothermal heat are currently stored in flooded mine workings, with the possibility of further expansion. The UK Coal Authority has about 40 minewater pumping stations aimed at reducing pollution, which remove 3,000 l s-1 at an average temperature of around 9-18°C. Expressed in terms of energy content this amounts to 63 MW if recovered. But this is just scratching the surface of the potential for large-scale district heating based on heat pumps, such as that planned at Seaham, County Durham to heat 1500 new homes. Community heating and wastewater treatment can be combined for all the former coal mining areas in Central Scotland, the North of England and Midlands and South Wales where population densities are still very high

See also: Lane, A.2021. How flooded coalmines could heat homes. BBC Future 7 July 2020. Taylor, M. 2021. Abandoned pits of former mining town fuel green revolution. The Guardian, 10 August 2021.

Is there a future for coal?

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Burning coal is far and away the main culprit for elevated atmospheric CO2 and global climatic warming. That is a consequence of the Industrial Revolution and a mode of production that centres on the market value of commodities rather than their intrinsic usefulness and thus on the continual generation of profit. As the main original energy source for this capitalist mode, whose viability depends on incessant economic growth, world coal production grew at an exponential rate through the 19th and 20th centuries, as did its influence on global climate. Beginning in the 1920s, coal was joined by other carbon-based fossil fuels (oil and natural gas) in massively increasing energy and greenhouse-gas production. In the data there is little sign of an appetite to reduce this dependence on carbon burning, renewable energy output accounting today for only a few percent of the energy demands of capital. Although coal’s energy contribution is flattening off to be replaced by those of oil and gas, in terms of CO2 emissions it still dominates. That is because oil and gas are carbon-hydrogen compounds rather than almost pure carbon in the case of coal. Unless burning fossil fuels is outlawed and economic growth is drastically curtailed, we are set to live on a far warmer planet.

Growth in energy supply from different sources since 1800 CE (Credit: ourworldindata.org)

For various reasons coal is unique in a social sense. Every producing area has large communities who depend on mining for income. Britain now produces vastly less coal than it did up to the 1990s, with wholesale closure of underground mines. Since 1960 these communities have lost over half a million jobs in mining, let alone those in related industries and those that served mining communities. Three decades on from the last round of closures, those communities remain socially devastated in many respects. A huge amount of coal still lies beneath them. Can it make a come-back? A recent study suggests that perhaps it can, with diametrically opposite environmental consequences.

It seems that surfaces of coal particles are able to take-up and store gases, increasingly so as pressure increases. Miners faced the consequences of that in the form of adsorbed carbon dioxide and methane (‘choke damp’ and ‘fire damp’) that were released when coal was mined underground. Miners’ safety lamps (invented in 1815 by Humphry Davy) enable them to monitor the risks of suffocation by CO2 or explosion of CH4 when the lamps dim or flare, respectively. Engineers at Edith Cowan University in Perth, Western Australia, experimentally measured the amounts of hydrogen adsorbed by crushed coal at different pressures (Iglauer, S et al. 2021. Hydrogen adsorption on sub-bituminous coal: Implications for hydrogen geostorage. Geophysical Research Letters, v. 48, article 2021GL092976; DOI: 10.1029/2021GL092976). From surface atmospheric pressure to 40 times that, adsorption increases rapidly, especially for hydrogen (from 0.05 to 0.25 grams per kilogram). At higher pressures it rises less rapidly to about 0.6 g kg-1 at 100 times atmospheric pressure, which is equivalent to a depth of about 500 m in a sedimentary rock formation. At deeper levels hydrogen adsorption remains about the same.

The experimental results suggest that large amounts of hydrogen can be stored in coal at quite shallow depths. The potential storage in a ton of fractured coal is about 600 kg, equivalent to about 12 cubic metres of liquid hydrogen, but without the need for containment and refrigeration. In the absence of oxygen, such storage would be safe and long-term. If feasible from an engineering standpoint, underground storage of hydrogen in coal seams to overcome one of the current barriers to a hydrogen-based industrial economy through the storage of energy generated by carbon-free technologies, such as wind, wave, tidal and solar generation that operate at highly variable rates, not suited to energy use patterns. Effectively, coalfields could become giant ‘batteries’ without the need to mine vast amounts of elements, such as lithium, needed for conventional batteries; provided that a sustainable means of repeated hydrogen recovery can be devised. A central technology of a future ‘hydrogen economy’ is that of the fuel cell in which hydrogen and oxygen combine using a catalyst to generate electricity, without any combustion and emitting only water vapour.

‘Green’ metal mining?

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A glance at statistics for the global consumption of any particular metal reveals much about the current unfairness of the world we live in. On a per capita basis, people in the developed, rich world use vastly more than do those in the less developed countries, on average. It is commonly said that in order for everyone to live in a fair world, the poor need more metals and other physical resources in order to match the living standards of the rich, or the wealthy will need to consume much less. A new factor in the equitability equation is the necessity to stave off CO2-induced global warming, largely through replacing energy from fossil fuels with that produced by a variety of ‘green’ sources. That carries with it another issue; the technologies for carbon-free energy generation, transmission, storage and use will consume a broad range of metals and other physical resources. These include cobalt and lithium, graphite, rare-earth elements and especially copper, whose annual production is set to soar.

Copper is particularly critical. If China alone fulfils its planned production of all-electric transportation, the demand for copper will over 2 billion tonnes requiring 119 years production at the current extraction rate of 20 Mt per year. The rush to electric cars has already forced copper demand above production, resulting in soaring prices on the world market. In the last year they have doubled, reaching US$10,000 per ton at the time ofwriting. Most metals are won by digging up their ores, often from considerable depths in the crust. Ores then have to be concentrated, smelted and the elemental metals refined. About 6 % of global energy is consumed by this process, adding CO2 and a variety of noxious gases to the atmosphere, let alone the stupendous amounts of uneconomic waste rock and polluted water. Copper is high up the list for environmental impact, being extracted from some of the world biggest mines. Like all physical resources, its extraction cannot be continued without further environmental deterioration. But is there a more sustainable way of extracting metals from the Earth?

Bingham Canyon copper mine in Utah, USA; at 4.5 km diameter and 1.2 km depth it is the world’s largest excavation. (Credit: Mining Magazine)

Under the right chemical conditions many metals can be dissolved, so longs as fluids can pass through the ore. One example is the use of sodium cyanide solution (known as a lixiviant) to dissolve gold from low-grade ore: so-called ‘heap leaching’. But this is done at the surface, either using newly crushed ore from an excavation or waste from earlier mining that could not extract fine-grained gold. A similar approach uses bacteria whose metabolism involves oxidation of sulfide ore minerals, resulting in chemical reactions that liberate their desirable metal content to solution in water. If buried orebodies are fractured in situ this kind of leaching will supposedly transform metal production, in an analogous fashion to fracking for gas and oil. Like fracking, current operations that involve both forms of hydrometallurgy generate highly toxic fluids, and in many cases extract only a fraction of the target metal. But a novel alternative has just emerged, which involves leaching based on electrical means (Martens, E. and 9 others 2021. Toward a more sustainable mining future with electrokinetic in situ leaching. Science Advances, v. 7, article eabf9971; DOI: 10.1126/sciadv.abf9971). It isn’t totally new, for it uses the same chemistry as in heap leaching. However, it does not involve shattering the orebody at depth. Instead, low-voltage currents are passed through the orebody which induce a lixiviant to migrate through the rock, along mineral-grain boundaries rather than through fractures. Fluid movement becomes more efficient over time as the host rock is artificially ‘weathered’ thereby making it permeable. In effect, electrokinetic leaching creates a kind of hydrothermal system in reverse, by replacing the chemically reducing conditions of ore deposition with oxidising dissolution and transportation.

So far, the method has only been demonstrated through a small-scale test of concept using drill core samples of ore from a copper mine. Tests over a few days consumed more than half the grains of a copper ore mineral (chalcopyrite) present in the ore sample. So, it seems to work and astonishingly rapidly too. No doubt metal-mining companies, who are currently coining it hand-over-fist during a boom in metal prices, will beat a path to the doors of the team of researchers. But is it an economic proposition? They authors will soon find out … More important, if it is deployed widely will it increase the sustainability of metal mining? At first glance, yes: by removing the need for excavation of ore, liberation of ore-mineral grains by milling and their separation from valueless waste and many other aspects of beneficiation at the surface. Yet, the bottom line is that mining companies deploy their capital not so much to make ingots of useful metal but primarily to yield profits.  Speeding up metal extraction and thereby its supply to the world market could drive down the price that they can get for each tonne. Perversely, it is perceived shortages on metals and the resulting inflation of price that really yield bonanzas. My guess is that the industry will continue mining in the present manner, with all its lack of sustainability and environmental impact, for that very reason. The real way to reduce damage is to reduce demand for metals: do people in general really need more of them and the goods in which they are bound up in such vast amounts?

Indian groundwater shortage threatens food production

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Farmers in India have been engaged in mass protests since September 2020. Their anger is directed at a series of laws introduced by the central government of Narendra Modi’s  Bharatiya Janata Party (BJP) that change farmers’ terms of trade. Agriculture in India also faces a future of reduced availability of groundwater on which farmers have become increasingly dependent, especially in the vast alluvial plains of the Ganges river system. The twin satellites of the Gravity Recovery  and Climate Experiment (GRACE), which chart changes in mass beneath the Earth’s surface, detected a major change in gravity over 3 million km2 of India’s largest area of agriculture in the northwestern Gangetic plains (Rodell, M. et al. 2009. Satellite-based estimates of groundwater depletion in India. Nature, v. 460, p.999-1002; DOI: 10.1038/nature08238). The data suggested a loss between 2002 and 2008 of around 109 cubic kilometres of water from the aquifers that support regional irrigation and the livelihoods of about 114 million people (see NASA summary). The loss of water and decline in well-water levels have continued since then.

Colour-coded GRACE data  from 2002 to 2008 showing the estimated drawdown in water levels in wells in NW India and NE Pakistan during this period. Green to dark-red colours indicate from 0 to 12 metres of decline (credit: Trent Schindler and Matt Rodell, NASA)

A recent comprehensive survey (Jain, M. and 8 others 2021. Groundwater depletion will reduce cropping intensity in India. Science Advances, v. 9, article eabd2849; DOI: 10.1126/sciadv.abd2849) uses satellite image and census data to document the actual changes in winter crops (those most dependent on irrigation) over the period 2001 to 2012. It roughly measures the realities of the unsustainable extraction of groundwater indicated by GRACE from 2002 to 2008. The study projects an average reduction of 20% in winter cropping across the whole of India, with some of the worst-hit areas being likely to experience a 68% loss. The dominant supplies of irrigation water are from countless tube wells and systems of canals supplied by dams or rivers. India has witnessed impressive gains in food production in the last half century, thanks to rapid and continuing growth in the number of tube wells driven by individual farmers. The livelihoods of about 600 million people depend on agriculture. There is no prospect of substituting either form of irrigation to maintain current levels of production. If increased canal supply was used to replace well water and reduce groundwater depletion, cropping intensity would still decline, albeit at about half the projected rate; however, that doesn’t take into account unpredictable droughts in surface water accumulation and movement.

Faced with this situation, it is hardly surprising that farmers fear for their families future and react massively to state intervention in their marketing and crop storage strategies.

For a wider context to the Indian agricultural crisis see also: The ecological roots of India’s farming crisis (Deutche Welle, 1 February, 2021)

Diamonds and the deep carbon cycle

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When considering the fate of the element carbon and CO2, together with all their climatic connotations, it is easy to forget that they may end up back in the Earth’s mantle from which they once escaped to the surface. In fact all geochemical cycles involve rock, so that elements may find their way into the deep Earth through subduction, and they could eventually come out again: the ‘logic’ of plate tectonics. Teasing out the various routes by which carbon might get to mantle is not so easily achieved. Yet one of the ways it escapes is through the strange magma that once produced kimberlite intrusions, in the form of pure-carbon crystals of diamond that kimberlites contain. A variety of petrological and geochemical techniques, some hinging on other minerals that occur as inclusions, has allowed mineralogists to figure out that diamonds may form at depths greater than about 150 km. Most diamonds of gem quality formed in unusually thick lithosphere beneath the stable, and relatively cool blocks of ancient continental crust known as cratons, which extends to about 250 km. But there are a few that reflect formation depths as great as 800 km that span two major discontinuities in the mantle (at 410 and 660 km depth). These transition zones are marked by sudden changes in seismic speed due to pressure-induced transformations in the structure and density of the main mantle mineral, olivine.

Diamond crystal containing a garnet and other inclusions (Credit: Stephen Richardson, University of Cape Town, South Africa)

Carbon-rich rocks that may be subducted are not restricted to limestones and carbon-rich mudstones. Far greater in mass are the basalts of oceanic crust. Not especially rich in carbon when they crystallised as igneous rocks, their progress away from oceanic spreading centres exposes them to infiltration by ocean water. Once heated, aqueous fluids cause basalts to be hydrothermally altered. Anhydrous feldspars, pyroxenes and olivines react with the fluids to break down to hydrated-silicate clays and dissolved metals. Dissolved carbon dioxide combines with released calcium and magnesium to form pervasive carbonate minerals, often occupying networks of veins. So there has been considerable dispute as to whether subducted sediments or igneous rocks of the oceanic crust are the main source of diamonds. Diamonds with gem potential form only a small proportion of recovered diamonds. Most are only saleable for industrial uses as the ultimate natural abrasive and so are cheaply available for research. This now centres on the isotopic chemistry of carbon and nitrogen in the diamonds themselves and the various depth-indicating silicate minerals that occur in them as minute inclusions, most useful being various types of garnet.

The depletion of diamonds in ‘heavy’ 13C once seemed to match that of carbonaceous shales and the carbonates in fossil shells, but recent data from carbonates in oceanic basalts reveals similar carbon, giving three possibilities. Yet, when their nitrogen-isotope characteristics are taken into account, even diamonds that formed at lithospheric depths do not support a sedimentary source (Regier, M.E. et al. 2020. The lithospheric-to-lower-mantle carbon cycle recorded in superdeep diamonds. Nature, v. 585, p. 234–238; DOI: 10.1038/s41586-020-2676-z). That leaves secondary carbonates in subducted oceanic basalts as the most likely option, the nitrogen isotopes more reminiscent of clays formed from igneous minerals by hydrothermal processes than those created by weathering and sedimentary deposition. However, diamonds with the deepest origins – below the 660 km mantle transition zone – suggest yet another possibility, from the oxygen isotopes of their inclusions combined with those of C and N in the diamonds. All three have tightly constrained values that most resemble those from pristine mantle that has had no interaction with crustal rocks. At such depths, unaltered mantle probably contains carbon in the form of metal alloys and carbides. Regier and colleagues suggest that subducted slabs reaching this environment – the lower mantle – may release watery fluids that mobilise carbon from such alloys to form diamonds. So, I suppose, such ultra-deep diamonds may be formed from the original stellar stuff that accreted to form the Earth and never since saw the ‘light of day’.

‘Mud, mud, glorious mud’

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Earth is a water world, which is one reason why we are here. But when it comes to sedimentary rocks, mud is Number 1. Earth’s oceans and seas hide vast amounts of mud that have accumulated on their floors since Pangaea began to split apart about 200 Ma ago during the Early Jurassic. Half the sedimentary record on the continents since 4 billion years ago is made of mudstones. They are the ultimate products of the weathering of crystalline igneous rocks, whose main minerals – feldspars, pyroxenes, amphiboles, olivines and micas, with the exception of quartz – are all prone to breakdown by the action of the weakly acidic properties of rainwater and the CO2 dissolved in it. Aside from more resistant quartz grains, the main solid products of weathering are clay minerals (hydrated aluminosilicates) and iron oxides and hydroxides. Except for silicon, aluminium and ferric iron, most metals end up in solution and ultimately the oceans.  As well as being a natural product of weathering, mud is today generated by several large industries, and humans have been dabbling in natural muds since the invention of pottery some 25 thousand years ago.  On 21 August 2020 the journal Science devoted 18 pages to a Special Issue on mud, with seven reviews (Malakoff, D. 2020. Mud. Science, v. 369, p. 894-895; DOI: 10.1126/science.369.6506.894).

Mud carnival in Brazil (Credit: africanews.com)

The rate at which mud accumulates as sediment depends on the rate at which erosion takes place, as well as on weathering. Once arable farming had spread widely, deforestation and tilling the soil sparked an increase in soil erosion and therefore in the transportation and deposition of muddy sediment. The spurt becomes noticeable in the sedimentary record of river deltas, such as that of the Nile, about 5000 years ago. But human influences have also had negative effects, particularly through dams. Harnessing stream flow to power mills and forges generally required dams and leats. During medieval times water power exploded in Europe and has since spread exponentially through every continent except Antarctica, with a similar growth in the capacity of reservoirs. As well as damming drainage these efforts also capture mud and other sediments. A study of drainage basins in north-east USA, along which mill dams quickly spread following European colonisation in the 17th century, revealed their major effects on valley geomorphology and hydrology (see: Watermills and meanders; March 2008). Up to 5 metres of sediment build-up changed stream flow to an extent that this now almost vanished industry has stoked-up the chances of major flooding downstream and a host of other environmental changes. The authors of the study are acknowledged in one Mud article (Voosen, P. 2020. A muddy legacy. Science, v. 369, p. 898-901; DOI: 10.1126/science.369.6506.898) because they have since demonstrated that the effects in Pennsylania are reversible if the ‘legacy’ sediment is removed. The same cannot be expected for truly vast reservoirs once they eventually fill with muds to become useless. While big dams continue to function, alluvium downstream is being starved of fresh mud that over millennia made it highly and continuously productive for arable farming, as in the case of Egypt, the lower Colorado River delta and the lower Yangtze flood plain below China’s Three Gorges Dam.

Mud poses extreme risk when set in motion. Unlike sand, clay deposits saturated with water are thixotropic – when static they appear solid and stable but as soon as they begin to move en masse they behave as a viscous fluid. Once mudflows slow they solidify again, burying and trapping whatever and whomever they have carried off. This is a major threat from the storage of industrially created muds in tailings ponds, exemplified by a disaster at a Brazilian mine in 2019, first at the site itself and then as the mud entered a river system and eventually reached the sea. Warren Cornwall explains how these failures happen and may be prevented (Cornwall, W. 2020. A dam big problem.  Science, v. 369, p. 906-909; DOI: 10.1126/science.369.6506.906). Another article in the Mud special issue considers waste from aluminium plants (Service, R.F. 2020. Red alert. Science, v. 369, p. 910-911; DOI: 10.1126/science.369.6506.910). The main ore for aluminium is bauxite, which is the product of extreme chemical weathering in the tropics. The metal is smelted from aluminium hydroxides formed when silica is leached out of clay minerals, but this has to be separated from clay minerals and iron oxides that form a high proportion of commercial bauxites, and which are disposed of in tailings dams. The retaining dam of such a waste pond in Hungary gave way in 2010, the thixotropic red clay burying a town downstream to kill 10 people. This mud was highly alkaline and inflicted severe burns on 150 survivors. Service also points out a more positive aspect of clay-rich mud: it can absorb CO2 bubbled through it to form various, non-toxic carbonates and help draw down the greenhouse gas.

Muddy sediments are chemically complex, partly because their very low permeability hinders oxygenated water from entering them: they maintain highly reducing conditions. Because of this, oxidising bacteria are excluded, so that much of the organic matter deposited in the muds remains as carbonaceous particles. They store carbon extracted from the atmosphere by surface plankton whose remains sink to the ocean floor. Consequently, many mudrocks are potential source rocks for petroleum. Although they do not support oxygen-demanding animals, they are colonised by bacteria of many different kinds. Some – methanogens – break down organic molecules to produce methane. The metabolism of others depends on sulfate ions in the trapped water, which they reduce to sulfide ions and thus hydrogen sulfide gas: most muds stink. Some of the H2S reacts with metal ions, to precipitate sulfide minerals, the most common being pyrite (FeS2). In fact a significant proportion of the world’s copper, zinc and lead resources reside in sulfide-rich mudstones: essential to the economies of Zambia and the Democratic Republic of Congo. But there are some strange features of mud-loving bacteria that are only just emerging. The latest is the discovery of bacteria that build chains up to 5 cm long that conduct electricity (Pennisi, E. 2020. The mud is electric. Science, v. 369, p. 902-905; DOI: 10.1126/science.369.6506.902). The bacterial ‘nanowires’ sprout from minute pyrite grains, and transfer electrons released by oxidation of organic compounds, effectively to catalyse sulfide-producing reduction reactions. NB Oxygen is not necessary for oxidation as its chemistry involves the loss of electrons, while reduction involves a gain of electrons, expressed by the acronym OILRIG (oxidation is loss, reduction is gain). It seems such electrical bacteria are part of a hitherto unsuspected chemical ecosystem that helps hold the mud together as well as participating in a host of geochemical cycles. They may spur an entirely new field of nano-technology, extending, bizarrely, to an ability to generate electricity from moisture in the air.

If you wish to read these reviews in full, you might try using their DOIs at Sci Hub.