Porphyry deposits and the fracking mechanism

brothers in arms
Porphyry sculpture of two of the four co-emperors of the late Roman Empire – the Tetrarchy (credit: mhobl via Flickr)

For about a century a style of mineral deposit that develops in and around shallow, silicic magma chambers has dominated world supplies of copper, molybdenum and, more rarely, tin. They are also enriched in other valuable elements, including gold and silver, which makes these deposits even more attractive to mine. Hosting them are fine-grained diorites and granodiorites that typically contain large crystals of quartz and feldspar set in the finer material. Technically such rocks are called porphyries; well not so technical because the name derives from many porphyries having a colour much valued by Egyptian and especially Roman  sculptors and architects – a reddish purple close to that on the hem of an nobleman’s toga. The dye comes from the ‘purple’ fish – the marine mollusc Murex brandaris – which the ancient Greeks referred to as porphura. In Rome, ‘The Purple’ were the nobs, and today they are the cardinals. The connection is coincidental, the best and most enduring rocks for sculpting and making pyramids are of this kind, but happen to be purple. Of course, there are igneous rocks with the eponymous texture but different colours, but stonemasons in the ancient world never bothered to give them a special name

The porphyritic texture signifies to virtually every geologist a magmatic history in which an igneous magma resided deep in the crust slowly crystallizing large mineral grains. Then, for one reason or another, it was blurted towards the surface. Porphyry copper and molybdenum deposits have a disturbingly phallic shape; a tall, rough cylinder capped by a bell-shaped zone of mineralisation. And they are pretty big, the largest at Bingham Canyon in Utah, USA once having been ~2.5 km tall and 0.5 km wide, with a 2 km, bell-shaped zone of mineralisation affecting the intrusion and its surrounding country rock.

Bingham Canyon Mine
The world’s largest open-pit mine in the porphyry copper deposit at Bingham Canyon Utah (credit: Wikipedia)

Porphyry ores are not much for the rock aficionado to shout about and they are characterized by very low grades of ore, the metal-sulfide ore minerals and any gold being barely visible. They are economic because there is a great deal of rock with copper and molybdenum contents often less than 0.5%, and economic gold values less than a part per million (0.03 troy oz t-1). The bulk and the diversity of metals make mining porphyry deposits profitable. The ore minerals occur in tiny cracks that pervade the deposits forming a ‘stockwork’. That is where this style of mineralisation has a link with fracking shales to release their gas content. Stockworks are produced by very high-pressure steam that explosively fractures every cubic metre of the orebody. Crystallisation of sulfides and barren minerals keeps the fractures open until the system runs out of steam and mineralising fluids. Modelling of the thermodynamics associated with porphyry intrusions now suggests that once pressure and temperature stabilise at the requisite levels the hydraulic fracturing becomes self-sustaining (Weis, P. et al. 2012. Porphyry-copper ore shells form at stable pressure-temperature fronts within dynamic fluid plumes. Science, v. 338, p. 1613-1616). The key is the ‘fracking’ and as ‘shells’ with the right conditions migrate through the upper part of the intrusive system groundwater is drawn in to the freshly permeable rock to dissolve, transport and, where chemical conditions permit, to precipitate metals in the cracks. The modelling suggests a fundamental process that extends from plutonic systems, through volcanic edifices, hydrothermal processes in shallower rocks and active geothermal systems that vent to the surface.

Stockwork in copper-molybdenum porphyry deposit in Mexico (credit: Sundance Minerals)
Stockwork in copper-molybdenum porphyry deposit in Mexico (credit: Sundance Minerals)

In many respects the universality of hydraulic fracturing associated with increased heat flow, which itself can affect the crust repeatedly, may be the key to the concept of ‘metallogenic provinces’. These are large areas in which economic mineralisation of many styles but with much the same ‘blend’ of metals seems to have formed again and again during crustal evolution. Such provinces emerged from exploration and mining to present explorationists with the old adage, ‘To find an elephant go to elephant country’. Now there may be a theoretical basis on which new discoveries may be made.

Fracking leaks

Cameron speaking in 2010.
David Cameron speaks (credit: Wikipedia)

The start of 2013 saw a massive puff from the British government for development of shale gas, Premier David Cameron crying ‘Britain must be at the heart of the shale gas revolution’. Fearful of the rapidly growing shift from Britain’s natural-gas self reliance to dependence on the Gulf, Russia and Norway the Conservative-Liberal  Democrat coalition gave the green light for ‘frack drilling’ to restart. This followed a pause following seismicity in the Blackpool area that attended Cuadrilla’s exploratory drilling into the gas-rich Carboniferous Bowland Shale thereabouts. There is also a nice sweetener for the new industry in the form of tax breaks.

English: Boris Johnson holding a model red dou...
Boris Johnson holds a model London red bus (Photo credit: Wikipedia)

London Mayor Boris Johnson, a possible contender for Tory leadership, seems pleased. And perhaps he should be, as the Lib-Con coalition will be tested because the junior partners depend electorally, to some extent, on ‘green’ credentials. The Lib-Dem Energy Minister, Ed Davey, seemingly favours an automatic halt to drilling should there be seismicity greater than 0.5 on the Richter scale; an energy level less than experienced every day in London from its Underground trains. Political commentators have forecast that green issues may exacerbate tensions within the coalition in the second half of its scheduled 5-year term, especially as the electorate seems set to reduce the Liberal Democrat partners to irrelevance in future elections.

Natural gas’s biggest ‘green’ plus is that being a hydrocarbon its burning releases considerably less CO2 than does its coal energy equivalent, the hydrogen content becoming water vapour. Yet the dominant gas is methane, which has a far larger greenhouse effect than the CO2 released by its burning. To avoid that presenting increased atmospheric warming, extracting natural gas needs to avoid leakage. Unfortunately for those bawling lustily about the economic potential of fracking source rocks such as the Bowland Shale, recent aerial surveys over US gas fields will come as a major shock. At the annual meeting of the American Geophysical Union in early December 2012 methane emissions from two large gas fields in the western US were released (Tollefson, J. 2013. Methane leaks erode green credentials of natural gas. Nature, v. 493, p. 12). They amount to 9% of total production, which would more than offset the climatic ‘benefit’ of using natural gas as a coal alternative.

A shift from coal to natural gas-fuelled power generation would slow down climatic warming, if leakage is kept below the modest level of 3.2% of production. So if the latest measurements are an unavoidable norm for gas fields then natural gas burning in fact increases global warming. Even more telling is that, until the shale ‘fracking revolution’, gas was produced by drilling into permeable reservoir rocks capped by a seal rock – usually a shale. The gas would not have leaked except from the well itself. Fracking, by design, increases the permeability of what would otherwise be a seal rock – hydrocarbon-rich shale – over a large area.

English: Schematic cross-section of the subsur...
Schematic cross-section illustrating types of natural gas deposits (credit: Wikipedia)

Aerial analyses to check emissions over oil and gas fields, let alone over shale-gas operations, are not widespread. However, the technology is not new. Where emissions are strictly enforced in populated areas, as over oil terminals and refineries, overflights to sample the air have been routine for several decades. Little mention is made of such precautionary measures in the promotion of fracking.

Another point is that as well as often being far from habitations, US shale-gas operations are generally into simple stratigraphy and structure. The Lower Carboniferous Bowland Shale now being touted as fuel for Britain’s escape from a descent into economic depression, with its estimated 200 trillion cubic feet of as potential, is intensely faulted and broadly folded, having experienced the Variscan orogeny at the end of the Palaeozoic Era. The complexity and pervasiveness of this brittle deformation is amply shown by geological maps of former coalfields that incorporate subsurface information from mine workings. The Bowland Shale lies below the Upper Carboniferous Coal Measures, many of the likely targets for fracking have never been subject to intensive underground mining simply because the Coal Measures were eroded away tens of million years ago. Consequently the degree to which many fracking targets may be riven by surface-breaking faults and fracture zones is not and possibly never will be known in the detail needed to assess widespread methane leakage.

Sometime in early 2013, the British Geological Survey is set to release estimates of the Bowland Shale gas reserves, in which its detailed mapping archives will have played the major role. That report will bear detailed scrutiny as regards the degree to which it also assesses potential leakage.

Possible snags and boons for CO2 disposal

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 CO, 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).

Fracking check list

Bergung der Opfer des Grubenunglücks
Aftermath of the 1906 mine explosion at Courrières, northern France; the largest mining disaster in Europe with 1099 fatalities. Image via Wikipedia

Britain is on the cusp of a shale-gas boom (see Britain to be comprehensively fracked? : EPN 14 October 2011) and it is as well to be prepared for some potential consequences. In extensively fracked parts of the US – the states of New York, Pennsylvania, Texas and Colorado – there are reports of water taps emitting roaring flames after dissolved methane in groundwater ignites. This is largely due to common-place household water supplies from unprocessed groundwater, which are rare in Britain. But there are other hazards (Mooney, C. 2011. The truth about fracking. Scientific American, v. 305 (Nov 2011), p. 62-67) that have enraged Americans in affected areas, which are just as likely to occur in Britain. In fact the nature of shale-gas exploitation by horizontal drilling beneath large areas poses larger threats in densely populated area, as the people of Blackpool have witnessed in the form of small earthquakes that the local shale-gas entrepreneur Cuadrilla admit as side effects of their exploratory operations .

Chris Mooney succinctly explains the processes involved in fracking shale reservoirs; basically huge volumes of water laced with a cocktail of hazardous chemicals and sand being blasted into shales at high pressure to fracture the rock hydraulically and create pathways for natural gas to leak to the wells. One risk is that this water has to be recovered and stored in surface ponds for re-use. About 75% returns to the surface and also carries whatever has been dissolved from the shales, which can be extremely hazardous. By definition a shale containing hydrocarbons creates strongly reducing conditions, which in turn can induce several elements to enter solution as well as easily dissolved salts; for instance divalent iron (Fe2+) is highly soluble, whereas more oxidised Fe3+ is not, so waters having passed through gas-rich shales will be iron-rich. But that is by no means the worst possibility; one of the most common iron minerals in sedimentary rocks is goethite (FeOOH), which adsorbs many otherwise soluble elements and compounds. In reducing conditions goethite can break down to release its adsorbed elements, among which is commonly arsenic. The blazing faucet hazard results from hydrocarbon gases leaking through imperfectly sealed well casings to enter shallow groundwater, where the gases can also create reducing conditions and release toxic elements and compounds into otherwise pure groundwater by dissolution of ubiquitous goethite, as in the infamous arsenic crisis of Bangladesh and adjoining West Bengal in India where natural reducing conditions do the damage.

What is not mentioned in the Scientific American article is the common association of hydrogen sulfide gas with petroleum, produced from abundant sulfate ions in formation water by bacteria that reduce sulfate to sulfide in the metabolism. This ‘sour gas’, as it is known in the oil industry, is a stealthy killer: at high concentrations it loses its rotten-eggs smell and in the early days of the petroleum industry killed more oil workers than did any other occupational hazard. Visit the spa towns of Harrogate in Yorkshire and Strathpeffer in northern Scotland and sample their waters for examples of what Carboniferous and Devonian gas-rich shales produce quite naturally: noxious stuff of questionable efficacy. The environmental effects of such natural seepage from gas-rich rocks tell a cautionary tale as regards fracking. The highly reducing cocktail of hydrocarbon and sulfide gases in rising, mineral-rich formation water kills the microbiotic symbionts that are essential to plant root systems for nutrient uptake die and so too do trees. The onshore Solway Basin of Carboniferous age in NW England illustrates both points, having many chalybeate springs as the sulfide- and iron-rich waters are euphemistically known and also a strange phenomenon in many of the deep valleys cut by glacial melt waters as land rose following the last glacial maximum. Once trees reach a certain height – and correspondingly deep root systems – they die, to litter the valley woodland with large dead-heads.  Also leaves on smaller trees turn to their autumnal colours earlier than on higher ground. Both seem to be due to minor gas seepages from thick sale sequences in the depths of the sedimentary basin. Indeed, both are botanical indicators to the hydrocarbon explorationist.

To recap, a common size of a fracking operation using several horizontal wells driven from a single wellhead is 4km in diameter entering gas-rich shales at up to 2 km depth. Each well can generate fractures of a hundred metres or more in the shales and surrounding rocks, as they have to for commercial production. In Britain, most of the sites underlain by shales with gas potential are low-lying agricultural- or urban land. The producing rock in the Blackpool area is the Middle Carboniferous Bowland Shale that lies beneath the Coal Measures of what was formerly the Lancashire coalfield, now a patchwork of expanding urban centres. On 23 May 1984 an explosion occurred in Abbystead, Lancashire at an installation designed to pump winter flood water between the rivers Lune and Wyre through a tunnel beneath the Lower to Middle Carboniferous Bowland Fells. The Abbystead Disaster coincided with an inaugural demonstration of the pumping station to visitors, of whom 16 were killed and 22 injured. Methane had escaped from Carboniferous shales to build up in the flood-balancing  tunnel soon after its construction. Methane build-ups were by far the worst hazard throughout the history of British coal mining, thousands dying and being maimed as a result of explosions. One of the largest death tolls in British coal-mining history was 344 miners at Hulton Colliery in Westhoughton, Lancashire in 1910 after a methane explosion; the methane may well have escaped from the underlying Bowland Shales.

Britain to be comprehensively fracked?

Tower for drilling horizontally into the Marce...
Drill rig in Pennsylvania aimed at hydraulic fracturing of the hydrocarbon-rich Marcellus Shale of Devonian age. Image via Wikipedia

In ‘Fracking’ shale and US ‘peak gas’ (EPN of 1 July 2010) I drew attention to the relief being offered to dwindling US self-sufficiency in natural gas by new drilling and subsurface rock-fracturing technologies that opens access to extremely ‘tight’ carbonaceous shale and the gas it contains. The item also hinted at the down-side of shale-gas. The ‘fracking’ industry has grown at an alarming rate in the USA, now supplying more than 20% of US demand for gas. This side of the Atlantic the once vast reserves of North Sea gas fields are approaching exhaustion. This is at a time when commitments to reducing carbon emissions dramatically depend to a large extent on hydrocarbon gas supplanting coal to generate electricity, releasing much lower CO2  by burning hydrogen-rich gases such as methane (CH4) than by using coal that contains mainly carbon. Without alternative, indigenous supplies declining gas reserves in Western Europe also seem likely to enforce dependency on piped gas from Russia or shipment of liquefied petroleum gas from those major oil fields that produce it. The scene has been set in Europe in general and Britain in particular for a massive round of exploration aimed at alternative gas sources beneath dry land. Unlike the US and Canada, the British are not accustomed to on-shore drilling rigs, seismic exploration and production platforms, and nor are most Europeans. Least welcome are the potential environmental and social hazards that have been associated with the US fracking industry, which seem a greater threat in more densely populated Europe.

The offshore oil and gas of the North Sea fields formed by a process of slow geothermal heating of solid hydrocarbons or kerogen in source rocks at a variety of stratigraphic levels, escape into surrounding rocks of the gases and liquids produced by this maturation, and their eventual migration and accumulation in geological traps. By no means all products of maturation leave shale source rocks because of their very low permeability. That residue may be much more voluminous than petroleum liquids and gases in conventional reservoir rocks; hence the attraction of fracking carbonaceous shales. British on-shore geology is bulging with them, particularly Devonian and Carboniferous lacustrine mudstones, Carboniferous and Jurassic coals, and the marine black shales of the Jurassic (see http://www.bgs.ac.uk/research/energy/shaleGas.html and https://www.og.decc.gov.uk/upstream/licensing/shalegas.pdf), to the extent that areas of potential fracking cover around a third of England, Wales and southern Scotland.

News is breaking of a major shale-gas discovery beneath Blackpool, the seaside resort ‘noted for fresh air and fun, where Mr and Mrs Ramsbottom went with Young Albert their son…’ (Albert poked a stick at Wallace the lion and was eaten), said by energy firm Cuadrilla to have gas reserves of 5.7 trillion m3. The announcement followed 6 months of exploratory drilling, and drew attention to the burgeoning interest by entrepreneurs in the upcoming 14th Onshore Licensing Round for petroleum exploration in Britain. It isn’t just from major petroleum companies, but in some cases even what amount to family businesses finding sufficient venture capital to spud wells; similar in many respects to the US fracking boom that began a mere 10 years ago.