Tag: methane

Milankovich precession and the Palaeocene-Eocene Thermal Maximum

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About 56 Ma ago there occurred some of the most dramatic biological changes since the mass extinction at the Cretaceous-Palaeogene boundary. They included rapid expansion and diversification of mammals and land plants, and a plunge in the number of deep-water foraminifera. Global cooling from the Cretaceous hothouse was rudely reversed by sudden global warming of about 5 to 10°C. Some climatologists have ascribed bugbear status to the Palaeocene-Eocene Thermal Maximum (PETM) as a possible scenario for future anthropogenic global warming. The widely accepted cause is a massive blurt into the Palaeocene atmosphere of greenhouse gases, but what caused it is enthusiastically debated. The climate shift is associated with a sudden decrease in the proportion of 13C in marine sediments: a negative spike in δ13C. Because photosynthesis favours the lighter 12C, organic matter has a low δ13C, so a great deal of buried organic carbon may have escaped from the ocean floor, most likely in the form of methane gas. However, massive burning of living terrestrial biomass would produce the same carbon-isotope signal, but absence of evidence for mass conflagration supports methane release. Methane is temporarily held in marine sediments in the form of gas hydrate (clathrate), an ice-like solid that forms at low temperatures on the deep seafloor. Warming of deep sea water or a decrease in pressure, if sea level falls, destabilise clathrates thereby releasing methane gas: the ‘clathrate gun hypothesis’. The main issue is what mechanism may have pulled the trigger for a monstrous methane release.

Massive leak of natural gas – mainly methane – off Sweden in the Baltic Sea, from the probably sabotaged Nord Stream pipeline. (Source: Swedish coastguard agency)

Many have favoured a major igneous event. Between 55.0 and 55.8 Ma basaltic magmatism– continuing today in Iceland – formed the North Atlantic Igneous Province. It involved large-scale intrusion of sills as well as outpourings of flood basalts and coincided with the initial rifting of Greenland from northern Europe (see: Smoking gun for end-Palaeocene warming: an igneous connection; July/August 2004). The occurrence of impact ejecta in end-Palaeocene sediments off the east coast of the US has spawned an extraterrestrial hypothesis for the warming, which could account for the negative spike in δ13C as the product of a burning terrestrial biosphere (see: Impact linked to the Palaeocene-Eocene boundary event; October 2016). Less headline-grabbing is the possibility that the event was part and parcel of the Milankovich effect: an inevitability in the complex interplay between the three astronomical components that affect Earth’s orbital and rotational behaviour: eccentricity, axial tilt and precession. A group of geoscientists from China and the US, led by Mingsong Li of Peking University, have investigated in minute detail the ups and downs of δ13C around 56 Ma in drill cores recovered from a sequence of Palaeocene and Eocene continental-shelf sediments in Maryland, USA (Li, M., Bralower, T.J. et al. 2022. Astrochronology of the Paleocene-Eocene Thermal Maximum on the Atlantic Coastal Plain. Nature Communications, v. 13, Article 5618; DOI: 10.1038/s41467-022-33390-x).

The study involved sampling sediment for carbon- and oxygen-isotope analysis at depth intervals between 3 and 10 cm over a 35 m section through the lower Eocene and uppermost Palaeocene. Calcium abundances in the core were logged at a resolution of 5 mm using an X-ray fluorescence instrument. The results link to variations in CaCO3 in the sediments across the PETM event. Another dataset involves semi-continuous measurements of magnetic susceptibility (MS) along the core. These measurements are able to indicate variations in delivery to the ocean of dissolved calcium and detrital magnetic minerals as climate and continental weathering vary through time. They are widely known to be good recorders of Milankovich cycles. After processing, the Ca and MS data sets show cyclical fluctuations relative to depth within the cores. ‘Tuning’ their frequencies to the familiar time series of Milankovich astronomical climate forcing reveals a close match to what would be expected if the climate fluctuations were paced by the 26 ka axial precession signal. My post of 17 June 2022 about the influence of precession over ‘iceberg armadas’ during the Pleistocene might be useful to re-read in this context. This correlation enabled the researchers to convert depth in the cores to time, so that the timing of fluctuations in carbon- and oxygen-isotope data that the PETM had created could be considered against various hypotheses for its cause. The ‘excursions’ of both began at the same time and reached the maxima of their changes from Palaeocene values over about 6,000 years. The authors consider that is far too long to countenance the release of methane as a result of asteroidal impact, or by massive burning of terrestrial vegetation. The other option that the beginning of the North Atlantic Igneous Province had been the trigger may also be ruled out on two grounds: the magmatism began earlier, and it continued for far longer. The onset of the PETM coincides with an extreme in precession-related climatic forcing. So Li et al. consider that a quirk in the Milankovich Effect could have played a role in triggering massive methane release. This might also explain features of the global calcium record in seafloor sediments as results of a brief period of ocean acidification during the PETM. Such an event would play havoc with carbonate-secreting organisms, such as foraminifera, by lowering the dissolved carbonate ion content on which they depend for their shells: hence their suffering considerable extinction. Of course, the other elements of astronomical forcing – eccentricity and axial tilt – would also have been operating on global climate at the time.  The long-term 100 and 405 ka eccentricity cycles may have played a role in amplifying warming, which may have resulted in increased burial of organic carbon and thus the amount of methane buried beneath the seabed.

Signs of massive hydrocarbon burning at the end of the Triassic

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One of the ‘Big Five’ mass extinctions occurred at the end of the Triassic Period (~201 Ma), whose magnitude matches that of the more famous end-Cretaceous (K-Pg) event. It roughly coincided with the beginning of break-up of the Pangaea supercontinent that was accompanied by a major episode of volcanism preserved in the Central Atlantic Magmatic Province (CAMP). Eastern North America, West Africa and northern South America reveal scattered patches of CAMP flood basalts, swarms of dykes and large intrusive sills. Like all mass extinctions, that at the Triassic-Jurassic boundary left a huge selection of vacant or depleted ecological niches ready for evolution to fill by later adaptive radiation of surviving organisms. Because it coincided with continental break-up and drift, unlike other such events, evolution proceeded in different ways on the various wandering land masses and in newly formed seas (see  an excellent animation of the formation and break-up of Pangaea – move the slider to 3 minutes for the start of break-up). The Jurassic was a period of explosive evolution among all groups of organisms. The most notable changes were among marine cephalopods, to give rise to a bewildering variety of ammonite species, and on land with the appearance and subsequent diversification of dinosaurs.

Pangaea at the end of the Triassic (top) and in Middle Cretaceous times (Credit: screen shots from animation by Christopher Scotese)

Many scientists have ascribed the origin of these events to the CAMP magmatic activity and the release of huge amounts of methane to trigger rapid global warming. In October 2021 one group focused on a special role for the high percentages of magma that never reached the surface and formed huge intrusions that spread laterally in thick sedimentary sequences to ‘crack’ hydrocarbons to their simplest form, CH4 or methane. A sedimentary origin of the methane, rather than its escape from the mantle, is indicated by the carbon-isotope ‘signature’ of sediments deposited shortly after the Tr-J event. The lighter isotope 12C rose significantly relative to 13C, suggesting an organic source – photosynthesis selectively takes up the lighter isotope.

By examining the element mercury (Hg) in deep ocean sediments from a Tr-J sedimentary section now exposed in Japan, scientists from China, the US and Norway have added detail to the methane-release hypothesis (Shen, J et al. 2022. Mercury evidence for combustion of organic-rich sediments during the end-Triassic crisis. Nature Communications, v. 13, article 1307; DOI:10.1038/s41467-022-28891-8). The relative proportions of Hg isotopes strongly suggest that the mercury had been released, as was the methane, from organic-rich sediments rather than from the CAMP magmas (i.e. ultimately from the mantle) through gasification and then burning at the surface.

The hypothesis is enlivened by a separate study (Fox C.P. et al. 2022. Flame out! End-Triassic mass extinction polycyclic aromatic hydrocarbons reflect more than just fire. Earth and Planetary Science Letters, v. 584, article 117418; DOI: 10.1016/j.epsl.2022.117418) that sees magmatic heating as being not so important. Calum Fox and colleagues at Curtin University, Western Australia analysed sediments from a Triassic-Jurassic sedimentary sequence near the Severn Bridge in SW England, focusing on polycyclic hydrocarbons in them. Their results show little sign of the kinds of organic chemical remnants of modern wildfires. Instead they suggest a greater contribution from soil erosion by acid rain that increased input of plant debris to a late Triassic marine basin

See also: How a major volcanic eruption paved the way for the rise of the dinosaurs Eureka Alert 23 March 2022;  Soil erosion and wildfire: another nail in coffin for Triassic era. Science Daily, 21 March 2022

Influence of massive igneous intrusions on end-Triassic mass extinction

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About 200 Ma ago, the break-up of the Pangaea supercontinent was imminent. The signs of impending events are spread through the eastern seaboard of North America, West Africa and central and northern South America. Today, they take the form of isolated patches of continental flood basalts, dyke swarms – probably the feeders for much more extensive flood volcanism – and large intrusive sills. Break-up began with the separation of North America from Africa and the start of sea-floor spreading that began to form the Central Atlantic Ocean: hence the name Central Atlantic Magmatic Province (CAMP) for the igneous activity. It all kicked off at the time of the Triassic-Jurassic stratigraphic boundary, and a mass extinction with a similar magnitude to that at the end of the Cretaceous. Disappearances of animals in the oceans and on continents were selective rather than general, as were extinctions of land plants. The mass extinction is estimated to have taken about ten thousand years. It left a great variety of ecological niches ready for re-occupation. On land a small group of reptiles with a substantial destiny entered some of these vacant niches. They evolved explosively to the plethora of later dinosaurs as their descendants became separated as a result of continental drift and adaptive radiation.

Flood basalts of the Central Atlantic Magmatic Province in Morocco (Credit: Andrea Marzoli)

The end-Triassic mass extinction, like three others of the Big Five, was thus closely associated in time with massive continental flood volcanism: indeed one of the largest such events. Within at most 10 ka large theropod dinosaurs entered the early Jurassic scene of eastern North America. The Jurassic was a greenhouse world whose atmosphere had about five times more CO2, a mean global surface temperature between 5 and 10°C higher and deep ocean temperatures 8°C above those at present. Was mantle carbon transported by CAMP magmas the main source (widely assumed until recently) or, as during the end-Permian mass extinction, was buried organic carbon responsible? A multinational group of geoscientists have closely examined samples from a one million cubic kilometre stack of intrusive basaltic sills, dated at 201 Ma, in the Amazon basin of Brazil that amount to about a third of all CAMP magmatism (Capriolo, M. and 11 others 2021. Massive methane fluxing from magma–sediment interaction in the end-Triassic Central Atlantic Magmatic Province. Nature Communications, v. 12, article 5534; DOI: 10.1038/s41467-021-25510-w).

The team focussed on fluid inclusions in quartz within the basaltic sills that formed during the late stages of their crystallisation. The tiny inclusions contain methane gas and tiny crystals of halite (NaCl) as well as liquid water. Such was the bulk composition of the intrusive magma that the presence of around 5% of quartz in the basalts would be impossible without their magma having assimilated large volumes of silica-rich sedimentary rocks such as shales. The host rocks for the huge slab of igneous sills are sediments of Palaeozoic age: a ready source for contamination by both organic carbon and salt. The presence of methane in the inclusions suggests that more complex hydrocarbons had been ‘cracked’ by thermal metamorphism. Moreover, it is highly unlikely to have been derived from the mantle, partly because methane has been experimentally shown not to be soluble in basaltic magmas whereas CO2 is. The authors conclude that both quartz and methane entered the sills in hydrothermal fluids generated in adjacent sediments. Thermal metamorphism of the sediments would also have driven such fluids to the surface to inject methane directly to the atmosphere. Methane is 25 times as potent as carbon dioxide at trapping heat in the atmosphere, yet it combines with the hydroxyl (OH–) radical to form CO2 and water vapour within about 12 years. Nevertheless during continuous emission methane traps 84 times more heat in the atmosphere than would an equivalent mass of carbon dioxide.

Calculations suggest about seven trillion tonnes of methane were generated by the CAMP intrusions in Brazil. Had the magmas mainly been extruded as flood basalts then perhaps global warming at the close of the Triassic would have been far less. Extinctions and subsequent biological evolution would have taken very different paths; dinosaurs may not have exploded onto the terrestrial scene so dramatically during the remaining 185 Ma of the Mesozoic. So it seems important to attempt an explanation of why CAMP magmas in Brazil did not rise to the surface but stayed buried as such stupendous igneous intrusions. Work on smaller intrusive sills suggests that magmas that are denser than the rocks that they pass through – as in a large, thick sedimentary basin – are forced by gravity to take a lateral ‘line of least resistance’ to intrude along sedimentary bedding. That would be aided by the enormous pressure of steam boiled from wet sedimentary rocks forcing beds apart. In areas where only thin sedimentary cover rests on crystalline, more dense igneous and metamorphic rocks, basaltic magma has a greater likelihood of rising through vertical dyke swarms to reach the surface and form lava floods.

Impact linked to the Palaeocene-Eocene boundary event

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The Palaeocene–Eocene (P-E) boundary at 55.8 Ma marks the most dramatic biological changes since the mass extinction at the Cretaceous-Palaeogene boundary 10 million years earlier. They included the rapid expansions of mammals and land plants and major extinction of deep-water foraminifera.  It was a time of sudden global warming (5-10°C in 10-20 ka) superimposed on the general Cenozoic cooling from the ‘hothouse’ of the Cretaceous Period. It coincided with a decrease in the proportion of 13C in marine carbonates.  Because photosynthesis, the source of organic carbon, favours light 12C, such a negative δ13C “spike” is generally ascribed to an unusually high release of organic carbon to the atmosphere.  The end-Palaeocene warming may have resulted from a massive release of methane from gas-hydrate buried in shallow seafloor sediments. But another process may yield such a signature; massive burning of organic material at the land surface. Since its discovery, the P-E thermal maximum has been likened to the situation that we may face should CO2 emissions from fossil-fuel burning continue to rise without control. Unsurprisingly, funds are more easily available for research on this topic than, say, ‘Snowball Earth’ events.

Climate change during the last 65 million year...
Climate change during the last 65 million years. The Paleocene–Eocene Thermal Maximum is labelled PETM. (Photo credit: Wikipedia)

Three seafloor sediment cores off the east coast of the US that include the P-E boundary have been found to contain evidence for an impact that occurred at the time of the δ13C “spike” (Schaller, M.F. et al. 2016. Impact ejecta at the Paleocene-Eocene boundary. Science, v. 354, p. 225-229). The evidence is dominated by tiny spherules and tear-shaped blobs of glass, some of which contain tiny crystals of shocked and high-temperature forms of silica (SiO2). These form part of the suite of features that have been used to prove the influence of asteroid impacts. Two other onshore sites have yielded iridium anomalies at the boundary, so it does look like there was an impact at the time. The question is, was it large enough either to cause vast amounts of methane to blurt out from shall-water gas hydrates or set the biosphere in fire? Two craters whose age approximates that of the P-E boundary are known, one in Texas the other in Jordan, with diameters of 12 and 5 km respectively; far too small to have had any global effect. So either a suitably substantial crater of the right age is hidden somewhere by younger sediments or the association is coincidental – the impact that created the Texan crater could conceivably have flung glassy ejecta to the area of the three seafloor drilling sites.

Almost coinciding with the spherule-based paper’s publication another stole its potential thunder. Researchers at Southampton University used a mathematical model to investigate how a methane release event might have unfolded (Minshull, T.A. et al. 2016. Mechanistic insights into a hydrate contribution to the Paleocene-Eocene carbon cycle perturbation from coupled thermohydraulic simulations. Geophysical Research Letters, v. 43, p. 8637-8644, DOI: 10.1002/2016GL069676). Their findings challenge the hypothesized role of methane hydrates in causing the sudden warming at the P-E boundary. But that leaves out the biosphere burning, which probably would have neded a truly spectacular impact.

More on mechanisms for ancient climate change

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Fracking check list

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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.

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