Tag: carbon isotopes

The end-Triassic mass extinction and ocean acidification

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Triassic reef limestones in the Dolomites of northern Italy. Credit: © Matteo Volpone

Four out of six mass extinctions that ravaged life on Earth during the last 300 Ma coincided with large igneous events marked by basaltic flood volcanism. But not all such bursts of igneous activity match significant mass extinctions. Moreover, some rapid rises in the rate of extinction are not clearly linked to peaks in igneous activity. Another issue in this context is that ‘kill mechanisms’ are generally speculative rather than based on hard data. Large igneous events inevitably emit very large amounts of gases and dust-sized particulates into the atmosphere. Carbon dioxide, being a greenhouse gas, tends to heat up the global climate, but also dissolves in seawater to lower its pH. Both global warming and more acidic oceans are possible ‘kill mechanisms’. Volcanic emission of sulfur dioxide results in acid rain and thus a decrease in the pH of seawater. But if it is blasted into the stratosphere it combines with oxygen and water vapour to form minute droplets of sulfuric acid. These form long-lived haze, which reflects solar energy beck into space. Such an increased albedo therefore tends to cool the planet and create a so-called ‘volcanic winter’. Dust that reaches the stratosphere reduces penetration of visible light to the surface, again resulting in cooling. But since photosynthetic organisms rely on blue and red light to power their conversion of CO­2­ and water vapour to carbohydrates and oxygen, these primary producers at the base of the marine and terrestrial food webs decline. That presents a fourth kill mechanism that may trigger mass extinction on land and in the oceans: starvation.

Palaeontologists have steadily built up a powerful case for occasional mass extinctions since fossils first appear in the stratigraphic record of the Phanerozoic Eon. Their data are simply the numbers of species, genera and families of organisms preserved as fossils in packages of sedimentary strata that represent roughly equal ‘parcels’ of time (~10 Ma). Mass extinctions are now unchallengeable parts of life’s history and evolution. Yet, assigning specific kill mechanisms involved in the damage that they create remains very difficult. There are hypotheses for the cause of each mass extinction, but a dearth of data that can test why they happened. The only global die-off near hard scientific resolution is that at the end of the Cretaceous. The K-Pg (formerly K-T) event has been extensively covered in Earth-logs since 2000. It involved a mixture of global ecological stress from the Deccan large igneous event spread over a few million years of the Late Cretaceous, with the near-instantaneous catastrophe induced by the Chicxulub impact, with a few remaining dots and ticks needed on ‘i’s and ‘t’s. Other possibilities have been raised: gamma-ray bursts from distant supernovae; belches of methane from the sea floor; emissions of hydrogen sulfide gas from seawater itself during ocean anoxia events; sea-level changes etc.

The mass extinction that ended the Triassic (~201 Ma) coincides with evidence for intense volcanism in South and North America, Africa and southern Europe, then at the core of the Pangaea supercontinent. Flood basalts and large igneous intrusions – the Central Atlantic Magmatic Province (CAMP) – began the final break-up of Pangaea. The end-Triassic extinction deleted 34% of marine genera. Marine sediments aged around 201 Ma reveal a massive shift in sulfur and carbon isotopes in the ocean that has been interpreted as a sign of acute anoxia in the world’s oceans, which may have resulted in massive burial of oxygen-starved marine animal life. However, there is no sign of Triassic, carbon-rich deep-water sediments that characterise ocean anoxia events in later times. But it is possible that bacteria that use the reduction of sulfate (SO42-) to sulfide (S2-) ions as an energy source for them to decay dead organisms, could have produced the sulfur isotope ‘excursion’. That would also have produced massive amounts of highly toxic hydrogen sulfide gas, which would have overwhelmed terrestrial animal life at continental margins. The solution ofH2S in water would also have acidified the world’s oceans.

Molly Trudgill of the University of St Andrews, Scotland and colleagues from the UK, France, the Netherlands, the US, Norway, Sweden and Ireland set out to test the hypothesis of end-Triassic oceanic acidification (Trudgill, M. and 24 others 2025. Pulses of ocean acidification at the Triassic–Jurassic boundary. Nature Communications, v. 16, article 6471; DOI: 10.1038/s41467-025-61344-6). The team used Triassic fossil oysters from before the extinction time interval. Boron-isotope data from the shells are a means of estimating variations in the pH of seawater. Before the extinction event the average pH in Triassic seawater was about the same as today, at 8.2 or slightly alkaline. By 201 Ma the pH had shifted towards acidic conditions by at least 0.3: the biggest detected in the Phanerozoic record. One of the most dramatic changes in Triassic marine fauna was the disappearance of reef limestones made by the recently evolved modern corals on a vast scale in the earlier Triassic; a so-called ‘reef gap’ in the geological record. That suggests a possible analogue to the waning of today’s coral reefs that is thought to be a result of increased dissolution of CO2 in seawater and acidification, related to global greenhouse warming. Using the fossil oysters, Trudgill et al. also sought a carbon-isotope ‘fingerprint’ for the source of elevated CO2, finding that it mainly derived from the mantle, and was probably emitted by CAMP volcanism. So their discussion centres mainly on end-Triassic ocean acidification as an analogy for current climate change driven by CO2 largely emitted by anthropogenic burning of fossil fuels. Nowhere in their paper do they mention any role for acidification by hydrogen sulfide emitted by massive anoxia on the Triassic ocean floor, which hit the scientific headlines in 2020 (see earlier link).

Curiosity rover hints at the carbon cycle on Mars

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The Mars Science Laboratory carried by the Curiosity rover is still functioning 10 years after a jetpack lowered Curiosity onto the surface of Gale crater. It includes a system aimed at scooping and drilling samples of soil and rock from the sedimentary strata deposited in the lake that once filled the crater about 3.5 to 3.8 billion years ago. The system on the rover is also capable of analysing the samples in various ways. A central objective of the mission was to obtain data on oxygen and carbon isotopes in carbon dioxide and methane released by heating samples, which uses a miniature mass spectrometer. In early 2022 a paper on Martian carbon isotopes was published in the Proceedings of the National Academy of Sciences (PNAS) that I have only just found (House, C.H. et al. 2022. Depleted carbon isotope compositions observed at Gale crater, Mars. Proceedings of the National Academy of Sciences, v. 119, article e2115651119; DOI: 10.1073/pnas.2115651119). PNAS deemed it to be one of the 12 most important of its articles during 2022.

Oblique view of Curiosity’s landing site in Gale crater on Mars, from which the rover has traversed the lower slopes of Mount Sharp. Credit: NASA-Jet Propulsion Laboratory

Carbon isotopic analyses chart the type and degree of fractionation between carbon’s two stable isotopes 12C and 13C. This is expressed by their relative abundances to one another in a sample and in a reference standard, signified by δ13C. The measure is a natural tracer of both inorganic and biological chemical processes: hence the potential importance of the paper by Christopher House and colleagues from the University of California, San Diego. The thin atmosphere of Mars contains both CO2 and traces of CH4, so a carbon cycle is part and parcel of the planet’s geochemical functioning. The ‘big question’ is: Did that involve living processes at any stage in the distant past and even now? Carbon held in various forms within Mars’s ancient rocks and soils may provide at least a hint, one way of the other. At the very least it should say something about the Martian carbon cycle.

House et al. focus on methane released by heating 22 samples drilled from sandstones and mudstones traversed by Curiosity up a slope leading from the floor of Gale crater towards its central peak, Mount Sharp.  The sampled sedimentary rocks span a 0.5 km thick sequence. Carbon in the expelled methane has δ13C values that range from -137 to +22 ‰ (per mil). Samples from six possibly ancient exposed surfaces were below -70 ‰. This depletion in 13C is similar to the highly negative δ13C that characterises carbon-rich sediments on Earth that were deposited at the Palaeocene-Eocene boundary. That anomaly is suspected to have resulted from releases of methane from destabilised gas hydrate on the sea floor during the Palaeocene–Eocene Thermal Maximum. Organic photosynthesis takes up ‘light’ 12C in preference to 13C, thereby imparting low δ13C to organic matter. In the case of the Mars data that might seem to point to the lake that filled Gale crater 3.5 to 3.8 billion years ago has contained living organisms of some kind. Perhaps on exposed surfaces of wet sediment primitive organisms consumed methane and inherited its δ13C. Some Archaean sediments of about the same age on Earth show similar 13C depletion associated with evidence for microbial mats that are attributed to the activities of such methanotrophs.

Before exobiologists become too excited, no images of possible microbial mats in Gale crater sediments have been captured by Curiosity. Moreover, there are equally plausible scenarios with no recourse to once-living organisms that may account for the carbon-isotope data,. Extreme depletion in 13C is commonly found in the carbon within meteorites, almost certainly inherited from the interstellar dust from which they accreted. It is estimated that the solar system passes through giant molecular clouds every 100 Ma or so: the low δ13C may be inherited from interstellar dust. Alternatively, because Mars has an atmosphere almost entirely composed or CO2 – albeit thin at present – various non-biological chemical reactions driven by sunlight or electrically charged particles may have reduced that gas to form methane and other compounds based on C-H bonds. Carbon dioxide still in Mars’s atmosphere is highly enriched in 13C, suggesting that earlier abiotic reduction may have formed 13C-depleted methane that became locked in sediments. Yet such an abundant supply of inorganic methane may have encouraged the evolution of methanotrophs, had life emerged on early Mars. No one knows …

It’s becoming a cliché that, ‘We may have to await the return of samples from the currently active Perseverance rover, or a crewed mission at some unspecifiable time in the future. The Curiosity carbon-isotope data keep the lamp lit for those whose livelihoods have grown around humans going to the Red Planet.

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.

Massive event in the Precambrian carbon cycle

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English: Cyanobacteria
Cyanobacteria: earliest producers of oxygen in the Precambrian. Image via Wikipedia

The entire eukaryote domain of life, from alga to trees and fungi to animals, would not exist had it not been for the emergence of free oxygen in the oceans and atmosphere about 2.4 billion years ago; thanks in large part to the very much simpler photosynthetic blue-green bacteria. The chemistry behind this boils down to organisms being able to transfer electrons from elements and compounds in the inorganic world to build organic molecules incorporated in living things. Having lost electrons the inorganic donors become oxidised, for instance ferrous iron (Fe2+ or Fe-2) becomes ferric iron (Fe3+ or Fe-3) and  sulfide ions (S2-) become sulfate (SO42-) and the organic products that receive electrons principally involve reduction of carbon, on the OilRig principal – Oxidation involves loss of electrons, Reduction involves gain. Since the Great Oxygenation Event (GOE), ferric iron and sulfate ions now account for 75% of oxidation of the lithosphere and hydrosphere while free oxygen (O2) is a mere 2-3 % (Hayes, J.M. 2011. Earth’s redox history. Science. V. 334, p. 1654-1655; an excellent introduction to the geochemistry involved in the GOE and the carbon cycle). Free oxygen is around today only because more of it is produced than is consumed by its acting to oxidize ferrous iron and sulfide ions supplied mainly by volcanism, and carbon-rich material exposed to surface processes by erosion and sediment transport.

Eukaryote life has never been snuffed out for the last two billion years or so, but it has certainly had its ups and downs. To geochemists taking the long view oxygen might well seem to have steadily risen, but that is hardly likely in the hugely varied chemical factory that constitutes Earth’s surface environments, involving major geochemical cycles for carbon, iron, sulfur, nitrogen, phosphorus and so on, that all inveigle oxygen into reactions. Tabs can be kept on one of these cycles – that involving carbon – through the way in which the proportions of its stable isotopes vary in natural systems. If all geochemistry was in balance all the time, all materials that contain carbon would show the same proportions of 13C and 12C as the whole  Earth, but that is never the case. Living processes that fix carbon in organic compounds favour the lighter isotope, so they show a deficit of 13C relative to 12C signified by negative values of δ13C. The source of the carbon, for instance CO2 dissolved in sea water, thereby becomes enriched in 13C to achieve a positive value of δ13C, which may then be preserved in the form of carbonates in, for instance, fossil shells that ended up in limestones formed at the same time as organic processes were favouring the lighter isotope of carbon. Any organic carbon compounds that ocean-floor mud buried before they decayed (became oxidised) conversely would add their negative δ13C to the sediment. Searching for δ13C anomalies in limestones and carbonaceous mudrocks has become a major means of charting life’s ups and downs, and also what has happened to buried organic carbon through geological time.

A most interesting time to examine C-isotopes and the carbon cycle is undoubtedly the period immediately following the GOE, in the Palaeoproterozoic Era (2500 to 1600 Ma). From around 2200 to 2060 Ma the general picture is roughly constant, high positive values of δ13C (~+10‰): more organic carbon was being buried than was being oxidised to CO2. However, in drill cores through the Palaeoproterozoic of NW Russia carbonate carbon undergoes a sharp decline in its heavy isotope to give a negative δ13C  (~-14‰) while carbon in organic-rich sediments falls too (to~-40‰): definitely against the general  trend (Kump, L.R. et al. 2011. Isotopic evidence for massive oxidation of organic matter following the Great Oxidation Event. Science. V. 334, p. 1694-1696). Oxygen isotopes in the carbonates affected by the depletion in ‘heavy’ carbon show barely a flicker of change: a clear sign that the 13C δ13C deficit is not due to later alteration by hydrothermal fluids, as can sometimes cause deviant δ13C in limestones. It is more likely that a vast amount of organic carbon, buried in sediments or dissolved in seawater was oxidised to CO2 faster than biological activity was supplying dead material to be buried or dissolved. In turn, the overproduction of carbon dioxide dissolved in seawater to affect C-isotopes in limestones. Such an event would have entailed a sharp increase in oxygen production to levels capable of causing the oxidation (~ 1% of present levels). Yet this was not the time of the GOE (2400 Ma) but 300-400 Ma later. A possible explanation is a burst in oxygen production by more photosynthetic activity, perhaps by the evolution of chloroplast-bearing eukaryotes much larger than cyanobacteria.

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Homes for hominin evolution

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African savannah exhibit at the National Zoolo...
Typical African savannah. Image via Wikipedia

Friedrich Engels’s notion in The Part Played by Labour in the Transition from Ape to Man (1876), encouraged by Darwin’s The Descent of Man (1871), that the road to modern humans began with walking on two legs, thereby freeing the hands for work and tool making has been central to discussion of human evolution for more than a century. The ‘descent from the trees’ that bipedalism signifies has long been supposed to stem from the replacement of tropical forests in East Africa by open woodland or savannah, but evidence to support that environmental change has been difficult to glean from the fossil record  since the Late Miocene. Even in terrestrial sediments plant remains are rare, so that much has rested on animal fossils in relation to the habitats of their living descendants: opinion is divided.

There is a round-about means of resolving this central issue: using the carbon-isotope record in fossil soils that depends on the fractionation effects of broadly different kinds of plants that once grew in the soils and the signature of that fractionation in carbonate nodules that formed in the soils. The d13C value (crudely the difference between the 13C/12C ratio of a sample and that of a carbon-rich standard) found in C4 plants (many grasses) is -16 to -10 ‰ whereas that in C3 plants (including almost all trees) it is much more depleted in the heavier 13C isotope (-33 to -24‰). Exchange of carbon between living and dead organic matter, and carbonates that are precipitated from soil waters through the intermediary of gases in the soil should leave a d13C signature in the carbonates that reflects the overall proportions of different photosynthetic plant groups living at the time the soil formed. The approach was developed in the early 1990s by Thure Cerling and Jay Quade of the US universities of Utah and Arizona respectively.

After a long gestation period, involving calibration using soils from different modern ecosystems, the soil C-isotope method has been applied painstakingly to palaeosols in which African hominin remains have turned-up (Cerling, T.E. and 9 others 2011. Woody cover and hominin environments in the past 6 million years. Nature, v. 476, p. 51-56). All the famous hominin sites from the Awash and Omo Valleys of Ethiopia and around Lake Turkana in Kenya, figure in this important study, in which the authors devise a proxy for ‘palaeo-shade’ based on their carbonate d13C data from 76 modern tropical soils: a good ‘straight-line’ plot of d13C against the fraction of woody cover at the different calibration sites. Applying the proxy to their 1300 samples of palaeosols they show convincingly that since about 6 Ma tree cover rarely rose above 40% in the homelands of all the East African hominins. From the times of Ardepithecus ramidus (~4 Ma) at Aramis in Ethiopia, through those of ‘Selam’ and ‘Lucy’, the 2.5 Ma first stone tools at Gona, the times when Africa was dominated by Homo erectus(1.8 to 1 Ma) to perhaps the first signs of modern human cranial remains (those with chins!) around 1 Ma, all hominins strode through open, grassy environments. One can imagine pleasured nods from the shades of Darwin and Engels now their prescience has finally been confirmed.

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