Milankovich precession and the Palaeocene-Eocene Thermal Maximum

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

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.

Homes for hominin evolution

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.