Hydrogen and how the Earth formed

A third piece with hydrogen as its focus in a couple of months? Well, from a galactic perspective there’s a lot of it about. Modern cosmology suggests that only 4.6% of the energy in the universe consists of elemental atoms made of protons, neutrons and electrons, dwarfed by dark energy and dark matter that are something of mystery. But of the more familiar energy equivalent, tangible matter (as in E=mc2), 74% of the universe is hydrogen, 24% is helium and the other 92 elements amount to just 2%. That tiny proportion of heavier elements was created by nucleosynthesis within stars from the two products of the Big Bang (H and He). Nuclear fusion reactions formed those with atomic numbers (protons in their nuclei) up to that of iron (26), whereas the heavier elements were created through neutron- and proton capture when the largest stars destroyed themselves cataclysmically as supernovae. Yet the planet whose surface we inhabit contains only minute amounts of helium and elemental hydrogen. Of course water at and beneath the surface, in the form of atmospheric vapour and locked within minerals retains some of the cosmically available hydrogen. But current estimates suggest that hydrogen accounts for a mere 0.03% of Earth’s mass. Despite the fact that some forms of radioactive decay generate alpha particles that become helium it forms a vanishingly small proportion of terrestrial mass.

The solar system formed around 4.6 billion years ago by a complex gravitational accretion of the gas and dust of an interstellar cloud: mainly H and He. Its dynamic collapse resulted in gravitational potential energy being transformed into heat: in the case of the Sun, sufficient to set off self-sustaining nuclear fusion. As a body grows in this way so does its gravity and thus the speed needed for matter to escape from its pull (escape velocity). As temperature increases so does the speed at which atoms of each element vibrate; the lower the atomic mass the faster the vibration and the greater the chance of escape. So the ‘blend’ of elements that an astronomical body retains during its early evolution depends on its gravity and its surface temperature. The Sun is so massive that very little has escaped its pull, despite a surface temperature of about 5 to 6 thousand degrees Celsius. Its composition is thus close to the cosmic average. Those of the giant planets Jupiter, Saturn, Uranus and Neptune are not far short because of their large gravities and low surface temperatures. Even today, the smaller Inner Planets are unable to cling on to elemental hydrogen and helium and nearly all that is left of the matter from which they formed is the 2% of heavier cosmic elements locked into solids, liquids and gases.

Processes in the early solar system were far more complicated than they are today. In the mainly gaseous disc, from which the solar system evolved, gravity dragged matter towards its centre. That eventually ignited nuclear fusion of hydrogen to form our star. More remote from its gravitational pull vortices aggregated dust into bodies known as planetesimals that in turn accreted to larger protoplanets. Solar gravity dragged gas from the inner solar system leaving rocky protoplanets, whereas gas was able to be attracted to the surface of what became the gas giants where their gravity outweighed that of the far-off Sun. This was complicated by a sort of Milankovich Effect on steroids in which protoplanets continuously changed their orbits and underwent collisions. The best known of these was between the protoEarth and a Mars-sized body that formed the Earth-Moon system, both bodies having deep magma oceans as a result of the huge energy focussed on them by the collision. What may have happened to the protoplanet that became Earth before the Moon-forming collision has been addressed by three geoscientists at the University of California Los Angeles and the Carnegie Institution for Science Washington DC, USA (Young, E.D. et al. 2023. Earth shaped by primordial H2 atmospheres. Nature, v. 616, p. 306–311; DOI: 10.1038/s41586-023-05823-0 [PDF request to: eyoung@epss.ucla.edu]).

A thick hydrogen-rich atmosphere’s interacting chemically with a protoplanet (left). A possible later stage (right) where iron oxide in the magma ocean of the Early Hadean after Moon formation oxidises a hydrogen atmosphere to form surface water (Credit: Sean Raymond 2023, Fig 1)

The focus of the work of Edward Young, Anat Shahar and Hilke Schlichting is directed at the possibility that the Earth-forming protoplanets originally retained thick hydrogen atmospheres. They use thermodynamic modelling of the equilibrium between hydrogen and silicate magma oceans that had resulted from the energy of their accretion. The authors’ main assumption is that insufficient time had elapsed during accretion for the protoplanets to cool and crystallise: a distinct possibility because loss of accretionary heat by thermal radiation would have been ‘blanketed’ by actively accreting dust and gas in orbit around the growing protoplanets. Effectively, the equilibrium would have been chemical in nature: reactions between highly reducing hydrogen and oxidised silicate melts or even vaporised rock evaporated from the very hot surface. The authors suggest that protoplanets bigger than Mars (0.2 to 0.3 times that of Earth) could retain a hydrogen-rich atmosphere long enough for the chemical reactions to come to a balance, despite high temperatures. There would have been no shortage of hydrogen at this early stage in solar system evolution: perhaps as much as 0.2% percent the mass of the Earth surrounding a protoplanet about half its present size.

Two outcomes may have emerged. Reaction between hydrogen and anhydrous silicates could produce H2O in amounts up to three times that currently in the Earth’s oceans, some locked in the magma ocean, some in the dense atmosphere. A by-product would have been iron oxide, giving the current mantle its oxidising properties known from the geochemistry of basaltic magmas.  Hydrogen might also have dissolved in molten iron alloys, thereby contributing to the nascent core. That second outcome would help explain why the modern core is less dense than expected for iron-nickel alloy, both solid and liquid. In fact densities calculated by geophysicists from the speeds of seismic waves that have travelled through the core are 5 to 10% percent lower than expected for the alloy. So the core must contain substantial amounts of elements with low atomic numbers.

Several other possibilities have been suggested to account for Earth’s abundance of water. Two popular ideas are comets arriving in the ‘settled’ times of the Hadean or by original accretion of hydrous chondrite meteorites, whose hydrogen isotope proportions match those of ocean water. Hydrogen as the light element needed in the core is but one possibility along with oxygen, sulfur and other ‘light’ elements. Also, the oxidising potential of the modern mantle may have resulted from several billion years of wet lithosphere being subducted. To paraphrase Sean Raymond (below), ‘other hypotheses are available’!

See also: Raymond, S.N. 2023. Earth’s molten youth had long-lasting consequences. Nature (News & Views), v. 616, p. 251-252; DOI: 10.1038/d41586-023-00979-1 [PDF request to: rayray.sean@gmail.com]

An early oxygenated atmosphere

The Earth’s earliest atmosphere undoubtedly had a chemistry dominated by carbon dioxide and nitrogen, together with transient water vapour, outgassed from volcanoes giving pervasive reducing conditions at the surface and in the oceans. Until the last couple of decades the only clear evidence of a switch to oxidising conditions and presumably significant atmospheric oxygen was direct, mineralogical evidence. The most obvious signs are ancient, reddened soils formed when soluble Fe2+ lost electrons to molecular oxygen to form the distinct red, orange and brown oxides and hydroxides of insoluble Fe3+ that impart a deep staining in even small quantities. Others include the disappearance from river-transported sediments of clearly transported grains of metal sulfides and uranium oxide that remain stable under reducing conditions but quickly break down in the presence of oxygen.

Widespread observations in Precambrian sediments, eventually linked with reliable radiometric ages, strongly suggested a fundamental environmental change at around 2.3 billion years ago: the Great Oxidation Event. A few such signs emerge from somewhat older rocks back to 2.7 Ga, but only the 2.3 Ga event created a permanent feature of our home world; at first toxic to many of the prokaryote life forms of earlier times but eventually a prime condition for the rise of the Eukarya and eventually metazoan animals. Isotopic analysis of sulfur from Precambrian sediments also gave hints of a more complex but much debated transition because of the way S-isotopes fractionate under different environmental conditions. Now other  indirect, isotopic approaches to redox conditions have become feasible, with a surprising result: powerful evidence that about 3 billion years ago there was appreciable atmospheric oxygen (Crowe, S.A. et al. 2013. Atmospheric oxygenation three billion years ago. Nature, v. 501, p. 535-538).

The Danish-South African-German-Canadian group relied on a fractionation process among the isotopes of chromium, which can exist in several oxidation states. When minerals that contain Cr3+  are weathered under oxidising conditions to release soluble Cr6+ the loss in solution preferentially removes the 53Cr isotope from residual soil. If the isotope enters groundwater with reducing conditions to precipitate some Cr3+ -rich material yet more 53Cr remains in solution. Eventually such enriched water may enter the oceans, where along with iron and other transition-group metal ions chromium can end up in banded iron formations (BIFs) to preserve isotopic evidence for oxidising conditions along it route from land to sea.

This image shows a 2.1 billion years old rock ...
Banded iron formation (BIF) from the Precambrian of North America belonging to the National Museum of Mineralogy and Geology in Dresden, Germany. (credit: Wikipedia)

The team analysed both a palaeosol and a BIF unit from a stratigraphic sequence in the Achaean of NE South Africa that is between 2980 and 2924 Ma old. A substantial proportion of the palaeosol is depleted in 53Cr whereas the lower part of the slightly younger BIF is significantly enriched. Changes in the concentration of redox sensitive elements, such as chromium itself, uranium and iron, in the two lithologies helps confirm the isotopic evidence for a major ~3 Ga oxidation event. It is possible to use the data to estimate what the atmospheric oxygen content might have been at that time: not enough to breathe, but significant at between 6 x 10­-5 to 3 x 10-3 the atmospheric level at present. Oxygen can be produced abiogenically through irradiation of water vapour in the atmosphere as well as by organic photosynthesis. However, the first route seems incapable of yield more than a billionth of present atmospheric concentrations, so the spotlight inevitably falls on a ‘much deep history’ of the action of blue-green bacteria (cyanobacteria) than hitherto suspected.