Earth’s water and the Moon

Where did all our water come from? The Earth’s large complement of H2O, at the surface, in its crust and even in the mantle, is what sets it apart in many ways from the rest of the rocky Inner Planets. They are largely dry, tectonically torpid and devoid of signs of life. For a long while the standard answer has been that it was delivered by wave after wave of comet impacts during the Hadean, based on the fact that most volatiles were driven to the outermost Solar System, eventually to accrete as the giant planets and the icy worlds and comets of the Kuiper Belt and Oort Cloud, once the Sun sparked its fusion reactions That left its immediate surroundings depleted in them and enriched in more refractory elements and compounds from which the Inner Planets accreted. But that begs another question: how come an early comet ‘storm’ failed to ‘irrigate’ Mercury, Venus and Mars? New geochemical data offer a different scenario, albeit with a link to the early comet-storms paradigm.

Simulated view of the Earth from lunar orbit: the ‘wet’ and the ‘dry’. (credit: Adobe Stock)

Three geochemists from the Institut für Planetologie, University of Münster, Germany, led by Gerrit Budde have been studying the isotopes of the element molybdenum (Mo) in terrestrial rocks and meteorite collections. Molybdenum is a strongly siderophile (‘iron loving’) metal that, along with other transition-group metals, easily dissolves in molten iron. Consequently, when the Earth’s core began to form very early in Earth’s history, available molybdenum was mostly incorporated into it. Yet Mo is not that uncommon in younger rocks that formed by partial melting of the mantle, which implies that there is still plenty of it mantle peridotites. That surprising abundance may be explained by its addition along with other interplanetary material after the core had formed. Using Mo isotopes to investigate pre- and post-core formation events is similar to the use of isotopes of other transition metals, such as tungsten (see Planetary science, May 2016). Continue reading “Earth’s water and the Moon”

A role for iron in the origin of life

Experiments aimed at suggesting how RNA and DNA – prerequisites for life, reproduction and evolution – might have formed from a ‘primordial soup’ have made slow progress. Another approach to the origin of life is investigation of the most basic chemical reactions that it engages in. Whatever the life form, prokaryote or eukaryote, its core processes involve reducing carbon dioxide, or other simple carbon-bearing compounds, and water to synthesise organic molecules that make up cell matter. Organisms also engage in metabolising biological compounds to generate energy. At their root, these two processes mirror each other; a creative network of reactions and another that breaks compounds down, known as the Krebs- and the reverse-Krebs cycles. In living organisms both are facilitated by other organic compounds that, of course, are themselves produced by cells. How such networks arose under inorganic conditions remains unknown, but three biochemists at the University of Strasbourg in France (Muchowska, K.B. et al. 2019. Synthesis and breakdown of universal metabolic precursors promoted by iron. Nature, v. 569, p. 104-107;  DOI: 10.1038/s41586-019-1151-1) have designed an inorganic experiment. They aimed to investigate how two simple organic compounds, which conceivably could have formed in a lifeless early environment, might have been encouraged to kick-start basic living processes. These are glyoxylate (HCOCO2) and pyruvate (CH3COCO2).

The most difficult chemical step in building complex organic compounds is inducing carbon atoms to bond together through C-C bonds; a process that thermodynamics tends to thwart but is accomplished in living cells by adenosine tri-phosphate (ATP). Previous workers focussed on interactions between reactive compounds, such as cyanide and formaldehyde, as candidates for the precursors of life, but such chemistry is totally different from what actually goes on in organisms. Joseph Moran, one of the co-authors of the paper, and his research group recently settled on five fundamental linkages of C, H and O as ‘universal hubs’ at the core of the Krebs cycle and its reverse. Kamila Muchowska and co-workers found that glyoxylate and pyruvate introduced into a simulated hydrothermal fluid that contains ions of ferrous iron (reduced Fe2+) were able to combine in producing all five ‘universal hubs. Ferrous iron clearly acted as a catalyst, through being a powerful reducing agent or electron donor, to get around the stringencies of classic thermodynamics. Moran’s team had previously shown that pyruvate itself can form inorganically from CO2 in water laced with iron, cobalt and nickel ions. Formation of glyoxylate in such a manner has yet to be demonstrated. Nevertheless, the two together in a watery soup of transition metal ions seem destined to produce an abundance of exactly the compounds at the root of living processes. In fact the experiment showed that all but two of the eleven components of the Krebs cycle can be synthesised inorganically.

407458aa.2
Metal-rich ‘black smoker’ at a hydrothermal vent on the mid-Atlantic ridge(credit: Kate Larkin, Seascape, Belgium)

Until the rise of free oxygen in the Earth system some 2400 Ma ago, the oceans would have been awash with soluble ferrous iron. This would have been especially the case around hydrothermal vents that result from the interaction between water and hot mafic lavas of the oceanic crust, together with less abundant transition-metal ions, such as those of nickel and cobalt. The ocean-vent hypothesis for the origin of life seems set for a surge forward.

See also: Katsnelson, A. 2019. Iron can catalyse metabolic reactions without enzymes.

Read more on Palaeobiology

A unifying idea for the origin of life

The nickel in stainless steel, the platinum in catalytic converters and the gold in jewellery, electronic circuits and Fort Knox should all be much harder to find in the Earth’s crust. Had the early Earth formed only by accretion and then the massive chemical resetting mechanism of the collision that produced the Moon all three would lie far beyond reach. Both formation events would have led to an extremely hot young Earth; indeed the second is believed to have left the outer Earth and Moon completely molten. All three are siderophile metals and have such a strong affinity for metallic iron that they would mostly have been dragged down to each body’s core as it formed in the early few hundred million years of the Earth-Moon system, leaving very much less in the mantle than rock analyses show. This emerged as a central theme at the Origin of Life Conference held in Atlanta GA, USA in October 2018. The idea stemmed from two papers published in 2015 that reported excessive amounts in basaltic material from both Earth and Moon of a tungsten isotope (182W) that forms when a radioactive isotope of hafnium (182Hf), another strongly siderophile metal, decays. Hafnium too must have been strongly depleted in the outer parts of both bodies when their cores formed. The excesses are explained by substantial accretion of material rich in metallic iron to their outer layers shortly after Moon-formation, some being in large metallic asteroids able to penetrate to hundreds of kilometres. Hot iron is capable of removing oxygen from water vapour and other gases containing oxygen, thereby being oxidised. The counterpart would have been the release of massive amounts of hydrogen, carbon and other elements that form gases when combined with oxygen. The Earth’s atmosphere would have become highly reducing.

Had the atmosphere started out as an oxidising environment, as thought for many decades, it would have posed considerable difficulties for the generation at the surface of hydrocarbon compounds that are the sine qua non for the origin of life. That is why theories about abiogenesis (life formed from inorganic matter) hitherto have focussed on highly reducing environments such as deep-sea hydrothermal vents where hydrogen is produced by alteration of mantle minerals. The new idea revitalises Darwin’s original idea of life having originated in ‘a warm little pond’. How it has changed the game as regards the first step in life, the so-called ‘RNA World’ can be found in a detailed summary of the seemingly almost frenzied Origin of Life Conference (Service, R.F. 2019. Seeing the dawn. Science, v. 363, p. 116-119; DOI: 10.1126/science.363.6423.116).

Isotope geochemistry has also entered the mix in other regards, particularly that gleaned from tiny grains of the mineral zircon that survived intact from as little as 70 Ma after the Moon-forming and late-accretion events to end up (3 billion years ago) in the now famous Mount Narryer Quartzite of Western Australia. The oldest of these zircons (4.4 Ga) suggest that granitic rocks had formed the earliest vestiges of continental crust far back in the Hadean Eon: Only silica-rich magmas contain enough zirconium for zircon (ZrSiO4) to crystallise. Oxygen isotope studies of them suggest that at that very early date they had come into contact with liquid water, presumably at the Earth’s surface. That suggests that perhaps there were isolated islands of early continental materials; now vanished from the geological record. A 4.1 Ga zircon population revealed something more surprising: graphite flakes with carbon isotopes enriched in 12C that suggests the zircons may have incorporated carbon from living organisms.

407458aa.2
A possible timeline for the origin of life during the Hadean Eon (Credit: Service, R.F. 2019, Science)

Such a suite of evidence has given organic chemists more environmental leeway to suggest a wealth of complex reactions at the Hadean surface that may have generated the early organic compounds needed as building blocks for RNA, such as aldehydes and sugars (specifically ribose that is part of both RNA and DNA), and the amino acids forming the A-C-G-U ‘letters’ of RNA, some catalysed by the now abundant siderophile metal nickel. One author seems gleefully to have resurrected Darwin’s ‘warm little pond’ by suggesting periodic exposure above sea level of abiogenic precursors to volcanic sulfur dioxide that could hasten some key reactions and create large masses of such precursors which rain would have channelled into ‘puddles and lakes’. The upshot is that the RNA World precursor to the self-replication conferred on subsequent life by DNA is speculated to have been around 4.35 Ga, 50 Ma after the Earth had cooled sufficiently to have surface water dotted with specks of continental material.

There are caveats in Robert Services summary, but the Atlanta conferences seems set to form a turning point in experimental palaeobiology studies.

Read more on Palaeobiology and Planetary science