Phytoplankton bloom in the Channel off SW England (Landsat image)
At present the central areas of the oceans are wet deserts; too depleted in nutrients to support the photosynthesising base of a significant food chain. The key factor that is missing is dissolved divalent iron that acts as a minor, but vital, nutrient for phytoplankton. Much of the soluble iron that does help stimulate plankton ‘blooms’ emanates from the land surface in wind blown dust (Palaeoclimatology September 2011) or dissolved in river water. A large potential source is from hydrothermal vents on the ocean floor, which emit seawater that has circulated through the basalts of the oceanic crust. Such fluids hydrate the iron-rich mafic minerals olivine and pyroxene, which makes iron available for transport. The fluids originate from water held in the muddy, organic-rich sediments that coat the ocean floor, and have lost any oxygen present in ocean-bottom water. Their chemistry is highly reducing and thereby retains soluble iron liberated by crustal alteration to emanate from hydrothermal vents. Because cold ocean-bottom waters are oxygenated by virtue of having sunk from the surface as part of thermohaline circulation, it does seem that ferrous iron should quickly be oxidised and precipitated as trivalent ferric compounds soon after hydrothermal fluids emerge. However, if some was able to rise to the surface it could fertilise shallow ocean water and participate in phytoplankton blooms, the sinking of dead organic matter then effectively burying carbon beneath the ocean floor; a ‘biological pump’ in the carbon cycle with a direct influence on climate. Until recently this hypothesis had little observational support. Continue reading “Soluble iron, black smokers and climate”→
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.
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.
A range of indirect evidence has been used to suggest that life originated deep in the oceans around hydrothermal vents, such as signs of early organic matter in association with Archaean pillow lavas. One particularly persuasive observation is that a number of proteins and other cell chemicals are constructed around metal sulfide groups. Such sulfides are common around hydrothermal ‘smokers’ associated with oceanic rift systems. Moreover, Fischer-Tropsch reactions between carbon monoxide and hydrogen produce quite complex hydrocarbon molecules under laboratory conditions. Such hydrogenation of a carbon-bearing gas requires a catalyst, a commonly used one being chromium oxide (see Abiotic formation of hydrocarbons by oceanic hydrothermal circulationMay 2004). It also turns out that fluids emitted by sea-floor hydrothermal systems are sometimes rich in free hydrogen, formed by the breakdown of olivine in ultramafic rocks to form hydroxylated minerals such as serpentine and talc. The fact that chromium is abundant in ultramafic rocks, in the form of its oxide chromite, elevates the possibility that Fischer-Tropsch reactions may have been a crucial part of the life-forming process on the early Earth. What is needed is evidence that such reactions do occur in natural settings.
A white carbonate mound forming at the Lost City hydrothermal vent field on the Mid-Atlantic Ridge (Credit: Baross 2018)
One site on the mid-Atlantic ridge spreading centre, the Lost City vent field, operates because of serpentinisation of peridotites exposed on the ocean floor, to form carbonate-rich plumes and rocky towers; ‘white smokers’. So that is an obvious place to test the abiotic theory for the origin of life. Past analyses of the vents have yielded a whole range of organic molecules, including alkanes, formates, acetates and pyruvates, that are possible precursors for such a natural process. Revisiting Lost City with advanced analytical techniques has taken the quest a major step forward (Ménez, B. et al. 2018. Abiotic synthesis of amino acids in the recesses of the oceanic lithosphere. Nature, advance online publication; DOI: 10.1038/s41586-018-0684-z). The researchers from France and Kazakhstan focused on rock drilled from 170 m below the vent system, probably beyond the influence of surface contamination from living organisms. Using several methods they detected the nitrogen-containing amino acid tryptophan, and that alone. Had they detected other amino acids their exciting result would have been severely tempered by the possibility of surface organic contamination. The formation of tryptophan implies that its abiotic formation had to involve the reduction of elemental nitrogen (N2) to ammonia (NH3). Bénédicte Ménez and colleagues suggest that the iron-rich clay saponite, which is a common product of serpentine alteration at low temperatures, may have catalysed such reduction and amino-acid synthesis through Friedel–Crafts reactions. Fascinating as this discovery may be, it is just a step towards confirming life’s abiogenesis. It also permits speculation that similar evidence may be found elsewhere in the Solar System on rocky bodies, such as the moons Enceladus and Europa that orbit Saturn and Jupiter respectively. That is, if the rock base of hydrothermal systems thought to occur there can be reached.
Related article: Baross, J.A. 2018. The rocky road to biomolecules. Nature, v. 564, p. 42-43; DOI: 10.1038/d41586-018-07262-8.
That seawater circulates through the axial regions of rifts associated with sea-floor spreading has been known since well before the acceptance of plate tectonics. The idea stems from the discovery in 1949 of brines with a temperature of 60°C on the central floor of the Red Sea, which in the early 60s turned out to be anomalously metal-rich as well. Advanced submersibles that can withstand the high pressures at great depth a decade later produced images of swirling clouds of sediment from large sea-floor springs, first on the Galapagos rift and subsequently on many others. The first shots were of dark, turbulent clouds, prompting the term ‘black smoker’ for such hydrothermal vents and it turns out that others produce light-coloured clouds – ‘white smokers’. Sampling revealed that the sediments in black smokers were in fact fine-grained precipitates of metallic sulfides, whereas those forming white smokers were sulfates, carbonates and oxides of barium calcium and silicon also precipitated from solute-rich brines produced by partial dissolution of ocean floor through which they had passes.
A black smoker with associated organism. (credit: Wikipedia)
Excitement grew when hydrothermal vents were shown to have complex animal ecosystems completely new to science. A variety of chemical evidence, most importantly the common presence of proteins and other cell chemicals built around metal sulfide groups in most living organisms, prompted the idea that hydrothermal vents may have hosted the origins of life on Earth. Many fossil vent systems also contain fossils; macrofossils in the Phanerozoic and microbial ones from the Precambrian. But tangible signs of life, in the form of mats ascribed to bacteria or archaea holding together fine-grained sediments, go back no further than 3830 Ma in the Isua area of SW Greenland. Purely geochemical evidence that carbonaceous compounds may have formed in living systems are ambiguous since quite complex hydrocarbons can be synthesised abiogenically by Fischer-Tropsch reactions between carbon monoxide and hydrogen. Signs of deep sea hydrothermal activity are common in any geological terrain containing basalt lavas with the characteristic pillows indicating extrusion beneath water. So to trace life’s origins all that is needed to trigger the interest of palaeobiologists are the oldest known pillow lavas. Until quite recently, that meant the Isua volcano-sedimentary association, but heating, high pressures and very strong deformation affected those rocks when they were metamorphosed half a billion years after they were formed; a cause for skepticism by some geoscientists.
The primacy of Isua metavolcanic rocks has been challenged by more extensive metamorphosed basalts in the Nuvvuagittuk area in Quebec on the east side of Hudson Bay, Canada. They contain hydrothermal ironstones associated with pillowed basalts that are cut by more silica-rich intrusive igneous rocks dated between 3750 and 3775 Ma. That might place the age of basalt volcanism and the hydrothermal systems in the same ball park as those of Isua, but intriguingly the basalts’ 146Sm-142Nd systematics suggest a possible age of magma separation from the mantle of 4280 Ma (this age is currently disputed as it clashes with U-Pb dates for zircon grains extracted from the metabasalts around the same as the age at Isua). Nonetheless, some parts of the Nuvvuagittuk sequence are barely deformed and show only low-grade metamorphism, and they contain iron- and silicon-rich hot spring deposits (Dodd, M.S. et al. 2017. Evidence for early life in Earth’s oldest hydrothermal vent precipitates. Nature, v. 543, p. 60-64; doi:10.1038/nature21377). As at Isua, the ironstones contain graphite whose carbon isotope proportions have an ambiguous sign of having formed by living or abiotic processes. It is the light deformation and low metamorphism of the rocks that gives them an edge as regards being hosts to tangible signs of life. Extremely delicate rosettes and blades of calcium carbonate and phosphate, likely formed during deposition, remain intact. These signs of stasis are in direct contact with features that are almost identical to minute tubes and filaments formed in modern vents by iron-oxidising bacteria. All that is missing are clear signs of bacterial cells. Ambiguities in the dating of the basalt host rocks do not allow the authors claims that their signs of life are significantly older than those at Isua, but their biotic origins are less open to question. Neither offer definitive proof of life, despite widespread claims by media science correspondents, some of whom tend metaphorically to ‘run amok ‘ when the phrase ‘ancient life’ appears; in this case attempting to link the paper with life on Mars …
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