A Surface Hydrothermal Source of Nitriles and Isonitriles.

Giant impacts can generate transient hydrogen-rich atmospheres, reducing atmospheric carbon. The reduced carbon will form hazes that rain out onto the surface and can become incorporated into the crust. Once heated, a large fraction of the carbon is converted into graphite. The result is that local regions of the Hadean crust were plausibly saturated with graphite. We explore the consequences of such a crust for a prebiotic surface hydrothermal vent scenario. We model a surface vent fed by nitrogen-rich volcanic gas from high-temperature magmas passing through graphite-saturated crust. We consider this occurring at pressures of 1-1000bar and temperatures of 1500-1700 ∘C. The equilibrium with graphite purifies the leftover gas, resulting in substantial quantities of nitriles (0.1% HCN and 1ppm HC3N) and isonitriles (0.01% HNC) relevant for prebiotic chemistry. We use these results to predict gas-phase concentrations of methyl isocyanide of ∼1 ppm. Methyl isocyanide can participate in the non-enzymatic activation and ligation of the monomeric building blocks of life, and surface or shallow hydrothermal environments provide its only known equilibrium geochemical source.

Evolution of the crustal phosphorus reservoir.

The release of phosphorus (P) from crustal rocks during weathering plays a key role in determining the size of Earth's biosphere, yet the concentration of P in crustal rocks over time remains controversial. Here, we combine spatial, temporal, and chemical measurements of preserved rocks to reconstruct the lithological and chemical evolution of Earth's continental crust. We identify a threefold increase in average crustal P concentrations across the Neoproterozoic-Phanerozoic boundary (600 to 400 million years), showing that preferential biomass burial on shelves acted to progressively concentrate P within continental crust. Rapid compositional change was made possible by massive removal of ancient P-poor rock and deposition of young P-rich sediment during an episode of enhanced global erosion. Subsequent weathering of newly P-rich crust led to increased riverine P fluxes to the ocean. Our results suggest that global erosion coupled to sedimentary P-enrichment forged a markedly nutrient-rich crust at the dawn of the Phanerozoic.

The evolution of the Galápagos mantle plume.

The lavas associated with mantle plumes may sample domains throughout Earth's mantle and probe its dynamics. However, plume studies are often only able to take snapshots in time, usually of the most recent plume activity, leaving the chemical and geodynamic evolution of major convective upwellings in Earth's mantle poorly constrained. Here, we report the geodynamically key information of how the lithology and density of a plume change from plume head phase to tail. We use iron stable isotopes and thermodynamic modeling to show that the Galápagos plume has contained small, nearly constant, amounts of dense recycled crust over its 90-million-year history. Despite a temporal evolution in the amount of recycled crust-derived melt in Galápagos-related lavas, we show that this can be explained by plume cooling alone, without associated changes in the plume's mantle source; results are also consistent with a plume rooted in a lower mantle low-velocity zone also sampling primordial components.

Proposed energy-metabolisms cannot explain the atmospheric chemistry of Venus.

Life in the clouds of Venus, if present in sufficiently high abundance, must be affecting the atmospheric chemistry. It has been proposed that abundant Venusian life could obtain energy from its environment using three possible sulfur energy-metabolisms. These metabolisms raise the possibility of Venus's enigmatic cloud-layer SO2-depletion being caused by life. We here couple each proposed energy-metabolism to a photochemical-kinetics code and self-consistently predict the composition of Venus's atmosphere under the scenario that life produces the observed SO2-depletion. Using this photo-bio-chemical kinetics code, we show that all three metabolisms can produce SO2-depletions, but do so by violating other observational constraints on Venus's atmospheric chemistry. We calculate the maximum possible biomass density of sulfur-metabolising life in the clouds, before violating observational constraints, to be ~10-5 - 10-3 mg m-3. The methods employed are equally applicable to aerial biospheres on Venus-like exoplanets, planets that are optimally poised for atmospheric characterisation in the near future.

Scum of the Earth: A Hypothesis for Prebiotic Multi-Compartmentalised Environments.

Compartmentalisation by bioenergetic membranes is a universal feature of life. The eventual compartmentalisation of prebiotic systems is therefore often argued to comprise a key step during the origin of life. Compartments may have been active participants in prebiotic chemistry, concentrating and spatially organising key reactants. However, most prebiotically plausible compartments are leaky or unstable, limiting their utility. Here, we develop a new hypothesis for an origin of life environment that capitalises upon, and mitigates the limitations of, prebiotic compartments: multi-compartmentalised layers in the near surface environment-a 'scum'. Scum-type environments benefit from many of the same ensemble-based advantages as microbial biofilms. In particular, scum layers mediate diffusion with the wider environments, favouring preservation and sharing of early informational molecules, along with the selective concentration of compatible prebiotic compounds. Biofilms are among the earliest traces imprinted by life in the rock record: we contend that prebiotic equivalents of these environments deserve future experimental investigation.

Iron isotopes trace primordial magma ocean cumulates melting in Earth's upper mantle.

The differentiation of Earth ~4.5 billion years (Ga) ago is believed to have culminated in magma ocean crystallization, crystal-liquid separation, and the formation of mineralogically distinct mantle reservoirs. However, the magma ocean model remains difficult to validate because of the scarcity of geochemical tracers of lower mantle mineralogy. The Fe isotope compositions (δ57Fe) of ancient mafic rocks can be used to reconstruct the mineralogy of their mantle source regions. We present Fe isotope data for 3.7-Ga metabasalts from the Isua Supracrustal Belt (Greenland). The δ57Fe signatures of these samples extend to values elevated relative to modern equivalents and define strong correlations with fluid-immobile trace elements and tungsten isotope anomalies (µ182W). Phase equilibria models demonstrate that these features can be explained by melting of a magma ocean cumulate component in the upper mantle. Similar processes may operate today, as evidenced by the δ57Fe and µ182W heterogeneity of modern oceanic basalts.

Origin of Life's Building Blocks in Carbon- and Nitrogen-Rich Surface Hydrothermal Vents.

There are two dominant and contrasting classes of origin of life scenarios: those predicting that life emerged in submarine hydrothermal systems, where chemical disequilibrium can provide an energy source for nascent life; and those predicting that life emerged within subaerial environments, where UV catalysis of reactions may occur to form the building blocks of life. Here, we describe a prebiotically plausible environment that draws on the strengths of both scenarios: surface hydrothermal vents. We show how key feedstock molecules for prebiotic chemistry can be produced in abundance in shallow and surficial hydrothermal systems. We calculate the chemistry of volcanic gases feeding these vents over a range of pressures and basalt C/N/O contents. If ultra-reducing carbon-rich nitrogen-rich gases interact with subsurface water at a volcanic vent they result in 10 - 3 ⁻ 1 M concentrations of diacetylene (C4H2), acetylene (C2H2), cyanoacetylene (HC3N), hydrogen cyanide (HCN), bisulfite (likely in the form of salts containing HSO3-), hydrogen sulfide (HS-) and soluble iron in vent water. One key feedstock molecule, cyanamide (CH2N2), is not formed in significant quantities within this scenario, suggesting that it may need to be delivered exogenously, or formed from hydrogen cyanide either via organometallic compounds, or by some as yet-unknown chemical synthesis. Given the likely ubiquity of surface hydrothermal vents on young, hot, terrestrial planets, these results identify a prebiotically plausible local geochemical environment, which is also amenable to future lab-based simulation.

The Melting Column as a Filter of Mantle Trace-Element Heterogeneity.

The observed variability of trace-element concentration in basaltic lavas and melt inclusions carries information about heterogeneity in the mantle. The difficulty is to disentangle the contributions of source heterogeneity (i.e., spatial variability of mantle composition before melting) and process heterogeneity (i.e., spatial and temporal variability in melt transport). Here we investigate the end-member hypothesis that variability arises due to source heterogeneity alone. We model the attenuation of trace-element variability introduced into the bottom of a one-dimensional, steady-state melting column. Our results show that the melting column can be considered to be a filter that attenuates variability according to the wavelength of heterogeneity, the partition coefficient of the trace element, melt productivity, and the efficiency of melt segregation. We further show that while the model can be fit to the observations, this requires assumptions inconsistent with constraints on the timescales of magma assembly. Hence, we falsify the end-member hypothesis and, instead, conclude that observed variability requires heterogeneity of melt transport. This might take the form of channels or waves and would almost certainly interact with source heterogeneity.