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International audience; Peptide chain formation from amino acids such as glycine is a key step in the emergence of life. Unlike their synthesis by living systems, how peptide chains grow under abiotic conditions is an open question given the variety of organic compounds discovered in various astrophysical environments, comets and meteorites. We propose a new abiotic route in the presence of protonated molecular dimers of glycine in a cold gaseous atmosphere without further need for a solid catalytic substrate. The results provide evidence for the preferential formation of mixed protonated dimers of glycine consisting of a dipeptide and a glycine molecule instead of pure protonated glycine dimers. Additional measurements mimicking a cosmic-ray impact in terms of internal excitation show that a single gas-phase collision induces polymerization via dehydration in both the mixed and pure dimer ions. Peptide chain growth is thus demonstrated to occur via a unimolecular gas-phase reaction in an excited cluster ion.

International audience; The seismic signature of the 410-km seismic discontinuity is generally attributed to the olivine to wadsleyite polymorphic transformation. However, apparent discrepancies exist between seismic and experimental observations. Among those, the sharpness of the discontinuity as inferred from the reflectivity of seismic waves is difficult to reconcile with the gradual nature of the olivine to wadsleyite transformation predicted by phase equilibria. In this study, we explore the contribution of the phase transition kinetics to the sharpness of the discontinuity by performing X-ray diffraction and sound velocity measurements on (Mg,Fe)2SiO4 with an unprecedented time resolution as a function of the reaction progress. Our data document for the first time a transient velocity softening phenomenon and attenuation which we relate to the formation of a metastable spineloid phase. In the Earth's mantle this transformation mechanism would affect the elastic gradient within the olivine-wadsleyite two-phase loop, potentially creating a low-velocity layer; hence explaining the unique sharpness and reflectivity of the discontinuity.

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The first definitive evidence for continental vents on Mars is the in situ detection of amorphous silica-rich outcrops by the Mars Exploration Rover Spirit. These outcrops have been tentatively interpreted as the result of either acid sulfate leaching in fumarolic environments or direct precipitation from hot springs. Such environments represent prime targets for upcoming astrobiology missions but remain difficult to identify with certainty, especially from orbit. To contribute to the identification of fumaroles and hot spring deposits on Mars, we surveyed their characteristics at the analog site of the Solfatara volcanic crater in central Italy. Several techniques of mineral identification (VNIR spectroscopy, Raman spectroscopy, XRD) were used both in the field and in the laboratory on selected samples. The faulted crater walls showed evidence of acid leaching and alteration into the advanced argillic-alunitic facies, with colorful deposits containing alunite, jarosite, and/or hematite. Sublimates containing various Al and Fe hydroxyl-sulfates were observed around the active fumarole vents at 90 °C. One vent at 160 °C was characterized by different sublimates enriched in As and Hb sulfide species. Amorphous silica and alunite assemblages that are diagnostic of silicic alteration were also observed at the Fangaia mud pots inside the crater. A wide range of minerals was identified at the 665 m diameter Solfatara crater that is diagnostic of acid-steam heated alteration of a trachytic, porous bedrock. Importantly, this mineral diversity was captured at each site investigated with at least one of the techniques used, which lends confidence for the recognition of similar environments with the next-generation Mars rovers.

Carbon capture and storage technologies are crucial for reducing carbon emission from power plants as a response to global climate change. The CarbFix project (Iceland) aims at examining the geochemical response of injected CO2 into subsurface reservoirs. The potential role of the subsurface biosphere has been little investigated up to now. Here, we used Thiobacillus thioparus that became abundant at the CarbFix1 pilot site after injection of CO2 and purified geothermal gases in basaltic aquifer at 400–800 m depth (4–8 MPa). The capacity of T. thioparus to produce sulfate, through oxidation of thiosulfate, was measured by Raman spectroscopy as a function of pressure up to 10 MPa. The results show that the growth and metabolic activity of T. thioparus are influenced by the initial concentration of the electron donor thiosulfate. It grows best at low initial concentration of thiosulfate (here 5 g.l−1 or 31.6 mM) and best oxidizes thiosulfate into sulfate at 0.1 MPa with a yield of 14.7 ± 0.5%. Sulfur oxidation stops at 4.3 ± 0.1 MPa (43 bar). This autotrophic specie can thereby react to CO2 and H2S injection down to 430 m depth and may contribute to induced biogeochemical cycles during subsurface energy operations.

Calcareous nannofossils are micrometric calcite platelets secreted by the photosynthetic algae named coccolithophores and incertae sedis. Calcareous nannoplankton inhabit the photic zone from coast to open-ocean and have left an abundant fossil record since the Triassic. Therefore, they constitute an interesting material for geochemical studies although they have been overlooked in comparison to foraminifera. We have analyzed manganese distribution and valence in six calcareous nannofossil species representing different ages (Recent to Jurassic) and geological settings (land sections and deep ocean core-tops) and with different structures to assess the potential of Mn as a paleobiological or paleoenvironmental proxy. Nano x -Ray Fluorescence ( xrf ) maps were established at the esrf id 22 ni and id 21 beamlines and Mn k -edge x -Ray Absorption Near Edge Structure ( xanes ) at id 21. Mn is more abundant in nannofossils from pre-Quaternary rock samples than from core-top samples. In nannofossil rock samples, Mn nano xrf maps show distributions correlated with primary crystalline organization whereas in nannofossil core-top samples, Mn is either absent or does not follow the crystal organization. X anes analyses show that Mn is in the form of MnCO3. All these observations argue for Mn incorporation within calcareous nannofossils controlled by diagenesis through overgrowth of secondary calcite (Ca, Mn)CO3. Crusts grew along the original crystal growth directions. The incorporation of Mn in some core-top samples highlights potential early diagenesis input when the detached platelet lies on the seafloor or is still in the water column. Mn should therefore be considered a critical tool to identify diagenetic overgrowth rather than primary environmental conditions.

Paleoceanographical reconstructions are often based on microfossil geochemical analyses. Coccoliths are the most ancient, abundant and continuous record of pelagic photic zone calcite producer organisms. Hence, they could be valuable substrates for geochemically based paleoenvironmental reconstructions but only Sr/Ca is exploited even if it remains poorly understood. For example, some murolith coccoliths species have very high Sr/Ca compared to the common 1-4 mmol/mol recorded in placolith coccoliths. In this study, we analyzed the elemental composition of the Middle Jurassic murolith Crepidolithus crassus by synchrotron-based nanoXRF (X-ray Fluorescence Spectroscopy) mapping focusing on Sr/Ca and compared the record to two placolith species, namely Watznaueria contracta and Discorhabdus striatus. In C. crassus, Sr/Ca is more than ten times higher than in both placoliths and seems higher in the proximal cycle. By comparison with the placoliths analyzed in the same analytical set-up and from the same sample, we exclude the impact of the diagenesis and seawater Sr/Ca to explain the high Sr/Ca in C. crassus. Based on comparisons to Pontosphaera discopora and Scyphosphaera apsteinii which also have high Sr/Ca, it seems more likely that high Sr/Ca in C. crassus is either due to the vertical elongation of the R-units of the proximal cycle or related to the action of the special polysaccharide controlling the growth of those vertically elongated R-units that may have affinities to Sr2+ . In order to apply the Sr/Ca proxy to muroliths, further investigations are needed on cultured coccoliths.

Serpentinization refers to the alteration of ultramafic rocks that produces serpentines and secondary (hydr)oxides under hydrothermal conditions. Serpentinization can generate H2, which in turn can potentially reduce CO/CO2 and produce organic molecules via Fischer–Tropsch type (FTT) and Sabatier type reactions. Over the last two decades, serpentinization has been extensively studied in laboratories, mainly due to its potential applications in prebiotic chemistry, origin of life in extreme environments, development of carbon‐free energies and CO2 sequestration. However, the production of H2 and organics during experimental serpentinization is hugely variable from one publication to another. The experiments span over a large range of pressure and temperature conditions, and starting compositions of fluid and solid phases are also highly variable, which collectively adds up to more than a hundred variables and leads to controversial results. Therefore, it is extremely difficult to compare results between studies, explain their variability and identify key parameters controlling the reactions. To overcome these limitations, we collected and analysed 30 peer‐reviewed articles including over 100 experimental parameters and ca. 30 mineral and organic products, hence building up a database can be completed and implemented in future studies. We then extracted basic statistical information from this dataset and demonstrate how such a comprehensive dataset is essential to better interpret available data and discuss the key parameters controlling the effectiveness of H2, CH4 and other organics production during experimental serpentinization. This is essential to guide the design of future experiments.

Several lines of evidence point to low rates of net primary production (NPP) in Archean oceans. However, whether Archean NPP was limited by electron donors or nutrients, particularly phosphorus (P), and how these factors might have changed over a billion years of recorded Archean history, remains contentious. One major challenge is to understand quantitatively the biogeochemical cycling of P on the early Earth. In Part I of this series (Hao et al., 2020), we estimated the weathering flux of P to the oceans as a function of temporally increasing continental emergence and elevation through Archean time. In Part II, we conduct thermodynamic and kinetic simulations to understand key processes of P cycling within the Archean ocean, including seafloor weathering, recycling of organic P, the solubility and precipitation of secondary phosphate minerals, and the burial diagenesis of P precipitates. Our calculations suggest low solubilities of apatite minerals in Archean seawater, primarily due to nearly neutral pH and high levels of Ca. This low solubility, in turn, implies a negligible contribution of apatite dissolution to P bioavailability in Archean seawater. We also simulate the solubility limits of common secondary P-bearing minerals, showing that vivianite would have been the least soluble P mineral in ferruginous Archean seawater (0.1–0.3 µM), even at moderate supersaturation states (Ω = 100 or 1000). If vivianite precipitation was kinetically favorable by microbial activities and mineral adsorption, the sinking flux of P as vivianite in Archean seawater could have reached the modern sinking flux, implying that vivianite precipitation was a potentially major sink for P in Archean oceans. During burial diagenesis, however, vivianite in porewater would have become less stable than Ca-phosphates of lower solubility. At elevated temperatures (>100 °C) associated with burial diagenesis and low-grade metamorphism, vivianite is predicted to react irreversibly with calcite to form apatite. Optimistic assumptions about the recycling efficiency of P on the Archean Earth lead us to estimate that by the end of the eon the total flux of P (continental weathering + recycling) could have supported NPP at levels up to 7% of the modern. The total flux of P would have been much lower on the early and middle Archean Earth, whereas fluxes of electron donors could have been higher, suggesting very low productivity and P-limitation of marine ecosystems during much of the eon. Comparing our estimates of NPP as limited by P supply with the estimate by Ward et al. (2019), in which NPP was limited by electron donors and metabolic efficiency, there could have been a transition between P-limited productivity in the early to middle Archean to electron donor-limitation closer to the eon’s end (assuming no oxygenic photosynthesis). Once oxygenic photosynthesis reached ecological significance, probably near the end of the Archean, our estimated flux of P would allow rapid oxidation of atmosphere.

International audience; In the context of the origin of life, clays have been proposed as possible materials to adsorb, protect and potentially foster the formation of complex bio molecules. In the present study, the adsorption of nucleotides onto clay surfaces has been tackled through classical molecular dynamics calculations. Various parameters have been varied by modelling the deoxyguanosine mono phosphate molecule at the basal surface of two clay minerals: montmorillonite and nontronite, at pH = 3 and 7, and in a 0.5 M NaCl solution in presence or absence of Ca2+ divalent cations. It has been firstly observed that counter cations in solution adopts a three-layers structure above the mineral basal surfaces which can be modified by the mineral composition, the location of the surface charge, and results in substantial effects on nucleotide adsorption. For montmorillonite, for which the charge is located in the octahedral (inner) layer, the two closest counter cations layers above the mineral surface are less populated while the third layer comprises the largest cations density. For nontronite, for which the negative charge is located on the surface oxygen atoms of the tetrahedral layer in contact with the aqueous solution, the first two counter cations layers are the most populated. The negative charge on the surface is thus screened by the first two layers above nontronite surface, and by only the third layer for montmorillonite. As a result, the negatively charged phosphate moiety of nucleotides can approach closer to the surface of nontronite by coordinating with the first two layers cations and the nucleobase adsorb on the surface in a parallel orientation maximizing Van der Walls interactions. On montmorillonite, the phosphate coordinates the cations of the third layer and thus remains rather far from the surface, which does not allow the nucleobase parallel binding. These theoretical results explain experimental results on the effect of mineral and solution composition on the adsorption of nucleotides on the surface of swelling clays.

One of the principal theories about the origin of life is based on the abiotic reduction of carbon oxides to various organic molecules in hydrothermal systems. This synthesis is most favored in ultramafic environments undergoing hydrothermal alteration where the serpentinization reaction efficiently produces H2. Nevertheless, decades of hydrothermal experiments have hardly succeeded in producing abundant organic volatiles such as CH4 and short-chain hydrocarbons. On another hand, natural observations have shown the occurrence of other abiotic compounds such as organic acids in fluids and carbonaceous matter (CM) within serpentinized rocks. But organic acids as carbon source and CM as product have not been investigated so far in experiments reproducing hydrothermal peridotite alteration. Here, we explored the effect of formic acid (HCOOH) on the serpentinization reaction and possible feedback effects on carbon speciation in both fluid and solid. We performed reactions at 300°C and 250 bar using peridotite powder (2, CO, and CO2. After 4 months, H2, CO, CO2, CH4 and short-chain alkanes (mainly ethane) were measured in the fluid, and the powder was completely indurated. The solidified powder displayed a black and white layering perpendicular to fluid diffusion. Its analysis showed the advancement of the serpentinization reaction, and the incorporation of carbon compounds into the solid phase. XRD analysis indicated 70% of serpentinization. SEM-EDX observations showed peculiar texture with large and localized euhedral magnetite grains alternating with larger magnetite grains mixed with C-enriched areas of long chrysotile fibers. FT-IR measurement attested of the widespread formation of carbonaceous material in the solid. Liquid analyses are under progress. Those first results suggest that serpentine formation not only provides additional H2 to the system, but also mineral surfaces that could play a role in the precipitation of carbonaceous material and carbon speciation in natural systems. The nature and formation mechanisms of this latter remain to be addressed but this opens new paths for abiotic organic synthesis under hydrothermal conditions. In addition to their implications as an abiotic carbon source for deep hydrocarbon degraders ecosystems, it could have important implications for the total carbon cycle.

The marked increase in seawater Mg/Ca during the Cenozoic is poorly understood, due to the limited availability of proxy data and uncertainty in elucidating the respective contributions of Mg sources and sinks through geological time1. Though established as a potentially large source of dissolved Mg over twenty years ago, the weathering of abyssal peridotites2 is a largely unexplored potential source of Mg to oceanic budgets. The release of magnesium from peridotite weathering can occur in high temperature environments, during serpentinisation near the ridge axis3, as well as low temperature off-axis environments where peridotite and serpentinite are altered to clays, carbonates and silicates4. The relative magnitude of Mg fluxes from these sources are poorly constrained. Recent studies, however, now provide a general method for estimating bulk crustal lithologies of mid-ocean ridges based on spreading rate (i.e. proportion and mass of basalts, gabbros, peridotites and serpentinised peridotite) through time5—enabling us to quantitatively assess potential Mg contributions from these different environments.We constructed a model for oceanic crustal weathering (proportional to depth below the seafloor) to develop estimates of the mass and isotopic composition of magnesium loss from peridotite during alteration in both high- and low-T environments. As Mg fractionation occurs predominantly in low-T reactions, the primary serpentinisation reaction in near-ridge environments is unlikely to result in isotopic differentiation. Comparably, the secondary low-T alterations, of both remaining peridotites (to clays and iron hydroxides) and serpentinite (e.g. to talc and dolomite) are likely to result in the fractionation of Mg. We extend our analysis to incorporate the fractionation of these systems4 and their release of Mg into the ocean. We completed our analysis by presenting a compilation of fluid data for magnesium concentrations in ultramafic bodies from hydrothermal systems, in order to evaluate our model.References(1) Staudigel, H. "Chemical fluxes from hydrothermal alteration of the oceanic crust." (2014): 583-606.(2) Snow, J.E. and Dick, H.J., 1995. Pervasive magnesium loss by marine weathering of peridotite. Geochimica et Cosmochimica Acta, 59(20), pp.4219-4235.(3) Seyfried Jr, W.E., Pester, N.J., Ding, K. and Rough, M., 2011. Vent fluid chemistry of the Rainbow hydrothermal system (36 N, MAR): Phase equilibria and in situ pH controls on subseafloor alteration processes. Geochimica et Cosmochimica Acta, 75(6), pp.1574-1593.(4) Liu, P.P., Teng, F.Z., Dick, H.J., Zhou, M.F. and Chung, S.L., 2017. Magnesium isotopic composition of the oceanic mantle and oceanic Mg cycling. Geochimica et Cosmochimica Acta, 206, pp.151-165.(5) Merdith, A.S., Atkins, S.E. and Tetley, M.G., 2019. Tectonic controls on carbon and serpentinite storage in subducted upper oceanic lithosphere for the past 320 Ma. Frontiers in Earth Science, 7, p.332.

Phosphorus (P) is the key nutrient thought to limit primary productivity on geological timescales. Phosphate levels in Archean marine sediments are low, but quantification of the P cycle and how it changed through a billion years of recorded Archean history remain a challenge, hindering our understanding of the role played by P in biosphere/geosphere co-evolution on the early Earth. Here, we design kinetic and thermodynamic models to quantitatively assess one key component of the early P cycle – continental weathering – by considering the emergence and elevation of continents, as well as the evolution of climate, the atmosphere, and the absence of macroscopic vegetation during the Archean Eon. Our results suggest that the weathering rate of apatite, the major P-hosting mineral in the rocks, was at least five times higher in the Archean Eon than today, attributable to high levels of pCO2,g. Despite this, the weathering flux of P to the oceans was negligible in the early Archean Eon, increasing to a level comparable to or greater than the modern by the end of eon, a consequence of accelerating continental emergence. Furthermore, our thermodynamic calculations indicate high solubilities of primary and secondary P-hosting minerals in the acidic weathering fluids on land, linking to high Archean pCO2,g. Thus, weathering of P was both kinetically and thermodynamically favorable on the Archean Earth, and river water could transport high levels of dissolved P to the oceans, as also supported by the observed P-depletion in our new compilation of Archean paleosols. Lastly, we evaluated the relative rates of physical erosion and chemical weathering of silicates during the Archean Eon. The results suggest that continental weathering on the early and middle Archean Earth might have been transport-limited due to low erosion rates associated with limited subaerial emergence and low plateau elevations; by the late Archean, however, continental weathering would have transited to kinetically-limited state because of continental emergence, increased plateau elevation, and weakening weathering rates. Overall, our weathering calculations together with paleosol evidence indicate an increasing flux of bioavailable P to the oceans through time, associated with late Archean continental emergence, reaching levels comparable to or higher than modern values by the end of the eon. Increased P fluxes could have fueled increasing rates of primary production, including oxygenic photosynthesis, through time, facilitating the irreversible oxidation of the Earth’s atmosphere early in the Proterozoic Eon.

International audience; Molecular hydrogen production occurs through the serpentinization of mantle peridotite exhumed at mid-ocean ridges. Hydrogen is considered essential to sustain microbial life in the subsurface; however, estimates of hydrogen flux through geological time are unknown. Here we present a model of the primary, abiotic production of molecular hydrogen from the serpentinization of oceanic lithosphere using full-plate tectonic reconstructions for the last 200 Ma. We find significant variability in hydrogen fluxes (1-70 • 1016 mol/Ma or 0.2-14.1 • 105 Mt/a), which are a function of the sensitivity of evolving ocean basins to spreading rates and can be correlated with the opening of key ocean basins during the breakup of Pangea. We suggest that the primary driver of this hydrogen flux is the continental reconfiguration during Pangea breakup, as this produces ocean basins more conducive to exhuming and exposing mantle peridotite at slow and ultraslow spreading ridges. Consequently, present-day flux estimates are ~7 • 1017 mol/Ma (1.4 • 106 Mt/a), driven primarily by the slow and ultraslow spreading ridges in the Atlantic, Indian, and Arctic oceans. As methane has also been sampled alongside hydrogen at hydrothermal vents, we estimate the methane flux using methane-to-hydrogen ratios from present-day hydrothermal vent fluids. These ratios suggest that methane flux ranges between 10 and 100% of the total hydrogen flux, although as the release of methane from these systems is still poorly understood, we suggest a lower estimate, equivalent to around 7-12 • 1016 mol/Ma (1.1-1.9 • 107 Mt/Ma) of methane.

International audience; In the context of the origin of life, phyllosilicate surfaces might favor the adsorption, concentration and reactivity of otherwise diluted prebiotic molecules. The primitive oceanic seafloor was certainly rich in Fe-Mg-rich phyllosilicates. The salinity of the primitive seawater remains largely unknown. Values ranging from 1 to 15 times modern salinity have been proposed and the salt composition of the primitive ocean also remains elusive although it may have played a role in the interactions between nucleotides and mineral surfaces. Therefore we studied the adsorption of 5'-monophosphate deoxyguanosine (dGMP) as a model nucleotide onto a Fe-rich swelling clay, i.e. nontronite, and an Al-rich phyllosilicate, i.e. pyrophyllite, for comparison. Experiments were carried out at atmospheric pressure, 25 degrees C and natural pH, with a series of salts NaCl, MgCl2, CaCl2, MgSO4, NaH2PO4 and LaCl3 in order to evaluate the effect of cations and anions on dGMP adsorption. The present study shows that nucleotides are adsorbed on both phyllosilicates via a ligand exchange mechanism. The phosphate group of the nucleotide is adsorbed on the lateral metal hydroxyls of the broken edges of phyllosilicates. The presence of divalent cations or molecular anions, such as phosphate or sulfate, tends to inhibit this interaction on mineral surfaces. However, in the presence of divalent cations, cationic bridging on the basal surfaces of the swelling clay also occurs and could induce a higher retention capacity of the swelling clays compared to non-swelling phyllosilicates in primitive and modern natural environments.

The abiotic polymerization of nucleotides and amino acids is a prerequisite for the emergence of life. It has been proposed that hydrothermal conditions might favor the polymerization of amino acid...

International audience; The evolution of the pore structure of compressed expanded vermiculite was investigated in situ under uniaxial stress up to 3200 bar using small-angle neutron and X-ray scattering. The studied samples have a lamellar texture in which the presence of oriented oblate pores was revealed by the anisotropic small-angle scattering patterns. The initial pore size distribution and the mechanical behaviour of the pellets at working pressure conditions are strongly related to the applied initial stresses used to pre-compact the vermiculite powder. Our study shows that the porous structure of the pellets was not modified under compression up to the pre-compaction pressure. Higher densification is associated with increasing anisotropy of the pore–matrix interface structure. The pore–matrix interface could be described with fractal geometry. The stress dependence of the system fractal dimension, apparent specific surface area and total porosity was determined and related to the meso- and macropore evolution under uniaxial stress.

The chemical evolution of early life requires the concentration of monomers to polymerize from the diluted primordial ocean. Transition metals such as Fe, Mn, and Zn, could have reached considerable levels in the early seawater and/or hydrothermal fluid but their influences on the adsorption of biomolecules have not been clearly addressed yet. In this study, we conducted batch adsorption experiments to explore effects of various metal cations (Li, Mg, Ca, Zn, Ni, and Mn) on the adsorption of selected nucleotides (dGMP, dAMP, and AMP) and adenosine onto nontronite and montmorillonite. We also varied the concentration of the cations and pH of the solutions to evaluate their effects. Our results show that Zn and to some extent Ni increase the adsorption of nucleotides and adenosine compared with Na, Mg, and Ca which are major salts in modern seawater. This increased adsorption is primarily attributed to the mediating role of transition metals between the clays and nucleotides and adenosine. The enhancing eff...

The payload of Mars 2020 space mission includes a deep UV resonance Raman and fluorescence spectrometer SHERLOC dedicated to the detection of luminescence and Raman signal of condensed carbon and aromatic organics that could potentially be biosignatures. Among minerals detected on Mars surface, phyllosilicates exhibit a strong affinity to organic molecules, including nucleotides, which adsorption mechanisms onto clay minerals have been well documented, whilst there is a lack of an overview of Raman studies of organics adsorbed onto phyllosilicates. Here, we used a deep UV resonant Raman setup to track down the signature of the nucleotide desoxyguanosine-5′-monophosphate (dGMP) adsorbed onto selected minerals, pyrophyllite, chlorite, nontronite and montmorillonite. Excitation with a 244 nm laser indeed avoids luminescence of natural phyllosilicates and enhances the Raman signal of the organic molecule chosen here as a model biosignature. However, the deep UV energy of the laser focused onto the samples may induce severe photo-damage to the organic compound without adequate precaution. We used the Raman signature of dGMP to characterize deep UV effect after an irradiation of several minutes (8–260 mJ) until a stable spectroscopic signal is detected and could show that it is sensitive to minute amount of dGMP and adsorption mechanism. The effect of widespread oxidants such as perchlorate on the Martian surface is also investigated here because of potential implication in the degradation of nucleotides under UV irradiation. In this study we also discuss the strategy for the detection and preservation of adsorbed biomolecules onto clay surfaces.

The solubility of carbonate minerals and aqueous carbonate speciation in deep fluids is of critical importance to the long-term carbon cycle. However, no experimental data exist in the calcium carbonate-water-salt system at pressures greater than 10 kbar. Here we present an integrated experimental and theoretical study of carbon speciation and solubility during equilibration of aragonite with NaCl solutions at 300 degrees C from 20 to 70 kbar. Using in situ Raman spectroscopy in a diamond anvil cell with NaCl concentrations up to 1.0 m (5.5 wt.%), bicarbonate and carbonate ions were the only C-bearing aqueous species spectroscopically detected in the fluids. The proportion of total dissolved bicarbonate to carbonate increased with NaCl concentration and was interpreted using a thermodynamic model to retrieve the dissociation constant of the NaHCO30 complex. The results were extended to higher temperatures using the Deep Earth Water (DEW) model to predict calcite solubility and speciation at 700 degrees C and 10 kbar in chloride solutions. With a one parameter extension of the Debye-Huckel model, the calculated solubilities agree with data from Newton and Manning (2002) up to 10 m NaCl where the solubility is about 250 millimolal. Such solubilities might contribute substantial transport of carbon in fluids at depth in subduction zones. (C) 2016 Elsevier B.V. All rights reserved.

Vibrational properties and structural changes under pressure of a highly luminescent molecular organic crystal have been investigated by ultraviolet resonant Raman spectroscopy with a 244-nm excitation. Resonant Raman modes of α-perylene crystal up to 1GPa were followed under hydrostatic pressure in an anvil cell with a sapphire window transparent to ultraviolet light. Nonlinear evolution of intra-molecular modes is induced by pressure. Abrupt shifts of Raman wavenumbers suggest structural and planar modifications of the molecules in the crystal. We interpret these shifts as a first-order phase transition to a lower volume of unit cell. The luminescence of perylene crystal is gradually modified as a consequence of these structural changes. The present experimental setup allows investigating with Raman spectroscopy very luminescent molecules involved in chemical reactions and molecular organic crystals under relatively high pressure (up to 1GPa). Copyright © 2016 John Wiley & Sons, Ltd.

International audience; Adsorption of prebiotic building blocks is proposed to have played a role in the emergence of life on Earth. The experimental and theoretical study of this phenomenon should be guided by our knowledge of the geochemistry of the habitable early Earth environments, which could have spanned a large range of settings. Adsorption being an interfacial phenomenon, experiments can be built around the minerals that probably exhibited the largest specific surface areas and were the most abundant, i.e., phyllosilicates. Our current work aims at understanding how nucleotides, the building blocks of RNA and DNA, might have interacted with phyllosilicates under various physico-chemical conditions. We carried out and refined batch adsorption studies to explore parameters such as temperature, pH, salinity, etc. We built a comprehensive, generalized model of the adsorption mechanisms of nucleotides onto phyllosilicate particles, mainly governed by phosphate reactivity. More recently, we used surface chemistry and geochemistry techniques, such as vibrational spectroscopy, low pressure gas adsorption, X-ray microscopy, and theoretical simulations, in order to acquire direct data on the adsorption configurations and localization of nucleotides on mineral surfaces. Although some of these techniques proved to be challenging, questioning our ability to easily detect biosignatures, they confirmed and complemented our pre-established model.

Icy environments may have been common on early Earth due to the faint young sun. Previous studies have proposed that the formation of large icy bodies in the early ocean could concentrate the building blocks of life in eutectic fluids and, therefore, facilitate the polymerization of monomers. This hypothesis is based on the untested assumption that organic molecules are virtually incompatible in ice Ih (hexagonal ice). In this study, we conducted freezing experiments to explore the partitioning behavior of selected amino acids (AAs; glycine, l-alanine, l-proline, and l-phenylalanine) between ice Ih and aqueous solutions analogous to seawater. We allowed ice crystals to grow slowly from a few seeds in equilibrium with the solution and used Raman spectroscopy to analyze in situ the relative concentrations of AAs in the ice and aqueous solution. During freezing, there was no precipitation of AA crystals, indicating that the concentrations in solution never reached their solubility limit, even when the droplet was mostly frozen. Analyses of the Raman spectra of the ice and eutectic solution suggested that considerable amounts of AAs existed in the ice phase with partition coefficients varying between 0.2 and 0.5. These observations imply little incompatibility of AAs in ice Ih during the freezing of the solutions, rendering the concentration hypothesis in a eutectic system unwarranted. However, incorporation into ice Ih could protect AAs from decomposition or racemization and significantly improve the efficiency of extraterrestrial transport of small organics. Therefore, this study supports the hypothesis of extraterrestrial delivery of organic molecules in icy comets and asteroids to the primitive Earth as suggested by an increasing number of independent observations. Key Words: Ice Ih-Partition coefficient-Amino acids-Polymerization-Extraterrestrial transport of organics. Astrobiology 18, 381-392.

Water-rich planetary bodies including large icy moons and ocean exoplanets may host a deep liquid water ocean underlying a high-pressure icy mantle. The latter is often considered as a limitation to the habitability of the uppermost ocean because it would limit the availability of nutrients resulting from the hydrothermal alteration of the silicate mantle located beneath the deep ice layer. To assess the effects of salts on the physical properties of high-pressure ices and therefore the possible chemical exchanges and habitability inside H 2 O-rich planetary bodies, we measured partitioning coefficients and densities in the H 2 O–RbI system up to 450 K and 4 GPa; RbI standing as an experimentally amenable analog of NaCl in the H 2 O-salt solutions. We measured the partitioning coefficient of RbI between the aqueous fluid and ices VI and VII, using in-situ Synchrotron X-ray Fluorescence (XRF). With in-situ X-ray diffraction, we measured the unit-cell parameters and the densities of the high-pressure ice phases in equilibrium with the aqueous fluid, at pressures and temperatures relevant to the interior of planetary bodies. We conclude that RbI is strongly incompatible towards ice VI with a partitioning coefficient K d (VI-L) = 5.0 ( ± 2.1 ) ⋅ 10 − 3 and moderately incompatible towards ice VII, K d (VII-L) = 0.12 ( ± 0.05 ) . RbI significantly increases the unit-cell volume of ice VI and VII by ca. 1%. This implies that RbI-poor ice VI is buoyant compared to H 2 O ice VI while RbI-enriched ice VII is denser than H 2 O ice VII. These new experimental results might profoundly impact the internal dynamics of water-rich planetary bodies. For instance, an icy mantle at moderate conditions of pressure and temperature will consist of buoyant ice VI with low concentration of salt, and would likely induce an upwelling current of solutes towards the above liquid ocean. In contrast, a deep and/or thick icy mantle of ice VII will be enriched in salt and hence would form a stable chemical boundary layer on top of the silicate mantle. Such a contrasted dynamics in the aqueous–ice VI–ice VII system would greatly influence the migration of nutrients towards the uppermost liquid ocean, thus controlling the habitability of moderate to large H 2 O-rich planetary bodies in our solar system (e.g., Ganymede, Titan, Calisto) and beyond.

Carbonate minerals may be recycled into the mantle at subduction zones. However, the evolution of carbonate minerals in equilibrium with aqueous fluids as well as the nature of the chemical species of dissolved carbon in the deep crust and mantle at high PT conditions are still unknown. In this study, we report an integrated experimental and theoretical study of the equilibration of CaCO 3 minerals with pure water at subduction zone conditions over the pressure and temperature ranges 5–80 kbar and 300–400 °C. The fluid speciation was studied using in situ Raman spectroscopy. The relative amounts of dissolved carbonate and bicarbonate were estimated from the corrected areas of the Raman bands of the carbonate and bicarbonate ions and used to constrain a theoretical thermodynamic model of the fluid speciation and solubility of aragonite. At 300–400 °C, our results indicate that the proportion of dissolved C present as CO 2 strongly decreases in fluids in equilibrium with aragonite at P > 10 kbar. CO 2 is replaced by HCO 3 − and CaHCO 3 + which predominate until P > 40 kbar, where CO 3 2− and CaCO 3 0 become the dominant C-species. At higher temperatures, the theoretical model indicates that CO 2 again becomes a major species in fluids in equilibrium with aragonite depending on the pressure.

Microbial life has been prevailing in the biosphere for the last 3.8 Ga at least. Throughout most of the Earth's history it has experienced a range of pressures; both dynamic pressure when the young Earth was heavily bombarded, and static pressure in subsurface environments that could have served as a refuge and where microbial life nowadays flourishes. In this review, we discuss the extent of high-pressure habitats in early and modern times and provide a short overview of microbial survival under dynamic pressures. We summarize the current knowledge about the impact of microbial activity on biogeochemical cycles under pressures characteristic of the deep subsurface. We evaluate the possibility that pressure can be a limiting parameter for life at depth. Finally, we discuss the open questions and knowledge gaps that exist in the field of high-pressure geomicrobiology.

International audience; Mineral surfaces may have played a role in the origin of the first biopolymers, by concentrating organic monomers from a dilute ocean. Swelling clays provide a high surface area for the concentration of prebiotic monomers, and have therefore been the subject of numerous investigations. In that context, montmorillonite, the most abundant swelling clay in modern environments, has been extensively studied with regard to adsorption and polymerization of nucleic acids. However, montmorillonite was probably rather marginal on the primitive ocean floor compared to iron-magnesium rich phyllosilicates such as nontronite that results from the hydrothermal alteration of a mafic or ultramafic oceanic crust. In the present paper, we study the adsorption of nucleotides on montmorillonite and nontronite, at various pH and ionic strength conditions plausible for Archean sea-water. A thorough characterization of the mineral surfaces shows that nucleotide adsorb mainly on the edge faces of the smectites by ligand exchange between the phosphate groups of the nucleotides and the -OH groups from the edge sites over a wide pH range (4-10). Nontronite is more reactive than montmorillonite. At low pH, additional ion exchange may play a role as the nucleotides become positively charged