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Amide bonds are fundamental products in biochemistry, forming peptides critical to protein formation, but amide bonds are also detected in sterile environments and abiotic synthesis experiments. The abiotic formation of amide bonds may represent a prerequisite to the origin of life. Here we report thermodynamic models that predict optimal conditions for amide bond synthesis across geologically relevant ranges of temperature, pressure, and pH. We modeled acetamide formation from acetic acid and ammonia as a simple analog to peptide bond formation, and tested this model with hydrothermal experiments examining analogous reactions of amides including benzanilide and related structures. We also expanded predictions for optimizing diglycine formation, revealing that in addition to synthesis becoming more favorable at near-ambient pressures (Psat) with increasing temperatures, the strongest thermodynamic drive exists at extremely high pressures (>15,000 bar) and decreasing temperatures. Beyond implications for life’s origins, the reactants and products involved in simple amide formation reactions can potentially be used as geochemical tracers for planetary exploration of environments that may be habitable.

The hydrous alteration of ultramafic rocks, known as serpentinization, generates fluids that can fuel microbial communities and enable the synthesis of simple organic compounds. Serpentinization reactions can proceed even at the ambient, low-temperature conditions present in continental aquifers raising questions about the limits of life deep in the Earth9s subsurface. Through thermodynamic calculations, we investigate various reactions that facilitate the transformation of oxic, slightly acidic rainwater into reduced, hyperalkaline fluids during low-temperature serpentinization. We explore a suite of factors (variabilities in temperature, host-rock compositions, fluid salinity, and the buffering capacity of various serpentinization-relevant minerals) that offer broad insights into the chemical environments formed through low-temperature serpentinization. Results of calculations show that alteration of olivine-rich lithologies will lead to fluids constrained by the chrysotile-brucite-diopside equilibrium assemblage, close in pH to those measured from the most alkaline fluids hosted in ultramafic rocks. Variabilities in the compositions of fluids hosted by continental serpentinizing systems can be attributed to a shift from being in equilibrium with diopside to calcite, among other reactions. Results of calculations also show that it would be difficult to distinguish fluids reacting with either fresh or altered ultramafic rocks based solely on their pH, and total dissolved Ca, Mg and Si content. Our models also account for Fe incorporation into solid solutions of serpentine and brucite and show that the global H2 flux from continental serpentinization could be considerably lower than estimates based on iron oxidation to magnetite only. Lastly, we present the energetic landscape available to subsurface microorganisms by focusing on two microbial process using H2: methanogenesis and hydrogen oxidation. Limited but available energy (0.2–1.7 calories/kg fluid) can be exploited by methanogens, permitting the possibility of deep communities in serpentinizing aquifers. More energy is available for methanogenesis (0.2–6 calories/kg fluid) and hydrogen oxidation (0–17 calories/kg fluid) when upwelling, deep-seated, serpentinization-generated fluids mix with shallow groundwater. Ultimately, predictions set forth in this study provide a framework for testing ideas that can explain the compositions of fluids and microbial communities sampled at ultramafic environments here on Earth and perhaps in the near future, on ocean worlds in our solar system.

Measured abundances of organic compounds can reveal information about the environments in which they formed. Since organic compounds can be mobilized and released from geologic and planetary settings, they have the potential to provide insights into environments that are difficult to observe directly. To advance our understanding of these environments, this study identifies organic reactions that approach metastable equilibrium in experiments, so that future studies can predict geochemical conditions in remote settings (e.g., deep Earth, extraterrestrial bodies) by monitoring reaction ratios of compounds involved in similar organic reactions. At high temperatures organic redox reactions can equilibrate, which allows comparisons with thermodynamic properties to yield estimates of reaction conditions. However, redox reactions may equilibrate too slowly to be applicable to lower temperature systems. To explore metastable equilibria at lower temperatures, we studied substitution reactions that tend to be faster than redox reactions. In this study, we demonstrate that oxygen- and nitrogen-bearing organic compounds at hydrothermal conditions undergo a series of simultaneous substitution reactions that rapidly approach steady-state ratios indicative of metastable equilibrium. Four sets of aqueous experiments were performed at 250 °C and 40 bar, each beginning with a single organic reactant: benzyl alcohol, benzylamine, dibenzylamine, or tribenzylamine. All reactant solutions were prepared with identical bulk elemental compositions by adjusting the concentrations of the starting organic compounds and adding ammonia as needed. After 2 h at hydrothermal reaction conditions, all of the model compounds were detectable in all four sets of experiments, evidence for reversibility of reactions among the compounds. After 72 h, reaction ratios between the model compounds converged in all four sets of experiments, consistent with approaches toward metastable equilibrium. Reaction ratios for ether and aldehyde formation reactions were also observed to group within a relatively small range, but without a clear convergence pattern, suggesting other non-redox reactions may approach metastable equilibrium. The approach to metastable equilibrium among the initial organic reactants could be observed and quantified even in the presence of competing redox reactions whose mechanisms are less understood, including dibenzylimine and toluene formation, which did not appear to reach steady-states. These findings identify classes of organic compounds and reactions that can reflect the conditions at which they last equilibrated and should be targeted for analysis in natural systems.

Significance Although catalysis by mineral surfaces has been considered to be important in prebiotic chemistry, the role of porous silica phases, with reactions taking place within specific confined environments, has not been explored. This paper proposes that structure direction through interaction of dissolved silica with organic species in aqueous solution produces porous silica catalysts for prebiotic organic reactions to form larger polymerized molecules, with possible control of chirality. This process may involve feedback and amplification if the organics produced by catalysis can also act as structure-directing agents for enhanced synthesis of the catalytic silica structures. To our knowledge, such structure direction and catalysis, though well known in materials science, have not been considered previously in the context of prebiotic chemistry.

Many experimental studies report rates of decomposition for amino acids under hydrothermal conditions without describing the kinetics of competing reactions or definitively characterizing individual reaction mechanisms. As a step toward comprehensive models for amino acid reactivity, this study provides a detailed description of the organic reaction kinetics and mechanisms for deamination of amine functional groups at acidic hydrothermal conditions, which favors their protonated aminium forms. Time series experiments yield hydrothermal deamination rates for model aminum compounds benzylaminium (BAH+) and α-methylbenzylaminium (α-CH3-BAH+), buffered at pH 3.3 at 250 °C and 40 bar (Psat). Both compounds are primary amines, but the amine group in the former is bonded to a primary carbon while in the latter to a secondary carbon; this difference has implications for reactivity that are relevant for naturally occurring amines. Deamination of the aminiums under these conditions forms alcohols as the major primary products. The deamination mechanisms were investigated by determining the reaction kinetics of ring-substituted BAH+ and α-CH3-BAH+ derivatives, which provided information on the nature of charge buildup in the transition state. The results for the deamination of BAH+ to form benzyl alcohol support nearly equal contribution from two reaction mechanisms, specifically unimolecular nucleophilic substitution (SN1, kSN1 ≈ 2.4 × 10−6 s−1) and bimolecular nucleophilic substitution (SN2, kSN2 ≈ 2.7 × 10−6 s−1), while α-CH3-BAH+ deaminates almost exclusively via a much faster SN1 mechanism (kα ≈ 7.6 × 10−4 s−1). These observed rates reinforce the notion that previously reported amino acid deamination rates may have resulted from catalysis mechanisms associated with certain reaction vessel materials (e.g., Pyrex and stainless steel). The observation of two competing mechanisms for BAH+ deamination/hydration implies that extrapolation of deamination rates to other temperatures is currently unreliable, since this is likely to be accompanied by a change in the predominant mechanism. However, this work establishes that mechanistic contributions can be quantified, which will enhance the accuracy of extrapolating deamination rates across the temperature and pH ranges common to aqueous geochemical environments.

Bulk gold was found to catalyze the Cannizzaro reaction of benzaldehyde and related disproportionation reactions in superheated water. At 200 °C and 1.5 MPa for ∼48 hours, benzaldehyde conversions increased linearly with added gold at low loadings, but this trend reversed at higher gold loadings. Ratios of the primary products benzoic acid and benzyl alcohol exceeded unity, increasing with increasing amounts of gold. These observations are attributed to the reactivity of benzyl alcohol in the presence of gold, which is proposed to react via cross-disproportionation with benzaldehyde to yield toluene and benzoic acid, transitioning to benzyl alcohol disproportionation that forms toluene and reforms benzaldehyde at higher gold loadings. Turnover frequencies for both benzaldehyde (0.00013 s−1) and benzyl alcohol (0.0011 s−1) were quite low and experiments of varied duration demonstrated that very few turnovers occurred under the reaction conditions. Proposed mechanisms for the catalyzed reactions include hydride transfer from gold-bonded alkoxides to surface gold atoms. These observations expand the known catalytic capabilities of bulk gold to include hydride transfer, a fundamental process in organic chemistry and biochemistry. The simple, environmentally benign reaction conditions are reminiscent of organic geochemical processes, with implications for both geomimicry and green chemistry approaches to chemical challenges.

Aldehydes represent an intermediate redox state of organic carbon and can be precursors to carboxylic acids via disproportionation. A model aldehyde, benzaldehyde, was subjected to hydrothermal experiments (250–350 °C, saturation pressure) to assess the kinetics and mechanisms of the reactions leading to carboxylic acids. The concentration dependence demonstrates the kinetics are second-order in benzaldehyde, consistent with a disproportionation reaction, which is reminiscent of the base-promoted Cannizzaro reaction known at lower temperatures. Arrhenius parameters for these rate constants trend well with data from most, but not all, previous studies for the reaction under supercritical conditions. The rate constants yielded an entropy of activation (ΔS‡) of −161 J mol–1 K–1, consistent with a bimolecular transition state at the rate-limiting step. Experimental yields of benzoic acid and benzyl alcohol were not equal, unlike what is expected for the disproportionation reaction. A kinetic model that includ...

The geochemistry of hot springs and the availability of oxidants capable of supporting microbial metabolisms are influenced by subsurface processes including the separation of hydrothermal fluids into vapor and liquid phases. Here, we characterized the influence of geochemical variation and oxidant availability on the abundance, composition, and activity of hydrogen (H2 )-dependent chemoautotrophs along the outflow channels of two-paired hot springs in Yellowstone National Park. The hydrothermal fluid at Roadside East (RSE; 82.4°C, pH 3.0) is acidic due to vapor-phase input while the fluid at Roadside West (RSW; 68.1°C, pH 7.0) is circumneutral due to liquid-phase input. Most chemotrophic communities exhibited net rates of H2 oxidation, consistent with H2 support of primary productivity, with one chemotrophic community exhibiting a net rate of H2 production. Abundant H2 -oxidizing chemoautotrophs were supported by reduction in oxygen, elemental sulfur, sulfate, and nitrate in RSW and oxygen and ferric iron in RSE; O2 utilizing hydrogenotrophs increased in abundance down both outflow channels. Sequencing of 16S rRNA transcripts or genes from native sediments and dilution series incubations, respectively, suggests that members of the archaeal orders Sulfolobales, Desulfurococcales, and Thermoproteales are likely responsible for H2 oxidation in RSE, whereas members of the bacterial order Thermoflexales and the archaeal order Thermoproteales are likely responsible for H2 oxidation in RSW. These observations suggest that subsurface processes strongly influence spring chemistry and oxidant availability, which in turn select for unique assemblages of H2 oxidizing microorganisms. Therefore, these data point to the role of oxidant availability in shaping the ecology and evolution of hydrogenotrophic organisms.

Alcohol dehydration by elimination of water is central to a series of functional group interconversions that have been proposed as a reaction pathway that connects hydrocarbons and carboxylic acids under geochemically relevant hydrothermal conditions such as in sedimentary basins. Hydrothermal dehydration of alcohols is an example of an organic reaction that is quite different from the corresponding chemistry under ambient laboratory conditions. In hydrothermal dehydration, water acts as the solvent and provides the catalyst, and no additional reagents are required. This stands in contrast to the same reaction at ambient conditions, where concentrated strong acids are required. Hydrothermal dehydration is thus of potential interest in the context of green chemistry. We investigated the mechanism of hydrothermal alcohol dehydration for a series of secondary alcohols using studies of kinetics and stereoelectronic effects to establish reaction mechanisms. The E1 elimination mechanism dominates over the corre...

Hydrothermal organic transformations occurring in geochemical processes are influenced by the surrounding environments including rocks and minerals. This work is focused on the effects of five common minerals on reactions of a model ketone substrate, dibenzylketone (DBK), in an experimental hydrothermal system. Ketones play a central role in many hydrothermal organic functional group transformations, such as those converting hydrocarbons to oxygenated compounds; however, how these minerals control the hydrothermal chemistry of ketones is poorly understood. Under the hydrothermal conditions of 300 °C and 70 MPa for up to 168 h, we observed that, while quartz (SiO2) and corundum (Al2O3) had no detectable effect on the hydrothermal reactions of DBK, iron-containing minerals, such as hematite (Fe2O3), magnetite (Fe3O4), and troilite (synthetic FeS), accelerated the reaction of DBK by up to an order of magnitude. We observed that fragmentation products, such as toluene and bibenzyl, dominated in the presence of hematite or magnetite, while use of troilite gave primarily the reduction products, e.g., 1, 3-diphenyl-propane and 1, 3-diphenyl-2-propanol. The roles of the three iron minerals in these transformations were further explored by (1) control experiments with various mineral surface areas, (2) measuring H2 in hydrothermal solutions, and (3) determining hydrogen balance among the organic products. These results suggest the reactions catalyzed by iron oxides (hematite and magnetite) are promoted mainly by the mineral surfaces, whereas the sulfide mineral (troilite) facilitated the reduction of ketone in the reaction solution. Therefore, this work not only provides a useful chemical approach to study and uncover complicated hydrothermal organic-mineral interactions, but also fosters a mechanistic understanding of ketone reactions in the deep carbon cycle.

Volatile Organic Compounds (VOCs) are ubiquitously present at low but detectable concentrations in hydrothermal fluids from volcanic and geothermal systems. Although their behavior is strictly controlled by physical and chemical parameters, the mechanisms responsible for the production of most VOCs in natural environments are poorly understood. Among them, benzene, whose abundances were found to be relatively high in hydrothermal gases, can theoretically be originated from reversible catalytic reforming processes, i.e. multi-step dehydrogenation reactions, involving saturated hydrocarbons. However, this hypothesis and other hypotheses are difficult to definitively prove on the basis of compositional data obtained by natural gas discharges only. In this study, therefore, laboratory experiments were carried out to investigate the production of benzene from cyclic hydrocarbons at hydrothermal conditions, specifically 300 °C and 85 bar. The results of experiments carried out in the presence of water and selected powdered minerals, suggest that cyclohexane undergoes dehydrogenation to form benzene, with cyclohexene and cyclohexadiene as by-products, and also as likely reaction intermediates. This reaction is slow when carried out in water alone and competes with isomerization and hydration pathways. However, benzene formation was increased compared to these competing reactions in the presence of sulfide (sphalerite and pyrite) and iron oxide (magnetite and hematite) minerals, whereas no enhancement of any reaction products was observed in the presence of quartz. The production of thiols was observed in experiments involving sphalerite and pyrite, suggesting that sulfide minerals may act both to enhance reactivity and also as reactants after dissolution. These experiments demonstrate that benzene can be effectively produced at hydrothermal conditions through dehydrogenation of saturated cyclic organic structures and highlight the crucial role played by minerals in this process.

Growth substrates that maximize energy yield are widely thought to be utilized preferentially by microorganisms. However, observed distributions of microorganisms and their activities often deviate from predictions based solely on thermodynamic considerations of substrate energy supply. Here we present observations of the bioenergetics and growth yields of a metabolically flexible, thermophilic strain of the archaeon Acidianus when grown autotrophically on minimal medium with hydrogen (H2) or elemental sulfur (S°) as an electron donor, and S° or ferric iron (Fe3+) as an electron acceptor. Thermodynamic calculations indicate that S°/Fe3+ and H2/Fe3+ yield three- and four-fold more energy per mol electron transferred, respectively, than the H2/S° couple. However, biomass yields in Acidianus cultures provided with H2/S° were eight-fold greater than when provided S°/Fe3+ or H2/Fe3+, indicating the H2/S° redox couple is preferred. Indeed, cells provided with all three growth substrates (H2, Fe3+, and S°) grew preferentially by reduction of S° with H2. We conclude that substrate preference is dictated by differences in the energy demand of electron transfer reactions in Acidianus when grown with different substrates, rather than substrate energy supply.

The influence of oxidation-reduction (redox) potential on the expression of biomolecules is a topic of ongoing exploration in geobiology. In this study, we investigate the novel possibility that structures and compositions of lipids produced by microbial communities are sensitive to environmental redox conditions. We extracted lipids from microbial biomass collected along the thermal and redox gradients of four alkaline hot springs in Yellowstone National Park (YNP) and investigated patterns in the average oxidation state of carbon (ZC), a metric calculated from the chemical formulae of lipid structures. Carbon in intact polar lipids (IPLs) and their alkyl chains becomes more oxidized (higher ZC) with increasing distance from each of the four hot spring sources. This coincides with decreased water temperature and increased concentrations of oxidized inorganic solutes, such as dissolved oxygen, sulfate, and nitrate. Carbon in IPLs is most reduced (lowest ZC) in the hot, reduced conditions upstream, with abundance-weighted ZC values between −1.68 and −1.56. These values increase gradually downstream to around −1.36 to −1.33 in microbial communities living between 29.0 and 38.1°C. This near-linear increase in ZC can be attributed to a shift from ether-linked to ester-linked alkyl chains, a decrease in average aliphatic carbons per chain (nC), an increase in average degree of unsaturation per chain (nUnsat), and increased cyclization in tetraether lipids. The ZC of lipid headgroups and backbones did not change significantly downstream. Expression of lipids with relatively reduced carbon under reduced conditions and oxidized lipids under oxidized conditions may indicate microbial adaptation across environmental gradients in temperature and electron donor/acceptor supply.

Dissolved organic carbon in hot springs reflects a range of sources and biogeochemical processes. We evaluated ~200 continental hot spring samples, with a range in pH and temperature, collected from the Tengchong hydrothermal region, Yunnan Province, China and Yellowstone National Park, Wyoming, USA. Dissolved organic carbon concentrations ranged from 16.7 µM to 2.97 mM. Acidic springs displayed the highest values and widest range in carbon concentration. Alkaline springs had a narrower range and lower average concentrations. Carbon composition was evaluated using ultraviolet absorption and 3D-fluorescence spectroscopy. Total fluorescence was correlated (p 97% of the total fluorescence. Our model includes three humic-like components, one protein-like component, and one novel component exclusively observed in highly acidic springs. The closest spectral match to the novel component is an acid-soluble lignin produced during high-temperature, acid digestion of wood pulp. Humic-like components were dominant in mid-pH springs (4

Glacial comminution of bedrock generates fresh mineral surfaces capable of sustaining chemotrophic microbial communities under the dark conditions that pervade subglacial habitats. Geochemical and isotopic evidence suggests that pyrite oxidation is a dominant weathering process generating protons that drive mineral dissolution in many subglacial systems. Here, we provide evidence correlating pyrite oxidation with chemosynthetic primary productivity and carbonate dissolution in subglacial sediments sampled from Robertson Glacier (RG), Alberta, Canada. Quantification and sequencing of ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) transcripts suggest that populations closely affiliated with Sideroxydans lithotrophicus , an iron sulfide-oxidizing autotrophic bacterium, are abundant constituents of microbial communities at RG. Microcosm experiments indicate sulfate production during biological assimilation of radiolabeled bicarbonate. Geochemical analyses of subglacial meltwater indicate that increases in sulfate levels are associated with increased calcite and dolomite dissolution. Collectively, these data suggest a role for biological pyrite oxidation in driving primary productivity and mineral dissolution in a subglacial environment and provide the first rate estimate for bicarbonate assimilation in these ecosystems. Evidence for lithotrophic primary production in this contemporary subglacial environment provides a plausible mechanism to explain how subglacial communities could be sustained in near-isolation from the atmosphere during glacial-interglacial cycles.

Saturn’s largest moon, Titan, has an atmosphere and surface that are rich in organic compounds. Liquid hydrocarbons exist on the surface, most famously as lakes. Photochemical reactions produce solid organics in Titan’s atmosphere, and these materials settle or snow onto the surface. At the surface, liquids can interact with solids, and geochemical processes can occur. The consequences of these processes can be explored using a thermodynamic model to calculate the solubilities of gases and solids in liquid hydrocarbons at cryogenic temperatures. The van Laar model developed in this study was parameterized using experimental phase equilibrium data, and accurately represents the data for the CH 4 –C 2 H 6 –C 3 H 8 –N 2 –C 2 H 2 chemical system from 90 to 110 K. The model generally gives more accurate results than existing models. The model also features a suitable balance between accuracy and simplicity, and can serve as a foundation for studies of fluvial geochemistry on Titan because it can be extended to any number of components while maintaining thermodynamic consistency. Application of the model to Titan reveals that the equilibrium composition of surface liquids depends on the abundance of methane gas in the local atmosphere, consistent with prior studies. The concentration of molecular nitrogen in Titan’s lakes varies inversely with the ethane content of the lakes. The model indicates that solid acetylene should be quite soluble in surface liquids, which implies that acetylene-rich sedimentary rocks would be susceptible to chemical erosion, and acetylene evaporites may form on Titan. The geochemical character of acetylene in liquid hydrocarbons on Titan appears to be intermediate to those of calcite and gypsum in surface waters on Earth. Specific recommendations are given of observational, experimental, and theoretical work that will lead to significant advancements in our knowledge of geochemical processes on Titan. This paper represents the beginning of a new kind of geochemistry, called cryogenic fluvial geochemistry, with Titan starring as the first example.

The environmental effects and bioavailability of nanoparticulate iron (Fe) to plants are currently unknown. Here, plant bioavailability of synthesized hematite Fe nanoparticles was evaluated using Arabidopsis thaliana ( A. thaliana ) as a model. Over 56-days of growing wild-type A. thaliana , the nanoparticle-Fe and no-Fe treatments had lower plant biomass, lower chlorophyll concentrations, and lower internal Fe concentrations than the Fe-treatment. Results for the no-Fe and nanoparticle-Fe treatments were consistently similar throughout the experiment. These results suggest that nanoparticles (mean diameter 40.9 nm, range 22.3–67.0 nm) were not taken up and therefore not bioavailable to A. thaliana . Over 14-days growing wild-type and transgenic (Type I/II proton pump overexpression) A. thaliana , the Type I plant grew more than the wild-type in the nanoparticle-Fe treatment, suggesting Type I plants cope better with Fe limitation; however, the nanoparticle-Fe and no-Fe treatments had similar growth for all plant types.

Many transformation reactions involving hydrocarbons occur in the presence of H 2 O in hydrothermal systems and deep sedimentary systems. We investigate these reactions using laboratory-based organic chemistry experiments at high temperature and pressure (300 °C and 100 MPa). Organic functional group transformation reactions using model organic compounds based on cyclohexane with one or two methyl groups provided regio- and stereochemical markers that yield information about reversibility and reaction mechanisms. We found rapidly reversible interconversion between alkanes, alkenes, dienes, alcohols, ketones, and enones. The alkane-to-ketone reactions were not only completely reversible, but also exhibited such extensive reversibility that any of the functional groups along the reaction path (alcohol, ketone, and even the diene) could be used as the reactant and form all the other groups as products. There was also a propensity for these ring-based structures to dehydrogenate; presumably from the alkene, through a diene, to an aromatic ring. The product suites provide strong evidence that water behaved as a reactant and the various functional groups showed differing degrees of reactivity. Mechanistically-revealing products indicated reaction mechanisms that involve carbon-centered cation intermediates. This work therefore demonstrates that a wide range of organic compound types can be generated by abiotic reactions at hydrothermal conditions.

Carbon can be a major constituent of crustal and mantle fluids, occurring both as dissolved ionic species (e.g., carbonate ions or organic acids) and molecular species (e.g., CO2, CO, CH4, and more complex organic compounds). The chemistry of dissolved carbon changes dramatically with pressure ( P ) and temperature ( T ). In aqueous fluids at low P and T , molecular carbon gas species such as CO2 and CH4 saturate at low concentration to form a separate phase. With modest increases in P and T , these molecular species become fully miscible with H2O, enabling deep crustal and mantle fluids to become highly concentrated in carbon. At such high concentrations, carbon species play an integral role as solvent components and, with H2O, control the mobility of rock-forming elements in a wide range of geologic settings. The migration of carbon-bearing crustal and mantle fluids contributes to Earth’s carbon cycle; however, the mechanisms, magnitudes, and time variations of carbon transfer from depth to the surface remain least understood parts of the global carbon budget (Berner 1991, 1994; Berner and Kothavala 2001). Here we provide an overview of carbon in crustal and mantle fluids. We first review the evidence for the presence and abundance of carbon in these fluids. We then discuss oxidized and reduced carbon, both as solutes in H2O-rich fluids and as major components of miscible CO2-CH4-H2O fluids. Our goal is to provide some of the background needed to understand the role of fluids in the deep carbon cycle. ### Carbon in aqueous fluids of crust and mantle Numerous lines of evidence indicate that carbon may be an important component of crustal and mantle fluids. Fluid inclusions provide direct samples of carbon-bearing fluids from a range of environments. Carbon species in fluid …

Hydrothermal fluids obtain organic compounds through diverse pathways. In submarine systems organic compounds are already dissolved in seawater that is heated and transformed into hydrothermal fluids through water-rock reactions. Microbes inhabiting hydrothermal systems produce metabolites that enter the fluids, and cells can be carried into the reaction zones by circulating fluids and pyrolyzed. Analogous sources of organic compounds can be anticipated in continental systems with the possible addition of novel plant- and soil-derived organic compounds from the surface. In addition, hydrothermal systems possess large potentials for abiotic organic synthesis that may add a novel suite of compounds. When sedimentary rocks are present, ancient biogenic organic matter can be mobilized or transformed by hot fluids. These transformations accompany the generation of petroleum, coal, and other fossil fuels, suggesting that expectations for hydrothermal transformations can be built on those that occur in sedimentary basins. Likewise, some types of ore deposition are accompanied by transformations of organic compounds, and metal-organic complexes may be involved in enhancing the transport of metals in ore-forming and other crustal fluids. With these thoughts in mind, this review starts with an inventory of the types of organic compounds found in hydrothermal systems and some ways that hydrothermal organic compounds are transformed. Methane can be generated biotically and abiotically from organic or inorganic reactants, and since it lacks a carbon-carbon bond, some researchers would not consider it to be an organic compound. Nevertheless, more data exist for methane in hydrothermal fluids than for any organic compound that fits the definition. Methane has been quantified in continental and submarine hydrothermal fluids, fumarolic gases associated with hydrothermal systems, oil-field brines, deep fluids in sedimentary basins and igneous basement rocks, fluids associated with active serpentinization, and fluid inclusions in minerals from ore deposits, sedimentary basins, and deep crustal settings (recent examples include: …

Studies of hydrothermal reactions involving organic compounds suggest complex, possibly reversible, reaction pathways that link functional groups from reduced alkanes all the way to oxidized carboxylic acids. Ketones represent a critical functional group because they occupy a central position in the reaction pathway, at the point where CAC bond cleavage is required for the formation of the more oxidized carboxylic acids. The mechanisms for the critical bond cleavage reactions in ketones, and how they compete with other reactions are the focus of this experimental study. We studied a model ketone, dibenzylketone (DBK), in H2O at 300 C and 70 MPa for up to 528 h. Product analysis was performed as a function of time at low DBK conversions to reveal the primary reaction pathways. Reversible interconversion between ketone, alcohol, alkene and alkane functional groups is observed in addition to formation of radical coupling products derived from irreversible CAC and CAH homolytic bond cleavage. The product distributions are time-dependent but the bond cleavage products dominate. The major products that accumulate at longer reaction times are toluene and larger, dehydrogenated structures that are initially formed by radical coupling. The hydrogen atoms generated by dehydrogenation of the coupling products are predominantly consumed in the formation of toluene. Even though bond cleavage products dominate, no carboxylic acids were observed on the timescale of the reactions under the chosen experimental conditions.

Summary Genes encoding nitrogenase (nifH) were amplified from sediment and photosynthetic mat samples collected in the outflow channel of Mound Spring, an alkaline thermal feature in Yellowstone National Park. Results indicate the genetic capacity for nitrogen fixation over the entire range of temperatures sampled (57.2°C to 80.2°C). Amplification of environmental nifH transcripts revealed in situ expression of nifH genes at temperatures up to 72.7°C. However, we were unable to amplify transcripts of nifH at the higher-temperature locations (> 72.7°C). These results indicate that microbes at the highest temperature sites contain the genetic capacity to fix nitrogen, yet either do not express nifH or do so only transiently. Field measurements of nitrate and ammonium show fixed nitrogen limitation as temperature decreases along the outflow channel, suggesting nifH expression in response to the downstream decrease in bioavailable nitrogen. Nitrogen stable isotope values of Mound Spring sediment communities further support geochemical and genetic data. DNA and cDNA nifH amplicons form several unique phylogenetic clades, some of which appear to represent novel nifH sequences in both photosynthetic and chemosynthetic microbial communities. This is the first report of in situ nifH expression in strictly chemosynthetic zones of terrestrial (non-marine) hydrothermal systems, and sets a new upper temperature limit (72.7°C) for nitrogen fixation in alkaline, terrestrial hydrothermal environments.

The majority of microorganisms in natural environments resist laboratory cultivation. Sometimes referred to as 'unculturable', many phylogenetic groups are known only by fragments of recovered DNA. As a result, the ecological significance of whole branches of the 'tree of life' remains a mystery; this is particularly true when regarding genetic material retrieved from extreme environments. Geochemically relevant media have been used to improve the success of culturing Archaea and Bacteria, but these efforts have focused primarily on optimizing pH, alkalinity, major ions, carbon sources, and electron acceptor-donor pairs. Here, we cultured thermophilic microorganisms from 'Sylvan Spring' (Yellowstone National Park, USA) on media employing different trace element solutions, including one that mimicked the source fluid of the inocula. The growth medium that best simulated trace elements found in 'Sylvan Spring' produced a more diverse and faster growing mixed culture than media containing highly elevated trace element concentrations. The elevated trace element medium produced fewer phylotypes and inhibited growth. Trace element concentrations appear to influence growth conditions in extreme environments. Incorporating geochemical data into cultivation attempts may improve culturing success.

Subglacial sediments sampled from beneath Robertson Glacier (RG), Alberta, Canada, were shown to harbor diverse assemblages of potential nitrifiers, nitrate reducers, and diazotrophs, as assessed by amoA , narG , and nifH gene biomarker diversity. Although archaeal amoA genes were detected, they were less abundant and less diverse than bacterial amoA , suggesting that bacteria are the predominant nitrifiers in RG sediments. Maximum nitrification and nitrate reduction rates in microcosms incubated at 4°C were 280 and 18.5 nmol of N per g of dry weight sediment per day, respectively, indicating the potential for these processes to occur in situ . Geochemical analyses of subglacial sediment pore waters and bulk subglacial meltwaters revealed low concentrations of inorganic and organic nitrogen compounds. These data, when coupled with a C/N atomic ratio of dissolved organic matter in subglacial pore waters of ∼210, indicate that the sediment communities are N limited. This may reflect the combined biological activities of organic N mineralization, nitrification, and nitrate reduction. Despite evidence of N limitation and the detection of nifH , we were unable to detect biological nitrogen fixation activity in subglacial sediments. Collectively, the results presented here suggest a role for nitrification and nitrate reduction in sustaining microbial life in subglacial environments. Considering that ice currently covers 11% of the terrestrial landmass and has covered significantly greater portions of Earth at times in the past, the demonstration of nitrification and nitrate reduction in subglacial environments furthers our understanding of the potential for these environments to contribute to global biogeochemical cycles on glacial-interglacial timescales.

Combining analytical data from hot spring samples with thermodynamic calculations permits a quantitative assessment of the availability and ranking of various potential sources of inorganic chemical energy that may support microbial life in hydrothermal ecosystems. Yellowstone hot springs of diverse geochemical composition, ranging in pH from 9 were chosen for this study, and dozens of samples were collected during three field seasons. Field measurements of dissolved oxygen, nitrate, nitrite, total ammonia, total sulfide, alkalinity, and ferrous iron were combined with laboratory analyses of sulfate and other major ions from water samples, and carbon dioxide, hydrogen, methane, and carbon monoxide in gas samples to evaluate activity products for ∼300 coupled oxidation–reduction reactions. Comparison of activity products and independently calculated equilibrium constants leads to values of the chemical affinity for each of the reactions, which quantifies how far each reaction is from equilibrium. Affinities, in turn, show systematic behavior that is independent of temperature but can be correlated with pH of the hot springs as a proxy for the full spectrum of geochemical variability. Many affinities are slightly to somewhat dependent on pH, while others are dramatically influenced by changes in chemical composition. All reactions involving dissolved oxygen as the electron acceptor are potential energy sources in all hot spring samples collected, but the ranking of dominant electron donors changes from ferrous iron, and sulfur at high pH to carbon monoxide, hydrogen, and magnetite as pH decreases. There is a general trend of decreasing energy yields depending on electron acceptors that follows the sequence: O 2 (aq) > NO 3 − ≈ NO 2 − ≈ S > pyrite ≈ SO 4 −2 ≈ CO(g) ≈ CO 2 (g) at high pH, and O 2 (aq) ≈ magnetite > hematite ≈ goethite > NO 3 − ≈ NO 2 − ≈ S ≈ pyrite ≈ SO 4 −2 at low pH. Many reactions that are favorable sources of chemical energy at one set of geochemical conditions fail to provide energy at other conditions, and vice versa . This results in energy profiles supplied by geochemical processes that provide fundamentally different foundations for chemotrophic microbial communities as composition changes.

We calculate the D/H ratio of CH 4 from serpentinization on Titan to determine whether Titan’s atmospheric CH 4 was originally produced inside the giant satellite. This is done by performing equilibrium isotopic fractionation calculations in the CH 4 –H 2 O–H 2 system, with the assumption that the bulk D/H ratio of the system is equivalent to that of the H 2 O in the plume of Enceladus. These calculations show that the D/H ratio of hydrothermally produced CH 4 would be markedly higher than that of atmospheric CH 4 on Titan. The implication is that Titan’s CH 4 is a primordial chemical species that was accreted by the moon during its formation. There are two evolutionary scenarios that are consistent with the apparent absence of endogenic CH 4 in Titan’s atmosphere. The first is that hydrothermal systems capable of making CH 4 never existed on Titan because Titan’s interior has always been too cold. The second is that hydrothermal systems on Titan were sufficiently oxidized so that C existed in them predominately in the form of CO 2 . The latter scenario naturally predicts the formation of endogenic N 2 , providing a new hypothesis for the origin of Titan’s atmospheric N 2 : the hydrothermal oxidation of 15 N-enriched NH 3 . A primordial origin for CH 4 and an endogenic origin for N 2 are self-consistent, but both hypotheses need to be tested further by acquiring isotopic data, especially the D/H ratio of CH 4 in comets, and the 15 N/ 14 N ratio of NH 3 in comets and that of N 2 in one of Enceladus’ plumes.

The discovery of CO 2 , CH 4 , and N 2 in a plume at Enceladus provides useful clues about the chemistry and evolution of this moon of Saturn. Here, we use chemical equilibrium and kinetic calculations to estimate the oxidation state of hydrothermal systems on early Enceladus, with the assumption that the plume's composition was inherited from early hydrothermal fluids. Chemical equilibrium calculations are performed using the CO 2 /CH 4 ratio in the plume, and kinetic calculations are conducted using equations from fluid dynamics and chemical kinetics. Our results suggest that chemical equilibrium between CO 2 and CH 4 would have been reachable at temperatures above ∼200 °C in hydrothermal systems. The oxidation state of the hydrothermal systems would have been close to the pyrrhotite–pyrite–magnetite (PPM) or fayalite–magnetite–quartz (FMQ) redox buffer (i.e., terrestrial-like) if the plume's CO 2 and CH 4 equilibrated in hydrothermal systems long ago. As for minerals, we suggest that iron metal would have been oxidized to magnetite by the escape of H 2 from the early satellite. Our calculations also indicate that, assuming CO 2 and CH 4 reached chemical equilibrium, magnetite would not have been oxidized to hematite in hydrothermal systems, perhaps due to insufficient H 2 escape. It is shown that, if Enceladus accreted as much NH 3 as comets contain, the presence of N 2 and deficiency of NH 3 in the plume can be understood in the context of chemical equilibrium in the C–N–O–H system. We conclude by proposing an evolutionary hypothesis in which the fairly oxidized nature of the plume can be explained by a brief episode of oxidation caused by short-lived radioactivity. These suggestions can be rigorously tested by acquiring gravity and isotopic data in the future.

Antimony is a regulated contaminant that poses both acute and chronic health effects in drinking water. Previous reports suggest that polyethylene terephthalate (PET) plastics used for water bottles in Europe and Canada leach antimony, but no studies on bottled water in the United States have previously been conducted. Nine commercially available bottled waters in the southwestern US (Arizona) were purchased and tested for antimony concentrations as well as for potential antimony release by the plastics that compose the bottles. The southwestern US was chosen for the study because of its high consumption of bottled water and elevated temperatures, which could increase antimony leaching from PET plastics. Antimony concentrations in the bottled waters ranged from 0.095 to 0.521 ppb, well below the US Environmental Protection Agency (USEPA) maximum contaminant level (MCL) of 6 ppb. The average concentration was 0.195+/-0.116 ppb at the beginning of the study and 0.226+/-0.160 ppb 3 months later, with no statistical differences; samples were stored at 22 degrees C. However, storage at higher temperatures had a significant effect on the time-dependent release of antimony. The rate of antimony (Sb) release could be fit by a power function model (Sb(t)=Sb 0 x[Time, h]k; k=8.7 x 10(-6)x[Temperature ( degrees C)](2.55); Sb 0 is the initial antimony concentration). For exposure temperatures of 60, 65, 70, 75, 80, and 85 degrees C, the exposure durations necessary to exceed the 6 ppb MCL are 176, 38, 12, 4.7, 2.3, and 1.3 days, respectively. Summertime temperatures inside of cars, garages, and enclosed storage areas can exceed 65 degrees C in Arizona, and thus could promote antimony leaching from PET bottled waters. Microwave digestion revealed that the PET plastic used by one brand contained 213+/-35 mgSb/kg plastic; leaching of all the antimony from this plastic into 0.5L of water in a bottle could result in an antimony concentration of 376 ppb. Clearly, only a small fraction of the antimony in PET plastic bottles is released into the water. Still, the use of alternative types of plastics that do not leach antimony should be considered, especially for climates where exposure to extreme conditions can promote antimony release from PET plastics.

Oxidations of phenylacetic acid to benzaldehyde, benzyl alcohol to benzaldehyde, and benzaldehyde to benzoic acid have been observed, in water as the solvent and using only copper(II) chloride as the oxidant. The reactions are performed at 250 °C and 40 bar, conditions that mimic hydrothermal reactions that are geochemically relevant. Speciation calculations show that the oxidizing agent is not freely solvated copper(II) ions, but complexes of copper(II) with chloride and carboxylate anions. Measurements of the reaction stoichiometries and also of substituent effects on reactivity allow plausible mechanisms to be proposed. These oxidation reactions are relevant to green chemistry in that they proceed in high chemical yield in water as the solvent and avoid the use of toxic heavy metal oxidizing reagents.

A compilation of experimental values of the infinite dilution partial molar Gibbs energy, enthalpy, and heat capacity of hydration together with partial molar volumes in water at 298.15 K and 0.1 MPa is presented for aliphatic nitriles and dinitriles. These data are treated in the framework of the first- and second-order group additivity methods. Thermodynamic properties are determined for the first-order CN group and for the following second-order groups: C-(CN)(C)(H)2, C-(CN)(C)2(H), and CN-(C). The relatively long-range dipole−dipole interactions of two terminal nitrile groups require additional corrections, {CN-(CH2)2-CN}corr and {CN-(CH2)3-CN}corr, for lower dinitriles. New experimental studies of aqueous branched mononitriles and lower dinitriles (particularly propanedinitrile) are required to expand the usefulness and accuracy of group contribution models for aqueous nitriles.

A compilation of experimental values of the infinite dilution partial molar Gibbs energy, enthalpy, and heat capacity of hydration, together with partial molar volumes in water at 298.15 K and 0.1 MPa is presented for aliphatic monoethers, diethers, and polyethers. These data are treated in the framework of the first- and second-order group additivity methods. However, third- and higher-order effects (i.e., interactions expressed beyond the nearest neighbors) are clearly present in aqueous ethers. The effects can be accounted for by the introduction of a number of corrections. For the second-order group contribution method, numerical values are determined for the following groups: C−(C)2(H)(O)ether, C−(C)3(O)ether, O−(C)2, C−(H)2(O)2, C−(C)(O)2(H), and corrections: a “ethoxyalkane” correction, {CH3−CH2−O−CH2}, and a “diether” correction, {O−(CH2)2−O}. For the first-order group contribution method, in addition to the “ether” O group, a large number of corrections appears to be necessary for accurate repr...

The hypothesis that the soluble fraction of the organic compounds present in carbonaceous chondrite meteorites was formed during aqueous alteration of the parent body was tested with masstransfer, reaction-path calculations. In these calculations, we start with likely compositions of the original parent body and asteroidal fluids that are far from thermodynamic equilibrium, and metastable and stable equilibrium constraints are imposed as the total Gibbs free energy of the parent body environment is minimized. The results of these calculations suggest that the classes of soluble organic compounds present in carbonaceous chondrite meteorites could have formed during relatively low temperature aqueous alteration of the meteorite parent body or bodies. The main controls on the potential for synthesis and transformation of organic compounds were the oxidation state of the rock/fluid system, the bulk composition of that system, and the temperatures that were achieved during the alteration event or events. It also appears that the alteration mineral assemblages were influenced by the presence of soluble organic compounds and reaction among them.

A compilation of experimental values of the infinite dilution partial molar Gibbs energy, enthalpy, and heat capacity of hydration, together with molar volumes in water at 298.15 K and 0.1 MPa, is presented for aliphatic esters. These data, combined with the related results for aliphatic hydrocarbons, monohydric alcohols, and ketones, are treated in the framework of the first- and second-order group additivity methods. Numerical values of the contributions to each of the thermodynamic properties are obtained by a least-squares procedure for the following first-order groups: CH3, CH2, CH, C, OH, CO, COO, and COOH as well as for the C−OH, C−CO, and C−COO corrections for the attachment of the polar groups to the tertiary carbon atom. For the case of the second-order group contribution method, numerical values are retrieved for the following groups: C−(C)(H)3, C−(C)2(H)2, C−(C)3(H), C−(C)4, C−(C)(H)2(O), C−(C)2(H)(O)alcohol, C−(C)3(O)alcohol, O−(H)(C), CO−(C)2, C−(CO)(H)2(C), C−(CO)(H)(C)2, C−(CO)(C)3, C−(C...

A simple method is presented for estimating the second cross virial coefficients for interactions involving water. It is based on the Tsonopoulos corresponding-states correlation and consists of a semiempirical equation for evaluating the mixture-specific parameter k12 of this correlation. The general structure of this equation is guided by a theory-based relation, which is valid for interactions between spherical nonpolar molecules. An empirical extension of this relation to interactions involving water was done by replacing the “energy” term with a function of the Gibbs energy of hydration of a compound at 298 K and 0.1 MPa. This correlation is supported by experimental B12 values for interactions between water and numerous compounds that differ greatly in size and strength of water−solute interactions. Limitations of this empirical correlation are briefly discussed. In addition, available B12 data for interactions between water and normal alkanes, from ethane to octane, strongly suggest the applicabili...

The hydrothermal system at Vulcano, Aeolian Islands (Italy), is home to a wide variety of thermophilic, chemolithoautotrophic archaea and bacteria. As observed in laboratory growth studies, these organisms may use an array of terminal electron acceptors (TEAs), including O2, , Fe(III), , elemental sulphur and CO2; electron donors include H2, , Fe2+, H2S and CH4. Concentrations of inorganic aqueous species and gases were measured in 10 hydrothermal fluids from seeps, wells and vents on Vulcano. These data were combined with standard Gibbs free energies () to calculate overall Gibbs free energies (ΔGr) of 90 redox reactions that involve 16 inorganic N-, S-, C-, Fe-, H- and O-bearing compounds. It is shown that oxidation reactions with O2 as the TEA release significantly more energy (normalized per electron transferred) than most anaerobic oxidation reactions, but the energy yield is comparable or even higher for several reactions in which , or Fe(III) serves as the TEA. For example, the oxidation of CH4 to CO2 coupled to the reduction of Fe(III) in magnetite to Fe2+ releases between 94 and 123 kJ/mol e−, depending on the site. By comparison, the aerobic oxidation of H2 or reduced inorganic N-, S-, C- and Fe-bearing compounds generally yields between 70 and 100 kJ/mol e−. It is further shown that the energy yield from the reduction of elemental sulphur to H2S is relatively low (8–19 kJ/mol e−) despite being a very common metabolism among thermophiles. In addition, for many of the 90 reactions evaluated at each of the 10 sites, values of ΔGr tend to cluster with differences < 20 kJ/mol e−. However, large differences in ΔGr (up to ∼ 60 kJ/mol e−) are observed in Fe redox reactions, due largely to considerable variations in Fe2+, H+ and H2 concentrations. In fact, at the sites investigated, most variations in ΔGr arise from differences in composition and not in temperature.

Gas seeps emanating from ophiolites at Yanartaş (Chimaera), Turkey, have been documented for thousands of years. Active serpentinization produces hydrogen and a range of carbon gases that may provide fuel for life. Here we report a newly discovered, ephemeral fluid seep emanating from a small gas vent at Yanartaş. Fluids and biofilms were sampled at the source and points downstream. We describe site conditions, and provide microbiological data in the form of enrichment cultures, scanning electron microscopy (SEM), carbon and nitrogen isotopic composition of solids, and PCR screens of nitrogen cycle genes. Source fluids are pH 11.95, with a Ca:Mg of ~200, and sediments under the ignited gas seep measure 60°C. Collectively, these data suggest the fluid is the product of active serpentinization at depth. Source sediments are primarily calcite and alteration products (chlorite and montmorillonite). Downstream, biofilms are mixed with montmorillonite. SEM shows biofilms distributed homogeneously with carbonates. Organic carbon accounts for 60% of the total carbon at the source, decreasing downstream to

Hydrothermal organic transformations under geochemically relevant conditions can result in complex product mixtures that form via multiple reaction pathways. The hydrothermal decomposition reactions of the model ketone dibenzyl ketone form a mixture of reduction, dehydration, fragmentation, and coupling products that suggest simultaneous and competitive radical and ionic reaction pathways. Here we show how Norrish Type I photocleavage of dibenzyl ketone can be used to independently generate the benzyl radicals previously proposed as the primary intermediates for the pure hydrothermal reaction. Under hydrothermal conditions, the benzyl radicals undergo hydrogen atom abstraction from dibenzyl ketone and para-coupling reactions that are not observed under ambient conditions. The photochemical method allows the primary radical coupling products to be identified, and because these products are generated rapidly, the method also allows the kinetics of the subsequent dehydration and Paal-Knorr cyclization reactions to be measured. In this way, the radical and ionic thermal and hydrothermal reaction pathways can be studied separately.

We present theoretical models of the composition, the relative abundances, and the stability of hydrated salts on the surface and in the icy shell of Jupiter's satellite Europa and discuss whether those salts have an oceanic origin. The evaluations were done with thermodynamic calculations of (1) salt dehydration equilibria at the conditions of the surface of Europa and its icy shell, (2) chemical equilibria involving solids and water vapor in the Na-K-Mg-Ca-S-Cl-H2O system at surface temperatures and variable partial pressures of water vapor, and (3) changes in aquatic chemistry and sequences of salt precipitation from freezing oceanic water, using cosmochemical, mass balance, and physical-chemical constraints on the elemental and ionic composition of the ocean. Mass balance calculations of total or partial extraction of elements into an ocean from a carbonaceous chondrite type mantle show that magnesium and sulfate rather than chloride and sodium could be the most abundant solutes in the ocean. Freezing oceanic water of this composition leads to brines that differ in composition from the original water and to deposition of ice and highly hydrated sulfates of Mg, Na, and Ca as well as alkali chlorides. After freezing is complete, highly hydrated salts remain stable in ice-bearing surface materials and throughout the icy shell. For hypothetical surface salt lag deposits, formed through sublimation/sputtering of ice and dehydration of salts, we predict hydration stratification with depth, approaching the highest hydration states in ice-bearing materials in the lowest parts of the deposits. We discuss the effects of fast disequilibrium freezing and variable dehydration rates of salts on the predicted mineral assemblages at the surface. All of our models, which are independent of observations, predict the predominance of Mg and Na sulfates in surface salts, in agreement with spectroscopic models for the nonicy surface material in the near infrared spectral region.

Thermodynamic calculations of metastable equilibria in the H‐ C‐O system are used to evaluate the stability of condensed polycyclic aromatic hydrocarbons (PAHs) and normal alkanes in the solar nebula. The effects of temperature, total pressure (governed by H2), the abundances of gaseous CO and H2O, as well mass accretion rate into the Sun and viscous efficiency at the nebula midplane are explored. We show that the inhibited formation of graphite and methane permits metastable existence of hydrocarbons with respect to the inorganic gases H2, CO, and H2O. Low temperatures, high pressures, high abundances of CO, low abundances of H2O, low accretion rates, and low viscous efficiencies favor stability of hydrocarbons. Condensed PAHs are stable relative to nominal abundances of the inorganic gases at temperatures below»450 K depending on the physical parameters adopted for the nebula. Normal alkanes with carbon numbers>10 are stable at temperatures 30‐60 degrees lower. During the evolution of the nebula, hydrocarbons have a thermodynamic potential to form in a narrow zone, which moved toward the Sun as the accretion rate decreased. At radial distances of 2‐4 AU, hydrocarbons had a potential to form at the time when the accretion rate was 10 i6:3 ‐10 i7:7 solar mass yr i1 , depending on the viscous efficiency. High temperature, low pressure, and a high CO/H2O ratio in the nebula increase the stability of PAHs compared with their alkylated versions and relative to their aliphatic counterparts with the same carbon number. The calculations reveal the thermodynamic possibility for nebular Fischer‐Tropsch type (FTT) synthesis of condensed hydrocarbons on the surface of mineral grains from CO and H2 in an H2O-depleted and/or CO-rich environment. c ∞ 2001 Academic Press

Experimental results of phase equilibria studies at elevated temperatures for more than twenty hydrocarbon-water systems were uniformly correlated within the framework of the Peng-Robinson-Stryjek-Vera equation of state in combination with simple mixing rules. This treatment allows evaluation of the Gibbs energy of hydration for many alkanes, 1-alkenes, cycloalkanes (derivatives of cyclohexane) and alkylbenzenes up to 623 K at saturated water vapor pressure and up to 573 K at 50 MPa. Results for homologous series show regular changes with increasing carbon number, and confirm the applicability of the group contribution approach to the Gibbs energy of hydration of hydrocarbons at elevated temperatures. The temperature dependence of group contributions to the Gibbs energy of hydration were determined for CH3, CH2, and CH in aliphatic hydrocarbons; C=C and H for alkenes; c-CH2 and c-CH in cycloalkanes; and CHar and Car in alkylbenzenes (or aromatic hydrocarbons). Close agreement between calculated and experimental results suggests that this approach provides reasonable estimates of Gibbs energy of hydration for many alkanes, 1-alkenes, alkyl cyclohexanes and alkylbenzenes at temperatures up to 623 K and pressures up to 50 MPa.

Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO2, and H2 below approximately 250-300 degrees C during rapid cooling of trapped magmatic or impact-generated gases. Depending on temperature, bulk composition, and oxidation-reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO2 ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01-0.001 together with high CO/CO2 ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO2 ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine-grain magnetite, formation of a CO-rich local gas phase, reduction of water vapor to H2, reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high-temperature quenching of CO-, H2-rich impact gases could have led to magnetite-catalyzed hydrocarbon synthesis.

An extensive compilation of experimental data yielding the infinite dilution partial molar Gibbs energy of hydration ΔhGO, enthalpy of hydration ΔhHO, heat capacity of hydration ΔhCpO, and volume V2O, at the reference temperature and pressure, 298.15 K and 0.1 MPa, is presented for hydrocarbons (excluding polyaromatic compounds) and monohydric alcohols. These results are used in a least-squares procedure to determine the numerical values of the corresponding properties of the selected functional groups. The simple first order group contribution method, which in general ignores nearest-neighbors and steric hindrance effects, was chosen to represent the compiled data. Following the precedent established by Cabani et al. (1981) , the following groups are considered: CH3, CH2, CH, C for saturated hydrocarbons; c-CH2, c-CH, c-C for cyclic saturated hydrocarbons; CHar, Car for aromatic hydrocarbons (containing the benzene ring); C=C, C≡C for double and triple bonds in linear hydrocarbons, respectively; c-C=C for the double bond in cyclic hydrocarbons; H for a hydrogen atom attached to the double bond (both in linear and cyclic hydrocarbons) or triple bond; and OH for the hydroxyl functional group. In addition it was found necessary to include the “pseudo”-group I(C-C) to account for the specific interactions of the neighboring hydrocarbon groups attached to the benzene or cyclic ring (in the latter case only for cis-isomers). Results of this study, the numerical values of the group contributions, will allow in most cases reasonably accurate estimations of ΔhGO, ΔhHO, ΔhCpO, and V2O at 298.15 K, 0.1 MPa for many hydrocarbons involved in geochemical and environmental processes.

Standard partial molal thermodynamic parameters for the aqueous chlorinated-ethylene species, perchloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), cis-1,2-dichloroethylene (cis-1,2-DCE), trans-1,2-dichloroethylene (trans-1,2,-DCE), and vinyl chloride (VC) have been estimated by using experimental gas-solubility data and correlation algorithms. The provided thermodynamic values may be used to calculate properties of reactions involving the aqueous chloroethylene species at a wide range of temperatures and pressures. Estimated values for the chloroethylenes were used, along with published values for minerals, gases, aqueous ions, and aqueous neutral organic species, to calculate the stability of chloroethylene species in equilibrium with the minerals magnetite, hematite, pyrite, and pyrrhotite in the subsurface. Estimated values for the aqueous chloroethylenes were also used to calculate reduction potentials for microbially-mediated reductive dechlorination half-reactions at elevated temperatures. Calculations indicate that all aqueous chloroethylene species are energetically favored to decompose to ethylene(aq) under a wide range of conditions in the subsurface, by both abiotic and biotic pathways. Anaerobic microbially mediated degradation is especially favored under conditions at least sufficiently reducing to promote sulfate-reduction, but not under conditions sufficient for microbial denitrification, pyrolusite reduction, or ferric-iron reduction.

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson–Kirkham–Flowers (HKF) equation of state yields standard partial molal entropies ( S °) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S ° is not available from either regression or calorimetric measurement, the values of S ° can be estimated from a linear correlation between standard partial molal entropies of association (Δ S ° r ) and standard partial molal entropies of aqueous cations ( S ° M ). The correlation is independent of cation charge, which makes it possible to predict S ° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (Δ Ḡ ° r ) and Gibbs free energies of formation (Δ Ḡ ° f ) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe +2 and Mg +2 than on the speciation of Zn +2 and Mn +2 .

Thermochemical calculations of metastable equilibria are used to evaluate the stability of condensed polycyclic aromatic hydrocarbons (PAHs) in cooling thermal gases and hydrothermal fluids on ancient Mars, which are roughly similar to their terrestrial counterparts. The effects of temperature, pressure, the extent of PAH alkylation, and the relative stability of PAHs and alkanes are considered. Inhibition of methane and graphite formation favors synthesis of metastable mixtures of hydrocarbons from aqueous or gaseous CO, CO2, and H2 below 200°–300°C. High-temperature quenching of H2 and CO in volcanic and impact gases and dynamic hydrothermal fluids also favor the synthesis of hydrocarbons. In addition, an excess of CO in cooling systems relative to equilibrium makes the synthesis from CO and H2 more favorable energetically than from CO2 and H2. Both the CO-H2 reactions through Fischer-Tropsch (FT) type processes and the CO2-H2 reactions could be catalyzed by magnetite. Volcanic gases and hydrothermal fluids related to mafic and ultramafic magmas and rocks are more favorable for FT type synthesis than those associated with oxidized Fe2O3-bearing rocks and regolith. We conclude that PAHs and aliphatic hydrocarbons on Mars and Earth could be formed without the contribution of biogenic carbon. Some PAHs could be formed because of pyrolysis of other hydrocarbons formed earlier by the FT type synthesis or other processes. If the PAHs found in the ALH 84001 martian meteorite formed together with other hydrocarbons through FT type synthesis, it may be possible to bracket the temperature of the synthesis. The approach presented here can be generalized to study the synthesis of hydrocarbons in terrestrial volcanic and hydrothermal processes.

Hydrothermal circulation can lead to fluid mixing on any planet with liquid water and a source of heat. Aqueous fluids with differing compositions, especially different oxidation states, are likely to be far from thermodynamic equilibrium when they mix, and provide a source of free energy that can drive organic synthesis from CO 2 and H 2 , and/or supply a source of geochemical energy to chemolithoautotrophic organisms. Results are presented that quantify the potential for organic synthesis during unbuffered fluid mixing in present submarine hydrothermal svstems, as well as hypothetical systems that may have existed on the early Earth and Mars. Dissolved hydrogen, present in submarine hydrothermal fluids owing to the high-temperature reduction of H 2 O as seawater reacts with oceanic crustal rocks, provides the reduction potential and the thermodynamic drive for organic synthesis from CO 2 (or bicarbonate) as hydrothermal fluids mix with seawater. The potential for organic synthesis is a strong function of the H 2 content of the hydrothermal fluid, which is, in turn, a function of the prevailing oxidation state controlled by the composition of the rock that hosts the hydrothermal system. Hydrothermal fluids with initial oxidation states at or below those set by the fayalite-magnetite-quartz mineral assemblage show the greatest potential for driving organic synthesis. These calculations show that it is thermodynamically possible for 100% of the carbon in the mixed fluid to be reduced to a mixture of carboxylic acids, alcohols, and ketones in the range 250-50°C as cold seawater mixes with the hydrothermal fluid. As the temperature drops, larger organic molecules are favored, which implies that fluid mixing could drive the geochemical equivalent of a metaholic system. This enormous reduction potential probably drives a large portion of the primary productivity around present seafloor hydrothermal vents and would have been present in hydrothermal systems on the early Earth or Mars. The single largest control on the potential for organic synthesis is the composition of the rock that hosts the hydrothermal system.

Mixing of hydrothermal fluids and seawater at the ocean floor, combined with slow reaction kinetics for oxidation/reduction reactions, provides a source of metabolic energy for chemolithotrophic microorganisms which are the primary biomass producers for an extensive submarine ecosystem that is essentially independent of photosynthesis. Thermodynamic models are used to explore geochemical constraints on the amount of metabolic energy potentially available from chemosynthetic reactions involving S, C, Fe, and Mn compounds during mixing of hydrothermal fluids with seawater. For the vent fluid used in the calculations (EPR 21 degrees N OBS), the model indicates that mixing environments are favorable for oxidation of H2S, CH4, Fe2+ and Mn2+ only below approximately 38 degrees C, with methanogenesis and reduction of sulfate or S degrees favored at higher temperatures, suggesting that environments dominated by mixing provide habitats for mesophilic (but not thermophilic) aerobes and thermophilic (but not mesophilic) anaerobes. A maximum of approximately 760 cal per kilogram vent fluid is available from sulfide oxidation while between 8 and 35 cal/kg vent fluid is available from methanotrophy, methanogenesis, oxidation of Fe or Mn, or sulfate reduction. The total potential for chemosynthetic primary production at deep-sea hydrothermal vents globally is estimated to be about 10(13) g biomass per year, which represents approximately 0.02% of the global primary production by photosynthesis in the oceans. Thermophilic methanogens and sulfate- and S degree-reducers are likely to be the predominant organisms in the walls of vent chimneys and in the diffuse mixing zones beneath warm vents, where biological processes may contribute to the high methane concentrations of vent fluids and heavy 34S/32S ratios of vent sulfide minerals. The metabolic processes taking place in these systems may be analogs of the first living systems to evolve on the Earth.

Correlations among experimentally determined standard partial molal thermodynamic properties of inorganic aqueous species at 25°C and 1 bar allow estimates of these properties for numerous monatomic cations and anions, polyatomic anions, oxyanions, acid oxyanions, neutral oxy-acid species, dissolved gases, and hydroxide complexes of metal cations. Combined with correlations among parameters in the revised Helgeson-Kirkham-Flowers (HKF) equation of state (Shock et al., 1992), these estimates permit predictions of standard partial molal volumes ( V ° ), heat capacities ( C ° P ), and entropies ( S ° ), as well as apparent standard partial molal enthalpies ( Δ H ° P,T ) and Gibbs free energies (ΔḠ° P,T ) of formation to 1000°C and 5 kb for hundreds of inorganic aqueous species of interest in geochemistry. Data and parameters for more than 300 inorganic aqueous species are presented. Close agreement between calculated and experimentally determined equilibrium constants for acid dissociation reactions and cation hydrolysis reactions supports the generality and validity of these predictive methods. These data facilitate the calculation of the speciation of major, minor, and trace elements in hydrothermal and metamorphic fluids throughout most of the crust of the Earth.

Thermodynamic modelling of organic synthesis has largely been focused on deep-sea hydrothermal systems. When seawater mixes with hydrothermal fluids, redox gradients are established that serve as potential energy sources for the formation of organic compounds and biomolecules from inorganic starting materials. This energetic drive, which varies substantially depending on the type of host rock, is present and available both for abiotic (outside the cell) and biotic (inside the cell) processes. Here, we review and interpret a library of theoretical studies that target organic synthesis energetics. The biogeochemical scenarios evaluated include those in present-day hydrothermal systems and in putative early Earth environments. It is consistently and repeatedly shown in these studies that the formation of relatively simple organic compounds and biomolecules can be energy-yielding (exergonic) at conditions that occur in hydrothermal systems. Expanding on our ability to calculate biomass synthesis energetics, we also present here a new approach for estimating the energetics of polymerization reactions, specifically those associated with polypeptide formation from the requisite amino acids.