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Hydrothermal dehydration is an attractive method for deoxygenation and upgrading of biofuels because it requires no reagents or catalysts other than superheated water. Although mono-alcohols cleanly deoxygenate via dehydration under many conditions, polyols such as those derived from saccharides and related structures are known to be recalcitrant with respect to dehydration. Here, we describe detailed mechanistic and kinetic studies of hydrothermal dehydration of 1,2- and 1,4-cyclohexanediols as model compounds to investigate how interactions between the hydroxyls can control the reaction. The diols generally dehydrate more slowly and have more complex reaction pathways than simple cyclohexanol. Although hydrogen bonding between hydroxyls is an important feature of the diol reactions, hydrogen bonding on its own does not explain the reduced reactivity. Rather, it is the way that hydrogen bonding influences the balance between the E1 and E2 elimination mechanisms. We also describe the reaction pathways and follow-up secondary reactions for the slower-dehydrating diols.

Thermodynamic characterization of the relative stabilities of chemical compounds is a pillar of conceptual models in various fields of geosciences. Analogous models applied to genomes can yield new information about the relationship between genomes and their geochemical environments. In this perspective article, we present a chemical and thermodynamic analysis of prokaryotic lineages that have been the target of previous phylogenomic studies of evolutionary adaptation to varying redox conditions. The thermodynamic model development begins by quantifying the effects of hydrogen activity (aH

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 formation of ketone products from carboxylic acids in the presence of minerals has not been considered in the interpretations of aqueous geochemistry, even though the formation of ketones is a ...

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.

Little is known of how the confluence of subsurface and surface processes influences the assembly and habitability of hydrothermal ecosystems. To address this knowledge gap, the geochemical and microbial composition of a high-temperature, circumneutral hot spring in Yellowstone National Park was examined to identify the sources of solutes and their effect on the ecology of microbial inhabitants. Metagenomic analysis showed that populations comprising planktonic and sediment communities are archaeal dominated, are dependent on chemical energy (chemosynthetic), share little overlap in their taxonomic composition, and are differentiated by their inferred use of/tolerance to oxygen and mode of carbon metabolism. The planktonic community is dominated by putative aerobic/aerotolerant autotrophs, while the taxonomic composition of the sediment community is more evenly distributed and comprised of anaerobic heterotrophs. These observations are interpreted to reflect sourcing of the spring by anoxic, organic carbon-limited subsurface hydrothermal fluids and ingassing of atmospheric oxygen that selects for aerobic/aerotolerant organisms that have autotrophic capabilities in the water column. Autotrophy and consumption of oxygen by the planktonic community may influence the assembly of the anaerobic and heterotrophic sediment community. Support for this inference comes from higher estimated rates of genome replication in planktonic populations than sediment populations, indicating faster growth in planktonic populations. Collectively, these observations provide new insight into how mixing of subsurface waters and atmospheric oxygen create dichotomy in the ecology of hot spring communities and suggest that planktonic and sediment communities may have been less differentiated taxonomically and functionally prior to the rise of oxygen at ∼2.4 billion years ago (Gya). IMPORTANCE Understanding the source and availability of energy capable of supporting life in hydrothermal environments is central to predicting the ecology of microbial life on early Earth when volcanic activity was more widespread. Little is known of the substrates supporting microbial life in circumneutral to alkaline springs, despite their relevance to early Earth habitats. Using metagenomic and informatics approaches, water column and sediment habitats in a representative circumneutral hot spring in Yellowstone were shown to be dichotomous, with the former largely hosting aerobic/aerotolerant autotrophs and the latter primarily hosting anaerobic heterotrophs. This dichotomy is attributed to influx of atmospheric oxygen into anoxic deep hydrothermal spring waters. These results indicate that the ecology of microorganisms in circumneutral alkaline springs sourced by deep hydrothermal fluids was different prior to the rise of atmospheric oxygen ∼2.4 Gya, with planktonic and sediment communities likely to be less differentiated than contemporary circumneutral hot springs.

Hydrogen (H2 ) is enriched in hot springs and can support microbial primary production. Using a series of geochemical proxies, a model to describe variable H2 concentrations in Yellowstone National Park (YNP) hot springs is presented. Interaction between water and crustal iron minerals yields H2 that partition into the vapour phase during decompressional boiling of ascending hydrothermal fluids. Variable vapour input leads to differences in H2 concentration among springs. Analysis of 50 metagenomes from a variety of YNP springs reveals that genes encoding oxidative hydrogenases are enriched in communities inhabiting springs sourced with vapour-phase gas. Three springs in the Smokejumper (SJ) area of YNP that are sourced with vapour-phase gas and with the most H2 in YNP were examined to determine the fate of H2 . SJ3 had the most H2 , the most 16S rRNA gene templates and the greatest abundance of culturable hydrogenotrophic and autotrophic cells of the three springs. Metagenomics and transcriptomics of SJ3 reveal a diverse community comprised of abundant populations expressing genes involved in H2 oxidation and carbon dioxide fixation. These observations suggest a link between geologic processes that generate and source H2 to hot springs and the distribution of organisms that use H2 to generate energy.

The rates of microbial and abiotic iron oxidation were determined in a variety of cold (T = 9–12 °C), circumneutral (pH = 5.5–9.0) environments in the Swiss Alps. These habitats include iron–bicarb...

Hot springs integrate hydrologic and geologic processes that vary over short- and long-term time scales. However, the influence of temporal hydrologic and geologic change on hot spring biodiversity is unknown. Here, we coordinated near-weekly, cross-seasonal (~140 days) geochemical and microbial community analyses of three widely studied hot springs with local precipitation data in Yellowstone National Park. One spring ('HFS') exhibited statistically significant, coupled microbial and geochemical variation across seasons that was associated with recent precipitation patterns. Two other spring communities, 'CP' and 'DS', exhibited minimal to no variation across seasons. Variability in the seasonal response of springs is attributed to differences in the timing and extent of aquifer recharge with oxidized near-surface water from precipitation. This influx of oxidized water is associated with changes in community composition, and in particular, the abundances of aerobic sulfide-/sulfur-oxidizers that can acidify waters. During sampling, a new spring formed after a period of heavy precipitation and its successional dynamics were also influenced by surface water recharge. Collectively, these results indicate that changes in short-term hydrology associated with precipitation can impact hot spring geochemistry and microbial biodiversity. These results point to potential susceptibility of certain hot springs and their biodiversity to sustained, longer-term hydrologic changes.

Thermodynamic calculations provide valuable insights into the reactions that drive the profound fluid transformations during serpentinization, where surface fluids are transformed into some of the ...

Sampling and genomic efforts over the past decade have revealed an enormous quantity and diversity of life in Earth's extreme environments. This new knowledge of life on Earth poses the challenge of understandingits molecular basis in such inhospitable conditions, given that such conditions lead to loss of structure and of function in biomolecules from mesophiles. In this review, we discuss the physicochemical properties of extreme environments. We present the state of recent progress in extreme environmental genomics. We then present an overview of our current understanding of the biomolecular adaptation to extreme conditions. As our current and future understanding of biomolecular structure–function relationships in extremophiles requires methodologies adapted to extremes of pressure, temperature, and chemical composition, advances in instrumentation for probing biophysical properties under extreme conditions are presented. Finally, we briefly discuss possible future directions in extreme biophysics.

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.

Serpentinization is a weathering process in which ultramafic rocks react with water, generating a range of products, including serpentine and other minerals, in addition to H₂ and low-molecular-weight hydrocarbons that are capable of sustaining microbial life. Lipid biomarker analyses of serpentinite-hosted ecosystems hold promise as tools for investigating microbial activity in ancient Earth environments and other terrestrial planets such as Mars because lipids have the potential for longer term preservation relative to DNA, proteins, and other more labile organic molecules. Here, we report the first lipid biomarker record of microbial activity in the mantle section of the Samail Ophiolite, in the Sultanate of Oman, a site undergoing active serpentinization. We detected isoprenoidal (archaeal) and branched (bacterial) glycerol dialkyl glycerol tetraether (GDGT) lipids, including those with 0–3 cyclopentane moieties, and crenarchaeol, an isoprenoidal GDGT containing four cyclopentane and one cyclohexane moieties, as well as monoether lipids and fatty acids indicative of sulfate-reducing bacteria. Comparison of our geochemical data and 16S rRNA data from the Samail Ophiolite with those from other serpentinite-hosted sites identifies the existence of a common core serpentinization microbiome. In light of these findings, we also discuss the preservation potential of serpentinite lipid biomarker assemblages on Earth and Mars. Continuing investigations of the Samail Ophiolite and other terrestrial analogues will enhance our understanding of microbial habitability and diversity in serpentinite-hosted environments on Earth and elsewhere in the Solar System.

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.

Reduction of carbon–carbon π-bonds has been demonstrated using iron powder as the reductant and simple powdered nickel as the catalyst in water as the solvent at 250 °C and the saturated water vapor pressure, 40 bars. Stereochemical, kinetic and electronic probes of the mechanism suggest reaction via a conventional Horiuti–Polyani process for hydrogenation at the nickel metal surface. Selective reduction of carbon–carbon π-bonds is observed in the presence of other functional groups. The reactions use benign and Earth-abundant reagents that are at low depletion risk and take place in water as the only solvent under conditions that are characteristic of many geochemical processes.

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...

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.

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.

Various classes of microbial and biomolecular evidence from global studies in marine and continental settings are used to identify a set of reactions that appear to support microbial metabolism during serpentinization of ultramafic rocks. Geochemical data from serpentinizing ecosystems in the Samail ophiolite of Oman are used to evaluate the extent of disequilibria that can support this set of microbial metabolisms, and to provide a ranking of potential metabolic energy sources in hyperalkaline fluids that are direct products of serpentinization. Results are used to construct hypotheses for how microbial metabolism may be supported in the subsurface for two cases: ecosystems hosted in rocks that have already undergone significant serpentinization, and those hosted by deeper, active serpentinization processes.

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.

Maximizing scientific return is critical to the success of space exploration. During the SUBSEA project, which explored the Sea Cliff vent site aboard the E/V Nautilus as an analog for hydrothermal systems on Ocean Worlds, we used forward geochemical modeling to guide decision-making during the process of exploration. Before the expedition, we performed 1670 reaction-path calculations to simulate water-rock interactions during hydrothermal circulation covering wide ranges of reaction conditions to predict the diversity of possible chemical compositions and energy available for chemosynthetic microorganisms at the Sea Cliff vents. Calculation of the information entropy of predicted concentrations of major solutes and pH allowed us to identify dissolved silica as the chemical species capable of yielding the most information about reaction conditions; as such, the measurement of this parameter was implemented aboard ship for our field program. Using telepresence, results of onboard chemical analyses of fluid samples collected during seafloor Dive n were sent to our shore-based scientific team, who processed the data and used the outcomes to inform the design of Dive n ​+ ​2. Combining data processing with forward modeling revealed, within just two dives, that all the observed fluids venting from 10 °C to 300 ​°C most likely resulted from simple conservative mixing between seawater and a common hydrothermal fluid end-member: the result of reaction of seawater with basalt at ≥350 ​°C. Identification of these reaction conditions early within the cruise allowed additional calculations to be performed to quantify the energy available from redox disequilibria as a function of vent-fluid temperatures as they exited the seafloor. These calculations can help inform and optimize real-time microbiological sampling and culture experiments onboard the ship during field expeditions. The success of our approach coupling forward modeling and onboard ship analyses allowed improved efficiency in completing process studies at the Sea Cliff vent site, providing time for further exploration and sampling of a newly discovered vent site: Apollo. This study demonstrates a novel application of forward and real-time modeling for scientific exploration that allows the time required for result-informed decision making to be reduced from years to hours – an essential breakthrough for future space exploration missions.

The biogenic elements, H, C, N, O, P and S, have a long cosmic history, whose evolution can still be observed in diverse locales of the known universe, from interstellar clouds of gas and dust, to pre-stellar cores, nebulas, protoplanetary discs, planets and planetesimals. The best analytical window into this cosmochemical evolution as it neared Earth has been provided so far by the small bodies of the Solar System, some of which were not significantly altered by the high gravitational pressures and temperatures that accompanied the formation of larger planets and may carry a pristine record of early nebular chemistry. Asteroids have delivered such records, as their fragments reach the Earth frequently and become available for laboratory analyses. The Carbonaceous Chondrite meteorites (CC) are a group of such fragments with the further distinction of containing abundant organic materials with structures as diverse as kerogen-like macromolecules and simpler compounds with identical counterparts in Earth's biosphere. All have revealed a lineage to cosmochemical synthetic regimes. Several CC show that asteroids underwent aqueous alteration of their minerals or rock metamorphism but may yet yield clues to the reactivity of organic compounds during parent-body processes, on asteroids as well as larger ocean worlds and planets. Whether the exogenous delivery by meteorites held an advantage in Earth's molecular evolution remains an open question as many others regarding the origins of life are. Nonetheless, the natural samples of meteorites allow exploring the physical and chemical processes that might have led to a selected chemical pool amenable to the onset of life. Graphical Abstract ᅟ.