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Quantitative information regarding the endmember composition of the gas and oil that flowed from the Macondo well during the Deepwater Horizon oil spill is essential for determining the oil flow rate, total oil volume released, and trajectories and fates of hydrocarbon components in the marine environment. Using isobaric gas-tight samplers, we collected discrete samples directly above the Macondo well on June 21, 2010, and analyzed the gas and oil. We found that the fluids flowing from the Macondo well had a gas-to-oil ratio of 1,600 standard cubic feet per petroleum barrel. Based on the measured endmember gas-to-oil ratio and the Federally estimated net liquid oil release of 4.1 million barrels, the total amount of C1-C5 hydrocarbons released to the water column was 1.7 × 1011 g. The endmember gas and oil compositions then enabled us to study the fractionation of petroleum hydrocarbons in discrete water samples collected in June 2010 within a southwest trending hydrocarbon-enriched plume of neutrally buoyant water at a water depth of 1,100 m. The most abundant petroleum hydrocarbons larger than C1-C5 were benzene, toluene, ethylbenzene, and total xylenes at concentrations up to 78 μg L-1. Comparison of the endmember gas and oil composition with the composition of water column samples showed that the plume was preferentially enriched with water-soluble components, indicating that aqueous dissolution played a major role in plume formation, whereas the fates of relatively insoluble petroleum components were initially controlled by other processes. [ABSTRACT FROM AUTHOR]

Subseafloor mixing of high-temperature hot-spring fluids with cold seawater creates intermediate-temperature diffuse fluids that are replete with potential chemical energy. This energy can be harnessed by a chemosynthetic biosphere that permeates hydrothermal regions on Earth. Shifts in the abundance of redoxreactive species in diffuse fluids are often interpreted to reflect the direct influence of subseafloor microbial activity on fluid geochemical budgets. Here, we examine hydrothermal fluids venting at 44 to 149 °C at the Piccard hydrothermal field that span the canonical 122 °C limit to life, and thus provide a rare opportunity to study the transition between habitable and uninhabitable environments. In contrast with previous studies, we show that hydrocarbons are contributed by biomass pyrolysis, while abiotic sulfate (SO42−) reduction produces large depletions in H2. The latter process consumes energy that could otherwise support key metabolic strategies employed by the subseafloor biosphere. Available Gibbs free energy is reduced by 71 to 86% across the habitable temperature range for both hydrogenotrophic SO42− reduction to hydrogen sulfide (H2S) and carbon dioxide (CO2) reduction to methane (CH4). The abiotic H2 sink we identify has implications for the productivity of subseafloor microbial ecosystems and is an important process to consider within models of H2 production and consumption in young oceanic crust. [ABSTRACT FROM AUTHOR]

Sampling of paired black smoker chimney linings and seafloor hydrothermal vent fluids supports the development of trace element proxies for sulfide mineral deposition environments by facilitating analyses of trace element partitioning between mineral and fluid phases under well-constrained physiochemical conditions. Here, concentrations of Co, Ni, Ga, Ag, and In in chalcopyrite lining 22 black smoker chimneys (29 for Co, Ag, and In) are measured using secondary ion mass spectrometry (SIMS) calibrated against inductively coupled plasma mass spectrometry (ICP-MS) and NIST-traceable reference solutions. To provide additional data on the trace element concentrations of vent fluid pairs for 19 of the 29 black smoker chimney linings investigated, this paper also presents new ICP-MS data for 33 hydrothermal vent fluids collected from the Tahi Moana-1, ABE, Tu'i Malila, and Mariner vent fields on the Eastern Lau Spreading Center and Valu Fa Ridge. The chalcopyrite black smoker chimney linings investigated represent a variety of temperature (269–395 °C), chemical (e.g., pH (at 25 °C) = 2.3–4.4), and geologic conditions. Electron microprobe results indicate that mineral stoichiometry ranges from stoichiometric chalcopyrite to mol Cu : mol Fe = 0.65. Trace element concentrations obtained by SIMS are: Co (<2 ng/g–760 μg/g), Ni (<17 ng/g–454 μg/g), Ga (<0.9 ng/g–48 μg/g), Ag (60 μg/g–3800 μg/g), In (<0.5 ng/g–270 μg/g). Concentrations of Ag in chalcopyrite strongly correlate with the free ion activity ratio of {Ag+}:{Cu+} in paired vent fluids, with high Ag concentrations in chalcopyrite indicating formation from near neutral vent fluids containing low Cu concentrations or low-pH vent fluids with high Ag concentrations attributable to subsurface Ag remobilization. Chalcopyrite with low Ag precipitates from low-pH Cu-rich fluids unaffected by extensive Ag remobilization. Concentrations of Ga and In in chalcopyrite exhibit a negative trend with vent fluid pH, possibly reflecting the strength of Ga and In OH− complexes. Thus, Ga and In concentrations differentiate Ag-rich chalcopyrite formed from near-neutral Cu-poor vent fluids or that formed from Ag-rich low-pH vent fluids. In contrast, Co and Ni exhibit no trend with fluid data, but correlate with mineral Cu:Fe ratios, possibly reflecting the greater availability of Fe(II) lattice sites or paired substitution of 2+ ions. Overall, this study demonstrates the potential of paired vent fluid and black smoker chimney samples to provide insight into the partitioning of trace elements in sulfide mineral deposition environments and related proxies of important fluid parameters such as pH and metal concentrations. This study also demonstrates the utility of SIMS to precisely analyze trace elements in chalcopyrite at high spatial resolutions and low detection limits. [ABSTRACT FROM AUTHOR]

The composition of submarine hydrothermal vent fluids is affected by a variety of processes, such as interaction of heated seawater with rocks and sediments, addition of magmatic fluids, as well as phase separation and segregation. How these processes specifically affect the vent fluid composition is still poorly understood. In particular, the relative role of phase separation and magmatic degassing, which is common in arc/back-arc hydrothermal systems, is not well known. To provide new insights into these processes, we analysed B contents and isotope ratios in hydrothermal vent fluids and volcanic rocks from the Manus Basin, Papua New Guinea, and Nifonea volcano, New Hebrides back-arc. These fluids show a range of salinities, gas contents, acidities, and host rock compositions; many of them are influenced by phase separation and by addition of magmatic volatiles (both CO 2 and SO 2 ). Previous studies of hydrothermal vents in arc/back-arc settings suggest that B contents and isotopic composition of vent fluids are controlled by interactions between seawater, basement and sediments, and propose that phase separation and magmatic fluids play only a subordinate role. In our study, we demonstrate that vent fluids with minor magmatic input indeed reflect the interaction between seawater and oceanic crust. In contrast, the low-salinity Nifonea fluids and some of the acid-sulphate fluids from the Manus Basin have higher B contents as expected, whereas other volatile-rich fluids from the Manus Basin show B depletions. The lack of correlation between B contents and the intensity of magmatic fluid influx (CO 2 and SO 2 ) may indicate that magma degassing is not responsible for the B enrichments or depletions in these vent fluids. B enrichments might be related to preferential partitioning of B into the vapour phase during phase separation under PT-conditions well above the two-phase curve and critical line (i.e. T >> T critical , P >> P critical ). However, this cannot explain the low B concentrations in the vapour-rich vent fluids from the Manus Basin and the low B isotope ratios in the Nifonea fluids. Instead, we propose that B concentrations and isotope ratios in submarine vent fluids largely depend on the residence and reaction time of the vent fluid in the subsurface. In general, all vent fluids are still influenced by water-rock interaction during hydrothermal circulation. However, vent fluids with short residence times define a trend towards lower B concentrations and isotope ratios, which can be explained by mixing between hydrothermal and magmatic fluid, which is similar to the composition of the host rock. In contrast, the B signature of the magmatic fluid can be overprinted due to preferential mobilisation of B from the oceanic crust into vapour-rich fluids at longer reaction times. Thus, B may provide a tool for estimating the extent of B leaching and hence hydrothermal alteration in the subseafloor. [ABSTRACT FROM AUTHOR]

Below the seafloor at deep-sea hot springs, mixing of geothermal fluids with seawater supports a potentially vast microbial ecosystem. Although the identity of subseafloor microorganisms is largely known, their effect on deep-ocean biogeochemical cycles cannot be predicted without quantitative measurements of their metabolic rates and growth efficiency. Here, we report on incubations of subseafloor fluids under in situ conditions that quantitatively constrain subseafloor primary productivity, biomass standing stock, and turnover time. Single-cell-based activity measurements and 16S rRNA-gene analysis showed that Campylobacteria dominated carbon fixation and that oxygen concentration and temperature drove niche partitioning of closely related phylotypes. Our data reveal a very active subseafloor biosphere that fixes carbon at a rate of up to 321 µg C⋅L-1⋅d-1, turns over rapidly within tens of hours, rivals the productivity of chemosynthetic symbioses above the seafloor, and significantly influences deep-ocean biogeochemical cycling. [ABSTRACT FROM AUTHOR]

Hosted in basaltic substrate on the ultra-slow spreading Mid-Cayman Rise, the Piccard hydrothermal field is the deepest currently known seafloor hot-spring (4957–4987 m). Due to its great depth, the Piccard site is an excellent natural system for investigating the influence of extreme pressure on the formation of submarine vent fluids. To investigate the role of rock composition and deep circulation conditions on fluid chemistry, the abundance and isotopic composition of organic, inorganic, and dissolved volatile species in high temperature vent fluids at Piccard were examined in samples collected in 2012 and 2013. Fluids from the Beebe Vents and Beebe Woods black smokers vent at a maximum temperature of 398 °C at the seafloor, however several lines of evidence derived from inorganic chemistry (Cl, SiO 2 , Ca, Br, Fe, Cu, Mn) support fluid formation at much higher temperatures in the subsurface. These high temperatures, potentially in excess of 500 °C, are attainable due to the great depth of the system. Our data indicate that a single deep-rooted source fluid feeds high temperature vents across the entire Piccard field. High temperature Piccard fluid H 2 abundances (19.9 mM) are even higher than those observed in many ultramafic-influenced systems, such as the Rainbow (16 mM) and the Von Damm hydrothermal fields (18.2 mM). In the case of Piccard, however, these extremely high H 2 abundances can be generated from fluid-basalt reaction occurring at very high temperatures. Magmatic and thermogenic sources of carbon in the high temperature black smoker vents are described. Dissolved ΣCO 2 is likely of magmatic origin, CH 4 may originate from a combination of thermogenic sources and leaching of abiotic CH 4 from mineral-hosted fluid inclusions, and CO abundances are at equilibrium with the water–gas shift reaction. Longer-chained n-alkanes (C 2 H 6 , C 3 H 8 , n- C 4 H 10 , i- C 4 H 10 ) may derive from thermal alteration of dissolved and particulate organic carbon sourced from the original seawater source, entrainment of microbial ecosystems peripheral to high temperature venting, and/or abiotic mantle sources. Dissolved ΣHCOOH in the Beebe Woods fluid is consistent with thermodynamic equilibrium for abiotic production via ΣCO 2 reduction with H 2 at 354 °C measured temperature. A lack of ΣHCOOH in the relatively higher temperature 398 °C Beebe Vent fluids demonstrates the temperature sensitivity of this equilibrium. Abundant basaltic seafloor outcrops and the axial location of the vent field, along with multiple lines of geochemical evidence, support extremely high temperature fluid-rock reaction with mafic substrate as the dominant control on Piccard fluid chemistry. These results expand the known diversity of vent fluid composition, with implications for supporting microbiological life in both the modern and ancient ocean. [ABSTRACT FROM AUTHOR]

Hot-spring fluids emanating from deep-sea vents hosted in unsedimented ultramafic and mafic rock commonly contain high concentrations of methane. Multiple hypotheses have been proposed for the origin(s) of this methane, ranging from synthesis via reduction of aqueous inorganic carbon (∑CO 2 ) during active fluid circulation to leaching of methane-rich fluid inclusions from plutonic rocks of the oceanic crust. To further resolve the process(es) responsible for methane generation in these systems, we determined the relative abundances of several methane isotopologues (including 13 CH 3 D, a “clumped” isotopologue containing two rare isotope substitutions) in hot-spring source fluids sampled from four geochemically-distinct hydrothermal vent fields (Rainbow, Von Damm, Lost City, and Lucky Strike). Apparent equilibrium temperatures retrieved from methane clumped isotopologue analyses average 310 - 42 + 53  °C, with no apparent relation to the wide range of fluid temperatures (96–370 °C) and chemical compositions (pH, [H 2 ], [∑CO 2 ], [CH 4 ]) represented. Combined with very similar bulk stable isotope ratios ( 13 C/ 12 C and D/H) of methane across the suite of hydrothermal fluids, all available geochemical and isotopic data suggest a common mechanism of methane generation at depth that is disconnected from active fluid circulation. Attainment of equilibrium amongst methane isotopologues at temperatures of ca. 270–360 °C is compatible with the thermodynamically-favorable reduction of CO 2 to CH 4 at temperatures at or below ca. 400 °C under redox conditions characterizing intrusive rocks derived from sub-ridge melts. Collectively, the observations support a model where methane-rich aqueous fluids, known to be trapped in rocks of the oceanic lithosphere, are liberated from host rocks during hydrothermal circulation and perhaps represent the major source of methane venting with thermal waters at unsedimented hydrothermal fields. The results also provide further evidence that water-rock reactions occurring at temperatures lower than 200 °C do not contribute significantly to the quantities of methane venting at mid-ocean ridge hot springs. [ABSTRACT FROM AUTHOR]

At deep-sea hydrothermal vents, a large source of potential chemical energy is created when reducing vent fluid and oxidizing seawater mix. In this environment, chemolithoautotrophic microbes catalyze exergonic redox reactions which in turn provide the energy needed to fuel their growth and the fixation of CO 2 into biomass. In addition to producing new organic matter, this process also consumes compounds contained both in vent fluid and entrained seawater ( e.g. H 2 , NO 3 − ). Despite their biogeochemical importance, such reactions have remained difficult to quantify due to methodological limitations. To address this knowledge gap, this study reports a novel application of isobaric gas-tight fluid samplers for conducting incubations of hydrothermal vent fluids at in situ temperature and pressure. Eighteen ~24 h incubations were carried out, representing seven distinct conditions that examine amendments consisting of different electron donors and acceptors. Microbial activity was observed in all treatments, and time series chemical measurements showed that activity was limited by electron acceptor supply, confirming predictions based on geochemical data. Also consistent with these predictions, the presence of nitrate increased rates of hydrogen consumption and yielded ammonium as a product of nitrate respiration. The stoichiometry of predicted redox reactions was also determined, revealing that the sulfur and nitrogen cycles are incompletely understood at deep-sea vents, and likely involve unknown intermediate redox species. Finally, the measured rates of redox processes were either equal to or far greater than what has been reported in previous studies where in situ conditions were not maintained. In addition to providing insights into deep-sea hydrothermal vent biogeochemistry, the methods described herein also offer a practical approach for the incubation of any deep-sea pelagic sample under in situ conditions. [ABSTRACT FROM AUTHOR]

Methane is a key component in the global carbon cycle, with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply substituted "clumped" isotopologues (for example, 13CH3D) has recently emerged as a proxy for determining methane-formation temperatures. However, the effect of biological processes on methane's clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on 13CH3D abundances and results in anomalously elevated formation-temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters. [ABSTRACT FROM AUTHOR]

On May 31, 2010, a direct acoustic measurement method was used to quantify fluid leakage rate from the Deepwater Horizon Macondo well prior to removal of its broken riser. This method utilized an acoustic imaging sonar and acoustic Doppler sonar operating onboard a remotely operated vehicle for noncontact measurement of flow cross-section and velocity from the well's two leak sites. Over 2,500 sonar cross-sections and over 85,000 Doppler velocity measurements were recorded during the acquisition process. These data were then applied to turbulent jet and plume flow models to account for entrained water and calculate a combined hydrocarbon flow rate from the two leak sites at seafloor conditions. Based on the chemical composition of end-member samples collected from within the well, this bulk volumetric rate was then normalized to account for contributions from gases and condensates at initial leak source conditions. Results from this investigation indicate that on May 31, 2010, the well's oil flow rate was approximately 0.10 ± 0.017 m³ s-1 at seafloor conditions, or approximately 85 ± 15 kg s-1 (7.4 ± 1.3 Gg d-1), equivalent to approximately 57,000 ± 9,800 barrels of oil per day at surface conditions. End-member chemical composition indicates that this oil release rate was accompanied by approximately an additional 24 ± 4.2 kg s-1 (2.1 ± 0.37 Gg d-1) of natural gas (methane through pentanes), yielding a total hydrocarbon release rate of 110 ± 19 kg s-1 (9.5 ± 1.6 Gg d-1). [ABSTRACT FROM AUTHOR]

The article discusses role of symbiotic organisms in creation of regional scale ecological niche partitioning. It explores the snail microbial symbiotic relationship which prevails at deep-sea hydrothermal vents that provides an opportunity for co-existence of both the organisms through utilization of their ecological habitats. It highlights that the process of niche evolution at the hydrothermal vent sites is dependent upon the physiological capacity of symbiotic organisms.

Most of the geologic CO 2 entering Earth's atmosphere and oceans is emitted along plate margins. While C-cycling at mid-ocean ridges and subduction zones has been studied for decades, little attention has been paid to degassing of magmatic CO 2 and mineral carbonation of mantle rocks in oceanic transform faults. We studied the formation of soapstone (magnesite-talc rock) and other magnesite-bearing assemblages during mineral carbonation of mantle peridotite in the St. Paul's transform fault, equatorial Atlantic. Clumped carbonate thermometry of soapstone yields a formation (or equilibration) temperature of 147 ± 13 °C which, based on thermodynamic constraints, suggests that CO 2( aq ) concentrations of the hydrothermal fluid were at least an order of magnitude higher than in seawater. The association of magnesite with apatite in veins, magnesite with a δ 13 . Melt-rock interaction related to gas-rich alkali olivine basalt volcanism near the St. Paul's Rocks archipelago is manifested in systematic changes in peridotite compositions, notably a strong enrichment in incompatible elements with decreasing MgO/SiO 2 in hydrothermal fluids point to magmatic degassing and melt-impregnation as the main source of CO 2 . Melt-rock interaction related to gas-rich alkali olivine basalt volcanism near the St. Paul's Rocks archipelago is manifested in systematic changes in peridotite compositions, notably a strong enrichment in incompatible elements with decreasing MgO/SiO 2 . These findings reveal a previously undocumented aspect of the geologic carbon cycle in one of the largest oceanic transform faults: Fueled by magmatism in or below the root zone of the transform fault and subsequent degassing, the fault constitutes a conduit for CO 2 -rich hydrothermal fluids, while carbonation of peridotite represents a vast sink for the emitted CO 2 ., Competing Interests: Competing interests statement:The authors declare no competing interest.

Single-celled microbial eukaryotes inhabit deep-sea hydrothermal vent environments and play critical ecological roles in the vent-associated microbial food web. 18S rRNA amplicon sequencing of diffuse venting fluids from four geographically- and geochemically-distinct hydrothermal vent fields was applied to investigate community diversity patterns among protistan assemblages. The four vent fields include Axial Seamount at the Juan de Fuca Ridge, Sea Cliff and Apollo at the Gorda Ridge, all in the NE Pacific Ocean, and Piccard and Von Damm at the Mid-Cayman Rise in the Caribbean Sea. We describe species diversity patterns with respect to hydrothermal vent field and sample type, identify putative vent endemic microbial eukaryotes, and test how vent fluid geochemistry may influence microbial community diversity. At a semi-global scale, microbial eukaryotic communities at deep-sea vents were composed of similar proportions of dinoflagellates, ciliates, Rhizaria, and stramenopiles. Individual vent fields supported distinct and highly diverse assemblages of protists that included potentially endemic or novel vent-associated strains. These findings represent a census of deep-sea hydrothermal vent protistan communities. Protistan diversity, which is shaped by the hydrothermal vent environment at a local scale, ultimately influences the vent-associated microbial food web and the broader deep-sea carbon cycle., (© 2022 John Wiley & Sons Ltd.)

Microbial eukaryotes (or protists) in marine ecosystems are a link between primary producers and all higher trophic levels, and the rate at which heterotrophic protistan grazers consume microbial prey is a key mechanism for carbon transport and recycling in microbial food webs. At deep-sea hydrothermal vents, chemosynthetic bacteria and archaea form the base of a food web that functions in the absence of sunlight, but the role of protistan grazers in these highly productive ecosystems is largely unexplored. Here, we pair grazing experiments with a molecular survey to quantify protistan grazing and to characterize the composition of vent-associated protists in low-temperature diffuse venting fluids from Gorda Ridge in the northeast Pacific Ocean. Results reveal protists exert higher predation pressure at vents compared to the surrounding deep seawater environment and may account for consuming 28 to 62% of the daily stock of prokaryotic biomass within discharging hydrothermal vent fluids. The vent-associated protistan community was more species rich relative to the background deep sea, and patterns in the distribution and co-occurrence of vent microbes provide additional insights into potential predator-prey interactions. Ciliates, followed by dinoflagellates, Syndiniales, rhizaria, and stramenopiles, dominated the vent protistan community and included bacterivorous species, species known to host symbionts, and parasites. Our findings provide an estimate of protistan grazing pressure within hydrothermal vent food webs, highlighting the important role that diverse protistan communities play in deep-sea carbon cycling., Competing Interests: The authors declare no competing interest.

Symbioses between invertebrate animals and chemosynthetic bacteria form the basis of hydrothermal vent ecosystems worldwide. In the Lau Basin, deep-sea vent snails of the genus Alviniconcha associate with either Gammaproteobacteria (A. kojimai, A. strummeri) or Campylobacteria (A. boucheti) that use sulfide and/or hydrogen as energy sources. While the A. boucheti host-symbiont combination (holobiont) dominates at vents with higher concentrations of sulfide and hydrogen, the A. kojimai and A. strummeri holobionts are more abundant at sites with lower concentrations of these reductants. We posit that adaptive differences in symbiont physiology and gene regulation might influence the observed niche partitioning between host taxa. To test this hypothesis, we used high-pressure respirometers to measure symbiont metabolic rates and examine changes in gene expression among holobionts exposed to in situ concentrations of hydrogen (H 2 : ~25 µM) or hydrogen sulfide (H 2 S: ~120 µM). The campylobacterial symbiont exhibited the lowest rate of H 2 S oxidation but the highest rate of H 2 oxidation, with fewer transcriptional changes and less carbon fixation relative to the gammaproteobacterial symbionts under each experimental condition. These data reveal potential physiological adaptations among symbiont types, which may account for the observed net differences in metabolic activity and contribute to the observed niche segregation among holobionts.

We examined the mineralogical, chemical and isotopic compositions of secondary fluid inclusions in olivine-rich rocks from two active serpentinization systems: the Von Damm hydrothermal field (Mid-Cayman Rise) and the Zambales ophiolite (Philippines). Peridotite, troctolite and gabbroic rocks in these systems contain abundant CH 4 -rich secondary inclusions in olivine, with less abundant inclusions in plagioclase and clinopyroxene. Olivine-hosted secondary inclusions are chiefly composed of CH 4 and minor H 2 , in addition to secondary minerals including serpentine, brucite, magnetite and carbonates. Secondary inclusions in plagioclase are dominated by CH 4 with variable amounts of H 2 and H 2 O, while those in clinopyroxene contain only CH 4 . We determined hydrocarbon abundances and stable carbon isotope compositions by crushing whole rocks and analysing the released volatiles using isotope ratio monitoring-gas chromatography mass spectrometry. Bulk rock gas analyses yielded appreciable quantities of CH 4 and C 2 H 6 in samples from Cayman (4-313 nmol g -1 CH 4 and 0.02-0.99 nmol g -1 C 2 H 6 ), with lesser amounts in samples from Zambales (2-37 nmol g -1 CH 4 and 0.004-0.082 nmol g -1 C 2 H 6 ). Mafic and ultramafic rocks at Cayman exhibit δ 13 C CH 4 values of -16.7‰ to -4.4‰ and δ 13 C C 2 H 6 values of -20.3‰ to +0.7‰. Ultramafic rocks from Zambales exhibit δ 13 C CH 4 values of -12.4‰ to -2.8‰ and δ 13 C C 2 H 6 values of -1.2‰ to -0.9‰. Similarities in the carbon isotopic compositions of CH 4 and C 2 H 6 in plutonic rocks, Von Damm hydrothermal fluids, and Zambales gas seeps suggest that leaching of fluid inclusions may provide a significant contribution of abiotic hydrocarbons to deep-sea vent fluids and ophiolite-hosted gas seeps. Isotopic compositions of CH 4 and C 2 H 6 from a variety of hydrothermal fields hosted in olivine-rich rocks that are similar to those in Von Damm vent fluids further support the idea that a significant portion of abiotic hydrocarbons in ultramafic-influenced vent fluids is derived from fluid inclusions. This article is part of a discussion meeting issue 'Serpentinite in the Earth system'.

The conditions of methane (CH 4 ) formation in olivine-hosted secondary fluid inclusions and their prevalence in peridotite and gabbroic rocks from a wide range of geological settings were assessed using confocal Raman spectroscopy, optical and scanning electron microscopy, electron microprobe analysis, and thermodynamic modeling. Detailed examination of 160 samples from ultraslow- to fast-spreading midocean ridges, subduction zones, and ophiolites revealed that hydrogen (H 2 ) and CH 4 formation linked to serpentinization within olivine-hosted secondary fluid inclusions is a widespread process. Fluid inclusion contents are dominated by serpentine, brucite, and magnetite, as well as CH 4( g ) and H 2( g ) in varying proportions, consistent with serpentinization under strongly reducing, closed-system conditions. Thermodynamic constraints indicate that aqueous fluids entering the upper mantle or lower oceanic crust are trapped in olivine as secondary fluid inclusions at temperatures higher than ∼400 °C. When temperatures decrease below ∼340 °C, serpentinization of olivine lining the walls of the fluid inclusions leads to a near-quantitative consumption of trapped liquid H 2 O. The generation of molecular H 2 through precipitation of Fe(III)-rich daughter minerals results in conditions that are conducive to the reduction of inorganic carbon and the formation of CH 4 Once formed, CH 4( g ) and H 2( g ) can be stored over geological timescales until extracted by dissolution or fracturing of the olivine host. Fluid inclusions represent a widespread and significant source of abiotic CH 4 and H 2 in submarine and subaerial vent systems on Earth, and possibly elsewhere in the solar system., Competing Interests: The authors declare no conflict of interest.

Arguments for an abiotic origin of low-molecular weight organic compounds in deep-sea hot springs are compelling owing to implications for the sustenance of deep biosphere microbial communities and their potential role in the origin of life. Theory predicts that warm H2-rich fluids, like those emanating from serpentinizing hydrothermal systems, create a favorable thermodynamic drive for the abiotic generation of organic compounds from inorganic precursors. Here, we constrain two distinct reaction pathways for abiotic organic synthesis in the natural environment at the Von Damm hydrothermal field and delineate spatially where inorganic carbon is converted into bioavailable reduced carbon. We reveal that carbon transformation reactions in a single system can progress over hours, days, and up to thousands of years. Previous studies have suggested that CH4 and higher hydrocarbons in ultramafic hydrothermal systems were dependent on H2 generation during active serpentinization. Rather, our results indicate that CH4 found in vent fluids is formed in H2-rich fluid inclusions, and higher n-alkanes may likely be derived from the same source. This finding implies that, in contrast with current paradigms, these compounds may form independently of actively circulating serpentinizing fluids in ultramafic-influenced systems. Conversely, widespread production of formate by ΣCO2 reduction at Von Damm occurs rapidly during shallow subsurface mixing of the same fluids, which may support anaerobic methanogenesis. Our finding of abiogenic formate in deep-sea hot springs has significant implications for microbial life strategies in the present-day deep biosphere as well as early life on Earth and beyond.

Simple alkyl thiols such as methanethiol (CH3SH) are widely speculated to form in seafloor hot spring fluids. Putative CH3SH synthesis by abiotic (nonbiological) reduction of inorganic carbon (CO2 or CO) has been invoked as an initiation reaction for the emergence of protometabolism and microbial life in primordial hydrothermal settings. Thiols are also presumptive ligands for hydrothermal trace metals and potential fuels for associated microbial communities. In an effort to constrain sources and sinks of CH3SH in seafloor hydrothermal systems, we determined for the first time its abundance in diverse hydrothermal fluids emanating from ultramafic, mafic, and sediment-covered midocean ridge settings. Our data demonstrate that the distribution of CH3SH is inconsistent with metastable equilibrium with inorganic carbon, indicating that production by abiotic carbon reduction is more limited than previously proposed. CH3SH concentrations are uniformly low (∼10(-8) M) in high-temperature fluids (>200 °C) from all unsedimented systems and, in many cases, suggestive of metastable equilibrium with CH4 instead. Associated low-temperature fluids (<200 °C) formed by admixing of seawater, however, are invariably enriched in CH3SH (up to ∼10(-6) M) along with NH4(+) and low-molecular-weight hydrocarbons relative to high-temperature source fluids, resembling our observations from a sediment-hosted system. This strongly implicates thermogenic interactions between upwelling fluids and microbial biomass or associated dissolved organic matter during subsurface mixing in crustal aquifers. Widespread thermal degradation of subsurface organic matter may be an important source of organic production in unsedimented hydrothermal systems and may influence microbial metabolic strategies in cooler near-seafloor and plume habitats.