Reeves
Eoghan P.
Reeves
Eoghan P.
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PreprintGeochemistry of hydrothermal fluids from the PACMANUS, Northeast Pual and Vienna Woods hydrothermal fields, Manus Basin, Papua New Guinea( 2010-10-29) Reeves, Eoghan P. ; Seewald, Jeffrey S. ; Saccocia, Peter J. ; Bach, Wolfgang ; Craddock, Paul R. ; Shanks, Wayne C. ; Sylva, Sean P. ; Walsh, Emily ; Pichler, Thomas ; Rosner, MartinProcesses controlling the composition of seafloor hydrothermal fluids in silicic back-arc or neararc crustal settings remain poorly constrained despite growing evidence for extensive magmatichydrothermal activity in such environments. We conducted a survey of vent fluid compositions from two contrasting sites in the Manus back-arc basin, Papua New Guinea, to examine the influence of variations in host rock composition and magmatic inputs (both a function of arc proximity) on hydrothermal fluid chemistry. Fluid samples were collected from felsic-hosted hydrothermal vent fields located on Pual Ridge (PACMANUS and Northeast (NE) Pual) near the active New Britain Arc and a basalt-hosted vent field (Vienna Woods) located farther from the arc on the Manus Spreading Center. Vienna Woods fluids were characterized by relatively uniform endmember temperatures (273–285°C) and major element compositions, low dissolved CO2 concentrations (4.4mmol/kg) and high measured pH (4.2–4.9 at 25°C). Temperatures and compositions were highly variable at PACMANUS/NE Pual and a large, newly discovered vent area (Fenway) was observed to be vigorously venting boiling (358°C) fluid. All PACMANUS fluids are characterized by negative δDH2O values, in contrast to positive values at Vienna Woods, suggesting substantial magmatic water input to circulating fluids at Pual Ridge. Low measured pH (25°C) values (~2.6 to 2.7), high endmember CO2 (up to 274 mmol/kg) and negative δ34SH2S values (down to -2.7‰) in some vent fluids are also consistent with degassing of acid-volatile species from evolved magma. Dissolved CO2 at PACMANUS is more enriched in 13C (-4.1‰ to -2.3‰) than Vienna Woods (-5.2‰ to -5.7‰), suggesting a contribution of slab-derived carbon. The mobile elements (e.g. Li, K, Rb, Cs and B) are also greatly enriched in PACMANUS fluids reflecting increased abundances in the crust there relative to the Manus Spreading Center. Variations in alkali and dissolved gas abundances with Cl at PACMANUS and NE Pual suggest that phase separation has affected fluid chemistry despite the low temperatures of many vents. In further contrast to Vienna Woods, substantial modification of PACMANUS/NE Pual fluids has taken place as a result of seawater of seawater ingress into the upflow zone. Consistently high measured Mg concentrations, trends of increasingly non-conservative SO4 behavior, decreasing endmember Ca/Cl and Sr/Cl ratios with increased Mg indicate extensive subsurface anhydrite deposition is occurring as a result of subsurface seawater entrainment. Decreased pH and endmember Fe/Mn ratios in higher Mg fluids indicate that the associated mixing/cooling gives rise to sulfide deposition and secondary acidity production. Several low temperature (≤80°C) fluids at PACMANUS/NE Pual also show evidence for anhydrite dissolution and water-rock interaction (fixation of B) subsequent to seawater entrainment. Hence, the evolution of fluid compositions at Pual Ridge reflects the cumulative effects of water/rock interaction, admixing and reaction of fluids exsolved from silicic magma, phase separation/segregation and seawater ingress into upflow zones.
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PreprintRare earth element abundances in hydrothermal fluids from the Manus Basin, Papua New Guinea : indicators of sub-seafloor hydrothermal processes in back-arc basins( 2010-05-02) Craddock, Paul R. ; Bach, Wolfgang ; Seewald, Jeffrey S. ; Rouxel, Olivier J. ; Reeves, Eoghan P. ; Tivey, Margaret K.Rare earth element (REE) concentrations are reported for a large suite of seafloor vent fluids from four hydrothermal systems in the Manus back–arc basin (Vienna Woods, PACMANUS, DESMOS and SuSu Knolls vent areas). Sampled vent fluids show a wide range of absolute REE concentrations and chondrite–normalized (REEN) distribution patterns (LaN/SmN ~ 0.6 – 11; LaN/YbN ~ 0.6 – 71; EuN/Eu*N ~ 1 – 55). REEN distribution patterns in different vent fluids range from light–REE enriched, to mid– and heavy–REE enriched, to flat, and have a range of positive Eu–anomalies. This heterogeneity contrasts markedly with relatively uniform REEN distribution patterns of mid–ocean ridge hydrothermal fluids. In Manus Basin fluids, aqueous REE compositions do not inherit directly or show a clear relationship with the REE compositions of primary crustal rocks with which hydrothermal fluids interact. These results suggest that the REEs are less sensitive indicators of primary crustal rock composition despite crustal rocks being the dominant source of REEs in submarine hydrothermal fluids. In contrast, differences in aqueous REE compositions are consistently correlated with differences in fluid pH and ligand (chloride, fluoride and sulfate) concentrations. Our results suggest that the REEs can be used as an indicator of the type of magmatic acid volatile (i.e., presence of HF, SO2) degassing in submarine hydrothermal systems. Additional fluid data suggest that near seafloor mixing between high–temperature hydrothermal fluid and locally entrained seawater at many vent areas in the Manus Basin causes anhydrite precipitation. Anhydrite effectively incorporates REE and likely affects measured fluid REE concentrations, but does not affect their relative distributions.
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PreprintHydrogen isotope exchange between n-alkanes and water under hydrothermal conditions( 2011-03-10) Reeves, Eoghan P. ; Seewald, Jeffrey S. ; Sylva, Sean P.To investigate the extent of hydrogen isotope (2H and 1H) exchange between hydrocarbons and water under hydrothermal conditions, we performed experiments heating C1–C5 n-alkanes in aqueous solutions of varying initial 2H/1H ratios in the presence of a pyrite-pyrrhotite-magnetite redox buffer at 323ºC and 35–36MPa. Extensive and reversible incorporation of water-derived hydrogen into C2–C5 n-alkanes was observed on timescales of months. In contrast, comparatively minor exchange was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding n-alkenes with H2 derived from the disproportionation of water. Rates of δ2H variation in C3+ n-alkanes decreased with time, a trend that is consistent with an asymptotic approach to steady-state isotopic compositions regulated by alkane-water isotopic equilibrium. Substantially slower δ2H variation was observed for ethane relative to C3–C5 n-alkanes, suggesting that the greater stability of C3+ alkenes and isomerization reactions may dramatically enhance rates of 2H/1H exchange in C3+ n-alkanes. Thus, in reducing aqueous environments, reversible reaction of alkenes and their corresponding alkanes facilitates rapid 2H/1H exchange between alkyl- and water-bound hydrogen on relatively short geological timescales at elevated temperatures and pressures. The proximity of some thermogenic and purported abiogenic alkane δ2H values to those predicted for equilibrium 2H/1H fractionation with ambient water suggests that this process may regulate the δ2H signatures of some naturally occurring hydrocarbons.
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ArticleApplication of B, mg, li, and sr isotopes in acid-sulfate vent fluids and volcanic rocks as tracers for fluid-rock interaction in back-arc hydrothermal systems(American Geophysical Union, 2019-11-15) Wilckens, Frederike K. ; Reeves, Eoghan P. ; Bach, Wolfgang ; Seewald, Jeffrey S. ; Kasemann, Simone A.The Manus Basin hosts a broad range of vent fluid compositions typical for arc and back‐arc settings, ranging from black smoker to acid‐sulfate styles of fluid venting, as well as novel intermediate temperature and composition “hybrid” smokers. We investigated B, Li, Mg, and Sr concentrations and isotopic compositions of these different fluid types as well as of fresh and altered rocks from the same study area to understand what controls their compositional variability. In particular, the formation of acid‐sulfate and hybrid smoker fluids is still poorly understood, and their high Mg concentrations are explained either by dissolution of Mg‐bearing minerals in the basement or by mixing between unmodified seawater and magmatic fluids. Mg isotope ratios of the acid‐sulfate fluids from the Manus Basin are seawater‐like, which supports the idea that acid‐sulfate fluids in this study area predominantly form by mixing between unmodified seawater and a Mg‐free magmatic fluid. Changes in the B, Li, and Sr isotope ratios relative to seawater indicate water‐rock interaction in all acid‐sulfate fluids. Further, the combination of δ7Li with B concentrations of the same fluids links changes in δ7Li to changes in (1) basement alteration, (2) water‐to‐rock ratios during water‐rock interaction, and/or (3) the reaction temperature. These isotope systems, thus, allow tracing of basement composition and acid‐sulfate‐driven alteration of the back‐arc crust and help increase our understanding of hydrothermal fluid‐rock interactions and the behavior of fluid‐mobile elements.
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ThesisLaboratory and field-based investigations of subsurface geochemical processes in seafloor hydrothermal systems(Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 2010-06) Reeves, Eoghan P.This thesis presents the results of four discrete investigations into processes governing the organic and inorganic chemical composition of seafloor hydrothermal fluids in a variety of geologic settings. Though Chapters 2 through 5 of this thesis are disparate in focus, each represents a novel investigation aimed at furthering our understanding of subsurface geochemical processes affecting hydrothermal fluid compositions. Chapters 2 and 3 concern the abiotic (nonbiological) formation of organic compounds in high temperature vent fluids, a process which has direct implications for the emergence of life in early Earth settings and sustainment of present day microbial populations in hydrothermal environments. Chapter 2 represents an experimental investigation of methane (CH4) formation under hydrothermal conditions. The overall reduction of carbon dioxide (CO2) to CH4, previously assumed to be kinetically inhibited in the absence of mineral catalysts, is shown to proceed on timescales pertinent to crustal residence times of hydrothermal fluids. In Chapter 3, the abundance of methanethiol (CH3SH), considered to be a crucial precursor for the emergence of primitive chemoautotrophic life, is characterized in vent fluids from ultramafic-, basalt- and sediment-hosted hydrothermal systems. Previous assumptions that CH3SH forms by reduction of CO2 are not supported by the observed distribution in natural systems. Chapter 4 investigates factors regulating the hydrogen isotope composition of hydrocarbons under hydrothermal conditions. Isotopic exchange between low molecular weight n-alkanes and water is shown to be facilitated by metastable equilibrium reactions between alkanes and their corresponding alkenes, which are feasible in natural systems. In Chapter 5, the controls on vent fluid composition in a backarc hydrothermal system are investigated. A comprehensive survey of the inorganic geochemistry of fluids from sites of hydrothermal activity in the eastern Manus Basin indicates that fluids there are influenced by input of acidic magmatic solutions at depth, and subsequently modified by variable extents of seawater entrainment and mixing-related secondary acidity production.
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PreprintThe origin of methanethiol in mid-ocean ridge hydrothermal fluids( 2014-03) Reeves, Eoghan P. ; McDermott, Jill M. ; Seewald, Jeffrey S.Simple alkyl thiols such as methanethiol (CH3SH) are widely speculated to form in seafloor hot spring fluids. Putative CH3SH synthesis by abiotic (non-biological) reduction of inorganic carbon (CO2 or CO) has been invoked as an initiation reaction for the emergence of proto-metabolism 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 mid-ocean ridge settings. Our data demonstrate that the distribution of CH3SH is inconsistent with metastable equilibrium with inorganic carbon, indicating 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 sedimented 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.
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PreprintNonequilibrium clumped isotope signals in microbial methane( 2015-02-09) Wang, David T. ; Gruen, Danielle S. ; Lollar, Barbara Sherwood ; Hinrichs, Kai-Uwe ; Stewart, Lucy C. ; Holden, James F. ; Hristov, Alexander N. ; Pohlman, John W. ; Morrill, Penny L. ; Konneke, Martin ; Delwiche, Kyle B. ; Reeves, Eoghan P. ; Sutcliffe, Chelsea N. ; Ritter, Daniel J. ; Seewald, Jeffrey S. ; McIntosh, Jennifer C. ; Hemond, Harold F. ; Kubo, Michael D. Y. ; Cardace, Dawn ; Hoehler, Tori M. ; Ono, ShuheiMethane 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, e.g., 13CH3D, has recently emerged as a proxy for determining methane-formation temperatures; however, the impact 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.
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PreprintChemistry of hot springs along the Eastern Lau Spreading Center( 2010-12-08) Mottl, Michael J. ; Seewald, Jeffrey S. ; Wheat, C. Geoffrey ; Tivey, Margaret K. ; Michael, Peter J. ; Proskurowski, Giora ; McCollom, Thomas M. ; Reeves, Eoghan P. ; Sharkey, Jessica ; You, Chen-Feng ; Chan, Lui-Heung ; Pichler, ThomasThe Eastern Lau Spreading Center (ELSC) is the southernmost part of the back-arc spreading axis in the Lau Basin, west of the Tonga trench and the active Tofua volcanic arc. Over its 397-km length it exhibits large and systematic changes in spreading rate, magmatic/tectonic processes, and proximity to the volcanic arc. In 2005 we collected 81 samples of vent water from six hydrothermal fields along the ELSC. The chemistry of these waters varies both within and between vent fields, in response to changes in substrate composition, temperature and pressure, pH, water/rock ratio, and input from magmatic gases and subducted sediment. Hot-spring temperatures range from 229º to 363ºC at the five northernmost fields, with a general decrease to the south that is reversed at the Mariner field. The southernmost field, Vai Lili, emitted water at up to 334°C in 1989 but had a maximum venting temperature of only 121ºC in 2005, due to waning activity and admixture of bottom seawater into the subseafloor plumbing system. Chloride varies both within fields and from one field to another, from a low of 528 mmol/kg to a high of 656 mmol/kg, and may be enriched by phase separation and/or leaching of Cl from the rock. Concentrations of the soluble elements K, Rb, Cs, and B likewise increase southward as the volcanic substrate becomes more silica-rich, especially on the Valu Fa Ridge. Iodine and δ7Li increase southward, and δ11B decreases as B increases, apparently in response to increased input from subducted sediment as the arc is approached. Species that decrease southward as temperature falls are Si, H2S, Li, Na/Cl, Fe, Mn, and 87Sr/86Sr, whereas pH, alkalinity, Ca, and Sr increase. Oxygen isotopes indicate a higher water/rock ratio in the three systems on Valu Fa Ridge, consistent with higher porosity in more felsic volcanic rocks. Vent waters at the Mariner vent field on the Valu Fa Ridge are significantly hotter, more acid and metal-rich, less saline, and richer in dissolved gases and other volatiles, including H2S, CO2, and F, than the other vent fields, consistent with input of magmatic gases. The large variations in geologic and geophysical parameters produced by back-arc spreading along the ELSC, which exceed those along mid-ocean ridge spreading axes, produce similar large variations in the composition of vent waters, and thus provide new insights into the processes that control the chemistry of submarine hot springs.
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PreprintClumped isotopologue constraints on the origin of methane at seafloor hot springs( 2017-11-12) Wang, David T. ; Reeves, Eoghan P. ; McDermott, Jill M. ; Seewald, Jeffrey S. ; Ono, ShuheiHot-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 (ΣCO2) 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 13CH3D, 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 to 370 °C) and chemical compositions (pH, [H2], [ΣCO2], [CH4]) represented. Combined with very similar bulk stable isotope ratios (13C/12C 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 to 360 °C is compatible with the thermodynamically-favorable reduction of CO2 to CH4 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.
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ArticleVolcanically hosted venting with indications of ultramafic influence at Aurora hydrothermal field on Gakkel Ridge(Nature Communications, 2022-10-31) German, Christopher R ; Reeves, Eoghan P ; Türke, Andreas ; Diehl, Alexander ; Albers, Elmar ; Bach, Wolfgang ; Purser, Autun ; Ramalho, Sofia P ; Suman, Stefano ; Mertens, Christian ; Walter, Maren ; Ramirez-Llodra, Eva ; Schlindwein, Vera ; Bünz, Stefan ; Boetius, AntjeThe Aurora hydrothermal system, Arctic Ocean, hosts active submarine venting within an extensive field of relict mineral deposits. Here we show the site is associated with a neovolcanic mound located within the Gakkel Ridge rift-valley floor, but deep-tow camera and sidescan surveys reveal the site to be ≥100 m across-unusually large for a volcanically hosted vent on a slow-spreading ridge and more comparable to tectonically hosted systems that require large time-integrated heat-fluxes to form. The hydrothermal plume emanating from Aurora exhibits much higher dissolved CH/Mn values than typical basalt-hosted hydrothermal systems and, instead, closely resembles those of high-temperature ultramafic-influenced vents at slow-spreading ridges. We hypothesize that deep-penetrating fluid circulation may have sustained the prolonged venting evident at the Aurora hydrothermal field with a hydrothermal convection cell that can access ultramafic lithologies underlying anomalously thin ocean crust at this ultraslow spreading ridge setting. Our findings have implications for ultra-slow ridge cooling, global marine mineral distributions, and the diversity of geologic settings that can host abiotic organic synthesis - pertinent to the search for life beyond Earth.
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PreprintIncorporation of water-derived hydrogen into methane during artificial maturation of source rock under hydrothermal conditions(Elsevier, 2022-08-12) Wang, David T. ; Seewald, Jeffrey S. ; Reeves, Eoghan P. ; Ono, Shuhei ; Sylva, Sean P.To investigate the origin of Csingle bondH bonds in thermogenic methane (CH4), a solvent-extracted sample of organic-rich Eagle Ford shale was reacted with heavy water (D2O) under hydrothermal conditions (350 bar) in a flexible Au-TiO2 cell hydrothermal apparatus at a water-to-rock ratio of approximately 5:1. Temperature was increased from 200 to 350 °C over the course of one month and the concentrations of aqueous species and methane isotopologues were quantified as a function of time. In general, production of hydrogen, CO2, alkanes, and alkenes increased with time and temperature. Methane formed during the early stages of the experiment at 200 °C was primarily C1H4 with some CH3D. With progressively higher temperatures, increasing proportions of deuterated isotopologues were produced. Near the end of the experiment, the concentration of CD4 exceeded that of all other isotopologues combined. These results suggest that competition between rates of kerogen-water isotopic exchange and natural gas generation may govern the D/H ratio of thermogenic gases. Furthermore, hydrogenation of kerogen by water may be responsible for hydrocarbon yields in excess of those predicted by conventional models of source rock maturation in which hydrocarbon generation is limited by the amount of organically bonded hydrogen.
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ArticleHot vent beaneath an icy ocean: the Aurora vend field, Gakkel Ridge, revealed(Oceanography Society, 2022-11-08) Ramirez-Llodra, Eva ; Argentino, Claudio ; Baker, Maria ; Boetius, Antje ; Costa, Carolina ; Dahle, Håkon ; Denny, Emily M. ; Dessandier, Pierre-Antoine ; Eilertsen, Mari H. ; Ferre, Benedicte ; German, Christopher R. ; Hand, Kevin ; Hilário, Ana ; Hislop, Lawrence ; Jamieson, John W. ; Kalnitchenko, Dimitri ; Mall, Achim ; Panieri, Giuliana ; Purser, Autun ; Ramalho, Sofia P. ; Reeves, Eoghan P. ; Rolley, Leighton ; Pereira, Samuel I. ; Ribeiro, Pedro A. ; Sert, Muhammed Fatih ; Steen, Ida H. ; Stetzler, Marie ; Stokke, Runar ; Victorero, Lissette ; Vulcano, Francesca ; Vågenes, Stig ; Waghorn, Kate Alyse ; Buenz, StefanEvidence of hydrothermal venting on the ultra-slow spreading Gakkel Ridge in the Central Arctic Ocean has been available since 2001, with first visual evidence of black smokers on the Aurora Vent Field obtained in 2014. But it was not until 2021 that the first ever remotely operated vehicle (ROV) dives to hydrothermal vents under permanent ice cover in the Arctic were conducted, enabling the collection of vent fluids, rocks, microbes, and fauna. In this paper, we present the methods employed for deep-sea ROV operations under drifting ice. We also provide the first description of the Aurora Vent Field, which includes three actively venting black smokers and diffuse flow on the Aurora mound at ~3,888 m depth on the southern part of the Gakkel Ridge (82.5°N). The biological communities are dominated by a new species of cocculinid limpet, two small gastropods, and a melitid amphipod. The ongoing analyses of Aurora Vent Field samples will contribute to positioning the Gakkel Ridge hydrothermal vents in the global biogeographic puzzle of hydrothermal vents.
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ArticleHydrothermal carbon reduction in the absence of minerals(Geochemical Society, 2024-07-25) Reeves, Eoghan P. ; Seewald, Jeffrey S.Abiotic synthesis of CH4 in seafloor hydrothermal fluids is generally assumed to occur via heterogeneous reactions on mineral surfaces. Stepwise homogeneous reduction of CO2 has, however, been suggested as an alternative (but sluggish) abiotic pathway to CH4, potentially via metastable species of intermediate oxidation states. In this study, we examine the effect of two temperature-dependent methylated species − methanol (CH3OH) and methanethiol (CH3SH), on homogeneous CH4 formation rates under long-term simulated hydrothermal conditions. Aqueous solutions containing formic acid (H13COOH, generating 13CO2 and H2) were heated with and without H2S at 300–325 °C (35 MPa) in a flexible Au reaction cell over several years without added minerals. Substantial 13C-labeled CH4 and CH3OH production from 13CO2 was observed over 4.3 yr, with aqueous CH4 formation varying with CH3OH abundance – a strong function of dissolved H2 abundance and, inversely, temperature. CH4 production was slower at 325 °C with lower CH3OH concentrations (in equilibrium with CO2 and H2), and faster at 300 °C, accompanying an equilibrium-controlled increase in CH3OH. Fastest CH4 production occurred at 300 °C following injection of H2S and H13COOH, which led to rapid formation (<4 days) of 13C-labeled CH3SH that subsequently decomposed over a further 0.8 yr, partly to 13CH4. Heating aqueous 13CH4 to 345–387 °C (33–35 MPa) in the presence of an oxidizing hematite-magnetite-pyrite assemblage, however, yielded no detectable CH3SH after 112 days indicating the reverse reaction is inhibited under favorable thermodynamics. Neither direct reduction of CO2 to CH3SH nor CO2-CH3SH equilibrium were evident at 300 °C, implying CH3SH and CH3OH play disparate roles in homogeneous carbon reduction to CH4. Longer chain hydrocarbons (C2+ alkanes) remained low throughout the experiments.