Hydrocarbons and oxidized organic compounds in hydrothermal fluids from Rainbow and Lost City ultramafic-hosted vents

The first building blocks of life could be produced in ultramafic-hosted hydrothermal systems considering the large amounts of hydrogen and methane generated by serpentinisation and Fischer–Tropsch-Type synthesis, respectively, in those systems. The purpose of this study was to detect and characterise organic molecules in hydrothermal fluids from ultramafic-hosted hydrothermal systems in the Mid-Atlantic Ridge (MAR) region. During the EXOMAR cruise 2005, fluids from the Rainbow (36°14′N) and the Lost City (30°N) hydrothermal fields were collected and treated by Stir Bar Sorptive Extraction (SBSE) and Solid Phase Extraction (SPE). The extracts were analysed by Thermal Desorption–Gas Chromatography–Mass Spectrometry (TD–GC–MS) and GC–MS, respectively. Compared to nearby deep seawater, hydrothermal fluids were clearly enriched in organic compounds, with a more diverse spectrum of molecules. We observed a very similar range of organic compounds in fluids from both sites, with a dominance of aliphatic hydrocarbons (C9–C14), aromatic compounds (C6–C16) and carboxylic acids (C8–C18). The occurrence of these compounds is supported by other field studies on serpentinites and sulfide deposits. Literature on thermodynamic data and experimental work has suggested the possible abiogenic origin of hydrocarbons and organic acids. In addition, it has been shown elsewhere that catalytic reactions producing hydrocarbons likely occur at both Lost City and Rainbow hydrothermal fields as suggested by the evolution of δ¹³C with increasing C number for methane, ethane, propane and butane. In order to investigate the origin of the organic molecules in the fluids, compound-specific carbon isotope ratio measurements were performed on n-alkanes and carboxylic acids, for which the δ¹³C values were in the range of ? 46 to ? 20‰ (vs. V-PDB). These preliminary data did not allow conclusive support or rejection of an abiogenic origin of the compounds. Indeed, predicting δ¹³C signatures in hydrothermal systems is likely to be complicated, due to differences in source δ¹³C signatures (i.e., of the C building blocks), and a variety of, mostly unknown, fractionation steps which may occur along the synthesis pathways. In addition, even though a fraction of the compounds detected in the fluids is likely abiotically produced, a dominance of biogenic sources and/or processes might hide their characteristic signature.     

Organic Sulfides in Hydrothermal Solution: Standard Partial Molal Properties and Role in Organic Geochemistry of Hydrothermal Environments

Thermodynamic properties for aqueous alkyl sulfides have been compiled and/or estimated through established methods. These properties are used to investigate reactions among various sulfur compounds in a variety of geological environments, ranging from sea floor hydrothermal systems to organic-rich sludge. Using thermodynamic data and the revised Helgeson-Kirkham-Flowers (HKF) equations of state, along with geochemical constraints imposed by the environment, it is possible to estimate the abiotic production of this class of organic sulfur compounds. For example, in hydrothermal systems in which H₂ and H₂S concentrations are buffered by the pyrite–pyrrhotite–magnetite (PPM) mineral assemblage, calculated equilibrium activities of dimethyl sulfide (DMS) are as high as 10⁻³ through formation reactions in which the environment contains millimolal concentrations of CO₂. Higher activities are obtained when DMS formation from CO is considered and when more reducing mineral assemblages are present.     

Hydrothermal systems and the emergence of life

The author reviews current thought about life originating in hyperthermophilic microorganisms. Hyperthermophiles obtain food from chemosynthesis of sulfur and have an RNA nucleotide sequence different from bacteria and eucarya. It is postulated that a hyperthermophile may be the common ancestor of all life. Current research efforts focus on the synthesis of organic compounds in hydrothermal systems.     

Thermodynamic model of ore-forming processes in a submarine island-arc hydrothermal system

A thermodynamic model suggested for ore-forming processes in a hydrothermal system (HS) in an island arc is based on the technique suggested earlier in [1] for simulating ore-forming hydrothermal systems in mid-oceanic ridges. This technique make use of the principle of flow-through multistep reactor and encompasses (a) the region where hydrothermal solutions are generated when seawater interacts with rocks (descending convection branch); (b) the region where material is transported with the solution at decreasing pressure (feeder channel); and (c) the region where the ore material is deposited (orebody). Hydrothermal systems in island arcs exhibit the following distinctive features taken into account in the model: (1) the composition of the host crustal rocks (rocks of mafic-acid composition instead of basalt and serpentinite) and (2) possible significant involvement of magmatic gases in the feeding of the hydrothermal system. The naturally occurring prototype of the simulated system is the hydrothermal system in the caldera of a submarine volcano in an island arc. The model is simulated in a number of variants in which the hydrothermal fluid is exogenic (heated seawater convecting through hot volcanic rocks), magmatic, or mixed (magmatic plus exogenic) is involved. The simulations were carried out using the HCh version 4.3 [2] program package for the multisystem H-O-K-Na-Ca-Mg-Fe-Al-Si-C-S-Cl-Cu-Zn-Pb-As-Sb-Ag-Au at temperatures of 25?C370°C and pressures of 10?C500 bar. The multisystem included 88 possible solid phases and aqueous solution with 95 species. The thermodynamic properties of compounds were calculated using the UNITHERM databank. The model is underlain by the principle of multiwave flow-through multistep reactor (MFTMR) with a starting rock/water (R/W) ratio of 1: 1. As progressively more solution portions passed through the rocks, the participation of fresh rock in the interaction accordingly diminished because the rock material was gradually exhausted in the system. The magmatic fluid had a composition selected based on data on fumaroles at Kudryavyi volcano [3] with a correction for the degassing pressure. The evolution of ore deposition was simulated in compliance with the scheme described in [4], which was implemented using the technology of ??openness from above?? [3]. The model was simulated with various compositions of the host rocks (basalts, andesites, dacites, and rhyolites) and the origin of the fluid (magmatic fluid alone, seawater alone, and variable proportions of both). Our simulation results indicate that the metallogeny (relative enrichment in Pb, As, Sb, or Ag) of island-arc ore deposits is controlled by the abundances of metals in the host rocks predominant in the hydrothermal system. The mineralogy and geochemistry of ores generated in arc hydrothermal systems are predetermined by the effective transport of metalloids (S, As, and Sb) that have a high migration capacity in these systems. Magmatic gases introduced in the hydrothermal systems play dualistic roles in the ore-forming processes. If the hydrothermal fluid in a hydrothermal system is dominated by magmatic components, deposits of native sulfur are formed, and the precipitation of base metal is thereby suppressed because of the high acidity of the generated hydrothermal solutions. The involvement of magmatic gases in an amount of a few percent in a hydrothermal system enhances the overall oregenerating potential of the system in terms of sulfide ores.     

Experimental abiotic synthesis of methanol in seafloor hydrothermal systems during diking events

The abiotic synthesis of organic compounds in seafloor hydrothermal systems is one mechanism through which the subsurface environment could be supplied with reduced carbon. A flow-through, fixed-bed laboratory reactor vessel, the Catalytic Reactor Vessel (CRV) system, has been developed to investigate mineral–surface promoted organic synthesis at temperatures up to 400°C and pressures up to 30 MPa, conditions relevant to seafloor hydrothermal systems. Here we present evidence that metastable methanol can be directly synthesized from a gas-rich CO₂–H₂–H₂O mixture in the presence of a mineral substrate. Experiments have been performed without a substrate, with quartz, and with a mixture of quartz and magnetite. Temperatures and pressures in the experiments ranged from 200°C to 350°C and from 15 to 18 MPa, respectively. Maximum conversion of 5.8×10⁻⁴% CO₂ to CH₃OH per hour was measured using a mixture of magnetite and quartz in the reactor. After passivation of the stainless steel reactor vessel, experiments demonstrate that methanol is formed at temperatures up to 350°C in the presence of magnetite, and that the formation rate decreases over time. The experiments also show a loss of surface reactivity at 310°C and a regeneration of surface reactivity with increased temperature up to 350°C. Concentrations of CO₂ and H₂ used in the experiments simulate periodic, localized and dynamic conditions occurring within the seafloor during and immediately following magmatic diking events. High concentrations of CO₂ and H₂ may be generated by dike injection accompanied by exsolution of CO₂ and reaction of dissolved H₂O with FeO in the magma to form H₂. The experiments described here examine how the ephemeral formation of an H₂–CO₂-rich vapor phase within seafloor hydrothermal systems may supply reactants for abiotic organic synthesis reactions. These experiments show that the presence of specific minerals can promote the abiotic synthesis of simple organic molecules from common inorganic reactants such H₂O, CO₂ and H₂ under geologically realistic conditions.     

Composition and origin of hydrothermal petroleum and associated lipids in the sulfide deposits of the Rainbow field (Mid-Atlantic Ridge at 36°N)

The lipid components in hydrothermal sulfide deposits from the Rainbow vent field (Mid-Atlantic Ridge at 36°N) were studied by gas chromatography/mass spectrometry. The Rainbow vent field is one of two known active hydrothermal systems related to abyssal circulation, where high-temperature fluids are formed during serpentinization of ultrabasic crustal rocks. The major amount of the extractable organic matter from the sulfides consists of normal and branched alkanes, UCM, PAHs, terpenoids, and fatty acids. The branched alkanes are comprised of unique gem-diethylalkane series, possibly from sulfide oxidizing bacteria, and biphytanes from archaea. The characteristic lipid and biomarker compounds found in the hydrothermal samples support a predominantly biological origin of the bitumens from the thermal transformation of the biomass of microorganisms (bacteria and archea) and minor macrofauna of this vent field. A search for molecular evidence for abiogenic thermocatalytic synthesis of organic compounds was negative. However, methane in the hydrothermal fluids and possibly a minor amount of the alkanes in the sulfides may be of an abiogenic origin in the Rainbow vent field.     

兰坪盆地三类主要铜银多金属矿床的稳定同位素地球化学

通过对兰坪盆地内三种主要成因类型（沉积-热液改造型、热水沉积-热液改造型和热液脉型）的铜银多金属矿床硫、碳、氢、氧同位素的研究,揭示了成矿作用过程的某些重要信息：矿石中的硫主要来自细菌还原的海水硫酸盐,但在沉积-热液改造型矿床中可能还有部分有机生物硫和深源火山硫的贡献;碳主要来自不同比值水/岩反应体系中碳酸盐岩地层的溶解结果,但在沉积-热液改造型矿床中还可能有深部地幔去气作用带来的CO2.成矿流体系以大气降水为主要补给源的盆地建造水,盆地建造水的运移成矿过程中可能伴有较为明显的蒸发作用.     

A demonstration of an affinity between pyrite and organic matter in a hydrothermal setting

One of the key-principles of the iron-sulphur world theory is to bring organic molecules close enough to interact with each other, using the surface of pyrite as a substrate in a hydrothermal setting. The present paper explores the relationship of pyrite and organic matter in a hydrothermal setting from the geological record; in hydrothermal calcite veins from Carboniferous limestones in central Ireland. Here, the organic matter is accumulated as coatings around, and through, pyrite grains. Most of the pyrite grains are euhedral-subhedral crystals, ranging in size from ca 0.1-0.5 mm in diameter, and they are scattered throughout the matrix of the vein calcite. The organic matter was deposited from a hydrothermal fluid at a temperature of at least 200°C, and gives a Raman signature of disordered carbon. This study points to an example from a hydrothermal setting in the geological record, demonstrating that pyrite can have a high potential for the concentration and accumulation of organic materials.     

Geochemical constraints on chemolithoautotrophic metabolism by microorganisms in seafloor hydrothermal systems

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

Fluid inclusions in hydrothermal ore deposits

The principal aim of this paper is to consider some of the special problems involved in the study of fluid inclusions in ore deposits and review the methodologies and tools developed to address these issues. The general properties of fluid inclusions in hydrothermal ore-forming systems are considered and the interpretation of these data in terms of fluid evolution processes is discussed. A summary of fluid inclusion data from a variety of hydrothermal deposit types is presented to illustrate some of the methodologies described and to emphasise the important role which fluid inclusion investigations can play, both with respect to understanding deposit genesis and in mineral exploration. The paper concludes with a look to the future and addresses the question of where fluid inclusion studies of hydrothermal ore deposits may be heading in the new millenium.     

Microbial Diversity in Hydrothermal Systems and Their Influence on Geological Environments

Abstract: Microorganisms found at terrestrial and seafloor hydrothermal systems are classified based on their optimum growth temperatures. Prokaryotes exhibiting optimum growth temperatures above 45C are defined as thermophiles, while those with optimum growth temperatures above 80C are called hyperthermophiles. Hyperthermophiles have chemically and thermodynamically stable cytoplasmic‐membrane consisting of ether–lipids. Hyperthermophiles observed at temperature up to 113C in seafloor hydrothermal areas should have thermostable proteins. Presumably, the thermostable proteins are replacing certain amino acid residue by proline instead of alanine in order to increase hydrogen bonds and salt bridges. Microorganisms inhabiting terrestrial and seafloor hydrothermal areas obtain energy mainly by use of chemical disequilibrium, so that their habitat may be restricted to the redox boundary between ambient water and reduced hydrothermal fluids. Among more than 200 species of cultivable thermophiles and hyperthermophiles, hyperthermophiles mainly obtain energy by sulfur reduction, because this reaction can produce energy efficiently at > 80C. Some hyperthermophilic sulfur reducers can reduce Cr(VI), Mn(IV), Fe(III), Co(III), As(V), Se(VI), Tc(VII), Au(III) and U(VI) through hydrogen or organic compounds that act as reducing agents for yielding energy. Some hyperther‐mophiles use W instead of Mo for activating their enzymes. Bacteria can pump out toxic metal ions from their cells, however toxic metal resistance systems of archaea, including hyperthermophiles, have not yet been studied. Methane producing hyperthermophiles can yield energy by the autotrophic reaction, when sufficient carbon dioxide and molecular hydrogen can be supplied and methane can be removed from hydrothermal systems. If nitrogen can be supplied into a hydrothermal system, hydrogen oxidization by nitrogen species (e.g. NO₃^‐, NO₂^‐, NO and N₂O) may be expected through the metabolism of some hyperthermophiles.     

若干以沉积岩为容矿围岩的热液矿床硫同位素地球化学研究

文章对与沉积岩容矿有关的热液广西高龙微细浸染型金矿、新疆霍什布拉克铅锌矿、广西盘龙铅锌矿和下雷锰矿等矿床硫化物进行硫同位素测定,硫同位素组成分别为-15.3‰~+15.6‰,-18.8‰~+24.2‰,-21.0‰~+26.4‰,-32.6‰~+32.2‰。硫同位素可以达到平衡(高龙、霍什布拉克、下雷),也可以没达到平衡(盘龙)。δ34SΣS值在+13‰~+28‰之间,表明与沉积岩容矿热液矿床中硫来源于海水硫酸盐还原硫,但不排除有岩浆硫的加入。     

Sulfur isotopic composition of hydrothermal precipitates from the Lau back-arc: implications for magmatic contributions to seafloor hydrothermal systems

The sulfur isotopic composition of sulfides and barite from hydrothermal deposits at the Valu Fa Ridge back-arc spreading center in the southern Lau Basin has been investigated. Sulfide samples from the White Church area at the northern Valu Fa Ridge have δ³⁴S values averaging +3.8‰ (n= 10) for bulk sphalerite-chalcopyrite mineralization and +4.8‰ for pyrite (n= 10). Barite associated with the massive sulfides exhibits an average of +20.7‰ (n= 10). Massive sulfides from the active Vai Lili hydrothermal field at the central Valu Fa Ridge have much higher δ³⁴S ratios averaging +8.0‰ for bulk sphalerite-chalcopyrite mineralization (n= 5), +9.3‰ for pyrite samples (n= 5), and +8.0‰ and +10.9‰ for a chalcopyrite and a sphalerite separate, respectively. The isotopic composition of barite from the Vai Lili field is similar to that of barite from the White Church area and averages +21.0‰ (n= 8). Sulfide and barite samples from the Hine Hina area at the southern Valu Fa Ridge have δ³⁴S values that are considerably lighter than those observed for samples from the other areas and average −4.9‰ for pyrite (n= 9), −4.0 and −5.7‰ for two samples of sphalerite-chalcopyrite intergrowth, and −3.4‰ for a single chalcopyrite separate. The total spread in the isotopic composition of sulfides from Vai Lili and Hine Hina is more than 20‰ over a distance of less than 30 km. The δ³⁴S values of sulfides at Hine Hina are the lowest values so far reported for volcanic-hosted polymetallic massive sulfides from the modern seafloor. Barite from the Hine Hina field also has unusually light sulfur with δ³⁴S values of +16.1 to +16.7‰ (n= 5). Isotopic compositions of the sulfides at Hine Hina indicate a dramatic decrease in δ³⁴S from ordinary magmatic values and, in the absence of biogenic sulfur and/or boiling, imply a unique ³⁴S-depleted source of probable magmatic origin. Sulfide-barite mineralization in the Hine Hina area is associated with a distinctive alteration assemblage consisting of cristobalite, pyrophyllite, kaolinite, opal-CT, talc, pyrite, native sulfur, and alunite. Similar styles of alteration are typically known from high-sulfidation epithermal systems on land. Alunite-bearing, advanced argillic alteration in the Hine Hina field confirms the role of acidic, volatile-rich fluids, and a δ³⁴S value of +10.4‰ for the sulfur in the alunite is consistent with established kinetic isotope effects which accompany the disproportionation of magmatic SO₂ into H₂S and H₂SO₄. The Hine Hina field occurs near the propagating tip of the Valu Fa back-arc spreading center (i.e., dominated by dike injections and seafloor eruptions) and therefore may have experienced the largest contribution of magmatic volatiles of the three fields. The sulfur isotopic ratios of the hydrothermal precipitates and the presence of a distinctive epithermal-like argillic alteration in the Hine Hina field suggest a direct contribution of magmatic vapor to the hydrothermal system and support the concept that magmatic volatiles may be an important component of some volcanogenic massive sulfide-forming hydrothermal systems. Received: 16 January 1997 / Accepted: 28 October 1997     

The influence of carbon source on abiotic organic synthesis and carbon isotope fractionation under hydrothermal conditions

A series of laboratory experiments were performed to investigate the relative contributions of CO and other single-carbon compounds to abiotic synthesis of organic compounds in hydrothermal environments. Experiments were conducted by heating aqueous solutions of CO, CO₂, HCOOH, or CH₄ at 250 °C under reducing conditions, and observing production of CH₄ and other hydrocarbons. Native Fe was included in the experiments as a source of H₂ through reaction with water and as a potential catalyst. Experiments with CO or HCOOH as the carbon source resulted in rapid generation of CH₄ and other hydrocarbons that closely resembled typical products of Fischer-Tropsch organic synthesis. In contrast, experiments using CO₂ or CH₄ as the carbon source yielded no detectable hydrocarbon products. Carbon isotope measurements of reaction products from the CO experiments indicate that the CH₄ and other hydrocarbons were substantially depleted in ¹³C, with CH₄ δ¹³C values 30 to 34‰ lighter than the initial CO. Most of the fractionation apparently occurs during attachment of CO to the catalyst surface and subsequent reduction to surface-bound methylene. The initial step in polymerization of these methylene units to form hydrocarbons involves a small, positive fractionation, so that ethane and ethene are slightly enriched in ¹³C relative to CH₄. However, subsequent addition of carbon molecules to the growing hydrocarbon chain proceeds with no net observable fractionation, so that the isotopic compositions of the C₃₊ light hydrocarbons are controlled by isotopic mass balance. This result is consistent with a previously proposed model for carbon isotopic patterns of light hydrocarbons in natural samples. The abundance and isotopic composition of light hydrocarbons produced with HCOOH as the carbon source were similar to those generated with CO, but the isotopic compositions of non-volatile hydrocarbons diverged, suggesting that the higher hydrocarbons were formed by different mechanisms in the CO and HCOOH experiments. The experiments indicate that CO, and possibly HCOOH, may be critical intermediates in the abiotic formation of organic compounds in geologic environments, and suggest that the low levels of these compounds present in most hydrothermal systems could represent a bottleneck restricting the extent of abiotic organic synthesis in some circumstances.     

Low temperature\lg f_{O_2 } - pH diagrams of sulfur isotope evolution in an equilibrium hydrothermal system

According to Sakai-Ohmoto's theory regarding the evolution of sulfur isotopes in hydrothermal systems, in conjunction of new data on chemical resaction equilibrium constants and equilibrium isotopic fractionation factors as well as on individual ion activity coefficients of aqueous sulfur species, the following lgfo₂.-pH diagrams are constructed:

1. mole fractions of aqueous sulfur species (X _i ),
2. stability fields of some minerals in the Fe-S-O system,
3. diagram depicting the oxidation-reduction-state ratio for aqueous sulfur species (R′)
4. isotopic compositions of sulfur compounds ( \(\delta S_1 ^{34} \) ).

     

Elevated concentrations of formate, acetate and dissolved organic carbon found at the Lost City hydrothermal field

Fluids from the ultramafic-hosted Lost City hydrothermal field were analyzed for total dissolved organic carbon and dissolved organic acids. Formate (36-158 μmol/kg) and acetate (1-35 μmol/kg) concentrations are higher than in other fluids from unsedimented hydrothermal vents, and are a higher ratio of the total dissolved organic carbon than has been found in most marine geothermal systems. Isotopic evidence is consistent with an abiotic formation mechanism for formate, perhaps during serpentinization processes in the sub-surface. Further support comes from previous studies where the abiological formation of low molecular weight organic acids has been shown to be thermodynamically favorable during hydrothermal alteration of olivine, and laboratory studies in which the reduction of carbon dioxide to formate has been confirmed. As the second most prevalent carbon species after methane, formate may be an important substrate to microbial communities in an environment where dissolved inorganic carbon is limited. Acetate is found in locations where sulfate reduction is believed to be important and is likely to be a microbial by-product, formed either directly by autotrophic metabolic activity or indirectly during the fermentative degradation of larger organic molecules. Given the common occurrence of exposed ultramafic rocks and active serpentinization within the worlds ocean basins, the abiotic formation of formate may be an important process supporting life in these high pH environments and may have critical implications to understanding the organic precursors from which life evolved.     

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.     

S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides

Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because ³⁴S/³²S ratios of vent fluid H₂S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different Δ³³S (≡δ³³S-0.515 δ³⁴S) values of up to 0.04‰ even if δ³⁴S values are identical. Detection of such small Δ³³S differences is technically feasible by using the SF₆ dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006‰ (2σ).Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H₂S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10°N, 13°N, and 21°S and Mid-Atlantic Ridge (MAR) 37°N yield Δ³³S values ranging from −0.002 to 0.033 and δ³⁴S from −0.5‰ to 5.3‰. The combined δ³⁴S and Δ³³S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13°N and marcasite from MAR 37°N are in isotope disequilibrium not only in δ³⁴S but also in Δ³³S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low Δ³³S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that ³³S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles.     

Dissolved organic carbon in ridge-axis and ridge-flank hydrothermal systems

The circulation of hydrothermal fluid through the upper oceanic crustal reservoir has a large impact on the chemistry of seawater, yet the impact on dissolved organic carbon (DOC) in the ocean has received almost no attention. To determine whether hydrothermal circulation is a source or a sink for DOC in the oceans, we measured DOC concentrations in hydrothermal fluids from several environments. Hydrothermal fluids were collected from high-temperature vents and diffuse, low-temperature vents on the basalt-hosted Juan de Fuca Ridge axis and also from low-temperature vents on the sedimented eastern flanks. High-temperature fluids from Main Endeavour Field (MEF) and Axial Volcano (AV) contain very low DOC concentrations (average = 15 and 17 μM, respectively) compared to background seawater (36 μM). At MEF and AV, average DOC concentrations in diffuse fluids (47 and 48 μM, respectively) were elevated over background seawater, and high DOC is correlated with high microbial cell counts in diffuse fluids. Fluids from off-axis hydrothermal systems located on 3.5-Ma-old crust at Baby Bare Seamount and Ocean Drilling Program (ODP) Hole 1026B had average DOC concentrations of 11 and 13 μM, respectively, and lowered DOC was correlated with low cell counts. The relative importance of heterotrophic uptake, abiotic sorption to mineral surfaces, thermal decomposition, and microbial production in fixing the DOC concentration in vent fluids remains uncertain. We calculated the potential effect of hydrothermal circulation on the deep-sea DOC cycle using our concentration data and published water flux estimates. Maximum calculated fluxes of DOC are minor compared to most oceanic DOC source and sink terms.     

Biomolecules in hydrothermal systems: Calculation of the standard molal thermodynamic properties of nucleic-acid bases, nucleosides, and nucleotides at elevated temperatures and pressures

Calculation of the thermodynamic properties of biomolecules at high temperatures and pressures is fundamental to understanding the biogeochemistry of hydrothermal systems. Ample evidence indicates that hyperthermophilic microbes interact chemically with their mineralogical environment in these systems. Nevertheless, little is known about the thermodynamic properties of the biomolecules involved in such processes. Recent advances in theoretical biogeochemistry make it possible to calculate these properties using the limited experimental data available in the literature, together with correlation and group additivity algorithms, reference model compounds, and the revised HKF equations of state. This approach permits calculation of the standard molal thermodynamic properties of the 120 common protonated and deprotonated nucleotides and their constituent nucleic-acid bases and nucleosides as a function of temperature and pressure. The requisite equations of state parameters can be calculated from experimental standard molal heat capacities, volumes, and compressibilities reported in the literature for nucleic-acid bases and nucleosides. Because no calorimetric or densimetric data are available for the nucleotides, experimental heats of reaction taken from the literature were used together with correlation and group additivity algorithms to generate provisional values of the corresponding equations of state parameters for the nucleotides. The thermodynamic properties and revised HKF equations of state parameters generated in the present study can be used to carry out comprehensive mass transfer and Gibbs energy calculations to describe and quantify the chemical interaction of minerals and microbes in hydrothermal systems.