Formation of meteorite hydrocarbons from thermal decomposition of siderite (FeCO3)

Thermal decomposition of siderite has been proposed as a source of magnetite in martian meteorites. Laboratory experiments were conducted to evaluate the possibility that this process might also result in abiotic synthesis of organic compounds. Siderite decomposition in the presence of water vapor at 300°C generated a variety of organic products dominated by alkylated and hydroxylated aromatic compounds. The results suggest that formation of magnetite by thermal decomposition of siderite on the precursor rock of the martian meteorite ALH84001 would have been accompanied by formation of organic compounds and may represent a source of extraterrestrial organic matter in the meteorite and on Mars. The results also suggest that thermal decomposition of siderite during metamorphism could account for some of the reduced carbon observed in metasedimentary rocks from the early Earth.     

Catabolic and anabolic energy for chemolithoautotrophs in deep-sea hydrothermal systems hosted in different rock types

Active deep-sea hydrothermal vents are hosted by a range of different rock types, including basalt, peridotite, and felsic rocks. The associated hydrothermal fluids exhibit substantial chemical variability, which is largely attributable to compositional differences among the underlying host rocks. Numerical models were used to evaluate the energetics of seven inorganic redox reactions (potential catabolisms of chemolithoautotrophs) and numerous biomolecule synthesis reactions (anabolism) in a representative sampling of these systems, where chemical gradients are established by mixing hydrothermal fluid with seawater. The wide ranging fluid compositions dictate demonstrable differences in Gibbs energies (ΔG_r) of these catabolic and anabolic reactions in three peridotite-hosted, six basalt-hosted, one troctolite-basalt hybrid, and two felsic rock-hosted systems. In peridotite-hosted systems at low to moderate temperatures (<∼45 °C) and high seawater:hydrothermal fluid (SW:HF) mixing ratios (>10), hydrogen oxidation yields the most catabolic energy, but the oxidation of methane, ferrous iron, and sulfide can also be moderately exergonic. At higher temperatures, and consequent SW:HF mixing ratios <10, anaerobic processes dominate the energy landscape; sulfate reduction and methanogenesis are more exergonic than any of the aerobic respiration reactions. By comparison, in the basalt-hosted and felsic rock-hosted systems, sulfide oxidation was the predominant catabolic energy source at all temperatures (and SW:HF ratios) considered. The energetics of catabolism at the troctolite-basalt hybrid system were intermediate to these extremes. Reaction energetics for anabolism in chemolithoautotrophs—represented here by the synthesis of amino acids, nucleotides, fatty acids, saccharides, and amines—were generally most favorable at moderate temperatures (22-32 °C) and corresponding SW:HF mixing ratios (∼15). In peridotite-hosted and the troctolite-basalt hybrid systems, ΔG_r for primary biomass synthesis yielded up to ∼900 J per g dry cell mass. The energetics of anabolism in basalt- and felsic rock-hosted systems were far less favorable. The results suggest that in peridotite-hosted (and troctolite-basalt hybrid) systems, compared with their basalt (and felsic rock) counterparts, microbial catabolic strategies—and consequently variations in microbial phylotypes—may be far more diverse and some biomass synthesis may yield energy rather than imposing a high energetic cost.     

The effect of methanogenesis on the geochemistry of low temperature water–Fe0–basalt reactions

Hydrogen gas produced in the subsurface from the hydration of mafic rocks is known to be a major energy source for chemolithotrophic life in extreme environments such as hydrothermal vents. The possibility that in situ anaerobic microorganisms present in the deep subsurface are sustained by low temperature H₂-generating water–rock reactions taking place around them is being investigated. Whether the growth and activity of H₂-utilizing microbes directly influences aqueous geochemistry, rates of mineral dissolution, and the chemical composition of the alteration products is also being quantitatively evaluated.To explore how microorganisms are affected by water–rock reactions, and how their activity may in turn affect reaction progress, laboratory experiments have been conducted to monitor the growth of a methanogenic Archaea in the presence of H_2(g) produced from low temperature water–Fe⁰–basalt reactions. In these systems, the conversion of Fe(II) to Fe(III) and subsequent hydrolysis of water is responsible for the production of H_2(g). To characterize key components of the geochemical system, time series measurements of H₂ and CH₄ gas concentrations, Fe and Si aqueous concentrations, and spatially resolved synchrotron-based analyses of microscale Fe distribution and speciation were conducted. Culture experiments were compared with an abiotic control to document changes in the geochemistry both in the presence and absence of the methanogen.In the control abiotic batch experiment, H₂ was continuously produced, until the headspace became saturated, while in the biotic experiments, microbial consumption of H₂ for methanogenesis draws H₂ down and produces CH₄. Purging the headspace gas reinitiates H₂ and CH₄ production in abiotic and culture experiments, respectively. Mass balance analysis of the amount of CH₄ produced suggests that the total H₂ production in microbial experiments does not exceed the abiotic experiment. Soluble Si concentrations, while buffered to relatively constant values, were higher in culture experiments than the abiotic control.Iron_(aq) concentrations appear to respond to perturbations of H₂ and CH₄ gas concentrations in both culture experiments and the abiotic control. A pulse of Fe preceded the rise in either H₂ or CH₄ production, and as the gas concentrations increased the Fe_(aq) decreased. Iron-bearing mineral assemblages change with increasing reaction time and mineral assemblages vary between culture experiments and the abiotic control. These geochemical trends suggest that there are different reaction paths between the culture experiments and the abiotic control.The hydration of mafic rocks is a common geologic reaction and one that has taken place on Earth for the majority of its history and is postulated to occur on Mars. These reactions are important because of their effect on the rheology and geochemistry of the ocean crust. While most often studied at temperatures of ～250 °C, this work suggests that at lower temperatures microorganisms may have a profound effect on what has long been thought to be solely an abiotic reaction, and may produce diagnostic mineral assemblages that will be preserved in the geological record.     

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.     

Experimental study of the hydrothermal reactivity of organic acids and acid anions: II. Acetic acid, acetate, and valeric acid

Organic acids and acid anions occur in substantial concentrations in many aqueous geologic fluids and are thought to take part in a variety of geochemical processes ranging from the transport of metals in ore-forming fluids to the formation of natural gas to serving as a metabolic energy source for microbes in subsurface habitats. The widespread occurrence of organic acids and their potential role in diverse geologic processes has led to numerous experimental studies of their thermal stability, yet there remain substantial gaps in our knowledge of the factors that control the rates and reaction pathways for the decomposition of these compounds under geologic conditions. In order to address some of these uncertainties, a series of laboratory experiments were conducted to examine the behavior of organic acids and acid anions under hydrothermal conditions in the presence of minerals. Reported here are results of experiments where aqueous solutions of acetic acid, sodium acetate, or valeric acid (n-pentanoic acid) were heated at 325°C, 350 bars in the presence of the mineral assemblages hematite + magnetite + pyrite, pyrite + pyrrhotite + magnetite, and hematite + magnetite. The results indicate that aqueous acetic acid and acetate decompose by a combination of two reaction pathways: decarboxylation and oxidation. Both reactions are promoted by minerals, with hematite catalyzing the oxidation reaction while magnetite catalyzes decarboxylation. The oxidation reaction is much faster, so that oxidation dominates the decomposition of acetic acid and acetate when hematite is present. In contrast to previous reports that acetate decomposed more slowly than acetic acid, we found that acetate decomposed at slightly faster rates than the acid in the presence of minerals. Although longer-chain monocarboxylic acids are generally thought to decompose by decarboxylation, valeric acid appeared to decompose primarily by “deformylation” to 1-butene plus formic acid. Subsequent decomposition of 1-butene and formic acid generated a variety of short-chain (≤C₄) hydrocarbons and moncarboxylic acids as well as CO₂. Valeric acid decomposition proceeded more rapidly (by a factor of 2) in the presence of hematite-magnetite-pyrite than with the other mineral assemblages, with the greater reaction rate apparently attributable to the effects of fluid chemistry. Valeric acid was observed to decompose at a substantially faster rate than acetic acid under similar conditions. The results suggest that decomposition of aqueous monocarboxylic acids may make a significant contribution to the conversion of petroleum to light hydrocarbons in natural gas and thermal fluids.     

Experimental constraints on the hydrothermal reactivity of organic acids and acid anions: I. Formic acid and formate

A series of hydrothermal experiments covering a range of temperatures from 175 to 260°C examined the decomposition of formic acid and formate and also investigated the production of formate from reduction of CO₂. Decomposition rates measured in this study, which were conducted in gold-TiO₂ reactors, were several orders of magnitude slower than those reported in previous studies conducted in steel and Ti-metal reactors, indicating the previous studies substantially overestimated the rate of the reaction owing to reactor catalysis. Although experiments were conducted with several different minerals present (hematite, magnetite, serpentinized olivine, NiFe-alloy), the decomposition rates were similar in each experiment once the effects of fluid pH were accounted for, suggesting that the minerals had no effect on the stability of formic acid or formate. At higher temperatures (>225°C), the rates of both the decomposition of formate and the reduction of CO₂ to formate were sufficiently rapid that reactions between dissolved CO₂ and formate rapidly attained a state of metastable thermodynamic equilibrium. The results suggest that the amount of formate in many subsurface and hydrothermal fluids is likely to be controlled by equilibrium with dissolved CO₂ at the prevailing oxidation state and pH of the fluid. This may account for the high concentrations of formate observed in strongly reducing environments such as serpentinites, as well as the low concentrations relative to other organic acid anions in mildly reducing environments such as oil-filed brines and formation waters in sedimentary basins. Although formate has been suggested to be a reaction intermediate in the formation of abiotic hydrocarbons from reduction of aqueous CO₂, production of hydrocarbons was not observed in any of the experiments, except for trace amounts of methane, despite high concentrations of formate and strongly reducing conditions.     

Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge

Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (μXRF), X-ray absorption spectroscopy (μΕXAFS), and X-ray diffraction (μXRD) in conjunction with focused ion beam (FIB) sectioning, and high resolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary sulfide and secondary oxyhydroxide minerals was resolved. The Fe-encrusted biofilms formed preferentially at pyrrhotite-rich (Fe_1−xS, 0 ? x ? 0.2) regions of the incubated chimney sulfide. At the nanometer spatial scale, particles within the biofilm exhibiting lattice fringing and diffraction patterns consistent with 2-line ferrihydrite were identified infrequently. At the micron spatial scale, Fe μEXAFS spectroscopy and μXRD measurements indicate that the dominant form of biofilm Fe is a short-range ordered Fe oxyhydroxide characterized by pervasive edge-sharing Fe-O₆ octahedral linkages. Double corner-sharing Fe-O₆ linkages, which are common to Fe oxyhydroxide mineral structures of 2-line ferrihydrite, 6-line ferrihydrite, and goethite, were not detected in the biogenic iron oxyhydroxide (BIO). The suspended development of the BIO mineral structure is consistent with Fe(III) hydrolysis and polymerization in the presence of high concentrations of Fe-complexing ligands. We hypothesize that microbiologically produced Fe-complexing ligands may play critical roles in both the delivery of Fe(II) to oxidases, and the limited Fe(III) oxyhydroxide crystallinity observed within the biofilm. Our research provides insight into the structure and formation of naturally occurring, microbiologically produced Fe oxyhydroxide minerals in the deep-sea. We describe the initiation of microbial seafloor weathering, and the morphological and mineralogical signals that result from that process. Our observations provide a starting point from which progressively older and more extensively weathered seafloor sulfide minerals may be examined, with the ultimate goal of improved interpretation of ancient microbial processes and associated biological signatures.     

Thermodynamic constraints on hydrogen generation during serpentinization of ultramafic rocks

In recent years, serpentinized ultramafic rocks have received considerable attention as a source of H₂ for hydrogen-based microbial communities and as a potential environment for the abiotic synthesis of methane and other hydrocarbons within the Earth’s crust. Both of these processes rely on the development of strongly reducing conditions and the generation of H₂ during serpentinization, which principally results from reaction of water with ferrous iron-rich minerals contained in ultramafic rocks. In this report, numerical models are used to investigate the potential influence of chemical thermodynamics on H₂ production during serpentinization. The results suggest that thermodynamic constraints on mineral stability and on the distribution of Fe among mineral alteration products as a function of temperature are likely to be major factors controlling the extent of H₂ production. At high temperatures (>∼315 °C), rates of serpentinization reactions are fast, but H₂ concentrations may be limited by the attainment of stable thermodynamic equilibrium between olivine and the aqueous fluid. Conversely, at temperatures below ∼150 °C, H₂ generation is severely limited both by slow reaction kinetics and partitioning of Fe(II) into brucite. At 35 MPa, peak temperatures for H₂ production occur at 200-315 °C, indicating that the most strongly reducing conditions will be attained during alteration within this temperature range. Fluids interacting with peridotite in this temperature range are likely to be the most productive sources of H₂ for biology, and should also produce the most favorable environments for abiotic organic synthesis. The results also suggest that thermodynamic constraints on Fe distribution among mineral alteration products have significant implications for the timing of magnetization of the ocean crust, and for the occurrence of native metal alloys and other trace minerals during serpentinization.     

Seafloor bioalteration of sulfide minerals: results from in situ incubation studies

We present results of incubation studies conducted at low temperatures (∼4°C) in the vicinity of a seafloor hydrothermal vent system. We reacted Fe-, S-, Cu-, and Zn-bearing minerals including pyrite, marcasite, chalcopyrite, sphalerite, elemental sulfur, and a portion of a natural chimney sulfide structure for 2 months at the Main Endeavour Segment of the Juan de Fuca Ridge in the Pacific Ocean. Our study utilizes Fluorescent In Situ Hybridizations (FISH), Scanning and Transmission Electron Microscopy (SEM, TEM), and light microscopic analysis. The surfaces of these minerals are solely colonized by Bacteria and not by Archaea. Colonization densities vary over an order of magnitude with the following sequence: elemental sulfur > chimney sulfide > marcasite > pyrite > sphalerite > chalcopyrite, and correspond well with the abiotic oxidation kinetics of these materials, excepting elemental sulfur, which is both the least reactive to oxidizing species and the most heavily colonized. Colonization densities also correspond with apparent degree of reaction (dissolution pitting + accumulation of secondary alteration products). Heavy accumulations of secondary Fe oxides on Fe-bearing minerals, most notably on the chimney sulfide, form in situ as the result of mineral dissolution and the activity of neutrophilic Fe-oxidizing bacteria. Results suggest that mineral-oxidizing bacteria play a prominent role in weathering of seafloor sulfide deposits, and that microbial utilization of mineral substrates contributes to biomass production in seafloor hydrothermal environments.