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 δ 13 C 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 δ 13 C 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 δ 13 C signatures in hydrothermal systems is likely to be complicated, due to differences in source δ 13 C 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
Both hydrogen and methane are consistently discharged in large quantities in hydrothermal fluids issued from ultramafic-hosted hydrothermal fields discovered along the Mid-Atlantic Ridge. Considering the vast number of these fields discovered or inferred, hydrothermal fluxes represent a significant input of H2 and CH4 to the ocean. Although there are lines of evidence of their abiogenic formation from stable C and H isotope results, laboratory experiments, and thermodynamic data, neither their origin nor the reaction pathways generating these gases have been fully constrained yet. Organic compounds detected in the fluids may also be derived from abiotic reactions. Although thermodynamics are favorable and extensive experimental work has been done on Fischer-Tropsch-type reactions, for instance, nothing is clear yet about their origin and formation mechanism from actual data. Since chemolithotrophic microbial communities commonly colonize hydrothermal vents, biogenic and thermogenic processes are likely to contribute to the production of H2, CH4, and other organic compounds. There seems to be a consensus toward a mixed origin (both sources and processes) that is consistent with the ambiguous nature of the isotopic data. But the question that remains is, to what proportions? More systematic experiments as well as integrated geochemical approaches are needed to disentangle hydrothermal geochemistry. This understanding is of prime importance considering the implications of hydrothermal H2, CH4, and organic compounds for the ocean global budget, global cycles, and the origin of life. Key Words: Hydrogen—Methane—Organics—MAR—Abiotic synthesis—Serpentinization—Ultramafic-hosted hydrothermal vents. Astrobiology 15, 381–399.
Seawater is constantly circulating through oceanic basement as a low-temperature hydrothermal fluid (<150°C). In cases when ultramafic rocks are exposed to the fluids, for instance during the initial phase of subduction, ferromagnesian minerals are altered in contact with the water, leading to high pH and formation of secondary magnesium hydroxide, among other -brucite, that may scavenge borate and phosphate from seawater. The high pH may promote abiotic formation of pentoses, particularly ribose. Pentoses are stabilized by borate, since cyclic pentoses form a less reactive complex with borate. Analyses have shown that borate occupies the 2' and 3' positions of ribose, thus leaving the 5' position available for reactions like phosphorylation. The purine coding elements (adenine, in particular) of RNA may be formed in the same general hydrothermal environments of the seafloor.
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