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.

The question of the abiogenic oil has been discussed and hydrothermal reactions have been suggested to abiotically generate hydrocarbons. Besides, ultramafic-hosted hydrothermal systems have been regarded as favourable environment for the emergence of life. Therefore, it is of great importance to investigate the presence of organic compounds in hydrothermal fluids. However, because of the sampling difficulties, the complexity of the matrix, the numerous interferences and the assumed trace level concentrations; it was considered a real challenge. Here we show that Stir Bar Sorptive Extraction (SBSE) coupled to Thermal Desorption – Gas Chromatography – Mass Spectrometry (TD-GC-MS) can be successfully applied to analyses of volatile and semi-volatile organic compounds in hydrothermal fluids. The method exhibited excellent reproducibility and conditioned samples appeared to be really stable for up to 3 years. This innovative and versatile technique was used to study the fluids from the ultramafic-hosted hydrothermal field Rainbow located at 36°14’N on the Mid-Atlantic Ridge (MAR). Despite relative stability for mineral composition and gas content is observed, analyses of fluids samples from 2005, 2007 and 2008 revealed more distinct organic compositions. In addition, results suggest the similarity of the organic content of the fluids regardless of the sampling location within the field, which may indicates the presence of a single reaction zone and that no further chemical reactions occur while fluids are transported to the seafloor.

Hydrocarbons gases (C₁-C₄) as well as larger organic compounds were reported elsewhere in fluids from the Rainbow and the Lost City ultramafic-hosted hydrothermal fields. Whereas hydrocarbon gases are likely abiogenic (Fischer-Tropsch Type reaction), the origin of larger molecules remains unclear. Our ability to differentiate between biotic and abiotic sources of organic compounds in deep-sea hydrothermal systems may give clues to the understanding of organic geochemistry on the early Earth. Here, we report a series of experiments of hydrothermal degradation (40 MPa / 200, 350 and 450°C) of the piezophile archaea Pyrococcus abyssi biomass, which provides supporting lines of evidence of the abiogenic origin of saturated hydrocarbons as well as of the possible biogenic origin of alkylated aromatic hydrocarbons, Polycyclic Aromatic Hydrocarbons (PAH) and C_12:0-C_16:0 fatty acids in fluids from ultramafic-hosted hydrothermal systems.

Amino acids are the fundamental building blocks of proteins that are required for the initiation of living organism, therefore they are key compounds in the origin of life quest. The abiotic production of amino acids within ultramafic-hosted hydrothermal systems was suggested a few decades ago and is strongly supported by thermodynamic data and experimental work. However, field data were clearly lacking and thus investigation of amino acids in fluids from ultramafic-hosted hydrothermal systems was of major importance. Even though amino acids analysis have been carried out routinely for several decades in various field of application, none of the currently available methods appeared suitable for our purpose because of the complexity of the hydrothermal fluids matrix (salts, minerals, gases) and the extremely low concentrations of amino acids that were expected. We took up the challenge and here we describe a method to detect underivatized amino acids down to the sub-ppb level in aqueous matrix by ion-pairing reverse-phase Ultra-high Performance Liquid Chromatography - Electrospray Ionisation - Quadrupole Time of Flight - Mass Spectrometry (UPLC-ESI-QTOF-MS). Characterisation and separation of 10 chosen proteinogenic amino acids was achieved and excellent linearity in the response was obtained for all amino acids with correlation coefficient > 0.9921. This analytical method was successfully applied to natural hydrothermal fluid samples from ultramafic-hosted vents of the Mid-Atlantic Ridge region. Tryptophan and Phenylalanine were clearly evidenced in the fluids and concentrations of Leucine reached 15-55 ppt. We suggest that other amino acids are present in hydrothermal fluids but occur for the major part as metal and/or clay complexes and could not be detected using current approach. Finally, concentrations of amino acids measured in the deep seawater reference sample were in good agreement with generally accepted background level in the deep ocean.