Characterisation of dissolved organic compounds in hydrothermal fluids by stir bar sorptive extraction - gas chomatography - mass spectrometry. Case study: the Rainbow field (36°N, Mid-Atlantic Ridge).

The analysis of the dissolved organic fraction of hydrothermal fluids has been considered a real challenge due to sampling difficulties, complexity of the matrix, numerous interferences and the assumed ppb concentration levels. The present study shows, in a qualitative approach, that Stir Bar Sorptive Extraction (SBSE) followed by Thermal Desorption - Gas Chromatography - Mass Spectrometry (TD-GC-MS) is suitable for extraction of small sample volumes and detection of a wide range of volatile and semivolatile organic compounds dissolved in hydrothermal fluids. In a case study, the technique was successfully applied to fluids from the Rainbow ultramafic-hosted hydrothermal field located at 36°14'N on the Mid-Atlantic Ridge (MAR). We show that n-alkanes, mono- and poly- aromatic hydrocarbons as well as fatty acids can be easily identified and their retention times determined. Our results demonstrate the excellent repeatability of the method as well as the possibility of storing stir bars for at least three years without significant changes in the composition of the recovered organic matter. A preliminary comparative investigation of the organic composition of the Rainbow fluids showed the great potential of the method to be used for assessing intrafield variations and carrying out time series studies. All together our results demonstrate that SBSE-TD-GC-MS analyses of hydrothermal fluids will make important contributions to the understanding of geochemical processes, geomicrobiological interactions and formation of mineral deposits.

Comparison of microbial communities associated with three Atlantic ultramafic hydrothermal systems.

The distribution of Archaea and methanogenic, methanotrophic and sulfate-reducing communities in three Atlantic ultramafic-hosted hydrothermal systems (Rainbow, Ashadze, Lost City) was compared using 16S rRNA gene and functional gene (mcrA, pmoA and dsrA) clone libraries. The overall archaeal community was diverse and heterogeneously distributed between the hydrothermal sites and the types of samples analyzed (seawater, hydrothermal fluid, chimney and sediment). The Lost City hydrothermal field, characterized by high alkaline warm fluids (pH>11; T<95 °C), harbored a singular archaeal diversity mostly composed of unaffiliated Methanosarcinales. The archaeal communities associated with the recently discovered Ashadze 1 site, one of the deepest active hydrothermal fields known (4100 m depth), showed significant differences between the two different vents analyzed and were characterized by putative extreme halophiles. Sequences related to the rarely detected Nanoarchaeota phylum and Methanopyrales order were also retrieved from the Rainbow and Ashadze hydrothermal fluids. However, the methanogenic Methanococcales was the most widely distributed hyper/thermophilic archaeal group among the hot and acidic ultramafic-hosted hydrothermal system environments. Most of the lineages detected are linked to methane and hydrogen cycling, suggesting that in ultramafic-hosted hydrothermal systems, large methanogenic and methanotrophic communities could be fuelled by hydrothermal fluids highly enriched in methane and hydrogen.

Alkaline fluid circulation in ultramafic rocks and formation of nucleotide constituents: a hypothesis.

Seawater is constantly circulating through oceanic basement as a low-temperature hydrothermal fluid (<150 degrees 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.