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Detection of trace concentrations of amino acid in aqueous solutions by Ion-pairing reversed-phase UPLC-ESI-QToF-MS: application to hydrothermal fluids
Stockholm University, Faculty of Science, Department of Geology and Geochemistry.
Laboratoire de géochimie et métallogénie, Ifremer, Brest, France. (Géosciences Marines)
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
Stockholm University, Faculty of Science, Department of Geology and Geochemistry.
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

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.

Keyword [en]
Amino acids, UPLC, QToF, hydrothermal
National Category
Analytical Chemistry Other Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
URN: urn:nbn:se:su:diva-29195OAI: oai:DiVA.org:su-29195DiVA: diva2:231457
Projects
MoMARnet
Available from: 2009-08-13 Created: 2009-08-13 Last updated: 2010-01-14Bibliographically approved
In thesis
1. Origin of organic compounds in fluids from ultramafic-hosted hydrothermal vents of the Mid-Atlantic Ridge
Open this publication in new window or tab >>Origin of organic compounds in fluids from ultramafic-hosted hydrothermal vents of the Mid-Atlantic Ridge
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Natural gas, primarily methane (CH4), is produced in substantial amounts in ultramafic-hosted hydrothermal systems. These systems could also generate oil (heavier hydrocarbons) and the first building blocks of life (prebiotic molecules). In the presence of iron bearing minerals, serpentinisation reactions generate H2. Subsequently, CH4 could be synthesised by Fischer-Tropsch Type (FTT) reaction (4H2 + CO2 → CH4 + 2H2O) which is an abiotic process. This has lead to the idea of abiotic formation of larger organic molecules. Both thermodynamics and laboratory work support this idea, yet field data have been lacking. This study focuses on determining the organic content of fluids from ultramafic-hosted hydrothermal systems from the Mid-Atlantic Ridge (MAR) and the origin of the compounds. Fluids were collected from the Lost City, Rainbow, Ashadze and Logatchev vent fields during the EXOMAR (2005), SERPENTINE (2007), MoMARDREAMnaut (2007) and MOMAR08-Leg2 (2008) cruises conducted by IFREMER, France. A SBSE-TD-GC-MS technique was developed and used to extract, concentrate, separate and identify compounds in the fluids. Hydrothermally derived compounds appeared to consist mainly of hydrocarbons and O-bearing molecules. In addition, some amino acids were detected in the fluids by ULPC-ESI-QToF-MS but their origin will need to be determined. The organic content of the Rainbow fluids did not show intra field variability unlike differences could be noted over the years. In order to address the question of the source of the molecules, compound specific carbon isotopic analyses were carried out and completed with a bacterial (Pyrococcus abyssi) hydrothermal degradation experiment. The δ13C data fall in the range of -40 to -30‰ (vs. V-PDB), but individual δ13C values preclude the identification of a biogenic or abiogenic origin of the compounds. The degradation experiment, however, suggests an abiogenic origin of a portion of saturated hydrocarbons whereas carboxylic acids would be biogenic, and aromatic compounds would be thermogenic.

Place, publisher, year, edition, pages
Stockholm: Department of Geology and Geochemistry, Stockholm University, 2009. 51 p.
Series
Meddelanden från Stockholms universitets institution för geologi och geokemi, ISSN 1101-1599 ; 336
Keyword
Serpentinisation, hydrocarbons, organic compounds, ultramafic, hydrothermal, geochemistry, origin of life
National Category
Other Earth and Related Environmental Sciences Other Chemistry Topics Geochemistry
Research subject
Geochemistry
Identifiers
urn:nbn:se:su:diva-29172 (URN)978-91-7155-913-5 (ISBN)
Public defence
2009-09-18, William-Olssonsalen, Geovetenskapens hus, Svante Arrhenius väg 8 C, Stockholm, 10:00 (English)
Opponent
Supervisors
Projects
MoMARnet
Note
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Submitted. Paper 3: Submitted. Paper 4: Submitted. Available from: 2009-08-27 Created: 2009-08-12 Last updated: 2009-08-27Bibliographically approved

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Konn, CécileMagnér, JörgenHolm, NilsAlsberg, Tomas
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