The origin of methanethiol in midocean ridge hydrothermal fluids

Simple alkyl thiols such as methanethiol (CH[subscript 3]SH) are widely speculated to form in seafloor hot spring fluids. Putative CH[subscript 3]SH synthesis by abiotic (nonbiological) reduction of inorganic carbon (CO[subscript 2] or CO) has been invoked as an initiation reaction for the emergence...

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Główni autorzy: Reeves, Eoghan, McDermott, Jill Marie, Seewald, Jeffrey S.
Kolejni autorzy: Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences
Format: Artykuł
Język:en_US
Wydane: National Academy of Sciences (U.S.) 2014
Dostęp online:http://hdl.handle.net/1721.1/91287
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author Reeves, Eoghan
McDermott, Jill Marie
Seewald, Jeffrey S.
author2 Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences
author_facet Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences
Reeves, Eoghan
McDermott, Jill Marie
Seewald, Jeffrey S.
author_sort Reeves, Eoghan
collection MIT
description Simple alkyl thiols such as methanethiol (CH[subscript 3]SH) are widely speculated to form in seafloor hot spring fluids. Putative CH[subscript 3]SH synthesis by abiotic (nonbiological) reduction of inorganic carbon (CO[subscript 2] or CO) has been invoked as an initiation reaction for the emergence of protometabolism and microbial life in primordial hydrothermal settings. Thiols are also presumptive ligands for hydrothermal trace metals and potential fuels for associated microbial communities. In an effort to constrain sources and sinks of CH[subscript 3]SH in seafloor hydrothermal systems, we determined for the first time its abundance in diverse hydrothermal fluids emanating from ultramafic, mafic, and sediment-covered midocean ridge settings. Our data demonstrate that the distribution of CH[subscript 3]SH is inconsistent with metastable equilibrium with inorganic carbon, indicating that production by abiotic carbon reduction is more limited than previously proposed. CH[subscript 3]SH concentrations are uniformly low (∼10[superscript −8] M) in high-temperature fluids (>200 °C) from all unsedimented systems and, in many cases, suggestive of metastable equilibrium with CH[subscript 4] instead. Associated low-temperature fluids (<200 °C) formed by admixing of seawater, however, are invariably enriched in CH[subscript 3]3SH (up to ∼10[superscript −6] M) along with NH[+ over 4] and low-molecular-weight hydrocarbons relative to high-temperature source fluids, resembling our observations from a sediment-hosted system. This strongly implicates thermogenic interactions between upwelling fluids and microbial biomass or associated dissolved organic matter during subsurface mixing in crustal aquifers. Widespread thermal degradation of subsurface organic matter may be an important source of organic production in unsedimented hydrothermal systems and may influence microbial metabolic strategies in cooler near-seafloor and plume habitats.
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spelling mit-1721.1/912872022-10-01T18:28:01Z The origin of methanethiol in midocean ridge hydrothermal fluids Reeves, Eoghan McDermott, Jill Marie Seewald, Jeffrey S. Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences Woods Hole Oceanographic Institution Reeves, Eoghan McDermott, Jill Marie Simple alkyl thiols such as methanethiol (CH[subscript 3]SH) are widely speculated to form in seafloor hot spring fluids. Putative CH[subscript 3]SH synthesis by abiotic (nonbiological) reduction of inorganic carbon (CO[subscript 2] or CO) has been invoked as an initiation reaction for the emergence of protometabolism and microbial life in primordial hydrothermal settings. Thiols are also presumptive ligands for hydrothermal trace metals and potential fuels for associated microbial communities. In an effort to constrain sources and sinks of CH[subscript 3]SH in seafloor hydrothermal systems, we determined for the first time its abundance in diverse hydrothermal fluids emanating from ultramafic, mafic, and sediment-covered midocean ridge settings. Our data demonstrate that the distribution of CH[subscript 3]SH is inconsistent with metastable equilibrium with inorganic carbon, indicating that production by abiotic carbon reduction is more limited than previously proposed. CH[subscript 3]SH concentrations are uniformly low (∼10[superscript −8] M) in high-temperature fluids (>200 °C) from all unsedimented systems and, in many cases, suggestive of metastable equilibrium with CH[subscript 4] instead. Associated low-temperature fluids (<200 °C) formed by admixing of seawater, however, are invariably enriched in CH[subscript 3]3SH (up to ∼10[superscript −6] M) along with NH[+ over 4] and low-molecular-weight hydrocarbons relative to high-temperature source fluids, resembling our observations from a sediment-hosted system. This strongly implicates thermogenic interactions between upwelling fluids and microbial biomass or associated dissolved organic matter during subsurface mixing in crustal aquifers. Widespread thermal degradation of subsurface organic matter may be an important source of organic production in unsedimented hydrothermal systems and may influence microbial metabolic strategies in cooler near-seafloor and plume habitats. Woods Hole Oceanographic Institution. Deep Ocean Exploration Institute InterRidge German Science Foundation (Cluster of Excellence) 2014-11-04T15:43:33Z 2014-11-04T15:43:33Z 2014-03 2014-01 Article http://purl.org/eprint/type/JournalArticle 0027-8424 1091-6490 http://hdl.handle.net/1721.1/91287 Reeves, Eoghan P., Jill M. McDermott, and Jeffrey S. Seewald. “The Origin of Methanethiol in Midocean Ridge Hydrothermal Fluids.” Proceedings of the National Academy of Sciences 111, no. 15 (March 27, 2014): 5474–5479. en_US http://dx.doi.org/10.1073/pnas.1400643111 Proceedings of the National Academy of Sciences Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf National Academy of Sciences (U.S.) PNAS
spellingShingle Reeves, Eoghan
McDermott, Jill Marie
Seewald, Jeffrey S.
The origin of methanethiol in midocean ridge hydrothermal fluids
title The origin of methanethiol in midocean ridge hydrothermal fluids
title_full The origin of methanethiol in midocean ridge hydrothermal fluids
title_fullStr The origin of methanethiol in midocean ridge hydrothermal fluids
title_full_unstemmed The origin of methanethiol in midocean ridge hydrothermal fluids
title_short The origin of methanethiol in midocean ridge hydrothermal fluids
title_sort origin of methanethiol in midocean ridge hydrothermal fluids
url http://hdl.handle.net/1721.1/91287
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