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Sulfur Accumulation in Pine Wood (Pinus sylvestris) Induced by Bacteria in Simulated Seabed Environment: Implications for Marine Archaeological Wood and Fossil Fuels
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
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2008 (English)In: International Biodeterioration & Biodegradation, ISSN 0964-8305, E-ISSN 1879-0208, no 62, 336-347 p.Article in journal (Refereed) Published
Abstract [en]

Fresh pine wood blocks were submerged in sulfate and iron(II) containing media, inoculated with bacterial consortia isolated from seawater, aiming to simulate the seabed conditions of the Vasa shipwreck (1628). The consortia contained erosion (EB) and sulfate-reducing bacteria (SRB). Sulfur K-edge x-ray absorption near edge structure (XANES) spectroscopy and scanning x-ray spectromicroscopy images showed that organic sulfur, mainly thiols (R-SH), had accumulated in the lignin-rich middle lamella in EB-degraded parts of the wood. The sulfur content in the wood increased more than 10 times in two years. In another series with active inoculums from marine archaeological wood, the sulfur XANES spectra showed after four years anaerobic treatment considerable amounts also of inorganic iron sulfides, Fe1-xS, which oxidized at atmospheric exposure. A sediment sample from the Vasa’s seabed was also rich in iron sulfides, including pyrite FeS2. X-ray fluorescence mappings of sulfur and phosphorous distributions indicate that scavenging SRB penetration, producing hydrogen sulfide in situ, is restricted to EB-degraded parts of the wood structure. The sulfur isotope depletion of 34S from d34S = 21‰ in marine sulfate to d34S = 6‰ and 1.8‰ for fractions of reduced sulfur and sulfate separated from a Vasa wood sample, respectively, suggests bacterial transformation. A fuller understanding of the routes of sulfur accumulation, as reactive iron sulfides and as organic sulfur, has important implications for improving conservation methods of marine archaeological wood. Moreover, the biogenic accumulation of organically bound sulfur specifically in lignin-rich parts of waterlogged wood has wider geochemical significance for fossil fuels of marine origin, as lignin-rich humic matter is important for the diagenetic formation of kerogens from anoxic marine sediments.

Place, publisher, year, edition, pages
2008. no 62, 336-347 p.
Identifiers
URN: urn:nbn:se:su:diva-25014ISI: 000261010500003OAI: oai:DiVA.org:su-25014DiVA: diva2:198720
Note
Part of urn:nbn:se:su:diva-7627Available from: 2008-05-13 Created: 2008-05-09 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Sulfur-Related Conservation Concerns in Marine Archaeological Wood: The Origin, Speciation and Distribution of Accumulated Sulfur with Some Remedies for the Vasa
Open this publication in new window or tab >>Sulfur-Related Conservation Concerns in Marine Archaeological Wood: The Origin, Speciation and Distribution of Accumulated Sulfur with Some Remedies for the Vasa
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Synchrotron-based sulfur spectroscopy reveals a common concern for marine archaeological wood from seawater: accumulation of reduced sulfur compounds in two pathways. The distribution of sulfur species in the oak wood cell structure was mapped by scanning x-ray spectro-microscopy (SXM). Organically bound sulfur was found within lignin-rich parts, identified mainly as thiols and disulfides by sulfur K-edge x-ray absorption near edge structure (XANES) spectroscopy. Particles of iron sulfides, which may form in the presence of corroding iron, appeared in wood cavities. Cores scanned by x-ray fluorescence (XRF) show that high sulfur accumulation is restricted to the surface layers for the Swedish shipwreck Vasa, while the distribution is rather uniform throughout the hull timbers of the Mary Rose, U.K. Laboratory experiments, exposing fresh pine to simulated seabed conditions, show that the organically bound sulfur develop in reactions between lignin, exposed by cellulose-degrading erosion bacteria, and hydrogen sulfide produced in situ by scavenging sulfate reducing bacteria. With bacteria inoculated from shipwreck samples also iron sulfides formed. The iron sulfides oxidise in high humidity, and are the probable main cause of the numerous outbreaks on the Vasa’s hull of acidic sulfate salts, which were identified by x-ray powder diffraction (XRD). The iron ions catalyse several wood-degrading oxidative processes. Multi-elemental analyses were performed by scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (ESCA). The present amounts of total S remaining in the Vasa and the Mary Rose are estimated to at least 2 tonnes. After the Vasa´s spray treatment with polyethylene glycol solutions ceased in 1979, the continuing oxidation processes are estimated to have produced 2 tonnes of sulfuric acid in the wood. Laboratory experiments to gently neutralize acidic Vasa wood by ammonia gas have been conducted with promising results.

Place, publisher, year, edition, pages
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi, 2008. 105 p.
Keyword
Sulfur accumulation, marine archaeological wood, Vasa, acidity, iron, ammonia, x-ray spectroscopy, cellulose
National Category
Chemical Sciences
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-7627 (URN)978-91-7155-624-0 (ISBN)
Public defence
2008-06-03, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 09:30
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Available from: 2008-05-13 Created: 2008-05-09 Last updated: 2011-01-11Bibliographically approved

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