Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Sulfur Accumulation in the Timbers of King Henry VIII’s Warship Mary Rose: A Pathway in the Sulfur Cycle of Conservation Concern
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
Show others and affiliations
2005 (English)In: Proceedings of the National Academy of Sciences of the United States of America, PNAS, ISSN 0027-8424, Vol. 102, no 40, 14165-14170 p.Article in journal (Refereed) Published
Abstract [en]

In marine-archaeological oak timbers of the Mary Rose large amounts of reduced sulfur compounds abound in lignin-rich parts such as the middle lamella between the cell walls, mostly as thiols and disulfides, whereas iron sulfides and elemental sulfur occur in separate particles. Synchrotron-based x-ray microspectroscopy was used to reveal this environmentally significant accumulation of organosulfur compounds in waterlogged wood. The total concentration of sulfur in reduced forms is ≈1 mass % throughout the timbers, whereas iron fluctuates up to several mass %. Conservation methods are being developed aiming to control acid-forming oxidation processes by removing the reactive iron sulfides and stabilizing the organosulfur compounds.

Place, publisher, year, edition, pages
2005. Vol. 102, no 40, 14165-14170 p.
Identifiers
URN: urn:nbn:se:su:diva-25011DOI: 10.1073/pnas.0504490102OAI: oai:DiVA.org:su-25011DiVA: diva2:198717
Note
Part of urn:nbn:se:su:diva-7627Available from: 2008-05-13 Created: 2008-05-09 Last updated: 2010-01-15Bibliographically 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
Opponent
Supervisors
Available from: 2008-05-13 Created: 2008-05-09 Last updated: 2011-01-11Bibliographically approved
2. Structure and bonding of sulfur-containing molecules and complexes
Open this publication in new window or tab >>Structure and bonding of sulfur-containing molecules and complexes
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Synchrotron-based spectroscopic techniques enable investigations of the many important biological and environmental functions of the ubiquitous element sulfur. In this thesis the methods for interpreting sulfur K-edge X-ray absorption near edge structure (XANES) spectra are developed and applied for analyses of functional sulfur groups. The influence of coordination, pH, hydrogen bonding, etc., on the sulfur 1s electronic excitations is evaluated by transition potential density functional theory. Analyses have been performed of reduced sulfur compounds in marine-archaeological wood from historical shipwrecks, including the Vasa, Stockholm, Sweden and the Mary Rose, Portsmouth, U.K.. The accumulation of sulfur as thiols in lignin-rich parts of the wood on the seabed is also a probable pathway in the natural sulfur cycle for how reduced sulfur enters fossil fuels via humic matter in anaerobic marine sediments. Sulfur K-edge XANES spectra for several biochemical model compounds and for coexisting isomeric sulfur species in cysteine and sulfite(IV) aqueous solutions have been analyzed with the aid of theoretical calculations. Cysteine derivatives are important for biochemical detoxification, and mercury(II) cysteine complexes in solution have been structurally characterized by means of Extended X-ray Absorption Fine Structure (EXAFS), Raman and 199Hg NMR spectroscopy. Lanthanoid(III) ions were found to coordinate eight dimethyl sulfoxide oxygen atoms in a distorted square antiprism in the solid state and in solution, by combining crystallography, EXAFS, XANES and vibrational spectroscopy. The mean M-O bond distances for the disordered crystal structures are in good agreement with those from the lattice-independent EXAFS studies. The different sulfur K-edge XANES spectra for the dimethyl sulfoxide ligands in the hexasolvated complexes of the trivalent group 13 metal ions, Tl(III), In(III), Ga(III) and Al(III), were interpreted by theoretical calculations.

Place, publisher, year, edition, pages
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi, 2007. 105 p.
Keyword
Sulfur species, x-ray absorption and vibrational spectroscopy, TP-DFT calculations
National Category
Chemical Sciences
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-6843 (URN)978-91-7155-423-9 (ISBN)
Public defence
2007-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2007-05-15 Created: 2007-05-04 Last updated: 2010-01-15Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Sandström, MagnusFors, Yvonne
By organisation
Department of Physical, Inorganic and Structural Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 88 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf