Sulfur and iron analyses of marine archaeological wood in shipwrecks from the Baltic Sea and Scandinavian waters

Analyses of marine archaeological wood from shipwrecks in the Baltic Sea area, Kronan, Riksnyckeln, Tattran, the Puck Bay Boat and the Ghost wreck, and at the Scandinavian West coast, the Göta wreck, Stora Sofia and the Viking shipwrecks of Skuldelev, show accumulation of sulfur compounds. The penetration profiles of sulfur and iron into the wood and the speciation of characteristic sulfur groups were evaluated by combining X-ray spectroscopic analyses, in particular S K-edge XANES (X-ray absorption near edge structure) and X-ray fluorescence, with ESCA and elemental analyses. The combined analyses support the hypothesis that hydrogen sulfide produced by sulfate-reducing bacteria reacts and accumulates at low iron concentration mainly as organically bound sulfur, which as in previous studies was found by X-ray spectro-microscopy to accumulate in lignin-rich parts of the wood cell walls. The presence of iron(II) ions from corroding iron promotes formation of pyrite and other iron(II) sulfides, which easily oxidise in aerobic conditions with high humidity. No significant differences in sulfur and iron accumulation were found in wood from shipwrecks in the east coast brackish water and the west coast seawater. Sediments from three wreck sites, the Göta wreck, Stora Sofia and Kronan, were analyzed to a depth of a few decimeters and showed especially at the Stora Sofia high sulfur concentrations, exceeding 3 mass%. S K-edge XANES analyses of the sediments showed mainly reduced forms of sulfur, in particular pyrite and iron(II) sulfides together with elemental sulfur.