<p>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 <i>Vasa</i>, while the distribution is rather uniform throughout the hull timbers of the <i>Mary Rose</i>, 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 <i>in situ</i> 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 <i>Vasa</i> and the <i>Mary Rose</i> are estimated to at least 2 tonnes. After the <i>Vasa´s</i> 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 <i>Vasa</i> wood by ammonia gas have been conducted with promising results.</p>

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.

Ziel der vorliegenden Arbeit war es, den Einfluss verschiedener Schwefel (S)-Düngemittel, der Leguminosenart und des Gemengebaus von Erbse (Pisum sativum L.) und Gerste (Hordeum vulgare L.) auf die Schwefelakkumulation sowie den Ertrag der Ackerbohne (Vicia faba L.), Schmalblättrige Lupine (Lupinus angustifolius L.) und Erbse zu erheben. In den Jahren 2012 bis 2014 wurden Feldversuche auf zahlreichen Standorten durchgeführt, um die Wirkung von Kieserit (MgSO4), Gips (CaSO4), elementarem S und Bittersalz (MgSO4 × 7H2O) auf die Körnerleguminosen zu testen. Die Düngung von Ackerbohne, Schmalblättriger Lupine und Erbse mit verschiedenen S-haltigen Düngemitteln führte unter den geprüften Feldbedingungen weder zu Ertragssteigerungen noch zu einer gesteigerten N-Akkumulation. Der S-Bedarf der drei Körnerlegunminosen wurde offenbar über natürliche Ressourcen gedeckt. Trotzdem zeigten sich Gips und Kieserit, teilweise auch Bittersalz als geeignete Düngemittel, um die S-Konzentration im Gewebe der Pflanzen zu erhöhen. Die S-Akkumulation im Spross der Ackerbohne (5-17 kg S ha-1), Schmalblättrigen Lupine (5-15 kg S ha-1) und Erbse (2-13 kg S ha-1) war gering und wurde von den Pflanzen an deren Bedarf angepasst. Im Gegensatz zu Ackerbohne (SHI 0,65) und Erbse (SHI 0,63), die S vorwiegend im Korn akkumulierten, sammelte die Schmalblättrige Lupine einen Großteil des aufgenommenen S im Stroh (SHI 0,40) an. Der Einfluss des Gemengeanbaus mit Gerste auf den S-Haushalt der Erbse war sehr gering. Die Erbse in Reinsaat nahm signifikant mehr S gemittelt über alle getesteten Düngemittel auf als das Gemenge aus Erbse und Gerste. Erbse und Gerste akkumulierten ähnlich hohe Mengen S im Spross pro Einheit Kornertrag. Um maximale Kornerträge sowie N- und S-Akkumulationen in einem substitutiv zusammengesetzten Gemenge aus Erbse und Gerste zu erzielen, wurde ein optimales Saatverhältnis von 42-88% keimfähiger Erbsensamen zu 12-58% keimfähigen Gerstensamen der jeweiligen Reinsaatstärke ermittelt. / The objectives of this study were to evaluate the influence of different sulfur (S) containing fertilizers, the legume species and of intercropping of pea (Pisum sativum L.) and barley (Hordeum vulgare L.) on sulfur accumulation and yield of faba bean (Vicia faba L.), narrow leaf lupin (Lupinus angustifolius L.) and pea. In the years 2012 to 2014 field trials have been conducted to test the effects of kieserite (MgSO4), gypsum (CaSO4), elemental S and epsom salt (MgSO4 × 7H2O) on grain legumes at several sites in Germany. Under the given environmental conditions, fertilization of faba bean, narrow leaf lupin and pea with different S containing fertilizers did not increase yield and nitrogen (N) accumulation. The S demand of the three grain legumes was low and obviously covered by S sources from the soil as well as atmospheric S deposition. However, gypsum, kieserite and epsom salt generated noticeable increases in S concentration in parts of the plants. S accumulation in shoots of faba bean (5-17 kg S ha-1), narrow leaf lupin (5-15 kg S ha-1) and pea (2-13 kg S ha-1) was comparatively low and has been adapted to the plants respective S demand. In contrast to faba bean (SHI 0,65) and pea (SHI 0,63), who accumulated S predominantly in seeds, narrow leaf lupin (SHI 0,40) accumulated the bulk of S in its straw. The influence of barley on peas S concentration was very low. Pea in pure stands accumulated significantly more S than the total intercrop of pea and barley, whereas pea and barley accumulated similar amounts of S in its shoots per unit seed yield. To achieve the maximum seed yield and maximum N and S accumulation in substitutive mixtures of pea and barley, a relative seed frequency of 42%–88% pea seeds to 12%–58% barley seeds of their monocrop seeding rate has been calculated to be optimal.