Gunnar Almkvist

Degradation of polyethylene glycol and hemicellulose in the Vasa

Abstract Mass spectrometric analysis of aqueous wood extracts from the Swedish warship Vasa reveals a serious chemical condition in the depth of the wood. The surface is less affected. Polyethylene glycol, used as conservation agent, is affected and partly degraded, and low-molecular fragments from hemicellulose are found at sites with high iron content and low pH. These findings imply a catalytic oxidative process and acidic hydrolysis in the wood, which contributes to a new picture of the challenge of long-term preservation of the Vasa.

K-edge XANES analysis of sulfur compounds: an investigation of the relative intensities using internal calibration.

Sulfur K-edge XANES (X-ray absorption near-edge structure) spectroscopy is an excellent tool for determining the speciation of sulfur compounds in complex matrices. This paper presents a method to quantitatively determine the kinds of sulfur species in natural samples using internally calibrated reference spectra of model compounds. Owing to significant self-absorption of formed fluorescence radiation in the sample itself the fluorescence signal displays a non-linear correlation with the sulfur content over a wide concentration range. Self-absorption is also a problem at low total absorption of the sample when the sulfur compounds are present as particles. The post-edge intensity patterns of the sulfur K-edge XANES spectra vary with the type of sulfur compound, with reducing sulfur compounds often having a higher post-edge intensity than the oxidized forms. In dilute solutions (less than 0.3-0.5%) it is possible to use sulfur K-edge XANES reference data for quantitative analysis of the contribution from different species. The results show that it is essential to use an internal calibration system when performing quantitative XANES analysis. Preparation of unknown samples must take both the total absorption and possible presence of self-absorbing particles into consideration.

Analysis of acids and degradation products related to iron and sulfur in the Swedish warship Vasa

Abstract Aqueous wood extracts from the historic Swedish warship Vasa have been analyzed by 1H-NMR spectroscopy, ion chromatography, and matrix assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry as part of studies on the chemical degradation related to increased levels of iron and sulfur. The results show that low molecular organic acids have accumulated in the Vasa wood after the 1961 salvage. The increased acidity was found in a context of chemical degradation of the wood polymers and the conservation agent polyethylene glycol (PEG) in iron-rich parts of the timber. Formic, glycolic and oxalic acid are all possible end-products of oxidative degradation of wood polymers, whereas hydrolysis of acetyl groups in xylan may have contributed to increased concentrations of acetic acid. MALDI-TOF spectra of PEG displaced towards low-molecular PEG oligomers, as reported earlier, were accompanied by increased levels of formic acid, indicating oxidative degradation of PEG. PEG with a carboxylic acid end group (PEGC) was observed to a minor degree in the wood. However, analysis of stored conservation treatment solutions showed high concentrations of PEGC yielding significant contributions to the acidity during the 1960s conservation period. PEGC was probably formed as a result of microbial processes during the early conservation regime. Calculations using concentrations and well-established acidity constants show that oxalic and formic acid are the primary contributors to a low pH in the wood. The increased acidity in the interior of the wood was found in the absence of sulfur compounds but in a context of iron. The majority of the sub-samples with significant levels of sulfate in the surface region with a prospective sulfur oxidation, however, showed neither a decreased pH nor significant depolymerization. This indicates that oxidation pathways of organically bound sulfur do not necessarily produce strong acids, and thereby free protons, as the final product. These observations imply opposing effects of iron and reduced sulfur species, with iron acting as a initiator in oxidative reactions of Fenton type, whereas the reduced organic sulfur compounds may act as anti-oxidants.

Fenton-induced degradation of polyethylene glycol and oak holocellulose. A model experiment in comparison to changes observed in conserved waterlogged wood

Abstract Degradation of polysaccharides and polyethylene glycol have recently been observed in the wood of the Swedish war-ship Vasa. The signs of degradation are highly correlated to the presence of iron compounds, indicating iron initiated reactions of Fenton type. In order to test this hypothesis pure polyethylene glycol (PEG, Mw =1500 u) and prepared oak holocellulose were oxidized by hyddroxyl radicals induced by Fentons reagent [Fe(II)/H2O2] in aqueous solution. The changes in molar weight distribution (MWD) were analysed by MALDI-TOF mass spectrometry and size exclusion chromatography. The changes in MWD were consistent to random scission of the polymers according to statistical simulations. By NMR analysis the main PEG degradation products formed were identified as PEG molecules with different end groups: alcohols, aldehydes and formate esters; the latter hydrolyse to formic acid. The all over results show close similarities to the situation observed in the Vasa wood and strengthen the hypothesis of oxidative degradation initiated by iron compounds in the wood.

Extraction of iron compounds from wood from the Vasa

Abstract In 2000, salt precipitates were found on surfaces of the Swedish warship Vasa, accompanied by low pH values, partly as a result of oxidation of accumulated sulfur compounds. One hypothesis is that oxidation of the sulfur compounds was catalysed by the large amounts of diverse iron compounds present in the wood. It is therefore of interest to develop a method to extract the iron compounds and simultaneously neutralise the acids. The iron compounds could be extracted using an aqueous solution of ethylenediimino-bis(2-hydroxy-4-methylphenyl)acetic acid (EDDHMA) or diethylenetriamine penta-acetic acid (DTPA) at alkaline pH, leaving only small amounts of iron compounds. The polyethylene glycol (PEG) used as the conservation agent, salts and other water-soluble compounds were co-extracted. The extraction rate was enhanced by stirring and by higher concentrations of the chelator, but diffusion of compounds through the wood was the most important factor for the overall extraction efficiency. Extraction of iron compounds from deep inside the wood is time-consuming and may take years. The results from this study imply that aqueous extraction with strong chelators at relatively high pH, 9–11, effectively removes iron compounds and neutralises the acids present. Although the results are promising, it is still too early to start major re-conservation of Vasa wood using extraction, as all the effects on the wood are not known, but such studies are in progress.

Impact of iron(II) and oxygen on degradation of oak - modeling of the Vasa wood

Abstract In the wood of the Swedish 17th century warship Vasa, iron (Fe)-catalyzed chemical degradation has taken place after the salvation in 1961, which is manifested in increased acidity accompanied by cellulose degradation and reduced strength in the oak hull. Model studies on fresh oak impregnated with Fe(II) also led to tensile strength (TS) reduction in the same order of magnitude as observed in the wood of the Vasa. In the present study, further experiments have been performed concerning the Fe-catalyzed wood degradation. Namely, the degree of wood degradation was monitored quantitatively by measurement of the O2 consumption of Fe(II)-impregnated oak, kept in closed vials with different relative humidities (RH), as a function of time. The initial O2 consumption was high and declined with time. After 200 days, the accumulated O2 consumption was 0.3–0.4 mmol g-1 wood. Degradation products with low molecular weight were analyzed. The release of CO2 and oxalic acid (OA) was positively correlated with RH (0.235 and 0.044 mmol g-1, respectively, at RH98% after 200 days). Samples kept for 1500 days at RH54% had accumulated 0.044 mmol OA g-1 wood, which is equal to the average OA content in the interior of Vasa oak (corresponding to 4 mg g-1). Oak samples, from which extractives had been removed prior to Fe(II) impregnation, did not change their O2 consumption or TS reduction compared to the nonextracted samples, indicating that extractives are not essential for cellulose degradation in this context.

Distribution of iron and sulfur and their speciation in relation to degradation processes in wood from the Swedish warship Vasa

Wood samples from the Swedish warship Vasa were analysed by scanning electron microscopy and X-ray absorption spectroscopy with the focus on speciation and distribution of iron and sulfur compounds in the wood matrix. Both these elements were found at high concentration (10–100 mg g−1) in the surface region as a result of former accumulation of iron sulfides, elemental sulfur and reduced organic sulfur species (ROSS). Below the surface region, iron was the dominating element (1–10 mg g−1) present both as iron(II) and iron(III) compounds, which diffused into the wood matrix from corroding iron bolts and other iron items during the time in the sea (1628–1961). Electron microscopy results revealed that iron and sulfur are present in a variety of particles of different sizes and compositions in the surface region, in contrast to the interior where few particles were found. Here, the presence of iron compounds of nano-particle size inside the cell walls enables a close contact between the wood polymers and reactive oxygen species originating from reactions with iron compounds. The presence of ROSS seems to have played an important role as scavengers of reactive oxygen species. Samples with high iron : ROSS ratio displayed evident signs of degradation as indicated by depolymerisation of wood components accompanied by increased acidity due to low molecular organic acids. The observations strengthen the hypothesis of the pro-oxidative and antioxidant properties of iron and ROSS compounds, respectively, and that the chemical activities of these elements play crucial roles in the long term preservation of wooden maritime artefacts.

Relations of density, polyethylene glycol treatment and moisture content with stiffness properties of Vasa oak samples

Abstract Treatment with polyethylene glycol (PEG) is the preferred method for the conservation of waterlogged archaeological wooden objects. However, PEG impregnation leads to softening and increased hygroscopicity of the material. The present study compiles experimental results concerning the full elastic properties of PEG impregnated archaeological wood from the Vasa ship in relation to its basic density, PEG content (PEGC) and moisture content (MC). The results show a correlation between a more porous microstructure and high PEGC, and consequently, higher MC. The PEG and moisture contribute to the mass of the wooden object as well as to the softening of the material, which are undesired properties in a larger load-carrying wooden structure. A compromise between the improved dimensional stability and degradation of mechanical properties should therefore be considered in the conservation of wooden objects treated with PEG.

Prediction of tensile strength in iron-contaminated archaeological wood by FT-IR spectroscopy - a study of degradation in recent oak and Vasa oak

Abstract Oak from the Swedish warship Vasa and recent oak that was aged after impregnation with iron(II) chloride has been analyzed by FT-IR spectroscopy and submitted to tensile strength testing. The aim was to investigate correlations between FT-IR bands in the fingerprint region, chemical degradation, and tensile strength in iron contaminated oak. The concentration of carboxylic functions increased and the acetyl groups in the hemicellulose fraction were decreasing as a function of degradation time. These changes are accompanied by reduced tensile strength and elevated content of oxalic acid (OA) in both Vasa wood and the impregnated recent oak samples. To evaluate the possibility to predict tensile strength from spectral data, chemometric modeling by partial least-squares (PLS) regression was applied. The strategy of repeated double cross validation (rdCV) allowed a realistic prediction of tensile strength. Overall, chemical changes and mechanical performances of iron contaminated wood are strongly correlated and thus FT-IR spectroscopy is suited to predict the strength properties of the degraded wood.

Mimicking of the strength loss in the Vasa: model experiments with iron-impregnated recent oak

Abstract Previous studies of the oak wood of the 17th century warship the Vasa have shown significant changes in the chemical and mechanical properties compared with recent oak. The most important factors contributing to these changes are the incorporation of iron compounds during waterlogging and the uptake of polyethylene glycol (PEG) in the course of the 17 years of preservation treatment. To investigate the effect of iron-dependent oxidative degradation reactions, recent oak wood samples were impregnated with aqueous iron(II) chloride solution (0.1 M) and thereafter exposed to air or pure oxygen at controlled relative humidity in long-term experiments followed by tensile strength (TS) measurements. The iron-impregnated samples exposed to oxygen displayed significant effects already after 1 week and the reduction in TS was ~50% after 1 year. The samples treated with additional PEG displayed less TS reduction, whereas the addition of cysteine had no effect. The size exclusion chromatography of treated samples showed that the average molecular weight of holocellulose had decreased. The results confirm that iron compounds have a detrimental effect in wood and indicate that PEG might act as an antioxidant for the degradation processes. Concerning the Vasa, it may be concluded that most degradation related to iron compounds and oxidative processes have taken place during the first period of conservation when the wood was exposed to oxygen in a still very humid state. Thus, the current rate of oxidative degradation under the present relatively dry museum conditions should be relatively low.