Effects of Biological and Chemical Degradation on the Properties of Scots Pine Wood-Part I: Chemical Composition and Microstructure of the Cell Wall.

Research on new conservation treatment for archaeological wood requires large amounts of wooden material. For this purpose, artificial wood degradation (biological-using brown-rot fungus Coniophora puteana, and chemical-using NaOH solution) under laboratory conditions was conducted to obtain an abundance of similar samples that mimic naturally degraded wood and can serve for comparative studies. However, knowledge about its properties is necessary to use this material for further study. In this study, the chemical composition and microstructure of degraded cell walls were investigated using FT-IR, XRD, helium pycnometry and nitrogen absorption methods. The results show that biological degradation caused the loss of hemicelluloses and celluloses, including the reduction in cellulose crystallinity, and led to lignin modification, while chemical degradation mainly depleted the amount of hemicelluloses and lignin, but also affected crystalline cellulose. These changes affected the cell wall microstructure, increasing both surface area and total pore volume. However, the chemical degradation produced a greater number of mesopores of smaller size compared to fungal decomposition. Both degradation processes weakened the cell wall's mechanical strength, resulting in high shrinkage of degraded wood during air-drying. The results of the study suggest that degraded wood obtained under laboratory conditions can be a useful material for studies on new consolidants for archaeological wood.

The Viscoelastic Behaviour of Waterlogged Archaeological Wood Treated with Methyltrimethoxysilane.

Waterlogged wood treatment with methyltrimethoxysilane (MTMS) proved effective in stabilising wood dimensions upon drying (anti-shrink efficiency of 76-93%). Before the method can be proposed as a reliable conservation treatment, further research is required that includes the evaluation of the mechanical properties of treated wood. The aim of the study was to characterise the effect of the treatment on the viscoelastic behaviour of archaeological waterlogged elm and oak wood differing in the degree of degradation. Dynamic mechanical analysis in the temperature range from -150 to +150 °C was used for the study. To better understand the viscoelastic behaviour of the treated wood, pore structure and moisture properties were also investigated using Scanning Electron Microscopy, nitrogen sorption, and Dynamic Vapour Sorption. The results clearly show that methyltrimethoxysilane not only prevents collapse and distortions of the degraded cell walls and decreases wood hygroscopicity (by more than half for highly degraded wood), but also reinforces the mechanical strength by increasing stiffness and resistance to deformation for heavily degraded wood (with an increase in storage modulus). However, the MTMS also has a plasticising effect on treated wood, as observed in the increased value of loss modulus and introduction of a new tan δ peak). On the one hand, methyltrimethoxysilane reduces wood hygroscopicity that reflects in lower wood moisture content, thus limiting the plasticising effect of water on wood polymers, but on the other hand, as a polymer itself, it contributes to the viscous behaviour of the treated wood. Interestingly, the effect of silane differs with both the wood species and the degree of wood degradation.

Ocean warming, more than acidification, reduces shell strength in a commercial shellfish species during food limitation.

Ocean surface pH levels are predicted to fall by 0.3-0.4 pH units by the end of the century and are likely to coincide with an increase in sea surface temperature of 2-4 °C. The combined effect of ocean acidification and warming on the functional properties of bivalve shells is largely unknown and of growing concern as the shell provides protection from mechanical and environmental challenges. We examined the effects of near-future pH (ambient pH -0.4 pH units) and warming (ambient temperature +4 °C) on the shells of the commercially important bivalve, Mytilus edulis when fed for a limited period (4-6 h day(-1)). After six months exposure, warming, but not acidification, significantly reduced shell strength determined as reductions in the maximum load endured by the shells. However, acidification resulted in a reduction in shell flex before failure. Reductions in shell strength with warming could not be explained by alterations in morphology, or shell composition but were accompanied by reductions in shell surface area, and by a fall in whole-body condition index. It appears that warming has an indirect effect on shell strength by re-allocating energy from shell formation to support temperature-related increases in maintenance costs, especially as food supply was limited and the mussels were probably relying on internal energy reserves. The maintenance of shell strength despite seawater acidification suggests that biomineralisation processes are unaffected by the associated changes in CaCO3 saturation levels. We conclude that under near-future climate change conditions, ocean warming will pose a greater risk to shell integrity in M. edulis than ocean acidification when food availability is limited.

Comparative toxicity of nanoparticulate CuO and ZnO to soil bacterial communities.

The increasing industrial application of metal oxide Engineered Nano-Particles (ENPs) is likely to increase their environmental release to soils. While the potential of metal oxide ENPs as environmental toxicants has been shown, lack of suitable control treatments have compromised the power of many previous assessments. We evaluated the ecotoxicity of ENP (nano) forms of Zn and Cu oxides in two different soils by measuring their ability to inhibit bacterial growth. We could show a direct acute toxicity of nano-CuO acting on soil bacteria while the macroparticulate (bulk) form of CuO was not toxic. In comparison, CuSO(4) was more toxic than either oxide form. Unlike Cu, all forms of Zn were toxic to soil bacteria, and the bulk-ZnO was more toxic than the nano-ZnO. The ZnSO(4) addition was not consistently more toxic than the oxide forms. Consistently, we found a tight link between the dissolved concentration of metal in solution and the inhibition of bacterial growth. The inconsistent toxicological response between soils could be explained by different resulting concentrations of metals in soil solution. Our findings suggested that the principal mechanism of toxicity was dissolution of metal oxides and sulphates into a metal ion form known to be highly toxic to bacteria, and not a direct effect of nano-sized particles acting on bacteria. We propose that integrated efforts toward directly assessing bioavailable metal concentrations are more valuable than spending resources to reassess ecotoxicology of ENPs separately from general metal toxicity.