The pulp and paper industry in New Zealand annually produces over one hundred thousand dry tonnes of solid waste due to the treatment of pulp and paper mill effluents, the majority of which is currently landfilled. The New Zealand Waste Management Strategy (2002) has set a target for the diversion of commercial organic wastes from landfill to beneficial use to exceed 95% by 2010 . Effluents produced by softwood pulp mills, such as in New Zealand, contain high concentrations of naturally derived resin extractive compounds that are toxic to fish and other aquatic organisms. Improvements in waste water treatment technology has enabled the industry to meet rigorous discharge standards, however, this has resulted in an increase in the production of pulp mill effluent solids which require disposal. This has become an issue for the pulp and paper industry, especially as current landfill space is limited. Land application has been used for many years as a means of disposal of pulp mill wastes. While most studies investigating land application of pulp mill effluent solids have concluded that the risk posed to the environment is low, few have investigated the potential toxicity of these wastes to soil organisms, and these studies did not directly address the effects of resin extractive compounds. Resin extractives have been shown to be recalcitrant and to accumulate in anaerobic sediments. It is not known to what extent resin extractives are bioavailable or degradable in land applied Pulp mill effluent solids (PMES), or their potential to bioaccumulate in soil organisms. This PhD thesis research sought to extend the knowledge on the environmental fate and effects of pulp mill effluent wastes. It focused on terrestrial systems, which have not been well studied in this respect. Four chemically distinct softwood pulp mill effluent solids, a primary treatment solid and three secondary treatment biosolids, were used to investigate their effects on soil organisms and soil functions. An interdisciplinary approach was adopted, which incorporated three main areas of study, as follows: 1. A comprehensive resin extractives analysis of the pulp mill effluent solids undertaken so that effects on soil organisms and soil functions could be related to the resin extractives chemistry of the individual pulp mill effluent solids tested. 2. A battery of bioassays used to investigate the toxicity of the selected pulp mill effluent solids. 3. A field trial set-up to investigate how pulp mill effluent solids affected soil functions and also to investigate the decomposition of pulp mill effluent solids and of resin extractives in these solids. Three hypotheses tested were: I. Pulp mill effluent solids are toxic to soil organisms. II. Resin extractives in pulp mill effluent solids are recalcitrant in the terrestrial environment. III. Pulp mill effluent solids will cause significant measurable negative impacts on soil functional capacity. A wide range of resin extractives compounds were identified in pulp mill effluent solids, and concentrations of individual compounds varied widely between the different pulp mill effluent solids tested. During the two years after field application of the pulp mill effluent solids, resin extractives declined, however, decay rates of individual compounds were variable. The decay rate of compounds was influenced by the type of pulp mill effluent solids containing these compounds and not by the initial concentration of compounds. All compounds, including resin acids, degraded rapidly in the applied primary solid and in one of the applied biosolids, with average half-lives calculated ranging from three to twelve months. In the other biosolids, resin acids were recalcitrant with average half-lives calculated to be nearly ten years. Laboratory bioassays conducted on oats, earthworms and enchytraeid worms indicated that pulp mill effluent solids had low toxicity to these organisms. An aquatic bioassay organism, however, was acutely affected by aqueous extracts from pulp mill effluent solids. Earthworms were shown to bioaccumulate some resin extractive compounds to a limited extent, indicating that resin extractives were bioavailable in pulp mill effluent solids. Enchytraeid reproduction was reduced by exposure to some pulp mill effluent solids but this was not correlated to resin extractives concentration of the solids tested. Field applied pulp mill effluent solids significantly enhanced the fluxes of CO2 from the soil surface. When mass losses of pulp mill effluent solids carbon were taken into account, it was shown that these solids had little effect on soil respiration. Needle litterbags were placed above and below pulp mill effluent solids and in the litter horizon of a control treatment for 12 months. Needle litter decomposition was not significantly different between treatments, however, changes in enzyme activities were detected in litter beneath pulp mill effluent solids compared to control needle litter that had not been exposed to pulp mill effluent solids. The decomposition rate of field applied pulp mill effluent solids was slow, with half-lives extrapolated to be between five and twenty five years. The decomposition rate appeared to be influenced by the pools of carbon available for decomposition, with primary solids decaying significantly faster than biosolids due to a higher cellulose component. The conclusions of the PhD thesis research are, therefore, that generally, pulp mill effluent solids used in the study were demonstrated to be relatively benign and appear to pose a low risk to the terrestrial ecosystem when applied to soil. However, a cautious approach is still recommended to land application, based on the extensive evidence of disruption to aquatic ecosystems, and because pulp mill effluent solids will take many years to decompose and resin acids are recalcitrant in some pulp mill effluent solids. Further research is recommended to elucidate mechanisms of action by resin extractives in soil organisms and the ultimate fate of these compounds in the soil compartment.

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Voltage-gated K+ (Kv) channels are known to cause serious disease upon their malfunction. Kv channels desensitised to voltage show inability to fully repolarise the membrane in excitable cells, which can make the membrane hyperexcited and in turn cause seizures such as in epilepsy, periodic ataxia or heart arrhythmia. Therefore, enhancers of Kv channels could serve as potential drugs. Some of these enhancers are polyunsaturated fatty acids and resin-acids which bind at the proteinlipid surface and affect the movement of the voltage sensor in the channel by a mechanism called the lipoelectric effect. To explore the lipoelectric modulation mechanism, we have performed an extensive computational study including docking and molecular dynamics simulations on resin-acid derivatives added to a model potassium channel called Shaker. Four derivatives, Wu32 and Wu50 that excite the channel and thus induce repolarisation of the membrane, as well as Wu18 and Wu27, who were found to be non-potent in previous experimental studies, have helped to point out a novel binding site in Shaker. The site is located between the pore and voltage-sensing domain of the channel and is in direct contact with the first gating charge arginine, R1, and the residue W454. We hypothesize that it is possible for resinacid derivatives to directly bind to the voltage-sensor when it is in an activated state, prolonging the time Shaker stays open. Further experimental studies on Shaker and human homologs are now needed to test our hypothesis. Therefore, we suggest recording the sensitivity of Shaker towards potent derivatives in combination with mutations of W454. If our findings of the novel binding site are correct, the suitability of Shaker as a model system for human Kv channel modulation by lipoelectric modulators can be questioned as W454 is replaced by small hydrophobic side chains in mammalian Shaker homologs.