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.

Recent studies have shown that dehydroabietic acid (DHAA), a resin acid present in pulp and paper mills, may have anti-estrogenic effects in fish. A chronic-exposure toxicity experiment using immature rainbow trout (Oncorhynchus mykiss) was conducted in order to assess the endocrine disrupting and liver metabolic effects of the wood extractives DHAA and β- sitosterol (BS) regularly present in pulp and paper mills and the model estrogen 17β-estradiol (E2). It was found that exposure to 5 ppm of E2 significantly increased hepatosomatic index (HSI), vitellogenin (VTG) and plasma sorbitol dehydrogenase (SDH). This effect was reduced by mixing E2 with DHAA, indicating that DHAA does not cause its anti-estrogenic effects indirectly due to liver damage. Exposure to 5 ppm of DHAA caused a significant increase in liver citrate synthase (CS), and liver ethoxyresorufin-O-deethylase (EROD) activity after 7 days, however, the fish recovered by 28 days. This study also determined the effect of 14 different pulp and paper mill effluent extracts on liver enzyme metabolism through alterations in the activity of liver lactate dehydrogenase activity (LDH) and CS. This activity varied greatly between mills but most showed an induction of CS after 28 days exposure through i.p. injection. The results of the study indicate that DHAA may alter energy metabolism as well as cause anti-estrogenic effects in female juvenile rainbow trout. / UOIT