The overall objective of this research is to identify and optimize enzymatic applications that have the potential to degrade middle lamella lignin, so as to decrease economic and environmental costs associated with the production of mechanical pulp. Non-productive binding of enzyme to lignin in lignocellulosic biomass reduces enzyme availability and efficiency. The elucidation of non-productive binding behavior between hydrolytic enzymes and lignocellulosic substrates could significantly improve the efficiency of corresponding industrial bioprocesses. The first part of this report presents a study that characterizes non-catalytic interactions between enzymes and fibre. The second part of this report presents the biochemical and mutational studies of a novel, small laccase SCO6712 from Streptomyces coelicolor. The findings from this research support the design, control, and optimization of enzymatic treatments of lignocellulosic fibres in the pulp and biofuel industries.

Little is known about the enzyme-substrate interactions occurring during the dechlorination of chloroform (CF) and 1,1,1-trichloroethane (1,1,1-TCA) by the enrichment culture containing Dehalobacters, hereafter called DHB-CF/MEL. Compound specific isotope analysis (CSIA) is used to investigate the factors which may affect the isotope fractionation observed for CF and 1,1,1-TCA dechlorination. This thesis reports the first isotope enrichment factors observed for CF biodegradation at -27.5‰ ± 0.9‰, thus providing fundamental information for comparing isotope enrichment factors observed during trichlorinated alkane degradation by DHB-CF/MEL. The thesis also reports how the presence of CF and 1,1,1-TCA influences isotope fractionation and explores the possible influence of substrate inhibition on isotope fractionation during 1,1,1-TCA dechlorination. The data suggests that substrate inhibition during 1,1,1-TCA dechlorination by DHB-CF/MEL may not affect carbon isotope fractionation. The results suggest that CSIA is a promising monitoring tool even for the simultaneous biodegradation of CF and 1,1,1-TCA at different 1,1,1-TCA starting concentration.

Private Environmental Preference (PEP), measured by the willingness to spend on pollution reduction and its casual factors. A PEP model is constructed for Canada, China, India, and USA using data from the World Value Survey and Structural Equation Models. The results revealed that the most important factors are: environmental organization membership, acknowledgement of global environmental problems, Machiavellian attitudes towards money, and confidence in governing bodies. Other significant factors include: the acknowledgement of local environmental problems, income level, occupational characteristics, and work ethic. The acknowledgement of global problems and confidence in governing bodies increase PEP, while Machiavellian attitudes towards money reduce PEP across all four countries. Environmental organizational membership on PEP increase PEP in Canada and USA, but decrease PEP in India. White-collar occupational characteristics have a positive effect on PEP in Canada, but negative in China and India. Policy recommendations are provided given these observations.

There have been no landscape-scale studies on earthworm populations in Canada comparing vegetation types; previous studies on edge habitats have been conducted in agricultural systems. I examined the spatial variations of earthworm populations by measuring abundance based on regional municipality, vegetation type, and edge habitat. Earthworms were sampled throughout the season across a gradient of vegetation types including meadow, forest edge, and interior at a local-scale; and at the landscape level with vegetation types including meadow, deciduous forest, pine plantation and mixed forest. Regional effects were more significant than vegetation type likely due to a gradient of soil characteristics in southern Ontario; edges had intermediate earthworm abundance and a higher proportion of epigeic species. My research provides insight into the patterns of earthworm populations in southern Ontario and the possible effects of edge creation through landscape fragmentation. Field sampling of earthworm parasitoid cluster-flies (Calliphoridae: Pollenia) using synomones was also discussed.

Forestry activities play a crucial role in climate change mitigation. To make carbon credits generated from such activities a tradable commodity, it is important to analyze the price dynamics of carbon markets. This dissertation contains three essays that examine various issues confronting world’s carbon markets. The first essay investigates cointegration of carbon markets using Johansen maximum likelihood procedure. All carbon markets of the world are not integrated. North American carbon markets show integration and so do the CDM markets. For future, the possibilities of arbitrage across world’s markets are expected to be limited, and carbon trading in these markets will be globally inefficient. There is a strong need of a global agreement that allows carbon trade to prevent climate change at the least cost options. The second essay evaluates various econometric models for predicting price volatility in the carbon markets. Voluntary carbon market of Chicago is relatively more volatile; and like other financial markets, its volatility is forecasted best by a complex non-linear GARCH model. The compliance market of Europe, on the other hand, is less volatile and its volatility is forecasted best by simple econometric models like Historical Averages and GARCH and hence is different from other markets. Findings could be useful for investment decision making, and for making choice between various policy instruments. The last essay focuses on agent based models that incorporate interactions of heterogeneous entities. Artificial carbon markets obtained from such models have statistical properties - lack of autocorrelations, volatility clustering, heavy tails, conditional heavy tails, and non-Gaussianity; which are similar to the actual carbon markets. These models possess considerably higher forecasting capabilities than the traditional econometric models. Forecast accuracy is further improved considerably through experimentation, when agent characteristics like wealth distribution, proportion of allowances and number of agents are set close to the real market situations.

Participatory action research (PAR) oriented by an eco-system health framework is one approach to involving marginalised peoples in their own problem solving. A PAR project during 2005-06 that engaged peri-urban farmers in Senegal using popular education documented change on environment and health perceptions and behaviour. Health as a theme took on greater importance, as farmers related good health to their ability to work and their overall productivity. Farmers came to better recognize the symptoms of pesticide poisoning and to establish more clearly the link between pesticide-related work practices and health effects. Less clear remained their recognition of symptoms and links with wastewater use practices, though malaria and parasitic infection were linked to urban agriculture. African worldviews, including notions of locus of power, were important determinants of perceived vulnerability to risks. Farmers cited fatigue as an important clue to the work-health interface and indicator of overall wellbeing. Farmers’ understanding evolved to become more dynamic, describing the complex web of environmentally-related health risk. By 2006, farmers experimented more with less toxic pest control methods, adjusted their clothing to protect their skin and mouth, and reduced some exposure pathways through improved hygiene behaviour. However, toxic pesticides continued to be used and exposure to wastewater with limited protection remained widespread. Change was dependent upon: the researcher’s deep understanding of how farmers learned; farmers’ trust in the purveyors of new information; and the clarity, consistency and relevance of messages devised. Change varied with farmers’ literacy; the language used; and the way in which tools and media were interpreted culturally and technically. The health belief model provided a partial explanation for changes in perceptions and behaviour. Social, political and economic barriers preventing change included: leaving the onus for change on farmers, diminishing the responsibility of pesticide manufacturers and governments; land tenure arrangements which reduced investment in health and environment protection; urban poverty and illiteracy; and eco-system constraints. Examination of the PAR process, its leadership, owners, tools and ideas developed, and knowledge created provided useful insight into issues of power and control.

The modeling results of current global aerosol models agree, generally within a factor of two, with the measured surface concentrations of black carbon (BC) and sulphate (SF) aerosols in rural areas across the northern continents. However, few models are able to capture the observed seasonal cycle of the Arctic aerosols. In general, the observed seasonality of the Arctic aerosols is determined by complex processes, including transport, emissions and removal processes. In this work, the representations of aerosol deposition processes (i.e., dry deposition, in-cloud and below-cloud scavenging) within the framework of the Canadian Global Air Quality Model – GEM-AQ are first enhanced. Through the enhancements in GEM-AQ, the seasonality of the Arctic BC and SF is reproduced, and the improvement in model performance extends to the rest of the globe as well. Then, the importance of these deposition processes in governing the Arctic BC and SF seasonality is investigated. It is found that the observed seasonality of the Arctic BC and SF is mainly caused by the seasonal changes in aerosol wet scavenging, as well as the seasonal injection of aerosols from surrounding source regions. Being able to reproduce the seasonality of the Arctic BC, the enhanced GEM-AQ allows more accurate assessment of the contributions of anthropogenic sources to the BC abundance in the Arctic air and deposition to the Arctic surface. Simulating results on regional contributions to the Arctic BC show a strong dependence on altitude. The results reinforce the previous finding of Eurasia being the dominant contributor to the surface BC in the Arctic, and suggest a significant contribution from Asian Russia. In addition to the seasonality of the Arctic aerosols, the inter-annual variation in the Arctic BC surface concentration is also investigated. To complement the 3-D GEM-AQ model, the atmospheric backward trajectory analysis, together with estimated BC emissions, is implemented as a computational effective approach to reconstruct BC surface concentrations observed at the Canadian high Arctic station, Alert. Strong correlations are found between the reconstructed and the measured BC in the cold season at Alert between 1990 and 2005, which implies that atmospheric transport and emissions are the major contributors to the observed inter-annual variations and trends in BC. The regional contributions estimated annually from 1990 through 2005 suggest that Eurasia is the major contributor in winter and spring to the near-surface BC level at Alert with a 16-year average contribution of over 85% (specifically 94% in winter and 70% in spring). A decreasing trend in the Eurasian contribution to the Arctic is found in this study, which is mainly due to regional emission reduction. However, the inter-annual variation in the North American contribution shows no clear trend.

Knowledge gaps related to mass transfer processes involved in passive air sampling of semivolatile organic compounds and factors potentially influencing passive sampling rates (PSRs) were addressed with controlled laboratory experiments, mass transfer modeling, and a field sampling campaign. The observed non-uniform SVOC distributions within porous passive sampling media (PSMs) contradict an assumption in an earlier passive air sampling theory and proved the existence of a kinetic resistance on the PSM side. This resistance can affect PSRs as revealed by a new PAS model which is based on fundamental laws of mass transfer in air and porous media. By considering mass transfer processes within the PSM, the model is able to explain the large variations of field calibrated PSRs with temperature and between SVOC species and the two-stage uptake process, which cannot be addressed by the earlier PAS theory. Because the PSM side kinetic resistance invalidates the assumption that depuration compounds added to the PSM prior to deployment are subject to the same kinetic resistance as the sampled SVOCs, PSRs derived from the loss rates of depuration compounds can differ from the actual PSRs of the sampled SVOCs. Using such PSRs could thus introduce additional uncertainty to PAS-derived air concentrations. Experiments using XAD-resin and silica-gel filled mesh cylinder as PSMs for the uptake of SVOCs and water vapor respectively revealed that sorbent in the inner portion of the PSM does not take part in chemical uptake; PSRs are thus proportional to the interfacial transfer area but not the amount of the sorbent. Accordingly, thinner PSM can be used to reduce the amount of sorbent while keeping or even increasing the PSRs. Optimized designs of PASs could be tested time efficiently using the gravimetrical approach based on water vapor uptake by silica gel.

Knowledge gaps related to mass transfer processes involved in passive air sampling of semivolatile organic compounds and factors potentially influencing passive sampling rates (PSRs) were addressed with controlled laboratory experiments, mass transfer modeling, and a field sampling campaign. The observed non-uniform SVOC distributions within porous passive sampling media (PSMs) contradict an assumption in an earlier passive air sampling theory and proved the existence of a kinetic resistance on the PSM side. This resistance can affect PSRs as revealed by a new PAS model which is based on fundamental laws of mass transfer in air and porous media. By considering mass transfer processes within the PSM, the model is able to explain the large variations of field calibrated PSRs with temperature and between SVOC species and the two-stage uptake process, which cannot be addressed by the earlier PAS theory. Because the PSM side kinetic resistance invalidates the assumption that depuration compounds added to the PSM prior to deployment are subject to the same kinetic resistance as the sampled SVOCs, PSRs derived from the loss rates of depuration compounds can differ from the actual PSRs of the sampled SVOCs. Using such PSRs could thus introduce additional uncertainty to PAS-derived air concentrations. Experiments using XAD-resin and silica-gel filled mesh cylinder as PSMs for the uptake of SVOCs and water vapor respectively revealed that sorbent in the inner portion of the PSM does not take part in chemical uptake; PSRs are thus proportional to the interfacial transfer area but not the amount of the sorbent. Accordingly, thinner PSM can be used to reduce the amount of sorbent while keeping or even increasing the PSRs. Optimized designs of PASs could be tested time efficiently using the gravimetrical approach based on water vapor uptake by silica gel.

Empirical investigation into afforestation and bioenergy carbon finance projects in Tanzania, Uganda and Moldova demonstrates that effective projects—both in terms of sustainable development and the generation of genuine carbon credits—are more likely to result when the state is able to bring carbon finance initiatives into alignment with national development objectives. Amongst the countries investigated, the most important factor in such alignment was, paradoxically, commitment liberal economic reforms. Contrary to the expectation that the performance of projects under the Kyoto Protocol’s Clean Development Mechanism (CDM) would be the same in states with similar administrative capacities, carbon finance projects were more effective in Uganda and Moldova than Tanzania. Commitment to liberal economic reforms in Uganda functions as an animating set of ideas that allows the state apparatus to work in a more purposeful manner and establish institutions and organizations which allow it to generate state power for low-carbon development. For CDM forest and bioenergy projects, the risk of unsustainability is mitigated by a land tenure system and investment regime that (i) offer opportunities for individual smallholders to engage directly with the carbon market and create incentives for domestic investors while (ii) also accommodating historical land governance practices. Genuine carbon credits were associated with project developers who possessed a latent organizational capacity for implementation and were motivated to pursue market opportunities—state forest agencies in Uganda and Moldova. However, the ability of the state to retain latent organizational capacity was restricted to sectors such as forestry that are less sophisticated technically; in the energy sector, such capacity was ceded to the private sector in Uganda and Moldova during structural adjustment. More skeptical of liberal economic policy, Tanzania has retained capacity in the energy sector; however, for the same reasons, it has not treated the CDM as a genuine opportunity. At current carbon prices, CDM projects investigated were effective when the state was able to play a developmental role in the economy. Whether commitment to liberal economic reforms can have similar developmental effects in other parts of the developing world is questionable—a different animating set of ideas may be important.