<p><font face="Helvetica"> <p align="left">The objectives of this study were:&nbsp / To review and understand flow and transport processes in unsaturated zones. In this study, particular emphasis is placed on understanding mechanisms that cause non-uniform (preferential) flow for two casestudies, namely the Cape Flats sandy environment and the Mpumalanga Highveld fractured rock environment.&nbsp / To evaluate the adequacy of models, in particular MACRO 5.0, in simulating flow and transport in the vadose zone, by making use of two case study sites (Cape Flats and Mpumalanga Highveld). Of particular importance is the evaluation of transfer coefficients to represent fluid and solute exchange between macropores and matrix.&nbsp / To run a sensitivity analysis with MACRO 5.0 in order determine which input model parameters are the most relevant in describing the effects of preferential flow in water and solute transport.</p> </font></p>

Current mining operators in the Athabasca oil sands deposit of Alberta, Canada have made commitments to zero discharge of oil sands process-affected waste materials (OSPM) from the mine site and rehabilitation of mined lands to a pre-mining state. As part of aquatic reclamation efforts, experimental test sites that contain a range of OSPM (solid and liquid components) were constructed to monitor the evolution and viability of aquatic habitats used as disposal sinks for OSPM produced by mining activities. In the present study, stable isotopes of carbon, nitrogen and sulphur were used to gauge some of the potential effects of OSPM site construction methods on aquatic food webs. Carbon and nitrogen isotopic signatures of sediment, dissolved inorganic carbon, dissolved organic carbon, particulate organic matter, periphytic material, plants, plankton, aquatic invertebrates and fish were used to assess differences related to the naphthenic acid (NA) concentration in OSPM and reference sites. For statistical analyses, sites were grouped into low (0 to 4 mg/L), medium (4 to 15 mg/L) and high (> 15 mg/L) NA concentrations. There were no significant differences in food web area or food web length among the low, medium and high NA concentration sites. In most cases, sample carbon isotope analyses of low, medium and high NA concentration sites were not significantly different, suggesting food web carbon sources did not include significant contributions from OSPM materials at OSPM sites. Significant differences, however, were found in the sample nitrogen isotope signatures between low, medium and high NA concentration sites. Ammonia from OSPM is suggested to be the main contributor to &delta;¹⁵N enrichment. <br /><br /> To determine the potential effects of site construction and OSPM within experimental test sites, carbon and sulphur stable isotopes of water, plankton, aquatic invertebrates and fish were analyzed. With the exception of <em>Chaoborus</em> and <em>Haliplus</em>, all carbon isotope signatures were not significantly different in constructed and reference sites. Also with the exception of <em>Haliplus</em>, sulphur isotope values for aquatic organisms from constructed and reference sites were significantly different. Aquatic organisms and water samples from constructed sites built in, or close, to the boundary of Kcw clays typically had &delta;³⁴S < 0 ?. Coinciding with depleted &delta;³⁴S signatures found in these aquatic systems were elevated sulphate concentrations. The waters at experimental test sites are in direct contact with the soil materials that facilitate the accumulation of sulphates as a result of the oxidation of substrate sulphide minerals. In general the results of the study suggest that aquatic food web structure and function do not change with the introduction of OSPM. Shifts in isotopic signatures suggestive of changes in food web structure, however, do occur when site construction exposes Kcw clays in the substrate.

Current mining operators in the Athabasca oil sands deposit of Alberta, Canada have made commitments to zero discharge of oil sands process-affected waste materials (OSPM) from the mine site and rehabilitation of mined lands to a pre-mining state. As part of aquatic reclamation efforts, experimental test sites that contain a range of OSPM (solid and liquid components) were constructed to monitor the evolution and viability of aquatic habitats used as disposal sinks for OSPM produced by mining activities. In the present study, stable isotopes of carbon, nitrogen and sulphur were used to gauge some of the potential effects of OSPM site construction methods on aquatic food webs. Carbon and nitrogen isotopic signatures of sediment, dissolved inorganic carbon, dissolved organic carbon, particulate organic matter, periphytic material, plants, plankton, aquatic invertebrates and fish were used to assess differences related to the naphthenic acid (NA) concentration in OSPM and reference sites. For statistical analyses, sites were grouped into low (0 to 4 mg/L), medium (4 to 15 mg/L) and high (> 15 mg/L) NA concentrations. There were no significant differences in food web area or food web length among the low, medium and high NA concentration sites. In most cases, sample carbon isotope analyses of low, medium and high NA concentration sites were not significantly different, suggesting food web carbon sources did not include significant contributions from OSPM materials at OSPM sites. Significant differences, however, were found in the sample nitrogen isotope signatures between low, medium and high NA concentration sites. Ammonia from OSPM is suggested to be the main contributor to &delta;¹⁵N enrichment. <br /><br /> To determine the potential effects of site construction and OSPM within experimental test sites, carbon and sulphur stable isotopes of water, plankton, aquatic invertebrates and fish were analyzed. With the exception of <em>Chaoborus</em> and <em>Haliplus</em>, all carbon isotope signatures were not significantly different in constructed and reference sites. Also with the exception of <em>Haliplus</em>, sulphur isotope values for aquatic organisms from constructed and reference sites were significantly different. Aquatic organisms and water samples from constructed sites built in, or close, to the boundary of Kcw clays typically had &delta;³⁴S < 0 ?. Coinciding with depleted &delta;³⁴S signatures found in these aquatic systems were elevated sulphate concentrations. The waters at experimental test sites are in direct contact with the soil materials that facilitate the accumulation of sulphates as a result of the oxidation of substrate sulphide minerals. In general the results of the study suggest that aquatic food web structure and function do not change with the introduction of OSPM. Shifts in isotopic signatures suggestive of changes in food web structure, however, do occur when site construction exposes Kcw clays in the substrate.

This thesis consists of three essays on risk management in crude oil markets. In the first essay, the valuation of an oil sands project is studied using real options approach. Oil sands production consumes substantial amount of natural gas during extracting and upgrading. Natural gas prices are known to be stochastic and highly volatile which introduces a risk factor that needs to be taken into account. The essay studies the impact of this risk factor on the value of an oil sands project and its optimal operation. The essay takes into account the co-movement between crude oil and natural gas markets and, accordingly, proposes two models: one incorporates a long-run link between the two markets while the other has no such link. The valuation problem is solved using the Least Square Monte Carlo (LSMC) method proposed by Longsta ff and Schwartz (2001) for valuing American options. The valuation results show that incorporating a long-run relationship between the two markets is a very crucial decision in the value of the project and in its optimal operation. The essay shows that ignoring this long-run relationship makes the optimal policy sensitive to the dynamics of natural gas prices. On the other hand, incorporating this long-run relationship makes the dynamics of natural gas price process have a very low impact on valuation and the optimal operating policy. In the second essay, the relationship between the slope of the futures term structure, or the forward curve, and volatility in the crude oil market is investigated using a measure of the slope based on principal component analysis (PCA). The essay begins by reviewing the main theories of the relation between spot and futures prices and considering the implication of each theory on the relation between the slope of the forward curve and volatility. The diagonal VECH model of Bollerslev et al. (1988) was used to analyse the relationship between of the forward curve slope and the variances of the spot and futures prices and the covariance between them. The results show that there is a significant quadratic relationship and that exploiting this relation improves the hedging performance using futures contracts. The third essay attempts to model the spot price process of crude oil using the notion of convenience yield in a regime switching framework. Unlike the existing studies, which assume the convenience yield to have either a constant value or to have a stochastic behaviour with mean reversion to one equilibrium level, the model of this essay extends the Brennan and Schwartz (1985) model to allows for regime switching in the convenience yield along with the other parameters. In the essay, a closed form solution for the futures price is derived. The parameters are estimated using an extension to the Kalman filter proposed by Kim (1994). The regime switching one-factor model of this study does a reasonable job and the transitional probabilities play an important role in shaping the futures term structure implied by the model.

Conventional fossil fuels are widely used, however there are growing concerns about the security of their supply, volatility in their prices and the environmental impacts of their extraction and use. The objective of this research is to investigate the potential for replacing conventional fuels in various applications, focusing on the Alberta oil sands industry. Such investigations require systems-level approaches able to handle multiple criteria, uncertainty, and the views of multiple stakeholders. To address this need, the following are developed: life cycle assessment (LCA) and life cycle costing models of polygeneration systems; a life cycle-based framework for multi-sectoral resource use decisions; and a method combining LCA and real options analyses to yield environmental and financial insights into projects. These tools are applied to options for utilizing oil sands outputs, both the petroleum resource (bitumen) and by-products of its processing (e.g., asphaltenes, coke), within the oil sands industry and across other sectors. For oil sands on-site use, multiple fuels are assessed for the polygeneration of electricity, steam and hydrogen, in terms of life cycle environmental and financial impacts; asphaltenes gasification with carbon capture and storage (CCS) is the most promising option, able to reduce greenhouse gas (GHG) emissions to 25% of those of current natural gas-based systems. Coke management options are assessed with the life cycle-based framework; the most promising options are identified as: Electricity generation in China through integrated gasification combined cycle; and, hydrogen production in Alberta, either for sale or use by the oil sands industry. Without CCS, these options have amortized project values ranging from $21 to $160/t coke. The application of the combined LCA and real options analyses method finds that uncertainty in natural gas and potential carbon prices over time significantly impacts decisions on coke management; the formulated decision tree identifies increases of 29% and 11% in the financial and GHG emissions performance, respectively, of the overall coke management project compared to pursuing the decision identified by the life cycle-based framework. While promising options for replacing conventional fossil fuels are identified through systems-level analyses, there are trade-offs to be made among the financial, risk and environmental criteria.

Conventional fossil fuels are widely used, however there are growing concerns about the security of their supply, volatility in their prices and the environmental impacts of their extraction and use. The objective of this research is to investigate the potential for replacing conventional fuels in various applications, focusing on the Alberta oil sands industry. Such investigations require systems-level approaches able to handle multiple criteria, uncertainty, and the views of multiple stakeholders. To address this need, the following are developed: life cycle assessment (LCA) and life cycle costing models of polygeneration systems; a life cycle-based framework for multi-sectoral resource use decisions; and a method combining LCA and real options analyses to yield environmental and financial insights into projects. These tools are applied to options for utilizing oil sands outputs, both the petroleum resource (bitumen) and by-products of its processing (e.g., asphaltenes, coke), within the oil sands industry and across other sectors. For oil sands on-site use, multiple fuels are assessed for the polygeneration of electricity, steam and hydrogen, in terms of life cycle environmental and financial impacts; asphaltenes gasification with carbon capture and storage (CCS) is the most promising option, able to reduce greenhouse gas (GHG) emissions to 25% of those of current natural gas-based systems. Coke management options are assessed with the life cycle-based framework; the most promising options are identified as: Electricity generation in China through integrated gasification combined cycle; and, hydrogen production in Alberta, either for sale or use by the oil sands industry. Without CCS, these options have amortized project values ranging from $21 to $160/t coke. The application of the combined LCA and real options analyses method finds that uncertainty in natural gas and potential carbon prices over time significantly impacts decisions on coke management; the formulated decision tree identifies increases of 29% and 11% in the financial and GHG emissions performance, respectively, of the overall coke management project compared to pursuing the decision identified by the life cycle-based framework. While promising options for replacing conventional fossil fuels are identified through systems-level analyses, there are trade-offs to be made among the financial, risk and environmental criteria.

A computational fluid dynamics model has been developed to examine the separation of an oil film from a spherical oil-coated particle falling through quiescent water due to gravity. Using this model, the separation process was studied as a function of the viscosity ratio of oil to water, R, and the ratio of viscous forces to surface tension, represented by the Capillary number Ca. The governing equations of this flow-induced motion are derived in a non-inertial spherical coordinate system, and discretized using a finite volume approach. The Volume-of-Fluid method is used to capture the oil/water interface. The model predicts two mechanisms for oil separation: at R less than 1, the shear difference between the particle/oil interface and the oil/water interface is not significant and Ca determines whether separation occurs or not; at R larger than 1, the shear difference is considerable, and the Ca effect becomes less dominant.

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