Naphthenic acids (NAs) are carboxylated alkanes and cycloalkanes concentrated in wastewater during oil sands processing. The general chemical formula is C{n}H{n+Z}O{2}, where n represents the number of carbon atoms and Z specifies a homologous family with 0-6 rings (Z=0 to Z=-12). The wastewater is acutely toxic to surface water organisms and is stored in tailings ponds with over 230 million m?? of fines tailings and free water. The purpose of this thesis was to provide a preliminary evaluation of the potential attenuation of NAs during groundwater flow from the ponds. Laboratory studies were conducted to evaluate possible attenuation mechanisms. Aerobes from aquifer material degraded 60% of the NAs over 20 weeks in laboratory microcosms. The greatest decrease occurred in the low molecular weight bicyclic homologues with 12 to 16 carbons. The microbial activity confirms that aerobic naphthenate-degrading bacteria occur naturally in the glacial aquifer near Suncor's Pond 2/3. These results support the hypothesis that limited aerobic biodegradation of the smaller components of NAs could occur relatively rapidly under field conditions. There was no measurable decrease in NA concentration over six months in anaerobic microcosms, although microbial activity did lead to sulfate-reducing and methanogenic conditions. The theoretical retardation in glacio-fluvial sands was calculated using soil-water partitioning coefficients (K{d}) determined by batch equilibration experiments using a mixture of naturally occurring naphthenic acids as well as the nine surrogates. The retardation (porosity of 0. 3, bulk density of 1. 5 g/mL) ranged from 1. 2 to 2. 6. However, no measurable sorption was seen at the field sites. Detailed characterization allows us to examine how the proportions of homologue, or groups of molecules with the same molecular weight and number of cycloalkane rings, vary. Aerobic biodegradation favoured removal of low molecular weight NAs. A 15% mass loss attributed to sorption caused no changes in the 3D signature. Thus, changes in NA "signature" in groundwater systems were then attributed to aerobic biodegradation. Three plumes were examined for evidence of attenuation of NAs via biodegradation. First, the individual samples were classified as background, possibly process-affected or process-affected using a combination of Piper diagrams, the stable isotopes oxygen-18 and deuterium, dissolved chloride and sodium, as well as the total naphthenic acids concentration. Second, in order to estimate attenuation due to dispersive dilution, a linear correlation line was drawn between various conservative tracers and the naphthenic acids concentration. This allowed the identification of certain samples as possibly having a lower concentration of NAs than could be expected from simple dispersive dilution. Third, the 3D signature of certain samples were examined for the presence of the aerobic biodegradation 3D signature. One site showed good evidence for aerobic biodegradation of naphthenic acids. A second site showed some evidence for biodegradation under methanogenic conditions but the evidence was not definitive. The evidence at the third site was contradictory and no conclusions could be drawn from it. This research suggests some attenuation of NAs by biodegradation may be possible during groundwater flow.

Naphthenic acids (NAs) are carboxylated alkanes and cycloalkanes concentrated in wastewater during oil sands processing. The general chemical formula is C{n}H{n+Z}O{2}, where n represents the number of carbon atoms and Z specifies a homologous family with 0-6 rings (Z=0 to Z=-12). The wastewater is acutely toxic to surface water organisms and is stored in tailings ponds with over 230 million m³ of fines tailings and free water. The purpose of this thesis was to provide a preliminary evaluation of the potential attenuation of NAs during groundwater flow from the ponds. Laboratory studies were conducted to evaluate possible attenuation mechanisms. Aerobes from aquifer material degraded 60% of the NAs over 20 weeks in laboratory microcosms. The greatest decrease occurred in the low molecular weight bicyclic homologues with 12 to 16 carbons. The microbial activity confirms that aerobic naphthenate-degrading bacteria occur naturally in the glacial aquifer near Suncor's Pond 2/3. These results support the hypothesis that limited aerobic biodegradation of the smaller components of NAs could occur relatively rapidly under field conditions. There was no measurable decrease in NA concentration over six months in anaerobic microcosms, although microbial activity did lead to sulfate-reducing and methanogenic conditions. The theoretical retardation in glacio-fluvial sands was calculated using soil-water partitioning coefficients (K{d}) determined by batch equilibration experiments using a mixture of naturally occurring naphthenic acids as well as the nine surrogates. The retardation (porosity of 0. 3, bulk density of 1. 5 g/mL) ranged from 1. 2 to 2. 6. However, no measurable sorption was seen at the field sites. Detailed characterization allows us to examine how the proportions of homologue, or groups of molecules with the same molecular weight and number of cycloalkane rings, vary. Aerobic biodegradation favoured removal of low molecular weight NAs. A 15% mass loss attributed to sorption caused no changes in the 3D signature. Thus, changes in NA "signature" in groundwater systems were then attributed to aerobic biodegradation. Three plumes were examined for evidence of attenuation of NAs via biodegradation. First, the individual samples were classified as background, possibly process-affected or process-affected using a combination of Piper diagrams, the stable isotopes oxygen-18 and deuterium, dissolved chloride and sodium, as well as the total naphthenic acids concentration. Second, in order to estimate attenuation due to dispersive dilution, a linear correlation line was drawn between various conservative tracers and the naphthenic acids concentration. This allowed the identification of certain samples as possibly having a lower concentration of NAs than could be expected from simple dispersive dilution. Third, the 3D signature of certain samples were examined for the presence of the aerobic biodegradation 3D signature. One site showed good evidence for aerobic biodegradation of naphthenic acids. A second site showed some evidence for biodegradation under methanogenic conditions but the evidence was not definitive. The evidence at the third site was contradictory and no conclusions could be drawn from it. This research suggests some attenuation of NAs by biodegradation may be possible during groundwater flow.

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Extraction of hydrocarbons from an Athabasca oil sand slurry were conducted using supercritical carbon dioxide (SC-CO2). The oil sand was slurried to a 1:1 ratio with water and experiments were conducted using a laboratory-scale batch supercritical fluid extraction (SFE) system. Preliminary tests revealed the importance of mixing rate on hydrocarbon yields. A 2^3 factorial experiment was then conducted to test the effect of temperature, pressure, and modifier (toluene) addition on hydrocarbon extraction yield. When toluene was absent, hydrocarbon extraction yields were greater at the high temperature (60°C); however, when toluene was present, the combination of low temperature (31°C) and high pressure (24.1MPa) provided greater extraction yields. The experiment that produced the highest cumulative hydrocarbon extraction yield was analyzed by GC-FID for product-quality. Two composite samples and one time series sample revealed a carbon distribution range of the extract centering on C25, corresponding to the light gas oil range as classified in petroleum fractions. / Environmental Science

This study investigates the extraction of hydrocarbons from oil sand using supercritical carbon dioxide (SC CO2). Experiments were carried out on three different types of oil sands. After some preliminary experiments, the feasibility of extracting hydrocarbons from oil sands by SC CO2 was confirmed and three experimental factors (pressure, temperature and mixing rate) were identified for further study. A two to the three factorial design was used to determine the significance of each factor and the significance of the interaction of the factors on the extraction efficiency. The extraction efficiency was calculated from Dean-Stark extraction analysis and was compared to the extraction efficiency based on gravimetric analysis. The results show that the extraction efficiency increased with pressure at a constant temperature. The effect of temperature on extraction efficiency is complex. The highest extraction efficiency was obtained at the high pressure (24.1MPa), high temperature (60C) and a mixing rate of 250rpm. / Environmental Science

L'injection de vapeur lors de la production des bruts lourds par SAGD soumet les roches réservoirs (sables bitumineux non consolidés ou faiblement consolidés) à une élévation de température (jusqu'à 280°C). L'apport de fluide chaud augmente la pression de pore, dilate le squelette rocheux et le fluide interstitiel, ce qui modifie le champ de contrainte in situ. Le travail de thèse, à forte connotation expérimentale, vise à contribuer à la caractérisation mécanique et acoustique des réservoirs bitumineux sous différentes conditions de température, de contrainte et de saturation. Les travaux ont été effectués sur des échantillons de sables bitumineux Canadiens, mais également sur un matériau modèle, un sable reconstitué artificiellement cimenté. Plusieurs techniques expérimentales ont été mises en œuvre pour caractériser les matériaux utilisés : tomographie RX, microtomographie RX, cryomicroscopie, RMN, etc. Des essais ont ensuite été effectués dans une cellule oedométrique, une cellule pétroacoustique et également dans une cellule triaxiale dite haute température qui a été développée dans le cadre de cette thèse.Les divers essais de chargement mécanique et thermique dans cette thèse ont permis d'enrichir les connaissances sur le comportement thermo-hydro-mécanique des sables bitumineux ainsi que celui des sables reconstitués. Les paramètres investigués ont été la dilatation thermique, la compressibilité sous chargement oedométrique et triaxial isotrope et la résistance au cisaillement. Les différentes mesures des propriétés acoustiques (vitesses Vp et Vs, atténuations et modules dynamiques) effectués sur les sables naturels et reconstitués ont montré l'importance des propriétés des fluides saturants, principalement de leur viscosité. Le bitume est un fluide viscoélastique avec une viscosité qui varie avec l'élévation de la température. Aux températures in situ, il se comporte comme un solide avec un module de cisaillement. L'approche théorique de Ciz et Shapiro (2007), permet de prendre en compte ce module de cisaillement du fluide visqueux et généralise l'équation de Biot Gassmann. Son utilisation a été validée sur nos essais. La modélisation prend en compte les aspect dispersifs et permet d'extrapoler aux fréquences sismiques des résultats acquis en laboratoire avec des fréquences ultrasonores. Les vitesses Vp et Vs diminuent avec le passage de la chambre de vapeur. Les variations sont faibles mais peuvent être identifiées par la sismique 4D / The steam assisted gravity drainage (SAGD) has been successfully used to enhance the recovery of heavy oil in Western Canada and Eastern Venezuela basins. Temperature, pressure and pore fluid variations during SAGD operations induce complex changes in the. properties of the heavy oil sand reservoir. This dissertation focuses on the geomechanical and acoustic behaviours of oil sand and how they change under various temperature, pressure and pore fluid conditions. Both natural oil sands samples and reconstituted samples were tested in this research program. Several experimental techniques have been used to characterize the materials including X-Ray tomography, X-ray microtomography, cryomicroscopy, NMR. Natural oil sands samples, characterized by high permeability, high porosity and an interlocked structure have been extracted from the estuarine McMurray Formation in Athabasca (Alberta, Canada). Reconstituted samples, made up of slightly cemented Fontainebleau sand, have been considered as possible analogues of the natural oil sands. Tests have been carried out in high pressure oedometer cells, in an isotropic pressure cell and in a new high temperature triaxial cell. The various geomechanical and thermal tests have been carried out to better understand the thermo-hydro-mechanical behaviour of natural oil sands and of reconstituted samples. The parameters investigated were the thermal dilatation, the bulk compressibility (under oedometric and isotropic loading) and the shear strength. The acoustic measurements (P and S-wave velocities, attenuations and dynamic modules, etc.) performed on natural oil sands and reconstituted samples showed the importance of the saturating fluids properties, mainly through viscosity. Bitumen has a viscoelastic behaviour with a non-negligible shear modulus that depends strongly on temperature and frequency and that allows shear wave propagation. The theoretical approach of Ciz and Shapiro (2007), that accounts for the effects of the shear modulus of the viscous fluid and generalizes the Biot – Gassmann equation, has been validated by our tests. The model takes into account the dispersive aspects and allows the results obtained in the laboratory with ultrasonic frequencies to be extrapolated to seismic frequencies. Velocities Vp and Vs decrease with the steam invasion. Changes are small but can be detected by 4D seismic

Dwindling conventional oil resources has caused exploration efforts to focus elsewhere. Bitumen from oil sands has emerged as one of the primary unconventional oil resources in use today. Quadrise Canada Corporation has harnessed this unconventional oil by developing their bitumen-in-water emulsion known as MSAR (Multi-Phase Superfine Atomized Residue). Fuel-in-water emulsions are linked to a combustion phenomenon known as micro-explosion, which are associated with an increase in combustion efficiency and decrease in harmful emissions. A study has been conducted of the MSAR fuel to help advance the optimization and modeling of its use in spray combustors so as to best harness the potential. Quantitative and qualitative data has been obtained during combustion experiments of the fuel that will attribute to this end. Additionally, a simplified statistical model is presented based on the governing equations to describe the atomization that occur as a result of micro-explosions of the MSAR fuel as well as a simple model to represent internal force needed for a micro-explosion to occur. The results of this study continue to reinforce the understanding that micro-explosions cannot be attributed to one overriding physical principal, but rather are th result from variations in turbulent, dynamic, and thermal forces.

Mature fine tailings (MFT), as a mixture of residual bitumen, sand, silt, fine clay particles and water, are a byproduct of oil sands extraction. The large volume, and poor consolidation and water release ability of MFT have been causing significant economic and environmental concerns. Therefore, several studies have been implemented on finding innovative dewatering/disposal techniques. As a result, different methods have been introduced and tested at a laboratory or a field scale, yet very few of these are commercially used in the oil sands industries. Despite the extensive research, an optimal solution has not been found due to the lack of technical or economic feasibility. In the present study, a novel approach that consists of the rapid dewatering of MFT by using a super absorbent polymer (SAP) to produce dense MFT is proposed. A comprehensive laboratory investigation on the geotechnical characteristics and behavior before and after treatment of MFT is conducted. The effects of SAP based dewatering and freeze/thaw cycles on the undrained shear strength of dewatered MFT by using a vane shear apparatus are studied. Furthermore, the ability of recycled SAP to dewater and densify MFT is assessed. Finally, this study provides the results of consolidation and hydraulic conductivity testing to evaluate the void ratio versus effective stress and hydraulic conductivity of MFT. The effects on the behavior and characteristics of MFT after amendment with usage of recycled SAP are also investigated. The results indicate that SAP has the ability to significantly dewater, densify and increase the undrained shear strength of MFT. Furthermore, when subjected to freeze/thaw cycles, the MFT dewatered with SAP shows an additional increase in strength and solid content. It is also found to be possible to regenerate the polymer (still within sachets) through light thermal drying, and the regenerated SAP can still significantly dewater and thus increase the shear strength and solid content of the MFT. In addition, the obtained high solid content affects and improves the compressibility of the material, thus resulting in low initial void ratios. On the other hand, low hydraulic permeability that is derived from low initial void ratios and consolidation is improved by the freeze/thaw process due to the interconnected voids created during the freezing process.

Mature fine tailings (MFT), as a mixture of residual bitumen, sand, silt, fine clay particles and water, are a byproduct of oil sands extraction. The large volume, and poor consolidation and water release ability of MFT have been causing significant economic and environmental concerns. Therefore, several studies have been implemented on finding innovative dewatering/disposal techniques. As a result, different methods have been introduced and tested at a laboratory or a field scale, yet very few of these are commercially used in the oil sands industries. Despite the extensive research, an optimal solution has not been found due to the lack of technical or economic feasibility. In the present study, a novel approach that consists of the rapid dewatering of MFT by using a super absorbent polymer (SAP) to produce dense MFT is proposed. A comprehensive laboratory investigation on the geotechnical characteristics and behavior before and after treatment of MFT is conducted. The effects of SAP based dewatering and freeze/thaw cycles on the undrained shear strength of dewatered MFT by using a vane shear apparatus are studied. Furthermore, the ability of recycled SAP to dewater and densify MFT is assessed. Finally, this study provides the results of consolidation and hydraulic conductivity testing to evaluate the void ratio versus effective stress and hydraulic conductivity of MFT. The effects on the behavior and characteristics of MFT after amendment with usage of recycled SAP are also investigated. The results indicate that SAP has the ability to significantly dewater, densify and increase the undrained shear strength of MFT. Furthermore, when subjected to freeze/thaw cycles, the MFT dewatered with SAP shows an additional increase in strength and solid content. It is also found to be possible to regenerate the polymer (still within sachets) through light thermal drying, and the regenerated SAP can still significantly dewater and thus increase the shear strength and solid content of the MFT. In addition, the obtained high solid content affects and improves the compressibility of the material, thus resulting in low initial void ratios. On the other hand, low hydraulic permeability that is derived from low initial void ratios and consolidation is improved by the freeze/thaw process due to the interconnected voids created during the freezing process.