Naphthenic acids (NAs) comprise a complex mixture of alkyl-substituted acyclic and cycloaliphatic carboxylic acids. NAs are present in wastewaters at petroleum refineries and in the process waters of oil sands extraction plants where they are primarily retained in large tailing ponds in the Athabasca region of Northern Alberta. The toxicity of these waters, primarily caused by NAs, dictates the need for their treatment.Bioremediation is considered as one of the most cost-effective approaches for the treatment of these wastewaters. Ex-situ bioremediation conducted in a bioreactor optimizes the microbial growth and activity by controlling environmental conditions resulting in efficient conversion of the contaminants to less harmful compounds. In this work, a circulating packed bed bioreactor (CPBB), with improved mixing, mass transfer and biomass hold-up has been used to study biodegradation of several model NA compounds: namely trans-4-methyl-1-cyclohexane carboxylic acid (trans-4MCHCA), a mixture of cis- and trans- 4-methyl-cyclohexane acetic acid (4MCHAA), and octanoic acid as well co-biodegradation of these naphthenic acids with octanoic acid, using a mixed culture developed in our laboratory. The biodegradation rates achieved for trans-4MCHCA in the CPBB are far greater than those reported previously in the literatures. The maximum biodegradation rate of trans-4MCHCA observed during batch operation was 43.5 mg/L-h, while a rate of 209 mg/L-h was achieved during continuous operation. Although cis-4MCHAA is more resistant to biodegradation when compared with trans-4MCHCA, the experimental results obtained from this study indicated both isomers were effectively biodegraded in the CPBB, with the maximum biodegradation rates being as high as 2.25 mg/L-h (cis-4MCHAA) and 4.17 mg/L-h (trans-4MCHAA) during batch operations and 4.17 mg/L-h(cis-4MCHAA) and 7.80 mg/L-h (trans-4MCHAA) during the continuous operation. Optimum temperature for biodegradation of 4MCHAA was determined as 25 aC. Furthermore, the biodegradation rate of single ring NAs (trans-4MCHCA and 4MCHAA) were found to be significantly improved through utilization of octanoic acid as a co-substrate. For example, the maximum biodegradation rate of trans-4MCHCA obtained during batch operation with the presence of octanoic acid was 112 mg/L-h, which was 2.6 times faster than the maximum value of 43.5 mg/L-h when trans-4MCHCA was used as a sole substrate. Similarly, the highest biodegradation rates of cis-4MCHAA and trans-4MCHAA were 16.7 and 28.4 mg/L-h in the presence of octanoic acid, which were 7.4 and 6.8 times higher than the maximum rates of 2.25 and 4.17 mg/L-h in the absence of octanoic acid.

An essential element of the reclamation strategy proposed by the oil sands mining industry in northern Alberta, Canada, includes the creation of wetlands for the bioremediation of mining waste materials. The mining process used to extract oil from these deposits results in the production of large volumes of process-affected water (OSPW) and sediments (OSPS), which must be incorporated into wetlands as a component of the reclaimed landscapes. Wood frogs (<i>Rana sylvatica</i>) are an abundant native species that might be expected to inhabit these reclaimed wetlands. The objective of this study was to determine potential detrimental effects of OSPW and OSPS on the growth and development of wood frogs. Several morphological (weight, length, condition factor) and biochemical (whole body tadpole thyroid hormone and triglyceride concentrations and metamorph hepatic glycogen concentration) endpoints were assessed in conjunction with hatchability and survivability of wood frog eggs and tadpoles exposed to process-affected materials (OSPM) under field and laboratory conditions.<p> As part of this study, assay techniques were optimized to enable simultaneous measurement of whole body 3,5,3-triiodothyronine (T3), thyroxine (T4) and triglyceride (TG) concentrations in wood frog tadpoles. These assays were used to monitor changes in T3, T4 and TG in wood frog tadpoles during development from hatching to metamorphosis (Gosner stages 19-46), to establish baseline levels for subsequent application of the assays to evaluate contaminant effects. The results indicated peak T3 and T4 concentrations occurred during metamorphic climax (Gosner stages 40-46) and prometamorphosis (Gosner stages 31-40), respectively. Maximal TG concentrations were also observed during prometamorphosis. These assays were further employed to assess body condition and development in wood frogs during a field study in 2005, and the following laboratory studies in 2006 and 2007.<p> In summer 2005, 29 reclaimed and five unimpacted wetlands were monitored for use by native amphibians, and tadpoles and newly-metamorphosed wood frogs were collected from a subset of sites as a preliminary assessment of contaminant effects. Endpoints such as metamorph hepatic glycogen and whole body tadpole T3, T4 and triglyceride concentrations were compared among six impacted and three reference wetlands. The surveys indicated 60% of OSPW-impacted wetlands were used by breeding adult amphibians, while wood frog tadpoles and newly-metamorphosed frogs were observed in 37 and 30% of OSPW wetlands, respectively. In general, lower whole body tadpole T3 and triglyceride concentrations were observed in wood frogs from wetlands containing OSPM. In contrast, hepatic glycogen concentrations in newly-metamorphosed frogs and whole body tadpole T4 and T3/T4 concentrations were comparable among the reference and impacted wetlands. In addition, the differences observed in total body weight and length of tadpoles and newly-metamorphosed wood frogs among OSPM and reference sites were likely due to minor differences in developmental stages of the animals collected from the various wetlands, rather than any contaminant effect.<p> In 2006 and 2007, wood frog eggs and tadpoles were exposed to several sources of OSPW and OSPS collected from reclaimed Suncor and Syncrude wetlands under controlled laboratory conditions. Hatchability was reduced in eggs exposed to water from only one of the OSPW sites, compared with the other process-affected ponds and the control water (P<0.05). In contrast, survivability of tadpoles was significantly reduced (P<0.05) in all the impacted sites in both years, with nearly all OSPW sites having <10% survival. The exposure study evaluated the toxicity of five types of OSPS. Results indicated no impact of OSPS exposure on survivability of tadpoles, but showed reduced whole body weight (in three OSPS treatments), length (in two OSPS treatments) and body condition (in one OSPS) of tadpoles exposed to process-affected substrates tested (P<0.05). Whole body T3 and T4 concentrations in tadpoles from OSPS treatments were not different from the control treatment, but tadpole TG concentration was reduced in groups exposed to two impacted substrates (P<0.05). Water quality measurements, including determination of dissolved metals were conducted in an initial attempt to relate any potential toxic effect on wood frog growth and development to specific contaminants.<p> Results of the laboratory studies strongly suggest that exposure to OSPW and OSPS may adversely affect wood frog growth and survival. However, these findings were not entirely consistent with field observations and results of concurrent mesocosm studies. Further research is therefore needed to fully evaluate the suitability of reclaimed oil sands wetlands to support indigenous amphibian population. Future work should focus on the cumulative effects of water and substrates, as well as the effect of OSPM ageing on acute and chronic toxicity.

No description available.

No description available.

This study is part of a three year project aimed to assess the effects of industrial water withdrawals on the ice regime of the Athabasca River. A 2-D numerical model was used to provide quantitative data for this effort. Freeze-up monitoring was carried out over two years along 80-km of the river from Fort McMurray to Bitumount. Summer bathymetric and winter ice surveys were conducted along with discharge measurements on a 5-km long detailed study reach that exhibited the full range of ice cover initiation processes. The data collected was used to build a CRISSP2D river ice process model for the simulation of freeze-up processes. An extensive parametric assessment was carried out to evaluate the capabilities of the model. Although it was not possible to simulate bridging, the simulated border ice agreed very well with field observations. Limitations of the model are addressed and future research recommendations are included. / Water Resources Engineering

Research Project (M.R.M.) - Simon Fraser University, 2005. / Research Project (School of Resource and Environmental Management) / Simon Fraser University.

With the rising demand for fossil fuels, Northern Canada has seen an unprecedented increase in petrochemical development. These developments are often associated with emissions of PAHs, a group of hydrophobic organic contaminants that are known to be carcinogenic and otherwise harmful to humans. Due to their hydrophobic nature, PAHs tend to bind to organic matter and can be produced through both anthropogenic and natural processes, making them ubiquitous in the environment. Therefore, in addition to impacts from petrochemical developments, changes to climatic conditions, such as increased forest fire disturbance and primary production also have the potential to alter delivery of organic carbon (OC) and PAHs to ecosystems. However, very little is known as to how the combined stressors of climate change and petrochemical development may affect environmental deposition of these contaminants. The concentrations and composition of parent and alkyl PAHs were analysed in radiometrically-dated sediment cores from lakes with one of four different types of petrochemical development in their catchments: (1) in-situ oil sands extraction (Cold Lake, AB); (2) open-pit oil sands extraction (Fort McMurray, AB); (3) abandoned conventional natural gas exploration (Mackenzie Delta Uplands, NWT); and (4) conventional gas and oil extraction (Cameron Hills, NWT). PAH deposition to lake sediments was also compared to climate reconstructions using climate proxies (diatom assemblages, inferred chlorophyll a and its diagenetic products, and Rock Eval carbon fractions as well as %OC). PAH sources were differentiated between potential pyrogenic and petrogenic origin over a period that extends to pre-industrial times using ratios of specific PAHs that can be traced to their potential source. Sediment cores from Cold Lake, AB showed concentrations of the sum of alkyl PAHs greater than those of parent PAHs, while all other cores show the reverse trend. A comparison of the % change of PAH concentrations from pre-development to post-development sediments between the four regions, showed that the greatest increase in concentrations of PAHs occurred in the Athabasca oil sands region. PAH profiles in the conventional regions have been historically dominated by mixed sources (pyrogenic PAHs from general background atmospheric inputs and petrogenic PAHs from the surrounding hydrocarbon-rich soils). While cores from the Fort McMurray area show a clear shift from pyrogenic sources (primarily wood and coal burning) in earlier sediments to petrogenic sources in more modern sediments, and the Cold Lake cores show some shifting sources to those dominated by pyrogenic sources in modern sediments. Organic carbon was significantly correlated with the sum of parent PAHs in 2 out of the 6 NWT cores that were examined for climate change impacts, while all other PAH parameters (concentration and composition) do not correlate significantly with any of the climate proxies. Establishing background concentrations and sources of PAHs in aquatic ecosystems is essential for understanding the natural environmental variations in these contaminants. Moreover, as both petrochemical activity and impacts from climate change are predicted to intensify in the future, studies such as this one allow us to build a solid understanding of how PAH deposition to northern lakes has responded to the warming climate and whether PAHs have been altered as a result of petrochemical activity.

Gegenstand dieser Arbeit ist die Entwicklung und Untersuchung eines Aufbereitungsprozesses zur Gewinnung von Bitumen aus kanadischem Athabasca Ölsand, der im Tagebau gewonnen wurde. Es wird ein mechanisch-thermisches Verfahren zur Fest-Flüssig-Trennung eingesetzt. Dabei handelt es sich um vier Schritte: (1) Suspendierung des Ölsandes mit den organischen Lösungsmitteln, Toluol und n-Heptan, (2) Filterkuchenbildung, (3) Waschung des Filterkuchens mit Wechsel der Waschflüssigkeiten (gradierte Waschung) und (4) Dampfbeaufschlagung. Der Prozess stellt eine Alternative zur herkömmlichen Heißwasser-extraktion des Ölsandes dar. Die Nachteile der Heißwasserextraktion sind ökologische Probleme, ein hoher Energie- und Frischwasserbedarf. Die Ziele des Alternativprozesses sind die Minimierung des Wasser- und Energiebedarfs, Vermeidung schädlicher Abfallstoffe sowie die Maximierung der Bitumenausbeute. Als Produkte sollen feststofffreies Bitumen und rückstandsfreier, deponierbarer Feststoff gewonnen werden.

The main objective of this research was to exploit the interrelations between the rheological behavior and nano-microstructure of complex fluids in solving two state-of-the-art problems, one in the field of biomedical engineering: controlling the amount and characteristics of bioaerosol droplets generated during coughing, and the other in the bitumen-heavy oil industry: characterizing the nano-microstructure of asphaltene particles in bitumen and heavy oil from their rheological behavior. For the first problem, effect of viscoelastic and surface properties of artificial mucus simulant gels on the size distribution and amount of airborne bioaerosol droplets generated during simulated coughing were investigated. The results revealed that suppressing the generation of bioaerosol droplets and/or reducing the number of emitted droplets to a minimum during coughing are practically achievable through modulation of mucus viscoelastic properties. While variation of surface tension did not show any change in the droplet size distribution, an increase in particle size was observed as the samples changed from elastic solid type to viscoelastic type to viscous fluid type samples. This knowledge will help in the development of a new class of drugs being developed at the University of Alberta, aimed at controlling the transmission of airborne epidemic diseases by modifying the viscoelastic properties of mucus. For the second problem, studies of viscoelastic behavior of Athabasca bitumen (Alberta) and Maya crude (Mexico) oil samples, along with their Nano-filtered and chemically separated-plus-reconstituted samples were performed. The results revealed that the rheological behaviors of the bitumen-heavy oil samples are governed by their multiphase nature. The rheological behavior of all feeds, permeates and retentate samples followed a single master curve over the entire temperature interval, consistent with that of a slurry comprising a Newtonian liquid plus a dispersed solid comprising non-interacting hard spheres. The behavior of asphaltenes in the reconstituted samples, however, was found to be significantly different from that in nanofiltered samples. The information about the characteristics and behaviors of asphaltenes obtained in this study will help better understand the asphaltene structures, and support the effort to determine solutions for numerous asphaltene-related industrial problems. In the long run, this knowledge will help to create more efficient extraction and upgrading processes for bitumen and heavy oils. / Thermo Fluids

Phase behaviour information is essential for the development and optimization of hydrocarbon resource production, transport and refining technologies. Experimental data sets for mixtures containing heavy oil and bitumen are sparse as phase behaviour data are difficult to obtain and cost remains prohibitive for most applications. A computational tool that predicts phase behaviours reliably for mixtures containing such ill-defined components, over broad temperature, pressure and composition ranges would play a central role in the advancement of bitumen production and refining process knowledge and would have favourable impacts on the economics and environmental effects linked to the exploitation of such ill-defined hydrocarbon resources. Prior to this work, predictive computational methods were reliable for dilute mixtures of ill-defined constituents. To include a much wider range of conditions, three major challenges were addressed. The challenges include: creation of a robust and accurate numerical approach, implementation of a reliable thermodynamic model, and speciation of ill-defined constituents like Athabasca Bitumen Vacuum Residue (AVR). The first challenge was addressed by creating a novel computational approach based on a global minimization method for phase equilibrium calculations. The second challenge was tackled by proposing a thermodynamic model that combines the Peng-Robinson equation of state with group contribution and related parameter prediction methods. The speciation challenge was addressed by another research group at the University of Alberta. Pseudo components they proposed were used to assign groups and estimate thermodynamic properties. The new phase equilibrium computational tool was validated by comparing simulated phase diagrams with experimental data for mixtures containing AVR and n-alkanes. There is good qualitative and quantitative agreement between computed and experimental phase diagrams over industrially relevant ranges of compositions, pressures and temperatures. Mismatch was only observed over a limited range of compositions, temperatures and pressures. This computational breakthrough provides, for the first time, a platform for reliable phase behaviour computations with broad potential for application in the hydrocarbon resource sector. The specific computational results can be applied directly to solvent assisted recovery, paraffinic deasphalting, and distillation and refining processes for Athabasca bitumen a strategic resource for Canada. / Chemical Engineering