Physical activation of oil-sands fluid coke, a dense carbonaceous material, using sulfur dioxide (SO2) was investigated as a means of utilizing a plentiful and inexpensive waste for elemental mercury (Hg) removal. A new model was developed to elucidate physical activation of dense carbonaceous materials. Experiments and model simulations revealed that, during activation with SO2, a sulfur-rich porous layer is formed around the periphery of the coke particles; this porous layer reaches a maximum thickness as a result of diffusion limitations; the maximum porous layer thickness is controlled by activation conditions and determines the maximum achievable specific surface area (SSA). Pre-oxidation in air prior to activation, acid washing after activation and smaller coke particle size all result in higher SSA. The highest SSA achieved was 530 m2/g, the highest yet found for oil-sands fluid coke with physical activation. If present, oxygen out-competed SO2 for carbon during activation. SO2 activation and porous layer formation did not occur until oxygen was depleted. Sulfur added to coke through SO2 activation is mainly in reduced forms which are more thermally stable than elemental sulfur in commercial sulfur-impregnated activated carbons (SIACs). TGA and elemental analyses revealed that only 17% of sulfur was removed at 800°C from SO2-activated coke under inert conditions, compared with 100% from a commercial SIAC. The role of sulfuric acid (H2SO4) in vapor Hg capture by activated carbon (AC) was studied due to conflicting findings in the recent literature. In the absence of other oxidizing species, it was found that Hg could be oxidized by oxygen which enhanced vapor Hg adsorption by AC and Hg absorption in H2SO4 solution at room and elevated temperatures. At 200°C, AC treated with 20% H2SO4 reached a Hg loading of more than 500 mg/g, which is among the highest Hg capacities yet reported. When oxygen was not present, S6+ in H2SO4 was found to act as an oxidizer of Hg, thus enabling Hg uptake by H2SO4-treated AC at 200°C. Treating the AC with SO2 at 700°C improved the initial rate of Hg uptake, with and without subsequent H2SO4 treatment.

If sufficiently persistent, semi-volatile organic contaminants (SVOCs) can travel long distances through the atmosphere from their points of release and become concentrated in cold, remote regions. As air is sampled for SVOCs to establish both their presence and the success of emission reduction efforts, it becomes helpful to determine sampling site proximity to sources and the origin of the sampled air masses. Comparing three increasingly sophisticated methods for quantifying source proximity of sampling locations, it was judged necessary to account for the actual history of the sampled air through construction of an airshed, especially if wind is highly directional and population distribution is very non-uniform. The airshed concept was improved upon by introducing a ‘geodesic’ grid of equally spaced cells, rather than a simple latitude/longitude grid, to avoid distortion near Earth’s poles and to allow for the comparison of airshed shapes. Assuming that a perfectly round airshed reveals no information about sources allows the significance of each cell of an airshed to be judged based on its departure from roundness. Combining air-mass histories with a 2 year-long series of SVOC air concentrations at Little Fox Lake in Canada’s Yukon Territory did not identify distinct source regions for most analytes, although γ-hexachlorocyclohexane appears to originate broadly in north-eastern Russia and/or Alaska. Based on this remoteness from sources, the site is judged to be well suited to monitor changes in the hemispheric background concentrations of SVOCs. A model-based exploration revealed wet-gaseous deposition as the dominant process responsible for cold-trapping SVOCs in mountain soils. Such cold trapping is particularly effective if precipitation rate increases with altitude and if temperature differences along the mountain are large. Considerable sensitivity of the modeled extent of cold-trapping to parameters as diverse as scale, mean temperature, atmospheric particle concentration and time relative to emission maxima is consistent with the wide variety of observed enrichment behaviour. Concentration gradients of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in air and soil measured on four Western Canadian mountains with variable distance from sources revealed source proximity as the main driver of concentrations at both the whole-mountain scale and along individual mountain transects.

Physical activation of oil-sands fluid coke, a dense carbonaceous material, using sulfur dioxide (SO2) was investigated as a means of utilizing a plentiful and inexpensive waste for elemental mercury (Hg) removal. A new model was developed to elucidate physical activation of dense carbonaceous materials. Experiments and model simulations revealed that, during activation with SO2, a sulfur-rich porous layer is formed around the periphery of the coke particles; this porous layer reaches a maximum thickness as a result of diffusion limitations; the maximum porous layer thickness is controlled by activation conditions and determines the maximum achievable specific surface area (SSA). Pre-oxidation in air prior to activation, acid washing after activation and smaller coke particle size all result in higher SSA. The highest SSA achieved was 530 m2/g, the highest yet found for oil-sands fluid coke with physical activation. If present, oxygen out-competed SO2 for carbon during activation. SO2 activation and porous layer formation did not occur until oxygen was depleted. Sulfur added to coke through SO2 activation is mainly in reduced forms which are more thermally stable than elemental sulfur in commercial sulfur-impregnated activated carbons (SIACs). TGA and elemental analyses revealed that only 17% of sulfur was removed at 800°C from SO2-activated coke under inert conditions, compared with 100% from a commercial SIAC. The role of sulfuric acid (H2SO4) in vapor Hg capture by activated carbon (AC) was studied due to conflicting findings in the recent literature. In the absence of other oxidizing species, it was found that Hg could be oxidized by oxygen which enhanced vapor Hg adsorption by AC and Hg absorption in H2SO4 solution at room and elevated temperatures. At 200°C, AC treated with 20% H2SO4 reached a Hg loading of more than 500 mg/g, which is among the highest Hg capacities yet reported. When oxygen was not present, S6+ in H2SO4 was found to act as an oxidizer of Hg, thus enabling Hg uptake by H2SO4-treated AC at 200°C. Treating the AC with SO2 at 700°C improved the initial rate of Hg uptake, with and without subsequent H2SO4 treatment.

If sufficiently persistent, semi-volatile organic contaminants (SVOCs) can travel long distances through the atmosphere from their points of release and become concentrated in cold, remote regions. As air is sampled for SVOCs to establish both their presence and the success of emission reduction efforts, it becomes helpful to determine sampling site proximity to sources and the origin of the sampled air masses. Comparing three increasingly sophisticated methods for quantifying source proximity of sampling locations, it was judged necessary to account for the actual history of the sampled air through construction of an airshed, especially if wind is highly directional and population distribution is very non-uniform. The airshed concept was improved upon by introducing a ‘geodesic’ grid of equally spaced cells, rather than a simple latitude/longitude grid, to avoid distortion near Earth’s poles and to allow for the comparison of airshed shapes. Assuming that a perfectly round airshed reveals no information about sources allows the significance of each cell of an airshed to be judged based on its departure from roundness. Combining air-mass histories with a 2 year-long series of SVOC air concentrations at Little Fox Lake in Canada’s Yukon Territory did not identify distinct source regions for most analytes, although γ-hexachlorocyclohexane appears to originate broadly in north-eastern Russia and/or Alaska. Based on this remoteness from sources, the site is judged to be well suited to monitor changes in the hemispheric background concentrations of SVOCs. A model-based exploration revealed wet-gaseous deposition as the dominant process responsible for cold-trapping SVOCs in mountain soils. Such cold trapping is particularly effective if precipitation rate increases with altitude and if temperature differences along the mountain are large. Considerable sensitivity of the modeled extent of cold-trapping to parameters as diverse as scale, mean temperature, atmospheric particle concentration and time relative to emission maxima is consistent with the wide variety of observed enrichment behaviour. Concentration gradients of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in air and soil measured on four Western Canadian mountains with variable distance from sources revealed source proximity as the main driver of concentrations at both the whole-mountain scale and along individual mountain transects.

No description available.

The rapid urbanization and industrialization has led to an increase of disposal petroleum hydrocarbons (PHC) and trace elements (TE) into the environment. These pollutants are considered as the most toxic contaminants in the world due to their persistence in the environment, and the long range of toxicological effects for living beings when their concentrations exceed critical thresholds. Recent concerns regarding the environmental contamination have initiated the development of several remediation technologies, including physico-chemical, biological and Dig and Dump approaches. In my thesis, gentle soil remediation options (GRO) were investigated at different scales for the reclamation of PHC and TE co-contaminated soil. In the first part of my thesis, laboratory experiments were performed to characterize PHC and TE contaminated soil as well as the indigenous microorganisms (bacteria and fungi) present in these contaminated soils. It was found that the studied aged contaminated soil had a negative effect on earthworm’s development and Lepidium sativum biomass. Moreover, a high respiration of microorganisms attributed to the transformation/ mineralization of organic matter or/and organic pollutants was observed. This presence of viable microorganisms suggested an adaptation of microorganisms to the contaminant. Further results showed that the long-term exposure of soil microorganisms to high PHC concentration and the type of isolation culture media did not influence the ability of isolates to effectively degrade PHC. However, phylogenic affiliation had a strong effect on PHC biodegradation. In the second part of my thesis, preliminary studies in greenhouse trials were performed to investigate the ability of Medicago sativa assisted by compost in the greenhouse aided-phytoremediation of PHC and TE. The results clearly showed that compost amendment into the soil promoted PHC degradation, M. sativa growth and survival, and phytoextraction of TE. Residual risk assessment after the phytoremediation trial also showed a positive effect of compost amendment on plant growth and earthworm development. Pilot-scale ecopile experiment carried out in the third part of this thesis allow a reduction of up to 80% of PHC and 20% of metals after 17 months. My thesis showed that alfalfa (M. sativa) and sunflower (Helianthus annus) plants were suitable for phytodegradation of PHC and phytoextraction of TE. The outcomes of my thesis can be extend to other plants and they bring a new level of understanding that can be helpful for further full-scale phytoremediation studies. / L'urbanisation rapide et les activités industrielles ont abouti à la contamination de l’environnement par les hydrocarbures pétroliers (HP) et les éléments traces (ET). Ces composés sont particulièrement toxiques en raison de leur persistance dans l'environnement, et de leurs effets toxicologiques sur les êtres vivants quand les concentrations de ceux-ci dépassent des seuils critiques. Les préoccupations de plus en plus croissantes sur la contamination de l'environnement ont favorisé le développement de plusieurs technologies de remédiation des sites contaminés par les approches biologiques, physico-chimiques et par l’excavation et l’entreposage. Dans cette thèse, des options douces d'assainissement des sols (ODA) ont été utilisées à différentes échelles pour la remédiation des sols contaminés par des mélanges des HP et des ET. Dans la première partie de ma thèse, des expériences en laboratoire ont été effectuées dans le but de caractériser les sols contaminés et les micro-organismes autochtones (bactéries et champignons) qu’ils contiennent. Malgré la contamination ancienne du sol, les résultats obtenus montrent des effets négatifs des contaminants sur le développement des lombrics et la biomasse de Lepidium sativum. En outre, une respiration élevée de microorganismes, attribuée à la transformation / minéralisation de la matière organique et / ou des polluants organiques a été observée. Cette présence de micro-organismes viables dans les sols contaminés suggère leur adaptation aux contaminants. Toutefois, d'autres résultats ont montré que l'exposition à long terme des microorganismes du sol à de fortes concentrations en HP et le type de milieu de culture utilisé pour l'isolation n'influencent pas la capacité des isolats microbiens à dégrader efficacement les HP. Cette capacité de biodégradation des HP est liée à la phylogénie des microorganismes. Dans la deuxième partie de cette thèse, les études préliminaires en serre ont été réalisées dans le but d’évaluer l’efficacité de phytoremédiation en utilisant Medicago sativa assistée par l’ajout du compost. Les résultats ont montré dans cette expérience que l’ajout du compost dans le sol favorise la dégradation des HP, la croissance et la survie de M. sativa, ainsi que la phytoextraction des ET. L’évaluation des risques résiduels après la phytoremédiation a également montré un effet positif de l'amendement du sol en compost sur la croissance des plantes et le développement des lombrics. L’expérience pilote réalisée sur le terrain dans la troisième partie de ma thèse a permis une réduction de 80% des HP et de 20% des ET après 17 mois. Ma thèse a démontré que la luzerne (M. sativa) et le tournesol (Helianthus annus) sont des choix judicieux de plantes pour la phytodégradation des HP et pour la phytoextraction des ET. Les résultats qui en résultent sont utiles pour d’autres études de phytoremédiation à grande échelle. / Den snabba urbaniseringen och industrialiseringen har lett till en ökning av petroleumkolväten (PHC) och olika spårämnen (TE) i miljön. Dessa föroreningar anses vara de mest giftiga föroreningarna i världen på grund av att de stannar kvar i miljön samt att de har toxikologisk påverkan på levande varelser. På senare tid har oron för dessa miljöföroreningar lett till utvecklingen av flera saneringstekniker, såsom fysiska, kemiska och biologiska metoder. I denna avhandling undersöktes enkla marksaneringsalternativ (GRO) på olika nivåer, för återvinning av PHC och TE från förorenad jord. I den första delen av denna avhandling, utfördes laboratorieförsök för att karakterisera PHC- och TE-förorenad jord samt av de inhemska mikroorganismerna (bakterier och svampar) som förekommer i dessa förorenade jordar. Det konstaterades att den studerade förorenade jorden hade en negativ inverkan på daggmaskars utveckling och biomassan av L. sativum. Dessutom kunde den höga respirationen bland mikroorganismerna tillskrivas omvandlingen och mineraliseringen av organiskt material och/eller de organiska föroreningar som observerades. Denna närvaro av livsdugliga mikroorganismer antydde att mikroorganismerna anpassat sig till föroreningssituationen på platsen. Ytterligare resultat visade dock att den långvariga exponeringen av höga PHC-koncentrationer i isolerade odlingsmedier, för mikroorganismer i jorden, inte påverkade förmågan för dessa att effektivt bryta ned PHC. Dock hade den fylogenetiska tillhörigheten en stark påverkan på bionedbrytning av PHC. I den andra delen av denna avhandling genomfördes preliminära studier i växthus där förmågan hos M. sativa undersöktes, med hjälp av kompost, gällande den växthusstödda fytosaneringen av PHC och TE. Resultaten visade att inblanding av kompost i jorden främjade nedbrytningen av PHC, tillväxten och överlevnadsgraden av M. sativa och fytoextraktion av Pb. Återstående riskbedömning efter fytosaneringen visade också en positiv effekt, när komposten användes, på växternas tillväxt och daggmaskarnas utveckling. Ett experiment med eco-bädd utfördes för den tredje delen av avhandlingen. Denna studie visade på en minskning på upp till 80% av PHC och 20% av metallerna. Denna avhandling visar att M. sativa och H. annus var lämpliga för nedbrytning av PHC och fytoextraktion av Pb och Cu. Resultaten från denna avhandling förväntas vara användbara för ytterligare studier av fytoremediering i fullskala.

No description available.

Thèse en cotutelle / Thesis under joint supervision / Les Peuples autochtones à travers le monde sont disproportionnellement touchés par le diabète. Parmi ces peuples, les Cris d’Eeyou Istchee et les Pekuakamilnuatsh, au Québec (Canada), ainsi que les Parikwene, en Guyane française (France), recourent à leur médecine locale pour soigner cette maladie. En 173 entrevues semi-dirigées, 208 participants venant de ces communautés et/ou travaillant dans leurs services de santé ont décrit ces médecines. Une méthode de recherche mixte, combinant des analyses thématiques à des statistiques multivariées, est développée pour analyser ces descriptions. Ces analyses ont montré que les participants cris, ilnu et parikwene décrivent leurs médecines en lien avec le diabète tant par les différents éléments du monde naturel, que les pratiques et coutumes locales qui en découlent, que les concepts les liant au territoire. Les pharmacopées à base animales et végétales font parties des thèmes les plus discutés. Plus de 381 espèces (109 animaux, 267 plantes, cinq lichens et champignons) lient les systèmes médicinales et alimentaires ensemble via des notions associées au bien-être ou aux propriétés organoleptiques. Au Québec, là où la population autochtone est plus impliquée dans les services de santé, il existe un rapprochement de la description des médecines locales entre le secteur de la santé et ses usagers. De façon générale, la place de l’alimentation dans les médecines locales ne peut être négligée dans le contexte du diabète. De plus, ces médecines sont indissociables du territoire qui offre un espace de guérison, de subsistance, et de continuité culturelle. Cela renvoie, in fine, à des questions importantes sur la reconnaissance des droits autochtones et des droits fonciers. / Indigenous Peoples around the world are disproportionately affected by diabetes. Amongst them, the Cree of Eeyou Istchee and the Pekuakamilnuatsh, from Québec (Canada), and the Parikwene, from French Guiana (France), resort to their local medicines to treat this disease. In 173 semi-structured interviews, 208 participants from these communities and/or working in their healthcare services described these medicines. A mixed-methods research approach, combining thematic analyses with multivariate statistics, was developed to analyse these descriptions. These analyses showed that Cree, Ilnu and Parikwene participants described their medicines related to diabetes through different elements of the natural world, the local practices and customs which result from them, as well as concepts linking them to the Land. Animal and plant-based pharmacopoeias are among the most discussed topics. In total, more than 381 species cited, including 109 animals, 267 plants, as well as five lichens and mushrooms, link the local dietary and medicinal systems together via notions associated with well-being or their organoleptic properties. In Québec, where Indigenous Peoples are more involved in their healthcare services, the representation of local medicines is much closer between healthcare workers and users. In general, the place of food in local medicines cannot be neglected in the context of diabetes. In addition, these medicines are inseparable from the Land which offers a space for healing, subsistence, and cultural continuity. This brings up important questions about the recognition of Indigenous rights and land rights.

Doctor of Philosophy / Department of Environmental Design & Planning Program / Lee R. Skabelund / The Restorative Urban Design (RUD) calls for a new urban design and planning approach targeting environmentally responsible re/development of urbanized areas through ecologically responsive impact mitigations. If implemented in a systematic manner, such re/developments can help move urban areas toward the successful restoration of the natural environment of which they are an inseparable part. The RUD model advocates more rigorous assessment and mitigation of urban impacts by carefully evaluating the environmental performance of urban re/developments within five primary dimensions: Atmosphere (emissions, pollutants, ozone depletion); Hydrosphere (stormwater, domestic water, wastewater); Lithosphere (land use, land cover, food and wastes); Ecology (habitat resilience, biodiversity, population and resources); and Energy (renewability, reduction and efficiency, transportation). The model relies on a scenario-comparison process in order to evaluate and optimize the performance of urban re/development projections through four critical scenarios, which are respectively: 1) Natural Baseline (NBASE); 2) Historic Progression (HPROG); 3) Trajectory Forecast (TFORE); and 4) Restorative Projection (RPROJ). The RUD Case Study illustrates how the principles and strategies of Restorative Urban Design can be applied specifically to a typical (densely developed) urban area, namely River North District in Chicago Metropolitan Area. The case study focuses exclusively on mitigation of a single critical human impact on the natural environment: Anthropogenic CO₂ Emissions. The case study focuses on the design assumptions by which the restorative urban re/development scenarios might exceed beyond the full mitigation of emissions into the global remediation by 2040. The restorative projections illustrate that only a certain portion of emissions can be effectively mitigated onsite (5 to 55%), and that the remainder of projected emissions (45 to 95%) need to be mitigated offsite in order to achieve the necessary sequestration and storage. The restorative research suggests that the mitigation of major human impacts on the natural environment – not only CO₂ emissions but also other major impacts – are likely to require significant urban transformations. Moving beyond the strategies of preservation and/or conservation, the restorative approach asserts that comprehensive environmental restoration is achievable if urban impacts are adequately estimated and then entirely mitigated onsite as well as offsite through a systematic process of urban re/development.

The research project upon which this dissertation is based focused on enhancing understandings of the nature of current First Nations/non-Aboriginal relations in environmental management. The project was undertaken as a collaborative initiative by the author, a non-Aboriginal doctoral researcher, in partnership with Walpole Island First Nation. The research served as an opportunity for co-producing knowledge on this subject across cultures and worldviews, and as an effort to build towards our shared aspiration of learning how distinct, yet inextricably linked, First Nations/non-Aboriginal understandings, approaches and worldviews can come together within a context of mutual respect and mutual benefit. The purpose of the research was to investigate the existence and types of issues leading to First Nations/non-Aboriginal tensions in environmental management, to analyze and unpack underlying causes of challenges identified via the research, and to construct avenues for relationship improvement. The research project was grounded in a specific investigation into relations in species at risk conservation and recovery in southern Ontario, Canada. The resulting dissertation is structured around three primary focal areas: 1) investigating and exposing colonial influences at play in Canada’s Species at Risk Act, and offering a new model for co-governance in this arena and beyond; 2) investigating relations surrounding efforts towards traditional ecological knowledge (TEK) transfer in species at risk work, with a focus on exploring issues identified in relation to intellectual imperialism; and 3) introducing and characterizing an original, reconceptualized approach to First Nations/non-Aboriginal relationships in academic research; this approach focused on ways in which investigatory practice can become a means of working towards broader reconciliation goals. Research findings from this dissertation indicate that colonial factors, often unevenly visible to actors involved in environmental management and research, continue to strongly affect the potential for positive, productive First Nations/non-Aboriginal relations in these spheres - including within the species at risk conservation and recovery arena examined here. Project results provide insight into the nature of the factors influencing relationships, as well as potential avenues for addressing the vitality of colonialism in contemporary relations and overcoming the influences on First Nations and on First Nations/non-Aboriginal relationships.