Strong electron correlations in electronic structure theory are purely quantum effects arising as a result of degeneracies in molecules and materials, and exhibit significantly different yet interesting characters than do weak correlations. Although weak correlations have recently been able to be described very efficiently and accurately within single particle pictures, less known are good prescriptions for treating strong correlations efficiently. Brute-force calculations of strong correlations in wave function theories tend to be very computationally-intensive, and are usually limited to small molecules for applications. Breaking symmetry in a mean-field approximation is an efficient alternative to acquire strong correlations with, in many cases, qualitatively accurate results. The symmetry broken in quantum chemistry has been traditionally of spin, in so-called unrestricted methods, which typically break spatial symmetry as a consequence, and vice versa, in most situations. In this work, we present a novel approach to accurately describing strong correlations with a mean-field cost by means of Hartree- Fock-Bogoliubov (HFB) theory. We are inspired by the number-symmetry-breaking in HFB, which, with an attractive particle interaction, accounts for strong correlations, while maintaining spin and spatial symmetry. We show that this attractive interaction must be restricted to the chemically-relevant orbitals in an active space to obtain physically meaningful results. With such constraints, our constrained pairing mean-field theory (CPMFT) can accurately describe potential energy curves of various strongly-correlated molecular systems, by cleanly separating strong and weak correlations. To achieve the correct dissociation limits in hetero-atomic molecules, we have modified our CPMFT functional by adding asymptotic constraints. We also include weak correlations by combining CPMFT with density functional theory for chemically accurate results, and reveal the connection between CPMFT and traditional unrestricted methods. The similarity between CPMFT and unrestricted methods leads us to the idea of constrained active space unrestricted mean-field approaches. Motivated by CPMFT, we partially retrieve spin-symmetry that has been fully broken in unrestricted methods. We allow symmetry breaking only in an active space. This constrained unrestricted Hartree-Fock (CUHF) is an interpolation between two extrema: the fully broken-symmetry solution and the symmetry preserved solution. This thesis defines the theory behind and reports the results of CUHF. We first show that, if an active space is chosen to include only open-shell electrons, CUHF reduces to restricted open-shell Hartree-Fock (ROHF), and such CUHF proves in many ways significantly

La nourriture traditionnelle (NT) (résultant principalement des ressources halieutiques et cynégétiques) présente de nombreux bénéfices pour les communautés autochtones. Elle apporte beaucoup d'éléments essentiels pour le maintien d'une bonne santé. En effet, en plus d'être nutritive, la NT englobe plusieurs autres aspects. Culturellement, la chasse et la pêche permettent la transmission du savoir et des valeurs traditionnelles aux futures générations, tout en valorisant la coopération et la cohésion sociale. D'un point de vue économique, les activités traditionnelles contribuent à l'autosuffisance alimentaire et perpétuent également les activités artisanales traditionnelles. Ces activités renforcent les liens que les peuples des Premières Nations ont avec leur environnement. Pour les Autochtones, le concept d'une bonne santé, implique un maintien des aspects sociaux, culturels, spirituels, nutritionnels et économiques, qu'apporte la NT. Par contre, la consommation de NT expose ces populations à des substances potentiellement toxiques à leur santé. Les poissons et mammifères marins sont souvent contaminés par du méthylmercure (MeHg) et autres contaminants associés alors que le gibier ainsi que la sauvagine contiennent des polluants organiques persistants et autres métaux lourds comme le cadmium et le plomb. De par son caractère neurotoxique, le MeHg peut causer de graves répercussions sur la santé telles que des difficultés motrices, sensorielles et cognitives. Les personnes les plus à risque sont celles consommant de grandes quantités de poissons et/ou de mammifères marins, c'est-à-dire les populations autochtones et les pêcheurs sportifs ou des sous-groupes plus vulnérables tels les enfants et les femmes enceintes. Au Canada, certains peuples autochtones, tels que les Inuits et les Cris, ont été et sont encore étudiés dans le but d'évaluer et de mieux comprendre les risques d'une exposition aux divers contaminants présents dans leur environnement. À ce jour, aucune étude n'a porté sur les effets de l'exposition environnementale au mercure (Hg) et autres contaminants, de même qu'aux effets potentiellement néfastes sur la santé dans les communautés innues (ou montagnaises), qui sont culturellement et géographiquement différentes des communautés Inuites et Cries. Il est fort probable que ces différences territoriales se reflètent à travers les espèces animales consommées qui pourraient présenter des profils de contamination différents et conséquemment sur les risques d'expositions environnementales reliés à leur alimentation. Dans le cadre du projet multidisciplinaire COMERN (Collaborative Mercury Research Network) et en adoptant une approche écosystémique, au sein de la communauté innue de Sheshatshiu (Labrador), le sujet proposé dans le cadre de ce doctorat a permis d'évaluer, dans un premier temps, que les résultats de Hg dans les cheveux des participants de l'étude ont montré des niveaux étonnamment faibles (niveaux d'exposition jugés acceptables selon les recommandations de Santé Canada) par rapport à leur consommation de poissons. En tenant compte de plusieurs paramètres, les niveaux de Hg dans le poisson des différentes espèces consommées, le nombre de repas de poisson de chaque espèce ainsi que la taille des portions consommées, l'apport de Hg pour chaque participant fut calculé. Les niveaux de Hg capillaires de chaque participant ont été mesurés et comparativement aux niveaux attendus (par des simulations informatiques), les niveaux étaient dix fois moins élevés, suggérant des différences d'assimilation du Hg. Dans un deuxième temps, les résultats obtenus ont permis d'apprécier les bienfaits de l'alimentation traditionnelle des lnnus et les bienfaits de la NT selon les apports nutritionnels de référence et sur l'indice de masse corporelle. Dans un troisième temps, des altérations neurologiques précoces pouvant être associées à l'exposition au Hg et autres contaminants ont été évaluées selon trois domaines neurologiques (moteur, sensoriel et cognitif). Les principaux résultats ont démontré que les performances des trois domaines analysés étaient affectées par des profils de contamination différents. Et finalement, cette étude a permis de révéler trois groupes distincts en lien avec leurs performances aux tests neurofonctionnels (groupe bonne mémoire, groupe bonne vision et groupe avec difficultés). Les principales investigations effectuées sur le groupe avec difficultés, ont confirmé des niveaux de contaminants significativement plus élevés comparativement aux deux autres groupes (groupe bonne mémoire et groupe bonne vision), nonobstant l'âge et le nombre de repas traditionnels consommés. En analysant les informations colligées à l'aide des questionnaires sociodémographiques, .portant sur les lieux de chasse et de pêche visités par les familles innues, il a été possible d'établir qu'une partie des zones de chasse et de pêche utilisées par le groupe avec difficultés abritaient également des infrastructures militaires. Par ailleurs, des sources médiatiques et scientifiques ont rapporté, pour ces emplacements militaires, des déversements ou de la mauvaise gestion des déchets (métaux lourds et composés organochlorés) dans le passé, qui ont eu pour conséquences, selon ces mêmes sources, de contaminer les eaux et les sols environnants. Les résultats à venir seront les premiers à documenter les effets du Hg et autres contaminants au niveau d'une population adulte d'Innus et parmi les quelques études portant sur les effets d'une exposition multiple sur une population adulte (hommes et femmes). Ces résultats seront d'abord utiles pour la communauté autochtone. Les informations recueillies guideront les intervenants locaux pour monter un plan d'intervention, d'éducation et de gestion des ressources en combinant le savoir local et les données scientifiques générées par l'étude. Deuxièmement, les résultats serviront à la communauté scientifique qui s'intéresse à la problématique du Hg et autres contaminants ainsi qu'aux effets possibles chez les Premières Nations. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Innu, Nourriture traditionnelle, Contaminants, Métaux, Mercure, BPC, Pesticides organochlorés, Exposition multiple, Tests neurofonctionnels, Indice de masse corporelle, Territoire.

Much is known about natural attenuation of contaminants in granular aquifers because many contaminant plumes in these aquifers have been intensively monitored with detailed sampling along cross sections positioned across the plumes (i. e. transects). However, little is known about natural attenuation of contaminant plumes in fractured rock. In this thesis study, strong natural attenuation of a persistent co-mingled plume of trichloroethylene (TCE) and an herbicide (metolachlor) in a 100 <em>m</em> thick dolostone aquifer used for municipal water supply in Cambridge, Ontario is shown based on detailed delineation of groundwater contaminant concentrations along a single transect located 150 <em>m</em> downgradient from the area where the metolachlor entered the dolostone and 300 <em>m</em> downgradient from the TCE source area. This delineation was accomplished using depth-discrete, multilevel groundwater monitoring systems in five cored holes and detailed analyses of contaminant concentration in rock cores. The maximum metolachlor concentration on the transect is a factor of 20 below the maximum concentration in the metolachlor source area and the maximum TCE concentration on the transect is lower by a factor of 100 from the TCE source area. <br /><br /> Matrix diffusion and strong temporal variability of the groundwater flow system caused by pumping of nearby municipal wells have likely caused strong natural attenuation of metolachlor and TCE and degradation has likely contributed to even stronger TCE attenuation. The transect shows rock core concentrations much higher than the groundwater concentrations in the multilevel systems at the same locations and in the conventional monitoring wells, which indicates that plume persistence is likely maintained by back diffusion from the rock matrix, which has very low hydraulic conductivity but substantial porosity, into the active groundwater flow in the fractures. <br /><br /> Metolachlor has been observed at very low concentrations and has persisted at these concentrations in the nearest municipal pumping well located approximately 780 <em>m</em> downgradient of the transect, however this well shows no detectable TCE. The relatively low concentrations along the transect and the replenishment of the plume by back diffusion suggests that a substantial increase of metolachlor or TCE in the municipal well is unlikely.

Much is known about natural attenuation of contaminants in granular aquifers because many contaminant plumes in these aquifers have been intensively monitored with detailed sampling along cross sections positioned across the plumes (i. e. transects). However, little is known about natural attenuation of contaminant plumes in fractured rock. In this thesis study, strong natural attenuation of a persistent co-mingled plume of trichloroethylene (TCE) and an herbicide (metolachlor) in a 100 <em>m</em> thick dolostone aquifer used for municipal water supply in Cambridge, Ontario is shown based on detailed delineation of groundwater contaminant concentrations along a single transect located 150 <em>m</em> downgradient from the area where the metolachlor entered the dolostone and 300 <em>m</em> downgradient from the TCE source area. This delineation was accomplished using depth-discrete, multilevel groundwater monitoring systems in five cored holes and detailed analyses of contaminant concentration in rock cores. The maximum metolachlor concentration on the transect is a factor of 20 below the maximum concentration in the metolachlor source area and the maximum TCE concentration on the transect is lower by a factor of 100 from the TCE source area. <br /><br /> Matrix diffusion and strong temporal variability of the groundwater flow system caused by pumping of nearby municipal wells have likely caused strong natural attenuation of metolachlor and TCE and degradation has likely contributed to even stronger TCE attenuation. The transect shows rock core concentrations much higher than the groundwater concentrations in the multilevel systems at the same locations and in the conventional monitoring wells, which indicates that plume persistence is likely maintained by back diffusion from the rock matrix, which has very low hydraulic conductivity but substantial porosity, into the active groundwater flow in the fractures. <br /><br /> Metolachlor has been observed at very low concentrations and has persisted at these concentrations in the nearest municipal pumping well located approximately 780 <em>m</em> downgradient of the transect, however this well shows no detectable TCE. The relatively low concentrations along the transect and the replenishment of the plume by back diffusion suggests that a substantial increase of metolachlor or TCE in the municipal well is unlikely.

Vårdrelaterade infektioner [VRI] skapar onödigt lidande för patienter, förlänger vårdtider och kostar samhället enorma summor varje år. Det är därför viktigt att öka personalens kunskaper och följsamhet till gällande föreskrifter angående basala hygienrutiner. Syftet med denna studie var att belysa vårdpersonalens följsamhet, synliggöra mindre uppmärksammade smittkällor och redogöra för de åtgärder med vilka man kan minska spridningen av VRI. Artiklar samt litteratur till denna systematiska litteraturstudie söktes främst via sökmotorn ELIN, tillgänglig vid Högskolan Dalarnas bibliotek samt Mora Lasaretts bibliotek och Orsa- och Moras kommunbibliotek. Artiklar som inkluderades var publicerade 2000-2009, tillgängliga i fulltext, ej avgiftsbelagda eller skrivna på andra språk än engelska och svenska. Resultatet visar att följsamheten hos vårdpersonalen var låg och att införandet av åtgärdsprogram i de flesta fall endast gav temporär förbättring av följsamheten och att vårdpersonalen efter kort tid återgick till ett felaktigt beteende. När personalens bristande kunskap ledde till felaktigt användande av skyddsutrustning såsom handskar och plastförkläden kunde detta vara en källa till spridning av VRI. Vårdpersonalens arbetskläder visade sig bära på flertalet potenta mikroorganismer som kan orsaka VRI. Även patientnära- och medicinsk utrustning visade sig bära på smittförande mikroorganismer. Slutsatserna av litteraturstudien visar att punktprevalensmätningar är en preventiv åtgärd som på sikt kan minska spridningen av dessa VRI. För att även på lång sikt förbättra vårdpersonalens följsamhet behövs kontinuerlig uppföljning av åtgärdsprogram och studier.

Whenever a new sensor or system comes online, engineers and analysts responsible for processing the measured data turn first to methods that are tried and true on existing systems. This is a natural, if not wholly logical approach, and is exactly what has happened in the advent of hyperspectral imagery (HSI) exploitation. However, a closer look at the assumptions made by the approaches published in the literature has not been undertaken. This thesis analyzes three key aspects of HSI exploitation: statistical data modeling, covariance estimation from training data, and dimension reduction. These items are part of standard processing schemes, and it is worthwhile to understand and quantify the impact that various assumptions for these items have on target detectability and detection statistics. First, the accuracy and applicability of the standard Gaussian (i.e., Normal) model is evaluated, and it is shown that the elliptically contoured t-distribution (EC-t) sometimes offers a better statistical model for HSI data. A finite mixture approach for EC-t is developed in which all parameters are estimated simultaneously without a priori information. Then the effects of making a poor covariance estimate are shown by including target samples in the training data. Multiple test cases with ground targets are explored. They show that the magnitude of the deleterious effect of covariance contamination on detection statistics depends on algorithm type and target signal characteristics. Next, the two most widely used dimension reduction approaches are tested. It is demonstrated that, in many cases, significant dimension reduction can be achieved with only a minor loss in detection performance. In addition, a concise development of key HSI detection algorithms is presented, and the state-of-the-art in adaptive detectors is benchmarked for land mine targets. Methods for detection and identification of airborne gases using hyperspectral imagery are discussed, and this application is highlighted as an excellent opportunity for future work.

Soil quality standards (SQSs) are one of the most important elements of management system for contaminated sites. In order to manage risks associated with soil contamination, risk based SQSs are used worldwide. However, in Turkey, the Soil Pollution Control Regulation in force was focusing mainly on the use of stabilized sludge on soil and was including standards for a limited number of parameters, mainly metals and some organic chemicals. Thus, existing SQSs were far away from providing common criteria for assessment of the soil quality. In this study, the aim was to develop human health risk based SQSs for Turkey. For derivation of risk based SQSs, the conceptual framework and technical infrastructure were established. SQSs were derived for 151 chemical substances and for three different land use types by incorporating generic site characteristics for Turkey. Since SQSs are highly sensitive to site conditions and chemical-specific data used in calculations, a Microsoft Excel based exposure model was developed as a technical tool. This tool serves for calculation of generic and site-specific SQSs and maintenance of the currency of the standards by allowing periodic update of data used in calculations. Besides, a hydrogeologic database was developed to provide information on the general soil and hydrogeologic characteristics that are used in derivation of SQSs. This database is ultimately, expected to serve for development of conceptual site models, sampling strategies, and derivation of dilution factors during risk assessment studies. As a result, this study presents a general perspective and approach for derivation of human health risk based SQSs. It is believed that the developed conceptual and technical infrastructure will contribute to contaminated site management and risk assessment studies conducted by the regulatory authorities and the other stakeholders in Turkey.

This research reports on an experimental and theoretical study of soil heating/air stripping and steam injection/vacuum extraction for remediation of MTBE and Diesel Contaminated Soils. Two one-dimensional mass transfer models were using to simulate the process of remediaction. Contaminant kinds(MTBE and Diesel)¡A contaminant concentration (152~13,912 mg/kg soil)¡Asoil temperature(38~120¢J)¡Asteam injection pressure(0.5~1.0 atm)¡A and the mass of steam used(0.379~0.730 kg/h)were employed as the experimental factors in this study. In soil heating/air stripping study, rising soil temperature will enhance the MTBE removed efficiency¡A it was shown in the concentration of effluent gas. Further, the flow rate at outlet of column was higher than that at inlet of column, it revealed MTBE transfers from liquid phase to gas phase and was removed by gas flow. The concentration of effluent gas curve in low initial MTBE concentration test was similar with high concentration test, but the mechanisms was quiet different¡Ait need advanced adsorption test to find the reasons. In medium initial MTBE concentration test¡Athe concentration of effluent gas curve showed linear shape. When using steam injection/vacuum extraction treating MTBE contaminated soil, it showed 90¢Mefficiency can be reached in one hour. In steam injection/vacuum extraction study, it showed higher initial diesel contaminant concentration¡Ahigher initial concentration of effluent gas. Further, in high initial diesel concentration test (13.912 g diesel/kg soil test and about 5g/ kg soil tests)¡Athe concentration of effluent gas curves had a dominant drop at early time in remediation, it revealed the injection steam flow was quiet large, so diesel didn¡¦t has enough time to transfer to gas phase, that the gas couldn¡¦t been saturation at outlet of column. But in low initial diesel concentration test (about 1 g diesel/kg soil tests), the concentration of effluent gas curves showed the typical NAPL remediation curve. The different with in high and low initial concentrations might from the complex composition of diesel. Because at the early time in remediaction of high initial diesel concentration, the low carbon numbers diesel could abundantly evaporate, it caused the high concentration of effluent gas. With the remediation time go by, the low carbon numbers diesel exhaust. So the main composition of effluent gas transfer to high carbon numbers diesel, that the concentration of effluent gas curve showed the slowly decline. For high initial diesel concentration test (13.912 g diesel/kg soil)¡A the efficiency was the highest (73.7¢M). For low initial diesel concentration test (about 1 g diesel/kg soil), the efficiency was the lost (about 20¢M). Further, the remediation of diesel contaminated soil exited a rapid removed period. Under the conditions of this study, the rapid removed period could remove more than 95¢Mcontaminant of diesel removed at hold remediation time. The experiment results also showed that larger the mass of steam injection, shorter the rapid removed period, and larger the steam injection pressure, longer the rapid removed period. When using soil heating/air stripping treating diesel contaminated soil, the removed efficiency was worse 10-20¢Mthan the same initial diesel contaminated concentration. In simulating remediation process, the prediction with the MTBE measured concentration yielded good agreement in NAPL model. But to get the better fit of diesel in NAPL model, it might set the ¡§could removed mass¡¨ to initial condition of model. In non-NAPL model, MTBE also showed good agreement with model, and the model enabled the prediction of the initial contaminant level in the soil.

Contamination of groundwater supplies by gasoline and other petroleum-derived hydrocarbons released from underground or aboveground storage tanks is a serious and widespread environmental problem. Corrosion, ground movement, and poor sealing can cause leaks in tanks and associated piping. Petroleum hydrocarbons contain methyl tertiary-butyl ether (MTBE) (a fuel oxygenate), benzene, toluene, ethylbenzene, and xylene isomers (BTEX), the major components of gasoline, which are hazardous substances regulated by many nations. MTBE possesses all the characteristics of a persistent compound in the subsurface: high solubility, low volatility, low sediment sorption, and resistance to biodegradation. The objectives of this study were to (1) evaluate the biodegradibility of MTBE under aerobic conditions, and (2) assess the potential of using the aerobic bioremediation technique to clean up aquifers contaminated by MTBE. In this study, microcosms were constructed to determine the feasibility of biodegrading MTBE by intrinsic microbial consortia (aquifer sediments) under aerobic and aerobic cometabolic conditions. In the cometabolic microcosms, propane, ethanol, and BTEX were applied as the primary substracts to enhance the biodegradation of MTBE. The inocula used in this microcosm study were aquifer sediments collected from the contaminated-zones of a petroleum-hydrocarbon (including MTBE) contaminated site. Microcosms were constructed with nutrient medium (or site groundwater), sediments, and MTBE solution in 70-mL serum bottles sealed with Teflon-lined rubber septa. MTBE was analyzed using purge-and-trap instrument following gas chromatography (GC)/flame ionization detector (FID). Results show that the indigenous microorganisms were able to biodegrade MTBE under aerobic conditions using MTBE as the sole primary substrate. Microcosms with site groundwater as the medium solution show higher MTBE biodegradation rate. This indicates that site groundwater might contain some trace minerals or organics, which could enhance the MTBE biodegradation rate. Results show that the addition of BTEX would also enhance the MTBE removal. However, no significant MTBE biodegradation was observed in microcosms with propane and ethanol as the primary substrates. This reveals that the supplement of the second carbon source might inhibit the degradation of MTBE due to the preferential removal of some organics over MTBE. Results from the microcosm study suggest that aerobic biodegradation plays an important role on the MTBE removal. Intrinsic bioremediation is a feasible technology to remediate the studied MTBE-contaminated site.

The purpose of this study was to evaluate the treatment efficiency of phenol contaminated soils by electrokinetic (EK) process conducted in sand boxes (60 cm¡Ñ30 cm¡Ñ30 cm; L¡ÑW¡ÑH). The electric field strength, electrode polarity reverse, and Fenton reagent were employed as the experimental factors in this study to assess the variations of soil characteristics, potential difference, and residual phenol concentration distribution during a treatment period of 20 days and after the treatment. It was found that the anode reservoir pH decreased to around 2 and the cathode reservoir pH increased to approximately 12 after 2~3 days of treatment in the no electrode polarity reverse system. However, the variation of pH in the anode and cathode reservoirs was less obvious in the case with electrode polarity reverse. No matter a constant potential system or a constant current system was employed, a general trend of a lower pH at the anode reservoir and a higher pH at the cathode reservoir would be found. The acid front generated at the anode reservoir flushed across the soil specimen toward the cathode and the base front advanced toward the anode. However, in the central region of sand box, unsaturated and saturated soil specimen maintain neutral. For EK or EK-Fenton experiments, under the constant potential conditions, the potential difference relative to the cathode versus the distance from anode was found to have a linear relationship at the beginning of the electrical potential application. As the treatment time elapsed, the potential gradient became non-linear. Nevertheless, there was no remarked potential gradient change in the case with electrode polarity reverse. Although capillarity has resulted in an increase of the moisture content of unsaturated soil (from 25.34% to 30% after 20 days), electroosmotic (EO) flow was not obvious in the unsaturated zone. For the experiments with electrode polarity reverse, they had a much greater EO flow quantity, the electroosmotic permeability coefficients for constant potential and constant current systems were 6.42¡Ñ10-6 cm2/V¡Es and 9.47¡Ñ10-6 cm2/V¡Es, respectively. It was also found that the existence of contaminants did reduce the EO flow quantity. Regardless of the employment of a constant potential or constant current system, the maximum destruction and removal efficiency (DRE) of phenol was obtained for EK-Fenton process. The maximum DRE values of phenol for both constant potential and constant current systems were found to be 78.06% and 80.11%, respectively. However, the DRE of phenol was found to be much lower for the system with electrode polarity reverse. It was postulated that the destruction efficiency of phenol was less obvious than the removal efficiency in the electrode polarity reverse system. In addition, a frequent reverse of electrode polarity also resulted in a frequent change of EO flow direction. Thus, a flow hysteresis of phenol in the soil compartment was found.