A method for the synthesis of a symmetrical fluorous tagged benzodithiol support has been developed through a seven-step synthetic pathway. The Wittig olefination and catalytic hydrogenation reactions were employed to attach two perfluoroalkyl chains in the o-positions of phthalaldehyde. These fluorous tags were used as soluble supports which facilitated the purification of the crude reaction mixtures using fluorous solid phase extraction (FSPE). A selective and high yielding dibromination reaction was developed to synthesize a fluorous tagged 1,2-dibromo aryl compound. A thorough study was carried out to demonstrate the ease of an aryl-sulfur bond formation with the 1,2-dibromo compound varying palladium catalysts and ligands. A new palladium catalyzed dithiolation reaction is reported to synthesize a surrogated dithiol, which was exploited as a precursor for the synthesis of hitherto inaccessible symmetrical fluorous tagged benzodithiol support. The utility of the benzodithiol was explored by the synthesis of benzodithianes with two aldehydes. The lithiated dithiane generated was further used to form a C-C bond employing the umpolung reaction. The ring-closing metathesis reaction using Grubbs II catalyst was performed to construct 5-membered and 6-membered spiro-ring systems. Several approaches were made to form a C-C bond with lithiated dithianes using various nitrogen containing electrophiles leading to N-heterocycles.

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Supercapacitor electrodes were fabricated at a high active mass loading and exhibited enhanced electrochemical capacitance. A conceptually new salting-out extraction processing technique for the synthesis of dispersed Mn3O4-carbon nanotube (CNT) nanocomposites was developed, alleviating the need for hydrophobic solvents. The choice of isopropyl alcohol and NaCl for the extraction process offer advantages of an easy upscaling of this process. The salting out technique was shown to work with Octanohydroxyamic acid (OHA) and Lauryl Gallate (LG) as extractors and dispersants, critical to the success of the extraction. Mechanisms for surface adsorption on Mn3O4 and CNT for both OHA and LG are discussed. A secondary project was also undertaken, to investigate the use of chlorogenic acid and 3,4,5 – trihydroxybenzamide, as co-dispersing agents for MnO2 and CNTs. These molecules are used due to their unique structural properties, which are discussed. The electrodes fabricated using these co-dispersants showed significant increases in their specific capacitances and SEM imaging indicated improved mixing, compared to samples prepared without dispersants. A specific capacitance of 6.5 F g-1 was achieve at low electrical resistance, attributed to the microstructure of electrodes prepared with the co-dispersant molecules. / Thesis / Master of Applied Science (MASc) / The ever-growing realization that our energy consumption as a civilization is not sustainable, has fueled people around the globe to imagine and design new methods of energy storage, in attempts to mitigate this issue. From the foundational works of scientists, it has become clear to see that there is not “one right answer”. Instead, the unique benefits and drawbacks of energy storage technologies should be balanced and applied in situations where their properties permit a high efficacy. The intention of this work is to assist in the development of new materials to be used for energy storage devices called electrochemical supercapacitors. Novel colloidal processing techniques were developed, leading to the fabrication of high-performance electrodes, and providing further insight to the structure-properties relationship of organic extractors and co-dispersing agents for the design of nanocomposites.

Shooting ranges concentrate significant quantities of heavy metals, especially lead as spent shot and bullets, on very small parcels of land. Samples taken from a shooting range near Blacksburg, VA, USA provide information about the reservoirs and pathways of lead at shooting ranges in an upland setting and humid environment. Metallic lead corrodes rapidly and develops a coating of corrosion products. The type and amount of corrosion products found on lead shot and bullets are best understood through examination of Eh-pH relationships. X-ray diffraction analysis identified hydrocerussite (Pb₃(CO₃)₂(OH)₂) as the corrosion phase present on lead shot recovered from the range. Hydrocerussite dissolution can produce soluble lead concentrations ranging from 2 ppb to 2 ppm for the soil pH values at this site. This soluble lead is captured by the soil. Sequential chemical extractions revealed that vertical lead migration beyond the A-horizon was minimal. The bound-to-Fe & Mn oxides and bound-to-carbonates soil fractions were identified as significant reservoirs for sequestration of lead in the soil. The highest concentration of extractable lead contained in the soil was directly correlated with the highest concentration of lead shot and bullets measured on the shotgun range surface. The geochemical framework for understanding the corrosion process, identifying the corrosion product(s) that control lead solubility, and identifying the geochemical barriers to lead migration that were employed at the Blacksburg, VA shotgun range, provides a basis for selecting best management practices for this and other shooting ranges. / Master of Science

The relationship between soil and wine quality has been recognized for generations but has had limited scientific validation. Vineyard soils in the eastern United States are largely unstudied although proper site selection and good soil management have the potential to improve fruit composition for high-quality wine production. Soils that provide excessive plant-available nutrients and water often produce vigorous vegetative growth and negatively influence fruit chemistry. We investigated three aspects of Eastern vineyard soils, including potassium availability, methods of reducing infiltration, and the influence of topsoil on fruit chemistry. Our first goal was to determine the best soil sampling, processing, and extraction methods for predicting potassium availability in Mid-Atlantic vineyard soils. Excessive potassium can result in high pH fruit, which negatively affects wine quality, but until now the best methods for predicting soil-available potassium had not been investigated. We found that moist-extracted soil sampled from 0-38 cm appear to best be suited predicting vine tissue potassium. Our second goal was to test methods of reducing rain infiltration at critical times during the growing season. One of the soil stabilizers we tested successfully reduced infiltration in field trials. Vineyard trials in 2021 were compromised by dry weather, but further research is ongoing. Our final project involved a three-year investigation where we attempted to isolate the influence of soil properties on grapevines and fruit composition by monitoring vines and fruit in single vineyard blocks. The most consistent result was positive relationships between topsoil and fruit titratable acidity, suggesting that the fruit was ripening earlier in vines growing in thinner topsoil. Topsoil depth better explained differences in fruit titratable acidity than other explanatory variables including crop load and sunlight exposure of fruit. Overall, this research increased our understanding of the soil properties that influence vine growth and fruit chemistry in the Eastern US. The results will help growers improve sampling methods, fruit chemistry, and increase resilience to soil and climate related challenges. / Doctor of Philosophy / The relationship between grapes, wine, and soil has been acknowledged since the Middle Ages when monks recognized that vineyards in different places produced different-tasting wine. However, it is difficult to determine exactly how soil affects grapes and wine. In the eastern United States, growers knew that some soils were not the best for growing high quality grapes for wine, such as those that provide excessive nutrients or water to the vines, but there was little information or scientific research about it. We wanted to help growers by investigating soil properties that affect fruit quality as well as potential soil management strategies that could improve fruit quality. We fine-tuned the process of collecting, processing, and analyzing vineyard samples that growers use to determine the potassium status of their vines. Potassium can affect fruit quality so testing for it before it can affect fruit quality is crucial. We found that sampling soil to a deeper depth than usual and keeping the sample moist instead of drying it were the best practices. We also determined the best way to complete the lab analysis to best predict how much potassium the soil can provide to the vines. For our second project, we found that commercial material intended for stabilizing dirt roads slowed the seeping of rain into soil. Future research will see if vineyards can use the soil stabilizer to reduce soil water during mid-summer rains to improve fruit quality. Our final project involved monitoring vineyards over three years to see how differences in soil properties affected vine growth and fruit chemistry. The main difference in soil was the thickness of topsoil throughout each vineyard. Where there was thin topsoil, the vines were smaller and produced fruit that was less acidic. These results are likely because those fruit were ripening earlier, but we were not able to identify a specific soil property that was affecting the fruit chemistry. Overall, our results will help vineyard growers better manage their soil to hopefully produce better-quality fruit and wine.

Antimoine (Sb) et tellure (Te), sont des contaminants peu étudiés (isotopes stables) et leurs radionucléides artificiels peuvent être rejetés dans le milieu aquatique lors des accidents nucléaires. La connaissance de leurs comportements biogéochimiques respectifs est nécessaire à l'évaluation du risque radiologique post-accidentel.Ce travail présente des données originales sur le comportement biogéochimique de Sb et de Te dans les systèmes de transition continent-océan, tels que l'estuaire de la Gironde et la rivière du Rhône. Un suivi de 14 ans et des campagnes océanographiques dans le bassin versant de l’estuaire de la Gironde ont permis d’identifier des concentrations, des flux, et des réactivités (variabilités spatio-temporelles et distribution solide/liquide) plus élevés pour Sb que pour Te, mettant en évidence un comportement additif pour Sb et de soustraction pour Te le long des gradients de salinité et de turbidité estuariennes. Des expériences couplant l’adsorption d’isotopes marqués sur des matières en suspension (MES) et des extractions sélectives des phases porteuses, suggèrent que les formes apportées de Sb et de Te sont plus mobiles et potentiellement plus biodisponibles que leurs équivalents naturels. De plus, l’observation de la bioaccumulation non-négligeable de Sb et de Te naturels dans les huîtres sauvages à l’embouchure de l’estuaire permet d’envisager une absorption potentielle de leurs homologues radioactifs.Ainsi, le développement de scenarios de dispersion de radionucléides rejetés dans les zones de transition dépendra (i) de la position géographique de la source (Rhône) et/ou de la zone de turbidité maximale (ZTM; système fluvio-estuarien de Gironde), (ii) de la situation hydrologique pendant et post accident, ainsi que (iii) de la réactivité biogéochimique et des temps de demi-vies des radionucléides. Les premiers scénarios de dispersion de radionucléides dans l'estuaire de la Gironde suggèrent (i) un transport préférentiel de Sb dissous vers la zone côtière, et (ii) une forte rétention de Te radioactif dans la ZTM si la dernière est présente en aval du site d’accident, impliquant le risque de migration saisonnière de la radioactivité vers la ville de Bordeaux pendant l’étiage suivant. Ainsi, la dynamique intra estuarienne (marée, débit et migration de la ZTM) sera le facteur prédominant dans le devenir de Te radioactif, depuis son rejet jusqu’à sa désintégration complète en iode radioactif. L’ensemble de ce travail met en évidence la nécessité d’une évaluation plus approfondie de la radiotoxicité potentielle de Sb et Te lors de leurs rejets en milieu aquatique. / Antimony (Sb) and tellurium (Te) are relatively uncommon contaminants (stable isotopes) and may form short-lived fission products (radionuclides) released into the environment during nuclear power plants accidents. Little is known about their respective biogeochemical behaviours, necessary for general contamination studies and post-accidental radiological risk assessment.This work provides original knowledge on Sb and Te biogeochemical behaviour in highly dynamic continent-ocean transition systems: the Gironde Estuary and the Rhône River. Concentrations, spatial/temporal variations, solid/liquid partitioning (Kd), and fluxes are studied from long-term records at the watershed scale. Four estuarine sampling campaigns during contrasting hydrological conditions show higher Sb solubility and Te particle affinity in the estuary than in the upstream fluvial reaches. Historical records (1984-2017) in wild oysters from the estuary mouth do not show clear trends of past or recent contamination, but measurable bioaccumulation suggests that potential uptake of radionuclides is likely to occur. Combined adsorption experiments using isotopically-labelled (spiked) Sb and Te, and subsequent selective extractions of carrier phases from suspended particulate matter (SPM) suggest that spiked Sb and Te are more mobile and potentially bioaccessible than their environmental (inherited) equivalents. Radiotracer adsorption experiments using environmentally representative concentrations of both Gironde and Rhône systems underpin that highly soluble elements may show contrasting reactivity between inherited and spiked forms.Radionuclide dispersion will greatly depend on (i) the geographical position of the source (Rhône) and/or the maximum turbidity zone (MTZ; Gironde fluvial-estuarine system), (ii) the succession of hydrological situations during and after the accident, and (iii) the biogeochemical reactivity and half-lives of the radionuclides. First scenarios on hypothetical dissolved radionuclide dispersion in the Gironde Estuary suggest (i) low sorption of Sb to the SPM, implying a transport of radionuclides in dissolved phase towards the coast, and (ii) high retention of Te within the MTZ, especially for accidental releases during flood conditions, linking the fate of radioactive Te to long estuarine SPM residence times (1-2 years). Potential upstream migration of Te radionuclides in the MTZ towards the city of Bordeaux during the following summer season and Te decay into radioactive iodine warrants further evaluation of the associated potential radiotoxicity.

Les accumulateurs nickel-hydrure métallique (NiMH) dominent actuellement le marché du stockage de l’énergie pour les véhicules hybrides. On estime à 1 milliard, le nombre de batteries NiMH produites chaque année. En fin de vie, le taux de recyclage de ces déchets électroniques reste faible, bien que la technologie NiMH contienne des quantités importantes de métaux onéreux et stratégiques. Deux grandes familles d’éléments chimiques coexistent sous forme de composés intermétalliques dans l’électrode négative: les métaux de transitions (TM) (Ni, Co, Mn et Fe) ainsi que les terres rares (REE) (La, Ce, Nd et Pr). Parmi les TM, le cobalt présente une criticité accrue. En effet, les minerais issus de réserves naturelles ne permettront pas de couvrir la demande croissante en cobalt liés au développement des technologies émergentes. Les REE produits à plus de 97 % en Chine sont au cœur des préoccupations de l’Union Européenne qui depuis 2010 pointe du doigt des techniques d’extractions dévastatrices pour l’environnement. C’est dans le but de répondre aux problématiques économiques et environnementales que le projet a été construit en associant l’entreprise de recyclage de batteries Recupyl® au laboratoire académique LEPMI grâce au financement du Labex CEMAM. L’objectif de ce travail est de proposer un procédé avec un faible impact environnemental pour le recyclage des métaux à partir de véritables accumulateurs NiMH. Pour cela, le remplacement de solvants volatiles organiques par des liquides ioniques, plus respectueux des principes de la ‘chimie verte’ sera étudié. En s’appuyant sur des procédés innovants d’extraction liquide-liquide et de récupération des éléments par hydrométallurgie et par électrochimie nous proposons une voie de valorisation des métaux présents dans ces batteries. / Nickel-metal hydride (NiMH) batteries are currently dominating the market of energy storage in hybrid electric vehicles. 1 billion cells are estimated to be produced each year. In their end-of-life, these electronical wastes exhibit low recycling rates, despite the fact that NiMH batteries contain high amounts of valuable and strategic metals. Two main metal families coexist as an intermetallic compound in negative electrodes: transition metals (TM) (Ni, Co, Mn and Fe) and rare earth elements (REE) (La, Ce, Nd and Pr). Among TM, cobalt exhibits the highest criticality rate. Indeed, natural ores will not cover the increasing cobalt demand linked to emerging technologies. REE produced at more than 97 % in China are at the centre of European Union’s preoccupations. To tackle economic and environmental issues, this project, supported by the labex CEMAM is a partnership between the company Recupyl® and the academic laboratory LEPMI. It aims at investigating on low environmental impact routes for the recycling of metals present in real spent NiMH batteries. This requires the replacement of volatile organic compounds by ionic liquids, respecting the principles of ‘green chemistry’. Based on innovative extraction and recovery processes of elements by hydrometallurgy and electrochemistry, we propose a flowsheet for the valorisation of metals from those batteries.

O objetivo deste trabalho foi comparar o tempo de tratamento em pacientes com e sem apinhamento apresentando inicialmente má oclusão de Classe II tratados com exodontia de quatro pré-molares. A amostra do estudo foi selecionada a partir do arquivo de modelos de gesso iniciais e pastas de pacientes já tratados na Faculdade de Odontologia de Bauru, no Departamento de Ortodontia. A amostra selecionada foi composta de 57 pacientes e dividida inicialmente em dois grupos. O grupo 1, que não apresentava apinhamento ou apresentava um leve apinhamento de 0 a 3 mm, foi constituído de 23 pacientes sendo 11 do gênero masculino e 12 do gênero feminino com idade inicial média de 13,13 anos (idade mínima de 10,67 e máxima de 18,25). O grupo 2, que apresentava apinhamento igual ou maior a 4 mm, foi constituído de 34 pacientes sendo 19 do gênero masculino e 15 do gênero feminino com idade inicial média de 13,07 anos (idade mínima de 11,08 e máxima de 18,33). Para comparar os tempos de tratamento dos grupos, a análise estatística feita foi o teste t, pois os dados obtidos apresentavam uma distribuição normal. Os resultados mostraram que não há diferença estatisticamente significante entre os tempos de tratamento do grupo 1 (2,51 anos) e do grupo 2 (2,49 anos). Sendo assim, os resultados sustentam a ideia de que o principal fator responsável pela semelhança entre os tempos de tratamento é a necessidade da correção anteroposterior do molar, que é igual para ambos os grupos. / The objective of this study was to compare the treatment time of bilateral complete Class II malocclusion with and without crowding treated with four premolar extractions, The sample was selected from arquive of beginning models and pastes of pacients treated at Bauru Dental School, department of Orthodontics. The selected sample was composed by 57 patients and divided into two groups. Group 1 presented no crowding or crowding 0-3 mm was composed by 23 patients being 11 male and 12 female with a mean age of 13,13 years (minimum age 10,67 and maximum age 18,25). Group 2 presented crowding 4 mm or more was composed by 34 patients being 19 male and 15 female with a mean age of 13,07 years (minimum age of 11,08 and maximum age of 18,33). To compare treatment times between groups, t test was performed. Results demonstrated that there was not significantly difference in treatment times of group 1 (2,51 years) and 2 (2,49 years). Thus, the results support the idea the principal factor responsible for similarity treatment times is the need of the molar relationship correction, which is similar in both groups.

O objetivo deste estudo retrospectivo foi comparar os resultados oclusais e a eficiência do tratamento das más oclusões de Classe I e de Classe II completa, ambas tratadas com extrações de quatro pré-molares. A eficiência do tratamento foi definida como a porcentagem de alterações oclusais pelo tempo de tratamento. O Grupo 1, constituído por 75 pacientes que apresentavam inicialmente má oclusão de Classe I, apresentava idade inicial média de 13.98 anos (D.P.: 2.08, mín.: 10.54 e máx.: 23.13), e o Grupo 2, composto por 32 pacientes que apresentavam inicialmente má oclusão de Classe II completa, bilateral, apresentava idade inicial média de 13.19 anos (D.P.: 1.58, mín.: 10.48 anos e máx.: 18.58 anos). As avaliações oclusais foram realizadas em modelos de gesso dos pacientes nas fases inicial e final utilizando os índices PAR e IPT. Os índices oclusais, o tempo de tratamento e o grau de eficiência dos grupos foram comparados pelo teste t. Os resultados demonstraram que o Grupo 1 obteve melhores resultados oclusais e maior porcentagem de alterações oclusais do que o Grupo 2. Entretanto, não houve diferença significante no tempo de tratamento e na eficiência dos protocolos de tratamento entre os grupos avaliados. / The objective of this retrospective study was to compare the occlusal outcomes and the treatment efficiency in the treatment of the Class I and Class II complete malocclusions, both treated with extraction of four premolars. The treatment efficiency was defined as the percentage of occlusal changes by the treatment time. The Group 1, composed by 75 patients who presented initially Class I malocclusion, presented initial mean age of 13.98 years (S.D.: 2.08, min.: 10.54 years and max.: 23.13 years), and the Group 2, composed by 32 patients who presented initially complete Class II, bilateral, presented initial mean age of 13.19 years (S.D.: 1.58, min.: 10.48 years and max.: 18.58 years). The occlusal evaluations were accomplished in study models of the patients in the initial and final phases using the indexes PAR and TPI. The occlusal indexes, the treatment time and efficiency of the groups were compared with the t test. The results demonstrated that the Group 1 achieved better occlusal outcomes and greater percentage of occlusal changes than the Group 2. However, there was no significant difference in the treatment time and efficiency in the treatment protocols between the groups considered.

Alors que de nombreuses études paléoenvironnementales traitent de l'évolution du climat et de la végétation au cours de l'Holocene, il n'existe que très peu d'études portant sur l'évolution des sols au cours de cette même période. Cependant, les propriétés physiques et chimiques des sols ayant un rôle clef au sein d'un écosystème, la reconstitution de l'histoire des sols constitue un enjeu important pour comprendre les changements environnementaux passés. Un des facteurs limitant pour reconstituer l'histoire des sols réside dans l'absence d'enregistrement continu des processus pédologiques sur de longues échelles de temps (103 à 104 ans). Notre intérêt s'est donc porté sur l'utilisation d'archives sédimentaires lacustres dans le but de reconstruire l'histoire de la couverture pédologique en lien avec celle de l'écosystème. Cette étude a été menée sur deux petites dépressions lacustres de l'étage subalpin (Vallée de la Maurienne, Savoie) ayant a priori des histoires de l'occupation humaine différentes. <br /><br />Dans un premier temps, une approche géochimique a été appliquée sur des sols actuels afin de caractériser les pédosignatures des processus de podzolisation et d'altération chimique. Il en résulte que les terres rares (numéros atomiques de 57 à 71) constituent un indicateur du degré d'altération chimique tandis que les proportions des complexes organo-métalliques d'Al et Fe permettent de tracer l'intensité de la podzolisation. Dans un deuxième temps, ces mêmes traceurs ont été mesurés sur deux séquences sédimentaires couvrant 4500 ans Cal. BP (lac du Thyl) et 13500 ans (lac du Loup). La comparaison de ces pédosignatures avec des marqueurs indépendants (végétation, climat, feux) révèle des pédogenèses progressives et régressives après la déglaciation de la fin du Tardiglaciaire. <br /><br />Les sols et l'environnement du lac du Loup sont caractérisés par une évolution progressive et stable menant aux forets de résineux et aux podzols actuels. L'enregistrement du lac du Thyl est plus contrasté : le développement progressif d'une forêt de pin cembro associé au processus de podzolisation est suivi par des perturbations secondaires (principalement l'augmentation du régime des feux) qui pourraient expliquer la mise en place d'une végétation semi-ouverte associée à des processus de dépodzolisation. <br />Finalement, ce travail a permit d'ajouter un volet pédologique aux études paléoenvironnementales classiques. Il en résulte que les deux schémas d'évolution des sols sont très cohérents avec les marqueurs indépendants et qu'ils offrent une meilleure résolution temporelle que l'on ne pourrait l'obtenir avec les chronoséquences.