Arsenic sorbs strongly to the surfaces of Fe(III) (hydr)oxides. Under aerobic conditions, oxygen acts as the terminal electron acceptor in microbial respiration and Fe(III) (hydr)oxides are highly insoluble, thus arsenic remains associated with Fe(III) (hydr)oxide phases. However, under anaerobic conditions Fe(III)-reducing microorganisms can couple the reduction of solid phase Fe(III) (hydr)oxides with the oxidation of organic carbon. When ferric iron is reduced to ferrous iron, arsenic is mobilized into groundwater. Although this process has been documented in a variety of pristine and contaminated environments, minimal information exists on the mechanisms causing this arsenic mobilization. Arsenic mobilization was studied by conducting controlled microcosm experiments containing an arsenic-bearing ferrihydrite and an Fe(III)-reducing microorganism, Geobacter metallireducens. Results show that arsenic mobility is strongly controlled by microbially-mediated disaggregation of arsenic-bearing iron nanoparticles. The most likely controlling mechanism of this disaggregation of iron oxide nanoparticles is a change in mineral phase from ferrihydrite to magnetite, a mixed Fe(III) and Fe(II) mineral, due to the microbially-mediated reduction of Fe(III). Although arsenic remained associated with the iron oxide nanoparticles and was not released as a hydrated oxyanion, the arsenic-bearing nanoparticles could be readily mobilized in aquifers. These results have significant implications for understanding arsenic behavior in aquifers with Fe(III) reducing conditions, and may aid in improving remediation of arsenic-contaminated waters. / Master of Science

This thesis examines the ill-fated Texan Santa Fe Expedition of 1841 to analyze the state of a lucrative market network in the Southwest. Cut off from Santa Fe, the hub of the network, Texas struggled economically as an independent nation. Commercially isolated and dealing with near- worthless paper money, Texans hoped that trade with the people of Santa Fe would divert wealth into their nation. To justify the expedition, Anglo-Texans used the rhetoric of Manifest Destiny and turned the trek into a liberation mission. Moreover, Texans desired an overland route to Santa Fe to attract merchants to their otherwise inactive ports. Texans invested much into the expedition both economically and culturally; however, the Texan Santa Fe Expedition ended in utter failure and convinced many Texans that annexation to the United States was the wiser path to take. / Master of Arts

Currently, the application of bioremediation requires extensive and costly monitoring due to limited understanding of the terminal electron accepting processes (TEAPs) that control biodegradation, which impairs the accurate quantification of contaminant mass loss. The measurement of redox conditions and evaluation of TEAPs are critical in assessing the capacity for bioremediation at any site. A series of batch microcosm experiments, using sediment collected from a gasoline-contaminated aquifer at Fort McCoy, Wisconsin, was designed to: 1) evaluate the role of Fe(III) in the development of TEAPs during biodegradation of benzene, toluene, ethylbenzene, and the xylenes (BTEX); 2) examine the biodegradation potential in different portions of the plume; and 3) compare methods of TEAP characterization. In general, the presence of Fe-oxides in microcosms inhibited methanogenesis. Although Fe-reducers did not actively degrade BTEX, Fe-reduction did occur, and most probable number (MPN) counts showed that added Fe(III) increased numbers of Fe-reducers in the microcosms. Methane production in microcosms constructed from sediment near the source area was ~5 times lower than levels produced by the mid-plume sediment. No Fe-reduction occurred in microcosms containing sediment from the source area. These results suggest that the source area has much lower biological activity than the mid-plume. TEAP characterization was conducted using a variety of methods, including geochemical indicators, redox dyes, MPN, and hydrogen concentrations. Monitoring of CH4 concentration yielded useful information in delineation of redox processes; Fe(II) monitoring was unreliable as a geochemical indicator. Redox dyes supplied basic information on reducing environments. MPN counts estimated microbial populations in lieu of faulty geochemical indicators, i.e., Fe(II). The measurement of H2 proved to be one of the more simple and reliable methods for TEAP identification. Results of this study indicate that TEAP characterization should include use of multiple methods; relying on geochemical indicators alone is not sufficient. / Master of Science

Les objectifs de cette étude de cas consistaient à identifier les barrières et les facteurs encourageant le recours aux soins prénatals dans la ville de Rosario en Argentine, ainsi qu'à dégager des orientations permettant d'optimiser l'utilisation des services. Les deux échantillons sont composés de nouvelles mères (n=11) et de dispensateurs (n=8) des services publics de santé municipaux de la ville de Rosario. La collecte a été réalisée à partir d'entrevues individuelles, à l'aide d'un guide d'entretien semi-ouvert. Les résultats de l'étude démontrent qu'il n'existe pas de barrières importantes à l'utilisation des services publics de santé prénatale dans la ville de Rosario. Les retards des premières consultations médicales ou l'absence de suivi seraient davantage en lien avec l'acceptation de la grossesse. Alors qu'il y a 15 ans la moitié des grossesses n'étaient pas suivies adéquatement, le corps médical estime que les femmes sur-utiliseraient maintenant les services de santé prénatale. Le déterminant le plus significatif de l'utilisation des soins prénatals est la conviction des femmes que le suivi de la grossesse est nécessaire pour le bien-être de leur fœtus. Les femmes qui ont eu un suivi de moins de 1 visite par mois ont manifesté de l'insatisfaction quant aux aspects médicaux et émotionnels des soins. Les femmes apprécient particulièrement la disponibilité de spécialités médicales et d'analyses (échographies), mais sont avant tout reconnaissantes d'avoir accès gratuitement aux soins. / The objectives of this case study were to identify factors that encourage women to consult healthcare services during pregnancy, as well as the barriers that prevent them from doing so. We also identify trends that could aid in formulating strategies to optimize prenatal care utilization in the city of Rosario in Argentina. We recruited 11 new-mothers and 8 healthcare workers in the public health sector of the municipality of Rosario. Data was collected based on partially open ended interviews. Results of the study show that there are no considerable barriers to public prenatal care utilization in Rosario. However, we did find a strong association between those women who delayed consultation regarding their pregnancy and those who had trouble accepting the fact that they were pregnant. The incidence of prenatal care utilization has increased dramatically from just fifteen years ago when only half of all pregnant women sought adequate prenatal care. As such, the medical community believes that women are now overusing the services. The most significant determinant of prenatal care utilization is the women's conviction that medical care during pregnancy is necessary for the well-being of their child. The women we studied are expecting at least one consultation per month during their pregnancy. Those who felt they did not have enough visits also expressed dissatisfaction with the medical and emotional aspects of their care. Although the women we talked to appreciated access to specialized medical care services and technologies, they were above all grateful for access to free healthcare.

Ce travail a pour but l’acquisition de connaissances fondamentales dans les équilibres de phases et les transformations de phases des alliages ternaires contenant du fer, du nickel et du cuivre.Cette étude est composée de trois parties : la première est consacrée aux équilibres de phase entre600°C et 1000°C dans le coin riche en fer du système ternaire Cu-Fe-Ni, la seconde concerne l’analyse des transformations de phases dans des alliages modèles suivant deux vitesses de refroidissement et la troisième étudie les alliages industriels.Cette approche expérimentale est appuyée par des calculs thermodynamiques. Une comparaison est effectuée avec les données issues de la littérature. Les sections isothermes à 600°C, 800°C et1000°C ont été reconfirmées. Les domaines triphasés αFe/γFe/γCu ont été déterminés à 600°C et800°C et semblent décalés vers de plus fortes teneurs en Ni. La lacune de miscibilité est moins étendue que celle calculée et ce particulièrement du côté du binaire Cu-Ni.Les transformations de phase γ→α apparaissant lors du refroidissement d’alliages Fe-xCu-10Ni et Fe-10Cu-xNi (0<x<15 % en masse) ont été étudiées. Elles sont observées dans tous les alliages refroidis lentement par dilatométrie sauf dans l’alliage binaire Fe-Cu. Les températures de transformation sont systématiquement inférieures aux températures d’équilibre et cet écart augmente lorsque les teneurs en Ni et Cu augmentent. La formation de la ferrite bainitique est favorisée par l’addition de Cu dans les alliages trempés Fe-xCu-10Ni et par l’addition de Ni dans les alliages Fe-10Cu-xNi tandis que la ferrite massive se forme préférentiellement lors du refroidissement lent. Une diminution des températures de transformation se produit lorsque la taille de grains est affinée et est reliée au processus d’accommodation plastique liée à la transformation.La composition et la vitesse de refroidissement jouent un rôle sur la dureté de ces alliages via la présence de Ni en solution solide ainsi que le nombre et la taille des précipités de Cu. / This work aims in getting fundamental knowledge of phase equilibria and microstructures of ternary alloys containing copper, nickel and iron. The thesis is composed of three parts: a first part is devoted to phase equilibria in the Fe-rich corner of the ternary Cu-Fe-Ni system between 600°C and 1000°C, a second part is devoted to the microstructures in these materials for model alloys, for two cooling rates and a third part is devoted to industrial alloys.Phase equilibria of the system are investigated in the range 600-1000°C using diffusion multiples in conjunction with selected equilibrated alloys. This experimental approach is supplemented by thermodynamic calculations. A comparison is drawn with data reported in the literature. The isothermal sections at 600°C, 800°C and 1000°C have been reconfirmed. The three-phase regions αFe/γFe/γCu are determined at 600°C and 800°C and appear shifted to a higher Ni content. The miscibility gap is narrower than the calculated, particularly on the Cu-Ni binary sides.Austenite/ferrite phase transformations occurring on cooling in Fe-xCu-10Ni and Fe-10Cu-xNi alloys,0<x<15 (mass%), have been studied. The influence of copper and nickel additions and of the cooling rate on the microstructure is discussed. Metastable transformations in slowly cooled alloys have been detected by dilatometry in all alloys except in the binary Fe-10Cu alloy: all the cooling transformation temperatures are systematically lower than the equilibrium temperature and the Ni and Cu addition decrease this transformation temperature. The formation of bainitic ferrite is favoured by copper additions in quenched Fe-xCu-10Ni alloys and by Ni addition in Fe-10Cu-xNi alloys while massive ferrite form preferentially during slow cooling. A decrease of the transformation temperatures is recorded when the alloys have a finer grain size likely related to plastic accommodation processes.The composition and cooling rate influence the hardness of the alloys mostly dependant on the amount of Ni in solid solution and on the rate and size of Cu precipitates.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Le problème de l’hydroplannage a fait l’objet de peu de travaux de simulation jusqu’à présent du fait de sa complexité : couplage fluide-structure, complexité de la structure du pneu du fait des matériaux en présence, contact avec l’asphalte, complexité de l’écoulement fluide résultant (interface extrêmement complexe,assèchement de la route, ventilation, développement éventuel de la turbulence et de cavitation). Dans ce contexte, Michelin, Centrale Nantes et NextFlowSoftware ont cherché récemment à évaluer la capacité du solveur SPH développé par ces deux derniers pour classifier des pneumatiques en fonction de la géométrie de leurs structures surfaciques, sans prendre en compte la phase gazeuse. Cela a permis de démontrer la faisabilité de telles simulations par méthode SPH, et même d’obtenir de bons résultats avec pour avantages de s’absoudre des difficultés liées au maillage. L’autre avantage conséquent d’utiliser la méthode SPH pour modéliser le fluide dans ce contexte est apparu dans sa capacité à se coupler relativement aisément à des solveurs classiques de type Eléments Finis pour le problème structurel. L’objectif du doctorat est triple, poursuivre la qualification du couplage SPH–Eléments Finis, en particulier en termes énergétiques, développer des schémas permettant d’assurer un bon compromis stabilité / précision / temps de calcul. Deuxièmement quantifier l’influence des différents phénomènes physiques en jeu pour déterminer lesquels doivent être modélisés. Enfin adapter des modélisations SPH permettant de prendre en compte simultanément les différents phénomènes influant pour réaliser des simulations du problème complet. / The aquaplaning problem has been the topic of simulation works emphasizing its complexity: fluid structure interactions, structures modelling, materials involved, contact with asphalt and the complexity of the resulting fluid flow (extremely complex interface, drying up the road, ventilation, possible development of turbulence and cavitation). As additional difficulty, the tire is a highly deformable body and fluid-structure interaction effects should be considered, leading to a challenging problem for the numerical modelling. Then Michelin, Ecole Centrale Nantes and NextFlow Software have recently tested the ability of the SPH solver developed by the two latter to classify tires based on their surface structure geometries, without considering the gas phase. In this context, the interest of SPH for modelling efficiently the aquaplaning flow has been underlined. The meshless and Lagrangian feature of SPH naturally avoid the problem of fluid/solid grid compatibility. The other significant advantage of the SPH method, in this context, appears in its ability to be relatively easily coupled to with conventional Finite Element solvers. The aim of this workis three fold. First, qualify the SPH-FE coupling strategy, especially in terms of energy and then develop schemes to ensure a good compromise among stability, accuracy and computation time. Second, quantify the influence of different involved physical phenomena to determine which should be modelled. Finally, adapt SPH models to simultaneously consider different phenomena and to performe simulations of the complete problem.

[pt] No presente trabalho, foi avaliado num modo sistemático o processo de eletrocoagulação (EC) usando eletrodos de alumínio e ferro como material de anodo e aço inoxidável como material de catodo, operando com diferentes parâmetros tais como: concentração inicial do óleo, distanciamento entre os eletrodos, relação área-volume (SA/V) e densidade de corrente. A redução da demanda química de oxigênio (DQO) e turbidez foram às principais variáveis respostas analisadas. Os ensaios foram feitos em batelada com um efluente sintético (5,1 litros) e com agitação magnética (150 rpm). A densidade de corrente e a relação SA/V foram os parâmetros com maior influência no processo. O aumento deles reduz notoriamente o tempo de tratamento. Os resultados mostraram que a eletrocoagulação, para os dois tipos de materiais (Fe/Al), conseguem uma excelente redução da DQO e da turbidez nas seguintes condições experimentais: densidade de corrente, 9,4 mA/cm(2), distanciamento entre os eletrodos, 10 mm, relação área-volume(SA/V), 30,35 m(2)/m(3) e 30 minutos de operação. Eficiências de redução de 99% e 98,3% foram alcançadas para a DQO e a turbidez com anodos de alumínio. Do mesmo modo 94,8% da DQO e 98,5% da turbidez para o caso do ferro foi reduzido do efluente sintético. O processo de eletrocoagulação, operando nessas condições envolve um custo total de 7,1 R$/m(3) e 5 R$/m(3) por metro cúbico para alumínio e ferro, respectivamente. Estes custos só incluem custo de energia e consumo dos eletrodos. A borra produzida foi de 2,23 kg/m(3) para alumínio e 2,76 kg/m(3) para o ferro. Finalmente, o consumo de energia foi de 4,15 kWh/m(3) e 3,72 kWh/m(3) para alumínio e ferro, respectivamente. Um tratamento de eletrocoagulação para um efluente oleoso sintético foi satisfatoriamente implementado do ponto de vista da redução destes parâmetros. / [en] In the present work, electrocoagulation process (EC) with aluminum and iron as materials for anode and stainless steel as cathode, under different operational parameters, such as: initial concentration of oil, distance between electrodes, area-volume relation (SA/V) and current density, were examined in a systematic manner. Chemical oxygen demand (COD) and turbidity removals were selected as a performance criteria. Tests were carried out batch-wise in an electrochemical cell (5.1 liter) with synthetic wastewater and with magnetic stirring (150 rpm); the current density and SA/V relation were found to be the most significant parameters, an increase of theses notably reduces the electrocoagulation required time for the treatment. The results have shown that electrocoagulation, using both kind of materials (Fe/Al), successfully removes the COD and turbidity in experimental conditions such as: the current density, 9.4 mA/cm(2), distance between electrodes, 10 mm; SA/V relation, 30.35 m(2)/m(3) and 30 minutes of operation . Removal efficiencies over 99% and 98.3% were measured for COD and turbidity, using anodes of aluminum. Likewise 94.8% of COD and 98.5% of turbidity were removed from synthetic wastewater, using anode of iron. Electrocoagulation process operated under theses conditions involves a total cost of 7.1 R$/m(3) for aluminum and 5 R$/m(3) for iron per meter cubic of treated wastewater. These costs only include energy cost and electrode consumptions. The sludge produced after electrocoagulation treatment was 2.23 kg/m(3) for aluminum and 2.76 kg/m(3) for iron, and the power requirements were 4.15 kWh/m(3) and 3.72 kWh/m(3) for aluminum and iron. An electrocoagulation treatment of a synthetic wastewater was successfully implemented from removal efficiency point of view.

O complexo R2TP está presente em eucariotos, de leveduras a humanos, e está envolvido no correto dobramento de outras proteínas e montagem de complexos multiproteicos. R2TP é formado pelas proteínas Rvb1, Rvb2, Tah1 e Pih1/Nop17 em levedura, e direciona as chaperonas à proteínas alvo durante a montagem dos complexos. Os clusters Fe/S são sintetizados nas mitocôndrias e posteriormente transferidos para o citoplasma. Dre2 é uma proteína que contém cluster Fe/S, e está envolvida na transferência desses clusterspara outras proteínas citoplasmáticas. Nosso laboratório identificou a interação entre a subunidade Nop17 do complexo R2TP e Dre2 pelo método de duplo-híbrido, mas o papel desta interação ainda não foi elucidado. O objetivo deste trabalho foi o de estudar o papel funcional da interação entre Dre2 e Nop17 e identificar seus domínios de interação. Nossos resultados mostram que a porção N-terminal de Nop17 interage com a porção C-terminal de Dre2 e esta interação é necessária para a manutenção dos níveis de Dre2 na célula, indicando que o complexo R2TP atue na montagem do complexo CIA, de proteínas citosólicas Fe/S, do qual Dre2 faz parte. Dre2 também afeta a estabilidade de Nop17, sugerindo que Dre2 possa transferir um clusterFe/S para Nop17. Os dados mostrados aqui, portanto, indicam que a interação Nop17-Dre2 seja mutuamente importante para a estabilidade das duas proteínas / The R2TP protein complex is present in eukaryotes from yeast to humans, and is involved in the correct assembly of other protein or ribonucleoprotein complexes. R2TP is formed by proteins Rvb1, Rvb2, Tah1 and Pih1/Nop17 in yeast, and directs chaperones to target proteins during complexes assembly. Fe/S clusters are synthesized in mitochondria and later transferred to the cytoplasm. Dre2 is a Fe/S cluster protein, involved in transferring of Fe/S clusters to cytoplasmic proteins. Our laboratory has identified the interaction between the R2TP subunit Nop17 and Dre2 in the two-hybrid system. The aim of this work was to study the functional role of the interaction between Dre2 and Nop17, and to identify their domains of interaction. The results show that the N-terminal portion of Nop17 interacts with the C-terminal region of Dre2, and that this interaction is necessary for maintaining the levels of Dre2 in the cell, which suggests that the R2TP complex affects the cytosolic iron-sulfur protein assembly complex (CIA), of which Dre2 is a subunit. Dre2 also affects Nop17 stability, suggesting that Dre2 may transfer a Fe/S cluster to Nop17. The data here indicate that the interaction Nop17-Dre2 is mutually important for these proteins stabilities.

The equilibrium diagrams are the starting point and the guideline to predict and control the microstructure that will form during processing materials. Despite experiments being necessary in binaries and ternaries systems, it is difficult to experimentally determine phase diagrams of higher orders systems over wide ranges of compositions and temperature. The CALPHAD (CALculation of PHAse Diagrams) method was developed in order to solve this problem. The essence is to optimize the parameters of thermodynamic models that describe the Gibbs free energies of each phase aiming to reproduce the experimental and estimated (abinitio) data. The compound energy formalism (CEF) is widely used in order to describe phases which present several sublattices. It allows the modeling of a large variety of phases and numerous methods have been developed to treat different situations. The activities in this work developed a new approach of the CEF (NACEF) based on a mathematic analysis of the parameters which leads to a new formulation of the Gibbs free energy function evolving new independent parameters in which new independent parameters are obtained to express the Gibbs free energy. This approach was used in this work to describe the intermetallic phases with two-sublattice in which the only defect type is anti-sites (A,B)a(A,B)b. The Al-Fe-Nb system was chosen due to its importance for the manufacturing process of several families of alloys currently used, e.g. steels, light alloys, and also for the development of new materials for high temperatures application. The binaries Al-Nb and Fe-Nb were reassessed and the Al-Fe-Nb system was assessed for the first time using literature information and new experimental data. / Os diagramas de equilíbrio são o ponto de partida e a diretriz para prever e controlar a microestrutura ao final do processamento de um material. Apesar de experimentos serem necessários em sistemas binários e ternários, é muito difícil determinar experimentalmente diagramas de fase de sistemas de ordens superiores numa vasta amplitude de composições e temperatura. A fim de solucionar este problema, o método CALPHAD (CALculation of PHAse Diagrams) foi desenvolvido. A essência consiste em aperfeiçoar os parâmetros de modelos termodinâmicos que descrevem as energias livres de Gibbs de cada fase de modo a reproduzir as informações experimentais ou estimadas (ab-initio). O compound energy formalism (CEF) é amplamente utilizado para descrever fases que apresentam várias sub-redes. Ele permite a modelagem de uma grande variedade de fases e vários métodos têm sido desenvolvidos para o tratamento de diferentes situações. As atividades deste trabalho ajudaram a desenvolver uma nova abordagem para o CEF (NACEF) com base em um estudo matemático dos seus parâmetros termodinâmicos que levou a uma nova formulação para função da energia livre de Gibbs envolvendo novos parâmetros independentes. Esta nova abordagem tem sido utilizado como parte do presente trabalho para modelar fases intermetálicas binárias constituídas de sub-redes cujo único defeito é do tipo anti-sítio (A,B)a(A,B)b. O sistema Al-Fe-Nb foi escolhido devido a sua importância para o processo de fabricação de diversas famílias de ligas usadas atualmente, e.g. aços, ligas leves e, além disto, é um sistema importante para o desenvolvimento de materiais para aplicações em altas temperaturas. Neste trabalho os binários Al-Nb e Fe-Nb foram reavaliados e o sistema Al-Fe-Nb foi modelado pela primeira vez utilizando as informações da literatura e novos dados experimentais.