Call number: LD2668 .T4 1986 M375 / Master of Science / Chemistry

A dissertation submitted to the Faculty of Engineering, University of the Witwatersrand, in fulfillment of the requirements for the degree of Master of Science in Engineering / South Africa, like many other developing countries, is faced with rapid urbanisation with the associated increase in the pollution load. Much of this pollution is destined for our watercourses, that eventually run into storage reservoirs which may be used for drinking water or recreational purposes. This pollution is usually attributed to human waste products which include nitrogenous wastes, phosphates, microorganisms, organic material and litter, A 6km stretch of the Jukskei river just downstream of Alexandra Township, was used to determine the different biological, physical and chemical processes that pollutants undergo during natural assimilation, their rates and efficiencies of assimilation in rivers and their impact Oil the environment downstream of the urban area. "Grab" samples were taken over a period which included both low-flow and storm events. Due to the high concentration of nutrients in the run-off from Alexandra Township, the major changes seen were in the biological conversion of organic nitrogen compounds and ammonia to nitrates, in the BOD and in the concentration of dissolved oxygen in the river, with lows of 1.1 to 1.5 mg/l 02 being recorded at Alexandra. A rapid rise in the concentration of faecal coliforms has been seen with a high of 31 million/100 ml being recorded at Alexandra in September, 1994. Sedimentation at the Alexandra site is also a common occurrence with a lot of adsorbed pollutants being effectively removed from the water column with the suspended solids. The QUAL2E water quality model, used by the EPA in the United States, was used to model the reactions that the nutrients, BOD and DO undergo. BOD and DO were modelled very well with r of 0.98 and 0.94 being calculated respectively. QUAL2E did not model tile dissolved potlutants, dissolved phosphorus and ammonia very well with the observed results showing a greater reduction ill these pollutants. A method by which these pollutants adhere to SS and settle out was / AC2017

Les technologies de traitement physico-chimique et biologique des eaux usées ne permettent pas un traitement efficace de l’azote puisque 40% est encore rejeté en rivière. La thèse porte sur le développement de nouveaux matériaux d’électrode pour la conversion des polluants azotés (nitrates, urée) en produits valorisables (NH3, H2) ou inertes (N2). Le travail consiste à synthétiser des matériaux composites constitués de nanoparticules mono ou bimétalliques jouant le rôle de catalyseurs, dispersées dans des carbones de grande surface spécifique. La forme ultra-divisée permet d’augmenter les surfaces actives et ainsi réduire les quantités de métal. Ces produits sont caractérisés par Microscopie Electronique à Balayage et en Transmission, par analyses ICP et DRX pour décrire leur morphologie, composition et structure. Des études électrochimiques analytiques sont ensuite réalisées à l’aide d’une MicroÉlectrode à Cavité afin de déterminer l’activité électro-catalytique des matériaux et accéder à des aspects mécanistiques. La première partie de la thèse a concerné l’électro-réduction des nitrates. Des composites Cu-Rh/C et Cu-Ni/C avec différentes compositions ont été synthétisés par une méthode chimique consistant à imprégner le carbone par des sels métalliques puis à les réduire par NaBH4 en présence d’un surfactant (CTAB). Les particules présentent des tailles d’environ 2 nm de diamètre. Ces bimétalliques présentent des courants plus élevés que ceux obtenus avec des particules monométalliques. En particulier, dans le cas du système Cu-Rh, il a été mis en évidence un comportement « bi-fonctionnel » où le cuivre réduit les nitrates en nitrites et le rhodium les nitrites en ammoniaque. Des matériaux composites ont ensuite été synthétisés dans les mêmes conditions mais en utilisant un carbone greffé afin de contrôler la dispersion et l’ancrage des nanoparticules. Pour cela, les carbones sont préalablement greffés par des groupements aryle avec substituant puis décorés des nanoparticules métalliques. Le but est de déterminer les conditions de greffage optimales conduisant aux réactivités les plus élevées en contrôlant l’épaisseur des films organiques greffés et la nature du substituant (-SH, -NH2, -COOH). La seconde partie de la thèse a concerné l’électro-oxydation de l’urée. Cette réaction est généralement effectuée sur des matériaux à base de nickel et, d’après la littérature, l’ajout d’un co-élément permet de modifier les propriétés électrochimiques (potentiel, intensité). Une étude sur des composites bimétalliques Ni100-xMx / C avec M = Co, Rh, Mn, Fe (selon la méthode déjà décrite ci-dessus) a été conduite pour déterminer le rôle de différents co-éléments. Le rhodium est apparu comme l’élément apportant la meilleure intensité et la meilleure stabilité. Une étude plus complète a alors été réalisée avec la synthèse de composites Ni100-xRhx / C avec différentes compositions par réduction des ions métalliques sous Ar/H2 dans un four à température modérée (500°C). L'oxydation électrochimique de l'urée est significativement améliorée par l'ajout de rhodium qui induit une forte diminution de la taille des nanoparticules (de 15 nm pour le nickel et à 2 nm le rhodium). Ce travail de thèse a montré l’intérêt d’utiliser des catalyseurs bimétalliques dispersés dans des matrices carbonées pour le traitement de polluants azotés. Elle confirme par ailleurs que la Microélectrode à Cavité est un outil performant pour l’étude des poudres grâce à la bonne résolution des signaux électrochimiques. La perspective la plus intéressante de ce travail est de poursuivre l’étude de l’électrocatalyse de l’urée sur les Ni-M/C pour pouvoir dépolluer l’urine tout en produisant à faible coût de l’hydrogène comme moyen de stockage de l’électricité renouvelable. Il a permis d’initier des collaborations avec d’autres laboratoires et un industriel de l’assainissement des eaux en vue de traiter de l’urine collectée à la source / Physico-chemical and biological wastewater treatment technologies do not allow efficient nitrogen treatment since 40% is still discharged into rivers. The thesis concerns the development of new electrode materials for the conversion of nitrogenous pollutants (nitrates, urea) into recoverable (NH3, H2) or inert products (N2). The work consists in synthesizing composite materials made of mono or bimetallic nanoparticles acting as catalysts, dispersed in large surface area carbons. The ultra-divided shape increases the active surface and thus reduces the amount of metal. These products are characterized by Scanning and Transmission Electron Microscopy, ICP and DRX analysis to describe their morphology, composition and structure. Electrochemical analytical studies are then carried out using a Cavity MicroElectrode to determine the electro-catalytic activity of the materials and access mechanistic aspects.The first part of the thesis concerned the electro-reduction of nitrates. Cu-Rh/C and Cu-Ni/C composites with different compositions were synthesized by a chemical method consisting of impregnating the carbon with metal salts and then reducing them with NaBH4 in the presence of a surfactant (CTAB). The particles are approximately 2 nm in diameter. These bimetals have higher currents than those obtained with monometallic particles. In particular, in the case of the Cu-Rh system, a "bi-functional" behavior has been demonstrated where copper reduces nitrates to nitrites and rhodium reduces nitrites to ammonia. Composite materials were then synthesized under the same conditions by using grafted carbon to control the dispersion and anchoring of nanoparticles. For this, the carbons are previously grafted by aryl groups with a substituent and then decorated with metal nanoparticles. The aim is to determine the optimal grafting conditions leading to the highest reactivity by controlling the thickness of the grafted organic films and the nature of the substituent (-SH, -NH2, -COOH). The second part of the thesis concerned the electro-oxidation of urea. This reaction is generally carried out on nickel-based materials and, according to the literature, the addition of a co-element makes it possible to modify the electrochemical properties (potential, intensity). A study on bimetallic composites Ni100-xMx / C with M = Co, Rh, Mn, Fe (according to the method described above) was conducted to determine the role of the different co-elements. Rhodium appeared as the element providing the best intensity and the best stability. A more complete study was then carried out by synthesizing Ni100-xRhx / C composites with different compositions through the reduction of metal ions under Ar/H2 in a furnace at moderate temperature (500°C). The electrochemical oxidation of urea is significantly improved by the addition of rhodium which induces a strong decrease in the nanoparticle size (from 15 nm for nickel to 2 nm for rhodium). This thesis work has shown the interest of using bimetallic catalysts dispersed in carbon matrices for the treatment of nitrogenous pollutants. It also confirms that the Cavity Microelectrode is a powerful tool for the study of powders thanks to the good resolution of electrochemical signals.The most interesting perspective of this work is to continue the study of urea electrocatalysis on Ni-M/C to be able to depollute urine while producing hydrogen at low cost for chemical storage of renewable electricity. It has enabled collaborations to be initiated with other laboratories and a water purification industrial company to treat urine collected separately

Desde a época da colonização, a cana-de-açúcar apresenta-se como um dos principais produtos da agricultura brasileira e, além disso, trata-se de um tipo importante de biomassa energética, servindo como base para todo o agronegócio sucroalcooleiro, responsável por empregos diretos e indiretos em todo o Brasil. Do seu processo de industrialização são obtidos produtos, tais como: o açúcar, o álcool (anidro e hidratado), o bagaço e a vinhaça. Nesse sentido, diante do aspecto da aplicação da vinhaça em práticas agrícolas, pode-se dizer que sempre ocorre a sua associação com processos de impactos ambientais. Assim sendo, conduziu-se a presente pesquisa buscando-se monitorar a dinâmica, em diferentes tipos de solo, de componentes químicos presentes na vinhaça, bem como, elaborar curvas de distribuição de efluentes presentes na vinhaça. A pesquisa foi conduzida em área experimental do Departamento de Ciências Exatas da ESALQ/USP, em casa de vegetação, onde foram distribuídas 50 bombonas, em blocos casualizados. A vinhaça foi coletada na Usina Costa Pinto do grupo COSAN no município de Piracicaba/SP e as dosagens de aplicação foram: 100 m³ ha-1; 150 m³ ha-1; 200 m³ ha-1; 250 m³ ha-1 e 300 m³ ha-1. As espécies analisadas foram: nitrato e potássio, assim como, o pH, condutividade elétrica e cálcio. As curvas de distribuição de efluentes foram confeccionadas para obtenção dos parâmetros de transporte do nitrato (utilizando-se o FIA Flow Injection Analysis, para as análises químicas) e potássio (Fotômetro de chama, para as análises químicas). Diante dos resultados obtidos, observou-se que as concentrações do íon nitrato apresentaram variação no solo, encontrando-se valores entre 3,6 a 119 mg L-1, no solo arenoso, e entre 1 e 70 mg L-1, no solo argiloso. Em relação ao potássio foram encontrados valores pontuais de 4,4 a 171,2 mg L-1, no solo arenoso (principalmente na profundidade de 60 cm), e entre 0 e 30 mg L-1, no solo argiloso. As concentrações de cálcio apresentaram variação no solo, sendo encontrados valores pontuais de 1,98 a 64,45 mg L-1, no solo arenoso, e entre 2,6 e 86,5 mg L-1, no solo argiloso. Os valores tanto do pH quando da C.E apresentaram variações no solo, tendo um intervalo para o pH de 6,4 a 7,75 para o solo arenoso e de 4,8 a 7,32 para o solo argiloso e a condutividade elétrica ficou em torno de 0,3 a 2,3 dS m-1 para o solo arenoso e de 0,23 a 0,75 dS m-1 para o solo argiloso. Em relação à curva de distribuição de efluentes da vinhaça, no solo argiloso, observou-se que tanto o potássio quanto o nitrato houve um maior deslocamento das curvas de eluição para a direita quando comparados com o solo arenoso indicando que os íons potássio e nitrato foram retidos com maior intensidade no argiloso em relação ao arenoso. Portanto, concluiu-se que: a percolação dos íons está diretamente relacionada com o tipo de solo e com a concentração de vinhaça e que a movimentação dos íons deve ser estudada em longos períodos para mostrar melhor a sua movimentação no perfil do solo. / While sugarcane has been one of the main crops in Brazilian agriculture since the time of colonization, it is now also a major source of biomass energy, serving sugarcane agribusiness and being responsible for many direct and indirect jobs in Brazil. Industrial processing of sugarcane leads to such products as sugar, alcohol (both hydrated and anhydrated), pulp and vinasse. One concern about the application of vinasse to agricultural operations relates to possible environmental impacts of vinasse. Hence, the present research had as objective to monitor of the dynamics, in different soil types, of chemical components present in vinasse, and to measure breakthrough curves (BTC´s) of vinasse from repacked columns. The research was carried out at the experimental facility of the Department of Exact Sciences, ESALQ, USP, a protected environment containing 50 boxes arranged in a random manner. The vinasse was collected at the Usina Costa Pinto COSAN site in the municipal district of Piracicaba, SP, and applied at rates of 100, 150, 200, 250 and 300 m³ ha-1. The analyzed elements were nitrate and potassium, but measurements were also made of pH, electric conductivity and calcium. The BTC´s were used to provide estimates of the transport parameters of nitrate (using flow-injection analysis for the chemical analyses) and potassium (using a photometer for the chemical analyses). The measurements showed that soil nitrate concentrations varied between 3,6 to 119 mg L-1 in the sandy soil, and between 1 and 70 mg L-1 in the clay soil. Observed potassium concentrations were between 4,4 to 171,2 mg L-1 in the sandy soil (mainly at a depth of 60 cm), and between 0 and 30 mg L-1 in the clay soil. Calcium concentrations were found to similarly vary from 1,98 to 64,45 mg L-1 in the sandy soil, and between 2,6 and 86,5 mg L-1 in the clay soil. The values of pH furthermore varied between 6,4 to 7,75 for the sandy soil and between 4,8 to 7,32 for the clay soil, while the electric conductivity was between 0,3 to 2,3 dS m-1 for the sandy soil and between 0,23 to 0,75 dS m-1 for the clay soil. The vinasse BTC´s of the clay soil showed that both potassium and nitrate were displaced considerably to the right (to higher pore volumes) as compared with the sandy soil. This indicates that the potassium and nitrate ions were kept (adsorbed) much stronger by the clay relative to the sandy soil. Ion transport rates hence were found to be a function of soil type. Results suggest that the transport of ions from the vinasse is best studied over relatively long periods of time, also in field soil profiles, to better show the long-term dynamics in the subsurface

A amônia presente em galpões fechados de criação de frangos afeta a saúde tanto dos animais como dos tratadores, além de ser um grave problema ambiental. O processo aqui recomendado faz uso de um material com grande capacidade de retenção tanto da amônia gasosa como na forma de seu hidróxido, NH4OH. Este absorvedor, um trocador catiônico sólido, preparado para a retenção seletiva da amônia, é inodoro, insípido e atóxico. Uma vez saturado com amônia, passa por um tratamento químico para a remoção deste composto, podendo ser reutilizado muitas vezes sem perda de sua capacidade retentora, tornando o processo mais econômico. A remoção deste material pode-se dar na forma de um sal de amônio que poderá ser utilizado como fertilizante. Ressalta-se ainda que a amônia recuperada nestes galpões avícolas, quando submetida a uma decomposição térmica catalítica, gera hidrogênio para uso em células a combustível, podendo fornecer energia elétrica no próprio local do trabalho. / The process here stressed uses a cátion exchange material. The aim of the present work has been to prepare a suitable cation exchanger material with excepecinally high selectivity for ammonia, as the cation NH4+ or as aqueous ammonia solution containing NH4OH hyroxide as well. Aliquots of the abovementioned exchangers were set up inside an chiken farm production near São Paulo city. Periodically the exchanger was removed to the laboratory and eluted with a convenient acid to regenerate the exchanger for the new cicle. The ammonia retention was quite high and presents no dificulty for its elution. The selected exchanger is a solid material, non toxic, without smell and have good physical properties. The first results encouraged us and our plants to do large experiments that in progress. This process is a contribution to remediation of the avicola local, removing the ammonia gas and suppressing grettly its smell and bad effect to the animals and even to workers

Introdução: O tratamento com nitrato fixo em pacientes com angina estável é comum na prática clínica. Contudo, os eventos adversos podem interferir na qualidade de vida relacionada à saúde (QVRS) e adesão ao tratamento medicamentoso. O objetivo do estudo foi comparar a QVRS e adesão ao tratamento em grupos de pacientes com angina estável em retirada e manutenção de nitrato. Métodos: Ensaio clínico randomizado conduzido com pacientes com angina estável em dois grupos: intervenção com retirada de nitrato e introdução de placebo e controle com manutenção de nitrato. Ambos os grupos receberam três avaliações: basal, 30 dias e 120 dias no período de quatro meses. A QVRS foi mensurada pelo Short Form Health Survey (SF-36) e Seattle Angina Questionnaire (SAQ), e a adesão foi aferida pela escala de Morisky e contagem de comprimidos. Resultados: 105 pacientes foram randomizados (51: placebo e 54: nitrato). Após quatro meses, observou-se maiores escores nos domínios de dor (63+19; 67+23; 72+24; P=0,004) e aspecto social (87+19; 91+21; 91+19; P=0,002) do SF-36 e no escore de limitação física (74+11; 78+10; 78+8; P=0,006) do SAQ no grupo nitrato, e redução do escore de estabilidade da angina (81+19; 72+20; 72+24; P=0,031) no grupo placebo. Contudo, o tamanho de efeito foi igual ou inferior a 0,42 nesses domínios. A adesão aferida no final entre os grupos foi significativamente maior no grupo intervenção (94% vs 80%; P=0,041) com a escala de Morisky, mas não houve diferença entre os grupos na contagem da medicação. Conclusão: Pacientes com angina estável em uso de nitrato em comparação aos pacientes com uso de placebo não tiveram comprometimento clinicamente relevante da QVRS, porém demonstraram pior adesão ao tratamento na escala de Morisky. / Background: Long-term nitrate treatment of stable angina is associated with adverse events and can interfere with health-related quality of life (HRQoL) and medication adherence. The aim of the present study was to compare HRQoL and adherence to treatment in patients with stable angina undergoing nitrate withdrawal and maintenance. Methods: Randomized clinical trial. Patients were allocated into an intervention group (nitrate withdrawal followed by introduction of placebo) or a control group (nitrate maintenance). The assessments were performed at baseline, 30 days, and 120 days with the Short Form Health Survey (SF-36) and the Seattle Angina Questionnaire (SAQ). Treatment adherence was measured by the Morisky scale and pill count. Results: 51 participants were randomized for replacement of nitrate with placebo and 54 for maintenance of treatment with nitrate. After four months, SF-36 scores increased for the bodily pain (P=0.004) and social functioning (P=0.002) in the nitrate maintenance group. Increased SAQ scores were also noted for physical limitations (P=0.006) in the nitrate maintenance group. SAQ score for angina stability (P=0.031) decreased in the placebo group. However, the effect size was small ! 0.42 in those domains. At the end of the study, adherence was significantly higher in the placebo group (P=0.041), but no difference was detected between the groups with the pill count method. Conclusion: HRQoL was similar in patients with stable angina using nitrate regularly as compared to patients undergoing nitrate withdrawal. However, adherence to treatment was lower in nitrate users according to the Morisky scale.

Chong Lung-wun. / Thesis (M.Sc.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 49-58). / Abstracts in English and Chinese. / Acknowledgement --- p.1 / Contents --- p.2 / Abstract --- p.4 / Chapter I. --- Introduction --- p.6 / Chapter 1. --- Nitrate therapy for angina patients --- p.7 / Chapter 1.1 --- The mode of action of nitrates --- p.8 / Chapter 1.2 --- Hypotheses for the nitrate tolerance --- p.9 / Chapter 1.2.1 --- The Sulfhydryl depletion hypothesis --- p.9 / Chapter 1.2.2 --- Neurohormonal hypothesis --- p.10 / Chapter 1.2.3 --- Plasma volumc expansion hypothesis --- p.10 / Chapter 1.2.4 --- Free-radical hypothesis --- p.11 / Chapter 2. --- Testosterone therapy for angina patients --- p.12 / Chapter 3. --- Nitric Oxide and Steroidogenesis --- p.13 / Chapter II. --- Materials and Methods --- p.14 / Chapter 1. --- Subjects --- p.14 / Chapter 2. --- Method for measuring nitrite and nitrate in plasma --- p.16 / Chapter 3. --- Method for the determination of total and free testosterone in blood --- p.24 / Chapter 3.1 --- Reagent preparation --- p.24 / Chapter 3.2 --- Assay procedure for total testosterone --- p.28 / Chapter 3.3 --- Assay procedure for free testosterone --- p.29 / Chapter 3.4 --- Determination of working antiserum for free testosterone assay --- p.30 / Chapter 4. --- Method for the determination of serum Cortisol --- p.31 / Chapter III. --- Result --- p.33 / Chapter 1. --- Summary of nitric oxide assay performance --- p.33 / Chapter 2. --- Summary of total testosterone assay performance --- p.34 / Chapter 3. --- Summary of free testosterone assay performance --- p.34 / Chapter 4. --- Data analysis --- p.35 / Chapter IV. --- Discussion --- p.43 / Chapter V. --- Conclusion --- p.47 / Chapter VI. --- References --- p.49

Vita. / Digitized by Kansas Correctional Industries

La composition des eaux pour les éléments biologiquement actifs comme les nitrates est contrôlée par les processus microbiens, qui dépendent eux-mêmes des conditions physico-chimiques du milieu. Les conditions chimiques et la structure des communautés bactériennes sont étroitement liées et l'influence des circulations hydrologiques sur la diversité microbienne est relativement mal contrainte. Or ces circulations hydrologiques issues de la structure physique du paysage sont déterminantes dans les processus biogéochimiques. Les relations entre les flux hydrologiques et le fonctionnement de l'écosystème sont abordées par 3 axes: (i) l'influence des flux verticaux sur l'activité et la structure des communautés bactériennes réduisant les nitrates (gène narG) ; (ii) l'influence des flux verticaux sur la structure des communautés bactériennes intégratives (gène de l'ARNr 16S) et fonctionnelles (gène narG); et (iii) l'influence des modifications des paramètres de forçage sur l'expression protéique par une approche Métaprotéomique. <br />Le premier axe a été analysé en utilisant des bio-réacteurs stimulants différents états redox et disponibilité en nutriment. Le second a consisté à suivre les changements de structure de communautés dans le temps (suivant les périodes de hautes et de basses eaux) et suivant la profondeur. Le troisième axe est abordé sous des conditions expérimentales à partir d'eau échantillonnée en profondeur, en contrôlant les paramètres de forçages (quantité et nature du carbone, quantité d'azote). Pour chaque bio-réacteur, une analyse du Métaprotéome par des empreintes peptidiques a été réalisée pour modéliser le fonctionnement de l'écosystème. <br />L'importance des circulations hydrologiques sur les communautés bactériennes a été confirmée en agissant directement sur la structure des communautés ou indirectement sur la disponibilité de ressources. Le manque de connaissance actuel dans les bases de données ne nous a pas permis d'aller aussi loin que nous l'aurions souhaité dans les expériences de protéomique. Il nous est impossible à l'heure actuelle de proposer un modèle de fonctionnement de niche écologique. Cependant, le protéome des cellules exposées aux deux sources de carbones a été montré comme significativement différent, laissant suggérer une réponse différentielle du système suivant la nature de la pollution induite.

L'approche pluri-scalaire des aquifères karstiques développée au cours de cette étude est basée sur des mesures hydrauliques, hydrochimiques et de déformation réalisées in situ sur deux sites expérimentaux.<br />Dans un premier temps, des investigations ont été menées à l'échelle de la fracture ou du groupe de fractures, sur le site de Coaraze (Alpes Méridionales, France). Durant une seconde phase, l'aquifère karstique a été abordé dans son ensemble. Le site choisi est l'aquifère de la source de Fourbanne (avant-pays jurassien). Ce site a été instrumenté de manière à étudier le comportement des volumes d'eau infiltrés en surface, lors de leur traversée de la zone non-saturée puis de la zone saturée.<br />Un contraste entre la signature hydrogéochimique des discontinuités perméables et celle des discontinuités peu perméables a été mis en évidence à l'échelle d'un groupe de discontinuités rocheuses, ainsi qu'une sensibilité hydraulique accrue des discontinuités peu perméables vis-à-vis de la déformation. La prise en compte du travail réalisé à l'échelle de la fracture ou du groupe de fractures dans l'étude de l'aquifère karstique dans sa globalité a permis d'établir un modèle conceptuel du transfert des éléments anthropiques à travers l'aquifère. De plus, il apparaît qu'une analyse fine du signal chimique drainé par la source permet de reconstituer les relations hydrauliques existant entre les volumes peu perméables et le conduit au sein de la zone noyée. Enfin, les mécanismes mis précédemment en évidence à plusieurs échelles permettent d'interpréter une réponse hydrochimique post-sismique enregistrée à la suite d'un séisme.