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bytes, checksum: f237dda690f871fec7cdaa9ad3751c02 (MD5) / Made available in DSpace on 2017-12-13T13:04:48Z (GMT). No. of bitstreams: 1 lopezaguilar_ma_me_jabo.pdf: 544471 bytes, checksum: f237dda690f871fec7cdaa9ad3751c02 (MD5) Previous issue date: 2017-11-07 / Consejo Nacional de Ciencia y Tecnología (CONACYT) / Considerando que a aplicação de molibdênio, via foliar, pode proporcionar aumentos na produção do milho-doce e que a época de aplicação pode afetar a efetividade de sua ação, realizou-se um experimento, no período de agosto a novembro de 2015, em Jaboticabal, SP, Brasil, com o objetivo de avaliar o desempenho agronômico do milho-doce em resposta à adubação molíbdica foliar e épocas de aplicação. O teor foliar de molibdênio (Mo) foi influenciado pela interação dos fatores. O maior teor foi observado quando se aplicou a maior dose de Mo (450 mg ha-1) na terceira época (45 dias após a emergência - DAE), o qual foi equivalente ao incremento de 1.2% no teor do micronutriente nas folhas em relação ao observado em plantas não tratadas com Mo. O teor de nitrogênio foliar também foi maior com a aplicação da dose mais alta de Mo. Máximo número (49.477) e produtividade (13.211 kg ha-1) de espigas comerciais foram obtidos com 315 e 311 g ha-1 de Mo, respectivamente. Máxima produtividade de grãos (5.055 kg ha-1) foi atingida com a dose de 334 g ha-1 do micronutriente. / Considering that the foliar application of molybdenum promotes an increased yield in sweet corn crop and that the application timing might affect its efficacy, this experiment was carried out from August to November of 2015, in Jaboticabal, Sao Paulo State, Brazil, aiming to evaluate the agronomic performance of sweet corn in response to rates and times foliar application of molybdenum. Molybdenum (Mo) foliar content influenced by the interaction between the assessed factors, with the highest value corresponding to the highest Mo dose (450 mg ha-1 ) at the third application moment (45 days after emergence – DAE), representing a 1,2% increase when compared to plants that did not receive this micronutrient. Foliar content of N also was enhanced with the application of the highest dose of Mo. The highest number (49,477) and yield (13,211 kg ha-1 ) of commercial ears were reached with 315 and 311 g ha-1 of Mo, respectively. The highest grain yield (5,055 kg ha-1 ) was obtained with 334 g ha-1 of the micronutrient. / 579743/410472

abstract: Molybdenum and uranium isotope variations are potentially powerful tools for reconstructing the paleoredox history of seawater. Reliable application and interpretation of these proxies requires not only detailed knowledge about the fractionation factors that control the distribution of molybdenum and uranium isotopes in the marine system, but also a thorough understanding of the diagenetic processes that may affect molybdenum and uranium isotopes entering the rock record. Using samples from the Black Sea water column, the first water column profile of 238U/235U variations from a modern euxinic basin has been measured. This profile allows the direct determination of the 238U/235U fractionation factor in a euxinic marine setting. More importantly however, these data demonstrate the extent of Rayleigh fractionation of U isotopes that can occur in euxinic restricted basins. Because of this effect, the offset of 238U/235U between global average seawater and coeval black shales deposited in restricted basins is expected to depend on the degree of local uranium drawdown from the water column, potentially complicating the interpretation 238U/235U paleorecords. As an alternative to the black shales typically used for paleoredox reconstructions, molybdenum and uranium isotope variations in bulk carbonate sediments from the Bahamas are examined. The focus of this work was to determine what processes, if any, fractionate molybdenum and uranium isotopes during incorporation into bulk carbonate sediments and their subsequent diagenesis. The results demonstrate that authigenic accumulation of molybdenum and uranium from anoxic and sulfidic pore waters is a dominant process controlling the concentration and isotopic composition of these sediments during early diagenesis. Examination of ODP drill core samples from the Bahamas reveals similar behavior for sediments during the first ~780ka of burial, but provides important examples where isolated cores and samples occasionally demonstrate additional fractionation, the cause of which remains poorly understood. / Dissertation/Thesis / Ph.D. Geological Sciences 2012

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O presente trabalho objetivou avaliar a capacidade de um sal mineral rico em molibdênio (Mo) em prevenir a intoxicação cúprica acumulativa (ICA), analisando variáveis clínicas, sangüíneas e os teores de cobre (Cu) e Mo hepático. Foram utilizados 25 ovinos da raça Ilede-France, aleatoriamente distribuídos em cinco grupos de cinco animais de cada, sendo que o grupo 1 recebia dieta contendo 80% volumoso e 20% concentrado, os grupos 2 e 3 recebiam 50% volumoso e 50% concentrado, e os grupos 4 e 5 recebiam a mesma dieta dos grupos 2 e 3 com a adição diária de 150 mg de sulfato de Cu até o término do experimento (150 d). Os grupos 1, 3 e 5 recebiam sal mineral contendo 300 ppm de Mo. Foram realizadas três biópsias hepáticas para determinação da concentração de Cu, Mo e Zn neste órgão e três ensaios de retenção aparente de Cu e Mo (0 d, 75 d, 150 d). Quinzenalmente, foi realizado exame clínico e coleta de amostras de sangue e urina. Três ovinos do grupo 4 e um do grupo 5 manifestaram ICA. Não existiu diferença entre a freqüência de mortalidade entre os grupos (P = 0,56). Os teores de Cu hepático nos ovinos com ICA (2450 ppm) foram superiores aos que não intoxicaram (1518 ppm). Quanto maior a ingestão de Mo na dieta menor foi o acúmulo de Cu hepático ao término do experimento (r = -0,72). Ovinos com ICA aumentaram a concentração de Zn hepático nas fases finais da intoxicação. A presença de altas atividades de GGT (>56,5 U/L) e de AST (>120 U/L) indicaram de maneira efetiva a presença de destacado acúmulo de Cu nos tecidos hepáticos (1000 ppm). / The aim of this project is to evaluate the capacity of a molybdenum-rich mineral salt in the prevention of cumulative cooper poisoning (CCP) in sheep, through clinical and blood exams and hepatic copper and molybdenum concentrations. Twenty five Ile-de-France sheep were randomly distributed into five groups of five animals each, where group 1 received a 80% forrage and 20% concentrate diet, groups 2 and 3 received a 50% forrage and 50% concentrate diet, and groups 4 and 5 received the same diet as groups 2 and 3 with a daily supplementation of 150mg of copper sulphate until the end of the experiment (150 d). Groups 1, 3 and 5 received a mineral salt with 300 ppm of molybdenum. For three times during the experiment (day zero, 45th and 105th day) a liver biopsy was carried out to evaluate the degree of copper accumulation in this organ. Clinical examination was followed every two weeks, as far as blood and urine samples were withdrawn. Three sheep from group 4 and one sheep from group 5 presented clinical picture of CCP. There was no difference in the frequency of mortality between groups 4 and 5 (P = 0.56). The liver copper concentration was higher in sheep with CCP (2450 ppm) compared to sheep that not presented CCP (1518 ppm). The higher the ingestion of molybdenum in the diet the lower the liver copper concentration at the end of the experiment (r = -0.72). Sheep with CCP had higher liver zinc concentration. The presence of high activity of GGT (> 56.5 U/L) and AST (>120 U/L) indicated effectively the high accumulation of copper in liver (> 1000 ppm).

nÃo hà / Nesse trabalho foram realizados estudos sobre a reaÃÃo de desprendimento de hidrogÃnio (RDH) em meio alcalino sob ligas de Ni-Mo obtidas por eletrodeposiÃÃo em diferentes condiÃÃes operacionais. Para efeito de comparaÃÃo tambÃm foram feitos testes em superfÃcies de Ni eletrodepositadas dentro das mesmas condiÃÃes utilizadas para as ligas de Ni-Mo. Para a eletrodeposiÃÃo das ligas foram preparados dois banhos eletrolÃticos, com Ni e Mo, de diferentes composiÃÃes e um outro banho apenas com Ni . O pH dos banhos foi ajustado com NH4OH. As ligas foram eletrodepositadas sob controle galvanostÃtico em densidade de corrente de 50 mA cm-2. O substrato utilizado foi o cobre. Utilizou-se trÃs valores de carga elÃtrica: 50, 100 e 150C. Outro parÃmetro de estudo foi o emprego da radiaÃÃo ultra-sÃnica a fim de comparar as ligas eletrodepositadas sob o efeito dessa radiaÃÃo com as obtidas na sua ausÃncia. Duas condiÃÃes de temperatura foram empregadas: ambiente (29ÂC) e 40ÂC. Os teores de Ni e de Mo nas superfÃcies eletrodepositadas foram obtidas por microanÃlise de energia dispersiva de raios-X (EDX). A anÃlise da morfologia superficial das camadas foi feita usando o microscÃpio eletrÃnico de varredura (MEV). Foram feitas anÃlises por voltametria cÃclica a fim de estimar a Ãrea eletroquimicamente ativa das superfÃcies de Ni e de Ni-Mo. As amostras com melhores Ãreas ativas foram selecionadas para os demais ensaios. Foram construÃdos diagramas de Tafel, (mantendo estado estacionÃrio, com o mÃtodo potenciostÃtico, aplicando 20 potenciais diferentes dentro da faixa de -1,6 V atà - 0,95 V), a fim de estudar a relaÃÃo corrente-potencial, o mecanismo e a energia de ativaÃÃo da RDH, em meio alcalino. O mecanismo da RDH nas amostras foi do tipo Tafel/Volmer com a etapa de Volmer determinante. Observou-se uma eletrodeposiÃÃo preferencial do nÃquel, e, que a utilizaÃÃo da radiaÃÃo de ultra-som elevou o teor de Mo e alterou a morfologia das camadas, produzindo trincas em algumas amostras. As amostras de Ni-Mo apresentaram boa estabilidade no ensaio de OperaÃÃo ContÃnua e valores de energia de ativaÃÃo inferiores aos obtidos para o Ni eletrodepositado / In this work it was accomplished studies about the hydrogen evolution reaction (HER) in alkaline middle under alloys of Ni-Mo obtained by electrodepositing in different operational conditions. By comparison, it was also made tests on the surfaces of Ni electrodeposited in the same conditions used for Ni-Mo alloy. For the alloy electrodepositing two electrolytic baths were prepared with Ni and Mo from different compositions and another bath just with Ni. The bath pHs were adjusted to the 9,5 value. The electrodeposits were obtained under galvanostatic control using plating solution with different molybdate ion concentration and current density of 50 mA cm-2. The substratum used was copper with 2 cm2 of geometric area. It was used three electric charge values: 50, 100 and 150C. Another study parameter was the employment of the ultra-sonic radiation in order to compare the electrodeposited alloys under the radiation effect with those obtained in absence. Two temperature conditions were used: room temperature (29ÂC) and 40ÂC. The amount of Ni and Mo on the electrodeposited surfaces was obtained by microanalysis of Energy Dispersive X-ray (EDX). The analysis of the superficial morphology of the layers was made using the Scanning Electron Microscopy (SEM). Electrochemical analyses were carried out by cyclic voltammetry in order to determinate the electrochemical active area on Ni and Ni-Mo surfaces. The better active areas samples were selected to others rehearsals. Tafel Diagrams were made, (maintaining stationary state, with the potenciostatic method, applying 20 different potentials inside of the strip of -1,6 V to - 0,95 V), in order to study the relation current-potential, the mechanism and the activation energy of RDH, in alkaline middle. The RDH mechanism used in the samples was the Tafel/Volmer type with the Volmer determining stage. A preferential nickel electrodepositing was observed, and by using ultrasound radiation waves it increased the amount of Mo and altered the morphology of the layers, producing, in some samples, cracks. The samples of Ni-Mo presented good stability in the long term test and minor activation energy values to the obtained for the Ni electrodepositing

O tratamento de rejeitos de determinados processos industriais vem ganhando importância, seja pelo impacto negativo do simples descarte no meio ambiente, seja pelo valor econômico de materiais e substâncias que podem ser eventualmente recuperados e reciclados. O rápido empobrecimento de reservas minerais primárias e o aumento de demanda de energia são problemas que merecem atenção especial. Neste contexto, a recuperação de metais existentes nos rejeitos de alguns processos de fabricação assume papel de maior importância. A recuperação do molibdênio presente em soluções nitro-sulfúricas, na forma de rejeitos líquidos do processo de fabricação de lâmpadas incandescentes e fluorescentes, não constitui exceção no que diz respeito à importância da reciclagem. Este rejeito, proveniente da dissolução dos mandris de conformação dos filamentos de tungstênio das lâmpadas, apresenta valores que podem ser recuperados e até reciclados no próprio processo. É o caso dos ácidos nítrico e sulfúrico. Já o molibdênio, presente em concentrações em torno de 40 a 90 g.L-1, pode ser recuperado e utilizado na fabricação de aços especiais, pigmentos, lubrificantes, adubo, etc. Neste trabalho foram desenvolvidos dois processos de recuperação deste rejeito. No primeiro, o rejeito é diluído e por cromatografia de troca iônica o molibdênio é recuperado. Os ácidos efluentes são destilados para a retirada da água. No segundo processo, o rejeito passa por uma destilação e ao mesmo tempo o molibdênio é precipitado. Em ambos os processos, os ácidos recuperados podem voltar à fábrica de lâmpadas para a dissolução dos mandris do filamento de tungstênio e o molibdênio encontra outras diferentes aplicações, além de possuir um valor significativo no mercado. / The waste treatment of certain industrial processes is becoming more important, either by the economic impact of simple disposal in the environment, or by the economic value of materials and substances that can eventually be recovered and recycled. The rapid depletion of mineral reserves and increasing primary energy demand are problems that deserve special attention. In this context, the recovery of metals present in waste of some manufacturing processes assumes a great importance. The recovery of molybdenum present in nitro-sulfur solutions in the form of liquid waste in the manufacturing process of incandescent and fluorescent lamps, is no exception with regard to the importance of recycling. The tailing from the dissolution of the molybdenum mandrel wires used in the conformation of the tungsten filament of electric lamps, has values that can be recovered and recycled to the process itself. Is the case of sulfuric and nitric acids. Molybdenum, present in concentrations around 40 to 90 g.L-1, can be recovered and used in the manufacture of special stainless steel, pigments, lubricants, fertilizer, etc.. In this work two processes for the recovery of this waste were proposed. At the first one, the waste is diluted and molybdenum is recovered by ion-exchange chromatography. The effluent acid from this process was distilled to extract water used in the dilution step. In the second case, the waste goes through a distillation while the molybdenum is precipitated. In both cases, the acids are recovered back to the lamp factory for the dissolution of the molybdenum mandrel wires and molybdenum finds other different applications, as well as having significant value in the market.