Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-22T17:15:11Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-22T17:15:11Z (GMT). No. of bitstreams: 0 / O excessivo processo de urbanização da Região Metropolitana de São Paulo resultou na perda das características naturais dos seus cursos d\'água ocasionando profundas alterações nos regimes de vazão e de qualidade. O objetivo desse estudo foi avaliar a concentração de metais tóxicos, os semi-metais As, Sb e Se e os elementos terras raras, presentes em amostras de sedimento superficiais coletadas nos Reservatórios Billings, Guarapiranga e Rio Grande. Os elementos Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Se e Zn foram determinados pela técnica de Espectrometria de Emissão Ótica com Plasma Indutivamente Acoplado (ICP OES). Alguns elementos maiores, traço e elementos terras raras (Ce, Eu, La, Lu, Nd, Sm, Tb e Yb) foram determinados pela técnica de Análise por Ativação Neutrônica Instrumental (INAA). A concentração de Hg total foi determinada pela técnica Espectrometria de Absorção Atômica com Geração de Vapor Frio (CVAAS). A validação das metodologias foi realizada por meio da análise de materiais de referência certificados. Para avaliar as possíveis fontes de contaminação antrópicas foram utilizadas as ferramentas de fator de enriquecimento (FE) e o índice de geoacumulação (IGeo). Os resultados obtidos pelas técnicas foram comparados com os valores orientadores TEL e PEL estabelecidos pelo CCME (Canadian Council of Ministers of the Environment) e adotados pela CETESB. Todos os pontos analisados apresentaram valores > TEL para todos os metais e dois pontos da represa Billings (BILL02100 e 02030), valores > PEL para As, Cr, Cu, Hg, Ni, Pb e Zn, provavelmente em decorrência do recebimento das águas do Rio Pinheiros e das bacias de drenagem do ribeirão Cocaia e Bororé. Os valores de FE e IGeo calculados apontaram possíveis contaminações antrópicas para Sb e Se para os elementos determinados por ICP OES e de As, Cr, Sb e Zn, por INAA. O reservatório Billings apresentou, em geral, as maiores concentrações para os elementos analisados, indicando uma má qualidade de seus sedimentos. Este estudo confirma a necessidade de um monitoramento frequente da qualidade do sedimento nos reservatórios estudados como procedimento indispensável para avaliação periódica da qualidade das bacias, considerando sua importância no fornecimento de água para a Região Metropolitana de São Paulo. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Foi desenvolvido um programa computacional escrito na linguagem de programação C++ denominado CALFRAC para quantificar o processo de cristalização fracionada em sistemas ígneos, utilizando para isso as concentrações dos elementos maiores, menores e traços. O algoritmo moderniza, torna mais eficiente e aprimora os programas publicados na literatura e possui a grande vantagem de poder calcular, automaticamente, todas as possíveis combinações de evolução das amostras envolvidas na diferenciação, além de associar aos cálculos os elementos-traço, os quais servem para confirmar os resultados sugeridos pelos ajustes dos elementos maiores e menores. O CALFRAC calcula a fração total subtraída do magma inicial e as frações referentes a cada mineral fracionado através do cálculo do balanço de massa, utilizando as concentrações de elementos maiores e menores, empregando os métodos de estimativa de máxima verossimilhança e dos multiplicadores de Lagrange para a resolução por mínimos quadrados, enquanto para os elementos-traço o programa utiliza a Equação de Rayleigh. Em ambos os casos a média dos erros percentuais relativos é usada como indicação das melhores evoluções. O programa CALFRAC foi aplicado na investigação da possibilidade de diferenciação por cristalização fracionada em amostras de soleiras de diabásio da Bacia do Paraná, que ocorrem nos municípios de Salto do Itararé, Ponta Grossa, Prudentópolis, Rebouças, Irati, Reserva e Jaguariaíva (PR), as quais foram coletadas para essa finalidade. Nas 33 amostras coletadas foram realizadas determinações de elementos maiores, menores e traços, incluindo terras raras, empregando-se os métodos de Fluorescência de Raios X e Ativação Neutrônica. Os resultados fornecidos pelo programa foram insatisfatórios, não sendo possível estabelecer um percurso de diferenciação das rochas mais primitivas para as mais diferenciadas das intrusões, devido ao fato de que provavelmente muitas das amostras analisadas representam a mistura de magmas com porções contendo acumulação de fases minerais causada pelo próprio processo de cristalização fracionada in situ. / CALFRAC is a computer program written in C++ programming language developed to quantify fractional crystallization processes in igneous systems. Major, minor and trace element concentrations are used as input for calculations. The new algorithm enhances and makes the program more efficient than those published in the literature. Besides it is capable to automatically calculating all possible rock sample combinations involving differentiation by fractional crystallization process, using in addition trace element concentrations to corroborate the results obtained by the fitting of major and minor element abundances. CALFRAC calculates the total fraction subtracted from the original magma and the percentage of each fractionated mineral by solving least-squares mass balance equations based on major and minor element concentrations. The methods of maximum likelihood estimate and Lagrange multipliers are used to solve the equations, whereas for the quantification of trace elements the program uses the Rayleigh Equation. In both cases the mean relative percentage errors is used as an indication of the best results. The program CALFRAC was applied to investigate the possibility of differentiation by fractional crystallization of diabase samples from Paraná Basin sills, which outcrop nearby Salto do Itararé, Ponta Grossa, Prudentópolis, Rebouças, Irati, Reserva and Jaguariaíva towns (PR). The 33 collected samples were analyzed for major, minor and trace elements, including rare earths, employing X-Ray Fluorescence and Neutron Activation methods. The program output was not satisfactory, since it was not possible to establish a differentiation sequence from the more primitive to the more differentiated rocks of the intrusions. This is probably due to the fact that many rock samples are the result of mixing of magmatic melts with mineral accumulation zones, which were formed by the in situ fractional crystallization process.

Foram determinadas as concentrações de terras raras (La, Ce, Nd, Sm, Eu, Tb, Yb e Lu) e outros elementos-traço (Cs, Rb, Ba, U, Th, Ta, Hf, Co e Sc) em 51 amostras representativas de derrames e soleiras das regiões norte e nordeste da Província Magmática do Paraná, que ocorrem no norte do estado de São Paulo e no sul de Minas Gerais. O método utilizado para estas determinações foi a técnica de ativação com nêutrons térmicos e epitérmicos, seguida de espectrometria gama de alta resolução, que forneceu resultados com elevados níveis de precisão e de exatidão (geralmente com valores inferiores a 10%), conforme atestado pelas concentrações determinadas no material geológico de referência JB-1. Os dados obtidos foram analisados conjuntamente com determinações de elementos maiores, menores e dos traços Sr, Y, Zr, Nb, Cr e Ni, realizadas por fluorescência de raios ? X. As rochas investigadas são quimicamente representadas por basaltos toleíticos, andesi-basaltos toleíticos e lati-basaltos, enquanto as mais evoluídas (MgO < 3%), que ocorrem de modo muito subordinado, são representadas por latitos e lati-andesitos, além de um riodacito. As rochas básicas (SiO2 < 55% e/ou MgO > 3%) são caracterizadas por apresentarem conteúdos de TiO2 maiores que 3%, sendo que grande maioria possui fortes semelhanças com os magmas-tipo Pitanga, embora tenham sido encontrados alguns derrames, localizados no norte do estado de São Paulo, geoquimicamente semelhantes aos magmas-tipo Urubici (típicos do sul da província). Rochas básicas com concentrações de TiO2 entre 2% e 3% foram também raramente encontradas, as quais representam equivalentes intrusivos de derrames Paranapanema. As rochas mais evoluídas só foram encontradas em soleiras e possuem características geoquímicas que indicam diferenciação a partir de magmas do tipo Pitanga. O comportamento de elementos maiores, menores e traços nas rochas intrusivas e extrusivas do tipo Pitanga, incluindo as mais diferenciadas, é compatível com um processo de evolução por cristalização fracionada envolvendo plagioclásios, clinopiroxênios e titano-magnetitas. A comparação entre derrames e soleiras do tipo Pitanga indica a atuação significativa de processos de diferenciação in situ nas rochas intrusivas, que causaram uma maior variabilidade composicional (soleiras: MgO entre 2,3% e 6,4%; derrames: MgO entre 3,2% e 5,5%). As rochas mais diferenciadas são também caracterizadas por anomalias positivas de európio, que sugerem o acúmulo de plagioclásio devido a esse processo de fracionamento. Os dados obtidos também reforçam que não houve participação significativa de componentes astenosféricos do tipo N-MORB, E-MORB e OIB na gênese das rochas básicas investigadas, as quais possuem grande similaridade geoquímica com os basaltos da Cadeia Rio Grande (sítio 516F) e Cadeia Walvis (sítio 525A), especialmente com os desta última, indicando o envolvimento do componente mantélico EMI. / It is presented the determination of rare earth (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) and other trace (Cs, Rb, Ba, U, Th, Ta, Hf, Co and Sc) element concentrations in 51 representative samples of flows and sills from northern and northeastern Paraná Magmatic Province, particularly those located at north of São Paulo State and south of Minas Gerais. The employed analytical method to those determinations was thermal and epithermal neutron activation analysis, followed by high resolution gamma ray spectrometry, which provided high precision and accuracy results (in general better than 10%), as verified by determinations in the international geological reference material JB-1. The obtained results were integrated with major, minor and trace (Sr, Y, Zr, Nb, Cr and Ni) elements determined by X-ray fluorescence. The investigated rocks are mainly represented by tholeiitic basalts, tholeiitic andesi-basalts and lati-basalts, with subordinate relatively evolved (MgO < 3wt%) lithotypes, which are represented by latites and lati-andesites, besides one rhyodacite. The basic rocks (SiO2 < 55% and/or MgO > 3%) are characterized by presenting TiO2 contents higher than 3wt%, very similar to Pitanga magma-type, although some flows, located at northern São Paulo State, geochemically similar to Urubici magma-type (typical of southern Paraná) were also found. Basic rocks having TiO2 contents between 2 and 3 wt% were rarely encountered and represent intrusive equivalents of Paranapanema flows. The more evolved rocks were just found in sills and have geochemical characteristics that indicate differentiation from Pitanga magma-types. Major, minor and trace element behaviour of intrusive and extrusive rocks of Pitanga type, including those differentiated ones, is compatible with evolution by fractional crystallization of plagioclases, clinopyroxenes and titanium magnetites. The comparison between flows and sills of Pitanga type indicates the significant role of in situ differentiation in the genesis intrusive rocks, causing its larger compositional variability (sills: MgO between 2.3 and 6.4wt%; flows: MgO between 3.2 and 5.5wt%). The most evolved rocks are also characterized by positive europium anomalies, which suggest plagioclase accumulation caused by such fractionation process. The obtained data also corroborate the lack of significant participation of N-MORB, E-MORB and OIB asthenospheric mantle components in the genesis of basic rocks, which present very close geochemical similarity with Rio Grande Rise (site 516F) and Walvis Ridge (site 525A) basalts, particularly with the last ones, indicating the involvement of EMI mantle component.

The radioactivity induced by neutrons in the materials of future fusion devices represents a central topic of safety- and environmental-related investigations. For the design and operation of future fusion devices, like the International Experimental Thermonuclear Reactor ITER or power plants like DEMO, the activation performance of the materials during operation and after shut-down has to be simulated. The European Activation System (EASY), consisting of the inventory code FISPACT and the activation library EAF, is the world wide reference system for these calculations. The activation of the fusion reactor materials, as well as the EASY system have to be tested experimentally. In the present work several samples of materials from the European fusion technology program were irradiated in neutron fields of DT neutron generators at TU Dresden and at Sergiev Posad near Moscow. The radioactivity following irradiation was determined several times during decay by ?×-spectroscopy. The results are analysed with EASY and ratios of the calculated-to-experimental activation (C/E) are determined, to find limits for the experimental validation of EASY. For the future improvement of EASY integral cross sections are obtained from these C/E and discussed in connection with the EAF data, energy differential measurements from the EXFOR System of the International Atomic Energy Agency (IAEA), other energy integral measurements and evaluated data from libraries in the JANIS system of the Nuclear Energy Agency (NEA). The investigated materials of the present work are Tungsten, Yttrium, CuCrZr and Lead. Tungsten is the preferred material for the divertor plates of fusion devices an a constituent of reduced activation structural materials. Yttrium is used in the ODS steels, which are candidate materials for the first wall and blanket structure of. The characteristic feature of ODS steels is to introduce Y2O3 oxide particles into structural materials like EUROFER to improve the high-temperature strength and to maintain superior radiation resistance. CuCrZr alloys are used as a heat sink in the first wall of the blanket and in the divertor. The CuCrZr alloys contain impurities in consequence of the production technology, which can have an influence on the activation performance and thus have to be known accurately. In this work the neutron activation analysis has proved to be an appropriate instrument to measure the amount of some special impurities. Lead acts as a neutron multiplier and coolant in breeding blanket concepts such as the European Test Blanket Modules (TBM) with liquid Pb-17Li. Due to some large discrepancies between the measured activities and those calculated with EASY for tungsten, these cross sections are analysed with recent models of the nuclear reaction mechanisms. The sensitivity of the obtained cross sections with respect to different reaction models and parameters is investigated and limits for new evaluations are obtained with respect to the experimental results. / Die von Neutronen induzierten Aktivitäten in den Materialien zukünftiger Fusionsreaktoren stellen einen zentralen Punkt in der Forschung zur Sicherheit und Umweltverträglichkeit der gesteuerten Kernfusion dar. Für die Konstruktion und den Betrieb von Fusionsreaktoren, wie den Internationalen Thermonuklearen Experimental-Reaktor ITER oder Demonstrationskraftwerke wie DEMO, werden Simulationsrechnungen zum Aktivierungsverhalten der Materialien während des Betriebs und nach Abschalten des Reaktor durchgeführt. Das European Activation System EASY, bestehend aus dem Inventarcode FISPACT und der Datenbibliothek EAF, ist dabei weltweit das Referenzinstrument für derartige Rechnungen. Sowohl das Programmpaket als auch das Aktivierungsverhalten der im Fusionsreaktor verwendeten Materialien müssen experimentell getestet werden. Im Rahmen dieser Arbeit wurden zu diesem Zweck Proben von Materialien aus dem europäischen Fusionstechnologieprogramm in Neutronenfeldern der DT-Neutronengeneratoren der TU Dresden, bzw. an SNEG-13 im russischen Sergiev Posad bestrahlt. Die entstehende Radioaktivität wurde im Anschluss an die Bestrahlung zu verschiedenen Abklingzeiten mittels Gammaspektroskopie bestimmt. Die gemessenen Aktivitäten individueller Nuklide werden mit EASY analysiert und die Verhältnisse von gemessener Aktivität zu berechneter (C/E) werden für die einzelnen Aktivitäten bestimmt. Damit werden die Grenzen für die experimentelle Bestätigung der EASY-Berechungen ermittelt. Zur zukünftigen Verbesserung von EASY werden aus den C/E experimentelle Eingruppenwirkungsquerschnitte ermittelt, die im Kontext der EAF-Daten, energiedifferentieller Messungen aus dem EXFOR System der International Atomic Energy Agency (IAEA), vorangegangener energieintegraler Experimente und eingeschätzter Bibliotheksdaten aus dem JANIS System der Nuclear Energy Agency (NEA) diskutiert werden. Bei den untersuchten Materialien handelt es sich um Wolfram, Yttrium, CuCrZr und Blei. Wolfram ist ein bevorzugtes Material für den Divertor des Fusionsreaktors und zudem Bestandteil gering aktivierbarer Strukturmaterialien. Yttrium wird als Zusatz in den so genannten ODS Stählen verwendet, die in der ersten Wand und im Blanket eingesetzt werden. Diese entstehen aus Strukturmaterialien wie dem europäischen EUROFER, die bereits früher auf ihr Aktivierungsverhalten untersucht wurden, durch Hinzufügen von Y2O3-Partikeln, wodurch sie bei höheren Temperaturen und Neutronenflüssen einsetzbar werden. CuCrZr wird als Wärmeleiter in der ersten Wand des Blankets und im Divertor eingesetzt. Als Legierung ist CuCrZr mit technologisch bedingten Verunreinigungen versetzt, die sich auf das Aktivierungsverhalten auswirken können und deshalb genau bekannt sein müssen. Die Neutronenaktivierung hat sich dabei im Rahmen dieser Arbeit ebenfalls als geeignetes Mittel erwiesen. Blei agiert als Neutronenmultiplikator und Kühlmittel in Brutblanketkonzepten wie dem europäischen Test Blanket Module (TBM) das flüssiges Pb-17Li verwendet. Infolge der deutlichen Diskrepanzen zwischen der experimentellen und der mit EASY berechneten Aktivitäten bei Wolfram wird eine Analyse der Wirkungsquerschnitte mit Hilfe aktueller Modelle zum Mechanismus von Kernreaktionen vorgenommen. Dabei wird die Sensitivität der ermittelten Wirkungsquerschnitte auf verschiedene Reaktionsmodelle und Parameter getestet und ein Rahmen für Neueinschätzungen der Daten unter Berücksichtigung experimenteller Ergebnisse ermittelt.

For several decades, the idea of flying and landing a less-than-man-rated nuclear reactor for planetary surface applications has been considered. This approach promises significant mass savings and therefore reduction in launch cost. To compensate for the lack of shielding, it has been suggested the use of in-situ materials for providing radiation protection. This would take the form of either raw dirt walls or processed soil materials into blocks or tile elements. As a first step in determining the suitability of this approach, it is necessary to understand the neutron activation characteristics of these soils. A simple assessment of these activation characteristics was conducted for both Martian and Lunar soils using ORIGEN2.2. An average composition for these soils was assumed. As a baseline material, commonly used NBS-03 concrete was compared against the soils. Preliminary results indicate that over 2.5 times more gamma-radiation production of these soils vs. concrete took place during the irradiation phase (a baseline of 2.4 x 1011 neutrons/sec-cm2 was assumed). This was due primarily to radiative capture on Na23 and Mn55 and subsequent decay of their activation products. This is does not necessarily disqualify these materials as potential shielding material since the -radiation output was only in the order of 4.2 x 108 photons/cm3-sec. Furthermore, these soils did not show any significant activity after shutdown of the neutron source (the reactor), since all activation products had very short half lives. Their performance in this area was comparable to that of NBS-03 concrete. / text

O fertilizante é considerado um componente essencial para a agricultura, pois sua utilização aumenta e repõe os nutrientes naturais do solo, perdidos por desgaste ou erosão. No processo de obtenção dos fertilizantes fosfatados, o concentrado de rocha reage com ácido sulfúrico concentrado produzindo ácido fosfórico e sulfato de cálcio (fosfogesso), como subproduto. O ácido fosfórico é utilizado para a produção do superfosfato triplo (TSP), superfosfato simples (SSP), monoamônio fosfato (MAP) e diamônio fosfato (DAP). A rocha fosfatada usada como matéria prima apresenta em sua composição radionuclídeos das séries naturais do urânio e tório. Durante o ataque químico do concentrado de rocha, as espécies presentes na reação, estáveis e radioativas, são redistribuídas entre o ácido fosfórico (matéria prima dos fertilizantes), e o fosfogesso, de acordo com sua solubilidade e características químicas. Enquanto os fertilizantes são comercializados, o fosfogesso fica estocado em pilhas podendo impactar o meio ambiente. Com a finalidade de entender a distribuição dos elementos e dos radionuclídeos no processo industrial de produção de fertilizantes fosfatados, foram analisadas amostras de concentrado de rocha, de fertilizantes (SSP, TSP, MAP e DAP) e fosfogesso de três procedências nacionais denominadas indústrias A, B e C. A técnica utilizada para a análise elementar foi a análise por ativação com nêutrons, que permitiu analisar os elementos Ba, Co, Cr, Fe, Hf, Na, Sc, Ta, Th, U, Zn e Zr, e as terras raras, La, Ce, Nd, Sm, Eu, Tb, Yb e Lu. Os resultados obtidos permitiram concluir que em geral, as terras raras se distribuem de forma homogênea em todos os fertilizantes e no fosfogesso, exceto o Lu. Os fertilizantes SSP e TSP apresentaram concentrações de todos os elementos analisados da mesma ordem de grandeza da rocha de origem. O mesmo comportamento foi observado nos fertilizantes MAP e DAP, exceto para os elementos Co, Sc e U. Os elementos pertencentes à série radioativa natural do urânio (238U, 234U, 230Th, 226Ra e 210Pb), do tório (232Th, 228Ra e 228Th) e o K-40, foram determinados por meio da espectrometria gama e alfa. As amostras de fertilizantes MAP e DAP, que são diretamente derivadas do ácido fosfórico, apresentaram baixa concentração para o 226Ra, 228Ra e 210Pb, enquanto que para o U e Th as concentrações encontradas foram da mesma ordem de grandeza da rocha de origem. Os fertilizantes SSP e TSP, que são obtidos pela mistura de ácido fosfórico com concentrado de rocha, apresentaram concentrações mais elevadas para os radionuclídeos das séries naturais. Avaliou-se a exposição devido a sucessivas aplicações de fertilizantes e fosfogesso, calculando-se a dose interna devida à aplicação por 10, 50 e 100 anos. Os valores encontrados estão abaixo do limite de 2,4 mSv a-1, mostrando que esta prática é negligenciável. / Fertilizer is considered an essential component for agriculture, because its use increases the natural soil nutrients, which are lost slow waste or erosion. The Brazilian phosphate fertilizer is obtained by wet reaction of igneous phosphate rock with concentrated sulphuric acid, giving as final product, phosphoric acid and dihydrated calcium sulphate (phosphogypsum) as by-product. Phosphoric acid is the starting material for triple superphosphate (TSP), single superphosphate (SSP), monoammonium phosphate (MAP) and diammonium phosphate (DAP). The phosphate rock used as raw material presents in its composition, radionuclides of the U and Th natural series in. During the chemical attack of the phosphate rock, this equilibrium is disrupted and the radionuclides and the elements migrate to intermediate, final products and by-products, according to their solubility and chemical properties. While the fertilizers are commercialized, the phosphogypsum is disposed in stack piles and can cause an impact in the environment. In order to evaluate the radionuclides and the elements distribution in the industrial process of phosphate fertilizer production, samples of concentrated rock, fertilizers (SSP, TSP, MAP and DAP) and phosphogypsum from three national industries (A, B and C), were analyzed. The characterization of the elements Ba, Co, Cr, Fe, Hf, Na, Sc, Ta, Th, U, Zn and Zr, and the rare earths La, Ce, Nd, Sm, Eu, Tb, Yb and Lu, were performed by instrumental neutron activation analysis. The results obtained showed that, in general, the rare earth elements are distributed uniformly in the fertilizers and phosphogypsum, except for Lu. The elemental concentration present in the fertilizers SSP and TSP are of the same order of magnitude of the source rock. The same behavior was observed in the fertilizers MAP and DAP, except for the elements Co, Sc and U. The radionuclides of the U series (238U, 234U, 230Th, 226Ra, 210Pb) and of the Th series (232Th, 228Ra, 228Th) and 40K were determined by gamma and alpha spectrometry. The fertilizers samples, with are derived directly from phosphoric acid, MAP and DAP, presented in their composition low activity concentrations for 226Ra, 228Ra and 210Pb. For U and Th, the concentrations founded in MAP and DAP are more significant, similar to the source rock. SSP and TSP fertilizers, which are obtained by mixing phosphoric acid with different amounts of phosphate rock, presented higher concentrations of all radionuclides of the natural series. Long-term exposure due to successive fertilizer and phosphogypsum application was evaluated. Internal doses due to the application of phosphate fertilizer and phosphogypsum for 10, 50 and 100 years were below 2.4 mSv y-1, showing that the radiological impact of such practice is negligible.

O fertilizante é considerado um componente essencial para a agricultura, pois sua utilização aumenta e repõe os nutrientes naturais do solo, perdidos por desgaste ou erosão. No processo de obtenção dos fertilizantes fosfatados, o concentrado de rocha reage com ácido sulfúrico concentrado produzindo ácido fosfórico e sulfato de cálcio (fosfogesso), como subproduto. O ácido fosfórico é utilizado para a produção do superfosfato triplo (TSP), superfosfato simples (SSP), monoamônio fosfato (MAP) e diamônio fosfato (DAP). A rocha fosfatada usada como matéria prima apresenta em sua composição radionuclídeos das séries naturais do urânio e tório. Durante o ataque químico do concentrado de rocha, as espécies presentes na reação, estáveis e radioativas, são redistribuídas entre o ácido fosfórico (matéria prima dos fertilizantes), e o fosfogesso, de acordo com sua solubilidade e características químicas. Enquanto os fertilizantes são comercializados, o fosfogesso fica estocado em pilhas podendo impactar o meio ambiente. Com a finalidade de entender a distribuição dos elementos e dos radionuclídeos no processo industrial de produção de fertilizantes fosfatados, foram analisadas amostras de concentrado de rocha, de fertilizantes (SSP, TSP, MAP e DAP) e fosfogesso de três procedências nacionais denominadas indústrias A, B e C. A técnica utilizada para a análise elementar foi a análise por ativação com nêutrons, que permitiu analisar os elementos Ba, Co, Cr, Fe, Hf, Na, Sc, Ta, Th, U, Zn e Zr, e as terras raras, La, Ce, Nd, Sm, Eu, Tb, Yb e Lu. Os resultados obtidos permitiram concluir que em geral, as terras raras se distribuem de forma homogênea em todos os fertilizantes e no fosfogesso, exceto o Lu. Os fertilizantes SSP e TSP apresentaram concentrações de todos os elementos analisados da mesma ordem de grandeza da rocha de origem. O mesmo comportamento foi observado nos fertilizantes MAP e DAP, exceto para os elementos Co, Sc e U. Os elementos pertencentes à série radioativa natural do urânio (238U, 234U, 230Th, 226Ra e 210Pb), do tório (232Th, 228Ra e 228Th) e o K-40, foram determinados por meio da espectrometria gama e alfa. As amostras de fertilizantes MAP e DAP, que são diretamente derivadas do ácido fosfórico, apresentaram baixa concentração para o 226Ra, 228Ra e 210Pb, enquanto que para o U e Th as concentrações encontradas foram da mesma ordem de grandeza da rocha de origem. Os fertilizantes SSP e TSP, que são obtidos pela mistura de ácido fosfórico com concentrado de rocha, apresentaram concentrações mais elevadas para os radionuclídeos das séries naturais. Avaliou-se a exposição devido a sucessivas aplicações de fertilizantes e fosfogesso, calculando-se a dose interna devida à aplicação por 10, 50 e 100 anos. Os valores encontrados estão abaixo do limite de 2,4 mSv a-1, mostrando que esta prática é negligenciável. / Fertilizer is considered an essential component for agriculture, because its use increases the natural soil nutrients, which are lost slow waste or erosion. The Brazilian phosphate fertilizer is obtained by wet reaction of igneous phosphate rock with concentrated sulphuric acid, giving as final product, phosphoric acid and dihydrated calcium sulphate (phosphogypsum) as by-product. Phosphoric acid is the starting material for triple superphosphate (TSP), single superphosphate (SSP), monoammonium phosphate (MAP) and diammonium phosphate (DAP). The phosphate rock used as raw material presents in its composition, radionuclides of the U and Th natural series in. During the chemical attack of the phosphate rock, this equilibrium is disrupted and the radionuclides and the elements migrate to intermediate, final products and by-products, according to their solubility and chemical properties. While the fertilizers are commercialized, the phosphogypsum is disposed in stack piles and can cause an impact in the environment. In order to evaluate the radionuclides and the elements distribution in the industrial process of phosphate fertilizer production, samples of concentrated rock, fertilizers (SSP, TSP, MAP and DAP) and phosphogypsum from three national industries (A, B and C), were analyzed. The characterization of the elements Ba, Co, Cr, Fe, Hf, Na, Sc, Ta, Th, U, Zn and Zr, and the rare earths La, Ce, Nd, Sm, Eu, Tb, Yb and Lu, were performed by instrumental neutron activation analysis. The results obtained showed that, in general, the rare earth elements are distributed uniformly in the fertilizers and phosphogypsum, except for Lu. The elemental concentration present in the fertilizers SSP and TSP are of the same order of magnitude of the source rock. The same behavior was observed in the fertilizers MAP and DAP, except for the elements Co, Sc and U. The radionuclides of the U series (238U, 234U, 230Th, 226Ra, 210Pb) and of the Th series (232Th, 228Ra, 228Th) and 40K were determined by gamma and alpha spectrometry. The fertilizers samples, with are derived directly from phosphoric acid, MAP and DAP, presented in their composition low activity concentrations for 226Ra, 228Ra and 210Pb. For U and Th, the concentrations founded in MAP and DAP are more significant, similar to the source rock. SSP and TSP fertilizers, which are obtained by mixing phosphoric acid with different amounts of phosphate rock, presented higher concentrations of all radionuclides of the natural series. Long-term exposure due to successive fertilizer and phosphogypsum application was evaluated. Internal doses due to the application of phosphate fertilizer and phosphogypsum for 10, 50 and 100 years were below 2.4 mSv y-1, showing that the radiological impact of such practice is negligible.

The nuclear design of fusion devices such as ITER (International Thermonuclear Experimental Reactor), which is an experimental fusion reactor based on the &amp;quot;tokamak&amp;quot; concept, rely on the results of neutron physical calculations. These depend on the knowledge of the neutron and photon flux spectra which is particularly important because it permits to anticipate the possible answers of the whole structure to phenomena such as nuclear heating, tritium breeding, atomic displacements, radiation shielding, power generation and material activation. The flux spectra can be calculated with transport codes, but validating measurements are also required. An important constituent of structural materials and divertor areas of fusion reactors is tungsten. This thesis deals with the measurement of the neutron fluence and neutron energy spectrum in a tungsten assembly by means of multiple foil neutron activation technique. In order to check and qualify the experimental tools and the codes to be used in the tungsten benchmark experiment, test measurements in the D-T and D-D neutron fields of the neutron generator at Technische Universität Dresden were performed. The characteristics of the D-D and D-T reactions, used to produce monoenergetic neutrons, together with the selection of activation reactions suitable for fusion applications and details of the activation measurements are presented. Corrections related to the neutron irradiation process and those to the sample counting process are discussed, too. The neutron fluence and its energy distribution in a tungsten benchmark, irradiated at the Frascati Neutron Generator with 14 MeV neutrons produced by the T(d, n)4He reaction, are then derived from the measurements of the neutron induced &amp;amp;#947;-ray activity in the foils using the STAYNL unfolding code, based on the linear least-square-errors method, together with the IRDF-90.2 (International Reactor Dosimetry File) cross section library. The differences between the neutron flux spectra measured by means of neutron foil activation and the neutron flux spectra obtained in the same assembly, making use of an NE213 liquid-scintillation spectrometer were studied. The comparison of measured neutron spectra with the spectra calculated with the MCNP-4B (Monte Carlo neutron and photon transport) code, which allows a crucial test of the evaluated nuclear data used in fusion reactor design, is discussed, too. In conclusion, this thesis shows the applicability of the neutron foil activation technique for the measurement of neutron flux spectra inside a thick tungsten assembly irradiated with 14 MeV from a D-T generator. / Die Konstruktion von Fusionsreaktoren wie ITER (International Thermonuclear Experimental Reactor), der ein experimenteller Fusionsreaktor ist und auf dem &amp;quot;Tokamak&amp;quot;-Konzept beruht, basiert unter neutronenphysikalischen Gesichtspunkten auf den Ergebnissen von umfangreichen Simulationsrechnungen. Diese setzen die Kenntnis der Spektren des Neutronen- und Photonenflusses voraus die besonders wichtig ist, weil sie, die möglichen Antworten der ganzen Struktur auf physikalische Prozesse vorauszuberechnen erlaubt wie z.B.: Heizen durch nukleare Prozesse, Tritium-Brüten, Atomverschiebung, Abschirmung von Strahlung, Leistungserzeugung und Materialaktivierung. Die Flußspektren können mittels Transportcodes berechnet werden, aber es werden auch Messungen zu ihrer Bestätigung benötigt. Ein wichtiger Bestandteil des Strukturmaterials und der Divertor-Flächen der Fusionsreaktoren ist Wolfram. Diese Dissertation behandelt die Messungen der Neutronspektren und ?fluenz in einer Wolfram-Anordnung mittels der Multifolien-Neutronenaktivierungstechnik. Um die anzuwendenden experimentellen Geräte und die Codes, die im Wolfram-Benchmark-Experiment eingesetzt werden, zu überprüfen und zu bestimmen, wurden Testmessungen in den D-T und D-D Neutronenfeldern des Neutronengenerator der Technischen Universität Dresden durchgeführt. Die Eigenschaften der D-T und D-D Reaktionen, die für die Erzeugung von monoenergetischen Neutronen verwendet werden, sowie die Auswahl der Aktivierungsreaktionen, die für Fusionsanwendungen geeignet sind und die Aktivierungsmessung werden detailliert vorgestellt. Korrekturen, die sich auf den Neutronen-Bestrahlungsprozess und auf den Probenzählungsprozess beziehen, werden ebenfalls besprochen. Die Neutronenfluenz und ihre Energieverteilung in einem Wolfram-Benchmark, bestrahlt am Frascati Neutronen Generator mit 14 MeV-Neutronen aus der T(d, n)4He Reaktion, werden aus den Messungen der &amp;amp;#947;-Strahlenaktivität, die von Neutronen in den Folien induziert ist, durch den STAYNL Entfaltungscode, der auf der Methode der kleinsten Fehlerquadrate basiert, zusammen mit der IRDF-90.2 Wirkungsquerschnitt-Bibliothek abgeleitet. Die Unterschiede zwischen den Neutronenflußspektren, die mit Hilfe der Multifolien-Neutronenaktivierung ermittelt wurden, und den Neutronenflußspektren, gemessen im selben Aufbau mit einem NE-213 Flüssigszintillator, wurden untersucht. Die gemessenen Neutronenspektren werden den aus MCNP-4B Rechnungen (Monte Carlo neutron and photon transport) ermittelten Spektren gegenüber gestellt. Der Vergleich stellt einen wichtigen Test der evaluierten Kerndaten für Fusionsreaktorkonzepte dar. Zusammenfassend zeigt diese Arbeit die Anwendbarkeit der Multifolien-Neutronenaktivierungstechnik bei Messungen der Neutronenflussspektren innerhalb eines massiven Wolframblocks bei Bestrahlung mit schnellen Neutronen aus D-T Generatoren.

Les activités nucléaires génèrent des déchets radioactifs classés selon leur niveau d’activité et la durée de vie des radioéléments présents. La garantie d’un classement et d’une gestion optimale nécessite une caractérisation précise. Les déchets de moyenne et haute activité, contenant des radioéléments à vie très longue, seront stockés en profondeur pendant plusieurs centaines de milliers d’années, à l’issue desquelles il est nécessaire de pouvoir garantir l’absence de risques pour l’homme et l’environnement, non seulement sur le plan radiologique, mais aussi en ce qui concerne des éléments stables, toxiques du point de vue chimique. Cette thèse concerne la caractérisation par activation neutronique de ces éléments toxiques, ainsi que celle des matières nucléaires présentes dans les colis. Elle a été réalisée dans le cadre d’une collaboration entre le Laboratoire de Mesures Nucléaires du CEA Cadarache, en France, et l’institut de Gestion des Déchets Radioactifs et de Sûreté des Réacteurs du centre de recherche FZJ (Forschungszentrum Jülich), en Allemagne. La première étude a consisté à valider le modèle numérique de la cellule d’activation neutronique MEDINA (FZJ) avec le code de transport Monte Carlo MCNP. Les rayonnements gamma prompts de capture radiative d’échantillons contenant des éléments d’intérêt (béryllium, aluminium, chlore, cuivre, sélénium, strontium et tantale) ont été mesurés et comparés aux simulations avec diverses bases de données nucléaires, permettant d’aboutir à un accord satisfaisant et validant le schéma de calcul en vue des études suivantes. Ensuite, la mesure des rayonnements gamma retardés de fissions induites sur les isotopes 235U et 239Pu a été étudiée pour des fûts de 225 L contenant des enrobés bitumineux ou une matrice béton, représentatifs de déchets produits en France et en Allemagne. Les rendements d’émission des rayonnements gamma retardés de fission d’intérêt, cohérents avec ceux publiés dans la littérature, ont été déterminés à partir des mesures d’échantillons métalliques d’uranium et de plutonium dans la cellule d’activation neutronique REGAIN du LMN. Le signal utile a ensuite été extrapolé par simulation MCNP pour une répartition homogène d’isotopes 239Pu ou 235U dans les matrices considérées, en utilisant le modèle numérique de MEDINA. Des signaux faibles, de l’ordre de 100 coups par gramme d’isotope 239Pu ou 235U, ont été obtenus. Pour le colis d’enrobés bitumineux, le niveau d’irradiation gamma très élevé, dû à une activité en 137Cs de l’ordre de 1 TBq par fût, nécessiterait l’utilisation d’une collimation et/ou d’écrans pour éviter la saturation de l’électronique de mesure, rendant indétectables les rayonnements gamma retardés de fission. Les colis de déchets bétonnés produits en Allemagne présentant un niveau d’activité plus faible, il a été possible d’estimer des limites de détection allant de 10 à 290 g d’isotope fissile 235U ou 239Pu, selon la raie gamma considérée, suite à la mesure du bruit de fond actif dans MEDINA avec une matrice béton maquette. Afin d’améliorer ces performances, le blindage du détecteur germanium de MEDINA a été optimisé à l’aide de simulations MCNP, montrant la possibilité de réduire les bruits de fond gamma et neutron d’un facteur 4 et 5, respectivement. La validation expérimentale de l’efficacité du blindage a été effectuée à partir de configuration simples à implémenter dans MEDINA, confirmant les facteurs de réduction attendus. Un blindage du détecteur optimal permettrait d’améliorer les limites de détection et aussi d’utiliser une source de neutrons d’intensité supérieure, comme un générateur de neutron à haut flux ou un accélérateur linéaire d’électrons avec une cible de conversion appropriée. / Nuclear activities produce radioactive wastes classified following their radioactive level and decay time. An accurate characterization is necessary for efficient classification and management. Medium and high level wastes containing long lived radioactive isotopes will be stored in deep geological storage for hundreds of thousands years. At the end of this period, it is essential to ensure that the wastes do not represent any risk for humans and environment, not only from radioactive point of view, but also from stable toxic chemicals. This PhD thesis concerns the characterization of toxic chemicals and nuclear material in radioactive waste, by using neutron activation analysis, in the frame of collaboration between the Nuclear Measurement Laboratory of CEA Cadarache, France, and the Institute of Nuclear Waste Management and Reactor Safety of the research center, FZJ (Forschungszentrum Jülich GmbH), Germany. The first study is about the validation of the numerical model of the neutron activation cell MEDINA (FZJ), using MCNP Monte Carlo transport code. Simulations and measurements of prompt capture gamma rays from small samples measured in MEDINA have been compared for a number of elements of interest (beryllium, aluminum, chlorine, copper, selenium, strontium, and tantalum). The comparison was performed using different nuclear databases, resulting in satisfactory agreement and validating simulation in view of following studies. Then, the feasibility of fission delayed gamma-ray measurements of 239Pu and 235U in 225 L waste drums has been studied, considering bituminized or concrete matrixes representative of wastes produced in France and Germany. The delayed gamma emission yields were first determined from uranium and plutonium metallic samples measurements in REGAIN, the neutron activation cell of LMN, showing satisfactory consistency with published data. The useful delayed gamma signals of 239Pu and 235U, homogeneously distributed in the 225 L matrixes, were then determined by MCNP simulations using MEDINA numerical model. Weak signals of about one hundred counts per gram of 239Pu or 235U after 7200 s irradiation were obtained. Because of the high gamma emission in the bituminized waste produced in France (about 1 TBq of 137Cs per drum), the use of collimator and/or shielding is mandatory to avoid electronic saturation, making fission delayed gamma rays undetectable. However, German concrete drums being of lower activity, their corresponding active background was measured in MEDINA with a concrete mock-up, leading to detection limits between 10 and 290 g of 235U or239Pu, depending on the delayed gamma line. In order to improve these performances, the shielding of MEDINA germanium detector was optimized using MCNP calculations, resulting in gamma and neutron background reduction factors of 4 and 5, respectively. The experimental validation of the shielding efficiency was performed by implementing easy-to-build configurations in MEDINA, which confirmed the expected background reduction factors predicted by MCNP. Thanks to an optimized detector shielding, it will also be possible to use a higher neutron emission source, like a high flux neutron generator or an electron LINAC with appropriate conversion targets, in view to further reduce detection limits.

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