This thesis focuses on the geochemistry of secondary minerals, mainly calcite but also others such as fluorite and Ca/Al silicates, precipitated throughout the last 1.5 billion years in fractures of crystalline rock, SE Sweden. The work was based on previous reconnaissance studies and has been possible thanks to access to high-quality drill cores and associated mapping data provided by the Swedish Nuclear Fuel and Waste Management Co (SKB). Concentrations of rare earth elements (REEs) and occasionally other metals were determined in a variety of secondary minerals from fractures (mainly open systems) and veins (mainly sealed systems) and in primary minerals from the bedrock. Stable-isotope composition was measured in the secondary minerals. The overall aim was to define the sources, uptake and fractionation of REEs in calcite, and a few other co-genetic minerals, precipitated throughout the geological history under conditions ranging from hydrothermal to low temperatures. Collectively, the findings of the individual studies show that there is no easy and straightforward control of REE abundance and fractionation in calcite and other minerals in fractures and veins in crystalline bedrock settings. For example, the REE features in calcite vary extensively within sub-generations of single vein-precipitating events, on micro scale in transects across individual veins, and unsystematically over the geological history characterised by successively decreasing temperatures of mineral formation. Although the REE content in, and release from, the crystalline bedrock can have an influence on REE distribution in calcite and other minerals, it is of overall minor importance within a given bedrock domain. The main advantage of determining REEs in secondary minerals in fractures and veins in crystalline rock is therefore, as revealed in this work, to assess the character and evolution of the conditions (including features of the paleofluids) during confined mineral-precipitating events.

The As- and Mo- bearing secondary mineral phases formed during the neutralization of uranium mill wastes were studied for a variety of ore blends including current and future ore sources at the Key Lake milling operation, northern Saskatchewan, Canada. A lab-scale plant model was employed to characterize secondary precipitates obtained during the mill waste neutralization process. Three scenarios of ore blends were processed through the lab-scale plant to produce mill waste solutions for neutralization before combination into final tailings. Slurry samples (n = 12) were collected from the secondary precipitates formed during the neutralization of mill wastes (raffinate) by precipitation with Ca(OH)2 (slaked lime) from pH 1.5 to 10.5. Synchrotron based X-ray absorption spectroscopy of mill and lab-scale plant precipitates showed arsenate adsorbed to ferrihydrite was the dominant As mineral phase regardless of pH or sample blend (53-77%), with fractional contributions from ferric arsenates, and adsorption to aluminum phases (AlOHSO4, As(OH)3 and hydrotalcite). Molybdate adsorbed to ferrihydrite was the dominant Mo mineral phase, regardless of pH or sample blend, with fractional contribution decreasing with increasing pH, and minor contributions from calcium molybdate, ferric molybdate and nickel molybdate. These results were used in geochemical modelling to predict the source terms for these mineral phases in tailings facilities. Sequestration of As and Mo in the model showed solubility was controlled by adsorption to both Fe and Al oxide surfaces as well as by direct precipitation with other dissolved constituents (Ni, Ca and SO4).The models developed pH profiles of mineral phase precipitation to explain the solubility of As, Mo, Fe, Al, Mg and Ni during sequestration from pH 1.5 to 10.5 that were consistent regardless of ore blend used in simulations. Since adsorption of anions to the surface of ferrihydrite has been shown to slow conversion to crystalline forms of Fe oxides (goethite and hematite) and sequestration of arsenate effectively controls As solubility at high pH (pH >10), As-bearing mineral phases are expected to be stable for thousands of years. With adsorption as well as direct precipitation considered, Mo phases though effectively sequestering below pH 8, became unstable and released Mo back into the tailings porewater (pH >10), as predicted by the thermodynamic model. Historical data obtained from as-discharged tailings as well as previously published U mill tailings studies agree with these findings.

As características vulcanológicas e geoquímicas das rochas vulcânicas da Formação Serra Geral (Eo-Cretáceo da Bacia do Paraná, América do Sul) foram integradas para avaliar os aspectos genéticos e a distribuição dos minerais secundários que são encontrados nas cavidades (vesículas, etc) dessas rochas. Mais de 70 afloramentos e pedreiras em uma área de 65.000 km2 no NE do estado do Rio Grande do Sul (Brasil) permitiram o reconhecimento dos padrões locais e regionais de distribuição dos minerais secundários. Sua distribuição em três pedreiras é apresentada em detalhes, evidenciando alterações quantitativas e qualitativas da mineralogia secundária a distâncias que podem ser inferiores a dez metros. Sete fatores principais definem os minerais que se formam nas cavidades. A composição do derrame de lava hospedeiro e as porosidades primárias e secundárias dos derrames de lava individuais e da seqüência vulcânica são muito importantes. Voláteis vulcânicos do próprio derrame de lava que abriga as cavidades foram responsáveis pela cristalização de minerais secundários nessas cavidades provavelmente apenas em circunstâncias muito específicas. O baixo gradiente geotérmico e a ausência de outras fontes de calor na bacia intracratônia do Paraná restringem o metamorfismo de soterramento como agente formador de minerais secundários provavelmente apenas a grandes profundidades. Metamorfismo de contato, representado pelo impacto de calor e de voláteis vulcânicos dos derrames de lava sobre derrames pré-existentes, é o principal processo de formação de minerais secundários de temperaturas mais altas (T>100ºC). Fenômenos meteorológicos (tempestades de poeira e chuva) durante o extravasamento dos derrames de lava e a interação dos derrames com águas superficiais criaram condições específicas e muito localizadas de formação de minerais secundários. Fluidos ascendentes do aqüífero Botucatu-Pirambóia sotoposto e fluidos descendentes do aqüífero contido no edifício vulcânico são os principais responsáveis pela formação de minerais de baixas temperaturas (T<100ºC). Essa interação de vários fatores e processos genéticos de intensidades variáveis foi responsável pela distribuição dos minerais secundários por "domínios". Domínios são definidos como volumes muito variáveis de rocha, de um ou mais derrames de lava, cujas cavidades abrigam as mesmas espécies minerais secundários com as mesmas morfologias e propriedades físicas (cor). Domínios normalmente são formados por rochas de derrames com as mesmas características vulcanológicas e da mesma composição química, apresentando tamanhos decamétricos a quilométricos. Os minerais cristalizam em todos os tipos de cavidades das rochas vulcânicas, mudam com o tipo e o tamanho das cavidades e se distribuem aleatoriamente nas paredes das cavidades. Muito freqüentes são pseudomorfoses, perimorfoses e minerais com feições de dissolução, demonstrando que os minerais secundários são os produtos de várias fases de cristalização e de dissolução que se sucederam nas cavidades. As temperaturas elevadas (T>100ºC) necessárias para a cristalização de apofilita, laumontita, escolecita, heulandita, estilbitaestellerita e mordenita restringem a formação desses minerais à duração do evento vulcânico Serra Geral. Minerais de temperaturas mais baixas (T<100ºC) e ampla distribuição são chabasita, calcita e minerais do Grupo da Sílica (calcedônia, ágata e quartzo macrocristalino), cada qual com condicionantes genéticos específicos. / The volcanological and geochemical characteristics of the volcanic rocks of the Serra Geral Formation (Eo-Cretaceous of the Paraná Basin, South America) were integrated to evaluate the genetic aspects and the distribution of the secondary minerals found in the cavities (vesicles, etc.) of these rocks. More than 70 outcrops and quarries in an area of 65.000 km2 in the NE of the state of Rio Grande do Sul (Brazil) made it possible to recognize local and regional distribution patterns of the secondary minerals. Their distribution in three quarries is presented in detail, showing quantitative and qualitative changes, sometimes at distances of less than ten meters. Seven main factors define the kind of secondary minerals in the cavities. The composition of the host lava flow and the primary and secondary porosities of the individual lava flows and of the volcanic succession are very important. Volcanic volatiles of the cavity-hosting lava flow itself very rarely allowed the crystallization of secondary minerals in its cavities, probably only in very specific settings. The low geothermal gradient and the absence of other heat sources in the intracratonic Paraná Basin limit burial metamorphism as a secondary mineral forming agent probably only to great depths. Contact metamorphism, represented by the impact of heat and volcanic volatiles of lava flows over earlier flows, is considered the main process for the generation of secondary minerals of higher temperatures (T>100oC). Meteorological phenomena (dust storms and rain) during the emplacement of the lava flows and the interaction of the flows with superficial waters created very specific and localized mineral-forming conditions. Ascending fluids from the underlying Botucatu-Pirambóia aquifer and descending fluids of the aquifer hosted in the volcanic edifice were responsible for low-temperature (T<100oC) minerals. This interaction of different genetic factors and processes of variable intensities generated a distribution of secondary minerals in "domains". Domains are very variable volumes of rocks, belonging to one or several lava flows, whose cavities host the same species of secondary minerals, with the same morphologies and physical properties (colors). Domains are usually formed by rocks from flows with the same volcanological characteristics and the same chemical composition, with sizes ranging from decametric to quilometric. The secondary minerals crystallize in all types of cavities of the volcanic rocks. They change according to the kind and the size of the cavities and occur randomly distributed on the walls of the cavities. Very frequent are pseudomorphosis, perimorphosis and minerals with dissolution features, proving that the secondary minerals are the product of several phases of crystallization and dissolution which happened in the cavities. The higher temperatures (T>100oC) necessary to crystallize apophyllite, laumontite, scolecite, heulandite, stilbite-stellerite and mordenite limit the formation of these minerals to the time of the volcanic Serra Geral event. Very frequent minerals of lower temperatures (T<100oC) are chabazite, calcite and minerals of the silica group (chalcedony, agate and macrocrystalline quartz), each one with specific genetic conditions.

As características vulcanológicas e geoquímicas das rochas vulcânicas da Formação Serra Geral (Eo-Cretáceo da Bacia do Paraná, América do Sul) foram integradas para avaliar os aspectos genéticos e a distribuição dos minerais secundários que são encontrados nas cavidades (vesículas, etc) dessas rochas. Mais de 70 afloramentos e pedreiras em uma área de 65.000 km2 no NE do estado do Rio Grande do Sul (Brasil) permitiram o reconhecimento dos padrões locais e regionais de distribuição dos minerais secundários. Sua distribuição em três pedreiras é apresentada em detalhes, evidenciando alterações quantitativas e qualitativas da mineralogia secundária a distâncias que podem ser inferiores a dez metros. Sete fatores principais definem os minerais que se formam nas cavidades. A composição do derrame de lava hospedeiro e as porosidades primárias e secundárias dos derrames de lava individuais e da seqüência vulcânica são muito importantes. Voláteis vulcânicos do próprio derrame de lava que abriga as cavidades foram responsáveis pela cristalização de minerais secundários nessas cavidades provavelmente apenas em circunstâncias muito específicas. O baixo gradiente geotérmico e a ausência de outras fontes de calor na bacia intracratônia do Paraná restringem o metamorfismo de soterramento como agente formador de minerais secundários provavelmente apenas a grandes profundidades. Metamorfismo de contato, representado pelo impacto de calor e de voláteis vulcânicos dos derrames de lava sobre derrames pré-existentes, é o principal processo de formação de minerais secundários de temperaturas mais altas (T>100ºC). Fenômenos meteorológicos (tempestades de poeira e chuva) durante o extravasamento dos derrames de lava e a interação dos derrames com águas superficiais criaram condições específicas e muito localizadas de formação de minerais secundários. Fluidos ascendentes do aqüífero Botucatu-Pirambóia sotoposto e fluidos descendentes do aqüífero contido no edifício vulcânico são os principais responsáveis pela formação de minerais de baixas temperaturas (T<100ºC). Essa interação de vários fatores e processos genéticos de intensidades variáveis foi responsável pela distribuição dos minerais secundários por "domínios". Domínios são definidos como volumes muito variáveis de rocha, de um ou mais derrames de lava, cujas cavidades abrigam as mesmas espécies minerais secundários com as mesmas morfologias e propriedades físicas (cor). Domínios normalmente são formados por rochas de derrames com as mesmas características vulcanológicas e da mesma composição química, apresentando tamanhos decamétricos a quilométricos. Os minerais cristalizam em todos os tipos de cavidades das rochas vulcânicas, mudam com o tipo e o tamanho das cavidades e se distribuem aleatoriamente nas paredes das cavidades. Muito freqüentes são pseudomorfoses, perimorfoses e minerais com feições de dissolução, demonstrando que os minerais secundários são os produtos de várias fases de cristalização e de dissolução que se sucederam nas cavidades. As temperaturas elevadas (T>100ºC) necessárias para a cristalização de apofilita, laumontita, escolecita, heulandita, estilbitaestellerita e mordenita restringem a formação desses minerais à duração do evento vulcânico Serra Geral. Minerais de temperaturas mais baixas (T<100ºC) e ampla distribuição são chabasita, calcita e minerais do Grupo da Sílica (calcedônia, ágata e quartzo macrocristalino), cada qual com condicionantes genéticos específicos. / The volcanological and geochemical characteristics of the volcanic rocks of the Serra Geral Formation (Eo-Cretaceous of the Paraná Basin, South America) were integrated to evaluate the genetic aspects and the distribution of the secondary minerals found in the cavities (vesicles, etc.) of these rocks. More than 70 outcrops and quarries in an area of 65.000 km2 in the NE of the state of Rio Grande do Sul (Brazil) made it possible to recognize local and regional distribution patterns of the secondary minerals. Their distribution in three quarries is presented in detail, showing quantitative and qualitative changes, sometimes at distances of less than ten meters. Seven main factors define the kind of secondary minerals in the cavities. The composition of the host lava flow and the primary and secondary porosities of the individual lava flows and of the volcanic succession are very important. Volcanic volatiles of the cavity-hosting lava flow itself very rarely allowed the crystallization of secondary minerals in its cavities, probably only in very specific settings. The low geothermal gradient and the absence of other heat sources in the intracratonic Paraná Basin limit burial metamorphism as a secondary mineral forming agent probably only to great depths. Contact metamorphism, represented by the impact of heat and volcanic volatiles of lava flows over earlier flows, is considered the main process for the generation of secondary minerals of higher temperatures (T>100oC). Meteorological phenomena (dust storms and rain) during the emplacement of the lava flows and the interaction of the flows with superficial waters created very specific and localized mineral-forming conditions. Ascending fluids from the underlying Botucatu-Pirambóia aquifer and descending fluids of the aquifer hosted in the volcanic edifice were responsible for low-temperature (T<100oC) minerals. This interaction of different genetic factors and processes of variable intensities generated a distribution of secondary minerals in "domains". Domains are very variable volumes of rocks, belonging to one or several lava flows, whose cavities host the same species of secondary minerals, with the same morphologies and physical properties (colors). Domains are usually formed by rocks from flows with the same volcanological characteristics and the same chemical composition, with sizes ranging from decametric to quilometric. The secondary minerals crystallize in all types of cavities of the volcanic rocks. They change according to the kind and the size of the cavities and occur randomly distributed on the walls of the cavities. Very frequent are pseudomorphosis, perimorphosis and minerals with dissolution features, proving that the secondary minerals are the product of several phases of crystallization and dissolution which happened in the cavities. The higher temperatures (T>100oC) necessary to crystallize apophyllite, laumontite, scolecite, heulandite, stilbite-stellerite and mordenite limit the formation of these minerals to the time of the volcanic Serra Geral event. Very frequent minerals of lower temperatures (T<100oC) are chabazite, calcite and minerals of the silica group (chalcedony, agate and macrocrystalline quartz), each one with specific genetic conditions.

As características vulcanológicas e geoquímicas das rochas vulcânicas da Formação Serra Geral (Eo-Cretáceo da Bacia do Paraná, América do Sul) foram integradas para avaliar os aspectos genéticos e a distribuição dos minerais secundários que são encontrados nas cavidades (vesículas, etc) dessas rochas. Mais de 70 afloramentos e pedreiras em uma área de 65.000 km2 no NE do estado do Rio Grande do Sul (Brasil) permitiram o reconhecimento dos padrões locais e regionais de distribuição dos minerais secundários. Sua distribuição em três pedreiras é apresentada em detalhes, evidenciando alterações quantitativas e qualitativas da mineralogia secundária a distâncias que podem ser inferiores a dez metros. Sete fatores principais definem os minerais que se formam nas cavidades. A composição do derrame de lava hospedeiro e as porosidades primárias e secundárias dos derrames de lava individuais e da seqüência vulcânica são muito importantes. Voláteis vulcânicos do próprio derrame de lava que abriga as cavidades foram responsáveis pela cristalização de minerais secundários nessas cavidades provavelmente apenas em circunstâncias muito específicas. O baixo gradiente geotérmico e a ausência de outras fontes de calor na bacia intracratônia do Paraná restringem o metamorfismo de soterramento como agente formador de minerais secundários provavelmente apenas a grandes profundidades. Metamorfismo de contato, representado pelo impacto de calor e de voláteis vulcânicos dos derrames de lava sobre derrames pré-existentes, é o principal processo de formação de minerais secundários de temperaturas mais altas (T>100ºC). Fenômenos meteorológicos (tempestades de poeira e chuva) durante o extravasamento dos derrames de lava e a interação dos derrames com águas superficiais criaram condições específicas e muito localizadas de formação de minerais secundários. Fluidos ascendentes do aqüífero Botucatu-Pirambóia sotoposto e fluidos descendentes do aqüífero contido no edifício vulcânico são os principais responsáveis pela formação de minerais de baixas temperaturas (T<100ºC). Essa interação de vários fatores e processos genéticos de intensidades variáveis foi responsável pela distribuição dos minerais secundários por "domínios". Domínios são definidos como volumes muito variáveis de rocha, de um ou mais derrames de lava, cujas cavidades abrigam as mesmas espécies minerais secundários com as mesmas morfologias e propriedades físicas (cor). Domínios normalmente são formados por rochas de derrames com as mesmas características vulcanológicas e da mesma composição química, apresentando tamanhos decamétricos a quilométricos. Os minerais cristalizam em todos os tipos de cavidades das rochas vulcânicas, mudam com o tipo e o tamanho das cavidades e se distribuem aleatoriamente nas paredes das cavidades. Muito freqüentes são pseudomorfoses, perimorfoses e minerais com feições de dissolução, demonstrando que os minerais secundários são os produtos de várias fases de cristalização e de dissolução que se sucederam nas cavidades. As temperaturas elevadas (T>100ºC) necessárias para a cristalização de apofilita, laumontita, escolecita, heulandita, estilbitaestellerita e mordenita restringem a formação desses minerais à duração do evento vulcânico Serra Geral. Minerais de temperaturas mais baixas (T<100ºC) e ampla distribuição são chabasita, calcita e minerais do Grupo da Sílica (calcedônia, ágata e quartzo macrocristalino), cada qual com condicionantes genéticos específicos. / The volcanological and geochemical characteristics of the volcanic rocks of the Serra Geral Formation (Eo-Cretaceous of the Paraná Basin, South America) were integrated to evaluate the genetic aspects and the distribution of the secondary minerals found in the cavities (vesicles, etc.) of these rocks. More than 70 outcrops and quarries in an area of 65.000 km2 in the NE of the state of Rio Grande do Sul (Brazil) made it possible to recognize local and regional distribution patterns of the secondary minerals. Their distribution in three quarries is presented in detail, showing quantitative and qualitative changes, sometimes at distances of less than ten meters. Seven main factors define the kind of secondary minerals in the cavities. The composition of the host lava flow and the primary and secondary porosities of the individual lava flows and of the volcanic succession are very important. Volcanic volatiles of the cavity-hosting lava flow itself very rarely allowed the crystallization of secondary minerals in its cavities, probably only in very specific settings. The low geothermal gradient and the absence of other heat sources in the intracratonic Paraná Basin limit burial metamorphism as a secondary mineral forming agent probably only to great depths. Contact metamorphism, represented by the impact of heat and volcanic volatiles of lava flows over earlier flows, is considered the main process for the generation of secondary minerals of higher temperatures (T>100oC). Meteorological phenomena (dust storms and rain) during the emplacement of the lava flows and the interaction of the flows with superficial waters created very specific and localized mineral-forming conditions. Ascending fluids from the underlying Botucatu-Pirambóia aquifer and descending fluids of the aquifer hosted in the volcanic edifice were responsible for low-temperature (T<100oC) minerals. This interaction of different genetic factors and processes of variable intensities generated a distribution of secondary minerals in "domains". Domains are very variable volumes of rocks, belonging to one or several lava flows, whose cavities host the same species of secondary minerals, with the same morphologies and physical properties (colors). Domains are usually formed by rocks from flows with the same volcanological characteristics and the same chemical composition, with sizes ranging from decametric to quilometric. The secondary minerals crystallize in all types of cavities of the volcanic rocks. They change according to the kind and the size of the cavities and occur randomly distributed on the walls of the cavities. Very frequent are pseudomorphosis, perimorphosis and minerals with dissolution features, proving that the secondary minerals are the product of several phases of crystallization and dissolution which happened in the cavities. The higher temperatures (T>100oC) necessary to crystallize apophyllite, laumontite, scolecite, heulandite, stilbite-stellerite and mordenite limit the formation of these minerals to the time of the volcanic Serra Geral event. Very frequent minerals of lower temperatures (T<100oC) are chabazite, calcite and minerals of the silica group (chalcedony, agate and macrocrystalline quartz), each one with specific genetic conditions.

京都大学 / 新制・課程博士 / 博士(地球環境学) / 甲第23352号 / 地環博第210号 / 新制||地環||40(附属図書館) / 京都大学大学院地球環境学舎地球環境学専攻 / (主査)教授 舟川 晋也, 教授 德地 直子, 准教授 渡邉 哲弘 / 学位規則第4条第1項該当 / Doctor of Global Environmental Studies / Kyoto University / DFAM

Made available in DSpace on 2015-03-26T13:53:05Z (GMT). No. of bitstreams: 1 texto completo.pdf: 3366105 bytes, checksum: 21d9cd8d6939505909287458fd835b76 (MD5) Previous issue date: 2008-07-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Acid drainage in sterile piles is a serious environmental problem faced by numerous mining companies, since the acidic water resulted from sulfide minerals exposed to weather conditions contains high levels of heavy metals and arsenic that can be toxic in the food chain. In this context, aiming to develop a method to reduce acidic water production, the objective of this work was to promote the formation of geochemistry barrier in an ore pile using microencapsulation of sulfides by iron oxides, as well as to stabilize compounds formed by the addition of phosphorus. Another aim was to accelerate this process by adding bacteria acidophilus and swarf. The study started by building ore piles into transparent rigid plastic containers that were subjected to three periods of flooding and drainage. At the end of each period, before draining the piles, the pH of flood depths was raised above 4 to precipitate Fe oxides and Fe sulfates that form the geochemistry barrier. The experiment was arranged in a complete randomized design divided into plots and split plots, in which the sources of variation (water addition, swarf, growth medium, bacterium and phosphorus), with three replications, constituted the plot treatments, the oxidation cycles constituted the split plot treatments, and time of sample collection constituted the split-split plot treatment. In each cycle, samples of the flood depth were taken for pH and electrical conductivity readings, as well as Fe, Mn, Al, Zn, Ni, Cd, Cu, S and As level determination. After the experimental period (400 days), mineral characterization of precipitates, morphometry of impregnated cross-sections of undeformed piles and test of stability of pyrite encapsulation were carried out. Results showed that the pH increased over the cycles for the treatments with water well above the treatments with culture medium. There was reduction in iron and sulfur levels in all treatments, which may have been caused by precipitation and/or even removal of these elements during the pile drainage. In all treatments, contents of Mn, Al, Zn, Ni, Cd, Cu and As found in the beginning of the first cycle were much higher than the maximum limit allowed by the Resolution 357/05 CONAMA for Class 1 and 2 waters. Even with reduction in the concentration of these elements over the cycles, the levels remained above the limits established by the resolution. After 400 days, flood depth analysis showed that the percentage of oxide formation in the pile was lower in the treatment with culture medium and iron, but higher in the treatment with water and iron. X-ray diffraction patterns showed jarosite, gypsum and szomolnokite precipitation. Stability of pyrite encapsulation was higher in the water-iron treatment but lower in the water treatment. Overall, during the experiment, the water-iron treatment gave the best results for mitigation of acid drainage in piles of sulfide materials. Treatments with bacterial inoculation may, nevertheless, have better results in a longer experimental period. / A drenagem ácida em pilhas de estéril é um sério problema ambiental enfrentado por muitas mineradoras, uma vez que as águas ácidas geradas pela exposição de minerais sulfetados às condições atmosféricas possuem elevados teores de metais pesados e arsênio que podem ter efeito tóxico para a cadeia trófica. Nesse sentido, visando desenvolver uma prática para redução da geração de águas ácidas, objetivou-se, neste trabalho, promover a formação de barreira geoquímica em uma pilha de minério com a microencapsulação de sulfetos por óxidos de ferro, além de buscar a estabilização dos compostos formados pela adição de fósforo. Buscou-se, além disso, acelerar este processo por meio da adição de bactérias acidófilas e limalha de ferro. Para este estudo foram construídas pilhas de minério dentro de recipientes de plástico rígido transparente, as quais foram submetidas a três períodos de inundação e drenagem. No fim de cada período, antes da drenagem das pilhas, o pH das lâminas de inundação foi elevado acima de quatro para precipitação dos óxidos e sulfatos de Fe, responsáveis pela formação de barreira geoquímica. O experimento foi montado em delineamento inteiramente casualizado em parcela dividida e subdividida, em que as fontes de variação (adição de água, limalha de ferro, meio de cultura, bactéria e fósforo) com três repetições, constituíram os tratamentos da parcela, os ciclos de oxidação constituíram os tratamentos da subparcela, e os tempos de coleta de amostras o tratamento da sub-subparcela. Em cada ciclo foram obtidas amostras da lâmina de inundação, onde foram feitas as leituras do pH e condutividade elétrica, além da dosagem dos teores de Fe, Mn, Al, Zn, Ni, Cd, Cu, S e As. Após o término do período experimental (400 dias), foi realizada a caracterização mineralógica dos precipitados, morfometria de cortes impregnados das pilhas indeformadas e teste de estabilidade da encapsulação de pirita. Os resultados revelaram que, no grupo de tratamentos com água, os valores de pH aumentaram ao longo dos ciclos, sendo bem superiores aos tratamentos com meio de cultura. Houve uma redução nos teores de ferro e enxofre em todos os tratamentos o que pode ter sido provocada pela precipitação e/ou até mesmo pela remoção destes elementos durante a drenagem da pilha. Em todos os tratamentos, os teores de Mn, Al, Zn, Ni, Cd, Cu e As observados no início do primeiro ciclo foram muito superiores ao limite máximo permitido pela Resolução CONAMA 357/05 para águas de classe 1 e 2. Mesmo com a redução da concentração destes elementos, ao longo dos ciclos, seus teores continuaram acima dos limites estabelecidos pela esolução. Após o período de 400 dias, a análise das lâminas mostrou que a porcentagem de formação de óxidos na pilha foi menor no tratamento com meio de cultura e ferro, e maior no tratamento com água e ferro. Os difratogramas de Raios-X revelaram a precipitação de jarosita, gipsita e zomoloquita. A estabilidade da encapsulação da pirita foi maior no tratamento com água e ferro e menor no tratamento com água. De forma geral, no período do experimento, o tratamento com água e ferro apresentou os melhores resultados no processo de mitigação da drenagem ácida em pilhas de materiais sulfetados. No entanto, em um período experimental maior, os tratamentos com inoculação bacteriana podem apresentar melhores resultados.

Ce travail porte sur l'utilisation des déséquilibres radioactifs dans les échantillons de sols totaux, et des fractions minérales séparées. Les objectifs étaient d'évaluer : 1) l'impact d'un changement de végétation et de la granulométrie de la roche mère dans les sols sur les déséquilibres, 2) les phases minérales secondaires capables d'enregistrer des informations temporelles, et leur séparation chimique et 3) l’information temporelle portée par les minéraux primaires. Ce travail a mis en évidence sur le site de Breuil-Chenue que les couches les plus profondes du sol (< 40cm) ne montrent pas d’impact de la végétation ou de la granulométrie de la roche mère sur les déséquilibres radioactifs. Les faibles vitesses de production du sol (~1-2 mm/ka) obtenues reflètent la très faible érosion physique affectant ce site situé sur un plateau. La seconde partie de ce travail a permis d'identifier un protocole permettant d’extraire les oxydes de fer sans création de fractionnement chimique. Enfin, l'analyse de biotites d’un profil du même site a montré que les déséquilibres U/Th permettaient de déterminer de façon indépendante les vitesses d’altération in situ des minéraux dans les sols. / The aim of the present study was to evaluate weathering and soil formation rates using U-Th disequilibria in bulk soil or separated minerals. The specific objectives of this work were to evaluate the use of U-Th chronometric tools 1) regarding the impact of a land cover change and the bedrock characteristics 2) in selected secondary mineral phases and 3) in primary minerals. On the Breuil-Chenue (Morvan) site, no vegetation effect neither a grain size effect was observed on the U-Th series in the deepest soil layers (< 40cm). The low soil production rate (1-2 mm/ka) is therefore more affected by regional geomorphology than by the underlying bedrock texture. In the second part of this work, based on a thorough evaluation of different technics, a procedure was retained to extract Fe-oxides without chemical fractionation. Finally, the analysis of biotites hand-picked from one of the studied soil profile showed that U- series disequilibria allow to independently determinate the field-weathering-rate of minerals.

Die vorliegende Arbeit wurde im Rahmen des BMBF-geförderten Projektes "Luft- und bodengestützte spektrometrische Untersuchungen zur Differenzierung reaktiv veränderter Braunkohlentagebaugebiete in Mitteldeutschland" (Vorhaben 02 WB 9667/5) als Kooperation zwischen dem GeoForschungsZentrum Potsdam (GFZ), dem Deutschen Zentrum für Luft- und Raumfahrt (DLR), der Gesellschaft für Angewandte Fernerkundung (GAF) und dem Umweltforschungszentrum Leipzig/Halle GmbH (UFZ) angefertigt. Grundidee des Projektes war es, die durch spektrometrische Erfassungsmethoden der Fernerkundung erhaltenen Überfliegungsdaten mittels konventioneller petrographischer, mineralogischer und geochemischer Analytik zu kalibrieren. Der Schwerpunkt dieser Arbeit lag dabei in der Charakterisierung der hydro- und geochemischen Veränderungen in den Kippensedimenten des im mitteldeutschen Raum südlich von Leipzig aufgeschlossenen Braunkohlentagebaus Zwenkau. Zu diesem Zweck wurden die Kippensedimente in Abhängigkeit des Schüttungsalters und der Lagerung untersucht sowie die spezifischen Merkmale der Kippenwässer und Bodengase erfaßt, um die im Kippenkörper ablaufenden chemischen, petrographischen und gefügemäßigen Veränderungen sowie die Wechselwirkungen zwischen den Sedimenten, Wässern und Bodengasen zu beschreiben. Schließlich wird ein Modell zur zeitlichen Entwicklung der Abraumförderbrückenkippe, beginnend bei ihrer Verkippung bis hin zu einem Alter von etwa 20 Jahren, vorgestellt, welches die beobachteten Erscheinungen bezüglich der auftretenden endogenen und exogenen Wechselwirkungsfaktoren gut erklärt. / This thesis was prepared in cooperation with the GeoForschungsZentrum Potsdam (GFZ), the Deutsches Zentrum für Luft- und Raumfahrt (DLR), the Gesellschaft für Angewandte Fernerkundung (GAF), and the Umweltforschungszentrum Leipzig/Halle (UFZ) in frame of the project "Airborne and laboratory spectroscopic studies for differentiation of reactively alterated lignite mining pits in Central Germany" (No. 02 WB 9667/5) which was gratefully supported by the Bundesministerium für Bildung, Wissenschaft, Forschung und Technologie (BMBF). The major idea of the project was to achieve a calibration of the spectroscopic data acquired by the remote sensing though the results obtained from conventionally petrographical, mineralogical and geochemical analyses. The main goal of this thesis was the characterization of the hydro- and geochemical alterations in the conveyor bridge dump of the open lignite mining pit Zwenkau which is located in the Central Germany District southern of Leipzig. Therefore, dependent on their ages in terms of dumping and their surface-near locations the dump sediments were investigated and the specific properties of the different types of dump water and soil gases were acquired as well in order to describe the ongoing chemical, petrographical and structural alterations and interactions between the sediments, the water and the soil gases in the conveyor bridge. Finally, a model of the chronological development of the overburden sediments starting from their spilling up to an age of about 20 years is proposed which well explains the observed phenomena regarding the appearing endogenous and exogenous interaction factors.

Die vorliegende Arbeit wurde im Rahmen des BMBF-geförderten Projektes "Luft- und bodengestützte spektrometrische Untersuchungen zur Differenzierung reaktiv veränderter Braunkohlentagebaugebiete in Mitteldeutschland" (Vorhaben 02 WB 9667/5) als Kooperation zwischen dem GeoForschungsZentrum Potsdam (GFZ), dem Deutschen Zentrum für Luft- und Raumfahrt (DLR), der Gesellschaft für Angewandte Fernerkundung (GAF) und dem Umweltforschungszentrum Leipzig/Halle GmbH (UFZ) angefertigt. Grundidee des Projektes war es, die durch spektrometrische Erfassungsmethoden der Fernerkundung erhaltenen Überfliegungsdaten mittels konventioneller petrographischer, mineralogischer und geochemischer Analytik zu kalibrieren. Der Schwerpunkt dieser Arbeit lag dabei in der Charakterisierung der hydro- und geochemischen Veränderungen in den Kippensedimenten des im mitteldeutschen Raum südlich von Leipzig aufgeschlossenen Braunkohlentagebaus Zwenkau. Zu diesem Zweck wurden die Kippensedimente in Abhängigkeit des Schüttungsalters und der Lagerung untersucht sowie die spezifischen Merkmale der Kippenwässer und Bodengase erfaßt, um die im Kippenkörper ablaufenden chemischen, petrographischen und gefügemäßigen Veränderungen sowie die Wechselwirkungen zwischen den Sedimenten, Wässern und Bodengasen zu beschreiben. Schließlich wird ein Modell zur zeitlichen Entwicklung der Abraumförderbrückenkippe, beginnend bei ihrer Verkippung bis hin zu einem Alter von etwa 20 Jahren, vorgestellt, welches die beobachteten Erscheinungen bezüglich der auftretenden endogenen und exogenen Wechselwirkungsfaktoren gut erklärt. / This thesis was prepared in cooperation with the GeoForschungsZentrum Potsdam (GFZ), the Deutsches Zentrum für Luft- und Raumfahrt (DLR), the Gesellschaft für Angewandte Fernerkundung (GAF), and the Umweltforschungszentrum Leipzig/Halle (UFZ) in frame of the project "Airborne and laboratory spectroscopic studies for differentiation of reactively alterated lignite mining pits in Central Germany" (No. 02 WB 9667/5) which was gratefully supported by the Bundesministerium für Bildung, Wissenschaft, Forschung und Technologie (BMBF). The major idea of the project was to achieve a calibration of the spectroscopic data acquired by the remote sensing though the results obtained from conventionally petrographical, mineralogical and geochemical analyses. The main goal of this thesis was the characterization of the hydro- and geochemical alterations in the conveyor bridge dump of the open lignite mining pit Zwenkau which is located in the Central Germany District southern of Leipzig. Therefore, dependent on their ages in terms of dumping and their surface-near locations the dump sediments were investigated and the specific properties of the different types of dump water and soil gases were acquired as well in order to describe the ongoing chemical, petrographical and structural alterations and interactions between the sediments, the water and the soil gases in the conveyor bridge. Finally, a model of the chronological development of the overburden sediments starting from their spilling up to an age of about 20 years is proposed which well explains the observed phenomena regarding the appearing endogenous and exogenous interaction factors.