O caulim do Rio Capim na Amazônia Oriental se constitui num depósito importante para o Brasil, ocupando lugar de destaque na produção mundial desta matéria prima mineral. Os modelos estabelecem uma origem para a caulinita vinculada ao intemperismo em condições lateríticas (Paleogeno Inferior) a partir de um substrato formado por rochas sedimentares da Formação Ipixuna (Cretáceo Superior). No perfil, destacam-se em ordem de importância entre os compostos de ferro, a hematita e a goethita, minerais pouco estudados no caulim do Rio Capim. A partir dos fácies principais do caulim (fácies caulim macio na base e caulim duro no topo), foram separados e concentrados os minerais de interesse para estudos de detalhe, utilizando a difratometria de raios X (DRX) e a espectrometria de infravermelho por transformada de Fourier (FTIR). Entre os parâmetros determinados, obtiveram-se estimativas da dimensão, forma, área superficial e substituição isomórfica. A interpretação dos resultados evidencia o potencial de aplicação das informações na estimativa do comportamento destes minerais durante o processo de beneficiamento e para a discussão do modelo genético dos perfis de caulim. As goethitas e hematitas de ambos os fácies possuem propriedades muito semelhantes, reforçando o modelo que especula sobre uma origem comum para a fácies caulim macio e caulim duro do perfil. Entre as propriedades, destacam-se a elevada cristalinidade e a baixa participação do alumínio em sua composição, proporcionando a estes minerais um comportamento com resistência moderada a elevada nos processos de lixiviação ácida e a tendência de dissolução preferencial da hematita. O conjunto de características dos óxidos e oxihidróxidos de ferro são compatíveis com uma formação em ambientes hidromórficos, com baixa influência da matéria orgânica a partir de soluções com baixa atividade do ferro, moderadamente redutoras a fracamente ácidas. Dentro do modelo genético da formação do caulim, sua origem não está associada à zona de laterização do perfil, sendo compatível com um ambiente saprolítico e hidromórfico. As propriedades observadas permitem afirmar que os processos naturais que favoreceram a formação da caulinita na base do manto de alteração foram suficientemente longos e intensos para promover a retirada do ferro destas fácies num processo não dissociado no tempo. No modelo, o caulim é uma fácies da base do perfil formado abaixo do nível freático de um espesso perfil laterítico em condições moderadamente redutoras e ácidas com elevada atividade do Si e do Al, porém, com carência de Al disponível para a formação da hematita e da goethita. Neste ambiente, haveria uma lenta mobilização do Fe dentro do perfil sem a necessidade do estabelecimento de um evento excepcional com uma elevada atividade da matéria orgânica, como previsto em alguns modelos. / The Rio Capim Kaolin from the eastern Amazon is recognized as one of the largest deposits of Brazil with a quality and volume that place this area amongst the most important deposits in the world. Despite the importance and the significant amount of studies about kaolin, many questions remain unanswered and the genesis of this occurrence is not well understood. Perhaps, the consensus today is the acceptance of the Rio Capim kaolin origin to be related to a lateritic weathering process during the Early Paleogene, period with favorable geotectonic, duration and climatic conditions to originate a thick cover with the development of a complete weathering profile above a substrate composed by sedimentary rocks of the Ipixuna Formation (Cretaceous). The models consider kaolin to be a bottom facies of a thick lateritic profile, but nowadays the upper lateritic facies was destroyed (probably by erosion periods along the middle to upper Paleogene). The kaolin profile has two facies: the bottom one, which is called soft kaolin, and the upper, differentiated one forming the flint kaolin. Most controversial points are related to the way that the flint kaolin was formed and the mechanism in which the iron was mobilized from the kaolin profile as a whole. This study aims to get some insight about the Rio Capim kaolin development using some properties measured from the iron oxides and oxyhydroxides. The iron and titanium minerals from the kaolin represent the most important contaminants, and a large effort is made by the industry to eliminate their influence but, despite this negative reputation, those minerals also represent a source of valuable information about the environmental conditions of the profile. Among them, hematite is the most widespread in the entire kaolin profile, followed by goethite, whose importance increases in the direction of the flint kaolin facies. Representative samples of kaolin facies were selected from the kaolin profile and submitted to an approach that allowed concentrating the iron minerals and eliminating the influence of kaolinite. Using X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR), a set of properties of the hematite and goethite were determined, including median crystal dimensions, shapes, specific surface area and mineral composition by estimating the isomorphous replacement of iron (Fe) by aluminum (Al). The results show that hematites and goethites do not have enough differences in their properties to support a genesis model with radical changes in their conditions . In terms of behavior to acid leaching, the observed variations were important to predict differences in the rate of mineral dissolution and possibilities of preferential dissolution of hematite in relation to goethite, promoting the increase of the yellow component with the leaching. Both hematite and goethite have high crystallinity and the isomorphous replacement of Fe by Al is low. Comparing the properties observed in synthetic and natural environments, the hematite and goethite from the Rio Capim kaolin profile have characteristics that relate these minerals to a formation environment in hydromorphic conditions where the influence of organic matter was low, with low iron activity, weakly reduced and acidic conditions. These conditions are found in a saprolitic domain in accordance with the bottom facies of a thick laterite profile. Despite agreeing with a laterite model, differences make it difficult to explain iron depletion by organic matter only (Pirabas Event) and the origin of flint kaolin facies by a subsequent and superimposed laterite period. With the hematite and goethite properties found in this study, it is possible to propose that the Rio Capim kaolin is the bottom facies of a laterite profile formed in the zone permanently below the water table. Contrasting with the upper laterite portion of the profile, the bottom zone is in hydromorphic conditions and allowed the fixation of Al and Si to form kaolinite by primary feldspar and mica minerals of the Ipixuna Formation. This environment promotes the slow depletion of iron without the need of an exceptional accumulation of organic matter. The flint kaolin facies was formed in the same period of the soft kaolin facies and the observed differences in the kaolinite morphology are only related to changes caused by the location of this facies in the intermediate zone characterized by the water table fluctuation, but again without the need of subsequent superimposed lateritic processes.

Made available in DSpace on 2015-03-26T13:53:11Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1969254 bytes, checksum: 19d302e3240e4d97656615d1561f4d44 (MD5) Previous issue date: 2009-12-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Sulfides exposition to atmosphere promotes its oxidation resulting in acid drainage and mobilization of heavy metals and metalloids in water. Arsenic (As) mobilization can be a serious problem due to anthropogenic activities in the presence of sulfide minerals such as arsenopyrite (FeAsS). The use of limestone gravel is a common practice to neutralize the acid drainage. In this process, mobilization of metals and metaloids is decreased by precipitation, co-precipitation or adsorption onto recently precipitated Fe oxides. In this work, the efficiency of limestone filters for As remotion from water and neutralization of acid drainage was evaluated under field conditions. Arsenic stability in sediments next to a gold exploitation area was evaluated by sequential extraction chemical analyzes. The efficiency of horizontal filters prototypes, containing soil materials combined with limestone, for acidity neutralization and As remotion from acid solutions, was also evaluated in laboratory. Water and sediment samples were collected from creeks in area close to a gold mineralization. Water samples were collected during wet and dry seasons, while sediments were collected only during the wet season. Measurements of pH, Eh, electric conductivity (EC), dissolved oxygen and temperature were registered immediately after water sampling and As concentrations were determined in laboratory. In sediment samples, it was determined texture, particle density, remaining As, organic carbon (OC); As, Al, Ca, Mg and P contents extracted by Mehlich-3, pH in water, potential acidity, As sequential extractions and total contents of As and Fe. In order to evaluate the prototypes, in laboratory, acid solutionswith approximately 58 mg L-1 As were applied throughout PVC modules filled with Laterite (LAT), an Oxisoil (SOLO), a 3:1 mixture of SOLO and organic waste (SOLO+RO), and with limestone gravel (BRITA). Twelve filtration cycles, totalizing applications of 6.2, 67.21, 99.74, 20.22, 10.13 g As, Fe, S, Mg and Ca per filter, respectively, were performed. The residence time of the solution in the filters, as well as pH, CE, acidity and As, Fe, S, Mg and Ca contents in the input and output solutions were monitored. In the field, contents of As in water samples were low, except in two points which presented values above 100 ug L-1. There was not a consistent behavior for As in water samples respective to the collection time, but it could be observed a trend to decrease As concentrations during dry season. In general, As content in sediments was related to the organic matter content. It was observed that sediments and limestone filters play an important role in As mobility in water streams affected by acid drainage. Arsenic was mainly associated to stable fractions of the sediments, with a mean of 58% of the As linked to Fe oxides and residual fractions, which present practically null mobility. In the laboratory, prototypes of limestone gravel filters removed approximately 26 and 23% of the As and Fe applied, respectively. There was no significant sulfate removing or pH alteration in the filtered solutions for all prototypes. However, significant levels of the total acidity neutralization were observed, directly related to the residence time. Prototypes with SOLO+RO presented the highest residence times. The use of soil containing filters associated to limestone filters removed 2.6 and 2.45 times the As and Fe, respectively, removed by the limestone filter. The prototype LAT/BRITA/SOLO presented highest As removal capacity, around 70% of the applied As, and the highest As removal rate, by 1.2 mg min-¹, among soil containing filters. However, the residence time was higher to the filters containing soil materials than to the limestone filters. This can be a disadvantage to the use of soil filters. Notwithstanding, the use of soil materials combined with limestone can be an important strategy to increase the safety of the systems for As removal and acid drainage neutralization during rainy season. / A exposição dos sulfetos ao ar atmosférico promove a sua oxidação, o que pode resultar na acidificação de águas de drenagem e a mobilização de metais pesados e de metalóides. A mobilização de arsênio (As) pode ser um sério problema decorrente de atividades antropogênicas, na presença de minerais sulfetados, como a arsenopirita (FeAsS). O uso de britas de calcário é uma prática bastante utilizada para neutralizar a drenagem ácida. Neste processo ocorre a limitação da mobilização de metais por precipitação, co-precipitação e adsorção em óxidos de Fe recentemente precipitados. O presente trabalho avaliou a eficiência de filtros de brita calcária na remoção de As; e a neutralização da drenagem ácida, em condições de campo. Também foi avaliada a estabilidade do As em sedimentos próximos a área de exploração de ouro, por meio análises químicas de extrações seqüenciais. Paralelamente, foi avaliada a eficiência de protótipos de filtros horizontais contendo materiais de solo em conjunto com filtros de brita calcária na neutralização da acidez e remoção de As de solução ácida, em laboratório. Em condições de campo, foram coletadas amostras de água e de sedimentos em córregos de áreas próximas a mineralização de ouro. As amostras de água foram coletadas nos períodos chuvoso e seco, ao passo que os sedimentos foram coletados apenas no período chuvoso. Foram determinados pH, Eh, condutividade elétrica (CE), oxigênio dissolvido e temperatura das amostras de água, imediatamente após a coleta e em laboratório foram determinadas as concentrações de As . Nos sedimentos foram determinados a textura, a densidade de partícula, o pH em água, a acidez potencial, o As-remanescente, o carbono orgânico (CO), os teores de As, Al, Ca, Mg e P extraídos por Mehlich-3, extrações seqüenciais de As, e os teores totais de As e Fe. Para avaliação dos protótipos, em laboratório, foram aplicadas soluções ácidas com aproximadamente 58 mg.L-1 de As através de módulos de PVC preenchidos com laterita (LAT), com Latossolo Vermelho-Amarelo (SOLO), com uma mistura do SOLO e um resíduo orgânico, na proporção 3:1 (SOLO+RO), e com brita calcária (BRITA). Foram realizados 12 ciclos de filtração, totalizando uma aplicação de 6,2; 67,2; 99,7; 20,2; 10,1 g de As, Fe, S, Mg e Ca por filtro, respectivamente. Foram monitorados o tempo de residência da solução nos filtros e os valores de pH, CE, acidez e teores de As, Fe, S, Mg e Ca nas soluções de entrada e saída dos filtros. Em condições de campo, as concentrações de As nas águas foram baixas, com exceção de dois pontos que apresentaram valores acima de 100 ug L-¹. Não se observou um comportamento consistente do As nas águas em relação às épocas de coleta, mas houve uma tendência de diminuição nas concentrações de As no período seco. De modo geral,o teor de As nos sedimentos apresentou certa relação com o teor de matéria orgânica. Verificou-se que os sedimentos e os filtros de brita calcária desempenham importante função no controle da mobilidade do As em cursos d água afetados por drenagem ácida. Nos sedimentos, o As está associado a frações mais estáveis, em média 58 % do total ligado a óxidos de Fe e à fração residual, de mobilidade praticamente nula. Em laboratório, os protótipos dos filtros de brita calcária retiveram aproximadamente 26 e 23 % do As e Fe aplicados, respectivamente. Não houve remoção significativa de sulfatos ou alteração significativa do pH nas soluções filtradas para todos os protótipos de filtros. No entanto, foram observados níveis significativos de neutralização da acidez total na solução filtrada, diretamente relacionados com os tempos de residência. Os protótipos com SOLO+RO apresentaram os maiores tempos de residência. O uso de filtros contendo solo associados a filtros de brita calcária promoveu retenções de até 2,6 e 2,45 vezes mais As e Fe, respectivamente, em relação aos filtros de brita apenas. O protótipo de composição LAT/BRITA/SOLO apresentou maior capacidade de remoção, cerca de 70 % do As aplicado, e maior taxa de remoção de As, cerca de 1,2 mg min-¹. No entanto, o tempo de residência dos protótipos com materiais de solo foi acentuadamente superior aos de brita calcária, o que pode ser uma desvantagem para seu emprego. Não obstante, o uso de materiais de solo em conjunto com brita calcária pode ser uma estratégia importante nos períodos de chuva para aumentar a segurança do sistema de remoção do As e neutralização da acidez das águas de drenagem.

O caulim do Rio Capim na Amazônia Oriental se constitui num depósito importante para o Brasil, ocupando lugar de destaque na produção mundial desta matéria prima mineral. Os modelos estabelecem uma origem para a caulinita vinculada ao intemperismo em condições lateríticas (Paleogeno Inferior) a partir de um substrato formado por rochas sedimentares da Formação Ipixuna (Cretáceo Superior). No perfil, destacam-se em ordem de importância entre os compostos de ferro, a hematita e a goethita, minerais pouco estudados no caulim do Rio Capim. A partir dos fácies principais do caulim (fácies caulim macio na base e caulim duro no topo), foram separados e concentrados os minerais de interesse para estudos de detalhe, utilizando a difratometria de raios X (DRX) e a espectrometria de infravermelho por transformada de Fourier (FTIR). Entre os parâmetros determinados, obtiveram-se estimativas da dimensão, forma, área superficial e substituição isomórfica. A interpretação dos resultados evidencia o potencial de aplicação das informações na estimativa do comportamento destes minerais durante o processo de beneficiamento e para a discussão do modelo genético dos perfis de caulim. As goethitas e hematitas de ambos os fácies possuem propriedades muito semelhantes, reforçando o modelo que especula sobre uma origem comum para a fácies caulim macio e caulim duro do perfil. Entre as propriedades, destacam-se a elevada cristalinidade e a baixa participação do alumínio em sua composição, proporcionando a estes minerais um comportamento com resistência moderada a elevada nos processos de lixiviação ácida e a tendência de dissolução preferencial da hematita. O conjunto de características dos óxidos e oxihidróxidos de ferro são compatíveis com uma formação em ambientes hidromórficos, com baixa influência da matéria orgânica a partir de soluções com baixa atividade do ferro, moderadamente redutoras a fracamente ácidas. Dentro do modelo genético da formação do caulim, sua origem não está associada à zona de laterização do perfil, sendo compatível com um ambiente saprolítico e hidromórfico. As propriedades observadas permitem afirmar que os processos naturais que favoreceram a formação da caulinita na base do manto de alteração foram suficientemente longos e intensos para promover a retirada do ferro destas fácies num processo não dissociado no tempo. No modelo, o caulim é uma fácies da base do perfil formado abaixo do nível freático de um espesso perfil laterítico em condições moderadamente redutoras e ácidas com elevada atividade do Si e do Al, porém, com carência de Al disponível para a formação da hematita e da goethita. Neste ambiente, haveria uma lenta mobilização do Fe dentro do perfil sem a necessidade do estabelecimento de um evento excepcional com uma elevada atividade da matéria orgânica, como previsto em alguns modelos. / The Rio Capim Kaolin from the eastern Amazon is recognized as one of the largest deposits of Brazil with a quality and volume that place this area amongst the most important deposits in the world. Despite the importance and the significant amount of studies about kaolin, many questions remain unanswered and the genesis of this occurrence is not well understood. Perhaps, the consensus today is the acceptance of the Rio Capim kaolin origin to be related to a lateritic weathering process during the Early Paleogene, period with favorable geotectonic, duration and climatic conditions to originate a thick cover with the development of a complete weathering profile above a substrate composed by sedimentary rocks of the Ipixuna Formation (Cretaceous). The models consider kaolin to be a bottom facies of a thick lateritic profile, but nowadays the upper lateritic facies was destroyed (probably by erosion periods along the middle to upper Paleogene). The kaolin profile has two facies: the bottom one, which is called soft kaolin, and the upper, differentiated one forming the flint kaolin. Most controversial points are related to the way that the flint kaolin was formed and the mechanism in which the iron was mobilized from the kaolin profile as a whole. This study aims to get some insight about the Rio Capim kaolin development using some properties measured from the iron oxides and oxyhydroxides. The iron and titanium minerals from the kaolin represent the most important contaminants, and a large effort is made by the industry to eliminate their influence but, despite this negative reputation, those minerals also represent a source of valuable information about the environmental conditions of the profile. Among them, hematite is the most widespread in the entire kaolin profile, followed by goethite, whose importance increases in the direction of the flint kaolin facies. Representative samples of kaolin facies were selected from the kaolin profile and submitted to an approach that allowed concentrating the iron minerals and eliminating the influence of kaolinite. Using X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR), a set of properties of the hematite and goethite were determined, including median crystal dimensions, shapes, specific surface area and mineral composition by estimating the isomorphous replacement of iron (Fe) by aluminum (Al). The results show that hematites and goethites do not have enough differences in their properties to support a genesis model with radical changes in their conditions . In terms of behavior to acid leaching, the observed variations were important to predict differences in the rate of mineral dissolution and possibilities of preferential dissolution of hematite in relation to goethite, promoting the increase of the yellow component with the leaching. Both hematite and goethite have high crystallinity and the isomorphous replacement of Fe by Al is low. Comparing the properties observed in synthetic and natural environments, the hematite and goethite from the Rio Capim kaolin profile have characteristics that relate these minerals to a formation environment in hydromorphic conditions where the influence of organic matter was low, with low iron activity, weakly reduced and acidic conditions. These conditions are found in a saprolitic domain in accordance with the bottom facies of a thick laterite profile. Despite agreeing with a laterite model, differences make it difficult to explain iron depletion by organic matter only (Pirabas Event) and the origin of flint kaolin facies by a subsequent and superimposed laterite period. With the hematite and goethite properties found in this study, it is possible to propose that the Rio Capim kaolin is the bottom facies of a laterite profile formed in the zone permanently below the water table. Contrasting with the upper laterite portion of the profile, the bottom zone is in hydromorphic conditions and allowed the fixation of Al and Si to form kaolinite by primary feldspar and mica minerals of the Ipixuna Formation. This environment promotes the slow depletion of iron without the need of an exceptional accumulation of organic matter. The flint kaolin facies was formed in the same period of the soft kaolin facies and the observed differences in the kaolinite morphology are only related to changes caused by the location of this facies in the intermediate zone characterized by the water table fluctuation, but again without the need of subsequent superimposed lateritic processes.

O caulim do Rio Capim na Amazônia Oriental se constitui num depósito importante para o Brasil, ocupando lugar de destaque na produção mundial desta matéria prima mineral. Os modelos estabelecem uma origem para a caulinita vinculada ao intemperismo em condições lateríticas (Paleogeno Inferior) a partir de um substrato formado por rochas sedimentares da Formação Ipixuna (Cretáceo Superior). No perfil, destacam-se em ordem de importância entre os compostos de ferro, a hematita e a goethita, minerais pouco estudados no caulim do Rio Capim. A partir dos fácies principais do caulim (fácies caulim macio na base e caulim duro no topo), foram separados e concentrados os minerais de interesse para estudos de detalhe, utilizando a difratometria de raios X (DRX) e a espectrometria de infravermelho por transformada de Fourier (FTIR). Entre os parâmetros determinados, obtiveram-se estimativas da dimensão, forma, área superficial e substituição isomórfica. A interpretação dos resultados evidencia o potencial de aplicação das informações na estimativa do comportamento destes minerais durante o processo de beneficiamento e para a discussão do modelo genético dos perfis de caulim. As goethitas e hematitas de ambos os fácies possuem propriedades muito semelhantes, reforçando o modelo que especula sobre uma origem comum para a fácies caulim macio e caulim duro do perfil. Entre as propriedades, destacam-se a elevada cristalinidade e a baixa participação do alumínio em sua composição, proporcionando a estes minerais um comportamento com resistência moderada a elevada nos processos de lixiviação ácida e a tendência de dissolução preferencial da hematita. O conjunto de características dos óxidos e oxihidróxidos de ferro são compatíveis com uma formação em ambientes hidromórficos, com baixa influência da matéria orgânica a partir de soluções com baixa atividade do ferro, moderadamente redutoras a fracamente ácidas. Dentro do modelo genético da formação do caulim, sua origem não está associada à zona de laterização do perfil, sendo compatível com um ambiente saprolítico e hidromórfico. As propriedades observadas permitem afirmar que os processos naturais que favoreceram a formação da caulinita na base do manto de alteração foram suficientemente longos e intensos para promover a retirada do ferro destas fácies num processo não dissociado no tempo. No modelo, o caulim é uma fácies da base do perfil formado abaixo do nível freático de um espesso perfil laterítico em condições moderadamente redutoras e ácidas com elevada atividade do Si e do Al, porém, com carência de Al disponível para a formação da hematita e da goethita. Neste ambiente, haveria uma lenta mobilização do Fe dentro do perfil sem a necessidade do estabelecimento de um evento excepcional com uma elevada atividade da matéria orgânica, como previsto em alguns modelos. / The Rio Capim Kaolin from the eastern Amazon is recognized as one of the largest deposits of Brazil with a quality and volume that place this area amongst the most important deposits in the world. Despite the importance and the significant amount of studies about kaolin, many questions remain unanswered and the genesis of this occurrence is not well understood. Perhaps, the consensus today is the acceptance of the Rio Capim kaolin origin to be related to a lateritic weathering process during the Early Paleogene, period with favorable geotectonic, duration and climatic conditions to originate a thick cover with the development of a complete weathering profile above a substrate composed by sedimentary rocks of the Ipixuna Formation (Cretaceous). The models consider kaolin to be a bottom facies of a thick lateritic profile, but nowadays the upper lateritic facies was destroyed (probably by erosion periods along the middle to upper Paleogene). The kaolin profile has two facies: the bottom one, which is called soft kaolin, and the upper, differentiated one forming the flint kaolin. Most controversial points are related to the way that the flint kaolin was formed and the mechanism in which the iron was mobilized from the kaolin profile as a whole. This study aims to get some insight about the Rio Capim kaolin development using some properties measured from the iron oxides and oxyhydroxides. The iron and titanium minerals from the kaolin represent the most important contaminants, and a large effort is made by the industry to eliminate their influence but, despite this negative reputation, those minerals also represent a source of valuable information about the environmental conditions of the profile. Among them, hematite is the most widespread in the entire kaolin profile, followed by goethite, whose importance increases in the direction of the flint kaolin facies. Representative samples of kaolin facies were selected from the kaolin profile and submitted to an approach that allowed concentrating the iron minerals and eliminating the influence of kaolinite. Using X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR), a set of properties of the hematite and goethite were determined, including median crystal dimensions, shapes, specific surface area and mineral composition by estimating the isomorphous replacement of iron (Fe) by aluminum (Al). The results show that hematites and goethites do not have enough differences in their properties to support a genesis model with radical changes in their conditions . In terms of behavior to acid leaching, the observed variations were important to predict differences in the rate of mineral dissolution and possibilities of preferential dissolution of hematite in relation to goethite, promoting the increase of the yellow component with the leaching. Both hematite and goethite have high crystallinity and the isomorphous replacement of Fe by Al is low. Comparing the properties observed in synthetic and natural environments, the hematite and goethite from the Rio Capim kaolin profile have characteristics that relate these minerals to a formation environment in hydromorphic conditions where the influence of organic matter was low, with low iron activity, weakly reduced and acidic conditions. These conditions are found in a saprolitic domain in accordance with the bottom facies of a thick laterite profile. Despite agreeing with a laterite model, differences make it difficult to explain iron depletion by organic matter only (Pirabas Event) and the origin of flint kaolin facies by a subsequent and superimposed laterite period. With the hematite and goethite properties found in this study, it is possible to propose that the Rio Capim kaolin is the bottom facies of a laterite profile formed in the zone permanently below the water table. Contrasting with the upper laterite portion of the profile, the bottom zone is in hydromorphic conditions and allowed the fixation of Al and Si to form kaolinite by primary feldspar and mica minerals of the Ipixuna Formation. This environment promotes the slow depletion of iron without the need of an exceptional accumulation of organic matter. The flint kaolin facies was formed in the same period of the soft kaolin facies and the observed differences in the kaolinite morphology are only related to changes caused by the location of this facies in the intermediate zone characterized by the water table fluctuation, but again without the need of subsequent superimposed lateritic processes.

Orientadores: Francisco Sergio Bernardes Ladeira, Fabiano Tomazini da Conceição / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-26T00:44:09Z (GMT). No. of bitstreams: 1 Leonardi_FernandaAparecida_D.pdf: 18605410 bytes, checksum: d9fd9c126cf0a37d4652a56b6d3c939c (MD5) Previous issue date: 2014 / Resumo: A teoria de pediplanação proposta por King em 1956 ganhou atenção no Brasil a partir da sua publicação sobre a evolução do relevo da porção oriental brasileira. Este trabalho de King suscitou críticas e reflexões da comunidade geomorfológica nacional. Além de King, muitos autores publicaram trabalhos com este enfoque, podendo-se destacar Moraes Rego (1932), De Martonne (1943), Freitas (1951), Almeida (1964), Bigarella e Ab¿Sáber (1964), Barbosa (1965), Bigarella e Andrade (1965), Braun (1971), entre outros. Apesar de uma certa estagnação após a década de 1980, a temática "paleosuperfícies" ganhou destaque nas últimas duas décadas, principalmente devido ao surgimento de novos métodos de análise, inclusive a possibilidade de datações absolutas em perfis de intemperismo. Este trabalho busca associar os perfis lateríticos de ferro aos patamares altimétricos, tratando os perfis lateríticos como marco cronoestratigráfico passível de datação, através de análises químicas, mineralógicas, macromorfológicas e de datação por (U-Th)/He dos perfis lateríticos de ferro. Duas áreas principais foram estudadas mais a fundo: o quadrante leste do Quadrilátero Ferrífero (região de Catas Altas), nas imediações da Serra do Caraça, apresentando uma superfície laterítica de ferro a 890m de altitude, com 10 Km de extensão, sob a Formação Fonseca, na qual foi amostrado um perfil laterítico de ferro; e o quadrante oeste do Quadrilátero Ferrífero, a região da Serra do Rola Moça e norte da Serra da Moeda, onde foi também amostrado um perfil laterítico de ferro, a 1400m de altitude aproximadamente, sob o itabirito in situ (na Serra do Rola Moça). Nestas áreas foram mapeadas a superfície laterítica de ferro e realizada analise geoquímica, mineralógica e de datação (U-Th)/He dos perfis lateríticos amostrados. As idades encontradas variam no perfil da região de Catas Altas de 33,09±1,11Ma a 0,71±0,05Ma e no perfil da Serra do Rola Moça de 6,08±0,20Ma a 0,43±0,04Ma. Os dados apontam que a superfície laterítica de ferro teve o início da sua elaboração a 33Ma atrás na região de Catas Altas, sendo que a goethita desde este momento vem dissolvendo e recristalizando, por isso as idades mais recentes. Portanto, a área do Quadrilátero Ferrífero estava exposta há 60Ma, isso significa que a configuração do relevo com os topos eram os mesmos há 60Ma, principalmente em se tratando da região da Serra do Caraça. Os materiais datados na Serra do Rola Mola vão ao encontro das idades elencadas para as áreas vizinhas, como é o caso da Mina do Capão Xavier na Serra da Moeda (em torno de 6 a 8 Ma). Por fim, na análise de paleosuperfícies não se pode associar os patamares altimétricos a antigas superfícies de aplainamento de forma direta. De acordo com o estudo regional no Quadrilátero Ferrífero, pode-se afirmar que independente dos patamates altimétricos o que prevalece na paisagem é a superfície Sul-Americana e não encontrou-se evidências seguras da Superfície Gondwana, mais antiga / Abstract: The theory of pediplanation proposed by King em 1956 has gained attention in Brazil since his publication about the evolution of the relief of the Brazilian eastern portion. This King's work has given rise to reviews and reflections from the national geomorphological community. Besides King, many authors have published with this approach, highlighting Moraes Rego (1932), De Martonne (1943), Freitas (1951), Almeida (1964), Bigarella and Ab¿Sáber (1964), Barbosa (1965), Bigarella and Andrade (1965), Braun (1971), among others. In spite of a certain stagnation after the decade of 1980, the theme "paleosurfaces" has been highlighted in the last two decades, mainly due to the uprising of new methods of analysis, including the possibility of absolute dating in intemperism profiles. This work aims to associate the iron laterite profiles with elevation levels by using laterite profiles as a chronostratigraphic mark possible to be dated, through chemical, mineralogical, macromorphological analysis and dating by (U-Th)/He of the laterite iron profiles. Two main areas have been studied deeper: the eastern quadrant of Quadrilátero Ferrífero (Catas Altas region), next to Serra do Caraça, showing a laterite iron profile at 890m of altitude, with 10km of extension, under Fonseca Formation, in which a laterite iron profile was sampled; and the western quadrant of Quadrilátero Ferrífero, Serra do Rola Moça region and northern Serra da Moeda, where a laterite iron profile was also sampled, at about 1400m of altitude, under the itabirite in situ (in Serra do Rola Moça). In these areas the iron laterite surface was mapped and the geochemical, mineralogical analysis and dating (U-Th)/He of the sampled laterite profiles was done. The ages found range in the Catas Altas region from 33,09±1,11Myr ago to 0,71±0,05Myr ago and in the profile of Serra do Rola Moça from 6,08±0,20 Myr ago to 0,43±0,04 Myr ago. The data show that the laterite iron surface began its forming 33Myr ago in Catas Altas region, regarding that from this moment goethite has been dissolving and recrystallizing, then, the more recent ages. Thus, Quadrilátero Ferrífero area was exposed 60Myr ago, this means that the configuration of the relief with the tops was the same 60Myr ago, especially being the Serra do Caraça region. The material dated in Serra do Rola Moça meet the ages listed for the neighboring areas, as Mina do Capão Xavier in Serra da Moeda (about 6 to 8 Myr ago). Finally, in paleosurface analysis altitude levels cannot be associated with former flattening surfaces in a direct way. According to the regional study in Quadrilátero Ferrífero, we can state that independently of the altitude levels, what prevails in the landscape is the Sul-Americana surface and we did not find secure evidence of the Gondwana surface, older / Doutorado / Análise Ambiental e Dinâmica Territorial / Doutora em Geografia

Le gisement nickélifère latéritique de Nouvelle-Calédonie, développé au toit de la Nappe des Péridotites, représente près de 20% des ressources mondiales en nickel. Afin de mieux comprendre la formation de ce gisement, notre étude, portant sur le massif de Koniambo, se singularise par la volonté de ne pas se focaliser uniquement sur la zone minéralisée. L’approche employée a combiné : i) l’analyse de la déformation interne de l’ensemble du massif, ii) la caractérisation isotopique de deux sous-produits supposés de l’altération supergène que ont les veines de quartz et les veines de magnésite, iii) la modélisation 3D du gisement nickélifère, basée sur les données de plus de 6000 forages de subsurface et sur l’étude d’affleurements ponctuels au sein de la zone minéralisée. L’évolution spatiale et temporelle de la déformation associée à la serpentinisation est décrite au travers des ~800 m d’épaisseur structurale du massif de Koniambo. La partie supérieure du massif, très fracturée, préserve la marque d’au moins deux événements précoces de déformation. Le premier est associé au réseau de failles à antigorite et le second au réseau de failles à serpentine polygonale. La semelle serpentineuse, épaisse de ~200 m, est constituée de brèches et mylonites et enregistre un cisaillement tangentiel diffus associé à la serpentine polygonale et à la magnésite. La semelle représente ainsi un niveau de décollement majeur en base de nappe. Entre la semelle et le haut du massif, un niveau intermédiaire est identifié, caractérisé par la présence de zones de cisaillement plurimétriques probablement connectées à la semelle. La caractérisation 3D de la distribution du nickelau sein du niveau saprolitique, à l’échelle du gisement comme à l’échelle de l’affleurement, permetde mettre en évidence l’existence de processus impliquant une redistribution non pas seulement verticale, comme il est classiquement admis, mais aussi latérale, mécanique ou associée à des fluides, à l’origine d’importants enrichissements locaux. L’analyse isotopique des veines de quartz associées au minerai garniéritique met en évidence les conditions d’hydrothermalisme de basse température associées à leur formation. La caractérisation structurale et isotopique (couplage ''isotopes stables'' et ''clumped isotope thermometry'') des veines de magnésite situées dans la semelle serpentineuse permet de documenter leur caractère syn-tectonique et la nature météorique et de basse température du fluide dont elles sont issues. Ceci nous amène à proposer que la tectonique active a pu faciliter l’infiltration de l’eau météorique impliquée dans le processus de latérisation depuis le sommet jusqu’à la base de la nappe. / The New Caledonia nickel laterite ore deposit, developed at the top of the Peridotite Nappe, hosts about 20% of the nickel resources worldwide. In order to better understand the formation of this eposit, our study, focusing on the Koniambo Massif, is not restricted to the ore zone but concerned with the whole peridotite pile. Our approach combined: i) the analysis of the internal deformation of the massif, ii) the isotopic characterization of quartz and magnesite veins which are suspected to represent by-products of the laterization process, iii) the 3D modelling of the lateritenickel ore deposit, based on a dataset of ~6000 subsurface boreholes and the study of some outcrops located into the mineralized area. The spatial and temporal evolution of the deformation associated with serpentinization is described across the ~800 m-thick rock pile of the Koniambo Massif. The upper part of the massif is densely faulted and preserves the record of two early deformation events. The first one is associated with synantigorite faults and the second one with syn-polygonal serpentine faults. The ~200m-thick serpentine sole is composed of breccias and mylonites and records pervasive tangential shearing associated with polygonal serpentine and magnesite. Thus, the serpentine sole represents a major décollement at the base of the nappe. Between the sole and the upper part of the massif, anintermediate structural level is identified, characterized by the presence of plurimetric shear zones that probably merge with the sole.The 3D characterization of the nickel distribution in the saprolite level, at both deposit and outcrop scales, gives evidence for processes implying not only vertical (as commonly assumed) but also lateral nickel redistribution. This lateral transport ismechanical or associated with fluids and leads to significant local enrichments. The isotopic characterization of the quartz veins associated with garnieritic ore shows that they formed under low temperature hydrothermal conditions. The structural and isotopic (coupling “stable isotope” and “clumped isotope thermometry”) characterization of the magnesite veins located at the serpentine sole shows that they are syn-tectonic and derived from low temperature meteoric water. As a result, we propose that active tectonics has enhanced the infiltration of the meteoric waters involved in the laterization process down to the base of the nappe.

Les eaux usées sont très souvent enrichies en phosphates issus des activités anthropiques, leur rejet dans le milieu naturel sans traitement adéquat entraîne une eutrophisation rapide du réseau hydrographique de surface. L’objectif de cette thèse est de caractériser et d’étudier la possibilité de rétention des phosphates des eaux sur des géomatériaux efficaces et disponibles en quantité suffisante en Côte Ivoire. A terme, ce travail permettra de valoriser des matériaux géologiques, sans intérêt minier, en produits aux applications environnementales. A cet effet la latérite le grès et le schiste ont été sélectionnés et préparés par broyage mécanique pour produire des fractions inférieures à 80 µm. Ces rétenteurs ont été analysés par diffraction des rayons-X, microscopie électronique à balayage (MEB) et à transmission (MET), spectroscopie infrarouge (IR). Les analyses texturales ont été conduites par volumétrie d’adsorption du diazote (N2) à 77K. La granularité a été déterminée par diffusion laser et par sédimentation. Les mesures de la capacité d’échange cationique (CEC), ont été effectuées par spectroscopies UV visible et par ICP-AES et ICP-MS. La synthèse de l’ensemble des données minéralogiques montre de forts pourcentages en oxydes et oxyhydroxydes de fer, d’aluminium et de calcium pour ces trois matériaux. Cette composition confère à la fraction fine des surfaces spécifiques de 34 ; 4,7 et 16,5 m2/g respectivement pour la latérite, le grès et le schiste. De plus les charpentes minérales des ces matériaux révèlent la présence de méso et microporosité. Les rétenteurs ont ensuite été évalués dans le traitement en batch d’un effluent synthétique obtenu par dissolution du dihydrogénophosphate de potassium (KH2PO4), dans l’eau distillée. Les doses optimales et les temps d’équilibres ont été déterminés. Les isothermes de rétention ont ensuite été construites à 20, 30 et 40°C. L’affinité des phosphates pour les trois adsorbants est plus importante pour la latérite, ensuite le grès et enfin le schiste. L’adsorption dépend fortement du pH. Les taux de rétention des phosphates sur le grès semblent indépendants de la température. En revanche, ceux de la latérite augmentent dans le sens contraire de la température et l’inverse pour le schiste. Plusieurs modèles cinétiques (pseudo-premier ordre, pseudo-second ordre, Elovich et de diffusion) ont été évalués, de même que les paramètres thermodynamiques. Les réactions d’adsorption sont parfaitement décrites par le modèle de pseudo-second ordre. Les données des équilibres d’adsorption permettent de définir des intervalles où l’adéquation aux modèles de Langmuir et Freundlich semble parfaite. Le mécanisme de rétention proposé suggère l’existence de deux types de sites. L’analyse par infrarouge (DRIFT) des matériaux après adsorption montre une part importante des interactions de type chimique dans la rétention des phosphates sur la latérite et le grès. L’ensemble des résultats obtenus confirme la possibilité d’utiliser la latérite, le grès et le schiste pour déphosphater les eaux. Cependant la latérite présente de plus fortes potentialités par rapport aux autres adsorbants testés / Wastewaters are often loaded in phosphate from human activities. The discharge of such wastewater without adequate treatment leads to rapid eutrophication of water bodies. The main of the present thesis was to characterize and investigate the removal efficiency of phosphate from water by natural geological material available in large amount in Ivory Coast. Ultimately, it has ambition to valorize geological material without mining interest for environmental purposes. For this research, the laterite, sandstone and shale were selected and prepared by mechanical crushing to obtain fine fractions below 80 µm. Detailed study to characterize these three rocks powder was performed, thus several mineralogical and physico-chemical properties were determinated by means of : X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), N2-adsorption/desorption techniques (BET), energy dispersive x-ray spectroscopy (EDX), particle size distribution, cation exchange capacity and chemical analyses by atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS). Data shows high percentages of iron, aluminum and calcium oxides and oxyhydroxides for these three materials. This composition confer to the fine fraction the specific surface of 34; 4.7 et 16.5 m2/g for laterite, sandstone and shale respectively. In addition, the mineral structures of these materials reveal the presence of meso-and microporosity. These materials were then evaluated in the batch treatment of synthetic liquid effluents containing pure KH2PO4. The optimal dosage and equilibrium times were detected. After, isotherms were built at 20, 30 and 40°C. It was shown that phosphate affinity for the three absorbents is more important for laterite, sandstone and shale. The absorption process is strongly depends on pH. Phosphate retention rate on sandstone seem not to depend on temperature, on the other hand, those of laterite increase on the contrary way of the temperature and vice versa for schist. Several kinetic models (pseudo first order, pseudo second order, Elovich and diffusion models) were evaluated as well as thermodynamic parameters. Absorption reactions are perfectly described by the pseudo second order. Absorption equilibrium data allow defining interval where Langmuir and Freundlich model seems perfect. The proposed retention mechanism suggests the existence of two kinds of sites. DRIFTS analyses of adsorbents after adsorption revealed chemical interaction on adsorption process onto laterite and sandstone. This study demonstrated that laterite, sandstone and shale are an effective adsorbent for phosphate removal from aqueous solution. However, laterite shows a strong potentiality compared to the two others adsorbents

Ni-laterites have the potential to become unconventional ore deposits for platinum group elements (PGE). This study was conducted to determine enrichment trends of PGE as a result of the Ni-laterization process. 6 samples were selected by mine workers from the protolith, saprolite, and limonite horizons of the Ni-laterite profile from the Acoje ophiolite block, Luzon, Philippines, and sent to Luleå University of Technology (LTU). 2 samples representing the protolith are described as dunite having undergone serpentinization, 1 sample is a massive chromitite from the saprolite layer of the laterite profile, 1 sample is a massive chromitite from the limonite layer of the laterite profile, and 2 samples are limonitic soils. Total PGE contents of the investigated Acoje samples range from 161-1180 ppb with the highest contents of PGE occurring in the limonite hosted chromitite, and the lowest contents in the saprolite hosted chromitite. C1 chondrite-normalized patterns reveal distinct trends of the PGE in the different sample types: dunite samples have a positive trend from Ir-Pd, the chromitite samples have a negative trend from Ru-Pd with a negative Ir anomaly and the limonite samples have a strong positive trend from Ir-Pd. Rare earth elements (REE) chondrite-normalized patterns of the samples show a negative Ce anomaly in the limonite while the dunite and saprolite-hosted chromitite have negative Eu anomalies. Cr# (Cr/[Al+Cr]) and Mg# (Mg/[Fe2++Mg]) were analyzed using automated mineralogy and produced Cr# values ranging from 0.67 – 0.77 and Mg# values from 0.46 – 0.59.  17 platinum group minerals (PGM) were identified from the Acoje samples: 9 from the dunite, 1 from the saprolite-hosted chromitite, 6 from the limonite-hosted chromitite and 1 from the limonite. Laurite ((Ru,Os)S2) was identified in samples A-02 and A-07 and is the only primary mineral identified. Secondary PGM, thought to have formed due to alteration processes during serpentinization, were identified as alloys composed of: Cu-Pd, Cu-Pt, Pt-Ni-Cu, Pt-Fe, Ir-Ni-(Pt,Fe), and Cu-Pt-Au-(Pd-Ag). PGM are small, measuring consistently <10 µm in diameter. Laurite occurs as inclusions in unfractured chromite. PGM alloys in the dunite samples occur along the boundary of sulfide minerals or within serpentine. PGM identified in the limonite-hosted chromitite occur along interstitial fractures within chromitite or in a Fe-Al oxide matrix within pore spaces.

Rocky plateaus are globally threatened ecosystems and the lateritic plateaus in northern section of the Indian Western Ghats/Sri Lanka Biodiversity Hotspot (NWG) are notable landscape features. The NWG are geologically distinct from and biologically isolated from the other two sections of the Western Ghats. The NWG is known to possess elevated levels of endemic flora their biotic relationships remain poorly understood. We present here the first quantitative multi-taxa comparative study of plateau fauna in the northern Western Ghats. Ants, water beetles and amphibians were selected for the comparison as they use different ecological resources from each other and at various times of year therefore may provide a wider representation of plateau usage. Distribution and endemism were expected to reflect distribution and isolation by plateau and inter-plateau environment related to elevational, latitudinal, climatic and land-use clines. The study explored patterns of amphibian, water beetle, ant and fungal distribution and sampling seasonal pools and terrestrial surfaces of 13 representative plateaus in western Maharashtra, with sites ranging from 67-1179 m and across 2° of (sub) tropical latitude. Distribution of all taxonomic groups was spatially non-random at all levels of organisation and across all spatial scales. At the macroscale assemblages differed significantly with climate related to elevation, latitude but at a local scale land-use and microhabitat availably had an impact. Ants displayed a large seasonal assemblage variation, responding to seed availability. Water beetles the ants (combined survey data) were the best surrogates for all taxa data with amphibians the weakest representatives. Infection by the fungal pathogen, Batrachochytrium dendrobatidis, was extensive but less intense below the escarpment. We report the first records of infection in 13 endangered and data deficient amphibian species in the Western Ghats. The plateaus of western Maharashtra have recently been recognised as fragile and threatened ecosystems most still lack adequate statutory protection. In the absence of peer reviewed comparative data, the importance of individual sites is difficult to demonstrate hampering evidence-based conservation decisions.

This article presents nano composite TiO2.Fe2O3/laterite materials, which were successfully prepared by hydrometallurgical method. The materials were modified using urea as the nitrogen source. The particles size of the materials is from 20-30 nanometers. The obtained materials can not only absorb arsenic compounds but also enhance the ability of converting As (III) or As (V) into Aso, which is removed from solution. Arsenic removal efficiency of these materials is high. Using sunlight in a hydraulic retention time, about 180 minutes, the arsenic value at the inflow was about 10 mg/L but the outflow was negligible. Covering TiO2.Fe2O3 nano on laterite have brought high economical efficiency, on one hand, it saved material and on the other hand, it can be continuously operated without the centrifugal separation of the nano material. / Bài báo này giới thiệu về phương pháp điều chế vật liệu nano TiO2.Fe2O3 biến tính nitơ được phủtrên đá ong bằng phương pháp thủy luyện. Vật liệu nano thu được có kích thước 20-30 nm. Vật liệu thu được không những có khả năng hấp phụ các hợp chất của asen mà còn có khả năng khử As (III) hoặc As (V) thành Asokhi được chiếu sáng. Sử dụng ánh sáng mặt trời chiếu vào hệ thống xử lý trong thời gian 180 phút có thể loại bỏ được gần như hoàn toàn asen ra khỏi nước mặc dù hàm lượng đầu vào là 10 mg/l. Việc phủ vật liệu TiO2.Fe2O3 nano lên đá ong đã mang lại hiệu quả kinh tế cao, một mặt nó tiết kiệm được vật liệu, mặt khác, vật liệu có thể sử dụng một cách liên tục mà không cần phải tách bằng phương pháp ly tâm.