Abstract Orogenic gold deposits from the Reefton goldfield in New Zealand hosted in Ordovician metasediments of the Greenland group have produce 67 tons of gold before 1951. The Blackwater mine in Waiuta account for about 1/3 of the gold production at Reefton prior 1951. The ore system at Blackwater consist of NE trending steeply dipping gold-bearing quartz veins (Birthday reef) occurring in faulted, sheared and folded alternating sequence of sandstone-mudstone metamorphosed to low greenschist facies and hydrothermally altered proximal to distal from the quartz vein. Host rock and ore forming fluids interaction resulted in a systematic change in the mineralogy and geochemistry of the wallrock developing a distinctive footprint of the ore system. The mineral assemblage subsequent to hydrothermal alteration is formed by quartz veining, chlorite, carbonates (minor calcite-dolomite-ankerite-siderite), albite, K-Mica and composite quartz-carbonate veining, carbonates spotting, pyrite, arsenopyrite, chalcopyrite, cobaltite, galena and in a lesser extent ullmannite, gersdorffite, pentlandite, millerite and sphalerite. Mass balance calculation based on geochemical data obtained by ultra-low detection analysis with a detection limit in part per trillion of Au, As and Sb provide new insight in the geochemical footprint of the ore system at Blackwater. A clear zone of roughly 40 meters (20 meters above and below the birthday reef) is enriched in Au, As and Sb up to respectively 6806%, 605% and 891% compared to the un-mineralised protolith. Furthermore, mass changes in K2O and Na2O indicate a consistent decrease in Na and increase in K in the vicinity of the Birthday reef reflecting the replacement of albite by K-mica. This is corroborated by pattern of alkali alteration index Na/Al for albite and 3K/Al for K-Mica showing similar trend. Carbonation and de/-hydration index also exhibits peaks in samples adjacent to the Birthday reef, though carbonation index is also influenced by carbonates content in the protolith or late carbonation that may not related to gold mineralisation. Using the indicators above-mentioned it is possible to define the mineralogical and geochemical “footprint” for the ore system in the host rock allowing to use this footprint as a tool for mineral exploration for orogenic gold deposits similar to Blackwater. Given that the geochemical footprint of orogenic gold deposit such as Blackwater is significantly wider than the economically viable part of the deposit defining the footprint of the ore system offers the potential for vectoring from sub-economic mineralisation towards higher-grade ore that is economically viable.

L'objectif de cette thèse était de modéliser à partir des expériences de percolation-réactive, les processus hydrodynamique et réactionnel qui gouvernent l'altération des ciments de puits. Différentes expériences ont été réalisées dans des conditions représentatives de celles du stockage du CO2. Des échantillons fracturés ont été utilisés pour injecter une saumure enrichie en CO2 à 60°C et 10MPa et à différentes pressions partielles de CO2. Le débit d'injection variait en fonction des propriétés hydrauliques de l'échantillon exposé. L'injection d'une saumure enrichie en CO2 à débit constant à travers une fracture supposée plane a permis d'étudier les modifications des propriétés hydrodynamiques et ces conséquences sur la géochimie et la microstructure du ciment altérée. L'impact dynamique de l'évolution microstructurale a été mis en évidence. Les expériences conduites sur des échantillons présentant de larges ouvertures, réalisées sur une durée de 5 h, ont montré que la perméabilité était maintenue constante le long de l'expérience. Trois couches d'altération se sont développées consécutivement à la dissolution de la portlandite et la décalcification des CSH. L'altération a entrainé la précipitation des carbonates et de la silice amorphe à proximité de la fracture. Dans le cas d'une expérience longue durée appliquant les mêmes conditions que précédemment on a observé que la croissance de la silice amorphe a entrainé la diminution de la perméabilité. Par ailleurs les expériences effectuées sur des échantillons présentant de faibles ouvertures, ont indiqué que la conversion de la portlandite en calcite conduit au colmatage de la fracture. L'évolution des assemblages de phases conduisant à la formation des carbonates et de la silice amorphe ont été modélisés à partir du code géochimique GEMS. Les mécanismes de diffusion et les processus de mise en place des couches d'altération ont été étudiés à partir d'un modèle analytique et d'un modèle de transport réactif à partir du code géochimique PHREEQC. Mots-clés Percolation-réactive, processus hydrodynamique et thermochimique, altération, ciments de puits, stockage du CO2, modélisation. / Title: “Experimental characterization and modelling of the alteration of fractured cement under CO2 storage conditions.”The main purpose of this thesis was to characterize and to model the hydrodynamic and thermochemical processes leading to the alteration of the wellbore cement materials under borehole conditions. Percolation experiments were performed on fractured cement samples under CO2 storage conditions (60°C and 10MPa). Injection flow rate was dictated by the fracture aperture of each sample. CO2 enriched brine was flowed along the fracture aperture, and permeability changes as well as chemical evolution of major cations were continuously acquired during the experiment time. Reaction paths developed by the alteration of the cement were characterized using microtomography and ESEM images. The experiments conducted using samples presenting large fracture apertures during 5h showed that permeability was maintained constant during the experiment time. Three reacted layers were displaying by the alteration of portlandite and CSH. Long term experiment conducted with large initial fracture aperture showed a decrease of the permeability after 15hours of CO2 exposure. Otherwise, experiments performed on samples presenting narrow apertures indicated the conversion of portlandite and CSH to calcite leading to the permeability reduction and the fracture clogging. Assemblages of phases and chemical changes were modelled using GEMS-PSI speciation code. We studied also using a coupled transport-reactive model the conditions leading to the cement alteration and the formation of associated layers.Key words: Hydrodynamic and thermochemical processes, alteration, wellbore cement, CO2 storage, percolation experiments, numerical modeling.

English abstract Hydrothermal systems related to highly evolved granitic magmas host diverse mineralization styles and provide an important source of economic metals. This master thesis concentrates on description and interpretation of geological structure, petrographic and textural variability, alteration zoning and calculation of time-integrated fluid fluxes recorded in highly evolved granites and tin-mineralized greisens of the Horní Blatná massif in the Western Krušné hory pluton. The massif is a composite intrusion, which consists of a large number of intrusive units emplaced during two stages. The first stage is represented by sparsely porphyritic fine-grained low-lithian annite granites that can be correlated with marginal granites (G2) of the Fichtelgebirge (Smrčiny) batholith or with intermediate granites (Walfischkopf type) of the Western Krušné hory (Erzgebirge) pluton. Intrusive batches of the second stage progressively evolve from medium- to coarse-grained serial high-lithian annite and zinnwaldite granites with topaz and rare tourmaline towards aphyric fine-grained zinnwaldite (or trilithionite) granites. This suite corresponds to the EIB2 and EIB3 facies of the younger intrusive complex in the Western Krušné hory (Erzgebirge) pluton and it can be compared to the G3 Waldstein and G4 units in...

Student Number : 9210081T - MSc dissertation - School of Geosciences - Faculty of Science / The occurrence of large, massive iron oxide deposits throughout the Bushveld Complex, South Africa, and its associated roof-rocks is well known. The style of mineralisation and the associated alteration exhibits many characteristics of iron oxide-copper-gold (IOCG) type deposits. The contained mineralisation is dominated by iron oxide and fluorite and is accompanied by a diverse polymetallic association, with anomalous fluorite, copper, gold, barite, uranium and LREE. The Ruigtepoort orebody, located in the western Bushveld Complex, is such an example and is surrounded by some 20 smaller occurrences in the upper stratigraphic portions of the Bushveld Complex, all displaying strong structural control. These IOCG bodies occur as narrow veins, hydrothermal breccias, subhorizontal sheets, or as pipe-like intrusions usually utilising pre-existing structures. Set in red Nebo granite, the mineralised core consists of severely chloritised rock that is haloed by progressively less-altered granite. The alteration passes from the chlorite core to more hematite-phyllosilicate-dominated alteration, to sericite-illite-dominated alteration; followed by the relatively fresh country granite. These alteration haloes dissipate rapidly away from the body over only a few metres. Sodic-calcic alteration described in other IOCG is not locally observed. Extensive zones of barren feldspar-destructive alteration exist, including K-metasomatism, sericitisation and silicification. Multiple alteration episodes appear to have occurred, resulting in extensive overprinting and a very complex paragenesis. The primary mineral assemblage consists of Fe-chlorite, fluorite, quartz, hematite, and specularite, with accessory pyrite and chalcopyrite. Multiple generations of hematite, quartz, fluorite and chlorite are also observed. At other localities, the assemblage is dominated by magnetite-actinolite-britholite. Significantly enriched concentrations of Au (2 g/t), Cu (0,45 wt%), Ba, Y and LREE are encountered in the small, mineralised core. A fluid mixing model is proposed characterised by an initial highly-saline, sulphur-poor magmatic fluid which mixed with a lower temperature oxidised, surficial fluid. Structure was probably a significant factor in determining the initial distribution of hydrothermal centres and the overall morphology of the entire system. Subsequently, continuous brecciation, alteration, mineral precipitation and fault activity helped develop the hydrothermal centres into a complex array of variably mineralised, lenticular, pipe-like and irregularly shaped breccia bodies.

O pluton Desemborque, de idade neoproterozóica, é parte do denominado Maciço Guaraú, aflorante na região sul do de estado de São Paulo e está inserido no contexto geológico da Província Graciosa. É composto por biotita sienogranito a álcali feldspato granito, metaluminosos a moderadamente peraluminosos, que apresentam assinaturas geoquímicas típicas de granitos de tipo-A, como conteúdos relativamente altos de álcalis, além de concentrações significativas de elementos LIL e HFS. Apresentam alteração hidrotermal em graus variáveis, claramente evidenciados tanto pelas texturas quanto pelas composições registradas em seus minerais essências e acessórios, destacando-se a albitização e a greisenização. Os feldspatos alcalinos são pertitas ou mesopertitas zonadas. Algumas composições químicas integradas exibem valores entre \'Or IND 53-58\'\'Ab4 IND 42-46\' (núcleos) e \'Or IND 68-71\'\'Ab4 IND 29-32\' (bordas). A maior parte das composições obtidas dos plagioclásios correspondem a albita, com poucos cristais classificados como oligoclásio sódico. Albita pura e pós magmática ocorre intersticialmente aos feldpastos ou como microvenulações. São encontradas duas fases micáceas estritamente magmáticas: biotitas castanhas (annita) e esverdeadas (protolitionita-siderofilita). Associadas ao processo de greisenização que substitui biotitas e feldspatos encontram-se micas verdes claras a incolores anteriormente definidas como zinnwaldita, que aqui são reclassificadas como fengita. Minerais acessórios foram examinados e estudados com imageamento BSE e análises quantitativas por EDS. Os mais comuns são: zircão, allanita, torita, cassiterita, galena, hematita, ilmenita, monazita, , columbita e fluoretos de terras raras. Entre eles, os primários (e.g zircão, allanita e cassiterita) exibem microestruturas ou transformações químicas relacionadas à processos tardios de alteração hidrotermal, enquanto outros foram desenvolvidos durante este processo, como torita, xenotímia e fluoretos de elementos terras raras e de ítrio. Os granitos típicos do Desemborque são bastante evoluídos e relativamente homogêneos com um estreito intervalo composicional, como \'SiO IND 2\' (76-77% em peso), álcalis (\'Na IND 2\'O até 4,1 % e \'K IND 2 O\' até 4,5 %), \'Al IND 2\'\'O IND 3\' (ca. 12%) e \'Fe IND 2\'\'O IND 3\' (~1%). Outros óxidos comuns contribuem com concentrações bem baixas como CaO e MgO. As rochas hidrotermais exibem relativo enriquecimento em\' Fe IND 2\'\'O IND 3\' (5,27 % em peso para o greisen) além de F, Rb, Sn e Li e empobrecimento em \'Na IND 2\'O (0,26%). As temperaturas de saturação em Zr fornecem valores entre 750-860º C, e que pode ser extrapolada como uma aproximação para a temperatura do líquido do sistema magmático. Dados geológicos, petrográficos e normativos indicam colocação em níveis rasos, com pressões não muito maiores que 1 kbar. Suas características remetem a cristalização em fugacidades de oxigênio relativamente baixas, uma exceção entre a associação aluminosa da Província Graciosa. As determinações de idades isotópicas U/Pb são problemáticas devido aos aspectos texturais dos cristais de zircão e componentes herdados. Após o tratamento dos dados chegou-se a uma idade estatisticamente mais confiável (590 ± 12 Ma) e em parte, coerente com a literatura. / The Neoproterozoic Desemborque Pluton is a part of the so-called Guaraú Granitic Massif, which crops out in the southern region of the state of São Paulo and is inserted in the geological context of Graciosa Province. It is made of metaluminous to moderately peraluminous biotite sienogranites and alkali-feldspar granites which present geochemichal signatures most typical of A-type granites, as for the relatively high total alkali, LILE and HFSE contents. It shows hydrothermal alteration imprinted to a variable grade, as clearly evidenced by textural as well as compositional features registered in its essential and accessory minerals, standing out albitization and greisenization. Alkali-fedspars are zoned perthite or meso-phertite. Some integrated chemical compositions gave values between \'Or IND 53-58\'\'Ab IND 42-46\' (crystal cores) and \'Or IND 68-71\'\'Ab4 IND 29-32\' (crystal rims). Most of the obtained plagioclase compositions correspond to albite, a minor number being classified as sodic oligoclase. Post-magmatic, almost pure albite, occurs intersticialy to feldspars or as minor veinlets. Two main types of magmatic micas were recognized: red-brown annitic biotite and a green protolitionite-siderofilite. Light green to colorless micas associated with the greisenization process that replaces biotite and feldspars previously called a zinwaldite-like mica were reclassified to fengite type. Accessory minerals were examined and studied with BSE imaging and EDS qualitative analysis. The most common are zircon, allanite, thorite, cassiterite, galena, hematite, ilmenite, monazite, xenotime, columbite, fluorite and REE fluorides. Among them, the primary ones (e.g., zircon, allanite, cassiterite) show micro-structural or chemical transformations related to the hydrothermal alteration, while others were developed during such process, as for thorite, xenotime, and the REE and Y fluorides. The main Desemborque granites are highly evolved and relatively homogenous, with a narrow chemical compositional range as for \'SiO IND 2\' (76-77% wt %), alkalis (\'Na IND 2O\' up to 4.1 % e \'K IND 2O\' up to 4.5 %), \'Al IND 2\'\'O IND 3\' (ca. 12%) e \'Fe IND 2\'\'O IND 3\' (~1%). Other common oxides contribute with very low concentrations like CaO and MgO. Hydrothermal rocks show relatively \'Fe IND 2\'\'O IND 3\'enrichment (up to 5.2 wt.% in the greisen sample) in addition F, Rb, Sn e Li and depletion in \'Na IND 2 O\' (down to 0.26 wt.%) Zircon saturation temperature gives values in the 750-800º C range, which approaches well the liquidus of such magmatic system. Geological, petrographic, and normative data indicate relative shallow emplacement levels, at pressures no greater than ca. 1 Kbar, and crystallization under a relatively low \'f IND O2\' , a exception in the aluminous association of the Graciosa Province. U/Pb isotopic age determinations are problematic due textural aspects of zircon cristals and inherited components. After the treatment of the data was reached a statistically more confiable age (590 ± 12 My) and, in part, coherent with the literature.

O vitrocerâmico formado a partir de cristais de anortita, como fase principal (CaAl2Si2O8), foi manufaturado para avaliações iniciais quanto à transformação de fase e de biocompatibilidade. Através da análise do estudo dilatométrico, verificou-se as faixas de temperaturas, onde o material sofre alterações microestruturais, através do processo de sinterização. Juntamente com essa análise, seguindo o mesmo ciclo de sinterização, através do tratamento térmico sob vácuo, com microscopia acoplada, registrou-se as imagens obtidas no exato momento em que as transformações microestruturais do material aconteceram. Para a avaliação de biocompatibilidade foi utilizado ensaios in vitro e in vivo, preconizados pela Internacional Standards Organization (ISO) 10993-5 e 10993-6, sendo utilizado (testes in vitro) a linhagem celular McCoy. Esse método, permitiu concluir a não citotoxicidade do vitrocerâmico, mesmo em altas concentrações do extrato e/ou material diretamente com as células não houve lise celular. Esses resultados obtidos viabilizaram os experimentos in vivo, que compreendeu a análise da toxicidade sistêmica a implantação do material em teste, diretamente ao tecido ósseo de cobaias (Rattus norvegicus albinus), durante 30 dias. A histologia da região do implante demonstrou caráter de biocompatibilidade in vivo do vitrocerâmico com cristais de anortita. Os resultados obtidos nesse estudo, corroboram para o direcionamento deste vitrocerâmico, em outros aspectos de avaliação, no âmbito de engenharia e sugere possível utilização do mesmo como biomaterial. / The vitroceramic formed starting from anortithe crystals as main phase (CaAl2Si2O8), it was manufactured for initial evaluations as for the phase transformation and biocompatibility. The analysis of the dilatometric study, it was verified the strips of temperatures, where the material suffers microstructures alterations, through the sinterization process. Together with that analysis, following the same sinterization cycle, through the thermal treatment under vacuum, with coupled microscopy, it registered images obtained in the exact moment in that the microstructure transformations of the material. For the biocompatibility evaluation it was used in vitro and in vivo tests, extolled by Standard International Organization (ISO) 10993-5 and 10993-6, being used (tests in vitro) the cellular lineage McCoy. This methods, allowed to conclude the non citotoxicity of the anorthite, even in high concentrations of the extract and/or material directly with the cells there was not cellular lise. Those obtained results made possible the experiments alive in, that it understood the analysis of the systemic toxicity and the implantation of the material in test, directly to the bone of animals (Rattus norvegicus albinus), for 30 days. The histological area of the implant, demonstrated character in vivo biocompatibility of the vitroceramic with anorthite crystals. The results obtained in that study, they corroborate for the direction of this vitrocerâmic, in other evaluation aspects, in the engineering extent and is suggests possible use of the same as biomaterial.

A hanseníase é uma das causas mais comuns de neuropatia periférica não traumática no mundo. O estudo propõe um método eletrônico não invasivo de avaliação da sensibilidade em paciente com hanseníase, comparando-os aos monofilamentos Semmes-Weinstein (convencional). Foram avaliados 30 pacientes do Ambulatório de Dermatologia do HCFMRP-USP pelos métodos eletrônico e convencional, consecutivamente. Cada paciente foi avaliado nos pontos das mãos e dos pés preconizados pelo Ministério da Saúde para avaliação de sensibilidade. Cada ponto foi mensurado pelo estesiômetro eletrônico 5 vezes, e posteriormente calculada a média das 3 medidas mais próximas. Para avaliar a variabilidade entre essas medidas, calculou-se o coeficiente de correlação intraclasse (ICC) cujo resultado foi aproximadamente 1 em todos os pontos, demonstrando repetibilidade dos mesmos. Através do coeficiente Kappa observou-se concordância entre os métodos estudados quanto às categorias (sensibilidade alterada e não-alterada), havendo concordância em mais de 75% e 63% nos pontos das mãos e dos pés, respectivamente. A porcentagem da concordância entre os 2 métodos observada nos 7 pontos da mão direita foi em média (somatório do percentual de valores concordantes de cada ponto divididos pelo número de pontos) 77,14% dos casos. Na mão esquerda a média de concordância foi de 75,71%. Nos 10 pontos do pé direito a média de concordância na avaliação de sensibilidade alterada e não alterada foi de 74,33%. Dos casos discordantes houve predominância (90,91% em média) de detecção de alteração de sensibilidade pelo estesiômetro eletrônico sem que os monofilamentos as detectasse. Nos 10 pontos do pé esquerdo, a concordância na avaliação foi em média 63,66% . Dos casos discordantes houve predominância (84,25% em média) de detecção de alteração de sensibilidade pelo estesiômetro eletrônico sem que os monofilamentos as detectasse, afinal, para os mesmos casos eles registraram sensibilidade não-alterada, portanto, normal. Apesar da concordância entre os pacientes com sensibilidades alterada e não-alterada pelo método Kappa, ao tratar-se de valores absolutos, os métodos foram diferentes. Essas diferenças entre seus valores podem ser atribuídas às particularidades de cada método, tais como espessura da superfície de contato a ser avaliada e o tipo de variável envolvida. Não se pode afirmar qual dos métodos é mais eficaz na detecção da alteração de sensibilidade do paciente com hanseníase, porém acredita-se nos resultados obtidos pelo estesiômetro eletrônico devido à metodologia criteriosa utilizada na sua aplicação e por ser uma variável contínua. Assim, o estesiômetro eletrônico mostrou ser um método quantitativo e de fácil aplicação clínica, capaz de avaliar as alterações de sensibilidade nos pacientes com hanseníase tanto no diagnóstico quanto no seu seguimento. / Leprosy disease is one of the most common causes of non traumatic peripheral neuropathy in the world. This study proposes a non invasive measurement with an electronic method for the leprosy patients\' evaluation, comparing them to Semmes- Weinstein monofilaments (the conventional one). Thirty patients of dermatology outpatient clinic of HCFMRP-USP were evaluated by the electronic and conventional methods consecutively. Each patient was evaluated on their hands and feet points that were standardized by brazilian Ministry of Health for sensitivity evaluation. Each point was measured by the electronic esthesiometer 5 times and after that it was calculated the mean of the 3 nearest ones measures. To evaluate the variability between these measures it was calculated the intraclass correlation coefficient (ICC). The result was aproximately 1 in all points, what demonstrated repeatability of them. Through Kappa coefficient it was observed agreement between the studied methods according to their categories (alterated and non alterated sensitivity) and there was agreement in more than 75% and 63% on the hands and feet points respectively. The addition of the percentage agreement values in each point was divided by the numbers of points resulting the percentage mean. The mean of agreement between the 2 methods on the 7 points of the right hand was 77.14%. On the left hand the mean of agreement was 75.71%. On all 10 points of the right foot the mean agreement on the alterated and non alterated sensitivity evaluation was 74.33%. There was predominance of 90.91% at mean on the detection of alterated sensitivity by the electronic esthesiometer with no detection by the monofilaments on the disagreement cases. On the left foot the agreement on the evaluation was 63.66% at mean. On the disagreement cases there was predominance of 84.25% at mean of the detection of alterated sensitivity by the electronic esthesiometer with no detection by the monofilaments, finally, for the same cases the last one registred non alterated sensitivity, therefore, normal. Besides the agreement between the patients with alterated and non alterated sensitivity through Kappa method, when the absolute values were observed, the methods were different. These differences between their values could be because of each method characteristics, such as the contact area thickness and the kind of variable involved. It is not possible to state which method is more effective on the detection of the sensitivity alteration on leprosy patients. However the results obtained by the electronic estesiometer seems to be reliable because of the strict methology used on its application. Than, the electronic estesiometer showed to be a method with an easy application, capable to evaluate the sensitivity alterations on leprosy patients.

O saprolito é um corpo geológico constituído pela mistura de minerais primários e secundários resultantes do intemperismo físico e químico, o qual mantém vestígios da estrutura original da rocha. Difere do solo pela evidente filiação litogenética e insignificante atividade biológica. Apesar das definições, no entanto, o limite e a distinção entre solo e saprolito nem sempre são claros, devido a continuidade entre estes corpos em termos de processos hidrológicos e geoquímicos, bem como de suas composições físicas e mineralógicas, o que gera grande confusão nas descrições morfológicas e na organização de informações. Devido ao caráter multidisciplinar das ciências envolvidas no estudo do saprolito e a dedicação parcial de todas elas, há uma grande carência de padronização de termos e procedimentos para sua caracterização e análise. O objetivo geral desta tese é a caracterização de saprolitos desenvolvidos a partir de variadas litologias, no intuito da elaboração de procedimentos para a descrição, classificação e análise de saprolitos. Especificamente objetivou-se avaliar detalhadamente os padrões de alteração física, mineralógica e geoquímica em materiais, influenciados por atributos litológicos relativos a composição mineralo-química e estrutural do material parental. Para tanto foram descritos e amostrados 15 perfis de alteração; compostos por solo, saprolito e rocha, derivados de rochas sedimentares e metamórficas na região Sudeste do Brasil, nos estados de São Paulo e Minas Gerais. As descrições demonstraram que os corpos saprolíticos avaliados podem ser agrupados em quatro tipos morfológicos principais, sendo propostas as seguintes categorias estruturais: contínua, fraturada, fragmentada e terrosa. Dentre todos saprolitos avaliados, aqueles derivados de rochas metamórficas apresentaram maior complexidade morfológica. Deste modo, 9 perfis filiados a xistos e gnaisses foram submetidos a análises físicas, geoquímicas e mineralógicas para avaliação dos processos de alteração e desenvolvimento de sistema de classificação. A composição mineralógica de solos e saprolitos se mostrou semelhante, entretanto, ocorreram dissimilaridades geoquímicas entre estes corpos. Atributos físicos como densidade e porosidade total não demonstraram diferenças significativas entre solo e saprolito, entretanto, ao se considerar isoladamente amostras de saprolito, houve correlação positiva entre a perda de massa e a porosidade total, tornando este último atributo útil `a proposta de classificação de saprolitos. / The saprolite is a geological body constituted by the mixture of primary and secondary minerals resulting of physical and chemical weathering, which retains traces of the original rock structure. It differs from the soil by the evident litogenetic affiliation and insignificant biological activity. Although the definitions, however, the limit and the distinction between soil and saprolite are not always clear, because the continuity between these bodies in terms of hydrological and geochemical processes, as well as their physical and mineralogical compositions, which creates great confusion in morphological descriptions and information network. Due to the multidisciplinary nature of the sciences involved and the partial dedication of all of them in the saprolite investigations, there is a great lack of standardization of terms and procedures for characterization and analysis. The overall objective of this thesis is the characterization of saprolite developed from various lithologies in order to draw up procedures for the description, classification and saprolite analysis. Specifically aimed to evaluate in detail the patterns of physical, mineralogical and geochemical changes in some materials influenced by lithological attributes how the mineralogical and chemical composition, as well as the structure of parental material. For this were described and sampled 15 weathering profiles, composed of soil, saprolite and rock derived from sedimentary and metamorphic rocks in southeastern Brazil, in the states of São Paulo and Minas Gerais. The descriptions shown that saprolite evaluated can be grouped into four main morphological types, proposed the following structural categories: continuous, fractured, fragmented and earthy. Among all evaluated saprolite, those derived from metamorphic rocks showed higher morphological complexity. Thus, 9 affiliated profiles schists and gneisses to have been subjected to physical, geochemical and mineralogical analyzes to evaluate the change processes and to developing the classification system of saprolites. The mineralogical composition of soils and saprolite was similar, however, there were dissimilarities regard geochemical attributes between this bodies. Physical properties such as density and porosity showed no significant differences between soil and saprolite, however, when considered in isolation saprolite samples, there was a positive correlation between weight loss and total porosity, making this last attribute able to integrate the proposed saprolite classification.

Ce travail de thèse s’intéresse aux interactions entre la solution et la pellicule d’altération, appelée gel, qui se forme lors de la lixiviation des verres borosilicatés d’intérêt nucléaire, et plus spécifiquement dans ce travail, sur le verre à six oxydes ISG. Afin de mieux comprendre les mécanismes de formation du gel, ainsi que ses propriétés de passivation, une étude combinant analyses expérimentales et simulations de dynamique moléculaire (DM) est réalisée.Dans un premier temps, l’étude se focalise sur la structure du verre sain dans le but de mieux appréhender les processus de lixiviation. Pour ce faire, des analyses par spectroscopie RMN sont réalisées. Les résultats sont comparés à ceux obtenus par DM afin de valider la simulation. Cette dernière permet alors une exploration complète de l’ordre à courte et moyenne distances. Elle montre en outre une distribution homogène des formateurs de réseau et l’absence de zones enrichies en bore. Ce dernier, que l’on sait fortement soluble, a tendance à fragmenter le réseau silicaté, affectant de ce fait sa réactivité.Les processus de formation du gel sont ensuite étudiés expérimentalement, dans des conditions favorisant la passivation (90 °C, pH 7, solution saturée en silice). Nous mettons en évidence un fort effet des éléments exogènes en solution, notamment les alcalins faiblement hydratés tels que le potassium et le césium. Ces derniers entrainent ainsi une chute marquée de l’altération du verre. Afin de comprendre cet effet, les gels formés en présence de différents alcalins sont caractérisés. Les analyses montrent un départ congruent du bore et du sodium, et une incorporation du potassium et du césium de la solution qui prennent le rôle de compensateur de charge des unités [AlO4]- assuré par le calcium dans les gels formés en milieux sans alcalin ou contenant des alcalins fortement hydraté comme le lithium ou le sodium. Les différents gels présentent des degrés d’hydratation variés, en accord avec les résultats de simulation de DM de la diffusion de l’eau dans une silice nanoporeuse en milieu alcalin. Ces simulations montrent que la combinaison d’effets stériques (taille des alcalins) et physico-chimiques (énergie d’hydratation) entraine une diminution de la quantité d’eau dans les porosités contenant des ions potassium ou césium.Par ailleurs, les différents gels obtenus dans les conditions d’altération précitées sont fortement polymérisés, indiquant une réorganisation du réseau silicaté à la suite du départ des éléments facilement hydrolysables comme le bore. Cette réorganisation a lieu sans hydrolyse complète des tétraèdres de silicium, ce qui invalide dans ce cas le modèle de formation des gels par dissolution congruente/précipitation. La spéciation de l’eau au sein du gel, obtenue en combinant ATG et RMN du proton, permet de plus de déterminer quantitativement la répartition des atomes d’oxygène au sein du gel (atomes d’oxygène pontants, non pontants ou H2O).Ces données sont alors utilisées pour l’interprétation d’expériences de traçage en milieu enrichi en eau marquée en 18O d’échantillons pré-altérés. Ces expériences, menées à différentes températures, mettent en évidence pour la première fois une réorganisation continue du réseau du gel, avec une diminution au cours du temps de l’accessibilité des espèces mobiles (H2O et hydroxyles) au verre sain du fait de la maturation de la porosité au sein du gel. Nous déterminons différentes diffusivités pour l’eau en fonction de la topologie du gel et proposons l’hypothèse que cette atténuation progressive de la réactivité du réseau soit à l’origine du caractère passivant du gel. / This work aims at understanding water interactions with the altered layer, called gel, formed during borosilicate nuclear glass corrosion. Specifically, we focus on the corrosion of the six oxides ISG. To better understand gel formation mechanisms, as well as gel passivating properties, experimental studies are combined to molecular dynamics simulations.First, this study focuses on the characterization of the pristine glass structure. Experimental analysis (NMR) provides some information to validate the simulated structure. As a result, an improved understanding of the pristine glass short- and medium-range orders is obtained. We also observe that network formers are homogeneously distributed, with no area enriched in boron for instance. Boron is known to be highly soluble, and tends to divide the silicate network, which would affect its reactivity.The gel formation is then studied experimentally in conditions favoring the passivating effect of the glass (90 °C, pH 7, silica-saturated solution). A strong effect of exogenous elements in solution, particularly weakly hydrated alkalis such as potassium and cesium, is observed, with a notable decrease of glass corrosion. To better understand this effect, all gels are characterized. A congruent release of boron and sodium is observed, while potassium and cesium are incorporated. They then act as charge compensator for [AlO4]- units. Calcium usually plays this role in gels formed in solutions with no alkali or containing strongly hydrated alkali such as lithium and sodium. The hydration degree differs for the various gels present, as confirmed by MD simulation of water diffusion in nanoporous amorphous silica in presence of alkali. These simulations highlight a combined impact of sterical effects (alkali size) and physicochemical effects (hydration energy) leading to a decrease of water quantity in the nanopores containing potassium and cesium.Moreover, all the gels formed in the above mentioned leaching conditions are highly polymerized, which indicates a reorganization of the network following the leaching of hydrolysable species such as boron. This reorganization happens without complete hydrolysis of silicon atoms, which invalidate the congruent dissolution/precipitation model in this case. Water speciation inside the gel is determined combining TGA and NMR, giving access to quantitative oxygen repartition in the gel (bridging oxygen, non-bridging oxygen or H2O).This data are then used for the interpretation of tracing experiments carried out in H218O rich solution on prealtered samples. The results demonstrate for the first time that the network reorganizes continuously over time, with a decrease of mobile species (H2O and hydroxyls) accessibility due to the maturation of the porosity within the gel. We determine various water diffusivities as a function of the gel topology and propose the hypothesis that this decreasing reactivity of the network is the source of the passivating nature of the gel.

A hemocromatose é uma desordem caracterizada por armazenamento alterado de ferro em órgãos vitais. A hemocromatose hereditária pode ser causada por mutações nos genes HFE, SLC40A1, HAMP, HJV e TfR2. A forma adquirida da doença pode ser ocasionada por sobrecarga de ferro, alcoolismo, infecção pelo vírus da hepatite C, anemias hemolíticas e doença hepática crônica. O objetivo deste estudo foi descrever as variantes do gene SLC401 em uma série de casos de pacientes em seguimento no ambulatório de Hematologia do Hospital das Clínicas da FMUSP com hemocromatose hereditária e adquirida e verificar se estas variantes poderiam estar associadas a um pior quadro de hemocromatose. No período de 2008 a 2011 foram coletadas 54 amostras de pacientes com diagnóstico prévio de hemocromatose, acompanhados no ambulatório de anemias do Hospital das Clínicas da Faculdade de Medicina da Universidade de São Paulo. Os pacientes foram separados, de acordo com a suspeita clínica, em dois grupos: 38 pacientes com Hemocromatose Hereditária e 16 pacientes com Hemocromatose Adquirida. O DNA foi extraído de sangue periférico pelo kit Qiamp Blood, e as amplificações dos exomas descrito por Wakusawa (2005). As reações de sequenciamento foram realizadas no aparelho AB 3130 e as sequências do gene editadas, alinhadas no programa Sequencer e comparadas com GenBank. Os pacientes com hemocromatose hereditária e adquirida (secundária) apresentaram uma frequência acima de 45% entre a faixa etária de 40 a 60 anos, mostrando uma sobrecarga de ferro mais tardia. O gênero masculino apresentou maior frequência em ambos os grupos (superior a 60%), já em relação à etnia/cor da pele, mais de 80% eram brancos. No diagnóstico laboratorial de ferritina, ferro, CTLF e IST dos pacientes com hemocromatose hereditária e adquirida (secundária) mostra que não houve diferenças significativas. As mutações no gene HFE nos pacientes com hemocromatose hereditária foram C282Y homozigose (21%) e na adquirida (secundária) H63D heterozigose (25%). Entre as mutações do gene HFE, não houve diferença estatística significativa nos grupos. A mutação foi identificada no éxon 3 do gene SLC40A1, no códon 80, descrita p.I80L (c.586C>A). No éxon 4 do gene SLC40A1 foram identificados 3 polimorfismos com a substituição de um nucleotídeo nas posições: c. A630G (190437579), c.648A>G (190437597), c.738Y>C (190437688). Já no éxon 6 foram identificados dois polimorfismos c.1014C>T (190430229) e c.1014Y>T (190430229). As mutações encontradas no gene HFE e SLC40A1 estão associadas com a sobrecarga férrica caracterizando a hemocromatose hereditária. Os polimorfismos encontrados no gene SLC40A1 foram identificados nos pacientes com hemocromatose hereditária e adquirida (secundária) numa frequência de 50%, semelhante aos doadores de sangue, sugerindo que este polimorfismo provavelmente não contribui para o desenvolvimento da doença. / Hemochromatosis is a disorder characterized by altered storage iron in vital organs. Hereditary hemochromatosis can be caused by mutations in the HFE gene, SLC40A1, HAMP, and HVJ TFR2. The acquired form of the disease can be caused by iron overload, alcoholism, infection by the hepatitis C virus, hemolytic anemias and chronic liver disease. The objective of this study was to describe variants of the SLC401 gene in a number of cases of patients being followed at hematology clinic Hospital das Clínicas FMUSP with hereditary hemochromatosis and acquired and verify that these variants could be associated with a worse hemochromatosis frame. In the period 2008 to 2011 were collected 54 samples from patients previously diagnosed with hemochromatosis, anemia accompanied the clinic of the Hospital das Clinicas, Faculdade de Medicina, Universidade de Sao Paulo. The patients were divided, according to clinical suspicion, into two groups: 38 patients with Hereditary Hemochromatosis and 16 patients with Acquired Hemochromatosis. The DNA was extracted from peripheral blood by Qiamp Blood Kit, and amplifications of exomas described by Wakusawa (2005). The sequencing reactions were performed in AB 3130 apparatus and the sequences of the gene edited, aligned in Sequencer program and compared with GenBank. Patients with hereditary hemochromatosis and acquired (secondary) had a frequency above 45% between the age group 40-60 years showing a later iron overload. The males showed higher frequency in both groups (over 60%), as compared to ethnicity / skin color, over 80% were white. In the laboratory diagnosis of ferritin, iron, TIBC and STI patients with hereditary hemochromatosis and acquired (secondary) shows no significant differences. Mutations in the HFE gene in patients with hereditary hemochromatosis C282Y homozygosity were (21%) and acquired (secondary) H63D heterozygosity (25%). Between HFE mutations, there was no statistically significant difference in the groups. The mutation was identified in exon 3 of the SLC40A1 gene at codon 80, described p.I80L (c.586C> A). In exon 4 of the SLC40A1 gene were identified polymorphisms 3 with substitution of a nucleotide in position: c. A630G (190,437,579), c.648A> L (190,437,597), c.738Y> C (190 437 688). Already in exon 6 were identified two polymorphisms c.1014C> T (190 430 229) and c.1014Y> T (190 430 229). The mutations found in the HFE gene and SLC40A1 are associated with iron overload characterizing hereditary hemochromatosis. The polymorphisms found in the SLC40A1 gene have been identified in patients with hereditary hemochromatosis and acquired (secondary) at a frequency of 50%, similar to blood donors, suggesting that this polymorphism will probably not contribute to the development of the disease.