Osteoporosis is a systemic bone disease with an increasing prevalence in the elderly population. There is conflicting opinion about whether osteoporosis affects the alveolar bone of the jaws and whether it poses a risk to the osseointegration of dental implants. The aim of the present study was to evaluate the effects of systemic glucocorticoid administration on the jaw bone density of minipigs. Thirty-seven adult female minipigs were randomly divided into two groups. Quantitative computed tomography (QCT) was used to assess bone mineral density BMD of the lumbar spine as well as the mandible and maxilla, and blood was drawn. One group of minipigs initially received 1.0 mg prednisolone per kg body weight daily for 2 months. The dose was tapered to 0.5 mg per kg body weight per day thereafter. The animals in the other group served as controls and received placebo. QCT and blood analysis were repeated after 6 and 9 months. BMD was compared between the two groups by measuring Hounsfield units, and serum levels of several bone metabolic markers were also assessed. A decrease in BMD was observed in the jaws from baseline to 9 months. This was more pronounced in the prednisolone group. Statistically significant differences were reached for the mandible (p < 0.001) and the maxilla (p < 0.001). The administration of glucocorticoids reduced the BMD in the jaws of minipigs. The described model shows promise in the evaluation of osseointegration of dental implants in bone that is compromised by osteoporosis.

La culture cellulaire traditionnelle en deux dimensions (2D) ne peut pas reproduire les propriétés des tissus observées dans des organes en trois dimensions (3D). Ces tissus, en particulier les tissus de soutien comme l'os, sont soumis à des contraintes mécaniques, facteurs majeurs de régulation des interactions cellulaires et cellules/matrices. Il y a donc un intérêt croissant pour les modèles 3D, afin de mieux comprendre les différents aspects du fonctionnement cellulaire et du remodelage osseux, dans des systèmes de moindre complexité que les modèles in vivo. Nous nous sommes intéressés ici aux cellules ostéoblastiques et à une de leur protéine matricielle, la sialoprotéine osseuse (BSP). La BSP appartient à la famille des "small integrin-binding ligand N-linked glycoproteins" (SIBLING), impliquées dans le développement, le remodelage et la minéralisation de l’os, et répondant rapidement à la contrainte mécanique. Notre objectif était d’analyser l’impact de cette protéine sur la différenciation ostéoblastique et l’ostéogénèse in vitro à partir de cellules de calvaria de souris présentant une extinction génique de la BSP (BSP-/-) cultivées en 2D et en 3D. Nous avons montré que les cellules BSP-/- présentaient un défaut de formation osseuse et de minéralisation qui est dépendant de la densité cellulaire. Puis nous avons développé et validé un bioréacteur perfusé et stimulable mécaniquement via le système ZetOsTM. Les premiers résultats obtenus avec cet outil contrôlé montrent que l’environnement 3D améliore la différenciation des cellules BSP-/-. Ces travaux restent à développer, notamment pour analyser l’effet des contraintes mécaniques sur ces cellules / Traditional (2D) cell culture cannot reproduce the tissue properties observed in 3 dimensional organs (3D). Weight-bearing organs such as bone are subjected to mechanical stresses, which are major regulating factors for cell and cell/matrix interactions. There is thus a growing interest in 3D culture models, in order to better understand the different aspects of cell function and bone remodeling in systems less complex than in vivo models. We are interested here in the osteoblastic cells and in one of their matrix proteins, the bone sialoprotein (BSP). BSP belongs to the family of the "small integrin -binding ligand N -linked glycoproteins" (SIBLING), involved in the development, remodeling and mineralization of bone, and responding quickly to mechanical stress. Our goal in this work was to analyze the impact of the absence of this protein on osteoblast differentiation and bone formation in vitro from mouse calvarial cells (MCC) with a gene knockout of BSP (BSP-/-), grown in 2D and 3D. We have shown that BSP-/- cells have a defect in bone formation and mineralization which is cell density dependent. We have developed and validated a perfused bioreactor able to apply mechanical stress to culture scaffolds via the ZetOsTM system. Our first results with this powerful tool show that a 3D environment improves BSP-/- cells differentiation. This work remains to be developed, in particular to analyze the effects of mechanical stress on these cells

La production ainsi que l'utilisation massive des produits chimiques pour divers usages, a résulté à leur introduction et accumulation dans l'environnement. Ces produits peuvent se transporter par différentes façons de leur source à des régions très lointaines de la planète, ce qui dépend de leur propriété physico-chimiques. Une quantité et variété importante de composés organiques sont utilisées dans l'agriculture comme pesticides, afin de protéger les cultures et augmenter les rendements. Les résidus de ces produits peuvent toujours se trouver dans les champs, puis sous l'effet des précipitations ils passent par lixiviation dans les fleuves et d'autres system aqueux. Les produits pharmaceutiques et les produits de soins personnels sont introduits dans l'environnement de façon continue par les eaux usés municipales. Ces substances manifestent, dans la plus part des cas, des effets perturbants sur les organismes vivants. Malgré leur concentration faible dans les eaux naturelles, le contact permanent des organismes aquatiques peut avoir des conséquences négatives telles que la modification du comportement sexuel observé chez les poissons d'eau douce. Dans le but de réduire ou éliminer la pollution chimique des eaux des nombreuses méthodes ont vu le jour, telles que: l'adsorption des polluants sur des adsorbants, la filtration membranaire, le traitement microbiologique, l'oxydation chimique et les procédés d'oxydation avancée. La plus part des méthodes utilisées dans les stations d'épuration des eaux ne détruisent pas efficacement les contaminants organiques. L'utilisation des méthodes physiques permet de les séparer de l'eau, ce qui nécessite des opérations supplémentaires pour leur élimination. Au contraire, les procédés d'oxydation avancée et en particulier les procédés électrochimiques d'oxydation avancée (méthodes développées récemment) se montrent plus efficace dans l'élimination des polluants toxiques et non-biodégradables, car ces procédés sont capables à conduire jusqu'à minéralisation totale de la matière organique. Le sujet de cette thèse repose donc sur l'application du procédé électro-Fenton qui est un procédé électrochimique d'oxydation avancée pour la destruction des contaminants organiques dans l'eau. Cette méthode fait appel aux radicaux hydroxyles (espèces très oxydantes et extrêmement réactives) pour l'élimination des polluants récalcitrants, qui sont produit in situ à travers le réactif du Fenton (H2O2 + Fe2+). Ce réactif est généré in situ électrochimiquement. . Dans ce procédé la nature du matériau de l'électrode a une importance cruciale. Ainsi nous avons étudié dans ce travail l'influence du matériel de l'anode et de la cathode sur l'efficacité du procédé électro-Fenton. Dans un premier temps nous avons étudié de manière systématique le pouvoir d'oxydation d'anode comme de différentes matériaux d'anodes tels que : BDD, Pt, DSA, PbO2, Feutre de carbone, Graphite et Fibre de carbone dans l'oxydation de l'antibiotique amoxicilline (AMX). Dans tous les cas une électrode d'acier inox a été utilisée comme cathode. La dégradation de AMX a été suivie par l'analyse CLHP alors que la minéralisation de ses solutions par l'analyseur du carbone organique totale (COT). Il s'est avéré que l'anode BDD a était l'anode la plus puissante pour l'oxydation de l'AMX tandis que l'anode DSA a présenté les performances les plus faibles. D'autre part, le feutre de carbone a présenté un comportement caractéristique; il était très efficace sur l'oxydation de l'AMX mais ces performances en minéralisation étaient médiocres. Dans l'étape suivante, quatre anodes (Pt, BDD, DSA and Feutre de carbone) ont été testées pour élucider leur influence sur l'efficacité du procédé électro-Fenton, en utilisant toujours une cathode de feutre de carbone. L'antibiotique sulfamethazine (SMT) a été choisi comme polluant modèle (...) / Permanent production and use of organic chemicals for many purposes has resulted in their introduction and accumulation in the environment. Depending on their physicochemical properties they can be transported by different ways from the source to very remote regions of the planet. Many organic chemicals are used in agriculture as pesticides for cultures protection or nutrient. Residues of these chemicals can always be found in fields, and under the effect of precipitations they leach and pass in streams and rivers. Pharmaceuticals and personal health care products and other house holding chemicals are continuously introduced in the environment through municipal wastewaters. These substances exhibit, in most of the cases, perturbation effects towards the living organisms, moreover the effect of many of them is not known yet. Despite their concentration in water is low, the exposure of organisms for long periods can lead to negative consequences, but these effects cannot be measured instantly. In order to reduce or avoid the pollution of water with chemicals many water treatment methods has been developed like adsorption of pollutants on adsorbents, membrane filtration, microbiological treatment, chemical oxidation with oxidizing agents and advanced oxidation processes. Most of the methods used in waste water treatment plants (WWTP) do not completely destroy the organic contaminants or they only separate the contaminants from water. Then they have to be deposed somewhere else remaining always a potential source of contamination. Advanced oxidation processes and in particular electrochemical advanced oxidation processes are methods developed later and are proven as more effective as they can completely oxidize the organic matter in water. The subject of this thesis is the use of electro-Fenton, an electrochemical advanced oxidation process for efficient destruction of organic pollutants in aqueous medium. In this method, organic pollutants are eliminated by H hydroxyl radicals (high oxidation power species) which are produced in situ through the Fenton's reagent (H2O2 + Fe2+) itself generated in the solution electrochemically and continuously. In this process, the electrode material is of fundamental importance in order to have an efficient process, so we have studied at large extent the influence of both cathode and anode material in this work. Firstly a systematic study on the oxidation capacity of the process of amoxicillin (AMX) as model pollutant with several anodes materials: BDD, Pt, DSA, PbO2 Carbon felt, Graphite and Carbon fibre was realised. In all cases a stainless steel electrode was used as cathode. The degradation of AMX was followed by HPLC analysis whereas the mineralization efficiency ot the process was measured by total organic carbon analyser (TOC). This revealed that BDD was the most efficient anode for AMX oxidation and DSA was the weakest one. Carbon felt showed a characteristic behaviour; it was very efficient on AMX oxidation but it could not transform AMX to CO2 and H2O. Afterwards four anodes were tested for their influence on electro-Fenton process efficiency namely Pt, BDD, DSA and Carbon felt, the cathode was always carbon felt. Sulfamethazine (SMT) was used as model pollutant. Apparent rate constants have given only moderate values of mineralization for currents lower than 100 mA. Here again the BDD anode was distinguished for its excellent mineralization capacity owing to the additional hydroxyl radicals and other oxidizing species introduced in the system. When electro-Fenton applied good degradation and mineralization results were obtained even with the DSA anode (...)

Orientadores: Roberto Perez Xavier, Antônio João Paes de Barros / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-18T19:24:22Z (GMT). No. of bitstreams: 1 Assis_RafaelRodriguesde_M.pdf: 63971305 bytes, checksum: 10519618069ab0467e9938bc90213f76 (MD5) Previous issue date: 2011 / Resumo: A Província Aurífera de Alta Floresta, porção centro-sul do Craton Amazônico, localiza-se entre os limites das províncias geocronológicas Ventuari - Tapajós (1,95-1,8 Ga) e Rio Negro - Juruena (1,8-1,55 Ga). Corresponde a uma unidade tectônica essencialmente composta por sequências plutono-vulcânicas geradas em ambiente de arcos magmáticos que se desenvolveram e se agregaram progressivamente no Paleoproterozóico. No segmento leste da província, na região que compreende os municípios de Nova Santa Helena - Peixoto de Azevedo - Guarantã do Norte - Novo Mundo (MT), rochas plutônicas e vulcânicas são as hospedeiras de mais de uma centena de depósitos auríferos que ocorrem concentrados ao longo do Cinturão Peru-Trairão, de direção NW-SW. Inseridos neste contexto, estão os depósitos Pé Quente e Francisco, alvos de estudo deste trabalho. O Depósito Pé Quente hospeda-se na suíte homônima, que compreende quartzo monzodiorito-monzodiorito a leucomonzonito, isotrópicos, inequigranulares a equigranulares. Apatita, rutilo e zircão correspondem às fases acessórias comuns na suíte. Nos arredores do depósito são individualizadas uma série de manifestações plutônicas mais tardias, não cogenéticas a Suíte Pé Quente, de composição eminentemente granítica e com biotita, hornblenda, titanita, apatita e magnetita como fases acessórias. Diques de vulcânicas são comuns na região e truncam todas as suítes supracitadas. A Suíte Pé Quente exibe afinidade geoquímica com as séries cálcio-alcalinas de médio K, metaa peraluminosas e magnesianas, semelhante aos granitos orogênicos do tipo I, enquanto que as demais suítes são cálcio-alcalinas de médio a alto K, metaluminosas e magnesianas, mas ligeiramente ferrosas. No geral, as observações petrográficas e geoquímicas indicam que essas suítes plutônicas correspondem a granitos do tipo I que teriam se originado em ambiente de arcos vulcânicos evoluindo para arcabouço pós-colisional. A Suíte Pé Quente foi submetida a expressivos estágios de alteração hidrotermal, a destacar: (i) forte alteração sódica com albita; (ii) alteração potássica com ortoclásio + microclínio; (iii) alteração sericítica; (iv) carbonatação; (v) alteração pervasiva a venular com muscovita grossa fibro-radial; (vi) silicificação com brechas e veios com textura do tipo pente subordinadas; (vii) alteração sódica fissural com quartzo + albita e; (viii) alteração propilítica mais tardia e regional. O minério no Deposto Pé Quente é representado pela paragênese pirita + barita ± hematita ± calcopirita ± galena, associada tanto à alteração sódica pervasiva mais precoce quanto à fissural (quartzo + albita). O ouro é mais frequente na alteração pervasiva, na qual ocorre incluso na pirita e exibe concentrações em Ag que variam de 14,2 a 46,3%. Estudos preliminares de inclusões fluidas na zona de minério disseminado indicam fluidos eminentemente aquo-carbônicos em coexistência com fluidos aquosos bifásicos. Os principais atributos geológicos do Depósito Pé Quente correspondem: (i) íntima associação com rochas originadas em arcabouço de arcos vulcânicos (granitos tipo I); (ii) alteração hidrotermal extensa e zonada, com oscilações nas aNa+, aK+, aH+ and aCa2+; (iii) minério que representa fluidos de natureza oxidada. Neste sentido, o Depósito Pé Quente reflete um sistema com múltiplos pulsos de fluidos hidrotermais possivelmente relacionados a estágios de desgaseificação da câmara magmática em um contínuo gradativo de rebaixamento da temperatura. A precipitação do minério aurífero teria ocorrido mediante imiscibilidade de fluidos em um sistema magmático-hidrotermal a elevadas temperaturas e ¿O2, típicos das raízes de sistemas auríferos do tipo pórfiro. O contexto geológico do Depósito do Francisco, no entanto, é distinto daquele observado no Depósito Pé Quente. A região de União do Norte, onde se localiza o Depósito do Francisco, é constituída por uma Unidade Vulcanoclástica epiclástica que aloja uma série de intrusões graníticas paleoproterozóicas. Essa unidade vulcanoclástica é composta por arenito arcoseano, arenito arcoseano lítico, grauvaca-feldspática e lentes de conglomerado polimítico matriz suportada, todos vulcanoclásticos. Esses sedimentos teriam sido provenientes da dissecação de antigos edifícios vulcânicos de composição intermediária e depositados em uma bacia de retroarco, próxima à área fonte. As suítes intrusivas são temporalmente representadas por plútons de (i) granodiorito com tonalito e quartzo monzodiorito subordinados; (ii) sieno-monzogranito e; (iii) pelo Pórfiro União do Norte, uma manifestação sub-vulcânica que consiste de álcali-feldspato granito porfirítico a monzogranito porfirítico. As duas primeiras suítes são cogenéticas e correlacionáveis à Suíte Intrusiva Matupá (1.872 ±12Ma), enquanto que o granito sub-vulcânico estaria relacionado as manifestações graníticas pós-colisionais do tipo A da Suíte Intrusiva Teles Pires (1.782 ±17 Ma a 1.757 ±16 Ma). Truncando todas essas unidades ocorrem diques de vulcânicas de composição traquibasáltica a dacítica. A litogeoquímica do Pórfiro União do Norte indica magmatismo eminentemente alcalino de alto potássico, ferroso e meta- a peraluminoso, enquanto que os diques de vulcânicas e as demais suítes plutônicas exibem afinididades geoquímicas com as séries cálcio-alcalinas de alto K, metaluminosas, magnesianas a ligeiramente ferrosas. Evidências de campo em conjunto com os dados litogeoquímicos ainda apontam para uma evolução do magmatismo com geração de rochas mais primitivas em ambiente de arcos vulcânicos (granodiorito; Suíte Intrusiva Matupá) até o alojamento de corpos altamente evoluídos (Pórfiro União do Norte; Suíte Intrusiva Teles Pires) em contexto pós-colisional. Todas essas unidades são ainda recobertas pelos sedimentos arenáceos da Formação Dardanelos, com idade máxima de deposição entre 1.987 ±4 Ma a 1.377 ±13 Ma. Na região de União do Norte desponta o Depósito do Francisco, o primeiro depósito epitermal polimetálico de intermediária sulfetação da Província Aurífera de Alta Floresta, e ao qual o ouro está associado a elevadas concentrações de metais de base (Zn+Pb±Cu). As zonas mineralizadas são representadas pela associação pirita + esfalerita + galena + hematita ± calcopirita ± magnetita ± digenita. O minério ocorre hospedado na Unidade Vulcanoclástica em veios com intensa silicificação e extenso halo de alteração sericítica. As alterações potássica, argílica e propilítica são as mais distais ao minério, sendo que as duas primeiras ocorrem intimamente associadas ao Pórfiro União do Norte. Estudos premilimares de inclusões fluidas realizados nas zonas mineralizadas indicam regime de fluidos eminentemente aquosos, com inclusões aquosas primárias que exibem heterogeneidade no grau de preenchimento pela fase de vapor (10-70%). Os principais atributos geológicos do depósito do Francisco podem ser considerados: (i) alteração hidrotermal e minério íntimamente associados a um granito sub-vulcânico (Pórfiro União do Norte) que teria se saturado em uma fase aquosa residual decorrente de sua cristalização; (ii) alunita, embora em pequenas concentrações, associadas a ocorrênicas de silica cap; (iii) minério hospedado em rochas sedimentares epiclásticas; (iv) zonas mineralizadas que frequentemente exibem texturas indicativas da percolação de fluidos em nível crustal raso; (v) minério aurífero associado tanto a elevadas concentrações de metais de base quanto de prata; (vi) paragênese do minério dominada por fases ricas em sulfetos, o que indica oscilações no estado de sulfetação do enxofre. Todas essas características são similares àquelas encontradas em depósitos epitermais polimetálicos de intermediária sulfetação. Devido à presença constante de texturas que tipificam a percolação de fluidos em nível crustal raso nas regiões internas, proximais e de contato do Pórfiro União do Norte, além da existência de apófises sub-vulcânicas intensamente sericitizadas e/ou silicificadas, é proposto que esta suíte tenha correspondido ao evento termal causativo da mineralização aurífera associada a metais de base do Depósito do Francisco. Desta forma, sugere-se que a Suíte Intrusiva Teles Pires, até o momento conhecida por ser estéril a ouro, possa ter potencial, mesmo que restrito às suas ocorrências sub-vulcânicas, para hospedar mineralizações auríferas com metais de base associados. Em adicional, o contexto pós-colisional em que o depósito se formou teria promovido a sua preservação quanto aos agentes erosivos, metamórficos e de deformação que posteriormente poderiam ter afetado e destruído o depósito. Neste contexto, a deposição do ouro no Depósito do Francisco ocorreu mediante aumento das condições de ¿O2 do fluido (precipitação de hematita) decorrente da entrada de fluidos externos e oxidantes (meteóricos), potencializada por eventos de fraturamento hidráulico quando o granito sub-vulcânico se saturou em uma fase fluida residual (expansão adiabática seguida de ebulição). As elevadas concentrações de metais de base aliadas ao processo de ebulição ainda sugerem que variações na temperatura e pH foram importantes na precipitação do minério. Neste cenário, as suítes plutônicas individualizadas neste trabalho começaram a ser geradas em um momento anterior ao magmatismo da Suíte Intrusiva Matupá (1.872 ±12Ma), com a colocação da Suíte Pé Quente. Com a continuidade do envento magmático, suítes graníticas mais evoluídas foram sendo geradas, até o alojamento da Suíte Intrusiva Teles Pires (~ 1.757 Ma), que representa a colocação de intrusões mais tardias (Pórfiro União do Norte), em plataforma continental pós-colisional (granito tipo A). A depender do modelo geotectônico adotado, o conjunto dessas suítes, portanto, teria sido criado durante a instalação dos arcos magmáticos Cuiú-Cuiú (2,1-1,9 Ga) e Juruena (1,8-1,75 Ga), ou então, no decorrer do Arco Magmático Ventuari-Tapajós (1,95 e 1,8 Ga). As informações aqui reunidas indicam que os depósitos estudados podem ser enquadrados em distintos sistemas mineralizados no modelo geral dos depósitos do tipo ouro pórfiro - epitermal, no qual a colocação de intrusões paleoproterozóicas teria correspondido às fontes geradoras de calor, fluidos e metais necessários para a instalação de um sistema magmático-hidrotermal. O Depósito Pé Quente corresponderia a um sistema de maior profundidade e temperatura, no qual a forte alteração sódica com albita, com fluidos oxidados eminentemente aquosos e aquo-carbônicos representariam as zonas mais profundas de depósitos auríferos do tipo pórfiro. Em contraste, o Depósito do Francisco seria correlato às mineralizações de níveis crustais mais raros, com grande aporte de fluidos meteóricos, e relativamente distais de intrusivas félsicas. Deste modo, as mineralizações auríferas com metais de base associados seriam equivalentes aos depósitos epitermais polimetálicos de intermediária sulfetação. / Abstract: The Alta Floresta Gold Province, eastern portion of the Amazon Craton, extends between the Ventuari - Tapajós (1.95 to 1.8 Ga) and Rio Negro - Juruena (1.8 to 1.55 Ga) geochronological provinces. This provinces represents a tectonic unit composed primarily of plutono-volcanic sequences generated in continental arc settings during the Paleoproterozoic. At the easternmost segment of the province, in region that comprises the districts of Nova Santa Helena - Peixoto de Azevedo - Guarantã do Norte - Novo Mundo (MT), a significant number of gold deposits are distributed along a NW-SW striking belt (Peru - Trairão belt). Within this belt, the Pé Quente and Francisco gold deposits, currently exploited by local prospectors (garimpeiros), are the main case studies of this work. The Pé Quente deposit is hosted by the Pé Quente Suite that consists of quartz-monzodiorite to leucomonzonite with apatite, rutile and zircon as accessory phases. Several other later granitic intrusions occur in the vicinity of the deposit, but geological relationships and geochemical data suggest neither genetic nor temporal links to the Pé Quente Suite. These suites are mainly granitic composition and have biotite, hornblende, titanite, apatite and magnetite as accessory phases. Volcanic dikes are often in the area and crosscut all these plutonic suites. The Pé Quente suite exhibits geochemistry affinities to the medium-K, calc-alkaline, meta- to peraluminous and magnesian granitic series, thus similar to the I-type orogenic granites, whereas the other suites are medium to high-K, metaluminous and magnesian, but slightly ferroan. Additionally, petrographic and geochemical data indicate that these rocks correspond to I-type granitic series that probably had been generated in a volcanic arc setting that have also evolved to a post-collisional one. The Pé Quente Suite has been affected by the following hydrothermal alteration types (temporal sequence): (i) strong sodic alteration with albite; (ii) potassic alteration with orthoclase and microcline; (iii) sericitic alteration; (iv) carbonate alteration represented by calcite; (v) pervasive to venular coarse muscovite alteration; (vi) silicification with breccias and comb-texture quartz veins; (vii) fissural sodic alteration that consists of quartz + albite and; (viii) later and regional propylitic alteration. The ore zones comprise pyrite + barite ± hematite ± chalcopyrite ± galena that are related to both earlier sodic alteration and later veins with quartz and albite. Gold generally occurs as small inclusions within pyrite and shows Ag concentrations that range from 14.2 to 46.3%. Preliminary studies of fluid inclusions within the disseminated ore-zones indicate carbonic fluids that coexisting with aqueous biphasic. The main geological feautures of this deposit are: (i) close association with rocks that have been originated in the onset of volcanic arcs (granite type I), (ii) widespread and zoned hydrothermal alteration, with oscillations in aNa+, aK+, aH+ and aCa2 +; (iii) ore that represents oxidized fluids. Therefore, the Pé Quente deposit is interpreted to have been formed from multiple pulses of hydrotermal fluids, possibly generated by episodes of magma degassing. The ore precipitation might have taken place by fluid immiscibility within a high-temperature and high-¿O2 system, similar to those related to root zones of porphyry systems. Very dissimilar from the Pé Quente gold deposit, the Francisco gold deposit, in the União do Norte region, is hosted by an epiclastic volcaniclastic unit that is crosscut by a series of Paleoproterozoic granitic intrusions. This unit contains mainly feldspathic-arenite and feldspathic-wake, besides lenses of matrix-supported conglomerate, both volcaniclastics. The sediments that compose the rocks of this unit have possibly derived from the erosion of old volcanic centers of intermediate composition in a active continental setting. Furthermore, the sediments might have been deposited in a retroarc basin, near to the source-area. The intrusive suites are sequentially represented by: (i) granodiorite with tonalite and quartz-monzodiorite subordinate; (ii) sieno- to monzogranite and; (iii) União do Norte Porphyry, a subvolcanic manifestation that comprises porphyritic alkali-feldspar granite and porphyritic monzogranite. The firt two suites are tentatively correlated with the Matupá Intrusive Suite (1.872 ±12Ma), whereas the porphyry could be related to the post-collisional A-type granitic rocks from the Teles Pires Intrusive Suite (1.782 ±17 Ma to 1.757 ±16 Ma). Mafic to felsic volcanic dikes that consist of trachybasalt, basaltic-trachyandesite, andesite and dacite crosscut both the volcaniclastic unit and the granitic suites. Litogeochemical data from the União do Norte Porphyry indicate that this suite represents an alkaline, high-K, magnesian to ferroan, meta- to slightly peraluminous magmatism, whereas the volcanic dikes and the two other plutonic suites exhibit geochemical affinities with to the calc-alkaline, high-K, metaluminous and magnesian to slightly ferroan series. Additionally, field and geochemical data indicate that the granitic suites represent a magmatic series that were probably formed in the onset of a volcanic arc setting, manly with granodioritic rocks (Matupá Intrusive Suite), which evolved to the emplacement of highly-evolved granitic rocks, such as the União do Norte Porphyry (Teles Pires Intrusive Suite) in a postcollisional setting. All these units are still overlain by arenaceous sediments of the Dardanelos Formation (1.987 ±4Ma to 1.377 ±13Ma). In this geological setting, the Francisco deposit represents the first intermediate-sulfidation epithermal gold mineralization associated with base metals (Zn+ Pb±Cu) in the Alta Floresta Gold Province. Pyrite + sphalerite + galena + chalcopyrite ± hematite ± magnetite ± digenite represent the ore zones, hosted at the Volcanilcasto unit. The ore occurs in veins with strong silicification and extensive sericitic halo. The potassic (ortoclase ± hematite ± quartz ± biotite), argillic (kaolinite + sericite + quartz ± hematite), propilitic (chlorite + epidote + magnetite ± actinolite ±calcite ± apatite ± pyrite ± chalcopyrite ± quartz ± shalerite ± margarite) alterations, plus the late-hematite veins, correspond to the distal hydrothermal alterations to the ore zone. The potassic and argililic alterations generally are closely associated to the União do Norte Porphyry. Preliminary studies of fluid inclusions within the ore zones indicate the presence of an aqueous fluid system represented by primary aqueous inclusions with heterogeneity in the vapor-phase filling degree (10-70%). The main geological feautures of the deposit are: (i) hydrothermal alteration and ore closely associated with a subvolcanic granite (União do Norte Porphyry) that could have saturated in an residual aqueous fluid phase due to its crystallization; (ii) alunite, although in small concentrations, associated to the occurrences of silica cap; (iii) ore zones hosted in epiclastic sedimentary rocks; (iv) ore zones that often exhibit textures that indicate fluid percolation at shallow crustal level; (v) gold ore associated either to high concentration of base metals and silver; (vi) ore paragenesis dominated by phases rich in sulfides that are indicative of oscillations in the sulfidation state of the sulfur. All these feautures are similar to those found in epithermal polymetallic deposits of intermediate sulfidation. Due to the constant presence of textures that typify the percolation of fluids in shallow crustal level in the inner, proximal and contact regions of the Porphyry North Union, besides the existence of subvolcanic apophyses strongly sericitized and/or silicified, it is proposed that this suite has been responsible by the causative thermal event of gold mineralization associated with base metals at the Francisco deposit. Therefore, it is suggested that the Teles Pires Intrusive Suite, so far known to be barren of gold mineralizations, may have potencial, even if restricted to occurrences of the subvolcanic from this suite, to host gold mineralizations with associated base metals. In addition, the post-collisional setting in which the deposit have been formed would have promoted its preservation from the later erosion, metamorphism and deformation events, which could have affected and destroyed the deposit. The ore precipitation might have taken place by increase in the ¿O2 of the fluid (hematite precipitation), possibly due to influx of oxidizing external fluids (meteoric) after hydraulic fracturing events when the subvolcanic granite had been oversaturated in a residual aqueous fluid phase. The high concentrations of base metals suggest that the variations on the temperature and pH of the fluid could have been an important key in the formation of the mineralized ore zones. In this context, the identified plutonic suites around the Pé Quente and Francisco would have been initially formed before the magmatic event that resulted in the Matupá Intrusive Suite (1.872 ±12Ma), with the emplacement of the Pé Quente suite. With the continuity of the magmatic event, more evolved granitic suites would have been created by the emplacement of the Teles Pires Intrusive Suite (~ 1757 Ma), which represents the later intrusions (União do Norte Porphyry) within a post-collisional setting. Therefore, depending on the tectonic model adopted, all of these suites would have been created during the installation of the magmatic arc Cuiú-Cuiú (2.1-1.9 Ga) and Juruena (1.8-1.75 Ga), or then, during the Ventuari-Tapajós Magmatic Arc (1.95 to 1.8 Ga). In this scenario, the Pé Quente and Francisco deposits could be classified as different mineralizing systems within the general model of gold-porphyry - epithermal, which the emplacement of Paleoproterozoic granitic intrusions may have served as source of heat, fluids and metals to the installation of the magmatic-hydrothermal system. The Pé Quente deposit, for instance, could correspond a system of greater depth and higher temperature, where the strong pervasive albite alteration plus highly oxidized-aqueous and carbonic fluids represent the root zones of porphyry gold deposits. The Francisco deposit, however, could be correlated to mineralization nested in shallow crustal levels with great influx of meteoric fluids and relatively distal from felsic intrusive subvolcanic granite. Therefore, the Francisco deposit could be similar to the polymetallic epithermal deposits of intermediate-sulfidation. / Mestrado / Metalogenese / Mestre em Geociências

Orientador: Roberto Perez Xavier / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-27T12:52:01Z (GMT). No. of bitstreams: 1 Assis_RafaelRodriguesde_D.pdf: 28529636 bytes, checksum: a178f7c0049490d9875ccc010692fdbb (MD5) Previous issue date: 2015 / Resumo: MINERALIZAÇÕES E FONTE DOS FLUIDOS. A Província Aurífera de Alta Floresta, porção centro-sul do Craton Amazônico, localiza-se entre os limites das províncias geocronológicas Ventuari ¿ Tapajós (1,95-1,8 Ga) e Rio Negro ¿ Juruena (1,8-1,55 Ga), ou entre as províncias tectônicas Tapajós ¿ Parima (2,03-1,88 Ga) e Rondônia ¿ Juruena (1,82-1,54 Ga), a depender do modelo adotado para o cráton. Ela é essencialmente constituída por sequências plutôno-vulcânicas derivadas de diversos arcos vulcânicos amalgamados no decorrer do Paleoproterozóico. No segmento leste da província, na região que compreende as cidades de Peixoto de Azevedo ¿ Matupá ¿ Guarantã do Norte ¿ Novo Mundo (MT), rochas plutônicas e vulcânicas de composição granítica hospedam mais de uma centena de depósitos auríferos concentrados ao longo do Cinturão Peru ¿ União do Norte, de direção NW-SE. Com base na paragênese e estilo do minério, essas mineralizações podem ser agrupadas em três tipologias principais: (1) Au ± Cu disseminados em sistemas graníticos e dominantemente representados por pirita e concentrações variáveis de calcopirita e hematita; (2) Sistemas filonares de Au ± Cu essencialmente constituídos por pirita com calcopirita subordinada; e (3) Au + metais de base confinados a veios e vênulas que truncam sequências vulcano-sedimentares sin- a pós-tectônicas. Neste contexto, três grupos principais de rochas plutônicas podem ser distinguidos: (1) embasamento granítico e granitóides antigos; (2) intrusões graníticas de composição sieno/monzogranítica que hospedam as principais mineralizações auríferas da província; e (3) hospedeiras sub-vulcânicas de composição monzogranítica a tonalítica. No conjunto, essas unidades representam um magmatismo cálcio-alcalino oxidado, hidratado, de médio a alto K, meta- a peraluminoso e ferroso a ligeiramente magnesiano, possivelmente derivado da fusão parcial da crosta inferior (manto metassomatizado) em ambiente de arcos vulcânicos. Embora a principal hospedeira plutônica (Granito Guarantã) exiba importantes características adakíticas, compreende-se que seu magma fonte tenha se formado nas porções profundas da crosta, com plagioclásio instável, mas granada e hornblenda estáveis. Os novos dados U-Pb em zircão (SHRIMP) indicam que as idades de cristalização do embasamento granítico variam de 1.980 ±8,8 Ma (Gnaisse Nova Guarita) a 1.978 ±8,1 Ma (tonalito foliado), enquanto as hospedeiras graníticas teriam se formado entre 1.904 ±4,6 Ma (Granodiorito X1), 1.901 ±6,8 Ma (Tonalito Pé Quente) e 1.863 ±4,8 Ma (Granodiorito Jorge) e as hospedeiras sub-vulcânicas entre 1.774 ±7,5 (Pórfiro União do Norte) e 1.773 ±5,7 Ma (quartzo-feldspato pórfiro X1). Os valores ?Nd(t) (-5,49 a -0.975) e as idades modelo TDM (2,36 a 2,02 Ga) sugerem magmas de derivação mantélica extraídos de fonte paleoproterozóica, em que a cristalização fracionada teria correspondido ao principal vetor de evolução petrogenética e, em menor escala, processos de contaminação crustal. Coletivamente, é proposto que esses litotipos tenham se originado a partir de três estágios magmáticos principais: (1) embasamento granítico e granitóides antigos no Orosiriano; (2) hospedeiras granodiorititicas-tonalíticas durante o Orosiriano tardio; e (3) pórfiros e sub-vulcânicas no Statheriano. Esses eventos estariam respectivamente associados à construção do (A) Arco Magmático Cuiú-Cuiú; (B) Arco Magmático Juruena; e (C) contexto pós-colisional do Arco Magmático Juruena. Neste arcabouço geológico, enquadram-se os depósitos magmático-hidrotermais do Pé Quente, Luizão, X1 e Francisco, correspondentes aos alvos de estudo dessa tese na escala de depósitos. Os depósitos Pé Quente (Suíte Pé Quente, 1,97-1,9 Ga), Luizão (Granito Novo Mundo; 1,97-1,96 Ga) e X1 (Granito Guarantã; 1,9 Ga), representam os principais exemplos de mineralizações de Au ± Cu disseminadas em sistemas graníticos, enquanto o depósito do Francisco (Pórfiro União do Norte; 1,77 Ga) seria o principal representante de mineralizações auríferas filonares associadas a metais de base. As zonas mineralizadas dos depósitos X1 e Luizão estão condicionadas a uma forte alteração fílica (muscovita grossa + quartzo + sulfetos) com abundantes concentrações de pirita, mas variável de calcopirita e hematita. Essas zonas estão circunscritas a uma intensa alteração potássica pervasiva com ortoclásio + microclínio ± hematita. Embora essas alterações também ocorram no depósito Pé Quente, seu minério está temporalmente relacionado tanto a uma alteração sódica precoce quanto à alteração fílica. No depósito do Francisco, contudo, o minério está confinado a veios de quartzo com extensos halos de alteração sericítica com pirita + esfalerita + galena ± calcopirita ±digenita disseminadas. Essas alterações são margeadas por uma forte alteração potássica com ortoclásio ± hematita, a qual está circunscrita a uma ampla zona de alteração propilítica de cunho regional. Assembleias de inclusões fluidas provenientes de cristais de quartzo dos depósitos Pé Quente e X1 indicam a coexistência de duas tipologias principais de fluidos: (1) um fluido aquoso de ampla salinidade (2,1 a 26,1% eq. NaCl) e de baixa a moderada temperatura (126,5°C a 268,4°C), coexistentes com fluidos (2) aquo-carbônicos de baixa salinidade (6,1 a 8,9% eq. NaCl), mas altas temperaturas (251,6° a 334,6°C), indicativas de aprisionamento heterogênio em condições de imiscibilidade em um sistema magmático-hidrotermal profundo. No depósito Luizão, o regime de fluidos é registrado por fluidos (1) aquoso-salinos (33,6-37% eq. NaCl) com temperaturas entre 200° e 280°C; coexistente com (2) fluidos aquosos bifásicos de baixa salinidade (2,5-15% eq. NaCl) e temperatura (95°-185°C), indicativos de processos de separação de fases em nível crustal mais raso quando comparado aos depósitos Pé Quente e X1. E finalmente, no depósito do Francisco, as assembleias de inclusões fluidas indicam fluidos eminentemente aquosos de baixa à moderada salinidade (até 24,7% eq. NaCl) e temperatura (85,3°C a 373,2°C), que exibem grande variação quanto ao grau de preenchimento pela fase de vapor (10-70%), sugestivos de processos de ebulição em nível crustal raso. Adicionalmente, os dados isotópicos para oxigênio, deutério e enxofre indicam forte componente magmática para os depósitos do Pé Quente, Luizão e X1, enquanto que no depósito do Francisco, fluidos eminentemente magmáticos teriam interagido com fluidos externos, possivelmente de origem meteórica. Em virtude das similaridades entre seus principais atributos geológicos, assembleias de inclusões fluidas e dados isotópicos, os depósitos Pé Quente, Luizão e X1 podem ser classificados como similares a depósitos do tipo ouro pórfiro, porém, posicionados em níveis crustais mais profundos do que os clássicos exemplos andinos, enquanto o depósito do Francisco seria equivalente às mineralizações epitermais de sulfetação intermediária. No âmbito dessas mineralizações, são reportadas as primeiras idades Re-Os em sulfetos provenientes das principais zonas auríferas dos depósitos supracitados, assim como as primeiras idades da alteração hidrotermal (40Ar/39Ar) associadas à zona mineralizada do depósito epitermal da província. As idades Re-Os em concentrados de pirita do depósito Pé Quente variam de 1.792 ±9 Ma a 1.784 ±11 Ma (idade modelo: 1.787 ±5,5 Ma), enquanto que para o Luizão elas estão compreendidas entre 1.790 ±9 Ma e 1.782 ±9 Ma (idade modelo: 1.787 ±6,2 Ma). No depósito X1, as idades Re-Os em molibdenita são coincidentes aos casos anteriores: entre 1.787 ±7 Ma e 1,785 ±7 Ma (idade modelo: 1.786 ±5 Ma). No depósito do Francisco, as idades 40Ar/39Ar em alíquotas de sericita oriundas do halo de alteração sericítico fornecem idades entre 1.779 ±6,28 a 1.777 ±6,3 Ma e, portanto, bastante similares aos depósitos disseminados de Au ± Cu. Em adicional, as idades 40Ar/39Ar da alteração fílica do depósito Pé Quente variam de 1.833,6 ±6,2 a 1.830,6 ±6.2 Ma, enquanto que no depósito X1 essas idades estão compreendidas entre 1.733,3 ±6,2 a 1.751,3 ±6,1 Ma. A grande uniformidade isotópica obtida para os depósitos disseminados de Au ± Cu fornece uma excelente idade isocrônica em 1.786 ±1 Ma, com idade modelo em 1.787 ±3,2 Ma, as quais permitem apontar para um único e estreito evento aurífero na Província, centrado no Statheriano e que teria durado aproximadamente 10 Ma. No conjunto, essas idades, portanto, demonstram a contemporaneidade das mineralizações com o alojamento de corpos porfiríticos sub-vulcânicos sin- a pós-colisionais na Província, correlacionados às suítes Colíder (quartzo-feldspato pórfiro X1) e Teles Pires (Pórfiro União do Norte), pertencentes ao terceiro evento magmático da província. Logo, as idades Re-Os diferem substancialmente das idades U-Pb das hospedeiras plutônicas graníticas dos depósitos investigados. Esse fato demonstra não haver qualquer conexão genética entre o plutonismo granítico e processos responsáveis pelas mineralizações auríferas da província, diferentemente dos três eventos auríferos até então propostos para a província: (1) 1,98-1,95 Ga (e.g. depósitos Luizão e Pé Quente); (2) 1,87-1,85 Ga (depósitos X1 e Serrinha) e (3) 1,77-1,79 Ga (depósito do Francisco). Essas idades abrem, portanto, novas perspectivas para a exploração aurífera na Província, visto que unidades vulcânicas e sub-vulcânicas de idade 1,78-1,77 Ga agora se tornam alvos potenciais à exploração / Abstract: The Alta Floresta Gold Province, eastern portion of the Amazon Craton, extends between the Ventuari ¿ Tapajós (1.95 to 1.8 Ga) and Rio Negro ¿ Juruena (1.8 to 1.55 Ga) geochronological provinces, or between the Tapajós ¿ Parima (2.03-1.88 Ga) and Rondônia ¿ Juruena (1.82-1.54 Ga), depending on the model used. The province is mainly composed of arc-type plutono-volcanic sequences amalgamated during the Paleoproterozoic. At the easternmost segment of the province, in region that comprises the districts of Peixoto de Azevedo ¿ Mautpá ¿ Guarantã do Norte ¿ Novo Mundo (MT), a significant number of gold deposits are distributed along a NW-SW striking belt (Peru ¿ União do Norte belt) hosted by plutonic and volcanic rocks of granitic composition. Based on ore and stype paragenesis, these gold mineralizations can be clustered into three main groups: (1) Au ± Cu disseminated within granitic systems and essentially represented by pyrite and variable amounts of chalcopyrite and hematite; (2) Au ± Cu-rich veins mainly composed of pyrite and subordinated chalcopyrite; and (3) vein-type Au + base metals that crosscut sin- to post-collisional volcano-sedimentary sequences. Whitin this context, three major groups of plutonic rocks may be distinguished: (1) basement and old granitoids; (2) granitic intrusions that vary in composition from tonalite to syeno/monzogranite and that host the major gold mineralizations within the province; and (c) subvolcanic hosts of tonalite to monzogranite composition. These units display affinities to the calc-alkaline, oxidized, hydrated, medium to high-K, meta- to peraluminous and ferrous to slightly magnesium (I-type granites), possibly derived from volcanic arc-type setting from partial melting of lower crustal sources (metasomatized mantle). Although the main granite host (Guarantã granite) exhibits an adakite-signature, it is understood that its magma might have been derived from a deep crustal level, with instable plagioclase, garnet and hornblende stable. The new SHRIMP U-Pb zircon ages suggest that the crystallization ages related to the granitic basement range from 1,980 ±8.8 Ma (Nova Guarita gneiss) to 1,978 ±8.1 Ma (foliated tonalite), where those obtained to plutonic granitic host rocks are between 1,904 ±4.6 Ma (X1 granodiorite), 1,901 ±6.8 Ma (Pé Quente tonalite) and 1,863 ±4.8 Ma (Jorge granodiorite), and those related to subvolcanic host rocks vary from 1,774 ±7.5 (União do Norte porphyry) to 1,773 ±5.7 Ma (X1 quartz-feldspar porphyry). The ?Nd(t) (-5.49 to -0.975) and TDM ages (2.36 to 2.02 Ga) are indicative of Paleoproterozoic mantle-derived magmas with fractional crystallization as the main vector of evolution to these lithotyepes, such as crustal contamination in minor importance. Collectively, these lithotypes can be clustered into three main magmatic stages: (1) Orosirian granitic basement and old granites; (2) Late Orosirian granodiorite-tonalite host intrusions; and (3) Statherian porphyries and subvolcanics. These events would related, respectively, the construction of (A) Cuiú-Cuiú magmatic arc; (B) Early Juruena magmatic arc; and (C) Post-collisional Juruena magmatic arc setting. Within this geological context, we have the Pé Quente, Luizão, X1 and Francisco magmatic-hydrothermal gold deposits, the main case of study in this work. The Pé Quente (Pé Quente suite; 1.97-1.9 Ga), Luizão (1.97-1.96 Ga) and X1 (Guarantã granite; 1.9 Ga) deposits represent the major disseminated Au ± Cu mineralization in granitic systems, whereas the Francisco deposit (União do Norte porphyry; 1.77 Ga) would correspond the principal exemple of vein-type gold + base metals. The Luizão and X1 ore-zones are related to a strongly and pervasive phyllic alteration (coarse-grained + quartz + sulfide) wich high concentrations of pyrite but variable chalcopyrite and hematite. These hydrothermal zones are limited by a strong and pervasive potassic alteration with orthoclase + microcline ± hematite. Although these hydrothermal alterations are also found in the Pé Quente deposit, its ore is temporally related both to an early sodic as phyllic alterations. At the Francisco deposit, however, the main ore-zones are restricted to quartz-rich veins with metric sericitic alteration halos (5 to 6 m) with disseminated pyrite + sphalerite + galena ± chalcopyrite ± digenite. Collecvely, these hydrothermal alterations are limited by a regional propylitic alteration. Fluid inclusion assemblages in quartz crystals from X1 and Pé Quente deposits reveal the presence of two types of ?uids: (1) aqueous two-phase inclusions with wide salinity (2.1-26.1 wt.% eq. NaCl) and homogenization temperatures (126.5°C to 268.4°C); and (2) H2O-CO2 inclusions of low salinity (6.1-8.9 wt.% eq. NaCl) and higher temperatures (251.6° to 334.6°C), suggestive of heterogeneous entrapment by immiscibility processes in a deep magmatic-hydrothermal system. At the Luizão deposits, the fluids regime revel the coexistence of two types of aqueous fluids: (1) a high salinity (33.6 to 37 wt% NaCl eq.) fluids represented by halite-bearing fluid inclusions with temperatures that range from 200° to 280°C; and (2) a low salinity (2.5 ¿ 15 wt% NaCl eq.) and lower temperature fluid represented by two-phase inclusions, indicating fluid phase-separation processes at shallower crustal level if compared the Pé Quente and X1 deposits. And finally, at Francisco deposit the fluids are mainly composed of low to moderate salinity (up to 24 wt.% eq. NaCl) and temperature (85.3° to 373.2°C) and salinity aqueous fluid inclusions with heterogeneity in the vapor-phase filling degree (10-70 vol.%), which are suggestive of boiling processes in a shallower crustal leve. Moreover, oxygen, deuterium and sulfur isotope data do indicate a strong magmatic signature to the Pé Quente, X1 and Luizão deposits, whereas in the Francisco deposit, fluids essentially magmatic may have interacted with meteoric fluids. Based on the similarities between the major geological attributes, fluid inclusions assemblages and isotopic data, the Pé Quente, X1 and Luizão deposit can be similar to gold-only, Cu-poor porphyry systems, however, placed within deeper crustal levels than those classically interpreted as andian-type porphyry, whereas the Francisco deposits would be equivalent to polymetallic epithermal deposits of intermediate sulfidation. About these gold mineralizations, this work reports for the first time Re-Os pyrite and molybdenite ages for the Au ± disseminated deposits, such as the firt hydrothermal alteration ages (40Ar/39Ar) related to the ore-zones of the epithermal systems from the province. The Re-Os pyrite ages for the Pé Quente deposit vary from 1,792 ±9 Ma to 1,784 ±11 Ma (model age: 1.787 ±5,5 Ma), whereas those for Luizão deposit are between 1,790 ±9 Ma and 1,782 ±9 Ma (model age: 1,787 ±6.2 Ma). The Re-Os molybdenite ages for X1 deposit are very similar to the previously deposits, because it range from 1,787 ±7 Ma to 1,785 ±7 Ma (model age: 1,786 ±5 Ma). At the Francisco deposit, the 40Ar/39Ar ages from sericite samples from sericitic halo vary from 1,779 ±6.28 to 1,777 ±6.3 Ma, therefore, very similar to those obtained to the Au ± disseminated deposits. Additionally, the 40Ar/39Ar ages to the phyllic alterations from Pé Quente deposit range from 1,833.6 ±6.2 to 1,830.6 ±6.2 Ma, whereas to the X1 deposit these ages are constrained between 1,733.3 ±6.2 to 1,751.3 ±6.1 Ma. The isotopic uniformity of the disseminated Au ± Cu deposits provides an excellent isochronous age at 1.786 ±1 Ma, with model age at 1.787 ±3.2 Ma, suggesting a major and unic Staherian gold metallogenetic event within the Alta Floresta Gold Province that would lasted approximately 10 Ma. These ages allow us to correlate the ore-forming processes with the post-collisional felsic magmatism of the Juruena arc, possibly associated to the emplacement of the Colíder (quartz-feldspat porphyry) and Teles Pires (União do Norte porphyry) suites, belonging to the third magmatic event that took place in the province. Therefore, the Re-Os sulfide ages are substantially different from the U-Pb zircon crystallization ages of the plutonic granitic host rocks. This demonstrates that there is no genetic connection between the emplacement of granitic plutons and the ore-forming processes responsible for the gold mineralization in the province, contrasting, therefore, to the three auriferous events so far proposed to the province: (i) 1.98-1.95 Ga (e.g. Luizão and Pé Quente deposits); (ii) 1.87-1.85 Ga (X1 and Serrinha deposits); and (iii) 1.77-1.79 Ga (e.g. Francisco deposit). These new Re-Os pyrite and molybdenite ages open new perspectives for gold exploration in the province as volcanic and sub-volcanic units of 1.78 to 1.77 Ga now may become prime targets / Doutorado / Geologia e Recursos Naturais / Doutor em Ciências

Orientador: Roberto Perez Xavier / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-28T02:16:57Z (GMT). No. of bitstreams: 1 Trevisan_VeronicaGodinho_M.pdf: 12082378 bytes, checksum: 8a62864dd0b76538367589ff9f11e172 (MD5) Previous issue date: 2015 / Resumo: O setor leste da Província Aurífera de Alta Floresta, Cráton Amazônico, Brasil, hospeda um grande número de depósitos de ouro na forma de veios, sistemas de veios em stockwork e disseminados associados à sequências plutôno-vulcânicas paleoproterozóicas, incluindo os depósitos filonares de Au + metais base Luiz e Au ± Cu Paraíba e Pezão. Descrição de testemunhos de sondagem, petrografia e geocronologia U-Pb SHRIMP IIe em zircão permitiram a caracterização dos diferentes atributos geológicos desses depósitos. A rocha hospedeira do depósito Paraíba é representada por biotita tonalito, enquanto que nos depósitos Luiz e Pezão corresponde a um biotita granodiorito intrudido por feldspato-pórfiro e sienogranito cortado por quartzo-pórfiro, respectivamente. As zonas de metassomatismo incluem as alterações clorítica, potássica com biotita e sericítica e, em direção aos setores distais, alterações potássica com K-feldspato e propilítica, preenchimento por carbonato, silicificação + preenchimento por quartzo e, vênulas pós-mineralização compostas por quartzo, carbonato, epidoto, sericita e/ou clorita. O veio de quartzo aurífero dos três depósitos apresenta textura maciça, enquanto que nos depósitos Luiz e Pezão é comum a ocorrência de texturas de preenchimento de espaços vazios em veios de quartzo e/ou quartzo + carbonato não mineralizados. As zonas mineralizadas do depósito Paraíba e Pezão são representadas por pirita + calcopirita, enquanto que no depósito Luiz a paragênese do minério é caracterizada por pirita + esfalerita + galena ± calcopirita. O regime de fluidos nas zonas de minério do depósito Paraíba é representado essencialmente por fluidos aquo-carbônicos, enquanto que nos depósitos Luiz e Pezão por fluidos aquosos bifásicos de baixa salinidade. Análises U-Pb SHRIMP IIe em zircão das rochas hospedeiras e feldspato-pórfiro Luiz forneceram idades de cristalização entre 2,01 e 1,97 Ga. A evolução do sistema hidrotermal dos depósitos indica redução da temperatura e incremento da ¿O2 e pH dos fluidos mineralizantes. A precipitação do minério no depósito Paraíba deve estar relacionada com o processo de imiscibilidade e interações fluido-rocha, enquanto que nos depósitos Luiz e Pezão pode ser atribuída a expansão adiabática seguida por boiling. A integração dos dados sugere que o depósito Paraíba se formou em um nível crustal mais profundo, enquanto que os depósitos Luiz e Pezão em níveis crustais mais rasos. A estreita relação espacial com plútons graníticos sugere que os depósitos Paraíba, Luiz e Pezão possam representar sistemas magmático-hidrotermais que se desenvolveram a partir da cristalização de corpos sub-vulcânicos (e.g. pórfiros), considerados com a possível fonte de fluidos, calor e metais para estes sistemas. Neste contexto, o depósito Paraíba pode ser considerado como um sistema filonar rico em ouro-quartzo hospedado por intrusões, enquanto que os depósitos Luiz e Pezão podem representar sistemas mineralizados similares a depósitos epitermais polimetálicos de sulfuração intermediária e rico em ouro-cobre de baixa sulfuração, respectivamente. Embora a idade da mineralização seja ainda desconhecida nos três depósitos, as relações geológicas entre as hospedeiras, os corpos sub-vulcânicos e zonas de minério, combinadas com os dados geocronológicos obtidos neste estudo e disponíveis na literatura, abrem a possibilidade de que a metalogênese do ouro no setor leste da província não esteja restrita a um único evento intrusivo (1.787 ± 3.2 a 1.786 ± 1 Ma), mas apontam para a possível existência de pelo menos dois eventos mineralizantes (~1.78 e ~1.97 Ga). Os dados geocronológicos U-Pb SHRIMP em zircão obtidos neste estudo sugerem a correlação das rochas graníticas hospedeiras com o primeiro evento magmático (1.98 a 1.97 Ga) do setor leste da província, ou mesmo a expansão desse intervalo de idades / Abstract: The easternmost sector of the Alta Floresta Gold Province, Amazon Craton, Brazil, hosts a significant number of disseminated, stockwork and vein-type gold deposits associated with paleoproterozoic plutonic-volcanic sequences, including the Luiz Au + base metals and the Paraíba and Pezão Au ± Cu vein-type deposits. Description of drill cores, petrography and U-Pb sensitive high-resolution ion microprobe (SHRIMP) IIe zircon geochronology allowed the characterization of the different geological attributes of these three deposits. At the Paraíba deposit the host lithotype is represented by biotite tonalite, whereas at the Luiz and Pezão deposits the host rocks encompass a biotite granodiorite intruded by a feldspar-porphyry and a syenogranite truncated by a quartz-porphyry, respectively. Metasomatic zones include chloritic, sericitic and potassic (biotite) alteration, and, outwards from the ore zones, carbonate infill, silicification plus quartz infill, potassic (K-feldspar) and propylitic alteration, besides post-mineralization quartz, carbonate, epidote, sericite and/or chlorite veinlets. The auriferous quartz veins in all deposits display massive texture, whereas barren quartz and/or quartz + carbonate veins at the Luiz and Pezão deposits commonly display open-space filling textures. Ore zones at Paraíba and Pezão deposits are represented by pyrite + chalcopyrite, whereas at Luiz deposit is characterized by pyrite + sphalerite + galena ± chalcopyrite. Fluid regime at the Paraíba ore zones encompasses aqueous-carbonic fluids, whereas at the Luiz and Pezão deposits are essentially characterized by low salinity two-phase aqueous fluids. U-Pb SHRIMP IIe zircon analysis of host rocks and Luiz feldspar-porphyry provided crystallization ages between 2,01 and 1,97 Ga. The evolution of the hydrothermal systems of these three deposits indicates a decrease in temperature and an increase in ¿O2 and pH of the fluid. Ore precipitation at the Paraíba deposit would be related to a combination of immiscibility process and fluid-rock interactions, while at the Luiz and Pezão deposits can be attributed to adiabatic expansion followed by boiling process. Data integration suggest that the Paraiba deposit may have originated at deeper crustal levels, whereas the Luiz and Pezão deposits would be positioned at shallower crustal levels. The close spatial relationship with granitic plutons suggests that the Paraíba, Pezão and Luiz deposits may be genetically linked to magmatic-hydrothermal systems, which developed as a result of the crystallization of sub-volcanic rocks (e.g. porphyries), considered as the possible source of fluids, heat and metals for these systems. In this context, the Paraíba deposit can be classified as an intrusion-hosted gold-quartz vein system, whereas the Luiz and Pezão deposits may represent mineralized systems similar to intermediate sulfidation polymettalic and low sulfidation gold-copper-bearing epithermal deposits, respectively. Although the mineralization ages are still unknown for these three deposits, the geological relationships between host and sub-volcanic rocks and ore zones, combined with geochronological data from this study and from literature, open the possibility that gold metallogeny within the province is not restricted to a single paleoproterozoic intrusive event (1.787 ± 3.2 to ± 1.786 1 Ma), but point to the possible existence of at least two mineralizing events (~ 1.78 and ~ 1.97 Ga). The U-Pb zircon geochronological data from this study suggest the correlation of the granitic rocks to the first magmatic event (1.98 to 1.97 Ga) in the easternmost portion of the province, or even an expansion of this age interval / Mestrado / Geologia e Recursos Naturais / Mestra em Geociências

Visualization and study of reconformation of polyelectrolytes (PEs) of different architecture is of great fundamental and practical interest. Verification of theoretical predictions with experiment is of essential importance. On the other hand, a wide range of bottom-up techniques based on patterning of matter on the length scale of a few nanometers have been recently developed. Particularly interesting is the possibility of using self-assembled single molecule structures as templates for the deposition of inorganic matter, in particular metals. Synthetic &amp;quot;normal-sized&amp;quot; polymers of various architecture, like poly-2-vinylpyridine (P2VP) or polystyrene-poly(2-vynil pyridine) P2VP7-PS7 star-like block copolymer, adsorbed on solid substrates have been visualized for the first time with molecular resolution by AFM in different conformation. This finding allowed us to study largely discussed problem, a coil-to-globule transition of PEs. It was found that PE molecules undergo conformational transitions from stretched worm-like coil to compact globule via set of necklace-like globules, as the fraction of charged monomers decreases with an increase of pH and ionic strength. These results are in good agreement with recently developed DRO theory for weakly charged flexible PEs in poor solvent. The size of the deposited single molecules correlates very well with molecular dimensions in solution obtained in light scattering experiments. PE single molecules of various architectures was mineralized in different conformations that constitutes the route to nanoparticles with desired shape (including wire-shape and star-shaped), size, and composition (including metallic, magnetic and semiconductive nanoparticles). It was shown that molecular details of the adsorbed linear flexible PE molecules determine the dimensions of the nanostructures after metallization and that observed sizes are consistent with the decoration of single molecules with nanoclusters. Thus those metallized nanoparticles (cluster assembles) reflect the conformation of original adsorbed PE molecules. The dimensions of the obtained nanowires are significantly smaller than those previously reported. All of these features are of the potential benefit in applications for nanodevices. Metallization of the PS7-P2VP7 improves AFM resolution due to the selective deposition of Pd clusters along the P2VP chains. For the first time, the number of the P2VP second generation arms of the heteroarm block-copolymer was directly counted in the single molecule AFM experiment. Simple contrasting procedure was developed to improve AFM visualization of positively charged polymer chains deposited on the substrates of relatively high roughness. This method allows increasing the thickness of the resulting structures up to 10 nm, and, consequently, provide visualization of polymer chains on rough surfaces. This innovation is important for the development of single molecule experiments with polymer chains. The reaction of HCF-anion could be used for recognition of polycation molecules, when polycations, polyanions and neutral molecules coexist on the surface. Recently, the study was strongly restricted to atomically smooth surfaces. The contrasting procedure extends the range of substrates (Si-wafers, chemically modified or patterned Si-wafers, polished glasses, polymer films, etc) appropriate for the experiments. Thus, polymer single molecules can be considered not only as representative of the ensemble molecules, but also as individual nanoscale objects which can be used for future nanotechnology for the fabrication of single molecule electronic devices. Also these findings are important from fundamental point of view, since developed approach can be successfully applied for investigation of various &amp;quot;classical&amp;quot; problems in polymer science, such as polymer reconformation, interpolyelectrolyte complex formation, polymer diffusion, adsorption, etc.

Age estimation is a common requirement in forensic, bioarcheological and biomedical practice. This master thesis deals with age estimation based on permanent tooth mineralization according to Demirjian et al. (1973). The research material consisted of orthopantomograms of 716 Czech and 743 French children aged between 4 and 15 years. The purpose of this study was to analyse the suitability of the original French-Canadian standards for age estimation (Demirjian a Goldstein, 1976) and the recent Belgian standards (Willems et al., 2001) in Czech and French population. Another aim of the study was to evaluate the accuracy of the neural network method that represents a completely new approach in data prediction. In order to express the accuracy of estimate we used mean and median of difference between chronological and dental age, and RMS error. Using logistic regression, differences in tooth mineralization between Czech and French population and between girls and boys were also evaluated. Our results indicate that the French-Canadian standards gave a consistent overestimation of dental age compared with chronological age. Mean difference was 0,33 years for Czech children and 0,45 and 0,46 years for French girls and boys, respectively. We found that Willem's method and neural network method were more...

Die Besonderheit der DNA-Nanotechnologie liegt in der Verwendung von DNA als Konstruktionsmaterial für die Herstellung von artifiziellen Strukturen im Nanometermaßstab (Seeman, 1982; Winfree et al., 1998). Diese DNA-Nanoobjekte, wie beispielsweise DNA-Nanoröhren, offerieren innovative und vielversprechende Anwendungsmöglichkeiten in verschiedenen Bereichen wie der Elektronik oder Medizin. Eine Herausforderung für die dauerhafte Verwendung von DNA-Nanoröhren stellt deren Stabilität dar. Einflussfaktoren wie die DNA-Nukleaseaktivitäten, die Ionenstärke und hohe Temperaturen können dabei eine langfristige Anwendung limitieren. Als ein Lösungsansatz für die Erhöhung der Beständigkeit wird eine gezielte Mineralisierung der DNA-Nanoröhren durch spezifische Fusionsproteine angestrebt. Ziel dieser Arbeit ist die dafür notwendige Herstellung und Charakterisierung der DNA-bindenden Fusionsproteine mit Mineralisierungsdomänen vorzustellen. Das umfasst das Auswählen geeigneter DNA-Bindungsproteine als Bestandteil der Fusionsproteine. In dieser Arbeit wurden die DNA-Bindungsproteine MutH und SBB aus Escherichia coli (E. coli) sowie Yku70p aus Saccharomyces cerevisiae (S. cerevisiae) aufgrund ihrer spezifischen Bindungseigenschaften dafür identifiziert. Damit können die Fusionsproteine sequenzspezifische oder -unspezifische Bindungen mit doppelsträngiger (engl. double stranded DNA, dsDNA) oder einzelsträngiger DNA (engl. single stranded DNA, ssDNA) eingehen. Es ist mittels Klonierung gelungen, verschiedene Fusionskonstrukte mit den genannten DNA-Bindungsproteinen zu generieren. Diese beinhalten ebenfalls das enhanced green fluorescent protein sowie den His6-Tag für den Expressionsnachweis und die Proteinreinigung. Weitere Varianten der Fusionskonstrukte bestehen zusätzlich aus der tobacco etch virus-Protease-Erkennungssequenz zur Entfernung des His6-Tags und der Domänen R5-Peptid (R5P) oder Poly-L-Arginin (PLR) für die Mineralisierung. Bestandteil dieser Arbeit sind Western-Blot-Analysen und mikroskopische Aufnahmen, welche die erfolgreiche heterologe Expression aller Fusionskonstrukte nachweisen. Aus den Ergebnissen der Expressions- und Löslichkeitsanalysen lässt sich schlussfolgern, dass insbesondere das Expressionslevel und die Synthese löslicher Proteine mit den Mineralisierungsdomänen eine Herausforderung darstellen. Ebenfalls in dieser Arbeit sind Versuche zur Optimierung mit verschiedenen Expressionsstämmen (E. coli und S. cerevisiae) und Expressionsparametern (Temperatur und Induktor-Konzentration) enthalten. Den Ergebnissen nach eignen sich besonders die Fusionsproteine MutH-EGFP-His6 und SSB-EGFP-His6 für die weiteren Experimente. Die Untersuchungen der DNA-Bindungseigenschaften erfolgten mittels Electrophoretic mobility shift assay (EMSA) und Rasterkraftmikroskopie (engl. atomic force microscopy, AFM). Diese Methoden mussten für jedes Fusionsprotein zuvor etabliert und optimiert werden. Zu Beginn stand das MutH-Fusionsprotein im Focus, wobei die durchgeführten EMSA-Untersuchungen die Spezifität zur GATC-Erkennungssequenz sowie zur dsDNA betrachteten. Die Charakterisierung mittels AFM diente als weitere Möglichkeit zur Analyse der DNA-Bindungseigenschaften. Zusätzlich kam in dieser Arbeit eine Variante des CRISPR/Cas9-Systems als Fusionsprotein für eine sequenzspezifische Adressierung von dsDNA zum Einsatz. Die EMSA- und AFM-Analysen deuteten dabei auf eine Interaktion von dem dCas9-Fusionsproteins und dsDNA hin. Weiterhin war das SSB-Fusionsprotein Bestandteil der Untersuchungen. Die Bindungsanalysen mittels EMSA zeigten, dass es bevorzugt mit ssDNA interagiert und nur eine geringe Affinität zu dsDNA vorliegt. Die Bindung zu ssDNA konnte ebenfalls erfolgreich anhand von AFM-Untersuchungen gezeigt werden. Zusammenfassend bestätigen die Ergebnisse die Funktionalität des MutH- und SSB-Fusionsproteins. Es konnten zudem erste Hinweise erbracht werden, die eine spezifische Bindung der Fusionsproteine an dsDNA oder ssDNA belegen. Mit dieser Arbeit ist es gelungen, Proteinderivate zu generieren und charakterisieren, wodurch eine entscheidende Grundlage für die gezielte Mineralisierung von DNA-Konstrukten geschaffen wurde.

Titanium alloys are frequently used in the medical field as bone implant materials due to their excellent biocompatibility and corrosion resistance. Yet, their elastic modulus is usually significantly higher than the one of bone, which can lead to a reduction of bone tissue at the implant site. The current research is therefore focused on the development of highly porous implants, which promise a low elastic modulus close to that of bone, an enhanced bone ingrowth and an improved vascularization. However, the appropriate pore size for an optimal osseointegration still remains unclear. To that end, a transparent tubular microsystem is developed to mimic such a porous microenvironment in order to study single bone cell behavior and early bone formation processes. The system is fabricated out of an implant material (β-stabilized Ti-45Nb (wt%)). It is demonstrated that the bulk material composition, which is consisting of a high Nb content, can be closely transferred to transparent thin films by using reactive sputtering. These films then self-assemble into tubular microscaffolds (TS) with a diameter range between 10-42 μm. Biological studies are subsequently performed to investigate the response (e.g. cell adhesion, migration, osteogenic differentiation) of human Mesenchymal Stem Cells (MSC) to the TS. It is shown that cells form fewer, more diffuse focal adhesion points inside the TS compared to a planar surface and the spatial confinement causes a switch in between amoeboid and mesenchymal migration modes. In addition, it is demonstrated that cells can survive inside the TS for at least 12 days during osteogenic differentiation and partly mineralize the TS interior. The observed mineralization process is furthermore linked to the formation of hydroxyapatite crystals inside dead cells bodies, which leads to a crystallization over time. All in all, the TS platform offers an easy way to identify key factors of bone cell-implant interactions that can be used to improve the biocompatibility of the bone-implant interface in the future.