Properties and origins of two byproducts from steelmaking plants, slag and acidic wastewater, are investigated in this report. The slags' suitability as neutralizing agents of acidic wastewater from the pickling process, with regard to amount of slag required and the environmental impact of the produced byproducts is investigated. Currently, lime concentrate – which is a finite resource – is used as a neutralizing agent at steel production plants. Because one of the most abundant components in slag is calcium oxide, which is also the active neutralizing substance in lime concentrate, slag is a potential neutralizing agent. A total number of eight slags – four slags from Outokumpu Stainless and four slags from Sandvik Materials Technology – are examined and compared to lime concentrate. Theoretical calculations and experimental trials are performed in order to determine if slag is able to neutralize acidic wastewater. The results show that all the slags are able to neutralize acidic wastewater, but not all slags have the same efficiency. The slags from SMT’s AOD-converter and SMT’s landfill are the most efficient in terms of total amount of neutralizing agent required to neutralize acidic wastewater. The results show that approximately four times more dry slag substance is required, when using the most efficient slag than when lime concentrate is used to neutralize acidic wastewater. The environmental and economic implications of the results are discussed. / Denna rapport undersöker egenskaperna hos de restprodukter som produceras vid ståltillverkningen, däribland slagg och surt avfallsvatten. Mer exakt bestäms slaggernas lämplighet att agera som neutraliserings reaktant i reningsporcessen av surt avfallsvattnet från betningsprocessen. Lämpligheten mäts i mängd slagg som krävs vid neutraliseringen samt restprodukternas miljömässiga påverkan. Idag används neutraliseringsmedlet kalkkoncentrat vid stålverken, vilket är en ändlig resurs. Då en av huvudsubstanserna i slagg är kalciumoxid, vilken också är den aktiva reaktanten i neutraliserings processen, genomförs experiment med slagg som neutraliseringsmedel. Totalt analyseras åtta slagger – fyra stycken slagger från Outokumpu Stainless och fyra stycken slagger från Sandvik Materials Technology. Slaggerna jämförs med referenstestersom utförts med kalk från vardera företag. Teoretiska beräkningar och experiment utförs för att undersöka om slagg kan neutralisera surt avfallsvatten. Resultaten visar att alla slagger fungerar som neutraliseringsmedel för det sura avfallsvattnet, dock med varierande effektivitet. Slaggen från SMT’s AOD-konverterslagg samt SMT’s deponis är mest effektiv när man ser till tillsattsmängd. Efter vidare beräkningar kan det konstateras att det krävs 4 gånger mer torrsubstans vid neutralisering med de mest effektiva slaggerna än vid neutralisering med kalkkoncentrat. Ekonomiska och miljömässiga innebörden av resultaten diskuteras. / Neutralsyra

Les maladies inflammatoires de l’intestin (MIIs) comprennent la colite ulcéreuse (CU) et la maladie de Crohn (MC). Elles résultent en l’inflammation chronique du tractus gastro-intestinal. Des études d’association pan-génomiques ont associé le locus 14q31, incluant les gènes galactosylceramidase (GALC) et G protein-coupled receptor 65 (GPR65), à ces pathologies. Nous avons déterminé que le variant le plus associé aux MIIs de cette région (rs8005161; p=2,35x10-14) est parfaitement corrélé (r2=1) à un variant codant dans le gène GPR65 (rs3742704: Ile231Leu). GPR65 code pour un récepteur couplé à des protéines G (RCPG) senseur de pH. Nous avons observé que GPR65 est exprimé dans les tissus lymphoïdes et mucoïdes en plus des lignées cellulaires immunitaires et des cellules immunes primaires humaines. Son expression augmente significativement dans les biopsies inflammées de patients atteints de la CU comparativement à des biopsies non-inflammées ou à des biopsies d’individus sains. GPR65, lorsqu’activée par un pH acide, stimule l’accumulation d’AMPc, la formation de fibres de stress et l’activation de la voie RhoA. GPR65 semble donc être un bon candidat pour l’étude de l’étiologie des MIIs. Nos objectifs étaient donc de définir les voies découlant de l’activation de GPR65 et d’évaluer l’impact de GPR65*231Leu sur ces voies. Nous avons utilisé des HEK293 exprimant de façon stable l’une ou l’autre des deux allèles de GPR65 et déficientes pour Gαs/olf, Gαq/11 ou Gα12/13 puisqu’il est connu que Gαs/olf activent l’adénylate cyclase, Gαq/11 mènent au relâchement de Ca2+ intracellulaire et peuvent activer certaines isoformes de l’adénylate cyclase et Gα12/13 régulent le remodelage du cytosquelette d’actine. Nous avons démontré que l’accumulation d’AMPc dépendante de l’activation de GPR65 par un pH acide est causée, au moins en partie, aux voies Gαs/olf et peu ou pas aux voies Gαq/11. Il ne semble pas y avoir un effet du variant GPR65*231Leu sur ces voies. Cependant, nous avons observé que le variant GPR65*231Leu réduit la formation de fibres de stress et inhibe l’accumulation d’actine filamenteuse (F-actine) dépendantes de l’activation de GPR65 par un pH acide. Des données préliminaires nous montrent que la formation de fibres de stress est causée, au moins en partie, aux voies G12/13. En conclusion, nous avons démontré que GPR65 active les voies Gαs/olf et Gα12/13 et que le variant codant associé aux MIIs altère le remodelage de l’actine. GPR65 pourrait donc potentiellement avoir un rôle dans la pathologie des MIIs. / Inflammatory bowel diseases, mainly comprising of ulcerative colitis (UC) and Crohn’s disease (CD), result in the chronic inflammation of the gastrointestinal tract. Genome-wide association studies have associated the 14q31 locus, including the genes galactosylceramidase (GALC) and G protein-coupled receptor 65 (GPR65), to those phenotypes. The most associated variant in this region for IBD (rs8005161; p=2,35x10-14) is correlated (r2=1) to a missense coding variant of GPR65 (rs3742704: Ile231Leu). GPR65 encodes a pH-sensing G protein-coupled receptor (GPCR). We observed that GPR65 is expressed in lymphoid and mucosal tissues as well as in immune cell lines and human primary immune cells. We also found that its expression is significantly increased in inflamed biopsies from UC patients compared to non-inflamed biopsies and biopsies from healthy controls. Upon activation by low pH, GPR65 stimulates accumulation of cAMP, formation of stress fibers and activation of the RhoA pathway. Thus GPR65 is a good candidate causal gene for the IBD pathology. Our objective, therefore, was to define pathways downstream of activation of GPR65 and to evaluate the impact GPR65*231Leu on these pathways. We used HEK 293 cells stably expressing one or the other allele of GPR65 and deficient for either Gαs/olf, Gαq/11 or Gα12/13 as it is known that Gαs/olf activates adenylyl cyclase, Gαq/11 leads to the release of intracellular Ca2+, which can also activate certain isoforms of adenylyl cyclase, and that Gα12/13 regulates actin cytoskeletal remodeling. We demonstrated that cAMP accumulation upon activation of GPR65 is, at least partly, due to the Gαs/olf pathway and only slightly or not at all to the Gαq/11 pathway. The coding variant, however, does not appear to have an effect on that pathway. In contrast, we observed that GPR65*231Leu variant reduces the GPR65-dependent stress fiber formation and inhibits the increase of filamentous actin (F-actin) content versus free globular-actin (G-actin) upon activation by low pH. Also, preliminary data showed that the stress fiber formation in HEK293 cells is due to the G12/13 pathways. In conclusion, we demonstrate that GPR65 activates both Gαs and Gα12/13, the coding variant alters the actin remodeling pathway and that GPR65 potentially has a causal role in IBD.

Les travaux présentés dans ce mémoire ont pour but de mieux comprendre les relations entre la microstructure des revêtements métalliques nanocristallisés et leurs propriétés électrochimiques et mécaniques. Les dépôts de nickel sont élaborés par électrodéposition en courant continu et en courant pulsé dans un bain au sulfamate de nickel avec des sels de haute pureté, sans additif afin de minimiser les risques de contamination. Une caractérisation précise des états métallurgiques développés est réalisée au moyen de diverses techniques (MEB, MET, DRX, AFM, EBSD, SIMS, GDOES) afin d’évaluer la microstructure à différentes échelles (taille de grain, texture, contraintes internes, type de joints de grains) et d’identifier les contaminants. Trois types de texture ont été développés, associés à différentes tailles d’hétérogénéités structurales allant du micromètre à quelques dizaines de nanomètres. Une loi dite “d’échelle” a été mise en évidence, permettant de corréler les résultats obtenus par les diverses méthodes d’analyse. L’affinement de la taille de grain se traduit par une augmentation de la contamination dans les dépôts et entraîne une augmentation de la microdureté. La loi de Hall-Petch est influencée par l’orientation cristallographique ce qui a pu être relié à la nature des joints de grains et à la contamination des revêtements. Une étude préliminaire de la réactivité électrochimique en milieu acide a montré le rôle marqué des effets de surface (contamination et rugosité de surface). La réalisation d’un polissage électrolytique sur les revêtements a permis d’étudier l’influence des paramètres métallurgiques (taille de grain, contamination, nature des joints de grains) sur la réactivité. Les courbes de polarisation dans le domaine anodique et dans le domaine cathodique ont été simulées à l’aide de modèles cinétiques. Les résultats obtenus suggèrent que les joints de grains ont un effet qui peut être activant ou désactivant suivant l’étape considérée, ces effets pouvant être atténués par la présence d’impuretés. Les modifications de propriétés mécaniques et électrochimiques des revêtements ne peuvent être attribuées à une diminution de la taille de grain seule. / The purpose of the work presented in this manuscript is to better understand the relations between the microstructure of nanocrystallized metal coatings and their electrochemical and mechanical properties. Nickel deposits are elaborated by electrodeposition using direct current and pulse current in a nickel sulphamate bath with salts of high purity and without additive, in order to minimize the risks of contamination. A precise characterization of the developed metallurgical states is carried out by means of various techniques (SEM, TEM, XRD, AFM, EBSD, SIMS, GDOES) in order to evaluate the microstructure on various scales (grain sizes, textures, internal stresses, type of grain boundaries) and to identify contaminants. Three types of texture were developed associated with various sizes of structural heterogeneities from about one micrometer to a few dozens of nanometers. A “scale” law, allowing to correlating the results obtained by the various methods of analysis was shown. The grain size refinement results in an increase of contamination in the deposits and involves an increase of microhardness. The Hall-Petch law is influenced by the crystallographic orientation which could be connected to the nature of grain boundaries and the contamination of the coatings. A preliminary study of the electrochemical reactivity in acidic media showed the marked role of the surface effects (contamination and roughness of surface). Electrolytic polishing of the coatings highlights the influence of the metallurgical parameters (grain size, contamination, nature of grains boundaries) on the reactivity. The polarization curves in anodic domain and cathodic domains were simulated using kinetic models. The obtained results suggest that grain boundaries can either activate or deactivate the electrochemical kinetics according to the considered stage, these effects being able to be constrained by the presence of impurities. The modifications of mechanical and electrochemical properties of the coatings cannot be ascribed to a reduction of the grain size alone.

L’objectif premier de notre projet était d’établir un modèle animal de douleur chronique orofaciale, lequel pourrait imiter la sensibilité retrouvée chez les patients souffrant de douleur orofaciale myalgique. Nous avons procédé à des injections intramusculaires de saline acide (2 injections à 2 jours d’intervalle pH 4.0) pour induire une sensibilisation mécanique des mucles massétérins. La réponse nocifensive a été mesurée à l’aide de filaments de von Frey avant et après ces injections dans des rats Sprague-Dawley. Par la suite, le potentiel analgésique de différents antagonistes des récepteurs glutamatergiques fût évalué par l’injection intramusculaire de ces antagonistes à différents moments. Nos résultats suggèrent que deux injections de saline acide, produisent une hypersensibilité mécanique signalée par l’augmentation du nombre de réponses à l’application de filaments de von Frey. Cet effet dure plusieurs semaines et est bilatéral, même lorsque les injections sont unilatérales, indiquant qu’une composante centrale est forcément impliquée. Toutefois, une composante périphérique impliquant les récepteurs glutamatergiques semble présider le tout puisque les antagonistes glutamatergiques, appliqués de façon préventive empêchent le développement de l’hypersensibilité. Cependant, le maintien de cette hypersensibilité doit dépendre de mécanismes centraux puisque l’application d’antagonistes une fois la sensibilisation induite, ne diminue en rien le nombre de réponses obtenues. Ce modèle semble approprié pour reproduire une hypersensibilité musculaire durable de bas niveau. Nos données indiquent que les récepteurs glutamatergiques périphériques participent à l’induction de cette hypersensibilité de longue durée. Nous croyons que ce modèle pourra éventuellement contribuer à une meilleure compréhension des mécanismes à l’origine des myalgies faciales persistantes. / The first objective of this project was to establish an animal model of chronic orofacial pain, which could mimic symptoms of patients suffering from orofacial myalgia. We used acidic saline injections (2 injections, 2 days apart at pH 4.0) in masseteric muscles to induce mechanical hypersensitivity. Nocifensive behavior was measured before and after the injections using von Frey filaments in male Sprague Dawley rats. Later, the potential analgesic effect of glutamate receptors antagonists was measured by intramuscular administration of these antagonists at different times. Our results suggest that two injections of acidic saline produce a mechanical hypersensitivity as reflected by the increased number of responses to applications of von Frey filaments. This effect lasts several weeks and is bilateral, even when the injections are unilateral, indicating that a central component must be involved. However, the initial stage of induction of this hypersensitivity involves peripheral glutamate receptors since injection of their antagonists before the second acidic saline injection prevents development of the nocifensive response, whereas their injection at later times is ineffective in blocking development of the response. This model based on a double injection of acidic saline seems appropriate to reproduce low intensity, long-lasting muscle pain. Our data suggests that peripheral glutamate receptors are involved in the induction of this long-term hypersensitivity. We believe that this model may contribute to a better understanding of the mechanisms behind persistent orofacial muscle pain.

As fosfolipases A2 (PLA2s) catalisam a hidrólise de ácidos graxos na posição sn-2 das membranas fosfolipídicas e liberam, como subprodutos, ácidos graxos livres. As PLA2s do grupo IIA são encontradas em peçonhas de serpentes da família Viperidae e desempenham diversas atividades apresentando potencial miotóxico, neurotóxico, hemolítico, edematogênico, citotóxico, hipotensivo, anticoagulante, inibição/ativação da agregação plaquetária, bactericida e pró-inflamatório. Esse trabalho teve como objetivo o isolamento e a caracterização funcional de uma PLA2 isolada da peçonha de Bothrops jararaca. Para a purificação dessa proteína, denominada BJ-PLA2-I, foram necessários três passos cromatográficos consecutivos: cromatografia de exclusão molecular em Sephacryl S-200, cromatografia de troca iônica em Source TM 15Q/50mL e cromatografia de troca iônica em MonoQ TM 5/50 GL. A BJ-PLA2-I apresentou elevado grau de pureza por SDS-PAGE e por cromatografia de fase reversa C18, em HPLC. Apresentou ainda, características ácidas, com pI em torno de 4,4 e teve a sua massa molecular determinada por dois métodos, obtendo-se valores bem próximos de 14,8 kDa (SDS-PAGE) e 14,2 kDa (MALDI-TOF). Esse fato é comum considerando que a espectrometria de massas é um método mais preciso e determina de maneira mais exata a massa molecular. O sequenciamento N-terminal da BJ-PLA2-I resultou em 60 resíduos de aminoácidos. O alinhamento múltiplo com outras fosfolipases A2 de serpentes do mesmo gênero mostrou similaridade entre elas, mostrando identidade de 100% com a BJ-PLA2, fosfolipase A2 Asp-49, também isolada da Bothrops jararaca. Esse dado levanta a hipótese de que a BJ-PLA2-I purificada neste trabalho e a BJ-PLA2 se tratam da mesma proteína, entretanto essa hipótese só poderá ser confirmada quando a sequência completa da BJ-PLA2-I for obtida. Outros dados encontrados neste trabalho reforçam essa hipótese, isso porque, avaliando a atividade fosfolipásica, o efeito sobre as plaquetas e o pI, tanto a BJ-PLA2-I quanto a BJ-PLA2 apresentaram características semelhantes. A BJ-PLA2-I, sendo uma Asp-49, mostrou alta atividade catalítica e efeito inibidor da agregação plaquetária induzida por ADP (20,5 ?g/mL inibiu 50 % da agregação plaquetária). Ela também foi capaz de induzir a migração leucocitária após a administração de diferentes concentrações (5, 10 e 20 ?g/mL) da BJ-PLA2-I. Esse dado também foi encontrado no ensaio em que a concentração de 10 ?g/mL foi fixada e variou-se o tempo de 2, 4 e 24 horas, observando-se principalmente a migração de neutrófilos. Além disso, verificou-se a liberação das citocinas IL-6 e IL-1?, de proteínas totais e de prostaglandina E2 na reação inflamatória induzida pela BJ-PLA2-I. No entanto, não foi observado a produção de TNF-?, IL-10 e leucotrieno B4. A BJ-PLA2-I caracterizou-se como uma PLA2 pró-inflamatória, produzindo inflamação local aguda. A BJ-PLA2-I foi avaliada quanto ao seu potencial antitumoral em três linhagens celulares distintas (PBMC, HL-60 e HepG2). Observou-se que a enzima em questão possui baixo potencial antitumoral para a linhagem HL-60, reduzindo o número de células tumorais em apenas cerca de 20% nas concentrações testadas. Verificou-se pequena alteração na viabilidade celular das células de PMBC, nas maiores concentrações testadas (160 e 80 ?g/mL) e, na linhagem HepG2 não foi encontrada nenhuma alteração. Concluindo, as informações adquiridas neste trabalho são de suma importância para a melhor compreensão dos mecanismos envolvidos nas atividades biológicas desempenhadas pelas PLA2s. Além disso, a BJ-PLA2-I pode servir como modelo molecular para a formulação de fármacos mais eficazes a serem utilizados no tratamento de várias doenças. / Phospholipases A2 (PLA2s) catalyze the hydrolysis of fatty acids in the sn-2 position of membrane phospholipids, releasing free fatty acids as by-products. PLA2s of group IIA are found in snake venoms of the Viperidae family and perform various activities, including myotoxic, neurotoxic, hemolytic, edematogenic, cytotoxic, hypotensive, anticoagulant, inhibition/activation of platelet aggregation, bactericidal and proinflammatory effects. This work aimed at the isolation and functional characterization of a PLA2 isolated from Bothrops jararaca venom. For the purification of this protein, called BJ-PLA2-I, three consecutive chromatographic steps were used (size exclusion chromatography on Sephacryl S-200, ion exchange chromatography on Source 15Q/50 mL, ion exchange chromatography on MonoQ 5/50 GL). Confirmation of the purity of BJ-PLA2-I was evaluated by SDS-PAGE and reverse phase HPLC using a C18 column. BJ-PLA2-I has acidic characteristics, with pI around 4.4, and its molecular mass was determined by two methods, obtaining values close to 14.8 kDa (SDS-PAGE) and 14.2 kDa (MALDI-TOF). The N-terminal sequencing of BJ-PLA2-I resulted in 60 amino acid residues. Multiple alignment with other phospholipases A2 of snakes of the same genus showed high similarity between them, showing 100% identity with BJ-PLA2, an Asp-49 phospholipase A2 previously isolated from Bothrops jararaca venom. This finding raises the possibility that the PLA2 purified in this work is the same protein previously described (BJ-PLA2), however, this assumption can only be confirmed when the complete sequence of BJ-PLA2-I is obtained. Other data obtained in this study support this hypothesis, considering that the phospholipase activity, the effect on platelets and pI of both BJ-PLA2-I and BJ-PLA2 showed to be similar. BJ-PLA2-I, being an Asp-49 PLA2, showed high catalytic activity and inhibitory effect on the platelet aggregation induced by ADP (20.5 ?g/mL inhibited 50% of the platelet aggregation). It was also able to induce leukocyte migration after the administration of different concentrations (5, 10 and 20 ?g/mL) of BJ-PLA2-I. This fact was also found when the concentration of 10 ?g/mL was fixed and response times were varied (2, 4 and 24 hours), observing especially neutrophil migration. Furthermore, there was a release of IL-6 and IL-1?, total proteins and prostaglandin E2 in the inflammatory reaction induced by BJ-PLA2-I, however, the production of TNF-?, IL-10 and leukotriene B4 was not observed. BJ-PLA2-I was characterized as a proinflammatory PLA2 producing acute local inflammation. BJ-PLA2-I was evaluated for its antitumor potential on three different cell lines (PBMC, HL-60 and HepG2). It was observed that this enzyme showed a low antitumor potential on HL-60 tumor cell line, reducing the number of tumor cells in only about 20% at the concentrations tested. There was little change in cell viability of PBMC cells in the higher concentrations tested (80 and 160 ?g/mL), but no change was found on HepG2 tumor cell line. In conclusion, the information obtained in this work are of utmost importance for better understanding the mechanisms involved in the biological activities induced by PLA2s. Furthermore, BJ-PLA2-I may serve as a molecular model for the formulation of more effective drugs to be used in the treatment of various diseases.

La Cordillère des Andes, issue de la subduction de la plaque Pacifique sous le continent Sud-Américain, est un système orogénique propice à la formation de grands systèmes volcaniques acides, dans lesquels coexistent des produits d’éruptions volcaniques explosives de grandes magnitudes et des laves et dômes, associés à des calderas mono- ou polygéniques. Ce mémoire de thèse apporte de nouvelles connaissances sur certains systèmes volcaniques acides du Sud du Pérou, dont les produits affleurent dans les canyons d’Ocoña-Cotahuasi-Maran (OCM). Ces canyons, les plus profonds des Andes (3 à 3,5 km), résultent de la combinaison des processus de soulèvement tectonique, d’incision, et d’érosion depuis 15 Ma. Les imposantes séries ignimbritiques exposées dans cette région (env. 10000 km²), témoignent de l’existence d’un volcanisme explosif de grande ampleur, associé à des systèmes acides peu connus d’après les études antérieures. Cette étude vise tout d’abord à obtenir une chrono-stratigraphie améliorée des événements ignimbritiques (groupes, unités) dans la région OCM pour mieux connaître les récurrences des super-éruptions dans cette région au cours des derniers 25 Ma. Ensuite, nous cherchons à localiser les sources des grandes unités et à identifier les éventuelles structures d’effondrement associées (calderas). Pour ce faire, nous avons combiné diverses techniques, associant l’étude de la stratigraphie et de la lithologie des dépôts volcaniques, les datations par la méthode 40Ar-39Ar des principales unités ignimbritiques et coulées de lave, l’imagerie satellitaire (Landsat, SPOT) et la pétrologie (assemblages minéralogiques, étude des textures et des compositions chimiques) et enfin, les mesures de densité et d’anisotropie de susceptibilité magnétique des ignimbrites (ASM) pour analyser les directions d’écoulement et tenter de localiser leurs sources. Ainsi, les résultats nous ont permis d’identifier huit événements ignimbritiques, dont six majeurs, datés entre ~24 Ma et ~2 Ma. Les âges des grandes unités (Nazca, Alpabamba, Huaylillas, Caraveli, Sencca inférieure et supérieure) montrent une récurrence moyenne de l’ordre de 4-5 Ma depuis 25 Ma. Les lithologies sont assez semblables, bien que les degrés de soudure varient beaucoup, allant de produits meubles jusqu’aux faciès eutaxitiques. L’étude pétrologique révèle des assemblages de minéraux assez homogènes, les paragenèses étant dominées par le quartz, le feldspath, la biotite, l’amphibole et des oxydes. Les volumes bruts des unités principales que nous avons déterminés se situent entre ~40 et ~500-800 km3. Cependant, il ne s’agit que de valeurs minimales, puisque nous considérons que les volumes initiaux sont au moins le double ou le triple, probablement dans la gamme ~100 à ~2400 km3. La distribution des unités ignimbritiques d’OCM et les résultats des analyses ASM désignent plusieurs zones sources. L’unité de Caraveli provient de la caldera de Trapiche, qui contient le lac Parinacochas. Cette structure que nous identifions, d'un diamètre de ~22 km, est située dans un bassin tectonique allongé selon la direction N-S. Elle est occupée dans sa partie ouest par un dôme résurgent de 800 m de haut, le Cerro Trompo Orjo. Les unités Huaylillas et Alpabamba, ainsi que les groupes Sencca (inférieure et supérieure) seraient issus d’une source entièrement recouverte par le massif volcanique quaternaire du Nevado Coropuna. Des estimations de volumes éruptifs suggèrent une atténuation significative du volcanisme ignimbritique depuis 9 Ma, peut-être liée à la maturation orogénique de l’Altiplano-Puna. En profondeur, le magmatisme a probablement contribué à l’épaississement crustal par adjonction de grands volumes de magma. (...) / The Andes, resulting from the subduction of Pacific plate under South-America continental plate, is an orogenic system suitable for large acidic volcanic systems formation. These structures display at the same time volcanic products from high magnitude explosive eruptions, lavas and domes, and mono- or polygenetic calderas. This manuscript brings a new expertise on some of the acidic volcanic systems in South Peru, which products outcrop in the Ocoña - Cotahuasi - Maran canyons (OCM). This canyons system, one of the deepest worldwide (up to 3.5 km), was created by combined tectonic uplift, incision and erosion processes since 15 Ma. Voluminous ignimbritic series widespread in this region (around 10000 km2) are evidences for a past high amplitude explosive volcanic activity related to little-known acidic systems. The topic of this study is to obtain an enhanced chrono-stratigraphy of the OCM region ignimbritic succession (groups and units). This would provide a better knowledge on the regional super-eruptions recurrence since the last 25 Ma. Then, we focus on localizing the largest ignimbrites sources and identify the possible related collapse structures (calderas). For that purpose we combine several studies, from stratigraphy, deposits lithology to 40Ar-39Ar dating of the main ignimbritic units and lava flows. We also use satellite imagery (Landsat, SPOT) and petrology (mineralogical assemblage, textures and geochemical composition). Finally, we measure the ignimbrites density and anisotropy of magnetic susceptibility (AMS) to determine their flowing directions and estimate their sources locations. Thus, the results let us identify eight ignimbritic events among which, six happened between ~24 Ma and ~2 Ma. The main units ages (Nazca, Alpabamba, Huaylillas, Caraveli, lower and upper Sencca) show an average recurrence of 4-5 Ma since 25 Ma. Lithologies are similar even if welding degrees ranges are spread from loose deposits to eutaxitic facies. Petrological study show quite homogeneous mineralogical assemblages since quartz, feldspar, biotite, amphibole and oxydes dominate the paragenesis. Our estimations of the main units bulk volumes range from ~ 40 to ~ 500-800 km3. However, these are only minimum values since we consider that initial volumes as twice or three times higher, probably in the range of ~100 to ~2400 km3. The OCM ignimbrite flow units distribution and the AMS study results indicate several regions as sources for these units. Caraveli unit flowed from Trapiche caldera in which the Parinacochas lake rests. This structure is estimated to be ~22 km of diameter and lays in a N-S orientated tectonic basin. Its western part is occupied with a 800 m high resurgent dome, named Cerro Trompo Orjo. Alpabamba and Huaylillas units, as Sencca units (lower and upper) would come from a source presently entirely covered with the quaternary massif of Nevado Coropuna. Estimations of eruptive volumes recall an important decrease of ignimbritic volcanism since 9 Ma, which might be related to simultaneous Altiplano-Puna orogenic growing. It is supported that deep magmatism have probably contributed to crustal thickening thanks to the addition of large volumes of magma. These results also involve that canyons erosion and incision would have taken place at a rate ranging from 150 to 500 m/Ma during the last 13 Ma. Given that the large-volume acidic system studied in this work is considerable, further research are necessary to improve these results.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-06-02T18:48:59Z No. of bitstreams: 1 ManuelFarias.pdf: 1389622 bytes, checksum: 6e4849f2b44871723791cde342c7bf04 (MD5) / Made available in DSpace on 2017-06-02T18:48:59Z (GMT). No. of bitstreams: 1 ManuelFarias.pdf: 1389622 bytes, checksum: 6e4849f2b44871723791cde342c7bf04 (MD5) Previous issue date: 2006-06-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / This is work treat of the acetaldehyde and labeled ethanol oxidations, both kinds in percloric acidic medium, 0,1 Mol L-1 HClO4 on the Pt polycrystalline surface with used conventional electrochemical and spectroscopy techniques (FTIRS in situ). From acetaldehyde, wanted to find the mean concentration that better favor the reaction to evolve for CO2 in the potential smaller from production of the kind. The concentration 0,01 Mol L-1 was better suitable, but the increase of the concentration in solution, this is pathway was whole inhibited. However, in the high potential the form to acetic acidic is favorable. For main cronoamperometry, acetaldehyde in the concentration 0,02 Mol L-1, were able proof results in situ FTIRS. According to potential, this is results was interpreted second pattern to consider: the pear adsorbed kinds (Langmuir-Hinshelwood) and other where consider only one adsorbed kinds between adsorbed (pattern Eley-Rideal mechanism). In the case of ethanol labeled oxidation (H3 13CO 12CH2OH), it is search to look into the path delineated from way severous of the reaction from to form CO2. The results showed that is product would to be results of the intermediates oxidations contained carbon from alcohol group and intermediates contained carbon from group methyl; however, the intermediates contained carbon alcohol group is mores able reactive in the zone potential searched in the work, is this mores, confronted with able reactive metil group. The path double that yield CO2 in the zone potential below 1,0 V, are yielded coupling bands 12COL and 13COL which coexist in below potential. In the presence kind 13COL in 0,4 V potential proof that of the efficiency of the platinum electrode for the oxygenation group metil in the zone below potential. In the potential largest that 1,0 V, where exist the formation continuous of carbon dioxide, the difference in the greatness bands associated from 12CO2 e 13CO2 (double path product contained carbon), was interpreted in the sense of the electrochemical conditions infortunable for remover hydrogen group metil; additional this is kind was to promote for yield from molecules, which not is able identify for whole technique. / Este trabalho trata das reações de eletrooxidações de acetaldeído comum e etanol isotopicamente marcado, ambas reações em superfície de platina policristalina em meio de ácido perclórico, HClO4, 0,1 Mol L-1, com a utilização de técnicas eletroquímicas convencionais e espectroscopia (FTIRS in situ). Para o acetaldeído, essa reação foi estuda com a dependência do potencial aplicado e a concentração do aldeído em solução, que melhor resultaram na transformação desta molécula a CO2. Assim, para o potencial 0,6 V, a concentração de aldeído 0,01 Mol L-1 foi a mais apropriada deduzida a partir de FTIRS in situ e, a concentração 0,02 Mol L-1 permitiu a geração de maior densidade de corrente e foi inferida a partir de cronoamperometria. Essa discrepância foi discutida em termos das reações específicas que resultam no sinal analítico para cada técnica. Dependendo da concentração do acetaldeído, a via de formação de CO2 foi completamente inibida e, em altos potenciais, prevalecia sempre a formação de ácido acético. Paralelamente, dependendo do potencial, estes resultados foram interpretados com base em modelos de mecanismos de reações que considera: um par de reagentes adsorvidos (mecanismo Langmuir-Hinshelwood) e apenas uma espécie adsorvida do par fundamental de reagentes (mecanismo Eley-Rideal). Para o etanol isotopicamente marcado (H3 13C 12CH2OH), foram investigados passos delineados pelas diferentes vias de reação de formação de CO2. Os resultados mostraram que este produto pode ser resultante da eletrooxidação de intermediários contendo o carbono do grupo álcool e do grupo metil, sendo que o intermediário contendo o carbono do grupo álcool, para toda a faixa de potenciais investigados, é bem mais reativo que o intermediário contendo o carbono do grupo metil. As vias duplas que geram CO2 em potenciais abaixo de 1,0 V são resultantes de bandas acopladas de 12COL e 13COL que coexistem em baixos potenciais. A presença de 13COL em 0,35 V foi encarada como uma evidência da eficiência da Pt para oxigenação do grupo metil em baixos potenciais. Em potenciais acima de 1,0 V, onde há produção contínua de dióxido de carbono, a diferença na magnitude das intensidades de bandas relativa ao 13CO2 e 12CO2 (das vias de origem de carbono), foi interpretada como sendo as referidas condições eletroquímicas desfavoráveis para desprotonação do metil.

<p>The goal of this study is to examine the environmental impacts of oil and gas exploration and production (E&P), the roles of legislation, and the environmental management strategies in the petroleum industry with respect to the Niger Delta region of Nigeria. The study seeks to suggest sustainable solutions to the endemic economic, social, and environmental problems associated with oil and gas E&P in the region. The focus is on the environmental control in the upstream (E&P) operations of the oil and gas industry as it affects the Niger Delta region of Nigeria with a view to proffering sustainable solutions.</p><p>The heavily polluting activities and environmental impacts of the upstream oil and gas operations in the Niger Delta have over the years taken a routine dimension and are endemic as a result of inadequate environmental legislations and ineffective enforcements. Sequel to these environmental impacts is militancy, adoption of expatriates, communal conflicts, inter-ethnic conflicts, human right abuses, restiveness and other social vices as the study reveals. These social and environmental impacts of oil and gas activities in this region bring impoverishment, abject poverty, hunger, squalor, birth disease, gene mutation, and death while exposing inhabitants of the region to afflictions and diseases as the study explicitly documents.</p><p>The study also reveals that the persistence rate of unrest, restiveness, militancy and other social vices is as a result of non-dialogue status between the different stakeholders, lack of infrastructural development, lack of basic amenities, high rate of unemployment, poor policy construct, federalized mineral right / resource ownership structure, and the monopolistic nature of Nigeria’s foreign exchange earning in petroleum resources.</p><p>In this dissertation, both proactive and corrective measures to curb the menace of the social, economic and environmental impacts of oil and gas exploration & production operations in Nigeria are presented and discussed with suggestions to sustainable solution and development, better environmental legislation, and better resource policy construct while advocating for good industrial practices in the petroleum industry with emphasis on the Niger Delta region of Nigeria.</p>

The goal of this study is to examine the environmental impacts of oil and gas exploration and production (E&amp;P), the roles of legislation, and the environmental management strategies in the petroleum industry with respect to the Niger Delta region of Nigeria. The study seeks to suggest sustainable solutions to the endemic economic, social, and environmental problems associated with oil and gas E&amp;P in the region. The focus is on the environmental control in the upstream (E&amp;P) operations of the oil and gas industry as it affects the Niger Delta region of Nigeria with a view to proffering sustainable solutions. The heavily polluting activities and environmental impacts of the upstream oil and gas operations in the Niger Delta have over the years taken a routine dimension and are endemic as a result of inadequate environmental legislations and ineffective enforcements. Sequel to these environmental impacts is militancy, adoption of expatriates, communal conflicts, inter-ethnic conflicts, human right abuses, restiveness and other social vices as the study reveals. These social and environmental impacts of oil and gas activities in this region bring impoverishment, abject poverty, hunger, squalor, birth disease, gene mutation, and death while exposing inhabitants of the region to afflictions and diseases as the study explicitly documents. The study also reveals that the persistence rate of unrest, restiveness, militancy and other social vices is as a result of non-dialogue status between the different stakeholders, lack of infrastructural development, lack of basic amenities, high rate of unemployment, poor policy construct, federalized mineral right / resource ownership structure, and the monopolistic nature of Nigeria’s foreign exchange earning in petroleum resources. In this dissertation, both proactive and corrective measures to curb the menace of the social, economic and environmental impacts of oil and gas exploration &amp; production operations in Nigeria are presented and discussed with suggestions to sustainable solution and development, better environmental legislation, and better resource policy construct while advocating for good industrial practices in the petroleum industry with emphasis on the Niger Delta region of Nigeria.

PMMA is a widely used biomaterial especially in the fields of orthopedia, orthodontia and ophthalmology. When biocompatibility is considered, modification of the biomaterials&amp / #8217 / surface may be needed to optimize interactions of the biomaterial with the biological environment. After the surface modifications one of the most important changes that occur is the change in the surface free energy (SFE). SFE is an important but an obscure property of the material and evaluation methods with different assumptions exist in the literature. In this study, SFE of pristine and oxygen plasma modified PMMA films were calculated by means of numerous theoretical approaches (Zisman, Saito, Fowkes, Berthelot, Geometric and Harmonic Mean and Acid-Base) using numerous liquids and the results were compared to each other to elucidate the differences of methods. Dispersive, polar, acidic and basic components of the SFE were calculated by the use of different liquid couples and triplets with the application of Geometric and Harmonic mean methods and Acid-Base approach. The effect of SFE and the components of SFE on the cell attachment efficiencies were examined by using fibroblast cells. It was observed that with the treatment of oxygen plasma, cell attachment capability and hydrophilicity of PMMA surfaces were altered depending on the applied power and duration of the plasma.