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This study geochemically characterized a proposed Carbon Capture and Storage project in northeast British Columbia, and presents new dissolution kinetics data for the proposed saline aquifer storage reservoir, the Keg River Formation. The Keg River Formation is a carbonate reservoir (89-93% Dolomite, 5-8% Calcite) at approximately 2200 m depth, at a pressure of 190 bar, and temperature of 105 °C. The Keg River brine is composed of Na, Cl, Ca, K, Mg, S, Si, and HCO3 and is of approximately 0.4 M ionic strength. Fluid analysis found the Keg River brine to be relatively fresh compared with waters of the Keg River formation in Alberta, and to also be distinct from waters in overlying units. These findings along with the physical conditions of the reservoir make the Keg River Formation a strong candidate for CO2 storage. Further work measured the dissolution rates of Keg River rock that will occur within the Keg River formation. This was performed in a new experimental apparatus at 105 °C, and 50 bar pCO2 with brine and rock sampled directly from the reservoir. Dissolution rate constants (mol!m-2s-1) for Keg River rock were found to be Log KMg 9.80 ±.02 and Log KCa -9.29 ±.04 for the Keg River formation. These values were found to be significantly lower compared to rate constants generated from experiments involving synthetic brines with values of Log KMg -9.43 ±.09, and Log KCa -9.23 ±.21. Differences in rates were posited as due to influences of other element interactions with the >MgOH hydration site, which was tested through experiments with brines spiked with SrCl2 and ZnCl2. Results for the SrCl2 spiked solution showed little impact on dissolution rates with rate constants of Log KMg -9.43 ±.09, and Log KCa -9.15 ±.21, however the ZnCl2 spiked solution did show some inhibition with rate constants of Log KMg -9.67 ±.04, and Log KCa -9.30 ±.04. Rate constants generated in this work are among the first presented which can actually be tested by full-scale injection of CO2. / Graduate

Chromium has been widely used in many industrial applications. As a result of chromite ore processing, large amounts of chromite ore processing waste (COPW) material that can be classified as hazardous have been produced and released into the environment. Therefore, knowledge of migration behavior and leaching rates of chromium through waste materials and soils are of primary concern for environmentally sound management of land-disposal hazardous wastes. Hask&ouml / k (1998) experimentally studied leaching rates of total Cr and Cr(VI) using laboratory columns packed with chromium COPW material produced by a sodium chromite plant. Based on the experimental results of Hask&ouml / k (1998), present study aim, through mathematical modeling, to understand the dissolution kinetics of chromium during leaching of COPW material and to investigate the effectiveness of intermittent leaching involving a sequence of batch (dissolution) and leaching (mass flushing) operational modes. Obtained results show that a coupled system of two first order differential equations was able to capture the essential characteristics of leaching behavior of COPW material. In addition, the kinetics of chromium dissolution from COPW appeared to be controlled by the difference between aqueous phase concentration and a saturation concentration, by the mass fraction of dissolvable chromium remaining in the solid phase, and finally by the contribution of a constant dissolution rate manifested as a steady-state tailing behavior. As a result of performed simulations it was seen that intermittent leaching could be 65%and 35% more effective than continuous leaching for total Cr and Cr(VI), respectively.

Geochemical processes involving the interaction of fluids and minerals occur in nearly every environment on the surface and in the crust of the Earth. The variety of fluid–mineral processes on the Earth is quite diverse, and these various processes can occur under a large range of geochemical conditions. Aqueous dissolution and alteration, hydration, protonation, solution–precipitation, diffusion, and fluid and isotope exchange are among the many fluid–mineral interaction processes that contribute to the overall cycling of elements on Earth. This dissertation uses analog experiments to examine fluid­–mineral interaction processes found in different geological environments and under a range of environmental conditions. The first part of this dissertation examines the reactive and diffusive exchange of oxygen isotopes that results from performing a dolomite breakdown experiment under a temperature, pressure, and fluid condition analogous to a contact metamorphic environment. The second two parts of the dissertation involve the development of new methods for the growth of nanocrystalline fayalite and intermediate composition olivine. The final two parts of this dissertation focus on the interaction of olivine with either H2O or acidic solutions (0.005 M H2SO4 or 0.01 M HCl) at low temperature and pressure. The first of these two parts experimentally uses different surface area olivine powders that are reacted with low pH fluids in non-buffered, closed system experiments where pH and solution composition are allowed to change. The second of these two parts uses various analytical techniques that can examines changes to the surfaces of olivine single crystals at the nanoscale resulting from experiments performed under environmental conditions where the fluid–mineral interaction transitions from dissolution at low temperature and pressure to alteration at moderate temperature and pressure. Though the individual projects contained within this dissertation are varied, they share the common theme of using experiments to examine fluid­–mineral interaction processes.

As forensic techniques employed in homicide investigation are refined, so are the methods by which perpetrators of these crimes attempt to eliminate evidence that could lead to their prosecution. Acid submersion is an increasingly popular method of body disposal due to its highly destructive effects upon organic tissues and their suitability for macroscopic analyses that could enable positive identification. Sixteen fleshed pig (Sus scrofa) forelimbs were submerged in hydrochloric acid, sulfuric acid, and sodium hydroxide (n = 2 per trial) under control conditions and heated to 40˚C or 100˚C, to determine whether dissolution of all tissues was possible quickly enough to ensure a practical method of disposal, and whether heating would accelerate this process. Hydrochloric acid (31-35%) under control conditions failed to dissolve all soft tissues, but destroyed all bones within 68 hours; at 40˚C the soft tissues still were not entirely dissolved, but all bones were destroyed within 24 hours. Sulfuric acid (93%) under control conditions destroyed all soft tissue within 52 hours and all bones within 28 days. Sulfuric acid at 40˚C destroyed all soft tissue in 2.75 hours and all bones within nine days; at 100˚C all soft tissues were destroyed within 0.75 hour and all bones within nine hours. Sodium hydroxide (20-30%) failed to dissolve the soft and hard tissues in all trials, but the rapidity of alterations observed was positively correlated to temperature. The present research indicates that these chemicals can destroy large, fleshed body parts and that this destruction can be accelerated through heating.

A talidomida (TLD) é um fármaco usado no tratamento de lesões associadas ao eritema nodoso leprótico, úlceras aftóides em pacientes HIV+/AIDS, algumas doenças crônico-degenerativas e mieloma múltiplo refratário à quimioterapia. Porém, apresenta problemas relacionados à sua farmacocinética, é pouco hidrossolúvel, e, por conseguinte, apresenta lenta e variável absorção no trato gastrintestinal. Uma proposta inédita que pode ser de interesse clínico é a formulação de uma dispersão sólida para a via oral, que permita a modulação da dissolução e biodisponibilidade da talidomida. O objetivo deste trabalho foi desenvolver e caracterizar dispersões sólidas (DS) contendo carreadores autoemulsionáveis e TLD, veiculado em cápsulas duras, a fim de melhorar as propriedades biofarmacêuticas do fármaco. Foram desenvolvidas formulações de TLD dispersa em Gelucire® (GEL) ou Kolliphor® (TPGS), associadas ou não a um adjuvante que em geral, diminui a recristalização de fármacos, a polivilpirrolidona (PVP K30). A técnica utilizada para preparar as DS foi o método de evaporação de solvente. A caracterização físico-química foi realizada por microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), calorimetria exploratória diferencial (DSC) acoplada a células de aquecimento (Hot Stage), sugeriu formação de DS semicristalinas. A espectroscopia Infravermelha (IV), juntamente com DRX, demonstrou que a porção cristalina remanescente corresponde ao polimorfo α. A dissolução in vitro do fármaco a partir das DS foi significativamente melhor quando comparada ao fármaco isolado ou ao controle com amido. No tempo limite de 120 minutos, as DS tiveram percentual de dissolução em torno de 90%, enquanto o fármaco isolado de 50%, e o controle com amido de 70%. O estudo de solubilidade aquosa com diferentes excessos de fármaco foi realizado com o intuito de verificar se as DS eram capazes de manter o aumento da solubilidade aparente (estado de supersaturação) por um longo período de tempo. Foram obtidos incrementos da solubilidade aparente de até 3x superiores a do fármaco isolado, mas a capacidade solubilizante das DS mostrou-se saturável. Como conclusão, os resultados das análises físico-químicas, perfil de dissolução e solubilidade sugerem que a associação da talidomida com os carreadores autoemulsionáveis proporcionou melhora nas propriedades biofarmacêuticas da TLD, e criam perspectivas de investigação futuras, tais como a avaliação da permeabilidade intestinal in vitro. / Thalidomide (TLD) is a drug used for the treatment of lesions associated to the erythema nodosum leprosum, aphthous ulcers in HIV + / AIDS patients, some chronic diseases, and multiple myeloma refractory to chemotherapy. However, the drug is poorly aqueous soluble, and therefore presents slow and variable absorption in the gastrointestinal tract. An innovative proposal, which could be of clinical interest, is the formulation of oral solid dispersions, which allow modulation of dissolution, solubility, and, therefore, bioavailability of thalidomide. The objective of this study was to develop and characterize solid dispersions (DS) containing self-emulsifying carriers and TLD, filled in hard capsules, aiming to improve the biopharmaceutical properties of the drug. TLD has been dispersed in Gelucire® (GEL) or Kolliphor® (TPGS), associated or not to an excipient that usually decreases the drug recrystallization, polyvinylpyrrolidone (PVP K30). The technique used for preparing the DS was the solvent evaporation method. The physicochemical characterization by scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) coupled to heating cells (Hot Stage), indicated the formation of semi crystalline DS. Infrared spectroscopy (IR), together with XRD, showed that the remaining crystalline portion corresponds to the polymorph α. The in vitro dissolution of the drug from the DS was significantly higher when compared to the drug alone, or the control with starch. At 120 min, the percentage of TLD dissolved from DS was around 90%, while drug alone showed 50% and drug+starch showed 70% dissolution. The aqueous solubility study performed with different drug excess assessed whether the DS were able to maintain the increase in apparent solubility (supersaturation state) for a long period of time. Increments around 3x were obtained in the apparent solubility, but the solubilizing ability of DS was found to be saturable. In conclusion, the results of physicochemical analysis, dissolution profile and aqueous solubility suggest that the association of thalidomide with self-emulsifying carriers provided improvement on the biopharmaceutical properties of TLD, and opened future research perspectives, such as the assessment of intestinal permeability in vitro.

Estudos paleoceanográficos são baseados em indicadores indiretos, ou seja, informações sedimentológicas, paleontológicas e geoquímicas que refletem as condições ambientais dos oceanos no passado geológico. Processos tafonômicos como a dissolução podem enviesar a informação contida nestes indicadores. Porém, quando corretamente identificada, a dissolução pode se tornar uma ferramenta para caracterizar mudanças oceanográficas, como variações na distribuição das massas d’água e a acidificação dos oceanos. O objetivo deste estudo é entender como ocorre este enviesamento, identificar indicadores que determinam a presença ou ausência da dissolução e identificar alterações oceanográficas no Quaternário tardio da Bacia de Pelotas em função deste processo. Esta tese compreende várias etapas, incluindo a realização de experimentos de dissolução em varias espécies de foraminíferos provenientes do oeste do Atlântico Sul, a comparação entre dados de fauna de foraminíferos planctônicos de sedimento com as condições ambientais do oceano Atlântico Sul e, finalmente, as análises de testemunhos do Quaternário tardio da Bacia de Pelotas (foraminíferos, cocolitoforídeos, teor de carbonato, granulometria, δ18O, AMS 14C). Os experimentos geraram um ranking de susceptibilidade à dissolução para foraminíferos, identificando Orbulina universa e Hoeglundina sp. como bons indicadores de pouca dissolução, além de identificar a razão entre foraminíferos planctônicos e bentônicos como imprópria para indicar o grau de dissolução. A análise da fauna de foraminíferos planctônicos do Atlântico Sul identificou maior enviesamento por condições ambientais de fundo em áreas com massas d’água mais corrosivas provenientes do sul, bem como o viés observado nas espécies frágeis pode ser relacionado aos erros em estimativas de paleotemperaturas baseadas em censos de fauna. Baseado nos indicadores aqui elaborados, combinado com outros indicadores comuns, as alterações oceanográficas na Bacia de Pelotas indicam um aumento da dissolução em períodos glaciais em função do avanço da Água Antartica de Fundo e da Água Circumpolar Superior. Finalmente, na parte conceitual desta tese, é proposta uma definição de zona tafonômicamente ativa para sistemas pelágicos, que deve considerar a coluna d’água como seu limite superior. / Paleoceanographic studies are based on proxy data, i.e. sedimentological, paleontological and geochemical information that reflect the environmental conditions of the oceans in the geological past. Taphonomic processes such as dissolution may bias the information contained in these proxies. However, when correctly identified, dissolution can become a tool to characterize oceanographic changes, such as variations in the water masses distribution and acidification of the oceans. The purpose of this study is to understand how this bias occurs, to identify proxies that determine the presence or absence of dissolution and to identify late Quaternary oceanographic changes in the Pelotas Basin as a function of this process. This thesis comprises several stages, including dissolution experiments on several foraminifera species from the western South Atlantic, comparison between sediment plankton foraminifera fauna data with environmental conditions of the South Atlantic Ocean, and finally, the analyses of late Quaternary of the Pelotas Basin cores (foraminifera, coccolith, carbonate content, grain size, δ18O, and AMS 14C). The experiments generated a ranking of susceptibility to dissolution for foraminifera, identifying Orbulina universa and Hoeglundina sp. as good proxies of low dissolution, besides identifying the planktonic and benthic foraminifera ratio as inappropriate for indicating the degree of dissolution. The analysis of the planktonic foraminifera fauna of the South Atlantic identified greater bias due to bottom environmental conditions in areas with more corrosive water masses from the south, as well as the observed bias in fragile species may be related to errors in paleotemperature estimates based on fauna census counts. Based on the proxies developed here, and other indicators frequently used, the late Quaternary oceanographic changes in the Pelotas Basin indicate an increase of the dissolution in glacial periods due to the advance of Antarctic Bottom Water and Upper Circumpolar Deep Water. Finally, in the conceptual part of this thesis, a taphonomically active zone for pelagic systems is proposed, which should consider the water column as its upper limit.

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A talidomida (TLD) é um fármaco usado no tratamento de lesões associadas ao eritema nodoso leprótico, úlceras aftóides em pacientes HIV+/AIDS, algumas doenças crônico-degenerativas e mieloma múltiplo refratário à quimioterapia. Porém, apresenta problemas relacionados à sua farmacocinética, é pouco hidrossolúvel, e, por conseguinte, apresenta lenta e variável absorção no trato gastrintestinal. Uma proposta inédita que pode ser de interesse clínico é a formulação de uma dispersão sólida para a via oral, que permita a modulação da dissolução e biodisponibilidade da talidomida. O objetivo deste trabalho foi desenvolver e caracterizar dispersões sólidas (DS) contendo carreadores autoemulsionáveis e TLD, veiculado em cápsulas duras, a fim de melhorar as propriedades biofarmacêuticas do fármaco. Foram desenvolvidas formulações de TLD dispersa em Gelucire® (GEL) ou Kolliphor® (TPGS), associadas ou não a um adjuvante que em geral, diminui a recristalização de fármacos, a polivilpirrolidona (PVP K30). A técnica utilizada para preparar as DS foi o método de evaporação de solvente. A caracterização físico-química foi realizada por microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), calorimetria exploratória diferencial (DSC) acoplada a células de aquecimento (Hot Stage), sugeriu formação de DS semicristalinas. A espectroscopia Infravermelha (IV), juntamente com DRX, demonstrou que a porção cristalina remanescente corresponde ao polimorfo α. A dissolução in vitro do fármaco a partir das DS foi significativamente melhor quando comparada ao fármaco isolado ou ao controle com amido. No tempo limite de 120 minutos, as DS tiveram percentual de dissolução em torno de 90%, enquanto o fármaco isolado de 50%, e o controle com amido de 70%. O estudo de solubilidade aquosa com diferentes excessos de fármaco foi realizado com o intuito de verificar se as DS eram capazes de manter o aumento da solubilidade aparente (estado de supersaturação) por um longo período de tempo. Foram obtidos incrementos da solubilidade aparente de até 3x superiores a do fármaco isolado, mas a capacidade solubilizante das DS mostrou-se saturável. Como conclusão, os resultados das análises físico-químicas, perfil de dissolução e solubilidade sugerem que a associação da talidomida com os carreadores autoemulsionáveis proporcionou melhora nas propriedades biofarmacêuticas da TLD, e criam perspectivas de investigação futuras, tais como a avaliação da permeabilidade intestinal in vitro. / Thalidomide (TLD) is a drug used for the treatment of lesions associated to the erythema nodosum leprosum, aphthous ulcers in HIV + / AIDS patients, some chronic diseases, and multiple myeloma refractory to chemotherapy. However, the drug is poorly aqueous soluble, and therefore presents slow and variable absorption in the gastrointestinal tract. An innovative proposal, which could be of clinical interest, is the formulation of oral solid dispersions, which allow modulation of dissolution, solubility, and, therefore, bioavailability of thalidomide. The objective of this study was to develop and characterize solid dispersions (DS) containing self-emulsifying carriers and TLD, filled in hard capsules, aiming to improve the biopharmaceutical properties of the drug. TLD has been dispersed in Gelucire® (GEL) or Kolliphor® (TPGS), associated or not to an excipient that usually decreases the drug recrystallization, polyvinylpyrrolidone (PVP K30). The technique used for preparing the DS was the solvent evaporation method. The physicochemical characterization by scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) coupled to heating cells (Hot Stage), indicated the formation of semi crystalline DS. Infrared spectroscopy (IR), together with XRD, showed that the remaining crystalline portion corresponds to the polymorph α. The in vitro dissolution of the drug from the DS was significantly higher when compared to the drug alone, or the control with starch. At 120 min, the percentage of TLD dissolved from DS was around 90%, while drug alone showed 50% and drug+starch showed 70% dissolution. The aqueous solubility study performed with different drug excess assessed whether the DS were able to maintain the increase in apparent solubility (supersaturation state) for a long period of time. Increments around 3x were obtained in the apparent solubility, but the solubilizing ability of DS was found to be saturable. In conclusion, the results of physicochemical analysis, dissolution profile and aqueous solubility suggest that the association of thalidomide with self-emulsifying carriers provided improvement on the biopharmaceutical properties of TLD, and opened future research perspectives, such as the assessment of intestinal permeability in vitro.