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.

abstract: Criminologists have directed significant theoretical and empirical attention toward the institution of marriage over the past two decades. Importantly, the momentum guiding this line of research has increased despite the fact that people are getting married far less often and much later in the life course than in any point in American history. The aim of this dissertation is to address this disconnect by focusing attention to nonmarital romantic relationships and their instability during emerging adulthood. To do so, it uses data from the Pathways to Desistance Study, a longitudinal study of 1,354 at-risk males and females who were adjudicated from the juvenile and adult systems in Phoenix and Philadelphia between 2000 and 2003. The project focuses attention to the following issues: (1) the effect of romantic dissolution on aggressive and income-based offenses; (2) the extent to which strain/negative emotionality and peer influence/exposure account for the effect of romantic dissolution on crime; and (3) the extent to which certain relationship and individual circumstances moderate the effect of romantic dissolution. The models reveal a few key findings. First, romantic dissolution is strongly related to an increase in both aggressive and income-based crime, but is more strongly related to income-based crime. Second, the effect of romantic dissolution is reduced when measures of strain/negative emotionality and peer influence/exposure measures are added to models, but the peer influence/exposure measures account for the strongest reduction. Finally, romantic dissolution does not serve as a positive life event among these at-risk youth, but its effect is exacerbated under a number of contexts (e.g. when an individual is unemployed). This study closes with a summary of these findings as well as its key limitations, and offers insight into potential policy implications and avenues of future research. / Dissertation/Thesis / Ph.D. Criminology and Criminal Justice 2013

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / Devido à degradaÃÃo progressiva dos corpos hÃdricos em geral, tem-se dado bastante atenÃÃo a alternativas para a recuperaÃÃo da qualidade de suas Ãguas. TÃcnicas de aeraÃÃo e oxigenaÃÃo artificial via injeÃÃo de ar ou oxigÃnio puro na Ãgua (plumas de bolhas) podem ser utilizadas para tal finalidade. Nesse contexto, o presente trabalho desenvolveu um modelo integral para avaliaÃÃo da transferÃncia de massa de plumas de bolhas circulares em ambientes nÃo estratificados, o qual à baseado em uma distribuiÃÃo radial do tipo Gaussiana das propriedades do escoamento e em relaÃÃes matemÃticas para o coeficiente de entrada turbulenta e o fator de amplificaÃÃo da quantidade de movimento devido à turbulÃncia. O impacto da transferÃncia de massa na hidrodinÃmica de plumas de bolhas foi investigado considerando diferentes diÃmetros de bolha, vazÃes de gÃs e profundidades em sistemas de aeraÃÃo e oxigenaÃÃo. Os resultados revelaram impacto significativo quando bolhas finas sÃo consideradas mesmo em profundidades moderadas. Bolhas mÃdias apresentaram, em geral, comportamento semelhante ao de bolhas grossas. As simulaÃÃes tambÃm indicaram que, em condiÃÃes de vazÃes relativamente baixas e elevadas profundidades, dissoluÃÃo e turbulÃncia podem afetar a hidrodinÃmica da pluma de bolhas, o que demonstra a importÃncia de se levar o fator de amplificaÃÃo da quantidade de movimento em consideraÃÃo. SimulaÃÃes utilizando o modelo proposto e modelos clÃssicos disponÃveis na literatura resultaram em boa concordÃncia tanto para processos de aeraÃÃo quanto de oxigenaÃÃo. Finalmente, foram apresentados estudos de caso para os dois processos. / Due to the progressive degradation of water bodies in general, alternatives have been studied so as to restore their water quality. Artificial aeration/oxygenation by injecting air/pure oxygen in the water (bubble plumes) can be used for this purpose. Hence, this study presents an integral model to evaluate gas transfer from circular bubble plumes in unstratified environments which is based on a radial Gaussian type distribution of plume properties and functional relationships for the entrainment coefficient and factor of momentum amplification due to turbulence. The impact of gas-liquid mass transfer on bubble plume hydrodynamics is investigated considering different bubble sizes, gas flow rates and water depths. Also simulations were run for aeration and oxygenation systems in order to provide the analysis of these effects. The results revealed a significant impact when fine bubbles are considered, even for moderate water depths. Medium bubbles present overall similar behavior as coarse bubbles. Additionally, model simulations also indicate that for bubble plumes with relatively low gas flow rates and high water depths, both dissolution and turbulence can affect bubble plume hydrodynamics, which demonstrates the importance of taking the momentum amplification factor relationship into account. For deeper water conditions, simulations of bubble dissolution using the present model and classical models available in the literature resulted in a very good agreement for both aeration and oxygenation processes. Finally, case studies involving those processes are presented.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2017-03-07T13:13:13Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO DAYANNE.pdf: 3522857 bytes, checksum: cf44960151386725475547d266f32f30 (MD5) / Made available in DSpace on 2017-03-07T13:13:13Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO DAYANNE.pdf: 3522857 bytes, checksum: cf44960151386725475547d266f32f30 (MD5) Previous issue date: 2016-03-04 / CAPES / O Tamoxifeno (TMX) utilizado no tratamento do câncer de mama, apresenta diversas desvantagens, elevada toxicidade, baixa solubilidade e precipitação no ambiente gástrico na forma de sal com aumento do risco de ocorrência de câncer de estômago. Os sistemas de dispersões sólidas (DS) têm sido utilizados com polímeros comerciais, Eudragit®, para liberação controlada e em determinados pH. Assim, o objetivo desse estudo foi desenvolver sistemas de dispersões sólidas para liberação pH dependente do tamoxifeno. Utilizou-se os polímeros Eudragit® RL 100, Eudragit® L 100 e TMX, pelo método de evaporação do solvente, obtendo DS10%, 20%, 30%, 40%, 50% e 60%, mistura física MF30% e dispersões binárias (DS binária) sem fármaco. A difração de Raios-X (DRX) mostrou amorfização das dispersões formadas nas proporções de 10%, 20%, 30%, 40%, 50% e 60%. Na MF30% foi constatada a cristalinidade do fármaco. Na análise térmica através das curvas (TG), foi observada aumento da temperatura de decomposição da DS binária. No DSC, para a MF30% foi observado o pico de fusão e as etapas de decomposição do fármaco. Já nas DS10%, DS20% e DS30% observou-se ausência desses picos. Para a DS binária a temperatura de transição vítrea (Tg) se assemelhou a Tg do Eudragit® L 100, aumentando estabilidade das DS. Na espectroscopia de Infravermelho (FTIR) foi verificado interações polímero-polímero através da diminuição e alargamento das bandas de 2601 cm-¹, atribuído ao grupamento livre do ácido carboxílico do Eudragit® L 100. Observou interação fármaco-polímero com ausência dos picos característicos do fármaco nas regiões de 1588 cm-¹, referente ao amônio quaternário, nas DS 10% e DS 20%, e diminuição da intensidade das bandas na DS 30%. Assim com o alargamento de banda das regiões 2601cm-1 do Eudragit® L100, sugerindo a interação do fármaco nessa região. A Microscopia Eletrônica de Varredura exibiu diferenças significativas nas dispersões sólidas DS30% e MF 30%. Para os testes de solubilidade nos meios pH 1,2 e 7,4 a solubilidade do TMX aumentou com a diminuição do pH já com adição de Tween80 no meio pH 7,4 a solubilidade do fármaco aumentou em até 26 vezes a concentração, melhorando a solubilidade do TMX nesse meio. As condições designadas na USP para formulação gastrorresistentes (pH 1,2) foram satisfatórias para as DS10% e DS20%. Porém, para DS30% a condição não foi alcançada devido a mudanças da permeabilidade do polímero, pela formação de iPECS. No pH 7,4 + Tween80 (0,4% p/v) houve controle na liberação do fármaco com aumento de solubilidade de até 200% para DS20% e Ds30%. Portanto, pode-se concluir que o método empregado foi eficaz na obtenção das dispersões com aumento da estabilidade do fármaco nos sistemas formados, atendendo as diretrizes da USP para formulações gastrorresistentes e liberando de forma modificada o fármaco no pH 7,4, com incremento solubilidade. Sendo um promissor sistema para futuras modificações e estudos. / Tamoxifen (TMX) used in the treatment of breast cancer, has several disadvantages, like high toxicity, low solubility and precipitation in the gastric environment in salt form with an increased risk of stomach cancer. Solid dispersions systems (DS) have been used with commercial polymers, Eudragit, for controlled release and certain pH. The aim of this study was to develop solid dispersion systems for pH dependent release of tamoxifen. It was used the polymers Eudragit RL 100, Eudragit L 100 and TMX, the solvent evaporation method, obtaining. DS10%, 20%, 30%, 40%, 50% and 60% physical mixture and binary dispersions PM30% (binary DS) no drug. The X-ray diffraction (XRD) showed amorphization of the dispersions formed in proportions of 10%, 20%, 30%, 40%, 50% and 60%. In PM30% was observed crystallinity of the drug. In the thermal analysis curves through (Tg), it was observed increase of the decomposition temperature of the binary DS. In DSC, for PM30% was observed melting peak of the drug and decomposition steps. Already in DS10%, DS20 and DS30% was observed the absence of these peaks. For binary DS glass transition temperature (Tg) resembled the Tg of Eudragit® L 100, increasing stability of the DS. In infrared spectroscopy (FTIR) was checked polymer-polymer interactions by lowering and widening of the bands 2601 cm-¹ assigned to the free carboxylic acid grouping of Eudragit® L 100 observed drug-polymer interaction with the absence of the characteristic peaks drug in the region of 1588 cm-¹, referring to quaternary ammonium, and the DS 10% DS 20%, and decreased intensity of the bands in DS30%. So, with the extension band of regions 2601cm-1 Eudragit® L100, suggesting the interaction of the drug in this region. The Scanning Electron Microscopy showed significant differences in solid dispersions DS30% and 30% MF. For solubility testing in pH 1.2 and 7.4 means the solubility of TMX increased with decreasing pH already with addition of Tween 80 at pH 7.4 means the solubility of the drug increased up to 26 times the concentration by improving TMX solubility in this medium. The conditions referred to in USP gastroresistant formulation (pH 1.2) were satisfactory for DS10 and DS20%. However, in DS30%, the condition was not achieved due to the polymer permeability changes by forming iPECS. At pH 7.4 + Tween 80 (0,4 w/v) there has been control drug release with increased solubility up to 200% for DS20 and DS30%%. Therefore, it can be concluded that the method employed was effective in obtaining the dispersions with increased drug stability in the systems formed, meeting the USP guidelines for gastroresistant formulations and modifying the release of the drug at pH 7.4, with increased solubility; and that it is a promising system for future modifications and studies.

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Diferentes estratégias de flotação (reagentes, pH e rota) têm sido utilizadas na separação entre apatita e carbonatos em todo o mundo. Há evidências na literatura de que a cristalinidade afeta a flotação de apatitas e calcitas com oleato de sódio. Além disso, a dissolução dos sais semi-solúveis pode influenciar a interação entre a superfície dos minerais e os reagentes de flotação, uma vez que o mecanismo de adsorção mais importante é a precipitação de oleato de cálcio na interface sólido/líquido. Portanto, o objetivo deste trabalho é investigar a relação entre cristalinidade, cinética de dissolução e resposta à flotação de apatitas e calcitas de diferentes gêneses (ígnea, metamórfica e sedimentar) e origens. Quatro tipos de minerais foram utilizados: purificados a partir de minérios, previamente purificados, naturalmente puros e amostras de coleção. As amostras foram caracterizadas por fluorescência de raios-X e microanálise (WDS/EDS). Características físicas como densidade (d), área superficial (S) e porosidade (P) também foram determinadas. O método de Rietveld aplicado à difração de raios-X foi usado tanto para comprovar a pureza das amostras como para estudar a cristalinidade dos minerais por meio da determinação dos parâmetros de rede (distâncias a e c, e volume da cela unitária- VCU), além do grau de cristalinidade (GC), tamanho de cristalito (TC) e microdeformação (MD). Ensaios de dissolução, conduzidos na ausência de CO2, forneceram a quantidade (mol) de íons Ca2+ (nCa2+) dissolvidos em função do tempo (t) e normalizada em relação à área superficial. Os resultados se ajustam a um modelo de primeira ordem: nCa2+ = Ca2+MAX(1- e-kt). Este procedimento permitiu calcular os valores da quantidade máxima de íons Ca2+ dissolvidos (Ca2+MAX), bem como da constante cinética (k). Além disso, a velocidade de dissolução foi determinada para a etapa rápida (VR), que caracteriza o início da reação, e para a etapa lenta (VL), que ocorre nas proximidades do estado estacionário. A resposta à flotação com oleato de sódio foi determinada por meio de experimentos de microflotação. Várias relações de causa e efeito são encontradas: flotabilidade (F) versus VR, e VR versus características intrínsecas (parâmetros de rede, de cristalinidade e físicos). VR foi selecionado para participar de tais modelos, pois, caracteriza o intervalo de tempo em que o condicionamento (1 minuto) e a microflotação (1 minuto) ocorrem. Observa-se que a flotabilidade dos minerais aumenta com o aumento de VR, sugerindo que apatitas e calcitas que disponibilizam mais íons Ca2+ em solução para interagir com o oleato, exibem mais elevada flotabilidade. Equações lineares de F em função de VR em pH 8 (R = 0,97 para apatitas e R = 0,66 para calcitas) e pH 10 (R = 0,95 para apatitas e R = 0,63 para calcitas) foram encontradas. Correlações lineares múltiplas foram utilizadas para relacionar VR (em pH 8 e 10) com as características intrínsecas que exercem maior influência sobre este parâmetro. Para as apatitas, VR foi equacionado em função de GC, TC e c, enquanto para as calcitas, os parâmetros GC, TC, d e P foram selecionados para compor o modelo. Os valores de VR calculados se ajustam aos observados dentro de um intervalo de confiança de 95%. As equações lineares propostas para as apatitas foram usadas para se estimar F das amostras de Anitápolis-SC e Tapira-MG, que não foram submetidas aos ensaios de dissolução. Os valores de F calculados estão em concordância com aqueles experimentalmente determinados. / Different flotation strategies (reagents, pH and route) have been adopted to separate apatite from carbonates around the world. Literature provides evidences that crystallinity affects flotation response of apatite and calcite with sodium oleate. Furthermore, dissolution of salt-type minerals influences the interaction between mineral surface and flotation reagents, because the most important adsorption mechanism is the surface precipitation of calcium oleate onto mineral/water interface. Therefore, the objective of this research is to investigate the relationship between crystallinity, dissolution kinetics and flotation response of apatites and calcites from different genesis (igneous, metamorphic and sedimentary) and origins. Four sorts of minerals were utilized: minerals purified from ores, minerals previously purified, naturally pure minerals and collection samples. They were characterized by X-ray fluorescence and X-ray microanalysis (WDS/EDS). Physical characteristics, as specific gravity (d), surface area (S) and porosity (P), were also determined. The Rietveld method applied to X-ray diffraction data was used either to probe the purity of samples or to study the crystallinity of the minerals by means of determining their lattice parameters (a and c dimensions plus lattice volume-VCU), in addition to crystallinity degree (GC), crystallite size (TC) and microstrain (MD). Dissolution experiments, conducted in the absence of CO2, yielded curves which relate the amount (mol) of dissolved Ca2+ ions (nCa2+) versus time (t), normalized by the surface area. They fit a first order model: nCa2+ = Ca2+MAX(1- e-kt). Curve fitting via exponential adjustment was accomplished to calculate values of the maximum amount of dissolved Ca2+ ions (Ca2+MAX) and the kinetic constant (k). In addition, the dissolution rate was determined for the fast step (VR), which characterizes the beginning of the reaction, and for the slow step (VL), as it tends to the steady state. Flotation response with sodium oleate was determined by microflotation experiments. Several cause-effect relationships are found: floatability (F) versus VR, and VR versus intrinsic characteristics of minerals (lattice, crystallinity and physical parameters). VR was selected to participate in the model because it characterizes the length of time along which reagent conditioning (1 minute) plus microflotation (1 minute) take place. It is observed that F increases as VR becomes greater, suggesting that samples of apatites and calcites which place more Ca2+ ions in solution to interact with oleate exhibit higher flotation performance. Linear equations of F versus VR at pH 8 (R = 0,97 for apatites and R = 0,66 for calcites) and pH 10 (R = 0,95 for apatites and R = 0,63 for calcites) were found. Likewise, multiple linear correlations were used to relate VR (at pH 8 and 10) with the intrinsic characteristics of apatites and calcites that affect VR to a greater extent. For apatites, VR was modeled as a function of GC, TC and c, while for calcites, the parameters GC, TC d and P were selected to compose the model. The calculated VR values fit the experimental ones within 95% of confidence. The linear equations developed for apatites were used to estimate floatability of the samples from Anitápolis-SC and Tapira-MG, which were not submitted to dissolution experiments. The values of calculated floatability are in agreement with the experimental ones.

Abstract This research aims at developing theory about the dissolution process of business-to-business relationships in tailored software context. Although dissolving business relationships can be viewed as one of the essential themes of marketing, the existing research on dissolution does not provide us with a holistic picture of the dissolution as a process. This research builds an empirically-grounded model of the business relationship dissolution process. First, a theoretical, tentative model of the process of business relationship dissolution is built. Second, empirical knowledge is acquired from a case study of business relationship dissolution in a software context. The case study data has been collected from various sources, from both seller and buyer organisations as well as network actors, through interviews and also from other written and oral sources in order to ensure triangulation. Third, the findings of the case study are compared to the tentative process model and the model is adjusted accordingly, thus developing the empirically-grounded process model. The process model includes three elements: the nature of the relationship, the factors influencing its dissolution, and the dissolution process. It incorporates both the time dimension and the multiplicity of the actors (individuals, companies, other relationships) involved into the model. The nature of the relationship is classified (terminal, continuous, episodic) as are the influencing factors and events (predisposing, precipitating and attenuating). The dissolution process is modelled by using stages, which describe the different action and time periods of the process, and by using levels, which describe the different actors who bring the process about. Six stages are distinguished: the communication stage, consideration stage, disengagement stage, enabling stage, restoration stage, and sensemaking / aftermath stage. The concept of stage is used to divide the complex process into more comprehensible periods and to emphasise that in each stage, managers' actions differ. The dissolution process does not always proceed through all the stages, nor have the stages any particular order.

Master of Science / Department of Geology / Saugata Datta / Elevated concentrations of arsenic (As) and fluoride (F) have been documented within the volcano-sedimentary aquifers of the Independence Basin Aquifer System in Guanajuato, Mexico which lies in the Mesa Central (MC) physiographic province on the northern edge of the Trans Mexican Volcanic Belt (TVMB). The geogenic sources of these contaminants are not well understood. This study adds to the existing record of the distribution of As and F contamination in the major aquifers of the basin by analyzing 24 water samples from five urban and rural areas. The mean As and F concentrations in the Cuenca Alto Rio Laja (CARL) aquifer on the western side of the basin were ~10 µg/L (median = 36 µg/L) and ~0.5 mg/L (median = 0.8 mg/L), respectively. In contrast, the mean As and F concentrations in the Laguna Seca (LS) aquifer on the eastern side of the basin were ~44 µg/L (median = 11 µg/L) and ~5.8 mg/L (2.6 mg/L), respectively. The high sodium, alkalinity, and low calcium concentrations observed in both aquifers are typical for fractured acid volcanic geothermal systems which have been observed in many Mexican states. Boron, lithium, and groundwater temperature showed positive correlations with As (R2 = 0.47, 0.68, and 0.55) and F (R2 = 0.31, 0.73, and 0.57) concentrations. These trace elements and elevated groundwater temperatures are indicators of water with hydrothermal origins. The drill cuttings from two boreholes ~500 m in depth were analyzed by X-ray diffraction, petrographic, and elemental analysis. This work revealed that the volcanic rocks of the CARL aquifer are primarily comprised of plagioclase, quartz, potassium-feldspar, calcite, volcanic glass, apatite, and iron oxyhydroxides. Additionally, there are layers of volcanic rocks comprised of pyroxene, plagioclase, quartz; amphibole, biotite, and apatite. The sedimentary rocks of the LS aquifer are comprised primarily of plagioclase, potassium feldspar, muscovite, biotite, volcanic glass, apatite, calcite, and quartz. These sedimentary rocks were deposited on volcanic rocks comprised of plagioclase, pyroxene, quartz, calcite, apatite, olivine, amphibole, hematite, chlorite, biotite, and ilmenite. To determine source zones the distribution of leachable F from the drill cuttings of both boreholes was examined through batch reactors. The leached F concentration profile revealed that the upper 140 m and lower 400 m of the western and eastern sides of the basin were the dominant source zones of leachable F. Overpumping in the IBAS has caused water table levels in this aquifer the decline over time. As these groundwater wells continue to be constructed to deeper depths to reach groundwater the release of As and F from these sources and the mechanisms controlling As and F from these subsurface lithologies needs to be understood. The release of both As and F from the rocks of the western and eastern side of the basin at 400 to ~500 m depths were examined through pH-adjusted batch reactors with groundwater from the CARL which contained initial As and F concentrations of ~7.9 µg/L and ~0.8 mg/L; respectively. The dissolution of F-bearing minerals and adsorption reactions with iron oxyhydroxides display a dominant control on the changes in As and F concentrations in the groundwater of the CARL aquifer. At pH 5, the rocks from the 400 – 500 m depth within the CARL aquifer reduced the initial concentrations of As and F to values of ~5.8 µg/L and ~0.5 mg/L, respectively, after 200 hours. Whereas at a pH of 9 these rocks leached F increasing its concentration to ~0.9 mg/L. The As concentration was reduced to ~6.3 µg/L. In contrast to the CARL aquifer rocks, the rocks of the LS aquifer released F at all three pH values as F-bearing minerals dissolved. Alongside F-bearing mineral dissolution, adsorption on to iron oxyhydroxide surfaces could be occurring as F concentrations continuously decreased after 50 hours of reaction. The As concentrations in the rocks from the 400 – 550 m depths of the LS aquifer released minor amounts of As at pH 7 and 9, increasing the concentration slightly until 50 hours of reaction. During the remaining 150 hours of reaction the As concentrations displayed a continuous decrease in concentration. At pH 5, however, As concentrations decreased to ~5.7 µg/L after 200 hours of reaction. The spatial and kinetic leaching patterns observed in this study, combined with the mapping of known As- and F-bearing minerals within major rock aquifer groups on the east and west side of the basin, will suggest initial release or mobilization mechanisms to future researchers. The mechanisms of initial release and transport of As and F through aquifers of the Independence Basin should be studied through a combination of laboratory experiments and reactive flow and transport modeling to determine the migration of As and F from source rocks to groundwater wells.

Philosophiae Doctor - PhD / Various formulations of the popular South African medicinal plant, Sutherlandia frutescens,are commercially available, with no documented specifications for quality assessment. With plans already underway for a clinical trial to assess its efficacy in HIV patients, there is a need for scientifically validated tests for the quality control of products of this plant. Chemical constituents of the plant are many and varied but it is still unclear which might be the most appropriate ones to monitor for activity or to describe the quality of the plant’s products. For quality control and regulatory purposes, the content and dissolution of flavonoids in the plant products can be assessed. However, these compounds are not monitored for regulation and there are as yet no HPLC or dissolution methods that can be employed for quality control of herbals like S. frutescens. Therefore, the objectives of this study were to assess the suitability of its flavonoid constituents as quality control (QC) marker compounds, and the suitability of content levels and dissolution tests of flavonoids as QC tools for S. frutescens products. To realise the afore-mentioned objectives, non-commercially available flavonoid compounds (sutherlandins) that could be used as marker compounds were isolated from S. frutescens. An HPLC assay was developed and validated for determination of flavonoid content in solution. Five S. frutescens materials viz leaf powder (LP), spray-dried aqueous extract (SDAE) and freeze-dried aqueous extracts (FDAE) were analysed for flavonoid content and dissolution. Dissolution tests were conducted for different S. frutescens materials and dissolution profiles of flavonoids in capsules containing these materials were compared using Q-release values, the similarity factor (f2) and mathematical models. To predict in vivo bioavailability of the flavonoids, in silico assessment of in vivo bioavailability of flavonoids (glycosides and aglycones) that may be contained in different S. frutescens materials was conducted. Sutherlandins A, B, C and D were successfully isolated (percentage purity approximately99 % for sutherlandins A, C and D, and 90 % for sutherlandin B) and identified, and used, along with other flavonoid compounds, for the development of a simple and robust HPLC method. Content of sutherlandins A, B, C and D, quercetin and kaempferol in different plant materials were 0.4 ± 0.3, 0.8 ± 0.2, 1.3 ± 0.2, 0.6 ± 0.1, 0.01 ± 0.02 and 0.08 ±0.1 %,respectively, and differed significantly (p < 0.001). In vitro dissolution showed faster dissolution of flavoniod glycosides compared to aglycones. The flavonoids from the LP and SDAE materials showed characteristics of immediate release with Q75 in ≤ 45 minutes, and delayed release from the FDAE material, i.e. Q75 > 45 minutes. The dissolution profiles of each flavonoid compared from different S. frutescens materials were different as signified by their f2 values which were all below 50. The mathematical models describing release were also different for each flavonoid from the different S. frutescens materials. For in vivo bioavailability modelling and prediction studies, the flavonoid aglycones met the conditions for oral bioavailability while the flavonoid glycosides did not. In conclusion, the sutherlandins isolated from S. frutescens proved to be good markers for HPLC assay and dissolution tests of S. frutescens materials. The HPLC method was suitable for assessing flavonoid levels in S. frutescens materials, and also showed differences in flavonoid content in these materials. The dissolution method was simple and reproducible, and Q-release values, the f2 and mathematical models proved to be good tools for differentiating between S. frutescens materials. In silico modelling showed that the flavonoid glycosides and aglycones differed in oral bioavailability. Although not presently required by the Medicines Control Council (MCC), quantification, release and dissolution studies and specifications may be employed as tools for routine analysis and for quality control of herbal drug formulations containing S. frutescens.