Thesis (Ph. D.)--University of Missouri-Columbia, 2004. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2004. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1999. / Typescript. Vita. Includes bibliographical references (leaves 92-107). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2008. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed June 2, 2009). Vita. Includes bibliographical references.

Orientador: Raquel Fernandes Pupo Nogueira / Banca: Eduardo Bessa Azevedo / Banca: Rosana Maria Alberici Oliveira / Resumo: O controle de microorganismos em determinados ambientes é um fator essencial para a conservação de alimentos e prevenção de patologias humanas. Diversos métodos de controle da presença de microorganismos já foram desenvolvidos e são amplamente utilizados; porém, cada um deles tem uma limitação, suscitando a busca por outros meios. Assim, o objetivo desse trabalho é o de avaliar o efeito da adição de metais de transição (Pd, Ag e Fe) ao TiO2 na desinfecção em fase gasosa pela fotocatálise heterogênea. Os ensaios foram realizados num reator que propiciou uma área de 720 cm2 de fotocatalisador e 16 watts de luz UV; a névoa de microorganismos após tratamento foi colhida em água estéril e sua quantificação foi realizada por semeadura em Plat Cont Agar. Dentre os fotocatalisadores preparados com o TiO2 comercial P25, os melhores resultados foram obtidos empregando-se o TiO2 com paládio fotodepositado, inativando respectivamente, E. coli, S. aureus e B. subtilis numa taxa de 53%, 91% e 90%, contra 46%, 30% e 31% para o TiO2 puro, demonstrando que a interação com o paládio produziu um efeito sinérgico aumentando a eficiência do fotocatalisador puro em até 200%. Considerando-se os fotocatalisadores sintetizados a partir do tetraisopropóxido de titânio, os melhores resultados foram obtidos com o TiO2 dopado com ferro, inativando respectivamente, E. coli, B. subtilis e S. aureus numa taxa de 48%, 48% e 47%, contra 31%, 22% e 25% para o TiO2 puro, mostrando que também neste caso ocorre um efeito sinérgico aumentando a eficiência do fotocatalisador em até 120%. Não há diferenças significativas (teste t) entre as radiações de 254 e 365 nm tanto para os ensaios de controle, utilizando somente radiação UV, quanto aquele com fotocatalisador irradiado, atribuída ao breve período de exposição de 15 segundos. / Abstract: The control of microorganisms in certain atmospheres is an essential factor for the conservation of foodstuff and prevention of human pathologies. Several methods of control of the presence of microorganisms have already been developed and they are widely used, however, each one of them has a limitation, prompting the search for other alternatives. Thus, the objective of this work is to evaluate the effect of the addition of transition metals (Pd, Ag and Fe) to TiO2 in the disinfection in gaseous phase by heterogeneous photocatalysis. The experiments were carried out in a reactor that provided a photocatalyst area of 720 cm2 and 16 watts of UV light; the mist of microorganisms after treatment was collected in sterile water and its quantification was made by innoculation in Plat Cont Agar. Among the prepared photocatalysts from commercial TiO2 P25, the best results were obtained by the use of TiO2 with Pd, inactiving respectively, E. coli, S. aureus and B. subtilis in a rate of 53%, 91% and 90%, against 46%, 30% and 31% for pure TiO2, demonstrating that the interaction with the Pd produced a synergistic effect increasing the efficiency of the pure photocatalyst up to 200%. Considering the photocatalyst synthesized starting from the titanium tetraisopropoxide, the best results were obtained with TiO2 doped with iron, inactivating respectively, E. coli, B. subtilis and S. aureus in a rate of 48%, 48% and 47%, against 31%, 22% and 25% for pure TiO2, showing that also in this case a synergistic effect increasing the efficiency of the photocatalyst in up to 120% occurs There are no significant differences (test t) between the radiations of 254 and 365 nm either for the control experiments using only UV radiation or those with irradiated photocatalyst, attributed to the brief exposure period of 15 seconds. / Mestre

Made available in DSpace on 2014-06-11T19:29:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-06-04Bitstream added on 2014-06-13T19:38:05Z : No. of bitstreams: 1 gomes_vm_me_araiq.pdf: 929356 bytes, checksum: 0382773c6ab6d0adec51194eeb9bcab8 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As questões ambientais vêm sendo discutida cientificamente nos últimos anos, devido à necessidade de conservar os compartimentos hidrosfera, atmosfera, e litosfera e as conseqüências sobre os organismos. Dentre os diversos poluentes indicadores de contaminação ambiental, os metais devem ser vistos com grande preocupação por serem elementos não degradáveis e que atingem toda a cadeia trófica. Sua presença, em concentrações elevadas, causa mortalidade de espécies e sua introdução no organismo humano, via cadeia alimentar, pode provocar inúmeras doenças, podendo levar até a morte. Atualmente, estudos de contaminação por espécies metálicas, bem como, a remediação de áreas impactadas, resultantes de atividades antrópicas ou não, tornou-se relevante. Espécies metálicas são utilizadas em vários processos industriais, devido suas propriedades físico-químicas, apresentando ampla aplicabilidade em diferentes setores. No processamento do couro, por exemplo, são utilizados geralmente sais de crômio trivalente, sendo o sulfato básico de crômio a forma mais empregada. O descarte inadequado dos resíduos de couro (aparas) contendo crômio, quando feito em solos sem estudo quanto ao impacto ambiental pode contaminar compartimentos por lixiviação e volatilização de compostos formados pela decomposição do material descartado. Na cidade de Dobrada, interior do Estado de São Paulo, resíduos de aparas de couro foram armazenados inadequadamente, ficando em contato direto com o solo por aproximadamente nove anos. O local que funcionou como um depósito dos resíduos se localiza próximo a zona urbana e acima de um importante manancial para a cidade. Tendo em vista a mobilidade do crômio, este está sendo transportado via lixiviação para as águas subterrâneas, superficiais e depositado nos sedimentos. Assim, os resultados desse trabalho mostram que a matéria... / Environmental issues have increasingly become a focus of scientific discussion in recent years, due to the need to preserve the hydrosphere, atmosphere and lithosphere, and address the consequences of environmental change on organisms. Amongst the various pollutants that are indicative of environmental contamination, metals should be viewed with especial concern, since these elements are not degradable and affect the entire trophic chain. Their presence at elevated concentrations causes species mortality, while their introduction into humans, via the food chain, can lead to a wide variety of diseases, or even death. Studies of contamination by metal species, as well as remediation of areas impacted by anthropogenic (and natural) action have become increasingly relevant. Metal species are used in various industrial processes, due to their physico-chemical properties, and are widely applicable in different sectors. For example, trivalent salts of chromium are normally used in the processing of leather, with the most common form employed being the basic chromium sulphate salt. In the absence of environmental impact studies, the inadequate disposal onto soils of leather residues (clippings) containing chromium can contaminate different compartments of the environment, due to leaching as well as volatilization of compounds formed during decomposition of the waste material. In the city of Dobrada, in the interior of São Paulo State, leather clipping wastes were stored improperly, in direct contact with the soil, for approximately nine years. The location that served as a waste repository is located close to an urban zone, and above an important water source supplying the city. Due to its mobility, chromium is transported by leaching to subterranean and surface waters, and is deposited in sediments. The results of the present work show that organic matter plays an important role... (Complete abstract click electronic access below)

Investigation of the ether extract of the liverwort Frullania franciscana (Howe) resulted in the isolation of the sesquiterpene lactone frullanolide. The separation techniques of thin-layer chromatography, dry column chromatography, and liquid column chromatography were evaluated. Only liquid column chromatography was found useful. Fractions from alumina liquid column separations had infrared spectra which resembled the published spectrum of frullanolide. The identity of the compound obtained from F. franciscana (Howe) was established after extensive purification by comparison of its infrared and nuclear magnetic resonance spectra with published spectra of frullanolide.

Skeletal muscle contains an internal membrane system called the sarcoplasmic reticulum (SR) whose function is to regulate the Ca2+ concentration of the myoplasm. Ca2+ is transported into the SR from the myoplasm via a Ca2+ dependent ATPase thus lowering the myoplasmic Ca2+ concentration. Ca2+ exits from the SR via a Ca2+ releqse pathway resultingin the increase of myoplasmic Ca2+. Muscles contract when the myoplasmic Ca2+ concentration is > 5 uM and relax when the Ca2+ concentration is lowered below 1 uM. The Ca2+ dependent ATPase has been extensively studied but the Ca2+ release system is less well understood. SR vesicles release their internal Ca2+ when a reactive thiol group is oxidized (oxidation-induced Ca2+ release). It is shown in this dissertation that oxidation-induced Ca2+ release is stimulated by adenine nucleotides with an order of effectiveness of: ATP > AMP-PCP > cAMP > AMP > adenine. The stimulatory effect is not dependent upon phosphorylation of a protein because AMP-PCP, a nonhydrolyzable analogue of ATP, is almost as effective as ATP in stimulating oxidation-induced Ca2+ release. It is also shown in this dissertation that photooxidation of histidyl residues results in an increase Ca2+ permeability of the SR. Unlike oxidation-induced Ca2+ release, photooxidation-induced Ca2+ release is Mg2+ independent, not inhibited by ruthenium red and inhibited by adenine nucleotides. Covalent modification of histidyl residues with ethoxyformic anhydride results in the increased permeability of SR vesicles. Similar to photooxidation-induced Ca2+ efflux, EFA-induced Ca2+ efflux is Mg2+ independent and is inhibited by ATP. The AMP-PCP protection of SR proteins from modification with EFA is similar to non-competitive inhibition with a KI = 50 uM. The photooxidation effect is not on membrane lipids but on a protein component which may be an ion transport system, other than the Ca2+ release protein, altered in such a way that it now transports Ca2+.

The focus of the thesis research was to investigate the surface reactivity of three different minerals, pyrite (FeS2), an ordered form of ferrihydrite (an iron oxyhydroxide phase), and birnessite (MnO2), toward environmentally relevant aqueous reactants. In particular, research was carried out with the goals of 1) understanding the redox chemistry of nitrite (NO2-) and nitrate (NO3-) on pyrite and 2) understanding the redox (photo) chemistry of arsenite (AsO2-, As(III)) on ordered ferrihydrite and birnessite. A motivation for all these studies stemmed in part from the recognition that NO2-, NO3-, and As(III) are all environmental pollutants when they are present at sufficiently high concentration in the environment. The removal of these species or conversion of each of them on mineral surfaces to more benign chemical species is of importance in the realm of environmental chemistry. In the case of NO2- and NO3- on pyrite, an additional and primary motivation for the research was that it has been hypothesized in the "origin-of-life" community that the reaction of NO2- and NO3- with iron sulfide (e.g., pyrite) may have played a role in the production of ammonia (NH3) on early Earth. Such prebiotic chemistry had been hypothesized to an essential step in the production of biomolecules that included proteins. With regard to the NO2- reaction with pyrite, results detailed in this thesis showed that ammonia in µmol/kg quantities could be produced by reacting NO2- in the presence of pyrite under anaerobic conditions. The concentration of NH3 (detected as ammonium, NH4+, in solution) was a strong function of the reaction temperature. At the lower temperatures studied (22oC and 70oC), a small amount of NH4+ was formed, but µmol.kg-1 amounts of NH4+ were formed at a reaction temperature of 120oC. Only about 5% of the initial NO2- concentration was converted to NH4+. In the NO3-/pyrite system, the NO3- reactant concentration remained unchanged at all the three reaction temperatures studied, consistent with the low amounts of NH4+ formed in these experiments. Finally, it was shown using in situ infrared spectroscopy that surface-bound NO formed on pyrite during the conversion of the nitrogen oxides to ammonia. Overall, it was shown that the kinetics of NH4+ formation was slower for NO3- than that observed for NO2-. Studies presented in this thesis that focused on the surface reactivity of As(III) on ordered ferrihydrite and birnessite nano particles showed that As(III) could be oxidized to arsenate (referred to as As(V)) in the presence of simulated solar radiation. In the ordered ferrihydrite circumstance the adsorption of As(III) and photo-induced oxidation to As(V) was compared to the same reaction on the more disordered and smaller ferrihydrite particles (known as "2-line" ferrihydrite). A comparison of the adsorption rate of As(III) on the two surfaces in the presence of light after normalizing for differences in surface area showed that the ordered ferrihydrite exhibited a higher arsenic adsorption rate. Also, the oxidation rate of As(III) to As(V) in the presence of light on the ordered ferrihydrite showed a strong dependence on the amount of dissolved oxygen in solution while the oxidation rate on the more disordered form showed no such dependence. It was proposed that differences in the rates of the heterogeneous oxidation rate of ferrous iron with dissolved oxygen on the two surfaces were the reason for this behavior. Finally, the photo-induced oxidation of As(III) to As(V) on Na- and K-birnessite at solution pHs of 5.0 and 7.4 was investigated. It was shown that the oxidation rate of As(III) to As(V) occurred at a faster rate on birnessite in the presence of light when compared to the same system in the dark. Mn(II) formed during the reductive dissolution of birnessite during the oxidation of As(III) was experimentally observed at pH 5.0, but not at pH 7.4. Experiments were also conducted that investigated the reductive dissolution of Na- and K-birnessite (having different sizes and average oxidation states) by As(III) under more alkaline conditions. These experiments were conducted at pH 8.5 and the post-reaction samples were analyzed with X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It was shown under these alkaline conditions using X-ray diffraction that structural changes occurred in/on both the Na- and K-birnessite during the As(III) oxidation reaction. / Chemistry

This thesis is concerned with measurements of persistent organic pollutants (POPs) in environmental samples. The POPs consist of several groups of compound with many isomers, hence analysing POPs in a complex environment is a This thesis is concerned with measurements of persistent organic pollutants (POPs) in environmental samples. The POPs consist of several groups of compound with many isomers, hence analysing POPs in a complex environment is a challenging task. Studies of the abundance or dynamics of such substances in the environment require careful consideration of several key steps. The environmental and analytical problems must be correctly defined, suitable analytes, sampling strategies and techniques must be selected, the chemical analyses must be reproducible and accurate, and the data evaluation protocols must be rigorous and appropriate. The aim of this thesis was to evaluate the use of pollutant profiles in order to assess complex patterns of environmental exposure. When combined with multivariate data analysis (MVDA) a maximum of information may be extracted from analytical data. Nevertheless, good quality data is essential for correct evaluation of the environmental phenomena under investigation. The precision and accuracy of a solid phase assisted liquid extraction method was therefore assessed by comparison to a reference method. The validated method was used in two human exposure studies. The concentrations of PCBs and dioxins were determined in human tissues from general populations in Sweden and Spain. Although it was concluded that the populations were exposed to similar degree to PCBs and dioxins, principal component analysis (PCA) showed that the compound profiles differed between the populations. PCA was also used to differentiate between occupationally exposed workers and matched controls and between exposed workers with recent and earlier exposure. In addition, the analysis indicated that the differences in PCB patterns in workers with recent and earlier exposure were related to differences in the metabolic degradation rates of individual PCBs. The PCA model was further used to select PCB congeners that were representative of each group. Finally, the emission of polycyclic aromatic hydrocarbons (PAHs) in a traffic tunnel was estimated by measuring 29 individual PAHs. The sampling periods were chosen to reflect a maximum variation in the traffic composition. An excellent prediction of the percentage of heavy-duty vehicles was obtained using partial least squares (PLS) regression. It was shown by PCA that it might be possible to predict source compositions at other locations with the aid of multivariate statistical tools. Thus, properly gathered pollutant profiles and MVDA may be combined to extract a large amount of significant information from environmental source and exposure data.