Thesis (Ph.D.)--University of Florida, 2008. / Adviser: Lawrence Kenny. Includes bibliographical references.

Thesis (B.S.)--University of Missouri, School of Mines and Metallurgy, 1922. / The entire thesis text is included in file. Typescript. Illustrated by author. Title from title screen of thesis/dissertation PDF file (viewed June 4, 2009)

Thesis (M.Sc.)--Memorial University of Newfoundland, 2006. / Bibliography: leaves 194-204. Also available online.

This literature review analyses and discusses different theories and results regarding impact of volcanic eruptions on climate change in Earth's history. Present global warming has been attributed to anthropogenic emissions of greenhouse gases, mainly carbon dioxide, however changes in global temperatures have occurred before the onset of anthropogenic emissions. Certain prehistoric climate changes are thought to be caused by emissions of volcanic gases to the atmosphere. Many studies have investigated the connection between volcanic events and subsequent changes in global temperatures. A majority have concluded that volcanic sulfur dioxide is the main direct and indirect climate forcing gas influencing temperatures over time. Increased volcanic activity over the last 15 years is thought to be an inhibiting factor on present global warming. This is supported by evidence of past volcanic events preceding global cooling and warming periods during Holocene and prehistoric times. Further, there are indications that factors such as geographical position, season, gas composition, magnitude and duration of an eruption influences the extent of the climate forcing.Records of climate such as ice cores and tree growth rings and isotopic characterization have made it possible to identify volcano eruptions over time and determine the identity of the erupting volcano. Past and present data from these can be used to gain a better understanding of past climate changes as well as making predictions about future changes as a result volcanic eruptions. However, accuracy regarding temporal and spatial resolution of these records is of great importance for the validity of the results.

xv, 108 p. : ill. (chiefly col.) / Aqueous aerosol surfaces are an important platform for chemical reactions through which gases are transported in the atmosphere. The chemical complexity of aqueous aerosols is well-established, but many questions remain about the molecular nature of their surfaces, particularly with respect to the uptake of gases. The pollutant sulfur dioxide, SO₂, has been implicated in environmental phenomena such as acid rain, climate change, and cloud formation. SO₂ is fundamentally interesting because it forms spectroscopically identifiable complexes with water at aqueous surfaces. This dissertation aims to understand how temperature and aqueous composition impact the formation of surface complexes between water and SO₂. Vibrational sum frequency spectroscopy (VSFS), a surface specific technique, is used to probe the vibrational modes of water and small organic molecules, investigating changes to the overall orientation, bonding environment, and structure of interfaces when aqueous surfaces are exposed to SO₂. SO₂ adsorption to water at tropospherically relevant temperatures (0--23 °C) is examined first. The results show enhanced SO₂ surface affinity at colder temperatures, with most of the topmost water molecules showing evidence of binding to SO₂ at 0 °C compared to a much lower fraction at room temperature. Surface adsorption results in significant changes in water orientation at the surface but is reversible at the temperatures examined. The surface and vibrational specificity of these studies can be used to distinguish between the effects of surface adsorption compared to bulk accommodation. This distinction is utilized to demonstrate that SO₂ complexation is independent of solution acidity, confirming that bulk absorption is unnecessary for surface adsorption to occur. Finally, the impact of the organic species succinic acid and formaldehyde on the formation of surface SO₂ complexes is examined. These experiments indicate that SO₂ surface complexation occurs primarily with water but that surface active organic species may interact with gases under certain circumstances, namely when the organic species are more chemically reactive towards the gas. These studies have important implications for atmospheric chemistry and the uptake of gases, particularly in the complex aqueous environments expected in the troposphere. / Committee in charge: Dr. Paul C. Engelking, Chair; Dr. Geraldine L. Richmond, Advisor Dr. Jeffrey A. Cina, Member; Dr. Thomas R. Dyke, Member; Dr. Alan D. Johnston, Outside Member

Orientador: Ivo Milton Raimundo Junior / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-10T14:29:52Z (GMT). No. of bitstreams: 1 Silva_KarimeRitaBentesda_D.pdf: 987159 bytes, checksum: fbf95cdeef4cddf9f7dda16d5efcb700 (MD5) Previous issue date: 2007 / Resumo: Foram construídos optodos para a determinação de SO2 em amostras de ar e de vinho, com base no cromóforo Pd2(dppm)2Cl2 [(bisdifenilfosfinometano-dicloreto de paládio (I)] imobilizado em matrizes de PVC [poli(cloreto de vinila)] e plastificadas com o-NPOE [o-nitrofeniloctiléter]. As membranas que apresentaram os melhores resultados continham 20% de PVC, 4% do cromóforo e 76% de o-NPOE, para uma massa final de 100 mg. Para amostras de ar, as membranas foram preparadas pela deposição de 200 mL de solução em filmes de poliéster, apresentando espessura média de 500 mm, faixa linear de resposta de 0-5 ppmv SO2, limite de detecção de 130 ppbv SO2 e tempo de vida útil de 2 meses ou 250 medidas. Esse optodo responde também para monóxido de carbono, na faixa linear de 1-5% de concentração. Para amostras de vinhos, as membranas foram preparadas pela deposição manual de 10 mL de solução em filmes de poliéster e foram obtidas faixas lineares de trabalho de 0-50 mg L para SO2 livre e 0-150 mg L para SO2 total, com limites de detecção da ordem de 0,37 e 0,70 mg L, respectivamente. Na validação do método, foi observada uma boa correlação com o método padrão, não havendo diferença significativa no nível de 95% de confiança. Observou-se que sacarose e etanol geram efeito de matriz. Para ambos os optodos, observou-se que é grande o efeito da umidade. Na presença de NO2, H2S, HCl e Cl2 10 ppmv a fase sensora é inutilizada. Também foi desenvolvido um optodo para a determinação de oxigênio dissolvido com base no fluoróforo PtOEP [octaetilporfirinato de platina] imobilizado em PDMS [poli(dimetilsiloxano)]. Os melhores resultados foram obtidos para as membranas preparadas a partir de uma solução contendo 8 x 10 mol L de PtOEP e 20% de sílica. A espessura média das membranas foi de 0,22 ± 0,02 mm. Foi obtido um limite de detecção de 0,077 mg L de O2 dissolvido e com desvio padrão relativo de 0,53%. A faixa linear de resposta foi de 0,07-5,95 mg L de O2 dissolvido em água. Observou-se que não há erro sistemático com o uso deste optodo, e que o mesmo pode ser empregado na determinação oxigênio dissolvido em amostras reais / Abstract: Optodes for determination of sulphur dioxide in air and wine samples were constructed, based on the dichloro-bis-(diphenylphosphino)-methane dipalladium I [Pd2(dppm)2Cl2] complex immobilised in PVC films, plasticised with onitrophenyloctylether [o-NPOE]. The sensing phase that presented best performance was prepared from a THF solution (1 mL), containing 20 mg PVC, 4 mg Pd complex and 76 mg o-NPOE. For air sample analysis, membranes were prepared by the deposition of 200 µL of the cocktail solution on polyester sheet (average thickness of 500 µm), presenting a linear response range of 0-5 ppmv SO2, detection limit of (0.13 ± 0.02) ppmv SO2 and lifetime of 2 months or 250 measurements. This optode also presented a linear response to carbon monoxide in the 1-5 % range. For wine samples, membranes were prepared by the manual deposition of 10 µL of the cocktail solution on polyester sheet, presenting linear response ranges of 0 -50 mg L for free SO2 and 0 -150 mg L for total SO2, with detection limits of 0.37 and 0.70 mg L, respectively. The results showed good correlation with the reference method, presenting no significant differences at the 95 % confidence level. It was observed that sucrose and ethanol affects slightly the sensitivity. For both optodes, it was observed a significant effect of the humidity, as well as poisoning by NO2, H2S, HCl and Cl2 10 ppmv. It was also developed an optode for determination of dissolved O2, based on the fluorophore platinum octaethylporphyrin [PtOEP] immobilised in polydimethylsiloxane [PDMS]. The membrane prepared from a solution containing 8 x 10 mol L PtOEP and 20 % silica presented the best performance, with an average thickness of 0.22 ± 0.02 mm. The optode showed a detection limit of 0.077 mg L dissolved O2, relative standard deviation of 0.53 % and a linear response range from 0.07 to 5.95 mg L O2. It was not observed a systematic error for the developed sensor, which can be applied to the determination of dissolved oxygen in water samples / Doutorado / Quimica Analitica / Doutor em Ciências

The adsorption of SO2 by metal oxides suspended in decane were studied by calorimetric titration. The adsorption per surface area decreases in order CuO > Cu2O > Fe2O3 > V2O5. An Andersen High Volume sampler was used to obtain particulate samples from five sites in Utah County. Particulate sulfur (IV) and sulfur (VI) was analyzed by thermometric titration with K2Cr2O7 and by a direct injection enthalpimetric determination using BaCl2. Results show that little oxidation of the S(IV) occurs after it is released from the Kennecott smelter stack.

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