Atmospheric aerosols play an important role in climate by scattering and absorbing radiation and by serving as cloud condensation nuclei. An aerosol’s optical or nucleation properties are driven by its chemical composition. Chemical aging of aerosols by atmospheric oxidants, such as ozone, alters the physiochemical properties of aerosol to become more hygroscopic, light absorbing, and viscous during transport. However the mechanism of these transformations is poorly understood. While ozone is a protective and beneficial atmospheric gas in the stratosphere, it is a potent greenhouse gas in the troposphere that traps heat near the Earth’s surface. It also impacts human heath by irritating the respiratory tract and exacerbating cardiovascular diseases. Additionally, ozone can alter the ecosystem through oxidizing plant foliage which can lead to deforestation and crop losses as well. Both gases and aerosols in the troposphere can react with ozone directly and indirectly with hydroxyl radicals. While daytime aging is thought to be primarily driven by photochemical processes and hydroxyl radicals, ozone is thought to be a key player in nighttime or dark aging processes that can alter the physicochemical properties of aerosols. Measured concentrations of trace gases and aged aerosol components in the field are higher than values predicted based on laboratory studies and computer simulations. Consequently, new experimental approaches are needed to narrow the gaps between observations and mechanistic understandings. In this dissertation, a plume of microdroplets was generated by pneumatically assisted aerosolization and then exposed to a flow of ozone before entering a mass spectrometer. This surface-specific technique allowed for the real-time analysis of reaction products and intermediates at the air-water interface. This work explores the in situ oxidation of iodide, a component of sea spray aerosols, by 0.05 – 13.00 ppmv ozone to explore how heterogeneous oxidation could enhance the production of reactive iodide species. Methods to study the reaction channels and intermediates were also established to not only determine a mechanism of iodide oxidation by ozone, but to enable the study of more complex systems. The developed approach was then applied to examine the oxidation of catechol and its substituted cousins, a family of compounds selected to model biomass burning and combustion emissions, at the air-water interface. While literature suggested that the primary mechanism of catechol oxidation by ozone would be the cleavage of the C1-C2 bond, it was determined that this was only a minor pathway. An indirect oxidation channel dominated heterogeneous processes at the air-water interface, giving rise to hydroxyl and semiquinone radicals that recombine to produce polyhydroxylated aromatics and quinones. This new mechanism of aging represents an overlooked channel by which brown, light-absorbing carbon aerosols are produced in the atmosphere. In addition, the work investigates how reactions on solid particulate aerosols proceed under variable relative humidity. Thin films were developed alongside a novel flow-through reactor to study of how aerosols are transformed by ozone and hydroxyl radicals when exposed to 50 ppbv - 800 ppmv of ozone. This system was employed to probe how catechol reacts with ozone under variable relative humidity. Further work was undertaken to model the adsorption process at the air-solid interface under variable humidity, permitting the estimation of the reactive uptake of ozone by the film at concentrations (50-200 ppbv) seen in rural and urban areas. Together, these results provide an increased understanding of how heterogeneous oxidation of aerosols contributes to aerosol aging processes as well as free radical production in the troposphere.

Dans le contexte des changements climatiques globaux, les arbres devront faire face à une atmosphère différente de celle présente actuellement. L'ozone et le CO2 sont deux des principaux gaz dont la hausse de la concentration est préoccupante. Nous avons étudié les effets de l'ozone et du fort CO2, seuls ou combinés, sur la biosynthèse et la teneur de la lignine, l'anatomie et les propriétés du bois de jeunes plants de peupliers (Populus tremula x alba) placés en conditions contrôlées dans des chambres phytotroniques. De plus, ces arbres étaient inclinés afin d'induire la formation de bois de tension. La voie de biosynthèse de la lignine est affectée majoritairement par l'ozone conduisant à une modification de la composition chimique du bois des arbres. L'ozone modifie l'anatomie du bois de tension en diminuant le nombre des vaisseaux formés, l'épaisseur des parois des fibres et augmentant le diamètre du lumen des vaisseaux. Le fort CO2 stimule la croissance des arbres et la production de biomasse mais ne semble pas modifier les propriétés du bois et la synthèse de lignine. L'interaction des deux gaz révèle un effet bénéfique du fort CO2 vis-à-vis des effets néfastes de l'ozone. La présence de fort CO2 limite la baisse du métabolisme des lignines et favorise l'allocation dans la partie moyenne des tiges des plants. Enfin, les propriétés du bois sont modifiées par les différents traitements suggérant une qualité différente pour l'utilisation future du bois. / In the context of global climate change, trees will have to cope with an atmosphere different from actual. Ozone and CO2 are two of the main gas whose increased concentration is worrying. We investigated the effects of ozone and elevated CO2 single or combined on the biosynthesis and content of lignin, wood anatomy and properties of young poplars (Populus tremula x alba) placed in controlled conditions in phytotronic chambers. Moreover, trees were bent to induce tension wood formation. The metabolism of lignin was mainly affected by ozone leading to a change in the chemical composition of wood. Ozone altered wood anatomy by reducing the vessel number, cell wall thickness of fibers and increasing lumen diameter of vessels. Elevated CO2 stimulated radial and height growth, and biomass production, but seemed to have no effect on wood properties and lignin biosynthesis. The interaction of the two gases showed a benefit effect of elevated CO2 against negative effects of ozone. Presence of high CO2 limited lignin metabolism decrease and promoted a better stem allocation of carbon in middle stem of plant. Wood properties were also altered by these treatments suggesting a different quality for the future use of wood.

La mammite est une inflammation de la mamelle, le plus souvent, en réponse à une invasion d’origine bactérienne. L’utilisation d’antibiotiques pour le traitement de cette pathologie n’est pas la solution idéale. Outre les problèmes engendrés pour la qualité du lait, l’apparition de résistance et l’inefficacité des traitements nécessitent de développer des méthodes alternatives. L’objectif de ces travaux de thèse était de vérifier si l’utilisation d’huile de tournesol ozonée comme moyen de lutte alternatif contre les mammites est envisageable. Dans un premier temps, l’effet des conditions d’ozonation sur la composition et sur l’activité antibactérienne de l’huile ozonée a été étudié pour déterminer les conditions optimales de synthèse d’un agent antibactérien. Les résultats ont montré que l’ajout d’eau et l’augmentation de la durée de la réaction permettaient l’obtention de valeurs d’indice de peroxyde plus élevées et d’une meilleure activité antibactérienne mettant en évidence la relation existant entre ces deux paramètres. Par la suite, l’activité antibactérienne d’huile de tournesol ozonée a été évaluée in vitro sur 59 espèces bactériennes isolées de cas déclarés de mammites chez des brebis. Le produit testé a prouvé son efficacité contre toutes les souches étudiées avec des concentrations minimales inhibitrices de croissance comprises entre 0,625 et 20 mg/mL. L’homologation de l’huile de tournesol ozonée comme préparation vétérinaire requiert d’avoir des données sur sa stabilité thermique et d’identifier les molécules actives. Les travaux menés ont montré que la composition de l’huile de tournesol ozonée stockée à −20 °C ou à +4 °C n’évoluait pas pendant une durée d’un an. Au contraire, des températures de stockage plus élevées entrainaient rapidement une diminution de l’indice de peroxyde et une augmentation de l’acidité. Cependant, ces modifications n’ont pas eu d’effet sur l’activité antibactérienne qui a gardé une valeur constante. Ces observations ont permis d’émettre des hypothèses sur l’identité des molécules actives. L’activité antibactérienne des huiles ozonées serait due à la présence d’ozonides, d’hydroperoxydes et d’acides nonanoïque et azélaïque. L’étude de la réaction d’ozonolyse sur un composé modèle, l’oléate de méthyle, a permis d’affiner ces hypothèses. En effet, l’activité antibactérienne spécifique de différentes fractions obtenues après purification d’oléate de méthyle ozoné a été évaluée. Toutefois, les ozonides purifiés et caractérisés par RMN n’ont pas montré d’activité dans la gamme de concentration testée. L’activité antibactérienne de l’huile de tournesol ozonée peut donc être attribuée aux hydroperoxydes, aux aldéhydes et aux acides carboxyliques à chaines courtes.

A oxidação é um método que visa a modificação do amido por agentes oxidantes diversos, introduzindo grupamentos funcionais e realizando cisão das ligações glicosídicas. Seus objetivos são reduzir a viscosidade do polissacarídeo, elevar a transparência da pasta e limitar sua retrogradação. O objetivo do presente estudo foi modificar os amidos de milho com diferentes teores de amilose e o amido de mandioca pelo tratamento com ozônio e também caracterizar as amostras oxidadas quanto às características moleculares, estruturais e funcionais, correlacionando-as entre si. O processo de oxidação foi efetivo em alterar diversas propriedades e funcionalidades dos amidos estudados, contudo de modos distintos para as diferentes fontes. Tais diferenças decorrem da composição e estrutura granular peculiares de cada um, promovendo diferentes taxas de degradação das lamelas amorfas e cristalinas e da presença de grupos carboxilas. A oxidação pelo ozônio nas condições estudadas reduziu a viscosidade apenas do amido de milho normal; no caso dos amidos de milho ceroso e de mandioca, a viscosidade foi ligeiramente aumentada. O amido de milho de alta amilose não apresentou viscosidade nas condições de analisadas pelo Rapid Visco Analyser, tanto antes como após a oxidação. O setback foi reduzido pelo processo oxidativo com o ozônio para os três amidos, tornando-os mais estáveis. A oxidação aumentou a claridade de pasta de todos os amidos. A ozonização também causou alterações no amido de milho ceroso e no de mandioca, de modo a proporcionar capacidade de expansão no forno, em índices próximos àqueles de amostras comerciais de polvilho azedo. Os demais amidos não se expandiram significativamente. A propriedade de expansão no forno foi afetada principalmente pela variação de entalpia de gelatinização dos amidos, mas também pelos teores de carboxilas e de carbonilas, fator de inchamento, quebra de viscosidade, setback, cristalinidade relativa e tamanho das cadeias ramificadas de amilopectina (cadeias B2 e B3 e tamanho médio). O uso do ozônio, portanto, poderá ser útil nesta modalidade de modificação dos amidos e, em especial para o amido de mandioca ou de milho ceroso, capacitando-os para a expansão no forno, o que poderia gerar produtos panificáveis mais padronizados do que os obtidos pelo polvilho azedo, ou sem as consequências da oxidação por métodos químicos mais agressivos, como o uso do hipoclorito de sódio. / Oxidation is a method which aims the starch modification by various oxidizing agents, introducing functional groups and performing the cleavage of glycosidic linkages. Its objectives are to reduce the polysaccharides viscosity, raising the transparency paste and minimizing retrogradation. The aim of this study was to modify the corn starch with different levels of amylose and the cassava starch using ozone and also to characterize the samples oxidized as the molecular, structural and functional characteristics, relating them with each other. The oxidation process was effective changing several properties and features of the studied starches, however, in different ways for the different sources. These differences come from having starches different composition and granular structure, providing different rates of degradation of amorphous and crystalline lamellae and the presence of carbonyl groups, and carboxyl formed. A reduction in viscosity was observed for the normal corn starch after oxidation, and an increase for the waxy maize and cassava starches. The high amylose corn starch showed no viscosity by Rapid Visco Analyser, before or after oxidation. The setback was reduced by the oxidation process with ozone for the three starches, rendering them more stable. Oxidation by ozone under the conditions studied increased paste clarity of all starches. Ozonation caused changes in the waxy corn and cassava starches, providing baking properties, in indices close to those of commercial samples of sour cassava starch. The other starches are not expanded significantly in the oven. The baking property was mostly affected by enthalpy of gelatinization of starches, but also by carboxyl and carbonyl contents, swelling factor, breakdown, setback, relative crystallinity and size of amylopectin branched chains (B2, B3 and medium size). So, the use of ozone may be useful in this starch modification modality, and in particular for cassava or waxy maize starches, enabling the expansion in oven, which could generate more standardized baking products than those obtained by sour cassava starch, or without consequences of oxidation using more aggressive chemical methods, such as sodium hypochlorite.

Mineral dust aerosols emitted from the Earth crust during various natural and anthropogenic processes continuously alter the chemical balance of the atmosphere via heterogeneous processes and thus, impact on the global climate. Understanding of heterogeneous chemistry and photochemistry on mineral dust has become vital to accurately predict the effect of mineral dust loading on the Earth's atmosphere. Here, laboratory measurements are coupled with model studies to understand heterogeneous chemistry and photochemistry in the atmosphere with the specific focus on reactions on mineral oxide surfaces. Heterogeneous uptake of gas phase HNO3 on well characterized metal oxides, oxyhydroxides and carbonates emphasized binding of nitric acid to these surfaces in different modes including monodentate, bidentate and bridging under dry conditions. It is becoming increasingly clear that the heterogeneous chemistry, including uptake of HNO3, is a function of relative humidity (RH) as water on the surface of these particles can enhance or inhibit its reactivity depending on the reaction. All the studied model systems showed a significant uptake of water with the highest uptake by CaCO3. Quantitative analysis of water uptake indicated formation of multilayers of water over these reactive surfaces. Under humid conditions, two water solvated nitrate coordination modes were observed that is inner-sphere and outer-sphere, which differ by nitrate proximity to the surface. Photochemical conversion of nitric acid to gas phase nitrous oxide, nitric oxide and nitrogen dioxide through an adsorbed nitrate intermediate under different atmospherically relevant conditions is shown using transmittance FTIR and XPS analysis. The relative ratio and product yields of these gas phase products change with relative humidity. Photochemistry of adsorbed nitrate on mineral aerosol dust may be influenced by the presence of other distinct gases in the atmosphere making it complicated to understand. This thesis converses formation of active nitrogen, NOx and N2O, and chlorine, ClOx, species in the presence of co-adsorbed trace gases, that could potentially regulate the peak concentration and geographical distribution of atmospheric ozone. Here we report formation of atmospheric N2O, from the photodecomposition of adsorbed nitrate in the presence of co-adsorbed NH3 via an abiotic mechanism that is favorable in the presence of light, relative humidity and a surface. Estimated annual production of N2O over the continental United States is 9.3+0.7/-5.3 Gg N2O, ~5% of total U.S. anthropogenic N2O emissions. Not only NH2 but also gaseous HCl react with adsorbed nitrate to activate "inert" N and Cl reservoir species, yielding NOCl, NOx, Cl and Cl2, through adsorbed nitrate under different atmospherically relevant conditions. Mineral dust aerosol is a major source of bioavailable iron to the ocean with an annual deposition of ~ 450 Tg of dust into the open ocean waters. In this study, we report enhanced Fe dissolution from nano scale Fe-containing minerals, i.e.alpha-FeOOH, beyond the surface area effects that can be attributed to the presence of more reactive sites on specific crystal planes exposed. We further report with clear evidence that aggregation impacts on dissolution. Proton-promoted dissolution of nanorods is nearly or completely quenched in the aggregated state. Acid type, presence of oxyanions and light are several other key factors responsible for regulating for iron dissolution. The work reported in this thesis provides insight into the heterogeneous chemistry and photochemistry of mineral dust aerosol under different atmospherically relevant conditions.

With a growing population and continuous accumulation of pollutants, water resources worldwide are quickly being depleted. Drastic improvements need to be made in both water conservation and treatment. Advanced oxidation processes (AOPs) have been developed to go above and beyond the capabilities of traditional wastewater treatment facilities to eliminate emerging contaminants from our water systems. AOPs increase the generation of hydroxyl radicals (•OH) in oxidation reactions, which are less selective and more reactive than other oxidants, such as ozone, so they are more effective at degrading persistent compounds. This study explored an AOP that utilizes ozonated multi-walled carbon nanotubes (MWCNTs) to generate •OH; past research has proven the success of this method of water treatment, showing a significant decrease in the effluent concentration of the tested compounds. However, these previous studies used a batch system with an initial aliquot of ozone, which would not be a feasible option in a commercial application. This research compares results from a semi-batch system with a continuous injection of ozone to these previous batch system studies to determine if continuous ozonation improves •OH generation capability, contaminant degradation, and the associated reaction kinetics. Results from batch studies had shown limitations to both •OH generation and contaminant degradation which were suspected to be due to ozone degradation; however, these results suggest that ozone availability is in fact not a limiting factor to •OH or contaminant degradation, and another mechanism must be at play. Further, to advance the AOP toward a commercially feasible design, a continuous flow-through system with a MWCNT embedded membrane was explored. The continuous system achieved 80% contaminant degradation in some cases, however, with varying retention times and efficiencies over time, the results were inconclusive and additional experimentation is required.

This diploma thesis follows the degradation of inkjet print by ultraviolet radiation and ozone effect for different types of papers. Colour test charts for the evaluation of accelerated ageing effect of ultraviolet light and gas fading were designed. These test charts were printed by dye-based inks on selected receiving media and exposed to ozone-enriched environment, UV radiation and their combination. The colorimetric values L* a* b* were calculated from spectral data of all patches of the test charts. The ozone effect on the prints was evaluated in the terms of total colour difference and dye concentration. The degradation of dye caused by ozone was observed also in a long-term period, after the contact of sample with ozone was terminated. Results of printed samples accelerated ageing by UV radiation and those that were influenced by the ozone effect were evaluated in the same way. It was found out that UV radiation and ozone treatment have a different effect on the degradation of dyes. The degradation rate is also strongly influenced by the receiving layer composition of papers used for inkjet printing. Also the catalytic effect of dyes was evaluated.

This thesis is focused on the effect of ozone on ink-jet prints. The knowledge about print technologies, materials for ink-jet printing, influence of environmental factors on the prints degradation and the methods of print lifetime estimation are discussed in the theoretical part of the thesis. Test-charts of 108 samples of C, M, Y primary colours and their overprints were prepared. I used two types of papers designed for ink-jet printing. These samples were exposed the effect of ozone in various concentrations to perform an accelerated aging experiment. Optical density values, La*b* coordinates, colour difference values were calculated from the measured spectral data. Changes of colours of the ink due to ozone exposure were determined and discussed. The validity of the reciprocal law due to ozone exposure was studied, too. The reciprocal behaviour was not confirmed for both types of the studied papers.

The aim of this diploma thesis is making design of device for setting tyres into the machine for ozone deterioration of tyres with following parametres: tyre size 295/80 R22,5, deployment profile of tyres, its foundation into the machine and sealing ozone atmosphere. The first part of this thesis contain research retailing to issues of tyre. After that there si presented design, which is completely making in programme Autodesk Inventor 2010. Calcutations are making in programme Mathcad 14 and deformation load, mainly construction, is making in programme Ansys 12.1. Finally there is making drawings.

The ozone decomposition reaction was performed in a 2.5cmx40cmx450cm two dimensional (2D) catalytic fluidized bed reactor. Commercial FCC catalyst impregnated with Fe2O3 was used at superficial gas velocities ranging between 0.006 m/s and 0.55 m/s. The onset velocity of the turbulent regime (uc) was determined as 0.4 m/s. The catalyst activity was optimized so that the effect of inter-phase mass transfer could be accentuated in the conversion reading. It was found that the general bubbling-turbulent model of Thompson et. al. (1999) combined with the mass transfer correlations of Kunii and Levenspiel (1991), Foka et. al. (1996) and Miyauchi et. al. (1980)gave reasonable predictions of the experimental data. The gradual improvement of reactor performance with an increase in superficial velocity (as predicted by the Thompson et. al. model) was not observed; instead a discontinuity of the reactor performance was noted in the vicinity of uc. More experimental work is required to substantiate this observation. Copyright / Dissertation (MEng)--University of Pretoria, 2009. / Chemical Engineering / unrestricted