Thesis (M.S.)--Florida State University, 2006. / Advisor: Guosheng Liu, Florida State University, College of Arts and Sciences, Dept. of Meteorology. Title and description from dissertation home page (viewed Sept. 15, 2006). Document formatted into pages; contains vii, 45 pages. Includes bibliographical references.

Originally issued as the author's thesis (Ph. D.)--Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 2005. / "September 2005". "Doctoral dissertation." "Department of origin: Geology and Geophysics." "Joint Program in Oceanography/Applied Ocean Science and Engineering"--Cover. Includes bibliographical references.

Thesis (Ph. D.)--Oregon State University, 2008. / Printout. Includes bibliographical references. Also available on the World Wide Web.

Thesis (M.Sc.)--York University, 2004. Graduate Programme in Earth and Space Science. / Typescript. Includes bibliographical references (leaves 164-174). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://gateway.proquest.com/openurl?url%5Fver=Z39.88-2004&res%5Fdat=xri:pqdiss&rft%5Fval%5Ffmt=info:ofi/fmt:kev:mtx:dissertation&rft%5Fdat=xri:pqdiss:MQ99373

Thesis (M.S.)--Montana State University--Bozeman, 2007. / Typescript. Chairperson, Graduate Committee: Mark L. Skidmore. Includes bibliographical references (leaves 69-75).

Cette thèse porte sur l’étude des composés organiques semi-volatils, notamment les pesticides et les composés nitro-aromatiques dans les deux compartiments l’eau et l’atmosphère. La première partie de ce travail concerne l'optimisation des différents paramètres expérimentaux (concentration initiale des composés, concentration de l’électrolyte support, température et la densité de courant imposé) de la dégradation de la cypermethrine et du 2-Nitrobenzaldehyde (2-NBA) par oxydation direct moyennant les électrodes de l'oxyde d'étain (SnO2) et le diamant dopé au bore (DDB). Cette dégradation a été suivie par les analyses de la demande chimique en oxygène (DCO) et la chromatographie en phase gazeuse. Les résultats obtenus montrent que le taux de minéralisation dépasse 80 % pour le cypermethrine en utilisant le DDB. La deuxième partie est consacrée à l'étude de la réactivité du bupirimate vis-à-vis de l’ozone et les radicaux OH• en phase hétérogène. Les résultats obtenus montrent que les valeurs de la constante cinétique pour la réaction du bupirimate avec les radicaux OH• et l’ozone sont respectivement de l’ordre de 1,06 x 10-12 et 5,4 x 10-20 (cm3 molecule-1 s-1). La durée de vie du bupirimate est de plusieurs mois par rapport à l'ozone et de quelques jours par rapport aux radicaux OH•. Les spectres UV et la réactivité homogène vis-à-vis des radicaux OH• du 2-Nitrobenzaldehyde (2-NBA) a été déterminé en phase gazeuse. Les études cinétiques ont été réalisées dans une chambre atmosphérique couplée à un spectromètre IR. Les résultats obtenus montrent que le 2-NBA est sensibles à la photolyse dans l’atmosphère et que sa réactivité vis-à-vis des radicaux OH• est non négligeable. En effet, la durée de vie atmosphérique de ce composé est relativement courte. Elle varie de quelques minutes à quelques heures. Le 2-NBA est donc non persistant dans l’atmosphère. / This thesis focused on the study of semi-volatile organic compounds (SVOC), including pesticides and nitro-aromatics compounds in the two compartments, water and atmosphere. The first part of this work concerns the optimization of the different experimental parameters in order to mineralize two compounds (cypermethrin and of 2-Nitrobenzaldehyd), those parameters are initial concentration of compounds, concentration of the electrolyte support, temperature and the density of the current imposed. This mineralization has been done by a direct oxidation through the electrodes of the tin oxide (SnO2) and Boron Doped Diamond (BDD). The degradation process has been followed by the DCO analyzes and the gas chromatography. It has been shown that the rate of mineralization exceeds 80 % for the cypermethrine compound using BDD electrode. The second part is devoted to study the reactivity of bupirimate in heterogeneous phase using ozone and OH radicals as oxidant. The obtained results show that the rate constant values of the analyte are (1,06 ± 0,87) x 10-12 and (5,4 ± 0,3) x 10-20 (cm3 molecule-1 s-1) relative to heterogeneous OH-oxidation and O3, respectively. Such values implicate tropospheric life-times that vary from a few days to several months, meaning that these compounds are relatively persistent and may be transported to regions far from their point of application. The UV-absorption spectra and homogeneous OH-reactivity of 2-Nitrobenzaldehyde compound in the gas phase are investigated. The kinetic studies have been carried out in an atmospheric chamber coupled to an IR spectrometer. The results obtained indicate that the compound studied is susceptible to photolysis in the atmosphere and he exhibit strong reactivity towards OH-radicals. Generally speaking, the atmospheric life-time of this compound is relatively short, in the order of a few minutes to hours and he is non-persistent. Rate constants present a slight variation with the temperature.

An idealized atmospheric model consisting of energy and moisture conservation equations is developed for studies of the ocean's role in climate. Testing under fixed oceanic conditions yields a climatology comparable with direct observations, as does the case when the interpentadal (1955–59; 1970–74) sea surface temperature fields are applied. The atmospheric model is then coupled to an ocean general circulation model as well as a thermodynamic ice model without the use of flux adjustments. When configured for a global realistic geometry, the model faithfully represents deep water formation in the Atlantic and Southern Oceans with upwelling throughout the Pacific and Indian Oceans. The model is then utilized to investigate the influence of meltwater discharge on the stability of North Atlantic Deep Water (NADW) production and the Younger Dryas (YD ∼ 14ka). Results suggest pre-YD meltwater is capable of diminishing NADW to the point where diversion of meltwater from the Gulf of Mexico to the St. Lawrence completely inhibits its production. The coupled model appears to be stable in this state, equivalent to the “Southern Sinking” equilibrium identified in previous models. Inclusion of the wind stress/speed feedback, however, has a dramatic effect causing a reestablishment of NADW production. The model is then configured in a four basin-two hemisphere sector geometry, crudely representative of the global oceans. Two identically formulated models (one of which employs flux adjustments) are then perturbed to assess the role of flux adjustments on the ocean's response to a “global warming-like” scenario. Significant global and basin-scale differences exist between the cases which is linked to the influence of the salt-flux adjustment on the overturning cells within the model Atlantic and Southern Oceans. Results further suggest that minimizing the coupling shock prior to applying the perturbation leads to results slightly closer between the models, although large differences still persist. The model is then configured for a highly idealized 60° sector geometry to study the influence of horizontal resolution and parameterized eddy processes on poleward heat transport. As resolution increases, the total oceanic heat transport steadily increases. This result is also evidenced in a parallel series of ocean-only model studies driven by restoring boundary conditions. In each case the increase in heat transport is associated with the steady currents. In particular the baroclinic gyre transport (our model analog of the transport associated with the “Warm Core” jet region of the Gulf Stream) increases by a factor of 5 between coarsest and finest resolution. Spontaneous decadal-scale variability is also found to exist in the higher resolution experiments (with the exception of one of the restoring cases). The oscillation is thermally driven by an advective-convective mechanism and linked to the value of the horizontal diffusivity employed. Increasing the diffusivity in the high resolution cases is enough to destroy the variability, while decreasing the diffusivity in the moderately coarse resolution case is enough to induce the variability. These results point to the importance of higher resolution in the oceanic component of current climate models, yielding enhanced poleward heat transports and revealing the existence of richer decadal-scale variability in models which require less parameterized viscosity and diffusion. / Graduate

The focus of this work is the development and improvement of chemistry schemes in both 1D and 3D atmosphere models, applied to exoplanets. With an ever increasing number of known exoplanets, planets orbiting stars other than the Sun, the diversity in the physical and chemical nature of planets and their atmospheres is becoming more apparent. One of the prime targets, and the focus of many observational and theoretical studies, are the subclass of exoplanets termed hot Jupiters, Jovian sized planets on very short period orbits around their host star. Due to their close orbit, with orbital periods of just a few days, the atmospheres of such planets are heated to very high temperatures (~1000-2000 K) by the intense irradiation from the star. In addition, it is expected that these planets should have synchronised their rotation with their orbital period, a phenomenon called tidal-locking, that leads to a permanently illuminated dayside and a perpetually dark nightside. This combination of intense heating and tidal-locking leads to an exotic type of atmosphere that is without analogue in our own Solar system. Observational constraints suggest that some of these atmospheres may be clear whilst others may be cloudy or contain haze. Some hot Jupiters appear to be inflated with radii larger than is expected for their mass. For the warmest hot Jupiters optical absorbing species TiO and VO are expected to be present, due to the thermodynamical conditions, where they can strongly influence the thermal structure of the atmosphere, yet so far these species have remained elusive in observations. Theoretical simulations of these planets appear to provide poor matches to the observed emission flux from the nightside of the planet whilst providing a much better agreement with the observed dayside flux. These outstanding questions can be tackled in two complimentary ways. Firstly, the number of exoplanets subject to intense observational scrutiny must be increased to improve the statistical significance of observed trends. Secondly, and in tandem, the suite of available theoretical models applied to such atmospheres must be improved to allow for a more comprehensive understanding of the potential physical and chemical processes that occur in these atmospheres, as well as for better comparison of model predictions with observations. In this thesis we present the development and application of one-dimensional (1D) and three-dimensional (3D) models to the atmospheres of hot exoplanets, with a focus on improving the representation of chemistry. One of the concerns of this work is to couple the radiative transfer and chemistry calculations in a one-dimensional model to allow for a self-consistent model that includes feedback between the chemical composition and the thermal structure. We apply this model to the atmospheres of two typical hot Jupiters to quantify this effect. Implications for previous models that do not include this consistency are discussed. Another major focus is to improve the representation of chemistry in the Met Office Unified Model (UM) for exoplanet applications, a three-dimensional model with its heritage in modelling the Earth atmosphere that has recently been applied to exoplanets. We discuss the coupling of two new chemistry schemes that improve both the flexibility and capabilities of the UM applied to exoplanets. Ultimately these developments will allow for a consistent approach to calculate the 3D chemical composition of the atmosphere taking into account the effect of large scale advection, one of the processes currently hypothesised to cause the discrepancy between model predictions and observations of the nightside emission flux of many hot Jupiters.

Made available in DSpace on 2014-10-09T12:32:34Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:10:06Z (GMT). No. of bitstreams: 1 03209.pdf: 3814458 bytes, checksum: 2c10a4330417ae0715e500a18b636f05 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Fisica, Universidade de Sao Paulo - IF/USP

Made available in DSpace on 2014-06-11T19:29:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-04-01Bitstream added on 2014-06-13T20:38:24Z : No. of bitstreams: 1 silva_dg_me_araiq.pdf: 925678 bytes, checksum: 23eefdaaaa6811fa33effc47c7fa764b (MD5) / A chuva é um mecanismo fundamental para a remoção de substâncias da atmosfera, cuja análise pode trazer informações importantes sobre a composição química da baixa troposfera local-regional. Neste trabalho, amostras de água de chuva foram coletadas no Instituto de Química de Araraquara, de janeiro de 2008 a dezembro de 2012. A determinação de carbono orgânico dissolvido (COD) e carbono orgânico não purgável (CONP) foi feita pelo analisador de carbono e a quantificação de AA e FA por derivatização com a solução ácida 2,4-DNPH, em que as respectivas hidrazonas formadas foram determinadas por cromatografia líquida de alta eficiência (CLAE) com detecção em 360 nm. O pH apresentou uma média ponderada pelo volume (MPV) de 5,6 (n= 107) e uma boa correlação com o íon Ca2+ (r= 0,5809), indicando que a ressuspensão do solo pode ter contribuído para neutralizar parte da acidez. A MPV das concentrações de K+ e Ca2+ foi de 3,9 (n= 106) e 4,8 (n= 105) μmol L-1, respectivamente, sendo que a concentração de K+ apresentou variação sazonal, com um aumento no período de safra da cana-deaçúcar, indicando a sua importante fonte na queima de biomassa. A MPV de COD (n= 118) encontrada em Araraquara foi de 263 ± 30 μmol L-1 sendo superior no período de safra da cana-de-açúcar (314 ± 46 μmol L-1; n= 74) do que no período de entressafra (182 ± 24 μmol L-1; n= 44). As concentrações de COD em Araraquara apresentaram correlações lineares significativas com K+ (0,8098) e com Ca2+ (0,6972), indicando que a queima de biomassa e a ressuspensão do solo são importantes fontes de emissão de carbono orgânico para a atmosfera. As concentrações de COD foram sempre superiores nos primeiros milímetros de chuva quando comparadas com o evento completo. Porém, o COD teve uma queda menos... / The rain is a fundamental mechanism for the removal of substances from the atmosphere, which analysis can provide important information on the local-regional composition. In this work, samples of rainwater were collected at the Institute of Chemistry of Araraquara, from January 2008 to December 2012. Determination of dissolved organic carbon (DOC) and non purgeable organic carbon (NPOC) was made by carbon analyzer and AA and FA were quantified after derivatization with acid solution of 2,4-DNPH, where the respective hydrazones formed were determined by high performance liquid chromatography (HPLC) with detection at 360 nm wavelength. The pH presented a volume weighted average (VWA) of 5.6 (n= 107) and presented significant correlation with Ca2+ (r = 0.5809) indicating that soil resuspension may have contributed to neutralization of part of the acidity. The VWA of K+ and Ca2+ concentration was 3.9 (n = 106) and 4.8 (n = 105) μmol L-1, respectively,and the concentration of K+ showed seasonal variation, with an increase during the period of sugarcane harvest, indicating its major source in biomass burning. The MPV DOC (n = 118) found in Araraquara was 263 ± 30 μmol L-1 being higher during the harvest of sugar cane (314 ± 46 μmol L-1, n = 74) than in nonharvest period (182 ± 24 μmol L-1, n = 44). The concentrations of DOC in Araraquara showed significant linear correlations with K+ (0.8098) and Ca2+ (0.6972), indicating that biomass burning and soil resuspension are important sources of organic carbon to the atmosphere. DOC concentrations were always higher in the first millimeters of rain in comparison with the entire event. However, the DOC had a less steep decrease, indicating that these species are removed from the atmosphere by the process of below cloud and in cloud. The percentage... (Complete abstract click electronic access below)