The gradual depletion of and dependence on fossil fuels, air pollution and global warming have all accelerated the development of alternative energy systems which use hydrogen as an energy carrier. The hybrid sulphur cycle (HyS) is the foremost electrothermochemical process that can produce hydrogen as the energy carrier. The HyS cycle consists of two units, namely the sulphuric acid decomposition reactor and the sulphur dioxide electrolyser (SDE). The SDE is responsible for the SO2 electrooxidation to sulphuric acid and protons at the anode and the electro–reduction of protons to hydrogen at the cathode. This research study focuses on the kinetic data collected from the prepared catalysts for SO2 electro–oxidation at the anode. Platinum dispersed on carbon, niobium pentoxide, tantalum pentoxide and zirconium dioxide as electrocatalysts were prepared using sodium borohydride as a reducing agent. These electrocatalysts were characterized using transmission electron microscopy and x–ray diffraction. Cyclic voltammetry was used to study the electrochemical active surface area (EAS) and the results showed that Pt/ZrO2–C had a higher EAS area than Pt/Ta2O5–C, Pt/Nb2O5–C and Pt/C. The high EAS of Pt/ZrO2–C can be explained by the low crystal size however after a series of linear polarisation scans Pt/ZrO2–C experiences a much greater area loss than all the other catalysts. Linear polarisation scans for each of the catalysts revealed that the influence of increased temperature and sulphuric acid concentration were showed improved results. Levich and Koutecky–Levich plots revealed that the SO2 oxidation is a multistep reaction on all the prepared catalysts and that there are regions which are kinetic and diffusion controlled and diffusion–only controlled. Pt/Ta2O5–C catalysts exhibited superior catalytic activity and stability compared Pt/Nb2O5–C, Pt/ZrO2–C and Pt/C. The Pt/ZrO2–C exhibited the most inferior catalytic activity and stability. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2011.

The gradual depletion of and dependence on fossil fuels, air pollution and global warming have all accelerated the development of alternative energy systems which use hydrogen as an energy carrier. The hybrid sulphur cycle (HyS) is the foremost electrothermochemical process that can produce hydrogen as the energy carrier. The HyS cycle consists of two units, namely the sulphuric acid decomposition reactor and the sulphur dioxide electrolyser (SDE). The SDE is responsible for the SO2 electrooxidation to sulphuric acid and protons at the anode and the electro–reduction of protons to hydrogen at the cathode. This research study focuses on the kinetic data collected from the prepared catalysts for SO2 electro–oxidation at the anode. Platinum dispersed on carbon, niobium pentoxide, tantalum pentoxide and zirconium dioxide as electrocatalysts were prepared using sodium borohydride as a reducing agent. These electrocatalysts were characterized using transmission electron microscopy and x–ray diffraction. Cyclic voltammetry was used to study the electrochemical active surface area (EAS) and the results showed that Pt/ZrO2–C had a higher EAS area than Pt/Ta2O5–C, Pt/Nb2O5–C and Pt/C. The high EAS of Pt/ZrO2–C can be explained by the low crystal size however after a series of linear polarisation scans Pt/ZrO2–C experiences a much greater area loss than all the other catalysts. Linear polarisation scans for each of the catalysts revealed that the influence of increased temperature and sulphuric acid concentration were showed improved results. Levich and Koutecky–Levich plots revealed that the SO2 oxidation is a multistep reaction on all the prepared catalysts and that there are regions which are kinetic and diffusion controlled and diffusion–only controlled. Pt/Ta2O5–C catalysts exhibited superior catalytic activity and stability compared Pt/Nb2O5–C, Pt/ZrO2–C and Pt/C. The Pt/ZrO2–C exhibited the most inferior catalytic activity and stability. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2011.

Electricity and power generation is an essential part of our life. However, powergeneration activities also create by-products (such as sulphur oxides, nitrogen oxides,carbon monoxide, etc), which can be dangerous when released to the atmosphere.Sensors, as part of the control system, play very vital role for the fluegas cleaning processes in power plants. This thesis concerns the development ofSilicon Carbide Field Effect Transistor (SiC-FET) gas sensors as sensors for sulfurcontaining gases (SO2 and H2S) used as part of the environmental control systemin power plants. The works includes sensor deposition and assembly, sensinglayer characterization, operation mode development, performance testing of thesensors in a gas mixing rig in the laboratory and field test in a desulfurization pilotunit, and both experimental and theoretical studies on the detection mechanismof the sensors. The sensor response to SO2 was very small and saturated quickly. SO2 is a verystable gas and therefore reaction with other species requires a large energy input.SO2 mostly reacts with the catalyst through physisorption, which results in lowresponse level. Another problem was that once it finally reacted with oxygen andadsorbed on the surface of the catalyst in form of a sulfate compound, it is desorbedwith difficulty. Therefore, the sensor signal saturated after a certain timeof exposure to SO2. Different gate materials were tested in static operation (Pt,Ir, Au), but the saturation phenomena occurred in all three cases. Dynamic sensoroperation using temperature cycling and multivariate data analysis could mitigatethis problem. Pt-gate sensors were operated at several different temperatures in acyclic fashion. One of the applied temperatures was chosen to be very high for ashort time to serve as cleaning step. This method was also termed the virtual multisensor method because the data generated could represent the data from multiplesensors in static operation at different temperatures. Then, several features of thesignal, such as mean value and slope, were extracted and processed with multivariatedata analysis. Linear Discrimination Analysis (LDA) was chosen since itiiiallows controlled data analysis. It was shown that it was possible to quantify SO2with a 2-step LDA. The background was identified in the first step and SO2 wasquantified in the second step. Pt sensors in dynamic operation and 2-step LDAevaluation has also demonstrated promising results for SO2 measurement in thelaboratory as well as in a desulfurization pilot unit. For a commercial sensor, algorithmhave to be developed to enable on-line measurement in real time. It was observed that Ir-gate sensors at 350oC were very sensitive to H2S. The responseobtained by Ir sensors to H2S was almost five times larger than that of Ptsensors, which might be due to the higher oxygen coverage of Ir. Moreover, Irsensors were also more stable with less drift during the operation as a result ofhigher thermal stability. However, the recovery time for Ir sensors was very long,due to the high desorption energy. Overall, the Ir sensors performed well whentested for a leak detection application (presence of oxygen and dry environment).The geothermal application, where heat is extracted from the earth, requires thesensor to be operated in humid condition in the absence (or very low concentration)of oxygen, and this poses a problem. Temperature cycle operation and smartdata evaluation might also be an option for future development. Along with the sensor performance testing, a study on the detection mechanismwas also performed for SO2 sensor, both experimentally and theoretically. The experimentincluded the study of the species formed on the surface of the catalystwith DRIFT (diffuse reflectance infrared frourier transform) spectroscopy and theanalysis of the residual gas with mass spectroscopy. Explanatory investigation ofthe surface reactions was performed using quantum-chemical calculations. Theoreticalcalculations of the infrared (IR) vibration spectra was employed to supportthe identification of peaks in the DRIFT measurement. Based on the study on theresidual gas analysis and quantum-chemical calculations, a reaction mechanismfor the SO2 molecule adsorption on the sensor surface was suggested.

O objetivo deste trabalho foi o analisar o impacto da resolução dos conjuntos de dados topográficos nas simulações das concentrações de dióxido de enxofre (SO2) emitido por uma fonte localizada no Sul do Brasil. Para isso foram realizadas duas simulações aplicando o modelo regional Weather Research and Forecasting acoplado com a química (WRF/Chem), configurado com duas representações do terreno de diferentes resoluções espaciais. Foram utilizados os dados padrão do modelo com melhor resolução, Global 30 Arc-Second Elevation (GTOPO), com aproximadamente 1 km, e inserido no bancos de dados do modelo as informações de terreno em alta-resolução do Radar Shuttle Topography Mission (SRTM) (30 metros). Para as emissões antrópicas do modelo foi elaborado um programa capaz inserir os volumes do poluente SO2 de forma horária expelidos pela chaminé, de acordo com as taxas de emissão medidos diretamente na fonte. O programa representou a emissão do poluente no ponto de grade correspondente a localização e a altura acima da superfície da chaminé da fonte. As simulações foram configuradas com os seguintes esquemas de parametrização: para microfísica de nuvens foi utilizado o Goddard Cumulus Ensemble; os esquemas de radiação de onda longa e curta foram o Goddard e o Rapid Radiative Transfer Model para modelos de circulação geral da atmosfera (MCGA); para a parametrização de cumulus o esquema utilizado foi o Grell 3D Ensemble Scheme; e para os esquemas de camada superficial e camada limite planetária foram utilizados os da teoria da similaridade do Fifth-Generation National Center for Atmospheric Research/Penn State Mesoscale Model (MM5) e o Yonsey University, respectivamente. A escolha desta combinação de esquemas foi definida a partir de um estudo inicial da sensibilidade do modelo à mudança das parametrizações. Os resultados dos experimentos numéricos alterando a topografia foram validados a partir dos dados de monitoramento das estações meteorológica e da qualidade do ar pertencentes à empresa responsável pelo empreendimento associado à fonte. Foi observado que as simulações com os dados SRTM expressaram o terreno da região de estudo mais próximo à realidade, representando o aspecto heterogêneo do relevo, ressaltando os picos e os vales. Os resultados das validações meteorológicas utilizando os dados topográficos indicaram melhoras nas simulações das variáveis meteorológicas: temperatura, umidade relativa, velocidade do vento e precipitação. Os experimentos com os dados topográficos GTOPO e SRTM no modelo WRF/Chem, configurado com as emissões horárias da fonte de Candiota, reproduziram o comportamento dos ventos para transporte de SO2 até as estações de monitoramento conforme os dados observados. Porém foram identificados padrões diferentes na representação das concentrações do poluente entre as duas simulações do modelo, associados aos escoamentos dos ventos representados pelos experimentos. A resolução da topografia afetou na simulação de SO2 devido ao aumento da forçante superficial induzida pelo terreno. Este aumento na forçante, influenciou a advecção da pluma de SO2, resultando em diferentes padrões das concentrações de SO2 no ponto de grade correspondente às estações de monitoramento. Contudo, os resultados das simulações das concentrações de SO2, tanto de forma horária quanto na abordagem das médias diárias, não indicaram uma relação linear entre a utilização de dados em alta resolução e a melhora na representação do SO2 pelo modelo WRF/Chem. / The objective of this work was to analyze the impact of the higher resolution topographic data sets in the simulations of the Sulfur dioxide (SO2) concentrations emitted by a source located Southern Brazil. Two simulations were performed applying the Weather Research and Forecasting model coupled with Chemistry – WRF/Chem, configured with two representations of the terrain with different spatial resolutions. The standard data of the model with the best resolution (approximately 1 km), Global 30 Arc-Second Elevation (GTOPO), and was inserted in the model databases the high-resolution (30 meters) terrain information of the Radar Shuttle Topography Mission (SRTM). For the anthropic emissions of the model, a program was developed capable of inserting the hourly SO2 pollutant volumes expelled by the chimney, according to the emission rates measured directly at the source. The program inserted these emissions into the grid point corresponding to the location and height above the surface of the emission source. The simulations were configured with the following parameterization schemes: for cloud microphysics Goddard Cumulus Ensemble; for the long and short wave radiation treatment it was used the Goddard and the Rapid Radiative Transfer Model for general circulation models; for the cumulus parameterization the scheme it was used the Grell 3D Ensemble Scheme; and for the surface layer and planetary boundary layer schemes, the similarity theory of the Fifth-Generation National Center for Atmospheric Research/Penn State Mesoscale Model (MM5) and the Yonsey University, respectively. The choice of this combination of schemes was defined from an initial study of the sensitivity of the model to the change of parametrizations. The results of the numerical experiments altering the topography were validated from the monitoring data of the meteorological stations and the air quality belonging to the company responsible for the enterprise associated to the source. It was observed that the simulations with the SRTM data expressed the terrain of the region of study closest to reality, representing the heterogeneous aspect of the terrain, highlighting the peaks and valleys. The results of the meteorological validations using the new topographic data indicated an improvement in the simulations of the meteorological variables: temperature, relative humidity, wind speed and precipitation. The experiments with the GTOPO and SRTM topographic data in WRF/Chem model, configured with the hourly emissions of the Candiota source, reproduced the winds behavior that transported the SO2 to the monitoring stations according to the observed data. However, different patterns were identified in the pollutant concentrations between the two simulations of the model, associated to the wind flows represented by the experiments. The topography resolution affected in the simulation of SO2 due to the increase of the surface forcing induced by the terrain. This increase in the forcing influenced the advection of the SO2 plume, resulting in different patterns of SO2 concentrations at the grid point corresponding to the monitoring stations. However, the results of simulations of SO2 concentrations, both hourly and in the approach of daily averages, did not indicate a linear relationship between the use of high resolution data and the improvement in the representation of SO2 by WRF/Chem model.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-04-25T17:15:28Z No. of bitstreams: 1 TESE - VERSÃO FINAL.pdf: 4689503 bytes, checksum: c4799e55135511337527c79f7891b204 (MD5) / Approved for entry into archive by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-05-12T17:17:49Z (GMT) No. of bitstreams: 1 TESE - VERSÃO FINAL.pdf: 4689503 bytes, checksum: c4799e55135511337527c79f7891b204 (MD5) / Made available in DSpace on 2016-05-12T17:17:49Z (GMT). No. of bitstreams: 1 TESE - VERSÃO FINAL.pdf: 4689503 bytes, checksum: c4799e55135511337527c79f7891b204 (MD5) / Os óxidos de enxofre, principalmente o SO2, são importantes poluentes atmosféricos que provocam sérios problemas ambientais. O SO2 pode ser produzido a partir de diversas fontes, incluindo fontes naturais. Dentre as fontes antropogênicas, a queima de combustível é responsável por cerca de 80% das emissões de SO2. Por essa razão, com o intuito de promover a melhoria na qualidade do ar, diversos órgãos ambientais desenvolveram programas com legislações específicas para a emissão de SO2. A fim de atender às legislações impostas pelos órgãos de controle ambiental, as indústrias buscaram formas diversificadas de controlar a emissão ou de reduzir a formação de SO2 nos seus processos. Dentre os processos de controle de emissão de SO2 destaca-se o processo de adsorção em que óxidos de metais de transição são aplicados como adsorventes para SO2. Os óxidos de ferro apresentam propriedades importantes que os tornam promissores para o abatimento de SO2 em correntes gasosas. Dessa forma, espinélios de ferro e magnésio dopados com Cu e Al foram preparados pelo método da combustão a fim de obter materiais de dimensões nanométricas. Os difratogramas de raios-X mostraram que para todos os materiais foi formada a fase espinélio, majoritariamente, e, que, os íons alumínio substituem isomorficamente os íons ferro. Porém, os materiais contendo cobre apresentaram fase CuO segregada, confirmado pelas análises de TPR e FTIR estrutural. Os perfis de dessorção termoprogramada de CO2 mostraram que a incorporação de Al promoveu a formação de sítios básicos e a presença de cobre diminui a basicidade do material. Os dados do DRX mostraram que os materiais contendo Al apresentaram diâmetro de cristalito menores resultando em melhores propriedades texturais (área superficial, diâmetro de poro e diâmetro de partícula), enquanto que a presença de cobre apresentou o efeito inverso ao observado para o alumínio. Os testes DeSOx mostraram que os materiais dopados com Al apresentaram melhores desempenhos, principalmente em altas temperaturas. No entanto, os materiais contendo cobre não apresentaram desativação total em nenhuma temperatura analisada, estes resultados estão de acordo com as propriedades ácido-base avaliadas nos perfis de TPD. Os resultados de DRIFTS-in situ evidenciaram que na ausência de oxigênio ocorre a formação de sulfatos e a presença de sulfitos foi observada pelos espectros de FTIR pós-teste. Os ensaios de adsorção na presença de CO e CO2 sugerem que não há uma competição pelos sítios, no entanto, houve deposição de compostos carbonáceos superficiais e formação de magnetita a partir de 500°C, confirmados por termogravimetria. As análises de EPR mostraram a presença de espécie Fe3+–O–Fe3+ de dimensões nanométricas, sugeridos como sítios de adsorção de SO2. O mecanismo proposto sugere que o centro redox para a sulfatação pode ser o átomo de ferro presente na espécie analisada no EPR, evidenciado pela região de oxidação nos ensaios de termogravimetria das amostras testadas. / Sulfur oxides, especially SO2, are important air pollutants causing serious environmental problems. The SO2 can be produced from diverse sources, including natural ones. Among the anthropogenic sources, fuel burning is responsible for about 80% of SO2 emissions. For this reason, several environmental agencies have developed programs with specific legislation for the emission of SO2 to promote improvements in air quality. In order to take account of the legislation imposed by environmental agencies, industries sought diverse ways to control the emission or to reduce SO2 formation in their processes. Among the SO2 emission control processes, it is possible to highlight the adsorption process in which the transition metal oxides are used as SO2 absorbents. The iron oxides have important properties that make them promising for SO2 abatement in gaseous streams. Thus, spinels of iron and magnesium doped with Cu and Al were prepared by combustion method to obtain nanometric materials. The XRD patterns of X-rays show that for all materials was formed mainly a spinel phase and that the aluminum ions isomorphically replace the iron ions, however, the materials containing copper showed segregated CuO phase, which was confirmed by analysis of TPR and FTIR structural. Thermal Programmed desorption profiles of CO2 show that the uptake Al promotes the formation of basic sites and the presence of copper reduces the basicity of the material. The XRD data shows that the materials containing Al have smaller crystallite diameter resulting in better textural properties (surface area, pore diameter and particle diameter), while the presence of copper has the opposite effect to that observed for aluminum. The DeSOx tests showed that the Al-doped materials were better, especially at high temperatures. Though the materials containing copper did not show complete deactivation analyzed in any temperature, these results are consistent with the acid-base properties evaluated in the TPD profiles. In-situ DRIFTS results showed that in the absence of oxygen the formation of sulfates occurs and the sulfites presence were observed by post-test FTIR spectra. The adsorption experiments in the presence of CO and CO2 suggest that there is no competition for the sites, however there was deposition of superficial carbonaceous compounds and formation of magnetite from 500°C that were confirmed by thermogravimetric analysis. EPR analysis showed the presence of species Fe3+–O– Fe3+ in nanometric dimensions that have been suggested as SO2 adsorption sites. The proposed mechanism suggested that the redox center to the sulfatation may be the iron atom presented in the analyzed species in the EPR, which was evidenced by the oxidation region in the thermogravimetric analysis of the samples teste

abstract: Among volcanic gases, sulfur dioxide (SO2) is by far the most commonly measured. More than a monitoring proxy for volcanic degassing, SO2 has the potential to alter climate patterns. Persistently active explosive volcanoes are characterized by short explosive bursts, which often occur at periodic intervals numerous times per day, spanning years to decades. SO2 emissions at those volcanoes are poorly constrained, in large part because the current satellite monitoring techniques are unable to detect or quantify plumes of low concentration in the troposphere. Eruption plumes also often show high concentrations of ash and/or aerosols, which further inhibit the detection methods. In this work I focus on quantifying volcanic gas emissions at persistently active explosive volcanoes and their variations over short timescales (minutes to hours), in order to document their contribution to natural SO2 flux as well as investigate the physical processes that control their behavior. In order to make these measurements, I first develop and assemble a UV ground-based instrument, and validate it against an independently measured source of SO2 at a coal-burning power plant in Arizona. I establish a measurement protocol and demonstrate that the instrument measures SO2 fluxes with < 20 % error. Using the same protocol, I establish a record of the degassing patterns at Semeru volcano (Indonesia), a volcano that has been producing cycles of repeated explosions with periods of minutes to hours for the past several decades. Semeru produces an average of 21-71 tons of SO2 per day, amounting to a yearly output of 8-26 Mt. Using the Semeru data, along with a 1-D transient numerical model of magma ascent, I test the validity of a model in which a viscous plug at the top of the conduit produces cycles of eruption and gas release. I find that it can be a valid hypothesis to explain the observed patterns of degassing at Semeru. Periodic behavior in such a system occurs for a very narrow range of conditions, for which the mass balance between magma flux and open-system gas escape repeatedly generates a viscous plug, pressurizes the magma beneath the plug, and then explosively disrupts it. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2015

O objetivo deste trabalho foi o analisar o impacto da resolução dos conjuntos de dados topográficos nas simulações das concentrações de dióxido de enxofre (SO2) emitido por uma fonte localizada no Sul do Brasil. Para isso foram realizadas duas simulações aplicando o modelo regional Weather Research and Forecasting acoplado com a química (WRF/Chem), configurado com duas representações do terreno de diferentes resoluções espaciais. Foram utilizados os dados padrão do modelo com melhor resolução, Global 30 Arc-Second Elevation (GTOPO), com aproximadamente 1 km, e inserido no bancos de dados do modelo as informações de terreno em alta-resolução do Radar Shuttle Topography Mission (SRTM) (30 metros). Para as emissões antrópicas do modelo foi elaborado um programa capaz inserir os volumes do poluente SO2 de forma horária expelidos pela chaminé, de acordo com as taxas de emissão medidos diretamente na fonte. O programa representou a emissão do poluente no ponto de grade correspondente a localização e a altura acima da superfície da chaminé da fonte. As simulações foram configuradas com os seguintes esquemas de parametrização: para microfísica de nuvens foi utilizado o Goddard Cumulus Ensemble; os esquemas de radiação de onda longa e curta foram o Goddard e o Rapid Radiative Transfer Model para modelos de circulação geral da atmosfera (MCGA); para a parametrização de cumulus o esquema utilizado foi o Grell 3D Ensemble Scheme; e para os esquemas de camada superficial e camada limite planetária foram utilizados os da teoria da similaridade do Fifth-Generation National Center for Atmospheric Research/Penn State Mesoscale Model (MM5) e o Yonsey University, respectivamente. A escolha desta combinação de esquemas foi definida a partir de um estudo inicial da sensibilidade do modelo à mudança das parametrizações. Os resultados dos experimentos numéricos alterando a topografia foram validados a partir dos dados de monitoramento das estações meteorológica e da qualidade do ar pertencentes à empresa responsável pelo empreendimento associado à fonte. Foi observado que as simulações com os dados SRTM expressaram o terreno da região de estudo mais próximo à realidade, representando o aspecto heterogêneo do relevo, ressaltando os picos e os vales. Os resultados das validações meteorológicas utilizando os dados topográficos indicaram melhoras nas simulações das variáveis meteorológicas: temperatura, umidade relativa, velocidade do vento e precipitação. Os experimentos com os dados topográficos GTOPO e SRTM no modelo WRF/Chem, configurado com as emissões horárias da fonte de Candiota, reproduziram o comportamento dos ventos para transporte de SO2 até as estações de monitoramento conforme os dados observados. Porém foram identificados padrões diferentes na representação das concentrações do poluente entre as duas simulações do modelo, associados aos escoamentos dos ventos representados pelos experimentos. A resolução da topografia afetou na simulação de SO2 devido ao aumento da forçante superficial induzida pelo terreno. Este aumento na forçante, influenciou a advecção da pluma de SO2, resultando em diferentes padrões das concentrações de SO2 no ponto de grade correspondente às estações de monitoramento. Contudo, os resultados das simulações das concentrações de SO2, tanto de forma horária quanto na abordagem das médias diárias, não indicaram uma relação linear entre a utilização de dados em alta resolução e a melhora na representação do SO2 pelo modelo WRF/Chem. / The objective of this work was to analyze the impact of the higher resolution topographic data sets in the simulations of the Sulfur dioxide (SO2) concentrations emitted by a source located Southern Brazil. Two simulations were performed applying the Weather Research and Forecasting model coupled with Chemistry – WRF/Chem, configured with two representations of the terrain with different spatial resolutions. The standard data of the model with the best resolution (approximately 1 km), Global 30 Arc-Second Elevation (GTOPO), and was inserted in the model databases the high-resolution (30 meters) terrain information of the Radar Shuttle Topography Mission (SRTM). For the anthropic emissions of the model, a program was developed capable of inserting the hourly SO2 pollutant volumes expelled by the chimney, according to the emission rates measured directly at the source. The program inserted these emissions into the grid point corresponding to the location and height above the surface of the emission source. The simulations were configured with the following parameterization schemes: for cloud microphysics Goddard Cumulus Ensemble; for the long and short wave radiation treatment it was used the Goddard and the Rapid Radiative Transfer Model for general circulation models; for the cumulus parameterization the scheme it was used the Grell 3D Ensemble Scheme; and for the surface layer and planetary boundary layer schemes, the similarity theory of the Fifth-Generation National Center for Atmospheric Research/Penn State Mesoscale Model (MM5) and the Yonsey University, respectively. The choice of this combination of schemes was defined from an initial study of the sensitivity of the model to the change of parametrizations. The results of the numerical experiments altering the topography were validated from the monitoring data of the meteorological stations and the air quality belonging to the company responsible for the enterprise associated to the source. It was observed that the simulations with the SRTM data expressed the terrain of the region of study closest to reality, representing the heterogeneous aspect of the terrain, highlighting the peaks and valleys. The results of the meteorological validations using the new topographic data indicated an improvement in the simulations of the meteorological variables: temperature, relative humidity, wind speed and precipitation. The experiments with the GTOPO and SRTM topographic data in WRF/Chem model, configured with the hourly emissions of the Candiota source, reproduced the winds behavior that transported the SO2 to the monitoring stations according to the observed data. However, different patterns were identified in the pollutant concentrations between the two simulations of the model, associated to the wind flows represented by the experiments. The topography resolution affected in the simulation of SO2 due to the increase of the surface forcing induced by the terrain. This increase in the forcing influenced the advection of the SO2 plume, resulting in different patterns of SO2 concentrations at the grid point corresponding to the monitoring stations. However, the results of simulations of SO2 concentrations, both hourly and in the approach of daily averages, did not indicate a linear relationship between the use of high resolution data and the improvement in the representation of SO2 by WRF/Chem model.

A 10.6 ym C02 laser operating a power range S P 200 watts was used to pump some select vibrational transitions in the NO2 molecule while monitoring the rotational transitions (91/9—'100/10), (232f 22 ~~"*242,23> ' (402,38 "393,37) in the (0, 0, 0) vibrational level and the (8q,8—*"^1,7) rotational transition in the (0, 1, 0) vibrational level. These rotational transitions were monitored by microwave probing to determine how the population of states in the rotational manifolds were being altered by the laser. Coincidences between some components of the V3-V2 band of N02 and the C02 infrared laser lines in the 10 um region appeared to be responsible for the strong interaction between the continuous laser beams and the molecular states.

O objetivo deste trabalho foi o analisar o impacto da resolução dos conjuntos de dados topográficos nas simulações das concentrações de dióxido de enxofre (SO2) emitido por uma fonte localizada no Sul do Brasil. Para isso foram realizadas duas simulações aplicando o modelo regional Weather Research and Forecasting acoplado com a química (WRF/Chem), configurado com duas representações do terreno de diferentes resoluções espaciais. Foram utilizados os dados padrão do modelo com melhor resolução, Global 30 Arc-Second Elevation (GTOPO), com aproximadamente 1 km, e inserido no bancos de dados do modelo as informações de terreno em alta-resolução do Radar Shuttle Topography Mission (SRTM) (30 metros). Para as emissões antrópicas do modelo foi elaborado um programa capaz inserir os volumes do poluente SO2 de forma horária expelidos pela chaminé, de acordo com as taxas de emissão medidos diretamente na fonte. O programa representou a emissão do poluente no ponto de grade correspondente a localização e a altura acima da superfície da chaminé da fonte. As simulações foram configuradas com os seguintes esquemas de parametrização: para microfísica de nuvens foi utilizado o Goddard Cumulus Ensemble; os esquemas de radiação de onda longa e curta foram o Goddard e o Rapid Radiative Transfer Model para modelos de circulação geral da atmosfera (MCGA); para a parametrização de cumulus o esquema utilizado foi o Grell 3D Ensemble Scheme; e para os esquemas de camada superficial e camada limite planetária foram utilizados os da teoria da similaridade do Fifth-Generation National Center for Atmospheric Research/Penn State Mesoscale Model (MM5) e o Yonsey University, respectivamente. A escolha desta combinação de esquemas foi definida a partir de um estudo inicial da sensibilidade do modelo à mudança das parametrizações. Os resultados dos experimentos numéricos alterando a topografia foram validados a partir dos dados de monitoramento das estações meteorológica e da qualidade do ar pertencentes à empresa responsável pelo empreendimento associado à fonte. Foi observado que as simulações com os dados SRTM expressaram o terreno da região de estudo mais próximo à realidade, representando o aspecto heterogêneo do relevo, ressaltando os picos e os vales. Os resultados das validações meteorológicas utilizando os dados topográficos indicaram melhoras nas simulações das variáveis meteorológicas: temperatura, umidade relativa, velocidade do vento e precipitação. Os experimentos com os dados topográficos GTOPO e SRTM no modelo WRF/Chem, configurado com as emissões horárias da fonte de Candiota, reproduziram o comportamento dos ventos para transporte de SO2 até as estações de monitoramento conforme os dados observados. Porém foram identificados padrões diferentes na representação das concentrações do poluente entre as duas simulações do modelo, associados aos escoamentos dos ventos representados pelos experimentos. A resolução da topografia afetou na simulação de SO2 devido ao aumento da forçante superficial induzida pelo terreno. Este aumento na forçante, influenciou a advecção da pluma de SO2, resultando em diferentes padrões das concentrações de SO2 no ponto de grade correspondente às estações de monitoramento. Contudo, os resultados das simulações das concentrações de SO2, tanto de forma horária quanto na abordagem das médias diárias, não indicaram uma relação linear entre a utilização de dados em alta resolução e a melhora na representação do SO2 pelo modelo WRF/Chem. / The objective of this work was to analyze the impact of the higher resolution topographic data sets in the simulations of the Sulfur dioxide (SO2) concentrations emitted by a source located Southern Brazil. Two simulations were performed applying the Weather Research and Forecasting model coupled with Chemistry – WRF/Chem, configured with two representations of the terrain with different spatial resolutions. The standard data of the model with the best resolution (approximately 1 km), Global 30 Arc-Second Elevation (GTOPO), and was inserted in the model databases the high-resolution (30 meters) terrain information of the Radar Shuttle Topography Mission (SRTM). For the anthropic emissions of the model, a program was developed capable of inserting the hourly SO2 pollutant volumes expelled by the chimney, according to the emission rates measured directly at the source. The program inserted these emissions into the grid point corresponding to the location and height above the surface of the emission source. The simulations were configured with the following parameterization schemes: for cloud microphysics Goddard Cumulus Ensemble; for the long and short wave radiation treatment it was used the Goddard and the Rapid Radiative Transfer Model for general circulation models; for the cumulus parameterization the scheme it was used the Grell 3D Ensemble Scheme; and for the surface layer and planetary boundary layer schemes, the similarity theory of the Fifth-Generation National Center for Atmospheric Research/Penn State Mesoscale Model (MM5) and the Yonsey University, respectively. The choice of this combination of schemes was defined from an initial study of the sensitivity of the model to the change of parametrizations. The results of the numerical experiments altering the topography were validated from the monitoring data of the meteorological stations and the air quality belonging to the company responsible for the enterprise associated to the source. It was observed that the simulations with the SRTM data expressed the terrain of the region of study closest to reality, representing the heterogeneous aspect of the terrain, highlighting the peaks and valleys. The results of the meteorological validations using the new topographic data indicated an improvement in the simulations of the meteorological variables: temperature, relative humidity, wind speed and precipitation. The experiments with the GTOPO and SRTM topographic data in WRF/Chem model, configured with the hourly emissions of the Candiota source, reproduced the winds behavior that transported the SO2 to the monitoring stations according to the observed data. However, different patterns were identified in the pollutant concentrations between the two simulations of the model, associated to the wind flows represented by the experiments. The topography resolution affected in the simulation of SO2 due to the increase of the surface forcing induced by the terrain. This increase in the forcing influenced the advection of the SO2 plume, resulting in different patterns of SO2 concentrations at the grid point corresponding to the monitoring stations. However, the results of simulations of SO2 concentrations, both hourly and in the approach of daily averages, did not indicate a linear relationship between the use of high resolution data and the improvement in the representation of SO2 by WRF/Chem model.

Memoria para optar al título de Geóloga / El presente trabajo tiene como objetivo la estimación de flujo de dióxido de azufre en penachos volcánicos mediante una cámara infrarroja. Nicair 1. Es posible medir el SO2 debido al alto contraste que tiene este gas en penachos volcánicos y la atmósfera circundante y la alta señal que posee el SO2 en el espectro centrado en los 8.6µm donde el vapor de agua es débil. La cámara infrarroja captó la señal recibida al fotografíar los penachos volcánicos y mediante el procesamiento de las imágenes según la metodología presentada en este trabajo, se obtuvieron las concentraciones lineales de SO2 (ppmm), las que junto a la estimación de la velocidad de desplazamiento, se integraron según transectas perpendiculares al desplazamiento del penacho para obtener las tasas de emisión (toneladas día-1). Se estimaron concentraciones lineales de SO2 en los volcanes Irruputuncu, Ollagüe y Láscar y solo en este último se calcularon las tasas de emisión en las cercanías al cráter (400 m de altura). Los resultados obtenidos indican emisiones inferiores a las 140 ton/día las que son coherentes con un estratovolcán en estado de quiescencia y la ausencia de cuerpo magmático superficial. Se propone profundizar en las aplicaciones de la cámara infrarroja, considerando que es un instrumento portable. Específicamente estimar tasas de emisión de SO2 en periodos más prolongados y estudiar las emisiones nocturnas. / Centro de Excelencia en Geotermia de Los Andes