Este trabalho teve como objetivo analisar as condições meteorológicas favoráveis e desfavoráveis à dispersão de poluentes, com ênfase no ozônio, nas áreas urbanas associadas à Região Metropolitana de São Paulo (RMSP) e a Grande Santiago (GS). Medidas de concentração de estações localizadas em ambas as áreas de estudo foram utilizadas para determinar o comportamento médio, o número de ocorrências de ultrapassagens de padrão de qualidade do ar e o aumento noturno das concentrações de ozônio num período de dez anos. Foi encontrado que o máximo horário acontece próximo das 14 horas (horário local) nas duas regiões, e que existe uma tendência à diminuição no número de ultrapassagens do padrão de qualidade do ar associado a este poluente. Na RMSP é possível observar um máximo secundário durante a madrugada, enquanto que este fenômeno não é claramente observado nos valores médios de concentração na GS. Com dados da Reanálise do NCEP/NCAR foi visto que a ocorrência deste fenômeno está associada a configurações sinóticas específicas na GS, enquanto que na RMSP não existe padrão sinótico específico que diferencie casos com e sem aumento de ozônio noturno. Um novo módulo fotoquímico (NPM), contendo 95 reações foi inserido no modelo BRAMS na tentativa de melhorar o prognóstico das concentrações de poluentes, principalmente em relação ao ozônio. O NPM mostrou melhor desempenho que o módulo fotoquímico original do modelo (SPM; Simple Photochemical Module) para todos os poluentes considerados, salvo o ozônio, para o qual o SPM apresentou melhores índices estatísticos em 5 das 7 estações avaliadas. As características locais associadas à ocorrência simultânea ou não de aumento na concentração de ozônio foram estudadas utilizando o modelo BRAMS com o módulo SPM ativado, sendo verificado que o aumento de ozônio na RMSP está associado, principalmente, ao transporte vertical deste poluente a partir de níveis mais elevados da atmosfera, enquanto que o transporte horizontal é a maior contribuição para o aumento das concentrações de ozônio durante o período noturno na GS. / This work aimed to analyze the favorable and unfavorable meteorological conditions for pollutant dispersion, especially ozone, at the Metropolitan Area of São Paulo (MASP) and the Greater Santiago (GS). Ozone concentration measurements from stations located in both urban areas were used to determinate the mean behavior, the number of standard air quality exceedances and the increase on nocturnal ozone concentration over a 10 years period. It was found that the diurnal maximum occurs around 14 local time in both urban areas, and that there is a diminishment tendency of the total cases of standard air quality exceedances during all period. A secondary maximum of ozone concentration was observed in MASP at night, which was not clearly seen on mean values over GS. By using the NCEP/NCAR Reanalysis data it was seen that the occurrence of this phenomenon is associated to specific synoptic patterns for GS, while there is no specific synoptic pattern for the MASP cases, with or without nocturnal increase in ozone concentrations. A New Photochemical Module (NPM), containing 95 reactions was coupled to BRAMS model in an attempt to improve the prediction of air pollutants, especially ozone. The NPM showed a better performance than the original module, the SPM (Simple Photochemical Module), for all considered pollutants but ozone. For this pollutant, the SPM presents better statistical indexes for 5 of the 7 stations analyzed. The local characteristics related to simultaneous occurrence of nocturnal ozone increase was studied using the SPM-BRAMS model, which showed that the secondary nocturnal maximum of ozone concentrations in MASP are related to vertical transport of this pollutant from higher levels of the atmosphere to the surface, while the horizontal transport is a major contributor to the increase of ozone concentrations in the GS during the night.

L'atmosphère terrestre a subi, au cours de son histoire précoce, de très violents changements dans sa composition chimique. L'émergence des premiers êtres vivants photosynthétique a provoqué la mise en place et la modification des grands cycles biogéochimiques. L'usage des isotopes comme traceurs des processus physico-chimiques actifs pendant ces périodes s'est développé depuis les années 80. L'observation de compositions isotopiques anormales dans certaines molécules atmosphériques (ozone notamment), similaires à celles observées dans les météorites par Clayton (1973), pose question. De nombreuses hypothèses ont été proposées pour expliquer ce phénomène "anormal". L'objectif principal de cette thèse de doctorat est de développer, par l'expérimentation, l'étude d'un certain nombre de réactions en phase plasma du point de vue isotopique. Seront particulièrement étudiées des réactions appelées réactions à trois corps de formation de l'ozone, où la formation d'un complexe intermédiaire excité entre en jeu dans les mécanismes de génération de ces fractionnements isotopiques anormaux. / The Earth's atmosphere has undergone, during its early history, very violent changes in its chemical composition. The emergence of the first photosynthetic living beings has led to the establishment and modification of major biogeochemical cycles. The use of isotopes as tracers of active physico-chemical processes during these periods has been developed since the 1980s. The observation of abnormal isotopic compositions in certain atmospheric molecules (ozone in particular), similar to those observed in meteorites by Clayton (1973), raises questions. Many hypotheses have been proposed to explain this "abnormal" phenomenon. The main objective of this doctoral work is to develop, through experimentation, the study of plasma reactions from an isotopic point of view. In particular, ozone formation third-body reactions, where the formation of an excited intermediate complex is involved in the mechanisms of generating these abnormal isotopic fractionations, will be studied.

L’utilisation de coproduits en tant que matière première provenant d’une autre voie industrielle, fait qu’il n’est plus considéré comme « déchet ». Leur valorisation est donc un axe de développement pour les entreprises agronomiques et agroalimentaires. Cependant, leur nouveau statut de « matière première » entraîne des contraintes pour les industriels.Celles-ci sont diverses selon les voies de destination : sanitaires, toxicologiques …Ce travail s’intéresse à deux coproduits issus de filières différentes de transformation végétale :(1) l’épiderme de pomme, comme source d’antioxydants. Leur valorisation passe par l’emploi de matières premières peu traitées d’un point de vue phytosanitaire qui pourront être a priori plus contaminées par des flores diverses.(2) Les broyats de végétaux issus de la culture céréalière comme matière première de produits biosourcés. Ils présentent naturellement de fortes contaminations en microorganismes sporulés.La valorisation de ces deux coproduits nécessite donc des traitements assainissants adaptés.Ainsi, il était indispensable de déterminer la nature, la variabilité et l’évolution des écologies microbiennes présentes sur ces coproduits par des techniques rapides de dénombrement ainsi que d’identification par biologie moléculaire. L’étude de différents procédés assainissants a également été réalisé pour combiner l’efficacité de désinfection à la préservation des qualités nutritionnelles (pomme) ou des propriétés physiques (broyats). / The use of byproduct as raw material from another industrial sector, facts that it is not considered any more as "waste". Their valuation is thus an axis of development for the agronomic and food-processing industry. However, their new consideration of "raw material" entails constraints for the industrialists. These constraints are diverse according to the destination ways of the byproduct: sanitary, toxicological… This work focus on two byproducts resulting from different vegetable process: (1) apple peels, as antioxidant source. Their valuation needs to use raw materials with low phytosanitary treatment, so these materials may be more contaminated by different floras. (2) Crushed vegetable matter stemming from cereal crop as raw material of biosourced products. They occur naturally a strong microbial spore contamination. The valuation of these two byproducts requires adapted cleaning treatments. So, it was the main thing to determine nature, variability and evolution of the present microbial ecologies of these byproducts by fast techniques of enumeration and identification by molecular biology. The study of different cleaning process was also realized to combine efficiency of disinfection with the preservation of nutritional qualities (apple) or physical properties (crushed vegetable matter).

Halogen chemistry plays an important role in spring time ozone and mercury depletion events (ODEs and MDEs) and may efficiently oxidize hydrocarbons such as the important greenhouse gas methane (CH4) in the polar marine boundary layer. This thesis presents a detailed study of bromine and chlorine chemistry in the Arctic boundary layer based on measurements of bromine and chlorine containing species using chemical ionization mass spectrometry (CIMS). The capability of CIMS to accurately measure bromine oxide (BrO) was demonstrated. The first direct measurements of hypobromous acid (HOBr) were achieved. Conditions that likely favor bromine activation (e.g. high wind speeds) was presented. To advance the understanding of bromine recycling, a time dependent model was built to simulate the bromine speciation. Unexpected high levels of molecular chlorine (Cl2) were observed at Barrow, AK, which had a large impact on methane oxidation and could contribute to ozone loss and mercury oxidation at Barrow, AK. Moreover, BrO levels observed at Summit, Greenland did not explain the under prediction of hydroxyl radical (OH). However, the enhanced OH was found to be coincident with elevated reactive gaseous mercury (RGM). In addition, airborne BrO measurements were found to be generally consistent with airborne observations of soluble bromide based on the response factors of mist chamber to the bromine species and bromine chemical mechanisms.

Halogen-driven ozone and nonmethane hydrocarbon losses in springtime Arctic boundary layer are investigated using a regional chemical transport model (CTM). Surface observation of O3 at Alert and Barrow and aircraft observations of O3 and hydrocarbons during the TOPSE experiment from February to May in 2000 are analyzed. We prescribe halogen radical distributions based on GOME BrO observations and calculated or observed other halogen radical to BrO ratios. GOME BrO shows an apparent anti-correlation with surface temperature over high BrO regions. At its peak, area of simulated near-surface O3 depletions (O3 LT 20ppbv) covers GT 50% of the north high latitudes. Model simulated O3 losses are in agreement with surface and aircraft O3 observations. Simulation of halogen distributions are constrained using aircraft hydrocarbon measurements. We find the currently chemical mechanism overestimate the Cl/BrO ratios. The model can reproduce the observed halogen loss of NMHCs using the empirical Cl/BrO ratios. We find that the hydrocarbon loss is not as sensitive to the prescribed boundary layer height of halogen as that of O3, therefore producing a more robust measure for evaluating satellite column measurement. Tropospheric tracer transport and chemical oxidation processes are examined on the basis of the observations at northern mid-high latitudes and over the tropical Pacific and the corresponding global 3D CTM (GEOS-CHEM) simulations. The correlation between propane and ethane/propane ratio is employed using a finite mixing model to examine the mixing in addition to the OH oxidations. At northern mid-high latitudes the model agrees with the observations before March. The model appears to overestimate the transport from lower to middle latitudes and the horizontal transport and mixing at high latitudes in May. Over the tropical Pacific the model reproduces the observed two-branch slope values reflecting an underestimate of continental convective transport at northern mid-latitudes and an overestimate of latitudinal transport into the tropics. Inverse modeling using the subsets of observed and simulated data is more reliable by reducing (systematic) biases introduced by systematic model transport model transport errors. On the basis of this subset we find the model underestimates the emissions of ethane and propane by 14 5%.

Biogenic isoprene plays an important role in tropospheric chemistry. We use HCHO column measurements by the Global Ozone Monitoring Experiment (GOME) to constrain isoprene emissions. Using the global Goddrad Earth Observing SystemChemistry (GEOS-Chem) as the forward model, a Bayesian inversion of GOME HCHO observations from September 1996 to August 1997 is conducted. Column contributions to HCHO from 12 sources including 10 terrestrial ecosystem groups, biomass burning, and industry are considered and inverted for 8 geographical regions globally. The a posteriori solution reduces the model biases for all regions, and estimates the annual global isoprene emissions of 566 Tg C yr-1, ~50% larger than the a priori estimate. Compared to the Global Emissions Inventory Activity (GEIA) inventory (~500 Tg C yr-1), the a posteriori isoprene emissions are generally higher at mid latitudes and lower in the tropics. This increase of global isoprene emissions significantly affects tropospheric chemistry, decreasing the global mean OH concentration by 10.8% to 0.95106 molecules/cm3. The atmospheric lifetime of CH3CCl3 increases from 5.2 to 5.7 years. Positive matrix factorization (PMF), an advanced method for source apportionment, is applied to TRAnsport of Chemical Evolution over the Pacific (TRACE-P) measurements and it is found that cyanogenesis in plants over Asia is likely an important emission process for CH3COCH3 and HCN. This approach also is applied to estimate source contributions to the tropospheric ozone (O3) with Tropospheric Ozone Production about the Spring Equinox (TOPSE) and TRACE-P measurements. The corresponding GEOS-Chem simulations are applied to the same factor-projected space in order to evaluate the model simulations. Intercontinental transport of pollutants is most responsible for increasing trend of springtime O3, while stratospheric influence is the largest contributions to troposperic O3 variability at northern middle and high latitudes. On the other hand, the overall tropospheric contributions to O3 variability are more important at northern low latitudes by long-range transport, biomass burning, and industry/urban emissions. In general, the simulated O3 variabilities are comparable with those of observations. However, the model underestimates the trends of and the contributions to O3 variability by long-range transport of O3 and its precursors at northern middle and high latitudes.

Novel integrated ozone contactor design and optimization tools which consist of an instrument that measures ozone decay kinetics, a program that performs predictive simulation, and an experimental method to examine mixing characteristics within the ozone contactor, were developed in this study. A multi-channel stopped-flow reactor (MC-SFR) is an instrument that performs automatic, real-time, and continuous analysis of ozone decay kinetics in natural waters. Ozone Contactor Model (OCM) is the software to simulate the performance of full-scale ozone bubble-diffuser contactors in support of current and future regulations regarding pathogen and bromate control in drinking water. The MC-SFR and OCM developed in this study were further applied to simulate Cryptosporidium parvum oocyst log inactivation and bromate formation in Linnwood Water Plant Ozone Facility (LWPOF) at Milwaukee Water Works, Milwaukee, WI and model predictions were verified with experimental results. Three dimensional laser induced fluorescence(3DLIF) allowed real time characterization of mixing conditions in a physical model ozone contactors by capturing fluorescence image emitted from a laser dye (i.e. Rhodamine 6G) using a high speed CCD camera. 3DLIF system was applied to analyze the hydrodynamics of two representative types of ozone contactor: direct discharge side-stream venturi injector (SVI) and multi-chambered fine bubble diffuser (FBD). Experimental results verified the presence of circulative swirling related for low dispersion for SVI reactor and the existence of non-ideal flow including short circuiting and internal recirculation in FBD reactor. Finally, integrated tools were applied to the design of a new ozone contactor under planning stage to assess current design and to recommend the improvement.

Two long-standing air quality challenges in the United States are the control of tropospheric ozone and particulate matter, both of which are responsible for widespread damage to human health and the environment. This thesis presents three modeling applications in support of policy development and regulatory actions for control of these pollutants in the eastern United States, taking advantage of recent advancements in sensitivity techniques in a regional Eulerian photochemical air quality model. A broad evaluation of regional atmospheric pollution and transboundary air quality management, including the international scale, and an analysis of successful transboundary management efforts are also presented. The first modeling application is an evaluation of local and interstate impacts on ozone and fine particulate matter (PM2.5) from ground-level and elevated nitrogen oxide plus nitrogen dioxide and from sulfur dioxide emissions from individual states. This analysis identifies states responsible for a significant amount of regional secondary pollution, and states which do not have independent control over much of their pollution concentrations. An average of approximately 77% of each state s ozone and PM2.5 concentrations that are sensitive to the emissions evaluated are found to be formed from emissions from other states. The second application is an assessment of impacts from emissions from a single power-plant on resulting regional ozone concentrations. Three sensitivity techniques and two 3D photochemical models are applied. Ozone increases greater than 0.5 ppbv are found over eight states downwind from the power-plant. The third application supports the extension of a body of research aimed at advancing understanding of the ozone formation potential, or reactivity , of VOCs for use in regional-scale, rather than urban-scale, regulations. Air quality impacts of VOCs emissions from solvent use and manufacture are presented, scientific barriers to accounting for reactivity in regulations are discussed, current and upcoming regulatory applications are described, and results from a regional scale evaluation of reactivity quantification are presented.

This study separated two parts: PART ¢¹ Meteorologically adjusted trends of ozone Since meteorological changes strongly affect ambient ozone concentrations, trends in concentrations of ozone upon the adjustment of meteorological variations are important of evaluating emission reduction efforts. This work is to study meteorological effects on the long-term trends of ozone concentration using a multi-variable additive model in Kaohsiung. The long-term trends of ozone concentration were analyzed using the Holland model (without meteorological-adjusted) and the robust MM Regression model (with meteorological-adjusted) based on the data of eight EPA air quality stations from 1997 to 2006 in Kaohsiung area. According to the result of the simulation, the simulated value of the robust MM-Regression model present more valid than the Holland model.The simulated results show that the long-term ozone concentration increases at 13.84% (or 13.06%) monthly (or annually) after meteorological adjustments, less than at 26.10% (or 23.80%) without meteorological adjustments in Kaohsiung county. The simulated results show that the long-term ozone concentration increases at 9.01% (or 6.88%) monthly (or annually) after meteorological adjustments, less than at 22.01% (or 19.67%) without meteorological adjustments in Kaohsiung city. Wind speed, duration of sunshine and pressure are the three dominant factors that influence the ground-level ozone levels in Kaohsiung area. PART ¢º Dispersion of air pollutants in the Hsuehshan Tunnel Concentrations of carbon monoxide (CO) and nitrogen oxides (NOx) were measured from November 14 ¡V 17 2008 in a cross-mountain Hsuehshan traffic tunnel stretching 12.9 km and containing eastward and westward channels. Air pollutants of CO (carbon monoxide) and NOx (nitrogen oxides) will be monitored at the inlet, outlet and vertical shafts of the tunnel. Meanwhile, numerical simulation of three-dimensional turbulent flow will be performed using STAR-CD software. Traffic and pollutant concentrations during the weekends exceeded those during the weekdays. Measured concentrations of CO at the two tunnel outlets (14.5 ¡V 22.8 ppm) were approximately three times higher than those at the two tunnel inlets (3.2 ¡V 7.3 ppm), while concentrations of NOx at the two tunnel outlets (1.9 ¡V 2.9 ppm) were approximately four to five times higher than those at the two tunnel inlets (0.3 ¡V 0.8 ppm). The outlet of vertical draft 2 had the highest pollutant concentrations (CO = 12.3 ppm; NOx = 1.9 ppm), followed by vertical drafts 1 and 3. Three-dimensional turbulence modeling results indicate that airflow in the tunnel was primarily driven by the combined effects of axial fans and vehicles. Results of this study demonstrate that simulated pollutant concentrations increase downstream and are vertically stratified, due to tailpipe exhausts close to tunnel floor. Simulations agreed fairly well with measurements.

Les échanges entre la stratosphère et la troposphère induits par le courant-jet de l'hémisphère Nord sont bien documentés. Cependant, peu de données sont disponibles dans les régions subtropicales, ce qui a longtemps limité les études des échanges stratosphère-troposphère dans ces régions, en relation d'une part à la barrière dynamique et au courant-jet subtropical de l'hémisphère sud, et, d'autre part, à la convection tropicale, nuages convectifs tropicaux, cyclones et zone de convergence intertropicale. <br /><br /> Se basant principalement sur l'analyse des radiosondages effectués à un rythme bimensuel par le laboratoire depuis 1992, complétés par diverses autres données expérimentales, satellitales, et des sorties du modèle dynamique global du centre européen ECMWF, une première approche qualitative a débouché sur l'identification et l'analyse de plusieurs cas d'étude. Les concepts d'agéostrophisme, de jet-streak et de frontogénèse d'altitude ont permis de caractériser et d'analyser la formation de plusieurs foliations subtropicales et gouttes froides d'altitude. <br /><br />Les échanges entre la stratosphère et la troposphère en relation avec la convection tropicale, ont été ensuite abordés, dans un cas de transfert subsident intense le 6 avril 1995 (300 ppbv à l'altitude 10 km), alors que la Réunion était dans la partie périphérique du cyclone Marlène, à environ 1000 km du centre du cyclone. Après vérification de la bonne prise en compte du cyclone par les données des modèles utilisés (NMC et ECMWF), l'analyse dynamique semble indiquer une extension horizontale assez limitée du transfert, qui serait constitué typiquement par des mécanismes dynamiques à méso-echelle. <br /><br /> Pour permettre un meilleur suivi temporel de la concentration d'ozone troposphérique, un lidar ozone a été installé à la Réunion. Les résultats obtenus dans le cadre de la campagne TRACAS en juillet 1998 ont montré des apports d'ozone ayant une origine stratosphérique dans la troposphère, d'une manière extrêmement régulière pendant le mois de campagne de mesure. L'analyse dynamique au moyen des données du modèle européen et des données Météosat a permis la mise en évidence d'un pli de la tropopause d'échelle planétaire. Ces mécanismes sont nécessairement différents de ceux mis en jeu dans les latitudes moyennes et pourraient être contrôlés par le flux de retour de mousson et la branche descendante de la cellule de Hadley.