Aromatic hydrocarbons constitute an important fraction (~20%) of total volatile organic compounds (VOCs) in the urban atmosphere. A better understanding of the aromatic oxidation and its association in urban and regional ozone and organic aerosol formation is essential to assess the urban air pollution. This dissertation consists of two parts: (1) theoretical investigation of the toluene oxidation initiated by OH radical using quantum chemical and kinetic calculations to understand the mechanism of O3 and SOA precursors and (2) experimental investigation of atmospheric new particle formation from aromatic acids. Density functional theory (DFT) and ab initio multiconfigurational calculations have been performed to investigate the OH-toluene reaction. The branching ratios of OH addition to ortho, para, meta, and ipso positions are predicted to be 0.52, 0.34, 0.11, and 0.03, respectively, significantly different from a recent theoretical study of the same reaction system. Aromatic peroxy radicals arising from initial OH and subsequent O2 additions to the toluene ring are shown to cyclize to form bicyclic radicals rather than undergoing reaction with NO under atmospheric conditions.Isomerization of bicyclic radicals to more stable epoxide radicals possesses significantly higher barriers and hence has slower rates than O2 addition to form bicyclic peroxy radicals. At each OH attachment site, only one isomeric pathway via the bicyclic peroxy radical is accessible to lead to ring cleavage. Decomposition of the bicyclic alkoxy radicals leads primarily to formation of glyoxal and methyl glyoxal along with other dicarbonyl compounds. Atmospheric aerosols often contain a considerable fraction of organic matter, but the role of organic compounds in new nanometer-sized particle formation is highly uncertain. Laboratory experiments show that nucleation of sulfuric acid is considerably enhanced in the presence of aromatic acids. Theoretical calculations identify the formation of an unusually stable aromatic acid-sulfuric acid complex, which likely leads to a reduced nucleation barrier. The results imply that the interaction between organic and sulfuric acids promotes efficient formation of organic and sulfate aerosols in the polluted atmosphere because of emissions from burning of fossil fuels, which strongly impact human health and global climate.

We derive tropospheric column BrO during the ARCTAS and ARCPAC field campaigns in spring 2008 using retrievals of total column BrO from the satellite UV nadir sensors OMI and GOME-2 using a radiative transfer model and stratospheric column BrO from a photochemical simulation. We conduct a comprehensive comparison of satellite-derived tropospheric BrO column to aircraft in-situ observations of BrO and related species. The aircraft profiles reveal that tropospheric BrO, when present during April 2008, was distributed over a broad range of altitudes rather than being confined to the planetary boundary layer (PBL). Perturbations to the total column resulting from tropospheric BrO are the same magnitude as perturbations due to longitudinal variations in the stratospheric component, so proper accounting of the stratospheric signal is essential for accurate determination of satellite-derived tropospheric BrO. We find reasonably good agreement between satellite-derived tropospheric BrO and columns found using aircraft in-situ BrO profiles, particularly when satellite radiances were obtained over bright surfaces (albedo >0.7), for solar zenith angle <80 degree and clear sky conditions. The rapid activation of BrO due to surface processes (the bromine explosion) is apparent in both the OMI and GOME-2 based tropospheric columns. The wide orbital swath of OMI allows examination of the evolution of tropospheric BrO on about hourly time intervals near the pole. Low surface pressure, strong wind, and high PBL height are associated with an observed BrO activation event, supporting the notion of bromine activation by high winds over snow. We also provide monthly climatological maps of free tropospheric BrO volume mixing ratio (VMR) derived using the so-called cloud slicing technique. In this approach, the derived slope of the total column BrO versus cloud pressure is proportional to free tropospheric BrO VMR. Estimated BrO VMR shows a minimum in the tropics and greater values at higher latitudes in both hemispheres. High tropospheric BrO VMR at high latitudes in spring could be influenced by near-surface bromine activation.

Intraregional variability in tropospheric environments during freezing rain events is investigated for the South Central United States. National Weather Service (NWS) Automated Surface Observing Stations (ASOS) are used to detect the occurrence of freezing rain, and rawinsonde observations (RAOB) employed to analyze lower tropospheric vertical profiles of temperature, dew point temperature, wind, and layer thicknesses during these periods. The study area consists of seven 100 mile radius RAOB proximity sub-regions centered around Peachtree City Georgia, Nashville Tennessee, Birmingham Alabama, Jackson Mississippi, Shreveport Louisiana, Little Rock Arkansas, and Springfield Missouri. A series of difference of means tests are performed to determine if statistically significant differences exist in mean values of selected tropospheric variables during periods of freezing rain between adjacent RAOB sites to determine the character of intraregional variability within the South Central United States. Results of these tests suggest 5 sub-regions exist in which freezing rain events can be forecast based upon thresholds and ranges of lower tropospheric environmental variables. As a final step, flow charts are developed for each of the 5 subregions to aid meteorologists in forecasting freezing rain within the Southeast United States. / Department of Geography

Made available in DSpace on 2014-10-09T12:28:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:45Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:08/01954-0

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Made available in DSpace on 2014-10-09T12:28:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:45Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O estudo desenvolvido nessa dissertação foi dividido em dois momentos. Na primeira parte foi apresentado a realização de uma calibração independente do sistema LIDAR Raman de vapor d\'água instalado no CLA seguindo uma metodologia desenvolvida na Howard University, baseada em uma análise cuidadosa da eficiência óptica dos componentes do sistema tendo como objetivo determinar essa eficiência e apresentar a resposta espectral do sistema. Após esse estudo, que permitiu obter um melhor entendimento da área instrumental do sistema, é apresentado, na segunda parte, uma análise preliminar das propriedades ópticas dos aerossóis na troposfera por meio da avaliação de alguns parâmetros como, por exemplo, os perfis verticais de extinção desses aerossóis, a LR e a SR, utilizando um sistema LIDAR Raman móvel desenvolvido pela Raymetrics Lidar Systems durante campanhas realizadas em alguns institutos de pesquisa no Estado de São Paulo. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:08/01954-0

Made available in DSpace on 2014-10-09T12:25:48Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:33Z (GMT). No. of bitstreams: 1 11315.pdf: 4284842 bytes, checksum: 94ad34802b7652ff6ef2b3584c12f794 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP / FAPESP:01/07304-8

Die Signale des Global Positioning Systems (GPS) ermöglichen nicht nur die präzise Positionsbestimmung an jedem Ort der Erde, sondern enthalten auch Informationen über den Wasserdampfgehalt der Atmosphäre. Aus diesen Informationen kann mit Hilfe tomographischer Verfahren die dreidimensionale Wasserdampfverteilung in der Troposphäre rekonstruiert werden. Dabei ist es von besonderem Interesse, wie zuverlässig die Wasserdampfverteilung alleine aus den Daten bodengestützter GPS-Netzwerke, d. h. ohne die Einbeziehung von Low Earth Orbitern (LEOs) oder von Wettersatelliten, bestimmt werden kann. Zu diesem Zweck werden GPS-Daten für unterschiedliche GPS-Netzwerke simuliert und auf ihre Eignung für eine tomographische Rekonstruktion untersucht. Besonders der Zusammenhang zwischen der Anzahl der Satelliten, der Stationsdichte und der in der tomographischen Rekonstruktion erreichbaren Auflösung ist dabei von großer Bedeutung. Aus diesem Grund erfolgt zunächst eine geometrische Bewertung der GPS-Eingangsdaten. Die Rekonstruktion eines 3D-Feldes und die dabei auftretenden Abweichungen zwischen dem originalen und dem rekonstruierten Feld werden abschließend an einem Beispiel dargestellt. / The signals of the global positioning system (GPS) can not only be used to obtain the precise position all over the world but carry also information about the water vapour distribution in the atmosphere. This 3D distribution can be reconstructed from the GPS data by means of tomographic techniques. Of special interest is the quality of the reconstructed 3D distribution using data from GPS ground stations alone, without regarding low earth orbiters (LEOs) and weather satellites. Therefore, GPS data have been simulated for different model networks. A subsequent data validation shows the correlation between the number of GPS satellites, the density of ground stations and the spatial resolution of the water vapour field which might be obtained from a tomographic reconstruction. Some selected data sets have been used to reconstruct a given 3D distribution and to analyse variations between the initial model field and the results obtained with different tomographic techniques.

Observé quotidiennement par des instruments à bord de satellites depuis les années 2000, le monoxyde de carbone (CO) est utilisé comme un traceur du transport de la pollution du fait de sa longue durée de vie (1 à 2 mois) dans la troposphère. Ce gaz est émis principalement par les activités anthropiques (transport, chauffage, industrie) et par les feux (naturels ou provoqués pour le brûlage de la biomasse). Le CO joue un rôle central dans la chimie troposphérique car il est détruit par le radical OH, et régule dès lors la capacité oxydante de l'atmosphère. La première partie de mon travail de thèse a consisté à valider les mesures de CO obtenues par l'instrument en occultation solaire ACE-FTS, en utilisant des observations indépendantes d'instruments sol, avion et satellite. Le deuxième volet de mon travail repose sur les données obtenues par la mission IASI, lancée en 2006 à bord du satellite MetOp-A. Nous disposons de 6 ans de données CO IASI qui sont utilisées afin d'étudier les épisodes de feux, de suivre les panaches de pollution lors de campagnes de mesures, d'établir des tendances, d'élaborer des prévisions de pollution (projet MACC), ou encore d'améliorer les inventaires d'émission. Mes travaux de thèse ont surtout concerné l'étude des variabilités temporelles et spatiales, et j'ai contribué à la validation des restitutions qui sont distribuées à une large communauté d'utilisateurs scientifiques. Enfin, le dernier volet de mon travail a consisté à quantifier et expliquer les différences entre les produits CO de MOPITT et de IASI, qui se place comme son successeur. Le poids du choix des hypothèses a priori inhérent aux algorithmes d'inversion est étudié : un nouveau produit MOPITT utilisant le profil et la matrice de variance-covariance a priori de IASI a été élaboré. Alors que les colonnes totales de ce nouveau produit se comparent bien au produit initial, l’influence du profil mais surtout de la matrice de variance-covariance a priori (qui autorise plus ou moins de variabilité lors de l’inversion) est démontrée lors de l’étude des profils. / Carbon monoxide (CO) is measured from space since the year 2000 by several instruments. CO plays an important role in atmospheric chemistry and climate as it is the largest sink of the hydroxyl radical (OH), and thus impacts the oxidizing power of the atmosphere and the concentrations of greenhouse gases (such as methane and ozone). CO is mainly formed by the incomplete combustion of fossil, bio-fuels and biomass burning. Due to its long lifetime (1 to 2 months) it is therefore used as a pollution tracer in the troposphere.The first part of this PhD work consists of validating CO measurements from the limb- viewing ACE-FTS instrument using a set of independent data measured by instruments onboard aircraft, satellites and at ground-based stations.The second part of my work consists of studying the temporal and spatial variability of CO and focuses on studying 6 years of CO data measured by IASI (Infrared Atmospheric Sounding Interferometer), launched in 2006 onboard the MetOp-A satellite. I contributed to the validation of the retrieved data, which are now widely distributed to the scientific community, with different applications. For example the study of fire events, the follow-up of pollution plumes during measurements campaigns, building inter-annual trends, generating pollution forecasts (MACC project), and improving emission inventories.The last part of my PhD work consists of quantifying and explaining the differences between MOPITT (Measurements Of Pollution In The Troposphere) and IASI CO products. Due to the fact that IASI will likely outlive MOPITT, it is essential to evaluate the CO retrievals from these instruments against each other. I studied the impact of the a priori assumptions choice which is a major component of the retrieval algorithms. A new MOPITT product using IASI a priori profile and covariance matrix is built. Total CO columns of this new product are globally in good agreement with the initial MOPITT product. Local differences are investigated and shown to be due to the influence of the a priori profile and mainly its a priori covariance matrix which can be seen when studying the shape of the retrieved profiles.

In der oberen Troposphäre und untersten Stratosphäre (OT/US) beeinflussen Aerosolpartikel im Submikrometerbereich den Strahlungshaushalt der Erde direkt und, was noch wichtiger ist, indirekt, da sie als Kondensationskern für Wolken dienen und somit die Spurengaskonzentrationen durch heterogene chemische Prozesse ändern können. Seit 1997 gibt es regelmäßige in situ Messungen der OT/US Partikel durch das Leibniz-Institut für Troposphärenforschung in Leipzig, Deutschland. Diese Messungen werden an Bord eines Passagierflugzeugs mit dem weltweit einzigartigen IAGOS-CARIBIC Messcontainer durchgeführt (www.iagos.org/iagos-caribic). In der vorliegenden Arbeit wurden die Partikelanzahlkonzentration und die Partikelgrößenverteilung im Submikrometerbereich der vergangenen Jahre ausgewertet. Dafür wurden die Daten von drei Kondensationspartikelzählern (CPC, Condensation Particle Counter) und einem optischen Partikelgrößenspektrometer (OPSS, Optical Particle Size Spectrometer) verwendet. Zunächst wurde im Labor eine umfangreiche Charakterisierung des IAGOS-CARIBIC OPSS hinsichtlich der Zähleffizienz durchgeführt. Weiterhin wurde eine Kalibrierung mit Polystyrol-Latex im geräterelevanten Bereich von 140 nm bis 1050 nm vorgenommen und daraus mit Hilfe der Mie-Streuung eine Funktion zur Datenauswertung für die OT/US entwickelt. Die statistische Analyse der IAGOS-CARIBIC OPSS und CPC Daten gibt einen guten Überblick über die in der OT/US vorkommenden Partikelanzahlkonzentrationen und stellt sicher, dass ein statistisch fundierter Datensatz für die Analyse zur Verfügung steht. Auf dieser Grundlage wurde zum ersten Mal eine detaillierte Analyse der raumzeitlichen Verteilung der Aitkenmode- und Akkumulationsmode-Partikelanzahlgrößenverteilung in der OT/US vorgenommen. Diese Analyse beinhaltet Weltkarten mit Medianwerten, Wahrscheinlichkeitsdichtefunktionen für spezielle Flugrouten und Partikelgrößenverteilungen entlang der Längengrade. Außerdem wurden die Partikelanzahlkonzentrationen zum ersten Mal mit dem globalen Klimamodell ECHAM-HAM verglichen. Dabei ergab sich, dass die Partikelanzahlkonzentration hauptsächlich von großräumigen Strömungsverhältnissen beeinflusst wird, was im Großen und Ganzen gut vom Modell wiedergegeben wird. Für die einzelnen Jahreszeiten wurden mit Hilfe der potentiellen Temperatur und äquivalenten Breitengrade die vertikalen Profile ausgewertet. Für die Analyse in Bezug auf die Aerosol-Mikrophysik und den Transport durch die Tropopause wurden auch die in IAGOS-CARIBIC gemessenen Spurengase, wie z.B. Ozon und Wasserdampf, hinzugezogen. Die Auswertung zeigt ebenfalls deutlich den Einfluss von Wolken in der oberen Troposphäre und verschiedene Austauschprozesse zwischen der Stratosphäre und Troposphäre. Außerdem wurde der Einfluss verschiedener Austauschprozesse auf die Partikelanzahlkonzentration untersucht: die Brewer-Dobson Zirkulation, warm conveyor belts, Isentropentransport und der Transport durch tropische, hochreichende konvektive Bewölkung. In der Vergangenheit wurde diese Analyse nur für atmosphärische Spurengase durchgeführt, und nun zum ersten Mal auch für Aerosolpartikel. Die hier präsentierten Ergebnisse zeigen eine umfangreiche Charakterisierung der Aitken- und Akkumulationsmode-Partikelanzahlkonzentration in der OT/US und den Einfluss von Austauschprozessen der Stratosphäre und Troposphäre auf die Partikel. Die Auswertungen tragen maßgeblich zum Verständnis und zur Vorhersage der Partikelanzahlkonzentration in Klimamodellen und damit schlussendlich zur Berechnung des Strahlungshaushalts der Erde und dessen zeitlicher Veränderung bei. / Submicrometer aerosol particles in the upper troposphere and lowermost stratosphere (UT/LMS) influence the Earth's radiation budget directly and, more important, indirectly, by acting as cloud condensation nuclei and by changing trace gas concentrations through heterogeneous chemical processes. Since 1997, regular in situ measurements of UT/LMS particles have been conducted by the Leibniz Institute for Tropospheric Research, Leipzig, Germany, using the world-wide unique IAGOS-CARIBIC observatory (www.iagos.org/iagos-caribic) onboard a passenger aircraft. In this thesis, UT/LMS aerosol particle number concentrations and the submicrometer aerosol particle size distribution as measured by three condensation particle counters (CPCs) and one Optical Particle Size Spectrometer (OPSS) are discussed. Before analyzing the measurement data from the UT/LMS region a throughout characterization of the IAGOS-CARIBIC OPSS with respect to the counting efficiency was carried out in the laboratory for the OPSS-relevant particle size range of 140 nm to 1040 nm diameter. After calibration with polystyrene latex (PSL) particles a theoretical response function, representative for the UT/LMS, was calculated with Mie theory to ensure a correct data analysis. The statistical analysis of the IAGOS-CARIBIC OPSS and CPC data gives a good overview of existing particle number concentrations in the UT/LMS and ensures a statistically sound data analysis. On this basis a detailed characterization of the spatio-temporal distribution of Aitken and accumulation mode particle number concentrations in the UT/LMS was carried out for the first time. This analysis includes global maps with median values, probability density functions for specific flight routes, and longitudinal distributions of the particle size distribution. Also a first comparison with the global climate model ECHAM-HAM was conducted. The analysis showed that the aerosol distributions are mainly influenced by large-scale circulation patterns which were, in gererel terms, well reflected by the global climate model. Moreover, seasonal vertical cross-sections for particle number concentrations, the potential temperature, and the equivalent latitude were generated. The results are interpreted with respect to aerosol microphysics and cross-tropopause transport using IAGOS-CARIBIC trace gases like ozone and water vapor. The influence of clouds in the troposphere and the different stratosphere-troposphere exchange processes are clearly visible. Furthermore, the influence of the major transport processes into the UT/LMS region on the aerosol particle number concentrations was investigated: the Brewer-Dobson circulation, warm conveyor belts, isentropic transport, and tropical deep convective cloud outflow. In the past this was done only for atmospheric trace gases, but now for the first time for aerosol particles. The findings presented in this study represent a comprehensive characterization of the Aitken and accumulation mode particle number concentration in the UT/LMS and the influence of stratospheric-tropospheric exchange processes on these particles. These findings may help to evaluate and improve predictions of particle number concentrations by climate models and finally the calculation of the Earth's radiation budget and its change over the years.