This dissertation is a collection of studies that investigates the issue of air pollution in the field of environmental chemistry. My thesis consists of research works done to measure the concentration of particulate matter (PM) and gas-phase species in ambient air. High concentrations of PM is a significant problem in Utah and in other regions of the world. Particles having an aerodynamic diameter of 2.5 micrometers and smaller play a crucial role in air pollution and pose serious health risks when inhaled. PM is composed of both organic and inorganic components. The organic fraction in PM ranges from 10-90% of the total particle mass. Several methods have been employed to measure the organic fraction of PM, but these techniques require extensive laboratory analysis, expensive bench top equipment, and do a poor job of capturing diurnal variations of the concentrations of ambient organic compounds. The Hansen Lab has developed a new instrument called the Organic Aerosol Monitor (OAM) which is based on gas chromatography followed by mass spectrometry detection platform for measuring the carbonaceous component of PM2.5 on an hourly averaged basis. Organic marker data collected in 2016 using the OAM was used in a Positive Matrix Factorization (PMF) analysis to identify the sources of PM in West Valley City, Utah. Additionally, data was collected in Richfield and Vernal, UT in 2017 - 2018 to quantitatively monitor the composition of organic markers of PM2.5. Some previously unidentified organic compounds in PM were successfully identified during this study, including terpenes, polycyclic aromatic hydrocarbons (PAHs), diethyl phthalate, some herbicides, and pesticides. Gas-phase species play a significant role in driving the formation of air pollutants in Earth's atmosphere. Traditional gas detection methods do not provide high temporally and spatially resolved data; therefore, it becomes important to detect and measure gas-phase species both qualitatively and quantitatively to better understand the sources of air pollution. An incoherent broadband cavity enhanced absorption spectrometer (IBBCEAS) combines a broadband incoherent light source, a stable optical cavity formed by two highly reflective mirrors and a charged-coupled device (CCD) detector to quantitatively measure the gas-phase compounds present in the atmosphere. The concentrations of formaldehyde (HCHO) were measured using IBBCEAS to investigate the sources of this hydrocarbon in Bountiful, Utah during 2019. Another important species is OH radical. It is one of the most predominant oxidizing species present in the atmosphere. It is found in low concentrations, 0.1 ppt. Detecting concentrations this low is challenging. A new IBBCEAS instrument has been designed and elements of this instrument were tested by measuring the OH overtones in a variety of short chained alcohols. A set of experiments were conducted to measure the absorption cross-sections for the 5th and 6th OH vibrational overtones in a series of short chained alcohols by IBBCEAS. Because OH radical's lowest energy electronic state occurs in the same wavelength region (i.e., 308 nm) that SO2 absorbs (300-310 nm), a study was conducted in which the concentrations of SO2 were measured using an IBBCEAS and compared with a commercially available SO2 monitor.

Im Rahmen der vorliegenden Arbeit wurden die Eigenschaften von atmosphärischen Aerosolpartikeln im tropischen Regenwald des Amazonasgebietes bestimmt. Dazu wurden die Daten einer fast einjährigen Lidarmesskampagne ausgewertet und diskutiert. Die Messungen wurden mit einem automatischen Mehrwellenlängen-Polarisations-Raman-Lidar im zentralen Amazonasbecken nahe Manaus, Brasilien, im Zeitraum von Januar bis November 2008 durchgeführt. Somit konnten erstmalig optische und mikrophysikalische Aerosoleigenschaften im Amazonasgebiet während der Regenzeit (ca. Dezember-Mai) und Trockenzeit (ca. Juni-November) höhenaufgelöst charakterisiert werden. Einleitend werden die meteorologischen Bedingungen im Amazonasgebiet erläutert und eine Literaturübersicht über Aerosolforschung in dieser Region gegeben. Das Messgerät sowie verschiedene Kalibrier- und Korrekturschemen, die zur Datenauswertung notwendig sind, werden vorgestellt. Auch Vergleiche mit anderen Messgeräten werden diskutiert. Diese zeigen, dass die aus den Lidarmessungen abgeleiteten Parameter von hoher Qualität sind. Anhand von Fallstudien werden mit Hilfe von Rückwärtstrajektorien und Satellitenmessungen typische Aerosolbedingungen am Messstandort diskutiert. Um die generellen Unterschiede zwischen Regen- und Trockenzeit zu quantifizieren, wird eine statistische Auswertung aller analysierten Lidarmessungen präsentiert. Die Analyse der Lidardaten zeigt, dass während der Regenzeit im Amazonasgebiet in ca. der Hälfte aller Fälle sehr saubere Bedingungen mit einer Aerosol Optischen Dicke (AOD) von weniger als 0.05 (bei 532 nm) vorherrschen können. Allerdings wurde in ca. 30% aller analysierten Fälle im Zeitraum von Januar bis Mai auch afrikanisches Aerosol, vornehmlich Saharastaub und Biomasseverbrennungsaerosol (BBA), am Messstandort detektiert. Dabei dominierte meist BBA die Aerosolpopulation, wie die Depolarisationsmessungen zeigten. In der Trockenzeit ist die Atmosphäre im Amazonasbecken hauptsächlich mit BBA aus Südamerika belastet. Daher ist die AOD im Durchschnitt um einen Faktor drei größ er als in der Regenzeit. BBA wurde zu dieser Jahreszeit regelmäßig bis zu einer Höhe von 4-6 km detektiert. Basierend auf den vorgestellten Langzeitmessungen werden erstmalig die optischen Eigenschaften von südamerikanischem BBA statistisch analysiert und diskutiert. / Continuous lidar measurements were performed in the Amazon rain forest for almost one year in 2008. The results of the automated multiwavelength-Raman-polarization lidar observations were presented in this dissertation. These measurements are the first long-term observations of the vertical aerosol structure ever made in the Amazon Basin. The advanced lidar observations were conducted 60 km north of Manaus in the central northern part of Amazonia. The area is widely covered with pristine rain forest. A HYSPLIT backward-trajectory analysis showed that the observations were representative on a regional scale for the central northern part of the Amazon rain forest. The general weather conditions in this region are characterized by a wet (December-June) and a dry season (July-November). During the dry season, a high fire activity occurs in Amazonia, which heavily influences the atmospheric conditions. With the lidar instrument, vertical profiles of the particle backscatter coefficient at 355, 532, and 1064 nm, of the particle extinction coefficient at 355 and 532 nm, and of the particle linear depolarization ratio at 355 nm can be determined. The results from the long-term lidar observations performed in Brazil contain a lot of new information about the aerosol conditions in the central northern Amazon Basin and corroborate certain findings from former aerosol measurements in Amazonia. It was shown for the first time that advection of Saharan dust together with biomass burning aerosol (BBA) from Africa occurred regularly throughout the wet season. In about one third (32%) of all lidar observations during the wet season, African aerosol was dominating the optical aerosol properties in Amazonia. The analysis of the vertical aerosol structure during such events revealed that the African aerosol arriving in the central northern Amazon Basin was usually trapped in the lowermost 3-3.5 km of the troposphere. To quantify the amount of Saharan dust and African smoke transported towards the lidar site, the dust contribution to the measured optical aerosol properties was separated by means of the measured particle depolarization ratio. This study led to the result that in about one half of the cases with African aerosol advection, smoke particles contributed to more than 50% to the total Aerosol Optical Depth (AOD). The smoke transport from Africa towards Amazonia occurred predominantly between January and April when the fire activity in Central Africa was highest. BBA is thus a major constituent of the aerosol plumes that are regularly transported from Africa towards Amazonia. This is a key finding of the presented study. During clean conditions, an AOD (532 nm) of less than 0.05 was observed and the aerosol was trapped in the lowermost 2 km of the troposphere. However, the analysis of the long-term data set revealed that these clean atmospheric conditions occurred in only 48% of all wet-season cases. One example for such background conditions was intensively discussed and it was shown that a major meso-scale rain event occurred in the Amazon region at the same time. This precipitation event was possibly partly responsible for the very low aerosol load. Two case studies from the dry season were presented for which BBA dominated the optical properties. In the first case, a comparable high aerosol load (AOD of 0.41) prevailed while in the second one, a medium aerosol load (AOD of 0.15) was observed. Aged BBA advected from regions south of the lidar site were identified to be the dominant aerosol species for both cases. However, very different geometrical, optical and microphysical properties of BBA (e.g., vertical layering, lidar ratio, Ångström exponent, effective radius, SSA) were observed on both days. In the first case, aerosol was present up to about 4.5 km. Extinction-related Ångström exponent s of about 1 and lidar ratios between 70 and 90 sr were found at different heights for the smoke aerosol. The BBA was highly absorbing (SSA of 0.81) at heights of the highest RH (85%), whereas above under dry conditions (RH=50%) only moderate absorption (SSA of 0.93) was detected. In the second case, smoke was detected up to 4.5 km, and Ångström exponent of about 2 and lidar ratios of 45-55 sr were measured in the aerosol layers. The BBA was only moderately absorbing indicated by SSA values between 0.92 and 0.94. The reason for the differences in the smoke properties could be the shorter travel time to the lidar site (<24 h), different aging processes (e.g., cloud/rain processing), or different burning conditions. In both cases, no depolarizing effects of the BBA could be observed. The strong contrast between the aerosol conditions in the dry season and the wet season were confirmed by the statistical analysis of all lidar observations in 2008. Due to the high BBA concentration in the atmosphere, the mean AOD of the dry season was found to be a factor of 3 higher than the mean AOD of the wet season (0.26 compared to 0.08 at 532 nm). Maximum AOD values were less than 0.55 (at 532 nm) and hence show that the lidar location was not in the direct vicinity of fire events. In only 7% of all cases in the dry season 2008, an AOD below 0.1 was observed. Also the maximum extinction and backscatter coefficient values in the dry season 2008 were 2-3 times higher than during the wet season of this year. The vertical aerosol distributions differ also significantly between the two seasons. In the wet season, the aerosol was mostly trapped in the lowermost 2.5 km, while in the dry season aerosol typically reached up to 4.5 km. Aerosol was occasionally detected up to 6.14 km in the dry season. The majority of the aerosol (95% of the AOD), however, was found to be on average below 2.3 km in the wet season and below 3 km in the dry season. During the wet season, lofted aerosol layers and multiple aerosol stratification was less frequent than in the dry season. The extent of BBA plumes during the dry season showed no correlation to the ML top height. Virtually uniform smoke haze layers were observed up to the AL top. Thus, pyro-convection and/or cloud-related mixing seem to be the major processes for the vertical distribution of BBA.

No description available.

Particulate matter suspended in air (i.e. aerosol particles) exerts a substantial influence on the climate of our planet and is responsible for causing severe public health problems in many regions across the globe. Human activities have altered the natural and anthropogenic emissions of aerosol particles through direct emissions or indirectly by modifying natural sources. The climate effects of the latter have been largely overlooked. Humans have dramatically altered the land surface of the planet causing changes in natural aerosol emissions from vegetated areas. Regulation on anthropogenic and natural aerosol emissions have the potential to affect the climate on regional to global scales. Furthermore, the regional climate effects of aerosol particles could potentially be very different than the ones caused by other climate forcers (e.g. well mixed greenhouse gases). The main objective of this work was to investigate the climatic effects of land use and air pollution via aerosol changes. Using numerical model simulations it was found that land use changes in the past millennium have likely caused a positive radiative forcing via aerosol climate interactions. The forcing is an order of magnitude smaller and has an opposite sign than the radiative forcing caused by direct aerosol emissions changes from other human activities. The results also indicate that future reductions of fossil fuel aerosols via air quality regulations may lead to an additional warming of the planet by mid-21st century and could also cause an important Arctic amplification of the warming. In addition, the mean position of the intertropical convergence zone and the Asian monsoon appear to be sensitive to aerosol emission reductions from air quality regulations. For these reasons, climate mitigation policies should take into consideration aerosol air pollution, which has not received sufficient attention in the past.

Deactivation of catalysts were investigated focusing on three industrial processes: 1) Selective Catalytic Reduction (SCR) for abatement of NOx from biomass combustion using V2O5-WO3 /TiO2 catalysts; 2) Catalytic oxidation of volatile organic compounds (VOC) from printing industries using a Pt/γ-Al2O3 catalyst; and 3) Ni and Pt/Rh catalysts used in steam reforming reaction of bio-syngas obtained from biomass gasification. The aim has been to simulate industrial conditions in laboratory experiments in order to comprehend influence of compounds affecting catalysts performance. Typical catalyst lifetimes in industrial processes are several years, which are a challenge when accelerating deactivation in laboratory scale experiments where possible exposure times are few hours or days. Catalysts can be introduced to deactivating compounds through different routes. The first method examined was gaseous exposure, which was applied to deactivate VOC oxidation catalyst through exposure of gaseous hexamethyldisiloxane. The second method involved wet impregnation and was used for impregnation of SCR catalyst with salt solutions. The third method was based on exposure and deposition of size selected particles of deactivating substances on the catalyst. The latter device was developed during this work. It was applied to monolithic SCR catalysts as well as to pellet catalysts intended for steam reforming of biomass gasification syngas. Deactivated SCR catalyst samples by size selected exposure method were verified and compared with SCR catalysts used in a commercial biomass boiler for 6 500 h. Evaluations of fresh and deactivated samples were investigated using BET surface area; chemisorption and temperature programmed desorption (TPD); surface morphology using Scanning Electron Microscopy (SEM) and poison penetration profile through SEM with an Electron Micro Probe Analyser (EMPA) also equipped with a energy dispersive spectrometer (EDS); chemical analysis of accumulation of exposed compounds by Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES); and influence on catalyst performance. The size selected generated particles of deactivating substances were characterized with respect to mean diameter and number size distribution through Scanning Mobility Particle Sizer (SMPS) and mass size distribution applying an Electric Low Pressure Impactor (ELPI). Results from catalyst characterization methods were useful tools in evaluation of catalyst deactivation routes. Understanding deactivation processes and impact on catalyst performance is vital for further optimization of catalysts with respect to performance and lifetime. Further research in this field can provide more resistant catalysts for application in industry leading to higher commercial benefits and further application of environmental catalysts in thermo-chemical conversion of biomass.

En cas de rejets de polluants ou de radionucléides dans l’atmosphère, l’estimation du lessivage des particules d’aérosol atmosphérique par les précipitations est une donnée essentielle pour évaluer la contamination de la biosphère. De nombreuses études se sont déjà intéressées à ce processus de dépôt humide, mais la plupart d’entre elles sont d’ordre théoriques ou ont été menées en laboratoire. Cette étude a donc pour objectif d’améliorer la connaissance du potentiel de lessivage des particules d’aérosol par les précipitations par une approche expérimentale en conditions in situ. Durant plusieurs mois, trois sites aux environnements distincts en termes de climatologie et d’empoussièrement ambiant ont été instrumentés pour disposer d’une palette de situations précipitations/empoussièrement la plus variée possible. Un disdromètre laser et un granulomètre (compteur électrique et/ou optique) ont mesurés respectivement les caractéristiques des précipitations et les concentrations de particules à une résolution temporelle élevée et sur une large gamme de diamètre. L’utilisation de ce couplage instrumental original a permis de déterminer les potentiels de lessivage pour des particules de la gamme nanométrique à supermicronique et pour différents types de précipitations (chutes de neige et pluies avec des hyétogrammes spécifiques). Dans un premier temps, le coefficient de lessivage ᴧ (paramètre décrivant la cinétique du processus) a été calculé en considérant l’effet global d’une précipitation. Cette approche « macroscopique » est limitée par l’influence de processus « concurrents », tels que l’advection ou les sources d’émissions de particules à proximité des sites de mesures. Pour minimiser l’impact de ces processus sur nos résultats, une seconde méthodologie basée sur la résolution temporelle élevée de l’instrumentation utilisée a été définie. Par cette approche « intra-évènementielle », les coefficients de lessivage ᴧ sont calculés sur de courtes périodes de temps, permettant ainsi d’étudier l’influence de la variabilité du diamètre des particules et des caractéristiques des précipitations sur ces coefficients. Les résultats obtenus par les deux types d’approches ont mis en évidence la nécessité de prendre en compte le diamètre des particules et les caractéristiques des précipitations pour modéliser fidèlement le lessivage des particules d’aérosol atmosphérique. En comparant les résultats des deux types de précipitations, la prédominance du lessivage par des chutes de neige par rapport au lessivage par la pluie a été illustrée. L’importance du diamètre des particules lessivées a été démontrée. Entre le mode « ultrafin » et le mode « grossiers », la variation du coefficient de lessivage est d’un ordre de grandeur (entre environ 2.10¯³et 2.10¯⁴ s¯¹). Le potentiel de lessivage minimum est obtenu pour des particules d’environ 100 nm, ce qui est cohérent avec la théorie du « Greenfield gap » (entre 0,1 et 1 µm). Pour les besoins de la modélisation, une paramétrisation robuste entre le coefficient de lessivage ᴧ et le diamètre des particules d’aérosol (de 10 nm à 10 µm) a été établie. Différentes relations entre le coefficient ᴧ et l’intensité pluviométrique sont proposées aussi pour différentes gammes de diamètre de particules et comparées notamment aux valeurs implémentées actuellement dans le modèle ldX utilisé à l’Institut de Radioprotection et de Sûreté Nucléaire. / In case of release of pollutant or radionuclides into the atmosphere, estimate of below-cloud scavenging of aerosol particles by precipitation (or washout) is an essential data to evaluate contamination of the biosphere. Many studies have already shown an interest to this wet deposition process, but most of them are theoretical or have been conducted in laboratories conditions. This study in situ conditions aims to improve knowledge of below-cloud scavenging of aerosol particles by precipitation. For several months, three sites with separate environments in terms of climate and ambient dust have been instrumented to have such a varied palette of precipitation/dust conditions as possible. A laser disdrometer and a granulomètre (electrical and/or optical counter) measure respectively precipitations characteristics and particles concentrations with a high temporal resolution (one minute). The use of this original instrumental coupling has allowed determining washout potentials for the nanometric size range of particles aerosol to the supermicronique size range and for different types of precipitation (snowfalls and rainfalls with specifics hyetograms).Initially, below-cloud scavenging coefficients ᴧ (parameter describing kinetic of this process) were calculated considering the gobal effet of a precipitation. This “macroscopic” approach is limited by the influence of “concurrent” processes, as advection or local emissions of aerosol particles close to the measurements sites. To minimise effect of these processes on our results, a second methodology based on the high temporal resolution of the instrumentation used was defined. With this “intra-event” approach, washout coefficients are calculated on short time scales, allowing study of impact of the variability of aerosol size and precipitations characteristics on these coefficients.Results obtained with the two approaches highlighted the need of considering particles diameter and characteristics of precipitation to model accurately below-cloud scavenging of aerosol particles. Comparing results for both type of precipitation, predomination of below-cloud scavenging by snowfalls compared with below-cloud scavenging by rainfalls was shown. The importance of the scavenged aerosol diameter was demonstrated. From the “ultrafine” size range to coarse mode of particles, below-cloud scavenging coefficient varies by an order of magnitude (from 2.10¯³ to 2.10¯⁴ s¯¹). Minimum potential is obtained for particles of about 100 nm, which is consistent with theory of “Greenfield gap” (from 0.1 to 1 µm). For modeling needs, a robust parametrization between washout coefficient ᴧ and aerosol particles diameter (from 10 nm to 10 µm) has been established. Also some relationships between coefficient ᴧ and rainfall intensity are proposed for different particles size range and compared in particular with values implemented in model ldX currently used at the French Institute of Radioprotection and Nuclear Safety.

Cette thèse a pour cadre la modélisation du dépôt de particules dans le poumon humain afin d'optimiser l'administration de médicaments par voie inhalée. La région alvéolaire du poumon jouant un rôle physiologique et fonctionnel crucial, l'objectif de ce travail est de mettre en place un modèle de dépôt au sein de la région acinaire qui soit intégrable à un modèle intégrant le poumon complet. Les deux premiers chapitres rappellent les caractéristiques anatomiques et fonctionnelles du poumon et en particulier de la région alvéolaire ainsi que les principes physiques mis en jeu lors de l'écoulement de l'air et du transport de particules dans l'arbre pulmonaire. Puis un modèle numérique d'écoulement dans une géométrie alvéolaire simplifiée est présenté. Le transport d'un bolus d'aérosol y est étudié par une approche eulérienne, au cours de plusieurs cycles respiratoires ; l'impact des irréversibilités de l'écoulement sur la dispersion du bolus est ensuite quantifié. Le dernier chapitre présente l'intégration des résultats précédents au sein d'un modèle analytique de dépôt de particules dans le poumon. Les résultats générés par ce modèle sont ensuite comparés aux données expérimentales issues de la littérature ou obtenues lors d'une étude clinique en cours, spécifiquement orientée sur la mesure du dépôt de particules dans les voies aériennes. Les résultats du modèle montrent une augmentation du dépôt de particules dans la région acinaire, présentant un bon accord avec les données expérimentales. Ce modèle pourrait aider à la conception de thérapies ciblant spécifiquement la région alvéolaire du poumon / The context of this thesis is the modelling of particle deposition in the human lung in order to optimise the administration of inhaled drugs. As the alveolar region plays a crucial role both physiologically and functionally, especially for systemic delivery, the objective of this work is to set-up a particle deposition model specific to the acinar region which could be integrated in whole lung deposition model. The first two chapters concentrate on the anatomical and functional aspects of the lung and on the physical principles involved in the flow and particle transport mechanisms in the lung. Then a computational fluid dynamics model was setup in a simplified alveolar geometry. Aerosol bolus transport was studied through an Eulerian approach, for one or several breathing cycles. The impact of flow irreversibilities on bolus dispersion was quantified. The last chapter deals with the integration of the previous results in an analytical model of particle deposition in the whole lung. The results generated by this model are then compared to experimental data from the literature or obtained from an ongoing clinical trial. The results of the new theoretical model show an increase of particle deposition in the acinar region which improves correlation of theory with experimental data. This model could favourably help designing therapies targeting the alveolar region of the lung

Neste trabalho foram estudadas as influências sazonais sobre as concentrações de hidrocarbonetos policíclicos aromáticos e n-alcanos no material particulado MP10, em novembro de 2001 a junho de 2002 (n = 23), e entre abril de 2003 e maio de 2004 (n=31), em continuidade aos estudos realizados no inverno de 2000 na RMSP. Todas as coletas do aerossol atmosférico ocorreram no Instituto de Astronomia, Geofísica e Ciências Atmosféricas da USP, situado na Cidade Universitária, na região oeste da cidade de São Paulo. Os parâmetros meteorológicos como temperatura, precipitação, umidade relativa, direção e velocidade do vento foram monitorados. Em média, nas estações mais frias foram obtidas as maiores concentrações de MP10, HPA e n-alcanos, em concordância com outros estudos. Os dados foram tratados com algumas ferramentas estatísticas, como análise de componentes principais e estudos das razões diagnósticas, sugerindo algumas fontes de emissões e apontando a emissão veicular como fonte majoritária destes poluentes atmosféricos. / The seasonal influences on the concentrations of polycyclic aromatic hydrocarbons (PAH) and n-alkanes in the particulate matter PM10 were studied in this work from November 2001 to June 2002 (n = 23), and between April 2003 and May 2004 (n=31), in continuity to the studies accomplished in the winter of 2000 in the metropolitan area of São Paulo (MASP). Atmospheric aerosol samples in this work were collected in an open area on the roof of the Department of Atmospheric Sciences of USP, located in the campus in the University of São Paulo, in the west area of the city of São Paulo. The meteorological parameters, as temperature, precipitation, relative humidity, direction and wind speed were monitored. On average, in the coldest stations they were obtained the largest concentrations of PM10, PAH and n-alkanes, in agreement with other studies. The data were treated with statistical tools such as Principal Component Analysis and studies of the diagnostic ratios, suggesting some sources of emissions and pointing the vehicular emission as majority source of these pollutant ones in the atmospheric.

Nuvens desempenham um papel fundamental no balanço radiativo terrestre, e o conhecimento de suas propriedades micro e macrofísicas é importante para o estudo do clima global. O desenvolvimento convectivo de nuvens está intimamente relacionado ao comportamento microfísico de seus hidrometeoros, os quais são influenciados pela variação nas concentrações de aerossóis disponíveis na atmosfera. Este trabalho utiliza o sensoriamento remoto por satélites para analisar a evolução diurna de propriedades ópticas de hidrometeoros de nuvens sobre a Amazônia. Para tanto, medidas de radiância efetuadas pelos canais 1, 2 e 4 do satélite geoestacionário GOES 13 para os anos de 2012, 2013, 2014 e 2015 foram aliadas a códigos computacionais de transferência radiativa visando a obtenção de estimativas de raios efetivos de gotas e partículas de gelo em nuvens convectivas. A variação temporal de parâmetros microfísicos ao longo do dia foi analisada durante as estações seca e úmida em dois locais prístinos e outros dois locais significativamente atingidos pela fumaça de queimadas na Amazônia. A profundidade óptica de aerossóis ( a em 550 nm) variou de 0,1 a 0,2 na maior parte do ano (estação úmida) sobre todos os locais. Na estação seca nos sítios prístinos observou-se um a em torno de 0,5 unidades, e de cerca de 0,8 nos sítios degradados. Os resultados mostram que para todos os locais analisados há 32% mais pixels de nuvens durante a estação úmida do que na seca. As distribuições relativas de refletâncias em 0,63 m e da temperatura de brilho em 11 m indicam que em todos os sítios e épocas do ano há predominância de nuvens menos espessas e mais quentes sobre a Amazônia. A análise da refletância em 3,90 m indicou que nos quatro locais ocorre uma redução do raio efetivo de hidrometeoros de nuvens quentes na estação seca em relação à estação úmida. A distribuição de raios efetivos é bimodal para todos os sítios e estações analisados, sendo a variação diurna dessa distribuição consistente com processos de desenvolvimento vertical de nuvens e crescimento de hidrometeoros. Esse mecanismo ocorre de maneira distinta em locais mais e menos poluídos, sendo que para regiões mais poluídas e desmatadas o desenvolvimento vertical de tamanhos de partículas na época seca se dá de maneira mais lenta do que na úmida. Para as áreas mais atingidas pela pluma de fumaça durante a estação seca os raios efetivos de gotas/cristais de gelo com temperatura de brilho maior que -20°C praticamente não mudam, sofrendo uma variação máxima de 2 m num período de 2 horas. Para o mesmo intervalo de temperaturas e de tempo a estação seca em ambientes mais limpos apresenta uma variação de até 6 m nos raios efetivos das partículas. Esse resultado é parcialmente compatível com modelos conceituais que procuram explicar efeitos microfísicos de aerossóis sobre o tamanho de hidrometeoros em nuvens. O atraso no crescimento vertical de hidrometeoros é mais pronunciado perto do meio dia solar e em locais onde as concentrações de aerossóis provenientes de queimadas são maiores. / Clouds play a key role in Earths radiative balance. The knowledge of its micro and macrophysical properties is important for the study of global climate. The life cycle of convective clouds is closely related to the microphysics of its hydrometeors, which are influenced by many factors including variations in the concentration of atmospheric aerosols. This study uses remote sensing by a satellite to analyze the diurnal evolution of reflective properties of clouds over Amazon. Radiance measurements performed by channels 1, 2 and 4 of the imager instrument onboard GOES-13 geostationary satellite, from 2012 to 2015, were analyzed using radiative transfer and computational codes. This allowed deriving estimates of the effective radius of cloud droplets and ice particles in convective clouds. The temporal variation of microphysical parameters throughout the day was analyzed during the dry and wet seasons at two pristine sites and two other sites significantly affected by biomass burning smoke in the Amazon. The aerosol optical depth ( a at 550 nm) ranged from 0.1 to 0.2 for most of the year (wet season) over all sites. In the dry season at the pristine sites a a of about 0.5 units was observed, while about 0.8 units were measured at the degraded sites. The results show that for all analyzed sites there were 32% more cloudy pixels during the wet season than in the dry season. The relative distribution of reflectance at 0.63 m and the brightness temperature at 11 m indicate that at all sites and times of the year there is a predominance of shallow warm clouds in the Amazon. The analysis of the reflectance at 3.90 m indicated that at the four sites a reduction of the effective radius of hydrometeors in warm clouds occurs in the dry season in comparison to the wet season. The distribution of effective radius is bimodal for all sites and seasons. The diurnal variation of this bimodal distribution is consistent with processes of vertical cloud development and hydrometeor growth. This mechanism occurs differently in the pristine and degraded sites. At polluted and deforested regions the vertical development of particle sizes in the dry season occurs more slowly than in pristine ones. For the areas more affected by smoke plumes during the dry season the effective radius of drops/ice crystals of clouds with brightness temperature greater than -20°C show small changes with height, undergoing a maximum variation of 2 m in 2 hours. For the same temperature range and time interval in the dry season, clouds in cleaner environments showed a variation up to 6 m in the effective radius of particles. This result is partly compatible with conceptual models that seek to explain microphysical effects of aerosols on the size of hydrometeors. The vertical growth delay of hydrometeors is more pronounced near local solar noon and in places where the concentration of smoke aerosols is higher.

Este trabalho tem como foco o entendimento das propriedades ópticas do aerossol na Amazônia utilizando várias técnicas: sensoriamento remoto em solo, sensoriamento remoto por satélites e medidas in situ. Propriedades ópticas medidas continuamente ao longo de mais de 15 anos pela rede AERONET na Amazônia foram analisadas buscando compreender como os eventos anuais de queima de biomassa e as emissões urbanas de Manaus afetam as propriedades das partículas. Medidas de longo prazo do sensor MODIS utilizando o sistema Giovanni da NASA foram úteis para caracterizar o impacto da pluma urbana de Manaus nas propriedades de aerossol e nuvens na Amazônia Central. A partir de medições in situ realizadas nas várias estações amostradoras do experimento GoAmazon2014/5, analisou-se em detalhes propriedades de absorção e espalhamento de aerossol antes e depois do impacto da pluma urbana de Manaus. Foi observada uma alta variabilidade na profundidade óptica do aerossol (AOD) bem como em outras propriedades, tais como absorção, espalhamento e distribuição de tamanho. Valores muito elevados de AOD foram observados em todos os sítios durante a estação seca, em particular na região do arco do desflorestamento. Análises dos expoentes Ångström de espalhamento e absorção separam as diferentes componentes absorvedoras do aerossol, entre eles o carbono elementar (EC), carbono orgânico (OC), poeira mineral e partículas biogênicas. Uma análise da forçante radiativa no topo da atmosfera em conjunto com a Matriz Ångström auxiliou no entendimento do papel da componente orgânica de espalhamento (OC) e da componente de absorção (BC) no aerossol de queimadas e urbano na forçante radiativa. A região menos afetada por queimadas na Amazônia foi caracterizada pela presença de um aerossol altamente espalhador durante a estação seca, com valores de albedo de espalhamento simples (SSA) na faixa de 0,91-0,94. Por outro lado, constatou-se valores médios de 0,85 a 0,89 em regiões fortemente impactadas por queimadas. Através de medidas in situ e medidas obtidas a partir da rede AERONET, foi possível observar significativo impacto da pluma de Manaus vento abaixo da cidade, especialmente na componente de absorção. O efeito da absorção do aerossol urbano na forçante radiativa é significativo, indo de uma forçante no sítio da EMBRAPA, antes da pluma, de -24 W/m² para cerca de -18 W/m² em Manacapuru, com o efeito da pluma de Manaus. A partir da análise de 12 anos de medidas dos sensores MODIS e MISR, observou-se alterações nas propriedades de nuvens e na carga atmosférica de aerossol. Foram analisadas a AOD, a temperatura do topo da nuvem e o raio efeito de gotículas de nuvens. Ficou clara a presença de nuvens mais altas e com raio efetivo menor em regiões com maior carga de aerossol, vento abaixo de Manaus. / This work focuses on understanding the optical properties of aerosol in the Amazon, using various techniques: remote sensing from the ground, remote sensing from satellites and in situ measurements. Aerosol optical properties continuously measured over more than 15 years carried out by the AERONET network in the Amazon were analyzed seeking to understand how the annual biomass burning emissions and urban emissions of Manaus affect particle properties. Long-term measurements of MODIS using the Giovanni NASA system were useful to characterize the impact of the urban plume of Manaus in the properties of aerosol and clouds in the central Amazon. Based on in situ measurements in the various sampling sites of the GoAmazon2014/5 experiment, the absorption and scattering properties of aerosol before and after the impact of Manaus urban plume were analyzed in detail. It was observed a large spatial and temporal variability in the aerosol optical depth (AOD) as well as in various properties such as absorption and scattering coefficients and size distribution. Very high levels of AOD were observed at all sites during the dry season, particularly in the deforestation arc region. Analysis of scattering and absorption Ångström exponents helps to identify different absorber components of the aerosol, including elemental carbon (EC), organic carbon (OC), mineral dust and biogenic particles. An analysis of the radiative forcing at the top of the atmosphere together with the Ångström Matrix helps in understanding the role of the scattering organic component (OC) versus the absorption component (BC) in biomass burning and urban aerosol particles in the radiative forcing. The region least affected by fires in the Amazon was characterized by a highly scattering aerosol during the dry season with Single Scattering Albedo (SSA) values in the range of 0.91-0.94, while we found mean values of 0.85 to 0.89 in heavily affected biomass burning regions. Through in situ measurements and AERONET observations it was possible to measure the significant impact of Manaus plume downwind of the urban area, especially in the absorption component. The effect of absorption of urban aerosol in the radiative forcing is significant, with measurements at the EMBRAPA site, before the impact of the plume, at -24 W/m² going to -18 W/m² in Manacapuru that is effect of the Manaus plume. It was also analyzed the changes in the properties of clouds and atmospheric aerosol loading over the last 12 years of MODIS and MISR measurements. The analysis of AOD, cloud top temperature and the radius of cloud droplets show a clear signal of Manaus plume. It was observed clouds with smaller effective radius in regions with higher aerosol load, downwind of Manaus.