Atmospheric particles play a crucial role in climate, visibility, air pollution, and human health. Reactions between gas-phase molecules and particles (heterogeneous reactions) affect not only the particle composition and morphology, but also the composition of the atmosphere. This thesis investigates the heterogeneous chemistry of organic mixtures and inorganic solutions coated with organic monolayers as proxies for atmospheric particles. The first topic of interest was the reaction between N₂0₅ and aqueous inorganic solutions coated with organic monolayers. The goal of this work was to better understand how organic monolayers on aqueous particles affect the mass transport and kinetics of N₂0₅ uptake by aqueous aerosols, and consequently what effectthe monolayer can have on predicted concentrations of N₂0₅ in the atmosphere. To investigate heterogeneous reactions of inorganic solutions coated with an organic monolayer a new rectangular channel flow reactor was developed. This newly developed flow reactor was described in detail and validated. Subsequently, the new flow reactor was used to study the reactive uptake of N₂0₅ on sulfuric acid solutions in the presence of a variety of 1- and 2-component monolayers with varying functional groups, solubilities, chain lengths, surface pressures, and molecular surface areas. Reactive uptake of N₂0₅ on aqueous sulfuric acid solutions was found to correlate most strongly with the molecular surface area or packing density of the monolayer. These results provide a good foundation for determining the influence of monolayers on heterogeneous reactions in the atmosphere, and highlight the need for characterization of monolayer surface properties of organic monolayers present on atmospheric particles. The second topic of interest was reactions between 0₃ and proxies for meat cooking aerosols with the goal to better understand the effect of the phase and microstructure of the mixtures on the lifetime of oleic acid (OA) in atmospheric particles. The reactive uptake of 0₃ was approximately 1 order of magnitude slower on binarysolid-liquid mixtures and multicomponent mixtures that closely represent compositions of meat-cooking aerosols compared to the liquid solutions. Lifetimes up to 75 min were obtained for these mixtures.

Atmospheric particles play a crucial role in climate, visibility, air pollution, and human health. Reactions between gas-phase molecules and particles (heterogeneous reactions) affect not only the particle composition and morphology, but also the composition of the atmosphere. This thesis investigates the heterogeneous chemistry of organic mixtures and inorganic solutions coated with organic monolayers as proxies for atmospheric particles. The first topic of interest was the reaction between N₂0₅ and aqueous inorganic solutions coated with organic monolayers. The goal of this work was to better understand how organic monolayers on aqueous particles affect the mass transport and kinetics of N₂0₅ uptake by aqueous aerosols, and consequently what effectthe monolayer can have on predicted concentrations of N₂0₅ in the atmosphere. To investigate heterogeneous reactions of inorganic solutions coated with an organic monolayer a new rectangular channel flow reactor was developed. This newly developed flow reactor was described in detail and validated. Subsequently, the new flow reactor was used to study the reactive uptake of N₂0₅ on sulfuric acid solutions in the presence of a variety of 1- and 2-component monolayers with varying functional groups, solubilities, chain lengths, surface pressures, and molecular surface areas. Reactive uptake of N₂0₅ on aqueous sulfuric acid solutions was found to correlate most strongly with the molecular surface area or packing density of the monolayer. These results provide a good foundation for determining the influence of monolayers on heterogeneous reactions in the atmosphere, and highlight the need for characterization of monolayer surface properties of organic monolayers present on atmospheric particles. The second topic of interest was reactions between 0₃ and proxies for meat cooking aerosols with the goal to better understand the effect of the phase and microstructure of the mixtures on the lifetime of oleic acid (OA) in atmospheric particles. The reactive uptake of 0₃ was approximately 1 order of magnitude slower on binarysolid-liquid mixtures and multicomponent mixtures that closely represent compositions of meat-cooking aerosols compared to the liquid solutions. Lifetimes up to 75 min were obtained for these mixtures.

Atmospheric particles play a crucial role in climate, visibility, air pollution, and human health. Reactions between gas-phase molecules and particles (heterogeneous reactions) affect not only the particle composition and morphology, but also the composition of the atmosphere. This thesis investigates the heterogeneous chemistry of organic mixtures and inorganic solutions coated with organic monolayers as proxies for atmospheric particles. The first topic of interest was the reaction between N₂0₅ and aqueous inorganic solutions coated with organic monolayers. The goal of this work was to better understand how organic monolayers on aqueous particles affect the mass transport and kinetics of N₂0₅ uptake by aqueous aerosols, and consequently what effectthe monolayer can have on predicted concentrations of N₂0₅ in the atmosphere. To investigate heterogeneous reactions of inorganic solutions coated with an organic monolayer a new rectangular channel flow reactor was developed. This newly developed flow reactor was described in detail and validated. Subsequently, the new flow reactor was used to study the reactive uptake of N₂0₅ on sulfuric acid solutions in the presence of a variety of 1- and 2-component monolayers with varying functional groups, solubilities, chain lengths, surface pressures, and molecular surface areas. Reactive uptake of N₂0₅ on aqueous sulfuric acid solutions was found to correlate most strongly with the molecular surface area or packing density of the monolayer. These results provide a good foundation for determining the influence of monolayers on heterogeneous reactions in the atmosphere, and highlight the need for characterization of monolayer surface properties of organic monolayers present on atmospheric particles. The second topic of interest was reactions between 0₃ and proxies for meat cooking aerosols with the goal to better understand the effect of the phase and microstructure of the mixtures on the lifetime of oleic acid (OA) in atmospheric particles. The reactive uptake of 0₃ was approximately 1 order of magnitude slower on binarysolid-liquid mixtures and multicomponent mixtures that closely represent compositions of meat-cooking aerosols compared to the liquid solutions. Lifetimes up to 75 min were obtained for these mixtures. / Science, Faculty of / Chemistry, Department of / Graduate

Neste estudo foi feita uma detalhada caracterização das propriedades óticas de partículas de aerossóis biogênicos, de poluição urbana e de queimadas na bacia Amazônia. Foram utilizadas diferentes abordagens, incluindo medidas in-situ e por sensoriamento remoto em várias localidades. Radiômetros solares da rede AERONET e instrumentos de medida de absorção (Aetalômetros e MAAP) e espalhamento (Nefelômetros) foram utilizados no experimento GoAmazon2014/5 que estudou o efeito das emissões urbanas de Manaus nas propriedades de aerossóis. Em regiões impactadas pela queima de biomassa, a forçante radiativa foi quantificada através de medidas da AERONET, separando as contribuições de carbono orgânico (OC) e elementar (EC). Com base apenas nas propriedades óticas dos aerossóis, foi feita uma análise qualitativa dos tipos de aerossóis dominantes durante a queima de biomassa na Amazônia, avaliando seus impactos no balanço radiativo. O OC emitido nas queimadas tem forte efeito de resfriamento no topo da atmosfera, com uma forçante radiativa de -53 ± 17 W/m². O EC é altamente absorvedor e, apesar de estar presente em menor quantidade que o OC, apresenta um forte efeito na forçante radiativa no topo da atmosfera, tornando-a significativamente menos negativa, com efeitos de até -12 ± 9 W/m². As propriedades de absorção e espalhamento associadas com as emissões urbanas da cidade de Manaus foram analisadas. Uma significativa diferença na componente de absorção da profundidade ótica foi observada entre dois sítios localizados vento acima e vento abaixo da pluma urbana. O efeito da absorção é notável principalmente na estação chuvosa, mas também pode ser observado com as plumas de queimadas na estação seca. A partir de medidas in-situ, foi observado que o albedo de espalhamento simples (SSA) médio diminui de 0,92 ± 0,06 antes de Manaus para 0,83 ± 0,11 na região impactada pela pluma urbana durante a estação chuvosa. Medidas in-situ do coeficiente de absorção do particulado PM10 foram realizadas em paralelo com o PM2.5 durante a estação chuvosa na reserva ZF2 para análise da absorção de partículas grossas biogênicas. Em condições de dominância do particulado biogênico, a absorção em 880 nm do PM10 é cerca de 10% superior à absorção do PM2.5 no mesmo comprimento de onda, inferindo a absorção da radiação por partículas biogênicas na moda grossa. / In this study, a detailed characterization of aerosol optical properties for the biological, urban pollution and biomass burning aerosols was performed in the Amazon basin. A number of different approaches were used, including in-situ and remote sensing measurements in several locations. As part of the GoAmazon2014/5 experiment, solar radiometers from AERONET Network and in-situ instruments measuring absorption (Aethalometers and MAAP) and scattering coefficients (Nephelometers) were used to assess the effect of Manaus urban emissions on the aerosol properties. In regions heavily affected by the biomass burning events, the radiative forcing retrieved by AERONET was quantified, separating the contributions of organic carbon (OC) and elemental (EC). Based exclusively on the aerosol optical properties, a qualitative analysis of the dominant aerosol types was performed in the Amazon, assessing its impact on the radiative balance. The OC emitted from biomass burn has strong cooling effect at the top of the atmosphere, presenting an instantaneous radiative forcing of -53 ± 17 W/m². The EC is highly absorbing and, despite its lower concentration compared to the OC, showed a strong effect on the instantaneous radiative forcing at the top of the atmosphere, making it significantly less negative, with an effect up to -12 ± 9 W/m². The absorption and scattering properties associated with the urban emissions from the Manaus city were analyzed. A significant difference on the absorption optical depth was observed between two sites located upwind and downwind of the urban plume, respectively. The effect of absorption is particularly remarkable in the rainy season, but can also be observed with the biomass burning plumes during the dry season. In-situ measurements showed that the averaged single scattering albedo (SSA) decreased from 0.92 ± 0.06 upwind to 0.83 ± 0.11 downwind of Manaus urban plume during the wet season. In-situ measurements of the spectral absorption coefficient of PM10 cut size were performed in parallel with the PM2.5 during the wet season at ZF2 reserve in order to study the light absorption by biological coarse particles. In atmospheric conditions with the dominance of biological particles, the PM10 absorption at 880 nm is up to 10 % higher than the PM2.5 absorption at the same wavelength, inferring the absorption of radiation by coarse mode biological particles.

The composition, concentration, and size of submicron aerosols were measured with a time resolution of five minutes by an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) at a rural location northwest of the Dallas-Fort Worth, TX, area for the month of June 2011. A TSI, Inc., Model AE51 aethalometer using an optical absorption technique also was deployed to measure black carbon (BC) concentrations. The total measured PM1 mass concentration ranged between 1.0 µg/m3 and 17.1 µg/m3, with a mean and standard deviation of 4.6± 2.7 µg/m3. Significant variability is observed in the time series of total PM1 and of all four HR-ToF-AMS species, particularly between June 21 and 25. The average aerosol composition was dominated by organic matter (52.1 ± 14.8%) and sulfate (28.8 ± 11.8%). Organic aerosol concentrations were positively correlated with tracers of combustion carbon monoxide (CO) and BC, the coefficients of determination were r2=064 and r2=0.48, respectively. Because of the large influence of organics on total aerosol concentration, organic data were analyzed in the context of ΔOA/ΔCO, which typically is used to investigate the relative importance of secondary organic aerosol. The average ∆OA/∆CO for the data used was 64.0 ± 26.9 µg/ (m3 ppmv), which is typical of an aged air mass. Other metrics of age include the ratio of OOAI (more oxidized) to total oxidized organic aerosol (OOA), the ratio of sulfate to total sulfur, the ratio of its oxidation products to isoprene, and the ratio of nitrogen oxides to total reactive nitrogen. All metrics point to aged air masses, but variations in these age matrices, particularly during one period of enhanced ΔOA/ΔCO, help elucidate the contributions of various precursors and processes to organic aerosols at the site.

Neste estudo foi feita uma detalhada caracterização das propriedades óticas de partículas de aerossóis biogênicos, de poluição urbana e de queimadas na bacia Amazônia. Foram utilizadas diferentes abordagens, incluindo medidas in-situ e por sensoriamento remoto em várias localidades. Radiômetros solares da rede AERONET e instrumentos de medida de absorção (Aetalômetros e MAAP) e espalhamento (Nefelômetros) foram utilizados no experimento GoAmazon2014/5 que estudou o efeito das emissões urbanas de Manaus nas propriedades de aerossóis. Em regiões impactadas pela queima de biomassa, a forçante radiativa foi quantificada através de medidas da AERONET, separando as contribuições de carbono orgânico (OC) e elementar (EC). Com base apenas nas propriedades óticas dos aerossóis, foi feita uma análise qualitativa dos tipos de aerossóis dominantes durante a queima de biomassa na Amazônia, avaliando seus impactos no balanço radiativo. O OC emitido nas queimadas tem forte efeito de resfriamento no topo da atmosfera, com uma forçante radiativa de -53 ± 17 W/m². O EC é altamente absorvedor e, apesar de estar presente em menor quantidade que o OC, apresenta um forte efeito na forçante radiativa no topo da atmosfera, tornando-a significativamente menos negativa, com efeitos de até -12 ± 9 W/m². As propriedades de absorção e espalhamento associadas com as emissões urbanas da cidade de Manaus foram analisadas. Uma significativa diferença na componente de absorção da profundidade ótica foi observada entre dois sítios localizados vento acima e vento abaixo da pluma urbana. O efeito da absorção é notável principalmente na estação chuvosa, mas também pode ser observado com as plumas de queimadas na estação seca. A partir de medidas in-situ, foi observado que o albedo de espalhamento simples (SSA) médio diminui de 0,92 ± 0,06 antes de Manaus para 0,83 ± 0,11 na região impactada pela pluma urbana durante a estação chuvosa. Medidas in-situ do coeficiente de absorção do particulado PM10 foram realizadas em paralelo com o PM2.5 durante a estação chuvosa na reserva ZF2 para análise da absorção de partículas grossas biogênicas. Em condições de dominância do particulado biogênico, a absorção em 880 nm do PM10 é cerca de 10% superior à absorção do PM2.5 no mesmo comprimento de onda, inferindo a absorção da radiação por partículas biogênicas na moda grossa. / In this study, a detailed characterization of aerosol optical properties for the biological, urban pollution and biomass burning aerosols was performed in the Amazon basin. A number of different approaches were used, including in-situ and remote sensing measurements in several locations. As part of the GoAmazon2014/5 experiment, solar radiometers from AERONET Network and in-situ instruments measuring absorption (Aethalometers and MAAP) and scattering coefficients (Nephelometers) were used to assess the effect of Manaus urban emissions on the aerosol properties. In regions heavily affected by the biomass burning events, the radiative forcing retrieved by AERONET was quantified, separating the contributions of organic carbon (OC) and elemental (EC). Based exclusively on the aerosol optical properties, a qualitative analysis of the dominant aerosol types was performed in the Amazon, assessing its impact on the radiative balance. The OC emitted from biomass burn has strong cooling effect at the top of the atmosphere, presenting an instantaneous radiative forcing of -53 ± 17 W/m². The EC is highly absorbing and, despite its lower concentration compared to the OC, showed a strong effect on the instantaneous radiative forcing at the top of the atmosphere, making it significantly less negative, with an effect up to -12 ± 9 W/m². The absorption and scattering properties associated with the urban emissions from the Manaus city were analyzed. A significant difference on the absorption optical depth was observed between two sites located upwind and downwind of the urban plume, respectively. The effect of absorption is particularly remarkable in the rainy season, but can also be observed with the biomass burning plumes during the dry season. In-situ measurements showed that the averaged single scattering albedo (SSA) decreased from 0.92 ± 0.06 upwind to 0.83 ± 0.11 downwind of Manaus urban plume during the wet season. In-situ measurements of the spectral absorption coefficient of PM10 cut size were performed in parallel with the PM2.5 during the wet season at ZF2 reserve in order to study the light absorption by biological coarse particles. In atmospheric conditions with the dominance of biological particles, the PM10 absorption at 880 nm is up to 10 % higher than the PM2.5 absorption at the same wavelength, inferring the absorption of radiation by coarse mode biological particles.

Over the last decades, it has become clear that the size and chemical composition of atmospheric aerosol (AA) has a major impact on both human health and a number of processes in the atmosphere. Although there are increasing efforts to describe the behavior of AA, many phenomena are still not sufficiently understood to be able to predict aerosol behavior and associated phenomena to a satisfactory degree. This PhD thesis describes aerosol behavior at high temporal resolution within three main topics. The first topic is the description of the chemical and size composition of the non-refractory PM1 (NR-PM1) fraction at the Prague - Suchdol suburban station and the study of the influence of meteorological phenomena on the behavior of this aerosol. In order to identify seasonal effects, measurements were carried out in summer and winter. Positive Matrix Factorization (PMF) analysis was performed in connection with the aerosol description at the station, which identified chemically resolved mass profiles of aerosol sources and their temporal evolution. The second topic is the penetration of aerosol particles from the outdoor to the indoor environment. The influence of particle size and chemical composition on the penetration of particles from the outdoor to the indoor environment was investigated by...

Page 7 was mistyped as being page 8. All content present is in logical order. / A simple method for computing the effect of atmospheric aerosol on the net solar radiation balance of the surface-lower atmosphere system is presented. It was found that in clear sky conditions at Goose Bay, Toronto and Winnipeg, for the period 1977 -1982, the presence of aerosol made the systems 10 -20% more efficient at absorbing radiation than if the aerosol was absent. Furthermore, surface albedo is shown to be the most important parameter governing the effect of aerosol on the net solar radiation balance in an aerosol system, while the effect of volcanic aerosol produced by El Chichon had a minor influence on the net solar radiation balance. / Thesis / Bachelor of Science (BSc)

Aerosols play important roles in atmospheric and environmental processes. Not only do they impact human health, they also affect visibility and climate. Despite recent advances made to under their sources and fate, there remains a limited understanding of the mechanisms that lead to the formation of aerosols and their ultimate fate in the atmosphere. These knowledge gaps provide the crux of the research reported herein, which has focused on identifying novel sources of atmospheric aerosol, characterizing its physical and optical properties, and rationalizing these properties using an in-depth knowledge of the molecular level mechanisms that led to its formation. Upon mowing, turfgrasses emit large amounts of green leaf volatiles which can then be oxidized by ozone to form SOA. Overall, the mowing of lawns has the potential to contribute nearly 50 µg SOA per square meter of lawn mowed. This SOA contribution is on the same order of magnitude as other predominant SOA sources (isoprene, monoterpenes, sesquiterpenes). Turfgrasses represent an interesting and potentially meaningful SOA source because they contribute to SOA and also because they cover large land areas in close proximity to oxidant sources. Another related SOA precursor is sugarcane, which is in the same family as turfgrass and is among the largest agricultural crops worldwide. Globally, the ozonolysis of sugarcane has the potential to contribute 16 Mg SOA to the atmosphere, compared to global estimates of SOA loading that range from 12-70 Tg SOA. In order to fully understand the role of atmospheric SOA on the radiative budget (and therefore climate), it is also important to understand its optical properties; its ability to absorb vs scatter light. Turfgrass and sugarcane produced SOA that was weakly absorbing while its scatter efficiency was wavelength and size-dependent. Interestingly, SOA formed under both dry (10% RH) and wet (70% RH) conditions had the same bulk chemical properties (O:C), yet significantly different optical properties, which was attributed to differences in molecular-level composition. The work presented herein represents a unique, inclusive study of SOA precursors. A complete understanding of the chemistry leading to SOA formation is used to understand its physical and optical properties and evaluate these large-scale effects of SOA from these precursors.

The effective air quality management in the heavy polluted areas has to be based on high-quality monitoring with properly designed monitoring network and targeted measurements, which provided information required to source apportionment. The thesis aim was to apportion sources of atmospheric aerosol based on highly time resolved data of mass concentration of size segregated aerosol, its temporal and spatial variability, elemental composition, OC/EC and size distribution of carcinogenic polyaromatic hydrocarbons. Sampling campaigns went during winter and summer in small settlement Březno by Chomutov, residential area Ostrava - Radvanice a Bartovice and Mladá Boleslav in the years 2008 - 2010, 2012, 2013. We determined mass concentrations of PM10, PM1-10, PM1.15-10 and PM0.15-1.5 and their size fraction ratios. Based on the size ratios, the source apportionment of fine fraction (PM0.15-1.15) with focus on PM0.34-1.15 is crucial. We examined seasonal and spatial variability of PM10, PM.2.5, PM1 and PM1-10. Based on the examination, we obtained representative highly-time resolved data with regards to season and sampling locality. We analysed dynamic of size distribution of particle-bond eight carcinogenic polycyclic hydrocarbons. Based on the results the source apportionment of PM0.34-1.15 is crucial....