No description available.

No description available.

No description available.

No description available.

Increasing levels of air pollution are prompting researchers to develop more reliable air pollution modeling approaches in order to protect the public and the environment from toxic contaminants and airborne pathogens. Although land use regression has long been used to assess exposure to air pollution, researchers are increasingly using machine learning algorithms to quantify the concentration of harmful pollutants—for this study black carbon (BC) and particle number (PN). Additionally, researchers are moving away from using fixed-site data in favor of using mobile monitoring data in a variety of locations to develop hourly empirical models of particulate air pollution. This study uses secondary data describing BC and PN pollutant levels, which are obtained from roads that bikers share in the more rural location of Blacksburg (VA). Machine learning (ML) algorithms are then built to develop accurate and reliable short-term empirical prediction models. Different pre-processing methods for the mobile monitoring data and various input variables are tested to assess how ML can be used effectively in this process. Three types of time-average models are developed (daytime, hourly average, and one second models). Various combinations of spatial and temporal input variables are used in the short-term models. The impact of adding more spatiotemporal variables (e.g., emissions) to machine learning models to improve model performance is assessed in the short-term models. Incorporating spatial and temporal autocorrelation is intended to develop more sophisticated validation approaches for identifying ML performance patterns—the goal of which is to predict concentration levels more accurately in comparison to using raw data without data reprocessing. The results show that the model developed using refined disaggregated data is able to detect the spatial distribution of the pollutant concentration at equivalent levels as the smoothed data models, although the latter display fewer errors. The performance of the short-term model including all variables is equivalent to the model omitting emissions. The ML results are compared to earlier stepwise regression model results, suggesting that ML has the ability to improve both long-term and short-term model accuracy. Our findings indicate that ML demonstrates higher predictive capacity in comparison to stepwise regression. The results from this study may be useful in enhancing the performance of ML through the incorporation of different data preprocessing tasks, as well as showing how different input variables contribute to the ML modeling process. The findings from this study could be used toward the development of environmental/eco-friendly routes that would decrease the risk for exposure to harmful vehicle-related emissions. / Doctor of Philosophy / Air pollution is a major environmental threat to human health, claiming the lives of millions of people each year, primarily as a result of fine particulate matter entering the respiratory system. As such, it is important to develop reliable and accurate air pollution modeling approaches in order to protect the public and the environment from toxic contaminants and pathogens in the air. Although an approach known as land use regression has long been used to assess exposure to air pollution, researchers are increasingly using machine learning (ML) algorithms to quantify the concentration of harmful pollutants—for this study black carbon and particle number, which is a generic assessment that captures a number of known airborne hazards. Additionally, researchers are moving away from using fixed-site data in favor of using mobile monitoring data in a variety of locations to develop hourly empirical models of particulate air pollution. In this study, machine learning algorithms are developed using secondary data collected from roads that bikers share, which are representative of pollution levels of particle number and black carbon in the more rural location of Blacksburg (VA), in order to develop accurate and reliable short-term empirical prediction models. Different pre-processing methods of the mobile monitoring data and various input variables are tested to assess how machine learning can be efficiently used in this process. Our findings indicate that machine learning demonstrates higher predictive capacity in comparison to stepwise regression. The results from this study are expected to be useful in enhancing the performance of machine learning through the incorporation of different data preprocessing tasks, as well as how different input variables contribute to the machine learning modeling process. The findings from this study could assist transportation planners and other stakeholders better assess pollution risks for bike riders and pedestrians. As such, this study's findings could be used toward the development of environmental/eco-friendly routes that would decrease the risk for exposure to harmful vehicle-related emissions.

Air quality management strategies in the US are developed largely from estimates of emissions, some highly uncertain, rather than actual measurements. Improved knowledge based on measurements of real-world emissions is needed to increase the effectiveness of these strategies. Consequently, the objectives of this research were to (1) quantify relationships among urban emissions sources, land use, and demographics, (2) determine the spatial and temporal variability of emissions, and (3) evaluate the accuracy of official emissions estimates. These objectives guided three field campaigns that employed a unique mobile laboratory equipped to measure pollutant fluxes by eddy covariance. The first campaign, conducted in Norfolk, Virginia, represented the first time fluxes of nitrogen oxides (NO_x) were measured by eddy covariance in an urban environment. Fluxes agreed to within 10% of estimates in the National Emissions Inventory (NEI), but were three times higher than those of an inventory used for air quality modeling and planning. Additionally, measured fluxes were correlated with road density and increased development. The second campaign took place in the Tijuana-San Diego border region. Distinct spatial differences in fluxes of carbon dioxide (CO₂), NO_x, and particles were revealed across four sampling locations with the lowest fluxes occurring in a residential neighborhood and the highest ones at a port of entry characterized by heavy motor vehicle traffic. Additionally, observed emissions of NO_x and carbon monoxide were significantly higher than those in emissions inventories, suggesting the need for further refinement of the inventories. The third campaign focused on emissions at a regional airport in Roanoke, Virginia. NOx and particle number emissions indices (EIs) were calculated for aircraft, in terms of grams of pollutant emitted per kilogram of fuel burned. Observed NO_x EIs were ~20% lower than those in an international databank. NO_x EIs from takeoffs were significantly higher than those from taxiing, but relative differences for particle EIs were mixed. Observed NO_x fluxes at the airport agreed to within 25% of estimates derived from the NEI. The results of this research will provide greater knowledge of urban impacts to air quality and will improve associated management strategies through increased accuracy of official emissions estimates. / Ph. D.

Exposure to air pollutants is a significant environmental health risk globally, yet understanding the precise health effects remains incomplete. While particulate matter (PM) exposure is traditionally used to assess air quality health impacts, emerging evidence suggests that specific components, such as black carbon (BC), may have varying effects. This dissertation investigates the respiratory tract deposition (RTD) of BC in developing regions, focusing on various transport microenvironments (TMEs) and employing a novel measurement technique under real-world conditions. The assessment of BC pollution in TMEs revealed significant exposure differences among commuters in developing regions. Open-sided vehicles like microbuses and Jeepneys exposed passengers to higher mean BC concentrations (12.8 μg m−3) compared to walking (4.9 μg m−3) and cable car rides (2.8 μg m−3). Despite this, pedestrians experienced the highest RTD of BC per trip (6.3 μg) due to higher minute ventilation and longer commute times. In Manila, Jeepney commuters had a substantially higher RTD dose rate (13.2 μg h−1) than walkers (6.3 μg h−1), mainly because of elevated BC concentrations inside Jeepneys (72 μg m−3 vs. 30 μg m−3). This work highlights the development of the MERDOC (MEasuring Real-world deposition Dose of black Carbon) system, a portable measurement tool designed to assess personal BC exposure, ventilatory parameters, and RTD in real-world scenarios. The MERDOC system demonstrated high operational efficiency, stability, and accuracy, with the deposition fraction (DF) of inhaled BC particles ranging from 39% to 48%. This novel method provided valuable data, particularly in regions with limited access to standard measurement tools, enhancing the understanding of air pollution-related health risks. In conclusion, this research underscores the complex dynamics of BC exposure in developing regions and the necessity for comprehensive strategies to mitigate associated health risks. The innovative MERDOC system significantly improves the accuracy of RTD measurements, providing essential data for informed policy-making and intervention efforts. Promoting active travel, using high-efficiency masks, and exploring alternative transportation modes like cable cars are recommended strategies to reduce BC exposure and enhance public health in urban areas of developing regions.:Bibliographische Beschreibung i Bibliographic Description ii List of Figures iv List of Symbols and Abbreviations v 1. Introduction 1 1.1 Aerosol Particles in a Nutshell 1 1.2 Aerosol Particles and Health 2 1.3 Black Carbon as a proposed additional parameter in health assessments 4 1.4 Exposure Assessment 6 1.5 Respiratory Tract Deposition (RTD) Assessment 8 1.5.1 Background on Human Respiratory Tract 10 1.5.2 Understanding the Fate of Inhaled Particles 13 1.5.3. Approaches and Techniques in RTD Studies 15 1.6 Objectives 18 2. Methods 19 2.1 Study design and Data collection 19 2.1.1 Assessing personal exposure and deposition in microenvironments 20 2.1.2 Feasibility of a novel measurement system 21 2.1.3 Randomized crossover study in young, healthy adults 22 2.2 Development of the portable measurement system 22 2.3 Ethical Considerations 24 3. Results and Discussions 24 3.1 Assessment of Commuter Exposure 24 3.2 Development of Experimental Method 25 3.3 Randomized Crossover Study Using the Developed Instrument 26 4. Summary and Conclusion 27 4.1 Study Limitations and Considerations 30 5. Outlook 31 Bibliography 32 Appended Papers 37 List of Publications included in this dissertation A Authors’ Contribution to the Papers B Publications not included in this dissertation C Acknowledgments D

Diversos estudos tiveram como objetivo determinar e caracterizar o aerossol atmosférico na cidade de São Paulo, quanto a seu tamanho e composição química, bem como encontrar as suas fontes emissoras e contribuições em massa para a região estudada. A coleta dos constituintes atmosféricos foi realizada na estação de amostragem do Laboratório de Análises dos Processos Atmosféricos (LAPAt) do Instituto de Astronomia, Geofísica e Ciências Atmosféricas (IAG) da Universidade de São Paulo (USP), localizada na zona oeste da cidade de São Paulo, geograficamente em 23°3334 S e 46°4400 O. O experimento foi realizado de 15 de agosto a 16 de setembro de 2016. Foram realizadas coletas de material particulado para análise da concentração em massa de sua fração fina inalável e composição química. A distribuição de tamanho para massa de material particulado foi determinada através da coleta com um impactador em cascata. A distribuição de tamanho para número foi obtida a partir de medidas com um Scanning Mobility Particle Sampler (SMPS) com o cálculo da concentração número de partículas (PNC) para o intervalo de 9 a 450 nm de diâmetro. Para estudar as relações entre os gases presentes na região amostrada com a radiação ultravioleta e com o PNC utilizamos os valores horários de concentrações dos gases (O3, NO, NO2 e NOX) e UV medidos na Rede Telemétrica da CETESB (Companhia de Tecnologia Ambiental do Estado de São Paulo). Os filtros coletados foram analisados pela técnica de Fluorescência de Raios-X dispersivo em energia (EDX). As concentrações de Black Carbon (BC) foram obtidas por refletância. Para a determinação das fontes de material particulado fino (MP2,5) foram utilizados os seguintes modelos receptores: Análise de Componentes Principais (ACP) e Fatoração de Matriz Positiva (FMP). Para análise de dispersão do poluente, utilizamos dados meteorológicos da estação climatológica do IAG situada no Parque do Estado. A concentração média de MP2,5 foi de 18,6 (±12,5) g/m³ e a concentração média de BC foi de 1,9 (±1,5) g/m³. As principais fontes encontradas, por ambos modelos receptores ACP e FMP, foram: veículos pesados (a diesel), veículos leves, queima de biomassa, ressuspensão de poeira de solo, pavimentos e construção, processos secundários e misturas de fontes. Os elementos-traço foram definidos em diferentes modas de tamanho: Al, Ca, Si e Ti com picos nas modas de acumulação, traçadores de ressuspensão de pavimento; Fe, Mn, P, K e Cr com picos na fração mais grossa da moda de acumulação, traçadores de emissões veiculares e queima de biomassa. Cu, Zn, Br, Pb, S e BC apresentam picos na fração mais fina da moda de acumulação, traçadores de emissões veiculares e queima de biomassa. / Several studies aimed to determine and characterize the atmospheric aerosol in the city of São Paulo, not only to its size and chemical composition, but as well as to find its emitting sources and mass contributions in the studied area. The atmospheric constituents were collected at the Laboratório de Análise dos Processos Atmosféricos (LAPAt) of the Institute of Astronomy, Geophysics and Atmospheric Sciences (IAG) of the University of São Paulo (USP), located in the western zone of the city of São Paulo Paulo, geographically at 23°33\'34\"S and 46°44\'00\" W. The experiment was conducted from August 15 to September 16 of 2016. Samples of particulate matter were collected to analyze the mass concentration and chemical composition of its inhalable fine fraction. The particulate mass size distribution was determined through the collection with a cascade impactor. The number size distribution was obtained from measurements with a Scanning Mobility Particle Sampler (SMPS) with the calculated number of particle concentration (PNC) for the range of 9 to 450 nm of the diameter. In order to study the relationships among the compounds present in the region and the PNC, we used the hourly values of the gaseous concentrations (O3, NO, NO2 and NOx) and UV measured in CETESB\'s Air Quality Telemetric Network in the State of São Paulo. The sampled filters were analyzed by the energy dispersive X-ray Fluorescence (EDX) technique to determine the elemental composition. The concentrations of Black Carbon (BC) were obtained by reflectance analysis. In order to determine the sources of fine particulate matter (PM2.5), the following Receptors Models were used: Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF). For air pollution dispersion analysis, we used meteorological data from the IAG climatological station located in the Southeast of the city. The mean MP2.5 concentration was 18.6 (± 12.5) g/m³ and the mean concentration of BC was 1.9 (± 1.5) g/m³ for the sampling period. The main sources found by both ACP and PMF models were heavy-duty vehicles (diesel), light-duty vehicles, biomass burning, resuspension of soil dust, pavements and construction, secondary processes and mixed sources. The trace elements were defined at different size distributions: Al, Ca, Si and Ti with peaks in accumulation fraction (related to pavement resuspension tracers); Fe, Mn, P, K and Cr with peaks in the largest fraction of accumulation mode, characteristic of vehicular emissions tracer and biomass burning. Cu, Zn, Br, Pb, S and BC presented peaks in the finer fraction of the accumulation mode, related to vehicle emissions tracer and biomass burning.

Diversos estudos tiveram como objetivo determinar e caracterizar o aerossol atmosférico na cidade de São Paulo, quanto a seu tamanho e composição química, bem como encontrar as suas fontes emissoras e contribuições em massa para a região estudada. A coleta dos constituintes atmosféricos foi realizada na estação de amostragem do Laboratório de Análises dos Processos Atmosféricos (LAPAt) do Instituto de Astronomia, Geofísica e Ciências Atmosféricas (IAG) da Universidade de São Paulo (USP), localizada na zona oeste da cidade de São Paulo, geograficamente em 23°3334 S e 46°4400 O. O experimento foi realizado de 15 de agosto a 16 de setembro de 2016. Foram realizadas coletas de material particulado para análise da concentração em massa de sua fração fina inalável e composição química. A distribuição de tamanho para massa de material particulado foi determinada através da coleta com um impactador em cascata. A distribuição de tamanho para número foi obtida a partir de medidas com um Scanning Mobility Particle Sampler (SMPS) com o cálculo da concentração número de partículas (PNC) para o intervalo de 9 a 450 nm de diâmetro. Para estudar as relações entre os gases presentes na região amostrada com a radiação ultravioleta e com o PNC utilizamos os valores horários de concentrações dos gases (O3, NO, NO2 e NOX) e UV medidos na Rede Telemétrica da CETESB (Companhia de Tecnologia Ambiental do Estado de São Paulo). Os filtros coletados foram analisados pela técnica de Fluorescência de Raios-X dispersivo em energia (EDX). As concentrações de Black Carbon (BC) foram obtidas por refletância. Para a determinação das fontes de material particulado fino (MP2,5) foram utilizados os seguintes modelos receptores: Análise de Componentes Principais (ACP) e Fatoração de Matriz Positiva (FMP). Para análise de dispersão do poluente, utilizamos dados meteorológicos da estação climatológica do IAG situada no Parque do Estado. A concentração média de MP2,5 foi de 18,6 (±12,5) g/m³ e a concentração média de BC foi de 1,9 (±1,5) g/m³. As principais fontes encontradas, por ambos modelos receptores ACP e FMP, foram: veículos pesados (a diesel), veículos leves, queima de biomassa, ressuspensão de poeira de solo, pavimentos e construção, processos secundários e misturas de fontes. Os elementos-traço foram definidos em diferentes modas de tamanho: Al, Ca, Si e Ti com picos nas modas de acumulação, traçadores de ressuspensão de pavimento; Fe, Mn, P, K e Cr com picos na fração mais grossa da moda de acumulação, traçadores de emissões veiculares e queima de biomassa. Cu, Zn, Br, Pb, S e BC apresentam picos na fração mais fina da moda de acumulação, traçadores de emissões veiculares e queima de biomassa. / Several studies aimed to determine and characterize the atmospheric aerosol in the city of São Paulo, not only to its size and chemical composition, but as well as to find its emitting sources and mass contributions in the studied area. The atmospheric constituents were collected at the Laboratório de Análise dos Processos Atmosféricos (LAPAt) of the Institute of Astronomy, Geophysics and Atmospheric Sciences (IAG) of the University of São Paulo (USP), located in the western zone of the city of São Paulo Paulo, geographically at 23°33\'34\"S and 46°44\'00\" W. The experiment was conducted from August 15 to September 16 of 2016. Samples of particulate matter were collected to analyze the mass concentration and chemical composition of its inhalable fine fraction. The particulate mass size distribution was determined through the collection with a cascade impactor. The number size distribution was obtained from measurements with a Scanning Mobility Particle Sampler (SMPS) with the calculated number of particle concentration (PNC) for the range of 9 to 450 nm of the diameter. In order to study the relationships among the compounds present in the region and the PNC, we used the hourly values of the gaseous concentrations (O3, NO, NO2 and NOx) and UV measured in CETESB\'s Air Quality Telemetric Network in the State of São Paulo. The sampled filters were analyzed by the energy dispersive X-ray Fluorescence (EDX) technique to determine the elemental composition. The concentrations of Black Carbon (BC) were obtained by reflectance analysis. In order to determine the sources of fine particulate matter (PM2.5), the following Receptors Models were used: Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF). For air pollution dispersion analysis, we used meteorological data from the IAG climatological station located in the Southeast of the city. The mean MP2.5 concentration was 18.6 (± 12.5) g/m³ and the mean concentration of BC was 1.9 (± 1.5) g/m³ for the sampling period. The main sources found by both ACP and PMF models were heavy-duty vehicles (diesel), light-duty vehicles, biomass burning, resuspension of soil dust, pavements and construction, secondary processes and mixed sources. The trace elements were defined at different size distributions: Al, Ca, Si and Ti with peaks in accumulation fraction (related to pavement resuspension tracers); Fe, Mn, P, K and Cr with peaks in the largest fraction of accumulation mode, characteristic of vehicular emissions tracer and biomass burning. Cu, Zn, Br, Pb, S and BC presented peaks in the finer fraction of the accumulation mode, related to vehicle emissions tracer and biomass burning.

La combustion du noir de carbone (NC) dans le creuset d'une thermobalance est contrôlée à la fois par la réaction et par le transport de l'oxygène jusqu'à la surface du lit et à l'intérieur du lit poreux de NC.Les expériences menées en modifiant la masse de NC ont montré que la concentration en oxygène peut tomber à zéro avant d'atteindre le fond du lit. Ainsi, à un instant donné, seule une partie du lit est en combustion. Cette masse, appelée masse critique (mc) dépend de la température. Elle passe de 35 mg à 570°C à 17,5 mg à 650°C.Un gradient d'oxygène s'établi donc dans le lit. La modélisation du transport interne de l'oxygène a montré que la diffusion de Fick constitue une bonne approximation pour représenter ce transport.Des conseils pour extraire correctement une constante cinétique à partir d'expériences thermogravimétrique sont donnés. La procédure est adaptée en fonction de la précision souhaitée.Ainsi, l'utilisation de faibles masses afin de réduire au mieux l'effet de la masse et l'exothermicité de la réaction est fortement conseillée. L'influence de la diffusion externe du gaz peut être réduite en utilisant des creusets de très faibles hauteurs, ou en mettant l'échantillon le plus proche de la bouche du creuset en remplissant le fond du creuset avec un matériau inerte. / Combustion of carbon black (CB) in the crucible of a thermobalance is controlled by both carbon reactivity and oxygen transport from the oxidizing flux to the surface of the bed and within the porous bed.The experiments conducted by changing the mass of CB showed that the oxygen concentration can fall to zero before the bottom of the bed. Thus, at a given time, only a part of the bed is burning. This mass, called critical mass (mc), depends to temperature. It went from 35 mg at 570°C to 17.5 mg at 650°C.An oxygen gradient is thus established in the bed. The Modelling of the internal transport of oxygen showed that the Fick diffusion is a good approximation to represent the transport.Advices to correctly extract a kinetic constant using thermogravimetric experiments are given. The procedure is adjusted depending to the precision desired.Thus, the use of low masses to best reduce the mass and exothermic reaction effects is strongly recommended. The influence of stagnant gas can be reduced by using crucibles with very low height, or by placing the sample closest to the mouth of the crucible by filling the bottom of the crucible with an inert material.