Biogenic volatile organic compounds (BVOCs) are naturally occurring organic compounds emitted by plants, trees, and ecosystems, exerting a profound influence on the Earth's atmosphere, air quality, climate, and ecosystem dynamics. This research project aims to advance our understanding of BVOC emissions and their implications through a comprehensive and multi-faceted investigation. We investigate the dynamics of BVOCs in the atmosphere through three key objectives. First, we introduce a novel enriching inlet that uses selective permeation to preconcentrate reactive organic gases in small sample flows for atmospheric gas sampling, enhancing the sensitivity and detection limits of analytical instruments. Enrichments between 4640% and 111% were measured for major reactive atmospheric gases at ultra low flow rates and roughly several hundred percent for ambient samples at moderately low flow rates. Second, we constrain light-dependency in BVOC emissions models by comparing modeled and long-term observed BVOC concentrations measured at a mid-canopy monitoring site in a southeastern US forest. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the Framework for 0-D Atmospheric Modeling (F0AM) were utilized to simulate emissions and chemical transformations, respectively to disentangle the time- and species-specificity of light dependency for various BVOC (α-pinene, camphene, and α-fenchene are completely light-independent and limonene, β-thujene, sabinene, and γ-terpinene are seasonally light-dependent). Finally, we examine these models deeper to investigate uncertainties and highlight current limitations due to variability in planetary boundary layer height (PBLH) datasets. We highlight the significance of simultaneous PBLH and BVOC measurements for improving the accuracy of BVOC concentration models. We show that a lack of co-located measurements is a large source of uncertainty in modeling BVOC concentrations. The successful completion of these objectives contributes to a better understanding of the complex interactions between BVOC emissions and atmospheric chemistry. / Doctor of Philosophy / Biogenic volatile organic compounds (BVOCs) are natural chemicals released by plants, trees, and ecosystems. They interact with combustion emissions such as those from vehicles (nitrous oxides or NOX species) in the presence of light to produce secondary pollutants such as ozone and particulate matter which significantly affect human health, Earth's atmosphere, air quality, climate, and ecosystems. This research aims to deepen our understanding of BVOC emissions and their effects through a detailed study of measurement and modeling techniques used to study BVOC. We accomplish this via three main goals. First, we introduce a new method to enhance the detection of reactive gases in small air samples, improving the sensitivity of currently available analytical instruments. This method showed significant improvements in detecting key atmospheric gases. Second, we examine how BVOC emissions depend on light by comparing models with long-term observations from a forest in the southeastern US. We used two models, Model of Emissions of Gases and Aerosols from Nature (MEGAN) and Framework for 0-D Atmospheric Modeling (F0AM), to simulate emissions and chemical changes, revealing that some BVOC emissions are completely light-independent processes, while others depend on the season. Finally, we examine these models deeper to investigate the uncertainties due to variability in planetary boundary layer height (PBLH) datasets (the layer of air closest to the Earth's surface where pollutants are concentrated). We show that a lack of BVOC and PBLH measurements made at the same location is a large source of uncertainty in modeling BVOC concentrations. Achieving these goals will enhance our understanding of the complex interactions between BVOC emissions and atmospheric chemistry.

Este estudo explora a obtenção da altura da camada limite planetária a partir de diferentes métodos e equipamentos, com foco na análise espectral do campo de vento do lidar Doppler. Realizou-se uma campanha de medição por 80 dias com dois lidars Dopplers comerciais com diferentes alcances verticais. Para o lidar com maior alcance vertical e consequetemente uma medida direta da altura da camada limite planetária, foi aplicado o método da variância da razão sinal-ruído e os resultados foram comparados aos valores de altura estimados a partir de dados de radiossondagem através de dois métodos distintos, o método da parcela e o método do número de Richardson bulk, o qual apresentou melhores resultados. Para o lidar com menor alcance vertical, aplicou-se a análise espectral que forneceu valores de comprimento de onda dos picos espectrais, proporcionais à altura da camada limite planetária. A constante de proporcionalidade para obtenção dos valores da altura da camada foi calculada comparando-se os resultados aos valores de altura estimados pela radiossondagem através do método do número de Richardson bulk, obtendo-se um valor de constante de proporcionalidade próximo ao sugerido na literatura. Entretanto, o conjunto de dados que mostrou boas estimativas dos picos espectrais foi bastante restrito, limitando a comparação ao longo do período entre os lidars. / This study explores the obtaining of the planetary boundary layer height through different methods and equipment, focusing on the spectral analysis of the wind field from Doppler lidar. An 80-day measurement campaign was conducted with two commercial Doppler lidars with different vertical ranges. For the lidar with greater vertical range and consequently a direct measurement of the planetary boundary layer heigth, the method of signal-to-noise ratio variance was applied and the results were compared to the height values estimated from radiosonding data using two different methods, the parcel method and the bulk Richardson number method, which presented better results. For the lidar with a lower vertical range, spectral analysis was applied, which provided wavelength values of the spectral peak, proportional to the planetary boundary layer height. The proportionality constant, in order to obtain the boundary height values, were calculated by comparing the height values estimated from the radiosonding data, using the bulk Richardson number method. Proportionality constant value close to the one found in the literature were obtained. However, the set of data that showed good estimates of the spectral peaks was very restricted, limiting the comparison over the period between the lidars.

Este estudo explora a obtenção da altura da camada limite planetária a partir de diferentes métodos e equipamentos, com foco na análise espectral do campo de vento do lidar Doppler. Realizou-se uma campanha de medição por 80 dias com dois lidars Dopplers comerciais com diferentes alcances verticais. Para o lidar com maior alcance vertical e consequetemente uma medida direta da altura da camada limite planetária, foi aplicado o método da variância da razão sinal-ruído e os resultados foram comparados aos valores de altura estimados a partir de dados de radiossondagem através de dois métodos distintos, o método da parcela e o método do número de Richardson bulk, o qual apresentou melhores resultados. Para o lidar com menor alcance vertical, aplicou-se a análise espectral que forneceu valores de comprimento de onda dos picos espectrais, proporcionais à altura da camada limite planetária. A constante de proporcionalidade para obtenção dos valores da altura da camada foi calculada comparando-se os resultados aos valores de altura estimados pela radiossondagem através do método do número de Richardson bulk, obtendo-se um valor de constante de proporcionalidade próximo ao sugerido na literatura. Entretanto, o conjunto de dados que mostrou boas estimativas dos picos espectrais foi bastante restrito, limitando a comparação ao longo do período entre os lidars. / This study explores the obtaining of the planetary boundary layer height through different methods and equipment, focusing on the spectral analysis of the wind field from Doppler lidar. An 80-day measurement campaign was conducted with two commercial Doppler lidars with different vertical ranges. For the lidar with greater vertical range and consequently a direct measurement of the planetary boundary layer heigth, the method of signal-to-noise ratio variance was applied and the results were compared to the height values estimated from radiosonding data using two different methods, the parcel method and the bulk Richardson number method, which presented better results. For the lidar with a lower vertical range, spectral analysis was applied, which provided wavelength values of the spectral peak, proportional to the planetary boundary layer height. The proportionality constant, in order to obtain the boundary height values, were calculated by comparing the height values estimated from the radiosonding data, using the bulk Richardson number method. Proportionality constant value close to the one found in the literature were obtained. However, the set of data that showed good estimates of the spectral peaks was very restricted, limiting the comparison over the period between the lidars.