The Tapered Element Oscillating Microbalance (TEOM) sampler is an EPA approved Federal Equivalent Method Sampler for measuring PM10 concentrations. The Center for Agricultural Air Quality Engineering and Science (CAAQES) owns two Rupprecht and Patashnick (R&P) Series1400a monitors. The R&P Series 1400a monitor uses the TEOM method to measure particulate matter (PM) concentrations and was approved by EPA in 1990 as an automated equivalent method PM10 sampler. Since its approval, many state air pollution regulatory agencies (SAPRAs) have located R&P Series 1400a monitors at community-oriented monitoring sites. Some SAPRAs have even located TEOM samplers at the property line of major sources to determine if the source is meeting its permit requirements for PMc emissions. This thesis presents the results of PM10 and TSP concentrations measured with TEOM and low-volume gravimetric samplers at two Texas cattle feedlots. The purpose of this research was to compare the performance of the R&P Series 1400a monitor to the low-volume gravimetric sampler when sampling PM from a feedlot. Furthermore, this research was conducted to avoid the inappropriate regulation of cattle feedlots that may occur in the future as a consequence of the TEOM sampler being used to measure PMc emissions. The results of this research demonstrate that relationship between the R&P Series 1400a monitor and the low-volume gravimetric sampler is linear. In general, it was observed that the TEOM sampler measured higher PM10 and TSP concentrations than the low-volume gravimetric sampler when sampling downwind from a cattle feedlot. The opposite results were observed when sampling was conducted upwind from the feedlot. The collected data demonstrates that the concentration difference between the two sampling methods is linearly dependent with the concentration intensity for the upwind sampling locations. This trend was shown to be statistically significant. Another linear relationship was observed between the concentration difference and the particle size (mass median diameter and geometric standard deviation) of the sampled dust. Although this trend was not statistically significant, it is believed that additional downwind concentration measurements would validate this relationship.

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Calcined coke is a high quality carbon material produced by calcining green petroleum coke. Calcining is the process of heating green petroleum coke in a kiln to remove excess moisture, extract all remaining hydrocarbons, and modify the crystalline structure of the coke into a denser, electrically conductive product. The final product, calcined coke, is primarily used to make carbon anodes for the aluminum industry and recarburizing agent for industries such as the steel industry. If not appropriately controlled, the calcining process could lead to excess production of particulate emissions from either handling or storing of raw coke, or from the stack emissions during the production of calcined coke. Though calcined coke has shown low hazard potential in human populations due to low volatile content, there remains some public health concern regarding the emissions from these facilities. This study is designed to evaluate the emissions of petroleum coke calcining facility and assess the public health concern from the processes engaged in the handling and storage of green coke as well as from the calcining process. The ambient air levels were measured from a calcining facility and compared with the standards promulgated by USEPA. The results showed that pollutant contribution from the facility, measured by monitoring carbon fraction of the emissions, was de-minimis. The current research also studied whether the exposure levels and health risks specified in various epidemiological studies correlate with the standards promulgated by USEPA to protect public health from petrochemical emissions.

Dans le Sud-Est de la France, le département des Alpes-Maritimes, singulier du fait de son relief contrasté, est soumis au jeu des brises et inversions thermiques nocturnes. L’agglomération littorale contribue aux émissions de particules qui sont un des polluants les plus nocifs pour la santé humaine. La pollution de l’air n’est évidemment pas répartie de manière homogène dans le temps et dans l’espace. Les topoclimats sont un protagoniste de la pollution de l’air au sein de cet espace littoral montagneux. La problématique centrale de cette thèse consiste donc à comprendre pourquoi et comment les topoclimats influencent la variabilité spatio-temporelle des concentrations de particules dans le sud-ouest du département, tout en considérant qu’ils ne sont pas seuls à expliquer les concentrations. Afin de répondre à cette question, plusieurs objectifs privilégiant les mesures de terrain, et la modélisation ont été fixés :- exploiter des données de concentrations de particules et de variables météorologiques acquises à l’aide de plusieurs appareils de mesures, de manière fixe et itinérante, en plusieurs endroits et à différentes échelles spatio-temporelles ;- caractériser les écoulements d’air à faible altitude à l’aide de ballons équilibrés (dits CLB) et les mettre en relation avec les niveaux de PM10 mesurés ; - caractériser chimiquement les PM10 pour évaluer la contribution des principales sources d’émissions ;- tester la capacité d’un logiciel de dispersion atmosphérique à simuler en relief contrasté les effets des topoclimats sur la variabilité spatio-temporelle des PM10.L’influence des topoclimats sur la pollution de l’air particulaire a été établie. / In the Southeastern of France, the department of the Alpes-Maritimes is singular by contrasting terrain and is submitted to breezes and temperature inversions. The coastal urbanization contributes to the particulate matters emissions that are part of the most harmful substances to human health. Air pollution is not spread heavenly in time and space, of course. Topoclimates are one of the protagonists of air contamination within this mountainous coastal area. The focus of this thesis work is to understand why and how topoclimates have impact on the spatio-temporal variability of particle concentrations in the Southwest of the department, while considering that they are not alone to explain the concentrations. The researcher identified several objectives to answer this question and he gave priority to ground measures and modeling: - To explore data about the particulate matters and meteorological characteristics that were collected through the use of several measuring tools, in a fixed and travelling way, in different places and on various spatio-temporal scales;- To identify and characterize air flows at low altitude with CLB (Constant Level Balloon) and cross compare them with the measured levels PM10; - To chemically analyse PM10 to assess the contribution of the main sources of emission;- To test the capacity of an atmospheric dispersion software to simulate the impact of topoclimates on the spatio-temporal variety of PM10 on mountainous and uneven landscapes.The influence of topoclimates on the air pollution has been scientifically established.

Over the last decades, there has been much attention on air quality, especially in urban environments. A significant factor effecting the air quality in the urban environment is airborne particulate matter (PM). Long-term exposure to PM causes increased risk for heart disease, decreased lung function, exacerbation of asthma, and lung cancer. Therefore, many countries have implemented exposure limits to the concentration of ambient PM in the urban environments. The toxicity of PM is dependent on several factors such as chemical composition, shape, adsorbed materials, and particle sizes (usually divided in ultrafine, fine and coarse particles). However, the relationship between different PM properties and developing health hazards are not clear. Therefore, further studies to investigate different properties of PM may contribute to understanding the influence of PM on human health.  In the present work, different novel methods to investigate sampled airborne PM and to investigate potential health effects have been used to increase the knowledge regarding street and wear particles. In study I, a sampling plan involving collecting one filter from Tapered Element Oscillating Microbalance (TEOM) monitoring stations used for Environmental monitoring each month for 20 months were developed. Particles on the filters were extracted into a suspension. TEOM particles were then studied with respect to constituents and variables that reflect their toxicity. The constituent and toxicity was found to be spatial and seasonal dependent. As a follow-up, in study II, TEOM filters from three geographical different cities were collected once a month for a year. The variation in particle mass measured with TEOM monitor, cadmium and lead contents, as well as endotoxin levels between locations and time points over the year was studied. The correlation between studied variables and biological effect was investigated. The results show that the concentration of metals and endotoxin in TEOM particles have no relationship to particle mass, while endotoxin levels coincided with pro-inflammatory response. These studies show that results from analyzing different variables on obtained particles from TEOM filters in combination with information about the ambient particle concentration, could be helpful in the evaluation of differences in the risk of breathing air at various locations.  The dominant road traffic particle sources are wear particles from the road and tyre interface, and from vehicle brake pads. The particle concentrations are highest in cities with high traffic amounts and a high frequency of braking. There are a few cell studies that have investigated the toxicological and biological effect of these wear particles, but there is a lack of knowledge regarding their effect on tissue level. Furthermore, the knowledge about importance of rock materials in pavement is deficient. To mitigate these knowledge gaps, the effect of different wear particles from pavement and brake pad were tested using a model with isolated perfused rat lungs in study III. The wear particles from the pavement showed a significant decrease of tidal volume compared to unexposed controls. The largest effect were found with quartzite stone material. Wear particles from brakes instead showed a larger effect on released proinflammatory cytokines. The study shows that the toxic effect on lungs exposed to airborne particles can be investigated using repetitive measurements of tidal volume. Furthermore, the study shows that the choice of rock material in road pavements has the potential to affect the toxicity of road wear particles. This should be considered in environments where the concentrations and exposures are high. The brake particles showed a different effect than stone particles, indicating the need to differentiate wear particles from different sources in relation to health effects. In summary, the present work have investigated different aspects of airborne particles collected from streets as well as generated wear particles. These indicate different important aspects of the particles that may be of importance to better understand their health effects.

State Air Pollution Regulation Agencies (SAPRAs) issue and enforce permits that limit particulate matter emissions from all sources including layer and broiler facilities, cattle feedyards, dairies, cotton gins, and grain elevators. In this research, a process was developed to determine distances from emitting sources to where the estimated concentrations were less than the National Ambient Air Quality Standards (NAAQS). These distances are a function of emission rates and meteorological conditions. Different protocols were used to develop emission factors for cattle feedyards and layer houses. Dispersion modeling with American Meteorological Society/Environmental Protection Agency Regulatory Model (AERMOD) was conducted to determine the emissions of particulate matter. These data were used to determine the distances from the sources to where the concentrations of particulate matter (PM) would be less than the NAAQS. The current air-permitting process requires that concentrations from a source do not exceed the NAAQS at the property line and beyond for the facility to be in compliance with its permit conditions. Emission factors for particulate matter less than 10 micrometers (PM10) were developed for cattle feedyards using a reverse modeling protocol and Tapered Element Oscillating Microbalance (TEOM) sampler data. Corrections were applied to the TEOM measurements to account for TEOM vs. filter-based low-volume (FBLV) sampler bias and over-sampling of PM10 pre-collectors. Invalid concentrations and dust peaks larger than mean ± 3 times the standard deviation were excluded from this study. AERMOD predictions of downwind concentrations at cotton gins were observed for compliance with 24-hour PM10 and PM2.5 NAAQS at property lines. The emissions from three cotton gins were analyzed at 50 m and 100 m distances. TEOM and FBLV samplers were used to collect 24-hour PM10 measurements inside a laying hen house. The distances to the property lines at which the emissions of PM10 were below the 24-hour average PM10 standards were estimated using AERMOD. The results suggested that the special use of the NAAQS for as the property-line concentration not to be exceeded, could be problematic to agriculture. Emission factors that were comparable of published emission factors were obtained in this study. Large distances to property lines were required when minimum flow rate recommendations were not considered. Emission factors that are representative of the emissions in a particular facility are essential; else facilities could be inappropriately regulated.

Particulate matter is increasingly linked to health effects not only for what was previously thought to be just a respiratory problem, but also for the cardiovascular system. Literature not only supports that high particulate matter over long periods of time is correlated to morbidity and mortality due to both cardiovascular and respiratory means, but that high levels of particulate matter, even in short bursts of high concentrations, may be the triggering mechanism for the onset of such problems. Due to automobiles being a prime source of particulate matter, roadway concentrations are often higher than those measured at off-road measurement sites run by various parts of the United States Government. Furthermore, the government run sites are averaged over timescales at a minimum of an hour and at a maximum of a running three-day twenty-four hour length. These are both so long that mesoscale information about the particulate matter, such as short duration high intensity bursts, would be completely removed from the dataset. This study utilizes a real-time portable instrumentation package, which can effectively measure particulate matter concentrations on the roadways of metro Atlanta. Measurements are taken both inside the cabin of a vehicle, which does have an in-cabin filtration system, and on a bicycle ridden along the streets without any form of filtration. These instruments, specifically calibrated handheld particle counters, did indeed find some spikes of particulates above the government s one-hour averages inside the cabin of a vehicle. Arguably more importantly, while riding a bicycle these handheld particle counters also found spikes of particulates approaching six times the amount monitored by the government sites, and several roadway averages that were higher than the off-road averages for the same time.

Dans le Sud-Est de la France, le département des Alpes-Maritimes, singulier du fait de son relief contrasté, est soumis au jeu des brises et inversions thermiques nocturnes. L'agglomération littorale contribue aux émissions de particules qui sont un des polluants les plus nocifs pour la santé humaine. La pollution de l'air n'est évidemment pas répartie de manière homogène dans le temps et dans l'espace. Les topoclimats sont un protagoniste de la pollution de l'air au sein de cet espace littoral montagneux. La problématique centrale de cette thèse consiste donc à comprendre pourquoi et comment les topoclimats influencent la variabilité spatio-temporelle des concentrations de particules dans le sud-ouest du département, tout en considérant qu'ils ne sont pas seuls à expliquer les concentrations. Afin de répondre à cette question, plusieurs objectifs privilégiant les mesures de terrain, et la modélisation ont été fixés :- exploiter des données de concentrations de particules et de variables météorologiques acquises à l'aide de plusieurs appareils de mesures, de manière fixe et itinérante, en plusieurs endroits et à différentes échelles spatio-temporelles ;- caractériser les écoulements d'air à faible altitude à l'aide de ballons équilibrés (dits CLB) et les mettre en relation avec les niveaux de PM10 mesurés ; - caractériser chimiquement les PM10 pour évaluer la contribution des principales sources d'émissions ;- tester la capacité d'un logiciel de dispersion atmosphérique à simuler en relief contrasté les effets des topoclimats sur la variabilité spatio-temporelle des PM10.L'influence des topoclimats sur la pollution de l'air particulaire a été établie.

The work described in this thesis focuses on the effects that adsorption processes on catalytic surfaces pose in controlling key steps that can affect and control reaction pathways. To that, the development of Nuclear Magnetic Resonance (NMR) relaxometry methods and the comparison with traditional catalytic was performed with a series of C5 and C6 unsaturated hydrocarbons on two different alumina supports, γ- and θ-Al2O3. The developed techniques were applied in the study of liquid phase selective hydrogenation of citral on 5% Pt/SiO2. Infrared (IR) spectroscopy, volumetric adsorption isotherms, dynamic isotherms via a Tapered Element Oscillating Microbalance (TEOM), temperature programmed desorption (TPD) as well as 13C T1 NMR and 1H 2D T1-T2 relaxometry methods were employed. Energies of adsorption as a function of coverage were obtained via adsorption isotherms and the particular surface adsorbate interactions were described with IR spectroscopy. For example, 1-pentyne showed the strongest interaction with the alumina (94 kJ mol-1) while 1-pentene presented a weaker interaction (46 kJ mol-1) on θ-Al2O3. Desorption energies obtained from TPD ranged 85 – 130 kJ mol-1, irrespective of the adsorbate. Reactivity of the aluminas was captured with TPD, TEOM and NMR relaxometry. Interaction of adsorbates with hydrocarbon occurred predominantly on weak adsorption sites. 13C NMR T1 relaxometry provided in addition atom-specific adsorbate-adsorbent interaction strengths, showing the molecular geometry of adsorption, and applied in co adsorption measurements. The selective hydrogenation of citral as a model α,β-unsaturated aldehyde and the effect of different solvents on the activity and product distribution was studied at 298 and 373 K. A series of polar protic, polar aprotic and non polar solvents was investigated. Results showed higher initial reaction rates in non polar solvents but higher selectivities towards desired products on polar protic solvents. Solvent used also affected by product formation. The strong variations in reaction rates and selectivities reported were related with adsorbate catalyst interactions, as well as solvent reactant interactions. For example, adsorption isotherms showed that ethanol notably reduced the adsorption capacity of citral as compared with hexane, related with the rate differences observed. ATR-IR measurements indicated solvent citral interactions were solely present in polar protic solvents in line with higher yields of geraniol and nerol. Finally, 13C T1 NMR and 1H 2D T1-T2 correlation experiments determined that the geometry of adsorption of citral, influenced by solvent, affected product selectivity, and that product adsorption affected selectivity and deactivation.