Spatial distribution of diurnal variations of aerosol properties in South Korea, both long term and short term, is studied by using 9 AERONET sites from 1999 to 2017 for long-term averages and from an additional 10 sites during the KORUS-AQ field campaign. The extent to which WRF-Chem model and the GOCI satellite retrieval can describe these variations is also analyzed. In daily average, Aerosol Optical Depth (AOD) at 550 nm is 0.386 and shows a diurnal variation of +20 to -30% in inland sites, respectively larger than the counterparts of 0.308 and ± 20% in coastal sites. Both the inland and coastal sites have their diurnal variation peaks in the early morning and in the evening with noontime and early afternoon valleys. In contrast, Angstrom exponent values in all sites are between 1.2 and 1.4 with the exception of the inland rural sites having smaller values near 1.0 during the early morning hours. All inland sites experience a pronounced increase of Angström Exponent from morning to evening, reflecting overall decrease of particle size in daytime. To statistically obtain the climatology of diurnal variation of AOD, a minimum of requirement of ~2 years of observation is needed in coastal rural sites, twice more than the urban sites, which suggests that diurnal variation of AOD in urban setting is distinct and persistent. AERONET, GOCI, WRF-Chem, and observed PM2.5 data consistently show dual peaks for both AOD and PM2.5, one at ~ 10 KST and another ~14 KST. While Korean GOCI satellite is able to consistently capture the diurnal variation of AOD, WRF-Chem clearly has the deficiency to describe the relatively change of peaks and variations between the morning and afternoon, suggesting further studies for the diurnal profile of emissions. Overall, the relative small diurnal variation of PM2.5 is in high contrast with large AOD diurnal variation, which suggests the need to use AOD from geostationary satellites for constrain either modeling or analysis of surface PM2.5 for air quality application.

The drivers of human health and changing climate are important areas of environmental and atmospheric studies. Among many environmental factors present in our biosphere, small particles, also known as ultrafine particles or UFPs, have direct and indirect pathways to affect human health and climatic processes. The rapid change in their properties makes UFPs dynamic and often challenging to quantify their effect on health and radiative forcing. To reduce uncertainty in the climate effects of UFPs and to strengthen the evidence on health effects, accurate characterizations of physical and chemical properties of UFPs are needed. In this thesis, two broad aspects of UFPs were investigated: (1) the development of particle instrumentation to study particle properties; and (2) measurement of physical and chemical properties of UFPs relevant to human health and climate. These two broad aspects are divided into four specific aims in this thesis. The measurement of UFP concentration at different locations in an urban location, from roadside to various residential areas, can be improved by using a mobile particle counter. A TSI 3786 Condensation Particle Counter (CPC) was modified for mobile battery-power operation. This design provided high-frequency, one second time resolution measurements of particle number and carbon dioxide (CO2). An independent electric power system, a central controller and robust data acquisition system, and a GPS system are the major components of this mobile unit. These capabilities make the system remotely deployable, and also offer flexibility to integrate other analog and digital sensors. A Volatility Tandem Differential Mobility Analyzer (V-TDMA) system was designed and built to characterize the volatility behavior of UFPs. The physical and chemical properties of UFPs are often challenging to measure due to limited availability of instruments, detection limit in terms of particle size and concentration, and sampling frequency. Indirect methods such as V-TDMA are useful, for small mass (<1 µg/m3), and nuclei mode particles (<30nm). Another advantage of V-TDMA is its fast response in terms of sampling frequency. A secondary motivation for building a V-TDMA system was to improve instrumentation capability of our group, thus enabling study of kinetic and thermodynamic properties of novel aerosols. Chapter four describes the design detail of the built V-TDMA system, which measures the change in UFP size and concentration during heated and non-heated (or ambient) condition. The V-TDMA system has an acceptable penetration efficiency of 85% for 10 nm and maintains a uniform temperature profile in the heating system. Calibration of V-TDMA using ammonium sulfate particles indicated that the system produces comparable evaporation curves (in terms of volatilization temperature) or volatility profiles to other published V-TDMA designs. Additionally the system is fully programmable with respect to particle size, temperature and sampling frequency and can be run autonomously after initial set up. The thesis describes a part of yearlong study to provide a complete perspective on particle formation and growth in a rural and agricultural Midwestern site. Volatility characterizations of UFPs were conducted to enable inference about particle chemistry, and formation of low volatile core or evaporation resistant residue in the UFP in the Midwest. This study addresses identification of the volatility signature of particles in the UFP size range, quantification of physical differences of UFPs between NPF1 and non-NPF events and relation of evaporation resistant residue with particle size, seasonality and mixing state. K-means clustering was applied to determine three unique volatility clusters in 15, 30, 50 and 80 nm particle sizes. Based on the proposed average volatility, the identified volatility clusters were classified into high volatile, intermediate volatile and least volatile group. Although VFR alone is insufficient to establish chemical composition definitively, least volatile cluster based on average volatility may be characteristically similar to the pure ammonium sulfate. The amount of evaporation residue at 200 °C was positively correlated with particle size and showed significant correlation with ozone, sulfur dioxide and solar radiation. Residue also indicated the presence of external mixture, often during morning and night time. Air quality science and management of an accidental urban tire fire occurring in Iowa City in May and June of 2012 were investigated. Urban air quality emergencies near populated areas are difficult to evaluate without a proper air quality management and response system. To support the development of an appropriate air quality system, this thesis identified and created a rank for health-related acute and chronic compounds in the tire smoke. For health risk assessment, the study proposed an empirical equation for estimating multi-pollutant air quality index. Using mobile measurements and a dispersion model in conjunction with the proposed air quality index, smoke concentrations and likely health impact were evaluated for Iowa City and surrounding areas. It was concluded that the smoke levels reached unhealthy outdoor levels for sensitive groups out to distances of 3.1 km and 18 km at 24 h and 1h average times. Tire smoke characterization was another important aspect of this study which provided important and new information about tire smoke. Revised emission factors for coarse particle mass and aerosol-PAH and new emission factors and enhancement ratios values for a wide range of fine particulate mass, particle size (0.001-2.5 µm), and trace gas were estimated. Overall the thesis added new instrumentation in our research group to measure various physical properties such as size, concentration, and volatility UFP. The built instruments, data processing algorithm and visualization tools will be useful in estimation of accurate concentration and emission factors of UFP for health exposure studies, and generate a fast response measurement of kinetic and thermodynamics properties of ambient particles. This thesis also makes a strong case for the development of an air quality emergency system for accidental fires for urban location. It provides useful evaluation and estimation of many aspects of such system such as smoke characterization, method of air quality monitoring and impact assessment, and develops communicable method of exposure risk assessment.

In June 2008, the Cedar River crested flooding more than 5,000 Cedar Rapids homes. Residents whose homes were flooded were invited to participate in this study. We characterized exposures and symptoms experienced by individuals inhabiting 73 flood-damaged homes. Exposures and questionnaire-based health assessments were compared at two levels of remediation, in-progress and completed. Homes with remediation in-progress (n=24), as compared to the completed homes (n=49), had significantly higher airborne concentrations of mold, bacteria, iPM, endotoxin and glucan. Residents of in-progress homes had a significantly higher prevalence of doctor diagnosed allergies (adjusted OR=3.08; 95%CI: 1.05-9.02) and all residents had elevated prevalence of self-reported wheeze (adjusted OR=3.77; 95%CI: 2.06-6.92) and prescription medication use for breathing problems (adjusted OR=1.38; 95%CI: 1.01-1.88) after the flood as compared to before. Proper post-flood remediation led to improved air quality and lower exposures among residents living in flooded homes. Recognition of endotoxin as a proinflammatory ligand for pattern recognition receptors has increased the demand for endotoxin assessment in studies of environmental lung disease. Measurements using the Limulus amebocyte lysate (LAL) assay of air and reservoir dust samples are routinely incorporated into epidemiologic studies. However, it is unknown if endotoxin reactivity in the LAL assay varies by its physical presentation as aggregates, as membrane components of whole bacteria or as shed membrane blebs or if this parallels differences in the inflammatory potency of endotoxin in vivo. Endotoxins as14C-labeled-lipooligosaccharide (14C-LOS) and 14C- labeled-lipopolysaccharide (14C-LPS) were produced from Neisseria meningitidis and Escherichia coli. The reactivity of the endotoxin presentations was assessed in the LAL assay and in vivo using a murine model. The LAL assay significantly underestimated the quantity of endotoxin in the whole bacteria form whereas there was no significant difference in detecting endotoxin in aggregate and bleb forms. The failure of the LAL assay to equally quantify endotoxin was not mirrored in vivo where all three presentations of endotoxin were equally inflammatory. The inability of the LAL assay to detect the full quantity of endotoxin presented in the whole bacteria form has troubling implications for exposure assessment studies. Various extraction methods were applied to samples of known endotoxin quantity to improve the detection ability of the LAL assay. Extraction using EDTA and Tris/EDTA significantly improved the detection of endotoxin compared to the reference method of extracting in pyrogen-free water. These extraction methods also significantly increased the quantity of endotoxin measured in house and barn dust samples. A higher quantity of endotoxin measured in the LAL assay corresponded to a higher neutrophilic response in vivo. A standardized methodology for endotoxin detection that mimics the in vivo response is necessary for accurate and consistent endotoxin analysis.

Ozone in indoor environments can pose a health risk to human occupants; around half of exposure to this pollutant occurs inside buildings. One approach to reducing indoor O3 levels is to mitigate O3 as it enters a building via outdoor air ventilation supply. Often, mechanical systems that introduce outdoor air into buildings are placed on building rooftops. At the urban scale, greenery has been shown to reduce levels of some harmful pollutants, including ozone and cities like Portland, OR, are mandating green roofs be built on large commercial buildings to increase urban green surfaces. We investigate if rooftop vegetation may act as a sink for O3 as transport occurs across a green roof. It is known that O3 can react with vegetated surfaces and the ground but there is scant empirical research on said pollutant dynamics on vegetated green roofs, and little data concerning pollutant interactions occurring on other rooftop designs. Essentially unstudied is the potential of rooftop designs to affect local concentrations of pollutants where building outdoor air supply may be co-located. In this study, we investigate O3 dry deposition using resistance uptake theory in an area that includes a green roof on a local big box retail store through a field study conducted during a two-week period in the Summer of 2017. Deposition velocities and subsequently surface resistances were measured. The 10th, 50th, and 90th percentiles for resistances were 54.8 s/m, 195.3 s/m, and 3692.9 s/m respectively. A 2-D advection-diffusion model of rooftop deposition is employed to describe transport across the green roof and sensitivity analysis was performed to compare the impact of different parameters. The sensitivity analysis demonstrated that the fetch length and the vegetation height had the biggest impact, followed by the meteorological parameters; the friction velocity and heat flux. The surface resistance had the least impact on deposition. An ideal case was used to demonstrate that even when conditions are maximized for deposition, the impact on the concentration gradient is minimal at best.

Sensors with very low power consumption are required so that they can last a long time without the need to replace the batteries very often. Low power sensors can save significant cost and time incurred in battery replacement, especially in establishments and organizations that span over several buildings, floors and rooms. In this thesis, we investigate the use of the low-power wireless protocol Z-wave for sensors solutions that can last for approximately 10 years. An algorithm was created and we concluded that 10 years on a 480 mAh battery is not possible and the expected years need to be lowered or we need to increase the battery capacity.

The impacts of transported and locally-produced pollutants on western US air quality during summer 2008 are studied using the multi-scale Sulfur Transport and Deposition Modeling system. Transported background (TBG) is an indicator of the influences from extra-regional emissions or the lower stratosphere. The magnitude of TBG is expected to increase as the emissions from international sources grow. This trend is especially important in the context of US air quality standards, which tend to become more stringent to protect human health and ecosystems. Forward sensitivity simulations in which the model boundary conditions and emissions are perturbed show that TBG strongly and extensively affect western US surface ozone (more than half of the total), compared to other contributors to background ozone (North American, NA, biomass burning, BB and biogenic emissions), and the impacts differ among various geographical regions and land types. The stratospheric ozone impacts are weak. The TBG ozone contributes most to western US ozone among all TBG species, and TBG peroxyacetyl nitrate is the most important species among ozone precursors. Compared to monthly mean 8-hour daily maximum ozone, the secondary standard metric "W126 monthly index" shows larger responses to TBG perturbations and stronger non-linearity to the size of perturbations. Overall the model-estimated TBG impacts negatively correlate to the vertical resolution and positively correlate to the horizontal resolution. The estimated TBG impacts weakly depend on the magnitude of uncertainties in the US anthropogenic emissions. The transport/subsidence processes that link airmasses aloft with the surface pollution level are analyzed by trajectories, time-lag correlation and adjoint sensitivity analyses. Various types of observations are used to identify source regions and transport processes, and to improve model prediction using the four-dimensional variational data assimilation during a long-range transport episode. The sectoral and geographical contributions to summertime US black carbon (BC) distributions are studied. NA emissions heavily (>70%) affect the BC levels from the surface to 5 km, while non-NA plumes compose more than half of the BC above 5 km. NA and non-NA BB, NA transportation and non-NA residential emissions are the major contributing sectors. Aircraft measurements during the California phase of the Arctic Research of the Composition of the Troposphere from Aircraft andSatellites (ARCTAS-CARB) field campaign show that BC/(organic matter + nitrate + sulfate) mass ratios fairly well represent BC's warming potential over southern California, which can be approximated by BC/(organic matter + sulfate) and BC/sulfate for plumes affected and unaffected by fires, respectively. The responses of BC/(organic matter + sulfate) and BC/sulfate to removing each emission sector indicate that mitigating NA transportation emissions has the highest potential for regional air quality and climate co-benefits. Contributions from NA BB and extra-regional emissions differ for summer and spring (April 2008).

Chapter II describes results from 197 rural households that were sampled over five continuous days for indoor and outdoor PM10, PM2.5, and endotoxin. Geometric mean indoor concentrations of PM10 and PM2.5 (21.2 πg m-3, 12.2 πg m-3) were larger than outdoor concentrations (19.6 πg m-3, 8.2 πg m-3; p =0.072, p<0.001). While geometric mean endotoxin levels were almost six times larger in outdoor air compared to indoor (1.47 EU m-3, 0.23 EU m-3; p <0.001). Airborne PM10 and endotoxin concentrations in a rural county were elevated compared to those previously reported in certain urban areas. Furthermore, during the harvest season, concentrations of endotoxin in ambient air approached levels that have been shown to cause decreased respiratory function in occupational workers. Chapter III evaluated the effectiveness of using Radiello passive monitors to measure hydrogen sulfide (H2S) in close proximity (<40 m) to a medium sized CAFO. A total of eight passive H2S monitors were deployed 7-14 days around a swine confinement for seven months. Additionally, a separate laboratory study was carried out to determine the monitor's H2S uptake rate. Concentrations of H2S measured near the confinement were varied and ranged from 0.6 to 95 ppb depending on the sampling period and proximity to the lagoon .The uptake rate provided by the supplier (0.096 ng ppb-1 min-1) was significantly larger (p=0.002) than the rate determined experimentally (0.062 ng ppb-1 min-1). In Chapter IV we evaluated the association between residential proximity to swine operations and childhood asthma. A metric was created to determine children's relative environmental exposure to swine CAFOs which incorporated facility size and distance and direction of the CAFO to the home. When controlling for six significant asthma risk factors, children with a larger relative environmental exposure to CAFOs had a significantly increased risk of physician-diagnosed asthma (OR=1.20, p=0.009). In stratified analysis that adjusted for a respiratory infection before the age of two years, the association between relative exposure and childhood asthma was significantly increased in children with a respiratory infection (OR=1.45, p=0.001) but not in children free from respiratory infection (OR=1.12, p=0.355).

Some suburbs within North West (NW) metropolitan Adelaide have lung cancer mortality up to twice that expected from state averages. Previous international research investigating high lung cancer rates in similar shared industrial and residential areas have had inconsistent results. This case control study was conducted to determine whether residential exposure to industry is a risk factor for lung cancer in NW Adelaide. Contemporary ambient air monitoring was undertaken as an indicator of future respiratory health risk. 142 lung cancer patients and 415 age, gender matched population controls were interviewed utilising an event history calendar. Lifetime exposure indices were calculated for cigarette smoking, passive smoking, occupation, air pollution (residential proximity to industry) and hobbies. Data was analysed utilising chi- quared and conditional logistic regression. Ambient carcinogens and fine particulates with potential industrial sources in the region were monitored in five locations. In the final multivariate model leaving school early, pack- years of cigarettes and not living in close proximity to the power station or light industrial area were statistically significant risk factors for lung cancer. A composite score of residential exposure to all industries was not significant. However cautious interpretation is required as it was noted participating controls resided significantly closer to industry than non-participants. Average concentrations of ambient carcinogens were within guidelines; however diesel exhaust particulate and Polycyclic Aromatic Hydrocarbons were elevated at sites in proximity to heavy vehicle traffic. Diurnal variations in PM[subscript 2.5] included weather and traffic-related short term peaks, and other peaks potentially related to industrial activity. Cigarette smoking is likely to be the primary cause of elevated lung cancer mortality in suburbs of NW Adelaide. The negative effect of residential exposure to two industries may be due to participation bias. Whilst having more thorough exposure assessment than previous research, this study may have been limited by low participation rates in cases and controls. Air monitoring data suggests there is not a significant public health risk at present; however these results are unlikely to be indicative of historical exposures. Future public health initiatives to curb high lung cancer mortality in the NW should focus on smoking prevention and reduction strategies. / Thesis (Ph.D.)--Department of Medicine and Department of Public Health, 2004.

The EPA press release dated February 23, 2004 states that the three Buckeye Egg Farm facilities had the potential to emit more than a combined total of 1850 tons per year of particulate matter (PM). This number was based on flowrate calculations that were three times higher than those measured as well as a failure to include particle size distributions in the emissions calculations. The annual PM emission for each facility was approximately 35 tons per year. The EPA was unjustified in requiring Buckeye Egg Farm to obtain Title V and PSD permits as the facilities could not have met the thresholds for these permits. Engineers need to be concerned with correctly measuring and calculating emission rates in order to enforce the current regulations. Consistency among regulators and regulations includes using the correct emission factors for regulatory permitting purposes. EPA has adopted AERMOD as the preferred dispersion model for regulatory use on the premise that it more accurately models the dispersion of pollutants near the surface of the Earth than ISCST3; therefore, it is inappropriate to use the same emission factor in both ISCST3 and AERMOD in an effort to equitably regulate PM sources. For cattle feedlots in Texas, the ISCST3 emission factor is 7 kg/1000 hd-day (16 lb/1000 hd-day) while the AERMOD emission factor is 5 kg/1000 hd-day (11 lb/1000 he-day). The EPA is considering implementing a crustal exclusion for the PM emitted by agricultural sources. Over the next five years, it will be critical to determine a definition of crustal particulate matter that researchers and regulators can agree upon. It will also be necessary to develop a standard procedure to determine the crustal mass fraction of particulate matter downwind from a source to use in the regulatory process. It is important to develop a procedure to determine the particulate matter mass fraction of crustal downwind from a source before the crustal exclusion can be implemented to ensure that the exclusion is being used correctly and consistently among all regulators. According to my findings, the mass fraction of crustal from cattle feedlot PM emissions in the Texas High Plains region is 52%.

In this thesis the sink-effect in indoor materials wasstudied using mathematical modelling and experimental studies.The sink-effect is a concept which is commonly used tocharacterise the ability of different indoor materials to sorbcontaminants present in the indoor air. The sorption process ismore or less reversible, i.e. molecules sorbed in materials athigh contaminant concentrations may again be desorbed at lowerconcentrations. Knowledge of the sorption capacity of materialsand the rate at which sorption and desorption takes place is offundamental importance for mathematical simulation of indoorair quality. The aim of this work is to contribute withknowledge about how the sink-effect can be described inmathematical terms and how the interaction parametersdescribing the sorption capacity and sorption/desorptionkinetics can be determined. The work has been of amethodological nature. The procedure has been to set upphysically sound mathematical models of varying complexity andto develop small-scale chamber experiments. Two differentdynamic chamber methods have been used. One is based on amodified standard FLEC-chamber while the other uses a chamberwith two compartments, one on each side of the material. The"twin-compartment" method was designed due to the observationthat the contaminant readily permeated straight through theselected materials, which resulted in uncontrolled radiallosses in the FLEC-chamber. In order to be useful forcomparison between experiments and calculations and parameterfitting, the boundary conditions in the chambers must beprecisely known and controlled. This matter has shown to be themost crucial and difficult problem in the research. A varietyof mathematical models for the sink-effect have been proposed.In some models advanced fluid simulations were used in order totest the influence ofill-defined flow boundary conditions. Theaim of the modelling is to find a formulation with a minimum ofinteraction parameters, which is generally useful, i.e. both insmall-scale laboratory environments and in full-scale like anoffice room. Estimated model parameters are shown to be able toyield a reasonably good fit to experimental data for thesorption process but a less satisfactory fit for the desorptionprocess. <b>Keywords:</b>sink-effect, sorption, adsorption, diffusion,indoor air quality, volatile organic compounds, VOC,contaminants, building materials