The increase in global population witnessed over recent years poses major threats to the quality of the air we breathe. Coupled with population growth in many developed countries, often driven by immigration, there have been substantial increases in the populations of developing countries. At the same time, an increasing number of individuals live in urban environments. In order to assess risk of exposure to hazardous air pollutants (air toxics) in the inner city, where a susceptible population resides, data obtained from high school students in the New York and Los Angeles TEACH (Toxic Exposure Assessment: A Columbia-Harvard Study) studies, were analyzed, with the three main objectives to: 1). Assess, characterize, quantify and compare directly-measured personal air toxics exposures from New York and Los Angeles; 2). Assess, quantify and compare the concentrations and temporal and spatial variability of air toxics measured in the outdoor urban microenvironments of these two cities; 3). Determine if personal air toxics exposures could be modeled using available time-activity information, coupled with measured microenvironmental air pollution inputs. The main findings of this research revealed substantial differences between New York and Los Angeles in the quantity and quality of particle-associated personal air toxics exposures in these two cities. Students across cities exhibited similar levels of personal exposure to particulate matter (PM 2.5) and to high levels of sulfates (greater in Los Angeles than New York; both likely of vehicular traffic origin). Different patterns of exposure to particle-associated air toxics was observed in the two cities and across seasons. In New York, students demonstrated substantially higher exposures to iron, cobalt, and manganese, likely of subway origin, than their counterparts in Los Angeles, who exhibited higher exposures to calcium, aluminum, magnesium (likely of crustal origin). Across seasons, within cities, differences were also detected, with higher levels of air toxics exposures shown in New York in the winter than in the summer for nearly 80% of the analytes, similar to the general pattern (winter vs. fall) in Los Angeles. With respect to outdoor air toxics concentrations, in general terms, crustal sources of air toxics were detected in both cities, though in Los Angeles these levels tended to be higher than in New York, often significantly. Anthropogenic sources were evident in each of the cities to varying degrees. Sulfates were detected at comparable high levels across both cities, though the levels tended to be higher and variability of concentrations of this air pollutant was greater Los Angeles than New York, likely reflecting differences both in patterns of traffic and built environment. Various approaches taken to model spatial and temporal variability of outdoor air toxics concentrations using mixed procedures showed city-specific, spatial and temporal variance patterns of air toxics. Using location and time (day) inputs, in New York, Zn, Pt, and Sn were among the elements with highest spatial variability in the summer, whereas in the winter, Co and La (possibly of subway origin) showed high spatial-temporal variance. In Los Angeles on the other hand, highest spatial to temporal variance ratios were noted for Cs, Ni and K in the fall and Ni, As and Mg in the winter. Each city also revealed different patterns of temporally dominant air toxics, consistent with variable-in-time excursions in air toxics reflecting remote, upwind sources. Using regression modeling that accounted for the distribution of measured personal air toxics, coupled with available time-activity diary data from TEACH and assignment of those activities to specific measured microenvironments, modeling of personal exposures yielded generally strong coefficients of determination, explanatory power and could be cross-validated. Important findings included the role of the indoor environment in predicting personal exposures and the degree to which a small percentage of time spent in the transit environment could affect exposures to trace elements from this source. Although the majority of elements could be predicted in large part by indoor exposures, not simply as a reflection of outdoor air toxics concentrations, the inclusion of other microenvironments, in many cases substantially increased the predictive power of the models generated. The research pursued in this thesis project further details and underscores the risk of air toxics exposures of young residents of the inner city, which, unlike workplace and environmental standards that traditionally may have been based on single exposures, are characterized by exposures to low level complex mixtures of air toxics. In aggregate, these mixtures may have different health consequences than more intense single pollutant exposures. Data generated here may help to inform planning of air quality monitoring approaches in the inner city, as well as provide one template for predictive modeling of human exposures to air toxics in that complex environment, to reduce the need for direct personal measurements to assess exposure risk. This may ultimately contribute to approaches to mitigate air toxics exposures and its consequences for an expanding global population residing in the world's inner cities.

Har, Tsoen Hei. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 53-58). / Abstract also in Chinese. / List of Figures --- p.i / List of Tables --- p.iii / List of Acronyms --- p.iv / Chapter Chapter 1: --- Introduction --- p.1 / Chapter Chapter 2: --- Background / Chapter 2.1 --- Tropical Rainfall --- p.4 / Chapter 2.2 --- Aerosol-rainfall interactions --- p.7 / Chapter Chapter 3: --- Land-sea difference in tropical rainfall / Chapter 3.1 --- Introduction --- p.11 / Chapter 3.2 --- Method / Chapter 3.2.1 --- Linear Trend Analysis --- p.12 / Chapter 3.2.2 --- Empirical Mode Decomposition --- p.13 / Chapter 3.3 --- Result --- p.16 / Chapter Chapter 4: --- Possible relation with aerosols / Chapter 4.1 --- Introduction --- p.28 / Chapter 4.2 --- Area division according to Aerosol Optical Depth (AOD) --- p.29 / Chapter 4.3 --- High aerosol areas / Chapter 4.3.1 --- Southeast China --- p.33 / Chapter 4.3.2 --- Northern India --- p.36 / Chapter 4.3.3 --- Sahara Desert --- p.38 / Chapter 4.4 --- Multifractal Detrended Fluctuation Analysis (MF-DFA) --- p.42 / Chapter Chapter 5: --- Conclusion --- p.50 / Bibliography --- p.53

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. Johannesburg, August 2015. / Petrol and diesel fumes are known to be anthropogenic sources of air pollutants that have a negative impact on both environmental and human health. In developing countries, attendants are still employed to pump fuel for customers. In South Africa gas pump attendants refuel vehicles with various octane unleaded petrol, lead replacement petrol (LRP) and diesel on a daily basis. Attendants are particularly at risk to adverse health effects associated with inhalation of hazardous air pollutants (HAPs). Of increasing concern in recent years are the volatile organic compounds (VOCs), with particular reference to the six aromatic hydrocarbons (benzene, toluene, ethyl benzene and three isomeric xylenes), namely the BTEX.

Exposure to air pollution is a leading cause of premature death worldwide. An increasing part of air pollution results from industrial activity and the production of energy. When unregulated, emissions of air pollutants constitute a market failure as polluters do not bear the costs imposed on society at large. My dissertation develops empirical methods to test the effectiveness and distributional effects of environmental policies designed to address this externality. To do so, I apply econometrics and data science techniques on large datasets from cutting-edge research in environmental science and engineering that I match with microeconomic data. The dissertation makes use of new datasets on air pollution derived from satellite imagery, as well as micro-level data on power plant operations and housing transactions across the United States. Chapter 1 assembles unit-level data to disentangle the factors that led US power plants to achieve the unprecedented reductions in emissions of the past fifteen years. I calculate the costs incurred by the electricity generation sector and compare these costs to the correspond- ing health benefits. In hedonic regressions, I use these shocks to emissions to estimate the demand for clean air with micro-level data on housing transactions. Chapter 2 studies the causal impacts and evaluates the distributional effects of stringent emissions markets that were put in place to target power plants emissions of air pollutants in the Eastern US. Chapter 3 uses new satellite imagery to document the inequalities in the exposure to air pollution in American cities and their recent evolutions.

Background: Three billion individuals worldwide rely on biomass fuel (crops, dung, wood) for cooking and heating, mostly in the developing world. Incomplete combustion of these biomass fuels in inefficient cookstoves leads to high levels of household air pollution (HAP). Health conditions resulting from HAP are responsible for approximately 1.6 million premature deaths each year. Of the diseases associated with HAP exposure, lower respiratory infections (LRIs) are the leading cause of death for children under five worldwide. There is a great need to understand the etiology of HAP-associated LRIs to inform health interventions and to improve treatments. Ultimately, however, the only way to prevent the disease burden from HAP is to stop exposure. Policies and programs to promote the use of clean fuels for cooking are a pivotal prevention strategy. Methods: All three studies draw from an established cohort in Ghana. The Ghana Randomized Air Pollution and Health Study (GRAPHS), was a cookstove intervention trial in Kintampo, Ghana. Participants were randomized to a more efficient biomass cookstove arm, a liquefied petroleum gas (LPG) stove arm, or the traditional cookstove arm (baseline). The principal outcome of GRAPHS was childhood pneumonia. The first chapter utilizes banked nasal swabs from GRAPHS to assess the relationship between HAP exposures and a panel of known respiratory pathogens. In the second chapter we leverage data on stove use during GRAPHS, and then follow a sub cohort 6 months prior to and 6 months after the GRAPHS termination date. We employ a novel construct, suspended use, to understand the factors associated with people stopping LPG use. The third chapter tests a new randomized intervention on a subset of the GRAPHS participants. We provide free cookstoves, and allocate participants to one of four arms: a behavior change intervention, an intervention where LPG fuel is directly delivered to their home, a dual intervention of behavior change and fuel delivery, or a control arm. We track their stove use to identify the most effective intervention on sustained use. Results: In Chapter 1, we find that the traditional cookstove users had a higher mean number of microbial species than the LPG (LPG: 2.71, 3-stone: 3.34, p<0.0001, n = 260). This difference was driven by increased bacterial (p<0.0001) rather than viral species presence (non-significant). Adjusted exposure-response analyses, however, produced null results. Chapter 2 identifies several factors associated with reduced or suspended LPG use of intervention cookstoves, including: experience of burns, types of food made, and access to biomass fuels. Finally, in Chapter 3 results show increased use for all three intervention arms, the largest for the direct delivery arm with an increased weekly use of 4.7 minutes per week (p<0.001). Conclusions: Transition away from traditional biomass stoves is projected to curb the health effects of HAP by mitigating exposure, but the full benefits of newer clean cookstove technologies can only be realized if use of these new stoves is absolute and sustained. This work enhances our understanding of the etiology of HAP-associated pneumonia, the drivers of clean cookstove suspension, and informs policies designed to promote clean cookstove sustained use, thus reducing the burden of disease associated with exposure. We recommend future use of the suspended use paradigm in research to inform future household energy interventions. Additionally, we encourage policymakers to incorporate health behavior change theory and approaches in cookstove intervention and promotion efforts.

Lichen sensitivity to air quality has been recognized in Europe for over 125 years: recently Federal agencies in this country have begun using lichens as air quality bioindicators. This study presents the results of three different approaches to air quality biomonitoring using lichens: (1) a lichen community analysis, (2) an elemental analysis of lichen tissue content, and (3) the growth of removable lichen transplants. The lichen community and elemental tissue content analyses were part of an air quality baseline on the Tongass National Forest in southeast Alaska. The lichen transplant experiment compared the growth of three different lichen species and evaluated and refined a transplant technique in western Oregon. Lichen communities were sampled on 50 Pinus contorta peatlands in southeast Alaska. These peatlands make good air quality biomonitoring sites because: (1) the trees are slow growing and provide stable substrates for lichen colonization; (2) many branches are at eye level, making the canopy epiphytes easily observable; (3) the scattered, open distribution of the trees allows for good air circulation on the sites; and (4) precipitation, light conditions, and relative humidity are high, which stimulate lichen growth. A total of 100 lichen species were encountered during whole-plot ocular surveys of each plot. Multivariate ordination revealed what appears to be a successional gradient represented by high cover of Bryoria species at older sites and high cover of Platismatia norvegica, P. glauca, Hypogymnia enteromorpha sens. lat. and H. inactiva at younger sites. A second pattern revealed by ordination analysis appears to be a climatic gradient with high Alectoria sarmentosa cover on moister, warmer sites, and high cover of Bryoria species on drier, colder sites. The first two gradients contained 35% and 21%, respectively, of the information in the analytical data set (cumulative r��=56%). Elemental tissue content of Alectoria sarmentosa was determined from 43 of the peatland plots in southeast Alaska. The range of values for 16 elements are reported and compared to other regional studies; the ranges of values for most elements were within normal background levels. Quality assurance techniques are described for separation of laboratory and field noise from elemental content signal. Principal components analysis was used to create three synthetic gradients of plot-level elemental content. The first three principal components captured 55% of the correlation structure among elements. Iron (r=-0.91), aluminum (r=-0.80) and chromium (r=-0.71) are all highly correlated with the first gradient. This gradient could represent sites enriched by elements from dirt; aluminum and iron silicates are both persistent and abundant components of weathered rock and soil. Potassium (r=-0.82), phosphorous (r=-0.63), zinc (r=-0.60), manganese (r=-0.58), magnesium (r=-0.51) and nickel (r=0.54) are correlated with the second gradient. Many of these elements are supplemented by salt water aerosols (Nieboer et al. 1978; Rhoades 1988). Lead (r=0.70) and cadmium (r=0.59) were correlated with the third axis. This gradients could represent enrichment from fossil fuel combustion. Recommendations for standardizing future regional studies of lichen elemental content are made. Removable lichen transplants were constructed using live thalli of known weight, a 5 cm length of nylon monofilament, silicone glue, and reusable attachment mechanisms. Transplants were returned to several sites in Western Oregon and were weighed every several months for 13 months. Reference standards for each species were used to correct for changes in lichen water content due to changes in lab humidity. Despite apparent vigor, Alectoria proved unsuitable for repeated weighings because of biomass loss due to fragmentation (average of 9% biomass loss). Growth of Evernia and Lobaria transplants differed both between species and between sites. Average growth over the 13 months for Evernia in the foothills and valley was 40% and 30% respectively; for Lobaria it was 16% and 15%. Differences in growth between species could be due to different: (1) growth rates; (2) sensitivities to air quality; (3) sensitivities to microhabitat; and (4) sensitivities to transplant trauma. Differences in growth between valley and foothill sites could be due to differences in: (1) micro- or macrohabitat conditions; and (2) air quality. / Graduation date: 1995

Secondary organic aerosol (SOA) generated through the partitioning of gas phase volatile organic carbon compounds (VOCs) into the condensed phase has both epidemiological and climatic impacts through the growth of particulate matter into relevant sizes for respiratory interactions and cloud condensation nuclei activity. Considering the complex chemistry involved with VOC oxidation and subsequent formation of SOA, bulk properties like oxidation state, often represented by O:C ratio, and volatility are used to simplify the representation of SOA in chemical transport models (CTMs) and the like [e.g. Tsimpidi et al. 2010]. This preference for bulk properties is supported by the availability of ambient measurement techniques to constrain model parameters and scenarios. The volatility of SOA is often described by treating it as a mixture of components with differing partitioning coefficients through the volatility basis set (VBS) approach rather than explicitly resolving the complex chemistry [Donahue et al., 2006]. This study presents a method of determining the volatility of an aerosol sample through the use of an optimizing thermodenuder (TD) instrument model that is used to fit laboratory data. Data collected using a volatility tandem differential mobility analyzer (VTDMA) setup consist of inlet and outlet particle size and number concentrations for select dicarboxylic acids - compounds known to contribute to atmospheric SOA. These are interpreted by the model through an iterative optimization routine to obtain estimates of volatility parameters (e.g. saturation concentrations) which are compared to available literature data. The instrument model is currently divided into two decoupled modules. The first resolves the flow field characteristics, obtaining the temperature profile, pressure variations, and radial velocity distribution of the TD, and the second resolves the gas to particle partitioning of aerosol with a given condensed-phase volatility distribution in the TD using the VBS approach as described in the literature. Solving the full hydrodynamic equations for the flow characteristics provides a better numeric representation of entry length and radial velocity variations and is an improvement over similar TD modeling studies in the literature. However, results indicate that coupling the two modules is necessary to more accurately resolve the suppression of evaporation due to buildup of organic vapors in the TD, even at the low mass concentrations involved with the presented experiments.

There has always been a desire to develop industrial processes that minimize the resources they use, and the wastes they generate. The problem is when new guidelines are forced upon long established processes, such as solvent based coating operations. This means instead of integrating an emission reduction technology into the original design of the process, it is added on after the fact. This significantly increases the costs associated with treating emissions. In this work the ultimate goal is the design of an “add-on” abatement system to treat emissions from solvent based coating processes with high destruction efficiency, and lower costs than systems in current use. Since emissions from processes that utilize solvent based coatings are primarily comprised of volatile organic compounds (VOCs), the treatment of these compounds will be the focus. VOCs themselves contain a significant amount of energy. If these compounds could be destroyed by simultaneously extracting the energy they release, operational costs could be substantially reduced. This thesis examines the use of model-based design to develop and optimize a VOC abatement technology that uses a Solid Oxide Fuel Cell (SOFC) for energy recovery. The model was built using existing HYSYS unit operation models, and was able to provide a detailed thermodynamic and parametric analysis of this technology. The model was validated by comparison to published literature results and through the use of several Design of Experiment factorial analyses. The model itself illustrated that this type of system could achieve 95% destruction efficiency with performance that was superior to that of Thermal Oxidation, Biological Oxidation, or Adsorption VOC abatement technologies. This was based upon design criteria that included ten year lifecycle costs and operational flexibility, as well as the constraint of meeting (or exceeding) current regulatory thresholds.

There has always been a desire to develop industrial processes that minimize the resources they use, and the wastes they generate. The problem is when new guidelines are forced upon long established processes, such as solvent based coating operations. This means instead of integrating an emission reduction technology into the original design of the process, it is added on after the fact. This significantly increases the costs associated with treating emissions. In this work the ultimate goal is the design of an “add-on” abatement system to treat emissions from solvent based coating processes with high destruction efficiency, and lower costs than systems in current use. Since emissions from processes that utilize solvent based coatings are primarily comprised of volatile organic compounds (VOCs), the treatment of these compounds will be the focus. VOCs themselves contain a significant amount of energy. If these compounds could be destroyed by simultaneously extracting the energy they release, operational costs could be substantially reduced. This thesis examines the use of model-based design to develop and optimize a VOC abatement technology that uses a Solid Oxide Fuel Cell (SOFC) for energy recovery. The model was built using existing HYSYS unit operation models, and was able to provide a detailed thermodynamic and parametric analysis of this technology. The model was validated by comparison to published literature results and through the use of several Design of Experiment factorial analyses. The model itself illustrated that this type of system could achieve 95% destruction efficiency with performance that was superior to that of Thermal Oxidation, Biological Oxidation, or Adsorption VOC abatement technologies. This was based upon design criteria that included ten year lifecycle costs and operational flexibility, as well as the constraint of meeting (or exceeding) current regulatory thresholds.

Atmospheric particulate matter pollution is a challenging environmental concern in both urban and remote locations worldwide. It is intrinsically difficult to control, given numerous anthropogenic and natural sources (e.g. fossil fuel combustion, biomass burning, dust, and seaspray) and atmospheric transport up to thousands of kilometers after production. In urban regions, fine particulate matter (particles with diameters under 2.5 m) is of special concern for its ability to penetrate the human respiratory system and threaten cardiopulmonary health. A second major impact area is climate, with particulate matter altering Earth s radiative balance through scattering and absorbing solar radiation, modifying cloud properties, and reducing surface reflectivity after deposition in snow-covered regions. While atmospheric particulate matter has been generally well-characterized in populated areas of developed countries, particulate pollution in developing nations and remote regions is relatively unexplored. This thesis characterizes atmospheric particulate matter in locations that represent the extreme ends of the spectrum in terms of air pollution the rapidly-developing and heavily populated Pearl River Delta Region of China, the pristine and climate-sensitive Greenland Ice Sheet, and a remote site in the Colorado Rocky Mountains. In China, fine particles were studied through a year-long field campaign at seven sites surrounding the Pearl River Delta. Fine particulate matter was analyzed for chemical composition, regional variation, and meteorological impacts. On the Greenland Ice Sheet and in the Colorado Rocky Mountains, the carbonaceous fraction (organic and elemental carbon) of particulate matter was studied in the atmosphere and snow pack. Analyses included quantifying particulate chemical and optical properties, assessing atmospheric transport, and evaluating post-depositional processing of carbonaceous species in snow.