Ozone in surface air is the primary cause of polluted air in the United States. The current ozone observing network is insufficient either to assess air quality or to fully inform our understanding of the factors controlling tropospheric ozone. This thesis investigates the benefit of an instrument in geostationary orbit for observing near surface ozone using Observing System Simulation Experiments (OSSEs). / Earth and Planetary Sciences

Land surface areas, which represent approximately 30% of the Earth’s surface, contribute largely to the complexity of the climate system by exchanging water, energy, momentum, and chemical materials with the overlying atmosphere. Because of the highly heterogeneous nature of the land surface and its rapid transformation due to human activities, future climate projections are less certain on regional scales than for the globe as a whole. The work presented in this dissertation is focused on a better understanding of regional-scale land–atmosphere interactions and their impacts on climate and air quality. Specifically, I concentrate my research on three typical regions in the United States (U.S.): 1) the Central U.S. (representing transition zones between arid and wet climates); 2) the Houston metropolitan region (representing a major urban area); and 3) the eastern U.S. (representing temperate forested regions). These regions are also chosen owing to the consideration of data availability. The first study concerns the roles of vegetation phenology and groundwater dynamics in regulating evapotranspiration and precipitation over the transition zones in summer months. It is found that the warm-season precipitation in the Central U.S. is sensitive to latent heat fluxes controlled by vegetation dynamics. Groundwater enhances the persistence of soil moisture memory from rainy periods to dry periods by transferring water to upper soil layers through capillary forces. Enhancement in soil moisture facilitates vegetation persistence in dry periods, producing more evaporation to the atmosphere and resulting in enhanced precipitation, which then increases soil moisture. The second study compares the impacts of future urbanization and climate change on regional air quality. The results show that the effect of land use change on surface ozone (O3) is comparable to that of climate change, but the details differ across the domain. The third study deals with the formation and distributions of secondary organic aerosols (SOA) — a largely overlooked but potentially important component in the climate system. Under future different climate scenarios, I found that biogenic emissions — an important precursor of SOA — are expected to increase everywhere over the U.S., with the largest increase found in the southeastern U.S. and the northwestern U.S., while changes in SOA do not necessarily follow those in biogenic emissions. Other factors such as partitioning coefficients, atmospheric oxidative capability, primary organic carbon, and anthropogenic emissions also play a role in SOA formation. Direct and indirect impacts from climate change complicate the future SOA formation. / text

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Passive removal materials (PRMs) are building materials or furnishings that can effectively control indoor pollution without substantial formation of chemical byproducts and without energy penalty. To assess clay wall plaster as an effective PRM for improving air quality by controlling ozone, perceived air quality (PAQ) was determined in the presence of eight combinations of an emitting and reactive pollutant source (new carpet), clay plaster applied to gypsum wallboard, and chamber air with and without ozone. A panel of 18 to 23 human subjects assessed air quality in twin 30 m3 chambers using a continuous acceptability scale. Air samples were collected immediately prior to panel assessment to quantify concentrations of C5 to C10 saturated n-aldehydes and two aromatic aldehydes that are commonly produced by reaction of ozone with carpet. Perceived Air Quality was most acceptable and concentrations of aldehydes were lowest when only clay plaster or both clay plaster and carpet were present in the chambers without ozone. The least acceptable PAQ and the highest concentrations of aldehydes were observed when carpet and ozone were present together; addition of clay plaster for this condition improved PAQ and considerably decreased aldehyde concentrations. Ozone deposition and byproduct emissions of the clay wall plaster were also assessed using 48 liter stainless steel chambers. Clay plaster applied to gypsum wallboard that had been exposed in a test house (UTest House) for one year effectively removed 88% of the ozone, and emitted high aldehyde concentrations when exposed to high purity air that did not increase when the material was exposed to ozone. The outcome of these experiments leads to speculation that the clay plaster adsorbed contaminants in the test house and then re-emitted them upon exposure to clean air in the small chambers. / text

Research in the use of ozone in water treatment conducted by many authors support the idea that the nature and characteristics of natural organic matter (NOM) present in raw water determines the efficiency of ozonation in water purification. An ozone contact chamber was designed and made to allow pre-ozonation of water to take place. The concentration of ozone in the chamber was determined using the Indigo method. For the duration of one year, water samples were collected from four different sampling sites and analyzed to determine their overall ecological status with regard to several variables such as pH, chlorophyll-a, SAC254, turbidity, DOC, algal species composition and sum of NOM. Two dams sites and two riverine sites were chosen, Hartbeespoort Dam (a hyper-eutrophic impoundment), Boskop Dam (a mesotrophic impoundment), Midvaal Water Company at Orkney and Sedibeng Water at Bothaville. The samples were treated in Jar Tests with FeCI3 and the same variables were measured. Preozonation followed by Jar Tests was performed on each sample at twoconcentrations of ozone and the variables were measured to examine the efficiency of ozonation. In general, the ph was high and stayed the same for all the samples and for all the treatments. DOC was variable and showed no relationship to any other variable or to the treatments. Hartbeespoort Dam was found to be a eutrophic impoundment characterized by high algal bloom of the cyanobacteria Microcystis sp., Turbidity, SAC254, and the sum of NOM were lower than for the riverine sites but higher than for Boskop Dam. The NOM constituted more intermediate molecular weight(1MW)and low molecular weight (LMW) fractions than the riverine sites. Ozone was effective in reducing chlorophyll-a, turbidity and SAC254 from Hartbeespoort Dam, but the presence of large numbers of algal cells interferes with its efficiency. Release of cell-bound organics after ozonation can lead to increases instead of decreases in these variables. Jar Test results demonstrate that ozonation improves water quality when compared to conventional treatment although the interference of algal cells can alter results. Boskop Dam is a mesotrophic impoundment characterised by low productivity, low SAC254, tow turbidity and low sum of NOM. However, it has a large portion of the LMW fraction of NOM present. This LMW fraction affects the treatment process as this fraction is not acted upon by ozone. Therefore it was found that ozonation did not improve the quality of the water when compared to conventional treatment. The two riverine sites, Midvaal and Sedibeng were similar to each other. Both sites had high algal productivity with high chlorophyll-a values indicative of algal blooms observed at certain times. These blooms consisted either of members of Bacillariophyceae or Chlorophyceae. High turbidity and SAC254 was observed during the rainy season and was related to the high percentage HMW and IMW fractions of NOM present. There was correlation between the turbidity and SAC254 of these sites leading to the assumption that the turbidity of the river is due to the presence of HMW humic fractions of NOM. Ozonation was effective in improving water quality with respect to turbidity, SAC254 and chlorophyll-a removal, both on its own and after conventional treatment when combined with a coagulant. However, the species of algae present affects ozonation as members of Bacillariophyceae are not affected by the actions of ozone because of the presence of a silica frustule whereas members of Chlorophyceae are easily removed by ozone. In general, ozone acts upon the HMW and LMW fractions of NOM causing them to breakdown into smaller fractions. Ozone has no effect on samples that have a high percentage of the LMW fraction of NOM. This LMW fraction is more readily removed by conventional treatment than by ozonation. The presence of large numbers of algal cells as well as the species of cells can negatively affect the treatment process with regard to ozone. / Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007.

Atlanta is one of the largest metropolitan areas in the southeastern United States and is the only area in the region currently listed in “serious” 1-hour ozone nonattainment. Despite its exceedance history, impacts on Atlanta’s urban forests have not been the focus of any major studies. The purpose of this study was to examine air pollution damage to vegetation using a foliar-injury survey on Stone Mountain. The objectives of this project included 1) establishing that pollution transport from Atlanta to Stone Mountain occurs, 2) determining the magnitude of ozone concentrations near Stone Mountain and 3) assessing sensitive plant species on Stone Mountain for foliar injury. Results from this study confirm that Stone Mountain is located downwind from Atlanta. Ozone concentrations were sufficiently high to damage vegetation and these consistently peaked in July. Foliar injury was present on understory species on Stone Mountain, but was not observed on loblolly pine species.

Oxidation of aqueous bromide into reactive, gas-phase bromine species has been of interest since the 1980’s, when the presence of bromine in the Arctic boundary layer was linked to ozone depletion events. We have investigated two different mechanisms for Br2 release from sea ice. We have shown that nitrate in sea ice can photolyze to produce OH, which can go on to form gas-phase Br2. This reaction is analogous to a known reaction that occurs in the aqueous phase. We have also investigated Br2 production from a heterogeneous reaction between gas-phase ozone and sea ice/seawater. We have determined ozone’s reactive uptake coefficient, and have shown how it varies with temperature, bromide concentration, ozone concentration and acidity. We have been able to decouple the bulk aqueous chemistry that occurs from the Langmuir-Hinshelwood surface chemistry, and quantify the relative contribution of each.

Oxidation of aqueous bromide into reactive, gas-phase bromine species has been of interest since the 1980’s, when the presence of bromine in the Arctic boundary layer was linked to ozone depletion events. We have investigated two different mechanisms for Br2 release from sea ice. We have shown that nitrate in sea ice can photolyze to produce OH, which can go on to form gas-phase Br2. This reaction is analogous to a known reaction that occurs in the aqueous phase. We have also investigated Br2 production from a heterogeneous reaction between gas-phase ozone and sea ice/seawater. We have determined ozone’s reactive uptake coefficient, and have shown how it varies with temperature, bromide concentration, ozone concentration and acidity. We have been able to decouple the bulk aqueous chemistry that occurs from the Langmuir-Hinshelwood surface chemistry, and quantify the relative contribution of each.

The cooperation of developing countries is commonly assumed to be essential for the establishment of effective regimes to manage global environmental interdependence. Yet their policies and perceptions have been inadequately studied. This thesis seeks to partially fill this gap in the literature with a detailed analysis of Indian policy on global environmental issues. It examines the cases of ozone depletion, climate change, and loss of biodiversity, and discusses developments up to the 1992 Earth Summit. The study addresses four broad questions about Indian policy: the process of policy making; the character of Indian interests and preferences; the nature and evolution of India's bargaining strategy; and the outcome of international negotiations for India. It reveals a complex picture of continuity and change in Indian policy. It demonstrates the enduring importance of traditions and values such as the "poverty is the greatest polluter" orthodoxy and the concepts of sovereignty, equity and Third World solidarity. It also highlights the impact of perceptions of vulnerability in relation to the North. It argues that Indian policy did not reflect purely powermaximising goals; policy makers were sometimes uncertain about where India's interests precisely lay, and felt constrained both by economic weakness and by the recognition of the mutual interest of all states in global environmental protection. This was reflected in the moderation in India's bargaining strategy. The Indian case suggests that developing countries did not regard their cooperation in the resolution of global environmental issues purely as a bargaining chip with which to extract concessions from the North. Still less did they perceive these issues as providing an opportunity to pose a macro-challenge to the North, linking agendas across issue areas. Instead, their goals reflected perceptions of constraints and mutual interests in bargaining with the North. Their bargaining strategy thus tended to be moderate and flexible, unlike the confrontational approach of the 1970s.

Oxygenated volatile organic compounds ((O)VOCs) contribute to ozone formation, affect the oxidising capacity of the troposphere and are sources of growth, and in some cases formation, of aerosols. It is therefore important to identify and quantify sources of (O)VOCs in the troposphere. In the late 1990s a unique technique for quantification of organic trace gas species, proton transfer reaction mass spectrometry (PTR-MS) was developed. PTR-MS potentially offers rapid response and high sensitivity without the need for sample pre-concentration. Concentrations can be derived from the PTR-MS either by calibration or can be calculated from measured ion count rates and kinetic considerations. In this work, the methodology of PTR-MS application is critically assessed. The uncertainties and inaccuracies associated with each parameter employed in the calculation of concentrations are reviewed. This includes a critical appraisal of models for the calculation of the collisional rate constant currently applied in the field of PTR-MS. The use of a model to account for the effects of the electric field, available in the literature but not previously applied to the PTR-MS, is advocated. Collisional rate constants employing each of the models discussed have been calculated for the reactions of H3O+ with over 400 molecules for PTR-MS. In PTR-MS it cannot be assumed that the product ion occurs only at the protonated non-dissociated mass. Few product distributions obtained from PTR-MS are cited in the literature, and even then the reaction chamber conditions (pressure, temperature and electric field strength) are not always specified. A large volume of product distributions for trace gases with H3O+ in select ion flow tube mass spectrometry (SIFT) exists in the literature and is reviewed. In SIFT, no electric field is applied to the reaction chamber and the extent and even nature of fragmentation can differ in PTR-MS. In addition to the application of an electric field, the energy in the reaction chamber can be increased by increasing the temperature or by variation of the reagent ion. In this work, the increase in energy via the three methods is approximated to enable a comparison of product distributions. The review of product distributions in PTR-MS, select ion flow drift tube mass spectrometry (SIFDT), variable temperature select ion flow tube mass spectrometry (VT-SIFT), SIFT, proton transfer reaction time of flight mass spectrometry (PTR-TOF-MS), proton transfer reaction ion trap mass spectrometry (PTR-ITMS) and electron ionisation mass spectrometry (EI-MS) is used alongside thermodynamic considerations to collate a list of potential contributors to a range of mass to charge ratios (m/z) in the PTR-MS. The need for further measurements of product distributions as a function of temperature, pressure and electric field strength for a wider range of (O)VOCs is highlighted. This enables dissociation to be better used as a tool for compound identification rather than being considered a hindrance. The collation of likely product distributions is applied to identify possible contributors to m/z observed during PTR-MS measurements of emission from cattle slurry. Field measurements were made during fertilisation of a grassland site south of Edinburgh in 2004 and 2005 and in laboratory-based measurements in 2006. Contextual reasoning, previous measurements and isotope ratios are used to narrow the list of possible contributors. Large concentrations of m/z cautiously identified as alcohols followed by a latter peak in carboxylic acids were observed during laboratory measurements. Increases in the corresponding m/z were also observed during the fertilisations. Other tentatively identified compounds emitted included phenol, methyl phenol, trimethylamine, and various sulphur containing compounds.