Mechanistic studies on the degradation of gasoline oxygenates by advanced oxidation technologies and the reaction of 4-methyl-1,2,4-triazoline-3,5-dione with tetracyclopropylethylene

Gasoline oxygenates (MTBE, methyl tert-butyl ether; DIPE, di-isopropyl ether; ETBE, ethyl tert-butyl ether; TAME, tert-amyl ether) are added to gasoline to boost octane and enhance combustion. The combination of large scale use, high water solubility and only minor biodegradability has now resulted in a significant gasoline oxygenate contamination occurring in surface, ground, and drinking water systems. Combination of hydroxyl radical formation and the pyrolytic environment generated by ultrasonic irradiation (665 kHz) leads to the rapid degradation of MTBE and other gasoline oxygenates in aqueous media. ^ The presence of oxygen promotes the degradation processes by rapid reaction with carbon centered radicals indicating radical processes involving O 2 are significant pathways. A number of the oxidation products were identified. The formation of products (alcohols, ketones, aldehydes, esters, peroxides, etc) could be rationalized by mechanisms which involve hydrogen abstraction by OH radical and/or pyrolysis to form carboncentered radicals which react with oxygen and follow standard oxidation chain processes. ^ The reactions of N-substituted R-triazolinediones (RTAD; R = CH 3 or phenyl) have attracted considerable interest because they exhibit a number of unusual mechanistic characteristics that are analogous to the reactions of singlet oxygen (1O2) and offer an easy way to provide C-N bond(s) formation. The reactions of triazolinedione with olefins have been widely studied and aziridinium imides are generally accepted to be the reactive intermediates. ^ We observed the rapid formation of an unusual intermediate upon mixing tetracyclopropylethylene with 4-methyl-1,2,4-triazoline-3,5-dione in CDCl 3. Detailed characterization by NMR (proton, 13C, 2-D NMRs) indicates the intermediate is 5,5,6,6-tetracyclopropyl-3-methyl-5,6-dihydro-oxazolo[3,2- b][1,2,4]-triazolium-2-olate. Such products are extremely rare and have not been studied. Upon warming the intermediate is converted to 2 + 2 diazetidine (major) and ene product (minor). ^ To further explore the kinetics and dynamics of the reaction activation energies were obtained using Arrhenius plots. Activation energies for the formation of the intermediate from reactants, and 2+2 adduct from the intermediate were determined as 7.48 kcal moll and 19.8 kcal mol−1 with their pre-exponential values of 2.24 × 105 dm 3 mol−1 sec−1 and 2.75 × 108 sec−1, respectively, meaning net slow reactions because of low pre-exponential values caused by steric hindrance. ^

Four essays of environmental risk-mitigation

Expected damages of environmental risks depend both on their intensities and probabilities. There is very little control over probabilities of climate related disasters such as hurricanes. Therefore, researchers of social science are interested identifying preparation and mitigation measures that build human resilience to disasters and avoid serious loss. Conversely, environmental degradation, which is a process through which the natural environment is compromised in some way, has been accelerated by human activities. As scientists are finding effective ways on how to prevent and reduce pollution, the society often fails to adopt these effective preventive methods. Researchers of psychological and contextual characterization offer specific lessons for policy interventions that encourage human efforts to reduce pollution. This dissertation addresses four discussions of effective policy regimes encouraging pro-environmental preference in consumption and production, and promoting risk mitigation behavior in the face of natural hazards. The first essay describes how the speed of adoption of environment friendly technologies is driven largely by consumers' preferences and their learning dynamics rather than producers' choice. The second essay is an empirical analysis of a choice experiment to understand preferences for energy efficient investments. The empirical analysis suggests that subjects tend to increase energy efficient investment when they pay a pollution tax proportional to the total expenditure on energy consumption. However, investments in energy efficiency seem to be crowded out when subjects have the option to buy health insurance to cover pollution related health risks. In context of hurricane risk mitigation and in evidence of recently adopted My Safe Florida Home (MSFH) program by the State of Florida, the third essay shows that households with home insurance, prior experience with damages, and with a higher sense of vulnerability to be affected by hurricanes are more likely to allow home inspection to seek mitigation information. The fourth essay evaluates the impact of utility disruption on household well being based on the responses of a household-level phone survey in the wake of hurricane Wilma. Findings highlight the need for significant investment to enhance the capacity of rapid utility restoration after a hurricane event in the context of South Florida.

Four Essays of Environmental Risk-Mitigation

Expected damages of environmental risks depend both on their intensities and probabilities. There is very little control over probabilities of climate related disasters such as hurricanes. Therefore, researchers of social science are interested identifying preparation and mitigation measures that build human resilience to disasters and avoid serious loss. Conversely, environmental degradation, which is a process through which the natural environment is compromised in some way, has been accelerated by human activities. As scientists are finding effective ways on how to prevent and reduce pollution, the society often fails to adopt these effective preventive methods. Researchers of psychological and contextual characterization offer specific lessons for policy interventions that encourage human efforts to reduce pollution. This dissertation addresses four discussions of effective policy regimes encouraging pro-environmental preference in consumption and production, and promoting risk mitigation behavior in the face of natural hazards. The first essay describes how the speed of adoption of environment friendly technologies is driven largely by consumers’ preferences and their learning dynamics rather than producers’ choice. The second essay is an empirical analysis of a choice experiment to understand preferences for energy efficient investments. The empirical analysis suggests that subjects tend to increase energy efficient investment when they pay a pollution tax proportional to the total expenditure on energy consumption. However, investments in energy efficiency seem to be crowded out when subjects have the option to buy health insurance to cover pollution related health risks. In context of hurricane risk mitigation and in evidence of recently adopted My Safe Florida Home (MSFH) program by the State of Florida, the third essay shows that households with home insurance, prior experience with damages, and with a higher sense of vulnerability to be affected by hurricanes are more likely to allow home inspection to seek mitigation information. The fourth essay evaluates the impact of utility disruption on household well being based on the responses of a household-level phone survey in the wake of hurricane Wilma. Findings highlight the need for significant investment to enhance the capacity of rapid utility restoration after a hurricane event in the context of South Florida.