Date of Award
Wiley, John B.
Suwannee River fulvic acid (SRFA) and humic acid (SRHA) were used as dissolved organic matter (DOM) and were applied to probe the effect of DOM. Addition of DOM resulted in decreased first order rate constants for all species selected. The inhibition became more significant as the hydrophobicity of the species increased. The decrease could not be simply attributed to the binding of hydrophobic species to DOM. This can be explained by the physical isolation of iron (II), which binds to hydrophilic sites of DOM and is the hydroxyl radical generation site, from hydrophobic pollutants which bind to hydrophobic sites of DOM. Accordingly, species which could compete agains t this physical isolation by DOM and bring iron (II) closer to target species could increase the degradation rates. This was observed with application of carboxymethyl-ß-cyclodextrin (CMßCD). Effects from concentration, structure of the target species and acidity etc., were studied. The increased degradation rates were observed even in the presence of DOM. Studies on ternary complexes of hydrophobic pollutants, iron (II) and CMßCD were carried with ESMS, UV and Fluorescence experiments and further calixarene derivatives. Along with the fact that CMßCD can increase the solubility of hydrophobic species and remove them from contaminated sites, this indicates a potential application to in-situ degradation systems. Initial two -phase studies were carried out with quartz sand deposited with polycholobiphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs). Successful degradations were observed with PCBs but not PAHs. The difference is attributed to the slow equilibrium of sorbed PAHs with dissolved CMßCD and the higher PAH loading used in these experiments. A halide sensor-molecule (1, 8-diphenylureaylnaphthalene), which performs with increasing fluorescence in the presence of fluoride and decreasing fluorescence with all other halides, was synthesized and reported. Studies using NMR and computer modeling with SPARTAN were carried out to compare the sensor-molecule with an analog, 2, 3-diphenylureaylnaphthalene. Both studies indicated that only fluoride can be accommodated in the space between the urea group protons to form a strong interaction. The sensor-molecule could to lead to improved sensors that overcome limitations with current fluorescence-quenching based anion sensors.
Xu, Guoxiang, "Environmental Remediation with Fenton Reagents and Synthesis of a Novel Halide Fluorescence Sensor" (2005). University of New Orleans Theses and Dissertations. 144.