The kinetics of nonylphenol and p-cresol destruction by hydrogen peroxide photolysis and Fenton's reaction was investigated under a variety of operating conditions in homogeneous, laboratory-scale batch reactor experiments. Models with no adjustable parameters successfully accounted for radical initiation by photolysis of H 2 O 2 or radical initiation by Fenton's mechanism, reaction of organic targets with hydroxyl radical, and radical scavenging and recombination mechanisms, as well as changes in solution pH due to evolution of carbon dioxide because of target mineralization. Simulations of the UV/H 2 O 2 and Fenton-based models can be used to anticipate the kinetics of advanced oxidation involving any target compound for which there is a known apparent second-order rate constant for reaction with hydroxyl radical. The presence of radical scavengers was successfully treated by the model, suggesting that the model can be generalized to the treatment of complex matrixes.
Solar-UV/H 2 O 2 advanced oxidation for destruction of trace organics was investigated under a variety of operating conditions in homogeneous, laboratory-scale batch reactor experiments. Fluorescein and p-cresol were selected as representative targets in the experiments. Half times for degradation of p-cresol ranged between 500 min with 2 mM H 2 O 2 and 20 min with 50 mM H 2 O 2 during high-solar irradiance experiments (around noon on July 15th). A kinetic model, previously developed for monochromatic light, was adapted for use with solar UV irradiance, using (i) calculated ground-level solar spectral irradiance for the date and time of the experiments and (ii) wavelength-dependent light attenuation in the reaction mixture. The model accurately represents experimental data without adjustable parameters. Model output included the time-dependent pH arising from complete mineralization of the targets. Observed radical scavenging effects were correctly predicted by the kinetic model. Contaminant transformation was also measured in a municipal secondary wastewater effluent matrix. Here, 2-D fluorescence spectroscopy was used as a measure of the time-dependent bulk organic characteristics in treated wastewater. Results indicated that solar-UV/H 2 O 2 advanced oxidation is capable of eliminating or drastically reducing the concentrations of organic constituents that remain in conventionally treated municipal wastewater effluent.
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