Sensitized photooxidation is a physicochemical process that can degrade many toxic and refractory organic pollutants. A trace quantity of sensitizer added to the waste absorbs visible light; electronically excited intermediates then transfer the energy to decompose the waste. Engeineering design criteria were developed for industrial waste treatment lagoons that would use sensitized photooxidation. Design criteria were developed regarding optimum lagoon pH, optimum sensitizer concentration, depth and sizing of lagoons, dissolved oxygen requirements, and effect of temperature on photooxidation rate. Treatment of the refractory pesticides bromacil, terbacil, and fluometuron was investigated using methylene blue and riboflavin as sensitizers. Methylene blue-sensitized photooxidation of the three pesticides was most efficient at basic pH. The optimum pH of riboflavin-sensitized photooxidaction varied and was substrate-dependent. A model was developed to predict sensitized photooxidation rate as a function of lagoon depth. The model is based on light intesnity, sensitizer extinction coefficient, and an applied quantum yeirld, all of which are integrated over wavelengths of visible light. The model serves as the basis of sizing photooxidation lagoons. A dissolved oxygen residual of 1 mg/1 was required to maintain maximum methylene blue-sensitized photooxidation rate. At least 4 mg/1 dissolved oxygen was necessary to maintain riboflavin-sensitized phooxidation at maximum levels. Oxygen uptake rates in sensitized phooxidation reactions were proportional to the concentration of substrate. Temperatures from 10 degrees to 35 degreees Celcius had no significant effect on sensitized photooxidation rates. Using the model developed, a methylene blue-sensitized phooxidation pilot lagoon was designed to treat a 30 mg/1 bromacil influent concentraion to 0.1 mg/1 bromacil in the effluent. For an influent flow of 0.263 m^3/min (0.1 MGD) waste, a 0.1 mg/1 methylene blue concentration, 36 cm depth, and 1870 m^2 surface area are required. A cost analysis was performed which indicated that sensitized photooxidation lagoons appear to be cost-compentitive with other industrial waste treatement systems.
Watts, Richard J.; Adams, V. Dean; and Middlebrooks, E. Joe, "Development of Design Criteria for Sensitizer Photooxidation Treatment Systems" (1985). Reports. Paper 17.