Effects of dissolved oxygen and iron aging on the reduction of trichloronitromethane, trichloracetonitrile, and trichloropropanone

Iron metal (Fe(0)) is a potent reductant capable of reducing a wide variety of halogenated organic compounds including disinfection byproducts (DBPs). These reduction reactions may play a role in DBP fate in iron water mains and potentially could be exploited to remove DBPs from drinking water or wastewater in a packed-bed configuration. Oxidants (i.e., dissolved oxygen (DO) and chlorine) present in the water, however, may decrease the DBP degradation rate by competing for reactive sites and rapidly aging or corroding the iron surface. Thus, batch experiments were performed to investigate the effect of DO on the degradation rates of selected DBPs by Fe(0). Experiments were performed under anaerobic conditions, in initially oxygen saturated buffer without DO control, and under controlled DO (approximately 4.0 or 8.0 mg l^-1) conditions. The effect of short-term (25-105 min) iron aging in DO-containing buffer on DBP degradation rate also was investigated in separate experiments. For fresh Fe(0), the degradation rates of trichloronitromethane (TCNM) and trichloroacetonitrile (TCAN) in initially oxygen saturated buffer were similar to their respective rates under anaerobic conditions. The degradation rate of 1,1,1-trichloropropanone (1,1,1-TCP), however, decreased significantly in the presence of DO and the effect was proportional to DO concentration in the controlled DO experiments. For a DO concentration of 4 mg l^-1, the degradation rate of the three DBPs was greater for longer aging times as compared to their respective rates after 25 min, suggesting the formation of a mineral phase that increased reactivity. For a DO concentration of 8 mg l^-1, the effects of increasing aging time were mixed. TCNM degradation rates were stable for all aging times and comparable to that under anaerobic conditions. The TCAN and 1,1,1-TCP degradation rates, however, tended to decrease with increasing aging time. These results suggest that the reduction of highly reactive DBPs by Fe(0) will not be affected by the presence of DO but that the reaction rates will be slowed by DO for DBPs with slower degradation kinetics.