Degradation of chloropicrin in the presence of zero-valent iron

Halonitromethanes (HNMs) are a class of halogenated disinfection by products formed upon the addition of chlorine to water containing organic matter. Batch experiments were performed to investigate the reaction pathways and kinetics of three HNMs (chloropicrin or trichloronitromethane [TCNM], dichloronitromethane [DCNM], and chloronitromethane [CNM]) with zero-valent iron (Fe-0). All three compounds reacted rapidly in the presence of Fe-0 (1.8-4.4 g/L) with methylamine (MA) as the final product. The geometric surface area-normalized rate constants decreased with decreasing halogenation: TCNM (301 L/[h-m(2)]) > DCNM (153 L/(h-m(2))) > CNM (45.9 L/[h-m(2)]). Nitromethane, an intermediate species, rapidly reacted to form MA (302 L/[h-m(2)]). These reactions all experienced some degree of mass transfer limitation (9-73%). The average carbon and chlorine mass balances for TCNM were > 85%, indicating that the major reaction products were recovered. The degradation of TCNM and DCNM proceeded via the parallel reaction pathways of hydrogenolysis and alpha-elimination. For TCNM, 60.7 +/- 8.7% of reaction proceeded via hydrogenolysis and 39.3 +/- 6.4% via alpha-elimination. Knowledge of HNM reaction pathways and kinetics in the presence of Fe-0 may be useful for predicting the fate of these compounds in drinking water distribution systems containing cast or ductile iron pipe and for developing treatment systems for HNM removal from water.