Formation and speciation of haloacetamides and haloacetonitriles for chlorination, chloramination, and chlorination followed by chloramination.

The formation of haloacetamides (HAcAms) and haloacetonitriles (HANs) from a solution containing natural organic matter and a secondary effluent sample was evaluated for disinfection by chlorination, chloramination, and chlorination followed by chloramination (ClNHCl process). The use of preformed monochloramine (NHCl) produced higher concentrations of HAcAms and lower concentrations of HANs than chlorination, while the ClNHCl process produced the highest concentrations of HAcAms and HANs. These results indicate that the ClNHCl process, which inhibited the formation of regulated trihalomethanes compared with chlorination, enhanced the formation of HAcAms and HANs. For disinfection in the presence of bromide, brominated dihaloacetamides and dihaloacetonitriles were formed, and the trends were similar to those observed for chlorinated species in the absence of bromide. The degrees of bromine substitution of dihaloacetamides and dihaloacetonitriles were highest for chlorination, followed by the ClNHCl process and then by the NHCl process. For the ClNHCl process, HAN formation kept gradually increasing with prechlorination time increasing from 0 to 120 min, while HAcAm formation increased only until it reached a maximum at around 10-30 min. These results suggest that the prechlorination time could be reduced to control the formation of HAcAms and HANs. During chloramination, the formation of HAcAms and HANs was lower when using preformed NHCl than when chloramines were formed in situ, with higher formation of HAcAms and HANs when chlorine was added before ammonia than vice versa for the secondary effluent; this finding suggests that preformed NHCl could be used to inhibit the formation of HAcAms and HANs during chloramination.