TY - JOUR
T1 - Rapid degradation of brominated and iodinated haloacetamides with sulfite in drinking water
T2 - Degradation kinetics and mechanisms
AU - Ding, Shunke
AU - Wang, Feifei
AU - Chu, Wenhai
AU - Cao, Zhongqi
AU - Pan, Yang
AU - Gao, Naiyun
PY - 2018/10/15
Y1 - 2018/10/15
N2 - The effective removal of haloacetamides (HAMs) as a group of emerging disinfection by-products is essential for drinking water safety. This study investigated the degradation of 10 HAMs, including chlorinated, brominated, and iodinated analogues, by sodium sulfite (S(IV)) and the mechanism behind it. The results indicated that all HAMs, excluding chlorinated HAMs, decomposed immediately when exposed to S(IV). The reductive dehalogenation kinetics were well described by a second-order kinetics model, first-order in S(IV) and first-order in HAMs. The degradation rates of HAMs increased with the increase of pH and they were positively correlated with sulfite concentration, indicating that the reaction of S(IV) with HAMs mainly depends on sulfite. The rank order and relative activity of the reaction of sulfite with HAMs depends on bimolecular nucleophilic substitution reaction reactivity. The order of the reductive dehalogenation rates of HAMs versus the substitution of halogen atoms was iodo- > bromo- >> chloro-. During reductive dehalogenation of HAMs by sulfite, the α-carbon bound to the amide group underwent nucleophilic attack at 180° to the leaving group (halide). As a consequence, the halide was pushed off the opposite side, generating a transition state pentacoordinate. The breaking of the C-X bond and the formation of the new C-S bond occurred simultaneously and HAM sulfonate formed as the immediate product. Results suggest that S(IV) can be used to degrade brominated and iodinated HAMs in drinking water and therefore should not be added as a quenching agent before HAM analysis to accurately determine the HAM concentrations produced during water disinfection.
AB - The effective removal of haloacetamides (HAMs) as a group of emerging disinfection by-products is essential for drinking water safety. This study investigated the degradation of 10 HAMs, including chlorinated, brominated, and iodinated analogues, by sodium sulfite (S(IV)) and the mechanism behind it. The results indicated that all HAMs, excluding chlorinated HAMs, decomposed immediately when exposed to S(IV). The reductive dehalogenation kinetics were well described by a second-order kinetics model, first-order in S(IV) and first-order in HAMs. The degradation rates of HAMs increased with the increase of pH and they were positively correlated with sulfite concentration, indicating that the reaction of S(IV) with HAMs mainly depends on sulfite. The rank order and relative activity of the reaction of sulfite with HAMs depends on bimolecular nucleophilic substitution reaction reactivity. The order of the reductive dehalogenation rates of HAMs versus the substitution of halogen atoms was iodo- > bromo- >> chloro-. During reductive dehalogenation of HAMs by sulfite, the α-carbon bound to the amide group underwent nucleophilic attack at 180° to the leaving group (halide). As a consequence, the halide was pushed off the opposite side, generating a transition state pentacoordinate. The breaking of the C-X bond and the formation of the new C-S bond occurred simultaneously and HAM sulfonate formed as the immediate product. Results suggest that S(IV) can be used to degrade brominated and iodinated HAMs in drinking water and therefore should not be added as a quenching agent before HAM analysis to accurately determine the HAM concentrations produced during water disinfection.
KW - Disinfection by-products
KW - Haloacetamides
KW - Reductive dehalogenation
KW - Sodium sulfite
KW - Sulfonate
UR - http://www.scopus.com/inward/record.url?scp=85053069719&partnerID=8YFLogxK
U2 - 10.1016/j.watres.2018.06.049
DO - 10.1016/j.watres.2018.06.049
M3 - Article
AN - SCOPUS:85053069719
VL - 143
SP - 325
EP - 333
JO - Water Research
JF - Water Research
SN - 0043-1354
ER -