Effects of pH on the speciation coefficients in models of bromide influence on the formation of trihalomethanes and haloacetic acids

This study investigated effects of pH, bromide and natural organic matter (NOM) level on yields and speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) in chlorinated water. Experimental data were obtained using two water sources, one with a medium (DOC = 1.4 mg/L and SUVA = 2.60 L mg−1 m−1) and the other with higher (DOC = 7.7 mg/L and SUVA = 4.26 L mg−1 m−1) organic carbon level. The experiments employed the simulated distribution system (SDS) procedure at varying bromide concentrations and pH values of 7.0, 8.5 and 10. The speciation of THMs and dihalogenated HAAs (DHAAs) was interpreted based on the modelling of mixed halogenation yields via dimensionless ratios of bromination/chlorination reaction rates at each halogen incorporation node. The approach allowed precise modelling of the speciation of THMs and DHAAs at all examined pHs. In the case of DHAA, the dimensionless ratios of the bromination/chlorination reaction rates were not consistently affected by pH variations. For THMs, increase of pH caused the values of the dimensionless bromination/chlorination reaction rates to decrease in the case of halogenation of the initial reaction sites indicating a decreasing preference toward bromination at this reaction node. A similar trend was observed for the reactivity of dichlorinated reaction intermediate denoted as SCl2 whose formation precedes the release of CHCl3 and CHBrCl2. A similar but less consistent trend was observed for intermediate SBrCl whose halogenation yields both CHBrCl2 and CHBr2Cl. An opposite trend of increasing preference towards bromination at higher pHs was observed monobrominated intermediate SBr and in some extent dibrominated intermediate SBr2. These results help develop detailed DBP speciation models which needed to better understand the generation and potential health effects of THMs and HAAs at varying operating conditions and ultimately to adopt measure to minimize their levels in drinking water systems. [Display omitted] •A model on the kinetic theory of halogen incorporation into reactive sites in NOM is used.•The speciation of THMs and HAAs at varying Br, SUVA and pH was accurately modelled.•pH variations do not change notably the model parameters of dihalogenated HAA formation.•High pH affected the sensitivity to bromide of halogenated intermediates generating THM.•The model adds insight on the generation of THM and HAA species by chlorination.