Selective Chlorination of Natural Organic Matter: Identification of Previously Unknown Disinfection Byproducts

Natural organic matter (NOM) serve as precursors for disinfection byproducts (DBPs) in drinking water production making NOM removal essential in predisinfection treatment processes. We identified molecular formulas of chlorinated DBPs after chlorination and chloramination in four Swedish surface water treatment plants (WTPs) using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chlorine-containing formulas were detected before and after disinfection and were therefore classified to identify DBPs. In total, 499 DBPs were detected, of which 230 have not been reported earlier. The byproducts had, as a group, significantly lower ratio of hydrogen to carbon (H/C) and significantly higher average carbon oxidation state (Cos), double bond equivalents per carbon (DBE/C) and ratio of oxygen to carbon (O/C) compared to Cl-containing components present before disinfection and CHO formulas in samples taken both before and after disinfection. Electrophilic substitution, the proposed most significant reaction pathway for chlorination of NOM, results in carbon oxidation and decreased H/C while O/C and DBE/C is left unchanged. Because the identified DBPs had significantly higher DBE/C and O/C than the CHO formulas we concluded that chlorination of NOM during disinfection is selective toward components with relatively high double bond equivalency and number of oxygen atoms per carbon. Furthermore, choice of disinfectant, dose, and predisinfection treatment at the different WTPs resulted in distinct patterns in the occurrence of DBP formulas.