Formation of known and unknown disinfection by-products from natural organic matter fractions during chlorination, chloramination, and ozonation.

Natural organic matter (NOM) is the main precursor of disinfection by-products (DBPs) formed during drinking water treatment processes. Previous studies of the relationships between DBP formation and NOM fractionation have mainly been focused on currently regulated DBPs and a few certain emerging DBPs. In this work, the Suwannee River NOM solution was fractionated into groups with different hydrophobicities using DAX-8 resins, and volatile and semi-volatile DBPs formed during the chlorination, chloramination and ozonation of the NOM fractions were examined by a nontargeted screening of comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry procedure. The results showed that a total of 302 DBPs representing nine chemical classes were detected, of which 266 were possibly newly detected, based on library searching with NIST 08 library (using similarity and reverse values of at least 600 and 700, respectively) and linear retention indices. The characterization of DBP precursors suggests that hydrophobic (HPO) NOM contains the major fraction of precursor for the formation of nitrogenous DBPs (contributing about 60% of the total nitrogenous DBPs) during all three disinfection processes. Much larger amounts of heterocyclic DBPs were formed from the HPO fraction than from the hydrophilic fraction during chlorination. During chloramination and ozonation, 5-15 times more ketones were formed from the hydrophilic fraction than from the HPO fraction. During ozonation, more than twice the amounts of esters and alcohols were formed from the hydrophilic fraction than from the HPO fraction. Three-dimensional excitation-emission matrix spectra suggest that similar to the formation of regulated DBPs, humic acid-like substances are probably the precursors of halogen-containing DBPs. Relatively higher nitrogenous DBPs formation from the HPO fraction might be because of the existence of protein-like materials.