Influence of pH and ozone dose on the content and structure of haloacetic acid precursors in groundwater.

This study investigated the effects of pH (6-10) and ozone dose [0.4-3.0 mg O(3)/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85 ± 0.18 mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65 % fulvic and 14 % humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309 ± 15 μg/L). Ozonation at pH 6-10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65-90 % achieved using 3.0 mg O(3)/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH 10 (up to 68 % HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1 ± 6.0 μg/mg DOC in raw water to 152 ± 8 μg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH 10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.