Ozonation of fulvic acid (FA) can result in diverse intermediate oxidation by-products, significantly affecting disinfection by-product (DBP) formation following chlorination. The objective of this study was to provide insight into ozone reaction intermediates and reveal the possible formation pathway of DBPs from ozonation of FA due to the formation of intermediate oxidation by-products. Aldehydes, aromatic acids, short-chain acids, chloroform, and dichloroacetic acid were detected at various ozone dosage additions. Aromatic acids were studied by using solid-phase extraction-ultra high-performance liquid chromatography (SPE-UPLC). This new analytical approach enables the extraction and analysis of highly polar carboxylic acids that are difficult to measure using conventional methods. The results showed that formaldehyde, acetaldehyde, glyoxal, methyl-glyoxal, fumaric, malonic protocatechuic, 3-hydroxybenzoic, and benzoic acid were predominant oxidation by-products. The yields of the four aldehydes increased steadily with ozone dosage. When ozone dosage was 2∼2.5 mg/l, the amount of carboxylic acids was largest, and the total amount of the carboxylic acids was about 5∼10 times higher than that of the aldehydes. Besides, hydroxybenzoic acids are the major precursor, although they have low content in ozone reaction solution, they have a great contribution to the DBP formation. This study provides a new perspective on ozonation natural organic matter, which contributes to understand the other sources of DBPs and thus broadens the knowledge of drinking water treatment.
Keywords: Aldehydes; Carboxylic acids; Chloroform; Dichloroacetic acid; Ozone.