Formation of Aldehydes and Carboxylic Acids in Humic Acid Ozonation

The purpose of this study was to determine the different kinds and concentrations of intermediates, and investigate on the effects of contact time and ozone (O₃) doses on the removal of humic acid (HA), which is served as the main disinfection by-product (DBP) precursor. Based on that, the knowledge gap of DBPs generated was made up. The results showed that HA was the major precursor material for aldehydes and carboxylic acids. The concentrations of aldehydes increased as contact time and O₃ doses, and reached up maximum at 2~10 min but approached a plateau at the higher O₃ doses. The concentrations of formic and acetic acids increased as contact time and O₃ doses. However, aromatic acids, including protocatechuic, 3-hydroxybenzoic, and benzoic acids, declined rapidly at longer reaction time and higher O₃ doses. It was worth mentioning that aromatic acids had been rarely reported. Besides, a possible formation pathway was proposed: (a) HA was degraded into fulvic acid (FA)-like compounds; (b) FA-like compounds were further converted into aromatic acids; (c) aromatic acids were transformed into low-molecular-weight organic matters; (d) chlorine reacted with aldehydes and/or carboxylic acids by addition, hydrolysis, and decarbonylation reactions, leading to DBP formation. Furthermore, not only HA were the main DBPs precursors, but also the oxidation intermediates of HA could be the DBPs precursors, and they gave a certain amount of DBPs. Consequently, aldehydes and carboxylic acids should be under control in drinking water treatment plants.