Persistent free radicals in natural organic matter activated by iron particles enhanced disinfection byproduct formation

The widespread presence of iron (Fe) particles and natural organic matter (NOM) in drinking water distribution systems (DWDS) can significantly affect tap water quality, contributing to aesthetic issues and potentially generating harmful disinfection byproducts (DBPs). This study revealed that Fe particles, when combined with humic acid (HA), substantially increased DBP formation during chlorination. Fe particles (particularly preformed Fe particles) significantly increased haloacetic acid (HAA) formation by activating the persistent free radicals (PFRs) in the HA. Compared with the control system without Fe particles, greater than 2 times of HAA increase were observed for the system with Fe pariticles. PFRs accumulated on Fe particle surface could generate hydroxyl radicals, facilitating the decomposition of HA into smaller molecules, which were more reactive with chlorine disinfectants, thus elevated the DBP formation including both known and unknown N-DBPs and Cl-DBPs. The DBP promotion effect of in-situ formed Fe particles was much less than that of preformed Fe particles although both in-situ formed and preformed Fe particles could accumulate PFRs from HA. In-situ formed particles primarily accumulated carbon-centered PFRs, while preformed particles accumulated oxygen-centered PFRs. To mitigate the Fe particle induced water quality risks, it is crucial to control iron pipe corrosion and iron release in DWDS. In addtion, the optimization of treatment processes such as coagulation and filtration to more completely remove NOM and Fe particles could help minimize the DBP formation.