Degrading surface-water-based natural organic matter and mitigating haloacetonitrile formation during chlorination: Comparison of UV/persulfate and UV/hydrogen peroxide pre-treatments

Haloacetonitriles (HANs) are unregulated disinfection by-products that are more toxic than regulated species. Therefore, efficient decomposition of HAN precursors prior to disinfection is crucial for allaying the potential HAN-induced health risks. This study investigated the key roles of ultraviolet-activated persulfate (UV/PS) treatment in alleviating HAN formation. The effects of UV/PS treatment were evaluated by correlating with the characteristics of organic matter in surface water and comparing with conventional UV/H₂O₂ treatment. Upon irradiating raw water samples and a Suwannee River humic acid solution spiked with 10 mM PS or H₂O₂ with 254 nm UV light, UV/PS treatment was found to be more potent than UV/H₂O₂ in mitigating the HAN production and degrading organic substances; moreover, UV/PS treatment effectively decreased the dissolved organic nitrogen (DON) content. In contrast, UV/H₂O₂ treatment did not induce any noticeable reduction in DON level. Furthermore, both UV/PS and UV/H₂O₂ treatments reduced the dichloroacetonitrile (DCAN) formation potential (FP), leading to strong correlations with the degradation of aromatic and humic-acid-like compounds. Notably, UV/PS treatment efficiently decreased the FP of bromochloroacetonitrile (BCAN) and dramatically reduced that of dibromoacetonitrile (DBAN) after a sharp increase; however, UV/H₂O₂ treatment gradually increased the DBAN-FP. Bromide was activated by sulfate radicals during UV/PS treatment, negatively correlating with the BCAN-FP and DBAN-FP, indicating that the formation of reactive bromine species increased the DBAN-FP; however, excessive oxidation possibly led to the recovery of inorganic bromine for decreasing the BCAN-FP and DBAN-FP. Additionally, UV/PS treatment effectively suppressed toxicity owing to its high reduction rate for brominated HANs; in contrast, UV/H₂O₂ treatment resulted in less significant BCAN and DBAN reductions, leading to minimal net reduction in toxicity. Overall, UV/PS treatment was remarkably effective at diminishing the toxicity of brominated HANs, underscoring its potential to mitigate drinking-water-related health risks.