Elimination efficiency of organic UV filters during ozonation and UV/H2O2 treatment of drinking water and wastewater effluent

The efficiency of elimination of organic UV filters by ozonation and UV254nm/H2O2 processes was assessed and predicted in simulated treatments of sewage-impaired drinking water and wastewater effluent in bench-scale experiments. Second-order rate constants (k) for the reactions of the eight UV filters with ozone and OH were determined by quantum chemical calculations and competition kinetics methods, respectively. The UV filters containing phenolic (ethylhexyl-salicylate, homosalate, and benzophenone-3) and olefinic moieties (4-methylbenzylidene-camphor, benzyl-cinnamate, and 2-ethylhexyl-4-methoxycinnamate) showed high ozone reactivity (k ≥ 8 × 104 M−1s−1 at pH 7), while those without such electron-rich moieties (isoamyl-benzoate and benzophenone) were ozone-refractory. All the UV filters showed high OH reactivity (k ≥ 6.2 × 109 M−1s−1). In concordance with the rate constant information, the phenolic and olefinic UV filters were efficiently eliminated by ozone treatment, requiring specific ozone doses of <0.5 mgO3/mgDOC for ∼100% elimination. The UV filters were eliminated by ≤ 38% at a UV fluence of 1500 mJ/cm2 in the UV254nm-only treatment. Rapid photoisomerisation between the E and Z geometric isomers was observed for the olefinic UV filter, benzyl-cinnamate. The addition of H2O2 (10 mg/L) greatly enhanced the elimination of all UV filters, indicating that OH was the main contributor to their elimination in the UV254nm/H2O2 treatment. A chemical kinetics approach developed previously for ozonation and UV/H2O2 processes was shown to predict the elimination of the UV filters in the tested water matrices reasonably well, demonstrating that the chemical kinetics method can be used for a priori prediction of micropollutant elimination in oxidative treatment processes for potable reuse of municipal wastewater effluents.