Reaction kinetics and degradation efficiency of halogenated methylparabens during ozonation and UV/H2O2 treatment of drinking water and wastewater effluent

Abstract

This study investigated the reaction kinetics and degradation efficiency of methylparaben and its halogenated products (Cl-, Br-, Cl,Cl-, Br,Cl-, and Br,Br-methylparabens) during ozonation and UV₂₅₄/H₂O₂ treatment. Second-order rate constants for reactions of the parabens with ozone and ^•OH were [Formula: see text] = 10⁷ - 10⁸ M^-1 s^-1 and [Formula: see text] = (2.3 - 4.3)× 10⁹ M^-1 s^-1 at pH 7. Species-specific [Formula: see text] values of the protonated and deprotonated parabens were closely related to phenol ring substituent effects via quantitative structure-activity relationships with other substituted phenols. The UV photolysis rate of the parabens [k_UV = (2.4 - 7.2)× 10^-4 cm² mJ^-1] depended on the halogenation state of the paraben and solution pH, from which species-specific quantum yields were also determined. In simulated treatments of drinking water and wastewater effluent, the parabens were efficiently eliminated during ozonation, requiring a specific ozone dose of > 0.26 gO₃/gDOC for > 97% degradation. During UV/H₂O₂ treatment with 10 mg L^-1 H₂O₂, the degradation levels were > 90% at a UV fluence of 2000 mJ cm^-2, except for Cl,Cl-methylparaben. Kinetic models based on the obtained reaction kinetic parameters could successfully predict the degradation levels of the parabens. Overall, ozonation and UV/H₂O₂ were effective in controlling parabens and their halogenated products during advanced water treatment.

Keywords: Hydroxyl radical; Micropollutant; Ozone; Paraben; UV/H(2)O(2).