Degradation of dyes by UV/Persulfate and comparison with other UV-based advanced oxidation processes: Kinetics and role of radicals

Abstract

This study investigated the degradation of methylene blue (MeB), methyl orange (MeO), and rhodamin B (RhB) by the UV/Persulfate (UV/PS) process. The dye degradation in the investigated UV-based Advanced Oxidation Processes (UV/AOPs) followed the first-order kinetic model. The second-order rate constant of the dyes with •OH, SO₄^•-, and CO₃^•- were calculated and found to be: k_•OH,MeB = 5.6 × 10⁹ M^-1 s^-1, [Formula: see text] = 3.3 × 10⁹ M^-1 s^-1, [Formula: see text] = 6.9 × 10⁷ M^-1 s^-1; k_•OH,MeO = 3.2 × 10⁹ M^-1 s^-1, [Formula: see text] = 13 × 10⁹ M^-1 s^-1, [Formula: see text] = 4.4 × 10⁶ M^-1 s^-1; k_•OH,RhB = 14.8 × 10⁹ M^-1 s^-1, [Formula: see text] = 5 × 10⁹ M^-1 s^-1, [Formula: see text] = 1 × 10⁷ M^-1 s^-1. The steady-state concentrations of •OH and SO₄^•- (including other reactive species) were determined using both chemical probes and modeling methods (Kintecus® V6.8). In the UV/PS, the dye degradation depends on the pH of the solution with the order: k_dye (at pH of 7) > k_dye (in acidic conditions) > k_dye (in alkaline conditions). The presence of water matrices had different impacts on dye degradation: 1) The HCO₃^- and Cl^- promoted the degradation efficiency of one dye, but also inhibited the degradation of other dyes; 2) Humic acid (HA) inhibited dye degradation as it scavenged both •OH and SO₄^•-. The degradation of the dyes by UV/PS was also compared with the UV/Chlorine (UV/HOCl) and UV/H₂O₂ and it was established that: 1) In UV/PS and UV/HOCl, SO₄^•- and RCS contributed to dye degradation more than •OH, while •OH played a major role in dye degradation by UV/H₂O₂; 2) The calculated toxicity in UV/PS was the lowest probably due to the low toxicity of by-products; 3) For MeO and RhB, the UV/PS process is more beneficial for the total organic carbon (TOC) removal compared to that of the UV/HOCl and UV/H₂O₂ processes; 4) The UV/PS showed lower cost than the UV/HOCl and UV/H₂O₂ systems for MeO, and RhB degradation but higher cost for MeB removal.

Keywords: Advanced oxidation process; Degradation; Dye removal; Kinetics; Oxidizing species.