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This study explored the potential use of a sulfate radical (SO ·−  4 )-based photochemical oxidation process to treat the commercial nonionic surfactant octylphenol polyethoxylate (OPPE) Triton™ X-45. For this purpose, the effect of initial S 2 O 2−  8  (0–5.0 mM) and OPPE (10–100 mg/L) concentrations on OPPE and its organic carbon content (TOC) removal were investigated at an initial reaction pH of 6.5. Results indicated that very fast OPPE degradation (100%) accompanied with high TOC abatement rates (90%) could be achieved for 10 and 20 mg/L aqueous OPPE at elevated S 2 O 2−  8  concentrations (≥2.5 mM). S 2 O 2−  8 /UV-C treatment was still capable of complete OPPE removal up to an initial concentration of 40 mg/L in the presence of 2.5 mM S 2 O 2−  8 . On the other hand, TOC removal efficiencies dropped down to only 40% under the same reaction conditions. S 2 O 2−  8 /UV-C oxidation of OPPE was also compared with the relatively well-known and established H 2 O 2 /UV-C oxidation process. Treatment results showed that the performance of S 2 O 2−  8 /UV-C was comparable to that of H 2 O 2 /UV-C oxidation for the degradation and mineralization of OPPE. In order to elucidate the relative reactivity and selectivity of SO ·−  4  and HO · , bimolecular reaction rate coefficients of OPPE with SO ·−  4  and HO ·  were determined by employing competition kinetics with aqueous phenol (47 μM) selected as the reference compound. The pseudo-first-order abatement rate coefficient obtained for OPPE during S 2 O 2−  8 /UV-C oxidation (0.044 min −1 ) was found to be significantly lower than that calculated for phenol (0.397 min −1 ). In the case of H 2 O 2 /UV-C oxidation however, similar pseudo-first-order abatement rate coefficients were obtained for both OPPE (0.087 min −1 ) and phenol (0.140 min −1 ). From the kinetic study, second-order reaction rate coefficients for OPPE with SO ·−  4  and HO ·  were determined as 9.8 × 10 8  M −1  s −1  and 4.1 × 10 9  M −1  s −1 , respectively. The kinetic study also revealed that the selectivity of SO ·−  4  was found to be significantly higher than that of HO · .

frontiers in chemistry

Advanced oxidation of the commercial nonionic surfactant octylphenol polyethoxylate Triton™ X-45 by the persulfate/UV-C process: effect of operating parameters and kinetic evaluation