title: Transformation of 4-tert-octylphenol by UV irradiation and by an H2O2/UV process in aqueous solution.
abstract: The transformation of the organic pollutant 4-(1,1,3,3-tetramethylbutyl)phenol (4-tert-octylphenol; OP) upon irradiation at 253.7 nm and by hydroxyl radicals generated by the photolysis (lambda(exc) = 253.7 nm) of hydrogen peroxide in aqueous solution has been studied. The quantum yield of direct OP photolysis in pure aqueous solution was evaluated to be 0.058 +/- 0.004 in aerated conditions ([O2] = 272 microM). The rate of photoreaction depends on oxygen concentration; it increases with increasing [O2]. 4-tert-Octylcatechol has been identified as one of the degradation products, together with a dimeric structure. The probable mechanism of OP photolysis involves photoejection of an electron from the singlet state, leading to the formation of the 4-tert-octylphenoxyl radical. In the presence of hydrogen peroxide, the degradation of octylphenol by hydroxyl radicals has been observed. The second-order rate constant was found to be (6.4 +/- 0.5) x 10(9) M(-1) s(-1) by direct measurement at various high concentrations of hydrogen peroxide and competitive kinetic measurements using atrazine as the competitor. The degradation products are 4-tert-octylcatechol, again, and 2-hydroxy-5-tert-octylbenzoquinone. The later product may arise from the oxidation of 4-tert-octylcatechol by hydrogen peroxide or from a subsequent reaction of hydroxyl radicals with 4-tert-octylcatechol. Kinetic modelling when using either purified water or natural water successfully simulated the elimination of 4-tert-octylphenol by UV and H2O2/UV processes.
authors.affiliation: Laboratoire de Chimie de l'Eau et de l'Environnement, UMR CNRS 6008, Université de Poitiers ESIP, 40 Avenue du Recteur Pineau, 86022 Poitiers, France. Patrick.Mazellier@univ-poitiers.fr
authors.forename: Patrick
authors.initials: P
authors.lastname: Mazellier
authors.forename: Julie
authors.initials: J
authors.lastname: Leverd