The decomposition of aqueous ozone by UV-vis radiation has been investigated with focus on the impact of ozone photolysis on the degradation of water pollutants during solar ozonation processes. The apparent first-order rate constants of the decomposition of ozone (k(obs)) have been determined at various pHs in the 4-9 range using radiation of different wavelengths in the UV-vis range. It was found that UVA-visible radiation (lambda > 320 nm) highly enhanced ozone decomposition, especially at pH 4, for which kobs was three-folded with respect to the process in the absence of radiation. Hydrogen peroxide was identified as a main intermediate of ozone photo-decomposition at pH 4. Experiments of degradation of oxalic acid by ozone showed that solar irradiation brings about an increase in the hydroxyl radical to ozone exposures ratio (R-ct). Finally, photo-ozonation (lambda > 300 nm) was shown advantageous over single ozonation in the mineralization of a selection of emerging contaminants (metoprolol, ibuprofen, N,N-diethyl-meta-toluamide and clofibric acid) in both ultrapure water and a synthetic secondary effluent. Thus, TOC removal in 2-h treatments increased from 10 to 25% in the absence of radiation to about 50% in the presence of radiation. (C) 2016 Elsevier B.V. All rights reserved.