Benzoylecgonine (BE), the main cocaine metabolite, has been detected in numerous surface water and treatment plants effluents in Europe and there is urgent need for effective treatment methods. In this study, the removal of BE by the UV254/H2O2 process from different water matrices was investigated. By means of competition kinetics method, the kinetic constant of reaction between BE and the photogenerated hydroxyl radicals ((OH)-O-center dot) was estimated resulting in k(OH/BE) = 5.13 x 109 M-1 s(-1). By-products and water matrices scavengers effects were estimated by numerical modeling of the reaction kinetics for the UV254/H2O2 process and validated in an innovative microcapillary film (MCF) array photoreactor and in a conventional batch photoreactor. The ecotoxicity of the water before and after treatment was evaluated with four organisms Raphidocelis subcapitata, Daphnia magna, Caenorhabditis elegans, and Vicia faba. The results provided evidence that BE and its transformation by-products do not have significant adverse effects on R. subcapitata, while D. magna underwent an increase of lipid droplets. C. elegans was the most sensitive to BE and its by-products. Furthermore, a genotoxicity assay, using V. faba, showed cytogenic damages during the cell mitosis of primary roots. (C) 2016 Elsevier B.V. All rights reserved.