The mineralization of acidic aqueous solutions with 230 and 115 ppm of herbicide 3,6-dichloro-2-methoxybenzoic acid (dicamba) in 0.05 M Na2SO4 of pH 3.0 has been studied by electro-Fenton and photoelectro- Fenton using a Pt anode and an O-2-diffusion cathode, where oxidizing hydroxyl radicals are produced from Fenton's reaction between added Fe2+ and H2O2 generated by the cathode. While electro-Fenton only yields 60-70% mineralization, photoelectro-Fenton allows a fast and complete depollution of herbicide solutions, even at low currents, by the action of UV irradiation. In both treatments, the initial chlorine is rapidly released to the medium as chloride ion. Comparative electrolyses by anodic oxidation in the absence and presence of electrogenerated H2O2 give very poor degradation. The dicamba decay follows a pseudo-first-order reaction, as determined by reverse-phase chromatography. Formic, maleic and oxalic acids have been detected in the electrolyzed solutions by ion-exclusion chromatography. In electro-Fenton, all formic acid is transformed into CO2, and maleic acid is completely converted into oxalic acid, remaining stable Fe3+ -oxalato complexes in the solution. The fast mineralization of such complexes by UV light explains the highest oxidative ability of photoelectro-Fenton. (C) 2003 Elsevier Science Ltd. All rights reserved.