Acidic aqueous solutions of the chlorinated aliphatic hydrocarbons 1,2-dichloroethane (DCA) and 1,1,2,2-tetrachloroethane (TCA) have been treated by the electro-Fenton (EF) process. Bulk electrolyses were performed at constant current using a BDD anode and an air diffusion cathode able to generate H(2)O(2) in situ, which reacts with added Fe(2+) to yield center dot OH from Fenton's reaction. At 300 mA, almost total mineralization was achieved at 420 min for solutions containing 4 mM of either DCA or TCA. Comparative treatments without Fe(2+) (anodic oxidation) or with a Pt anode led to a poorer mineralization. The better performance of the EF process with BDD is explained by the synergistic action of the oxidizing radicals, BDD(center dot OH) at the anode surface and center dot OH in the bulk, and the minimization of diffusional limitations. The decay of the initial pollutant accomplished with pseudo first-order kinetics. Chloroacetic and dichloroacetic acids were the major by-products during the degradation of DCA and TCA, respectively. Acetic, oxalic and formic acids were also identified. The proposed reaction pathways include oxidative and reductive (cathodic) dechlorination steps. Chlorine was released as Cl(-), being further oxidized to CIO(3)(-) and, mostly, to CIO(4)(-), due to the action of the largely generated BDD(center dot OH) and center dot OH. (C) 2011 Elsevier B.V. All rights reserved.