The degradation of solutions with 0.260 mM of the diazo dye Congo Red at pH 3.0 has been studied by electrochemical advanced oxidation processes (EAOPs) like anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF) with a 6W UVA light. Experiments were made in a 100 mL stirred tank reactor with a boron-doped diamond (BOO) anode and an air-diffusion cathode at constant current density (j). In these systems, organics were mainly destroyed by (OH)-O-center dot formed at the anode surface from water oxidation and/or in the bulk from Fenton's reaction between added Fe2+ and cathodically generated H2O2. The oxidation power of the EAOPs increased in the sequence AO-H2O2 < EF < PEE. Almost total mineralization was attained after 360 min of PEF at j >= 66.7 mA cm(-2) due to the parallel photolytic action of UVA light. In all the EAOPs, increasing j enhanced the degradation process, but with a loss of mineralization current efficiency and higher energy consumption. Congo Red decay always obeyed a pseudo-first-order kinetics. The study of the Congo Red degradation in a 2.5 L solar flow plant with a Pt/air-diffusion cell confirmed the viability of the solar PEF (SPEF) treatment at industrial scale. Optimum conditions were found for 0.260 mM of Congo Red with 0.50 mM Fe2+ at 100 mA cm-2, yielding almost total mineralization in 240 min with about 49% current efficiency and 0.45 kWh (g DOC)(-1) energy consumption. LC-MS analysis of treated solutions allowed the identification of 21 aromatic intermediates and 13 hydroxylated derivatives, including diazo, monoazo, biphenyl, benzene, naphthalene and phthalic acid compounds. Tartatic, tartronic, acetic, oxalic and oxamic acids were detected as final carboxylic acids in all the EAOPs. The fast photodecarboxylation of the Fe(III)-carboxylate complexes explained the higher oxidation ability of the photo-assisted methods of PEF and SPEF. The initial N of the dye was mainly lost as N-volatile products and mineralized to NO3- ion and in lesser extent to NH4+ ion, whereas its initial S was converted into SO42- ion. (C) 2015 Elsevier B.V. All rights reserved.