Electrochemical oxidation (ECOx) of 1-hydroxy-2,4-dinitrobenzene (or 2,4-dinitrophenol: 2,4-DNP) in aqueous solutions by electrolysis under galvanostatic control was studied at Pb/PbO2, Ti/SnO2, Ti/IrxRuySnO2 and Si/BDD anodes as a function of current density applied. Oxidative degradation of 2,4-DNP has clearly shown that electrode material and the current density applied were important parameters to optimize the oxidation process. It was observed that 2,4-DNP was oxidized at few substrates to CO2 with different results, obtaining good removal efficiencies at Pb/PbO2, Ti/SnO2 and Si/BDD anodes. Trends in degradation way depend on the production of hydroxyl radicals ((OH)-O-center dot) on these anodic materials, as confirmed in this study. Furthermore, HPLC results suggested that two kinds of intermediates were generated, polyhydroxylated intermediates and carboxylic acids. The formation of these polyhydroxylated intermediates seems to be associated with the denitration step and substitution by (OH)-O-center dot radicals on aromatic rings, this being the first proposed step in the reaction mechanism. These compounds were successively oxidized, followed by the opening of aromatic rings and the formation of a series of carboxylic acids which were at the end oxidized into CO2 and H2O. On the basis of these information, a reaction scheme was proposed for each type of anode used for 2,4-D oxidation. (C) 2014 Elsevier B.V. All rights reserved.