The increasing demand for clean industrial processes has intensified the use of electrodialysis in the treatment of metal containing effluents and encourages the investigation of the different phenomena involved in the transport of metal ions through cation-exchange membranes. Ion sorption, chronopotentiometric and current-voltage characteristics have been obtained to characterize the transport of sodium and iron through homogeneous and heterogeneous cation-exchange membranes. The heterogeneous membranes having a broader pore size distribution showed increased electrical resistances with solutions of trivalent iron, which may be caused by the blockage of the smallest pores by multivalent ions. However, for both types of membranes an unexpected decrease of the electrical resistance with increasing current densities was verified with concentrated solutions of Fe-2(SO4)(3). This behavior was explained to be a consequence of the dissociation of FeSO4+ ions into more conductive Fe3+ and SO42- ions as the depleting solution layer becomes diluted. When tested with multicomponent mixtures, the homogeneous perfluorosulfonic membranes show an increased preference for Na+ ions at low current densities and, once Na+ ions are depleted from the membrane surface Fe3+ ions are transported preferentially at higher current densities. On the contrary, both Na+ ions and Fe(III) species are responsible for the ion transport through the heterogeneous membranes within the ohmic regime of currents. (C) 2014 Elsevier B.V. All rights reserved.