During electrodialysis (ED) treatment of solutions with different Mg/Ca ratios (R = 0, 1/20, 1/10, 1/5 and 2/5) and in different pH conditions (acid, neutral and basic), foulings on ion-exchange membranes were previously characterized and identified, by the way of X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. A mineral fouling was observed in neutral and basic conditions (for R = 1/5 and 2/5) on the anion-exchange membrane (AEM) concentrate side and in basic conditions on the cation-exchange membrane (CEM) concentrate side as well as on the diluate side for R = 1/5 and 2/5. The objectives of this present work were to link the morphological characterization and identification of membrane fouling to electrodialytic parameters and cation migration kinetics. It appeared that the CEM permselectivity was severely affected in basic conditions for R >= 1/5. The consequence of this alteration was the migration of OH- through the CEM, a pH increase in the diluate compartment and different treatment durations. The calcite observed on AEM concentrate side for Mg/Ca : 1/5 would be due first to the particular operating conditions such as the recirculation of the concentrate solution, and also to the supersaturated conditions reached or not at the AEM interface and favourable pH conditions. (C) 2008 Elsevier B.V. All rights reserved.