This article presents the first non destructive measurements of salt ions transport through fired-clay brick during electrokinetic desalination using nuclear magnetic resonance technique. The effect of the strength of an applied electric field on the migration of salt ions is examined by varying the electrical potential gradients from 0.75–2 V cm-1 across the specimens. The measurements show that for electrokinetic to exceed ion transport by diffusion a minimum level of applied voltage is necessary. Below this threshold salt transport by diffusion is dominant over electromigration. The effect of advection on the salt transport is studied by introducing a hydraulic gradient across the specimen. The results show that advection is a major transport process in the materials studied. To assess the relative magnitude of the various active transport processes during electrokinetic desalination, a scale analysis on the basis of dimensionless numbers is presented. The value of these numbers determines which transport mechanism will dominate the desalination process in a given sample length and time scale.