The study of ion transport processes on non-polymer coated bare oxide covered iron and zinc surfaces showed that the presence of adsorbed ions determines the ion distribution on oxide/metal surfaces in humid atmosphere. For fundamental studies of ion ingress at polymer/oxide/metal interfaces, already the transport analysis in the absence of the polymer reveals important mechanistic aspects. Sophisticated spectroscopic techniques were applied for the correlation of electrochemical data with local surface chemistry. In-situ Scanning Kelvin Probe (SKP) measurements of the local interfacial potentials of oxide covered iron and zinc substrates and ex situ time-of-flight secondary ion mass spectroscopy (ToF-SIMS) analysis showed that the surface layer charge influences the ion transport processes. A model is proposed to explain the basic mechanism of hydrated ion transport on oxide covered zinc and iron. (c) 2008 Elsevier Ltd. All rights reserved.