Some metal contaminants, such as Al3+, Ni+2, Fe2+ and Cr3+, are produced during reactions in heat exchangers, stacks, and other fuel/water management system components. Due to the gradual build-up of these contaminants generated in the system, direct methanol fuel cell (DMFC) membrane electrode assemblies (MEAs) deteriorate steadily with increasing operation time. Hence, this study systematically investigates the effects of metal cations by supplying various concentrations of metal solutions to the fuel stream at constant-current densities, with the aim of understanding the mechanism and influence of metal contamination on a DMFC MEA. Various electrochemical diagnostic techniques are used to determine the main cause of MEA degradation, including electrochemical impedance spectroscopy, electrode polarization, and methanol stripping voltammetry. In addition, the critical concentration of metal cations in methanol fuel is investigated for high DMFC MEA stability. Further, various novel methods for mitigating the influence of the metal contaminants on the performance of a DMFC are suggested and verified. (c) 2013 Elsevier B.V. All rights reserved.