Iron (Fe) is an unintentional impurity present in pure magnesium (Mg) and Mg alloys, albeit nominally in low and innocuous concentrations (< 100 ppmw). Since Fe, like most metals, is more noble than Mg, the presence of Fe impurities can serve as cathodic sites within the Mg matrix. During anodic polarization of Mg, incongruent dissolution can lead to undissolved Fe impurities accumulating upon the Mg surface, permitting an increase in the overall rate of hydrogen evolution. The experimental manifestation of the incongruent dissolution of Mg, has not yet been clarified, wherein, the extent and efficiency of Fe enrichment during anodic polarization is not known, and also the increase in the hydrogen evolution rate due to Fe enrichment has not been quantified. In this work, Mg specimens with Fe concentration between 40 to 13,000 ppmw were examined in 0.1 M NaCl to obtain a quantitative relation between the Fe concentration and the rate of cathodic hydrogen evolution. These base-line alloys were then anodically polarized to facilitate surface Fe enrichment, and subsequently again cathodically polarized to determine the impact of prior dissolution and Fe enrichment on the subsequent hydrogen evolution. A simple model to predict Fe enrichment was used to analyze the electrochemical data and predict the extent and efficiency of Fe enrichment. (C) The Author(s) 2015. Published by ECS. All rights reserved.