Atomic emission spectroelectrochemistry (AESEC) was used to monitor the release of Al from 99.99% aluminum (1199 alloy) and Al. Mg, and Cu from 2024 Al alloy in 30 g/l NaCl electrolyte as a function of pH. The cathodic dissolution of Al was demonstrated and attributed to an increase in the pH at the interface due to the water reduction reaction. The dissolution of Mg was also observed but was a more complex function of current probably depending on the interfacial pH and the Al dissolution rate. The detachment of copper-rich particles was observed as very rapid spectroscopic emission transients (peak width < 10 ms). (C) 2010 Elsevier Ltd. All rights reserved.