The Magotteaux Mill((R)) system was used to quantify the galvanic interaction between four types of grinding media (mild steel, 15% chromium, 21% chromium, and 30% chromium media) and arsenopyrite, in situ of the mill. The galvanic current was determined from the polarization curves of individual electrodes, in situ of the mill. The high chromium media had a significantly weaker galvanic interaction with arsenopyrite, and produced a very much lower amount of oxidized iron species in the mill discharge than mild steel medium. Increasing the dissolved oxygen in the mill slurry enhanced galvanic interaction. A theoretical model was developed to describe the relationship between galvanic current and oxidized iron species in the slurry, as measured by EDTA extraction. The electrochemical data were correlated with the measurement of oxidation products after grinding under different conditions. The stronger the galvanic interaction, the higher the amount of hydrophilic oxidized iron species in the mill discharge. Copper(II) was used to activate arsenopyrite, which slightly altered the grinding environment, as well as the interaction between the grinding media and arsenopyrite. (c) 2005 Elsevier B.V. All rights reserved.