The galvanic effect between the main associated mineralogical phases in a mineral sphalerite concentrate was evaluated using an alternative methodology. Comparative voltammetric studies were performed between high purity galena mineral (94.65%) and sphalerite concentrate (content of 78.11% sphalerite, ZnS; 13.64% galena, PbS; 0.57% chalcopyrite, CuFeS2; 0.41% cadmium sulfide, CdS; and 0.11% arsenopyrite, FeAsS) using carbon paste electrodes (C PE) in order to identify galvanic interactions that affect their reactivity. The electrolyte was an aqueous solution of 0.1 M NaNO3 (pH 6.5). The results showed that, in sphalerite concentrate, the electrochemical reactivity of the galena was diminished and displaced to more positive potentials with respect to the high purity galena. mineral response. This behavior can be attributed to the galvanic protection offered by the sphalerite on the galena, thereby avoiding its free oxidation. On the other hand, sphalerite oxidation was diminished by the formation of a passive products film that is dissolved to more positive potentials which provokes oxidation of other minerals like CuFeS2, (Zn,Cd)S and FeAsS present in a minor proportion in the sphalerite concentrate. (C) 2006 Elsevier B.V. All rights reserved.