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|Results of an electrochemical study using carbon paste electrodes of pyrite and pyrrhotite samples suggest that the mineralogical impurities associated with these minerals are the determinant factor on their reactivity under alteration systems. These results were supported by mineralogical and leachate chemistry data from leach cell tests run on these samples. Pyrite reactivity decreases in the presence of associated impurities due to a galvanic effect whereas pyrrhotite reactivity appears to be controlled by the formation of a passivating layer, which overcome impurities effect. Electrochemical responses of sulfide-bearing samples provided valuable information on the prediction of ARD generation.|