Prudent control of ore pulp chemistry via parameters such as redox potential (Eh), dissolved oxygen (DO) and pH, can markedly improve the flotation recovery, grade and selectivity of sulphide minerals. In this paper, the electrochemical reactivities of two pyrite minerals and their impact on chalcopyrite flotation are investigated using oxygen demand test and froth flotation. Changes in the surface chemistry/speciation are also investigated using X-ray photoelectron spectroscopy (XPS) and EDTA extraction technique. The oxygen demand test shows that the different pyrite ores display significantly different electrochemical reactivity. Furthermore, continuous aeration of the pulp reduces the reactivity of the pyrite ores. Solution and surface analysis results suggest the formation of hydroxide surface coatings on the pyrite surface as aeration progresses, preventing or minimising further oxidative reactions from taking place in the pulp. Flotation results showed that the flotation response of chalcopyrite is influenced by the pulp DO/Eh, and therefore the type and reactivity of the pyrite associated with it. (C) 2013 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.