In the flotation of platinum group minerals pyroxene is a major gangue mineral. This study shows using zeta potential and ToF-SIMS analyses that when pyroxene is exposed to copper, nickel and/or calcium ions in solution at alkaline pHs a surface reaction occurs between the hydroxy species, in the case of copper and nickel, or divalent calcium ions and the pyroxene surface which influences the floatability of the pyroxene. Following exposure to copper and nickel ions at pH 9 addition of SIBX resulted in the pyroxene floating readily. It is also shown, in the case of copper, that the activating effect of the adsorbed copper hydroxy species can be reduced by the addition of complexing amines prior to SIBX. Proposals are made to explain these observations.