The effect of sodium bisulphite on the xanthate-induced flotation of copper-activated sphalerite has been studied using batch flotation testing, surface analysis techniques (XPS and ToF-SIMS), and FTLR. The various techniques have been used to identify the mechanisms of interaction of sulphite ions with both collector and the sphalerite surface. The results indicate that sodium bisulphite depressed the flotation of sphalerite particles pre-treated with copper and xanthate at pH 9 with nitrogen and air purging. It was found that sodium bisulphite interacts with the sphalerite surface, as well as with xanthate in its adsorbed state. Based on the evidence obtained in the present study, and in conjunction with previous work, the mechanisms involved in the depression of the xanthate-induced flotation of copper-activated sphalerite by sulphite are proposed. It is suggested that copper xanthate decomposition on the surface of the activated sphalerite and the decomposition of the hydrophobic copper-sulphide-like species on the sphalerite surface are the active mechanisms for sphalerite depression by sodium bisulphite. (c) 2005 Elsevier B.V. All rights reserved.