The effects of major components of calcium and sulphate species present in recycled process water on galena flotation has been investigated through Hallimond flotation, zeta-potential, diffuse reflectance FTIR spectroscopy and XPS measurements using pure galena mineral. The significance of process water species in flotation has been understood using deionised water, process water and simulated tap water containing equivalent calcium and sulphate ions concentration as in process water. Hallimond flotation indicated marginally lower recoveries of galena in the presence of calcium and sulphate ions using potassium amyl xanthate as collector. Zeta-potential shows the adsorption of calcium ions whereby the potential are seen to increase while sulphate ions have no significant effect. FTIR and XPS studies revealed surface calcium carbonate and/or calcium sulphate species in process water which affected xanthate adsorption. Presence of surface oxidised species such as sulfoxy, hydroxyl species on galena at pH 10.5 in deionised and process water was also revealed. (C) 2012 Elsevier Ltd. All rights reserved.