Crystalline structure and surface properties significantly affect the floatability of metal sulphides. In this study, a novel methodology to modify zinc sulphide (ZnS) crystals was proposed to improve the floatability of the crystals. Initially, ZnS crystals, synthesised from zinc hydroxide (Zn(OH)(2)) and sulphur (S) under hydrothermal conditions, were used to assess the floatability. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were employed to analyse the crystalline structure and surface properties of the sulphides. Conventional flotation tests were performed to evaluate the floatability. The effects of mineraliser (KOH) concentration, precursor (Zn(OH)(2)) concentration, hydrothermal temperature and holding time on the floatability of the ZnS crystals were investigated. The optimal flotation recovery of ZnS (82.53%) was obtained with a KOH concentration of 5 mol/L, a Zn(OH)(2) concentration of 10%, a holding time of 4 h and a hydrothermal temperature of 260 degrees C. Then, sludge containing fine and amorphous zinc compounds, which was generated during the disposal of metallurgical waste water, was employed to test the recovery of valuable metals using modified hydrothermal sulphidation. The results show that the recovery of Zn in the sludge can reach 66.3% under the optimal conditions. (C) 2012 Elsevier Ltd. All rights reserved.