Copper was continuously and selectively precipitated with Na2S to concentrations below 0.3 ppb from water containing around 600 ppm of both Cu and Zn in a Continuously Stirred Tank Reactor. The pH was controlled at 3 and the pS at 25 (pS = -log(S-2-)) by means of an Ag2S sulfide selective electrode. Copper's recovery and purity were about 100%, whereas the total soluble sulfide concentration was below 0.02 ppm. X-ray diffraction (XRD) analysis showed that copper precipitated as hexagonal CuS (covellite). The mode of the particle size distribution (PSD) of the CuS precipitates was around 36 mu m. The PSD increased by high pS values and by the presence of Zn. Depending on the turbulence, the CuS precipitates can grow up to 200 mu m or fragment in particles smaller than 3 mu m in a few seconds. Zn precipitation with Na2S at pH 3 and 4. in batch, always lead to Zn concentrations above 1 ppm. Zn precipitated as cubic ZnS (spharelite). (C) 2008 Elsevier B.V. All rights reserved.