Smithsonite is a readily dissolvable carbonate mineral that is naturally hydrophilic, making recovery of this ore by flotation difficult. The flotation results showed that conditioning with only sodium sulfide (Na2S) did not successfully allow the smithsonite samples to float, whereas treatment with a combination of S(II), Pb(II) and xanthate (with Na2S as the sulfurizing reagent, lead ions (Pb(II)) as the activator, and xanthate as the collector) improved the flotation of smithsonite, achieving a mass recovery of 95.8%. A combination of analytical techniques, including X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS), in conjunction with depth profiling, was used to investigate the chemical nature of the sulfur and lead species on the smithsonite surface. For S(II)conditioned smithsonite, a layer of ZnS formed on the smithsonite (ZnCO3) substrates; this newly formed ZnS coating was amorphous or poorly crystallized. For smithsonite samples conditioned with S(II) and Pb (II), the microstructures and the phase constituents, obtained by AFM and XRD analyses, confirmed the formation of the PbS species with a cubic galena structure on the surface. XPS depth profiling showed that the PbS layer was 18-nm thick, which corresponds to 30 PbS molecular layers. This study presents direct evidence that the coating of the activation product, PbS, on the smithsonite surface was similar to a relatively thick galena layer, which led to successful flotation. (C) 2018 Elsevier B.V. All rights reserved.