The performance of copper and copper-based alloys in working environments is controlled by the composition of the layers formed on their surfaces. Herein, we report the detailed structural and compositional analyses of the layers formed on the surface of Cu, Cu-Ni, Cu-Zn and Cu-Ni-Zn upon their use in both NaCl and Na2S-polluted NaCl solutions. In clean NaCl environments, X-ray photoelectron spectroscopy (XPS) analysis revealed that Cu2O is the major compound formed over the surfaces of pure Cu and Cu-Ni, whereas mixed oxides/hydroxides were detected over the surfaces of Cu-Zn (Cu2O and ZnO) and Cu-Ni-Zn alloy (CuO, ZnO, Cu(OH)(2) and Ni(OH)(2)). However, in Na2S-polluted NaCl environments, sulphide compounds (such as Cu2S) were detected on the surfaces of Cu-Ni and Cu-Zn. X-ray diffraction (XRD) analysis confirmed the XPS findings, where Cu2O was confirmed in case of Cu and CuO in case of Cu-Ni-Zn in pure NaCl solutions. However, in sulphide-polluted media, compounds such as Cu-4(S-2)(2)(CuS)(2) were identified in case of Cu-Ni, and CuS in case of Cu-Zn. Further, the morphology of the surface of Cu-Ni-Zn tested in Na2S-polluted NaCl solution looks compact and has a wide band gap (4.47 eV) as revealed from the UV-vis absorption measurements. Therefore, the formation of mixed oxides/hydroxides and/or sulphides on the surface of Cu-Ni-Zn alloy is ultimately responsible for the enhancement of its dissolution resistance. (C) 2015 Elsevier B.V. All rights reserved.