Characterization of copper and ammonia interactions with the passive layer that impedes gold dissolution with thiosulfate based electrolytes at extended time frames was performed with electrochemistry and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Generalized two-dimensional correlation spectroscopy (2DCOS) was also employed to assist interpretation of the collected SHINERS spectra. Growth of the complex passive layer mixture on a polycrystalline gold electrode immersed in a 0.10 M Na2S2O3 electrolyte was found to initially proceed through formation of sulfides adsorbed to the gold electrode surface (SERS band at ca. 326 and 309 cm(-1)) followed by rapid transformation to cyclo-S-8 (474, 218, and 152 cm(-1)) and polysulfides/polythionates (459 cm(-1)). After stable formation of the passive film, the addition of Cu2+ resulted in the partial removal of the passive layer. The removal of the components of the passive layer proceeded according to the following sequence; polysulfides were fastest, cyclo-S-8 next, followed by S-(ads)(2-). The end product was observed to be a combination of copper and gold sulfides. In an independent study, the addition of ammonia displayed a similar ability to remove the passive layer constituents, albeit at much slower rates. From these observations it can be concluded that copper and ammonia play a vital function in preventing passive layer formation, allowing increased mass transport of thiosulfate and the oxidant across the electrode electrolyte interface, thereby allowing a higher gold extraction efficiency. (C) 2016 Elsevier Ltd. All rights reserved.