Thiosulfate system is considered an interesting alternative leaching process for precious metals. Nevertheless, most of the literature published on these conventional thiosulfate leaching solutions has been focused on the use of ammonia and copper to generate the cupric tetraamine complex, which acts as a catalytic oxidant for silver. However, ammonia toxicity is also a detrimental issue in terms of the process sustainability. For that reason, thiosulfate-nitrite-copper solutions were studied as an alternative less toxic system for silver leaching. In this work, the effect of the thiosulfate concentration (0.07 M, 0.1 M and 0.15 M) and temperature (room temperature, 30, 35, 40 and 45 degrees C) on the metallic silver leaching kinetics is presented for the S2O3-NO2-Cu system. The results show that the thiosulfate concentration plays an important role in the S2O3-NO2-Cu-Ag system since it controls the silver leaching kinetics. On the other hand, an increase in temperature favors the silver recovery. Finally, the SEM-EDS analysis, the X-ray mapping and the X-ray diffractograms show that the solid silver particles are coated by a Cu, S and 0 layer for the 0.07 M and 0.1 M thiosulfate experiments, which is consistent with the formation of antlerite (Cu-3(SO4)(OH)(4)); while the 0.15 M thiosulfate scenario produced a layer composed only of Cu and S, revealing the formation of stromeyerite (CuAgS). The UV-Visible technique confirmed the in-situ generation of copper-ammonia complexes for the 0.07 M leaching condition; however, these complexes are not formed at the 0.15 M condition. (C) 2015 Elsevier Ltd. All rights reserved.