Leach residues, produced during pilot and demonstration scale medium temperature (150 degrees C) hydrometallurgical processing of sulfide ores contain amorphous/poorly crystalline and metastable nano-scale iron oxides/oxyhydroxide phases. These phases control the properties of the residue and contain a relatively high loading of the valuable (Cu, Ni) metals. Residue samples from CESL and Vale pilot and demonstration plant medium temperature processes were characterized using different techniques. Poor agreement between total iron analysis by inductively coupled plasma mass spectroscopy (ICP-MS) and quantitative X-ray powder diffraction QXRPD indicated the presence of amorphous/poorly crystalline iron oxide phases. QXRPD coupled with sequential extraction was used for quantification of the amorphous iron phases. Amorphous iron oxides/oxyhydroxides were found to be a major source of copper and nickel losses to the residue. The distribution of copper and nickel into the amorphous and crystalline iron oxide phases was determined by a two-stage sequential extraction process. Association of copper and nickel to the amorphous phases was found to be approximately 2-4 times higher than with the crystalline iron oxide phases. (C) 2016 Elsevier B.V. All rights reserved.