NiO/Al2O3 mechanical mixtures and impregnated catalytic materials have been prepared and analysed by XRD, DR-UV-vis-NIR, skeletal FT-IR, XPS, FE-SEM techniques. The presence of the carcinogenic and easily reducible NiO phase (bunsenite) is detected by XRD, DR-vis and DR-NIR with a sensitivity limit well lower than 1000 ppm, which is the lower limit by law to classify a NiO-containing waste, such as spent catalysts, as dangerous. This species is also observed by XPS and FE-SEM with a similar sensitivity limit. Hardly reducible surface dispersed Ni2+ species are also observed by DR-vis with a sensitivity limit lower than 1000 ppm. A surface spinel-like phase, with a composition NixAl2O3+x,with x <= 0.25 is formed at higher loadings, and is distinguished from the highly dispersed Ni2+ species using IR and XRD. This defective surface spinel like species can be distinguished from stoichiometric bulk NiAl2O4 by applying DR-NIR spectroscopy. The stoichiometric bulk nickel aluminate phase NiAl2O4 (which is also classified as carcinogenic) does not form from gamma-Al2O3 or delta-Al2O3 and nickel species at temperatures up to 1073 K. (C) 2016 Elsevier B.V. All rights reserved.