Both X-ray total reflection and X-ray Raman scattering techniques were combined to discriminate chemical environments in depth-profiling studies using an energy dispersive system. This allowed, for the first time, to resolve oxidation state on surface nanolayers with a low-resolution system. Samples of pure Cu and Fe oxidized in tap water and salty water, respectively, were studied in the Brazilian synchrotron facility using monochromatic radiation and an EDS setup. The measurements were carried out in total reflection geometry with incident energy lower and close to the K absorption edge of both elements. The results allowed observing the presence of very thin oxide layers, usually not observable with conventional geometries of irradiation. They also permit the identification of the compound present in a particular depth of the sample with nanometric, or even subnanometric, resolution using a low-resolution system.