Strong electrostatic coupling between the local structure of metal-supported oxide ultra-thin films and the charge state of adsorbed species (such as Au atoms and O-2 molecules) is at the origin of a co-existence of alternative adsorption configurations, with drastically different structural and electronic characteristics. This effect may contribute also to the stabilization of oxide phases of unusual stoichiometries, where the ion valences are compensated by an electron exchange with the metal substrate. We report an analysis of the spectroscopic signatures of such differently charged adsorbates and unusual oxide phases, including valence and core electrons spectroscopies and vibrational characteristics. We show that the adsorbate charge states can be identified by their signature in the electronic states around the Fermi level and by the modification of the vibrational frequencies of adsorbed probe molecules. Moreover, core level analysis may contribute to the identification of the oxygen-rich phase, formed at high oxygen exposure. The detailed theoretical investigation of the spectroscopic signatures of alternative adsorption configurations and adsorbate charge states supplies a set of data, which may help the experimental identification of such species.