Two zirconium alloys (Zr-2.5%Nb) - one oxidized in a pressurized water reactor, the other oxidized in autoclave and used as reference - are analyzed by combining synchrotron-based scanning transmission and fluorescence X-ray microscopy and micro-X-ray absorption spectroscopy (micro-XAS). Two-dimensional zirconium distribution maps recorded on the neutron irradiated and the non-irradiated autoclaved Zr-2.5%Nb alloys clearly allow the localization of the oxide and the metal parts of the interface with a micrometer spatial resolution. Micro-XAS investigations make possible the determination of the speciation of zirconium and niobium both in the oxide and the metal parts of the interface for the irradiated and non-irradiated samples. The coordination environment and/or the valency of zirconium and niobium in the metal and the oxide parts of the interface have been determined for both materials, and interpreted on the basis of comparison with metal and oxide reference compounds. (c) 2008 Elsevier B.V. All rights reserved.