The study of internal interfaces using spatially resolved electron energy loss near-edge structure (ELNES) appears to allow the determination of local atomic environments and valence states of interfacial atomic species via a simple fingerprint formulism. Using the results of multiple scattering theory, this formulism is investigated in depth for the case of diffusion bonded niobium/-alumina interfaces and conclusions are drawn in terms of the available information content. The prospects for employing ELNES as a probe of the medium-range order present at interfaces are also considered.