The partial Al and O valence spectral densities of alpha- and gamma-al
umina in bulk and in the superficial zone of the samples are investiga
ted using x-ray emission spectroscopy induced by electrons. These vale
nce states are mixed over the whole width of the band. We show that ch
anges in the atomic environment affect the hybridization of states in
a narrow energy range. For the gamma-phase and superficial zones of th
e two phases, increased hybridization is observed. This is correlated
with an increase in the covalent character of Al-O bonds at the surfac
e and the gamma-phase. Defect states are observed both in the gap betw
een O 2s and O 2p states and in the optical gap; for the alpha-phase,
a structure is seen at about 1 eV above the top of the valence band wh
ich we interpret as due to an oxygen-vacancy state.