We report an electron-energy-loss-spectroscopy study of the characteristic oxygen K and iron L2,3 edges in FeO, Fe3O4, ±-Fe2O3, and -Fe2O3 thin films. Data have been processed for quantitative elemental analysis and for detailed comparison of the different fine structures (energy position and width as well as relative intensities). Oxygen edge profiles are sensitive to the local bonding and symmetry properties on the excited anion. The features of the prepeak at the onset are governed by the 3d components in the hybridized unoccupied pd wave functions. They can be described in a molecular-orbital scheme and depend on the first coordination shell. Oscillations at higher energies are interpreted in terms of backscattering from the next coordination shells. The intense white lines on the iron L2,3 edges are due to strong 2p63dn'2p53dn+1 excitations, and the recorded changes of relative intensity (or branching ratio) are predominantly governed by strong Coulomb and exchange interactions on the excited cation. © 1991 The American Physical Society.