We apply synchrotron radiation assisted X-ray fluorescence (SR-XRF), SR-XRF mapping as well as micro- and conventional X-ray absorption fine structure (mu-XAFS and XAFS) spectroscopies in order to study the bonding environment of Fe and Zn in vitrified samples that contain electric arc furnace dust from metal processing industries. The samples are studied in the as-cast state as well as after annealing at 900 degrees C. The SR-XRF results demonstrate that annealing does not induce any significant changes in the distribution of either Fe or Zn, in both the as-cast and annealed glasses. The mu-XAFS spectra recorded at the Fe-K and Zn-K edges reveal that the structural role of both Fe and Zn remains unaffected by the annealing procedure. More specifically, Fe forms both FeO(6) and FeO(4) polyhedra, i.e. acts as an intermediate oxide while Zn occupies tetrahedral sites.