The adsorption of oxygen and water vapor on a number of specially prepared alpha-Fe2O3 samples was measured gravimetrically at 25 degrees C. The samples themselves were prepared from a steel-pickling chemical waste(97 wt% FeSO4 . 7H(2)O) by roasting the original material at 700 degrees C for 5 h in air, oxygen, and nitrogen. Estimated surface coverages by the adsorbed oxygen and water vapor were made on the basis of nitrogen-adsorption-based surface areas, while the nature of the sample surfaces was investigated by both X-ray photoelectron spectroscopy (XPS) and field emission SEM (FESEM) techniques. In addition a depth profiling study utilizing a sputtering argon beam and XPS was undertaken. Morphological studies using FESEM showed that, while the surface areas were essentially the same (27-29 m(2)/g) for all three samples, the sample prepared in nitrogen had a significantly larger particle size than the other two. These studies also indicated that neither oxygen nor water vapor adsorption caused any significant structural changes. The differing sample preparations resulted in differing oxygenated surfaces for the alpha-Fe2O3 samples, with the degree of oxygenation decreasing in the order of preparatory gases : oxygen, (wet) air, nitrogen. The amounts of both oxygen and water vapor adsorbed were in inverse proportion to the original degree of surface oxygenation, though the amounts of both represented fractional coverage at best, While the water vapor adsorption was always greater than that of oxygen, the former was more weakly adsorbed, as was indicated by the ease of desorption. Depth profiling failed to indicate any bulk diffusion of oxygen but could not be considered reliable since even the attenuated argon beam used here still brought about reduction of surface iron. Both oxygen and dissociative water adsorption are thought to involve surface sites of high coordination unsaturation. Oxygen is postulated to adsorb on such poorly oxygenated sites primarily as O-2(-); however, O-2(-) and possibly O- or Fe = O are also thought to play a role.