This study investigated the effect of iron-containing mordants on the discoloration of human dentin. Dentin wafers with intact enamel borders were treated with one of several acid solutions containing iron. After exposure to aqueous sodium sulfide, color change was evaluated colorimetrically. X-ray photoelectron spectroscopy (XPS) and energy dispersive x-ray spectrometry (EDS) were used to probe surfaces for the presence of iron. Changes in surface morphology were evaluated by scanning electron microscopy (SEMI. The results indicated that dentin treated by iron-containing solutions always discolored when the sodium-sulfide concentration exceeded 9.7 mM; variability in discoloration occurred below this level. XPS detected iron in enamel but not in dentin, while EDS detected iron in both enamel and dentin. Since XPS probes the upper atomic layers, these results indicate that acid-demineralized dentin absorbs iron; however, a water wash removes iron from the uppermost dentin surface, suggesting that the iron is physically absorbed. When exposed to sodium sulfide, at least some of the iron remaining in the bulk region is able to migrate to the surface to form iron-sulfide compounds. Based on SEM findings, discoloration is associated with the formation of a surface film on dentin.