Batch experiments and X-ray photoelectron spectroscopic (XPS) analyses were performed to study the reactions between arsenate [As(V)], arsenite [As(III)] and zero-valent iron [Fe(0)]. The As(III) removal rate was higher than that for As(V) when iron filings (80-120 mesh) were mixed with arsenic solutions purged with nitrogen gas in the pH range of 4-7. XPS spectra of the reacted iron coupons showed the reduction of As(III) to As(0). Soluble As(III) was formed when As(V) reacted with Fe(0) under anoxic conditions. However, no As(0) was detected on the iron coupons after 5 days of reaction in the As(V)-Fe(0) system. The removal of the arsenic species by Fe(0) was attributed to electrochemical reduction of As(III) to sparsely soluble As(0) and adsorption of As(III) and As(V) to iron hydroxides formed on the Fe(0) surface under anoxic conditions. When the solutions were open to atmospheric air, the removal rates of As(V) and As(III) were much higher than under the anoxic conditions, and As(V) removal was faster than As(III). The rapid removal of As(III) and As(V) was caused by adsorption on ferric hydroxides formed readily through oxidation of Fe(0) by dissolved oxygen.