Under natural conditions, arsenic is often associated with iron oxides and iron(III) oxidative capacity towards As(III) is well known. In this study, As(HI) and As(V) removal was performed using synthesised iron(III) phosphate, either amorphous or crystalline. This solid can combine (i) As(III) oxidation by iron(III) and (ii) phosphate substitution by As(V) due to their similar properties. Results showed that adsorption capacities were higher towards As(III), leading to Fe2+ and HAsO42- leaching. Solid dissolution and phosphate/arsenate exchange led to the presence of Fe3+ and PO43- in solution, therefore various precipitates involving As(V) can be produced: with Fe2+ as Fe-3(AsO4)(2)center dot 8H(2)O((s)) and with Fe3+ as FeASO(4)center dot 2H(2)O((s)). Such formations have been assessed by thermodynamic calculations. This sorbent can be a potential candidate for industrial waste treatment, although the high release of phosphate and iron will exclude its application in drinking water plants. (c) 2005 Elsevier B.V. All rights reserved.