Phosphate adsorption on hematite was characterized as a function of pH (3.5-8.9) and phosphate concentration (5-500 mu M) by in situ ATR-FTIR spectroscopy. Under most conditions a mixture of different (inner-sphere) phosphate complexes existed at the hematite surface, with the relative importance of these complexes varying with pH and surface coverage. Experiments using D2O and H2O indicated the presence of two protonated phosphate surface complexes at pH/pD = 3.5-7.0. Comparison to spectra of protonated aqueous phosphate species suggested that these surface complexes are monoprotonated. The difference in the IR spectra of these complexes is tentatively interpreted to result from a different surface coordination. with one surface complex coordinated in a monodentate binuclear (bridging) fashion, and the second as a monodentate mononuclear complex. Alternatively, the bridging complex may be a (protonated) monodentate mononuclear complex exhibiting strong hydrogen bonding to an adjacent surface site. and the second species a monodentate complex exhibiting limited hydrogen bonding. Formation of the bridging complex is favored at lower pH values and higher surface loadings in the 3.5-7.0 pH range. At the highest pH values studied (8.5-9.0) a third complex, interpreted to be a nonprotonated monodentate mononuclear complex, is present along with the monodentate monoprotonated surface species. The importance of the nonprotonated monodentate complex increases with increasing surface coverage at these high pH values. (c) 2007 Elsevier Inc. All rights reserved.