Sorption of Zn(II)((aq)) on hematite (alpha-Fe2O3) nanoparticles (average diameter 10.5 nm) and microparticles (average diameter 550 nm) has been examined over a range of total Zn(II)((aq)) concentrations (0.4-7.6 mM) using Zn K-edge EXAFS spectroscopy and selective chemical extractions. When ZnCl2 aqueous solutions were reacted with hematite nanoparticles (HN) at pH 5.5, Zn(II) formed a mixture of four- and six-coordinated surface complexes [Zn(O,OH)(4) and Zn(O,OH)(6)] with an average Zn-O distance of 2.04 +/- 10.02 angstrom at low sorption densities (Gamma +/- 1.1 mu mol/m(2)). On the basis of EXAFS-derived Zn-Fe3+ distances of (3.10-3.12) +/- 0.02 angstrom, we conclude that both Zn(O,OH)(6) and Zn(O,OH)(4) adsorb on octahedral Fe3+ (O,OH)(6) or pentahedral Fe3+ (O,OH)(5) surface sites on HN as inner-sphere, mononuclear, bidentate, edge-sharing adsorption complexes at these low sorption densities. It is possible that polynuclear Zn complexes are also present because of the similarity of Zn and Fe backscattering. At higher Zn(II) sorption densities on hematite nanoparticles (Gamma >= 3.38 mu mol/m(2)), we observed the formation of Zn(O,OH)(6) surface complexes, with an average Zn-O distance of 2.09 +/- 0.02 angstrom, a Zn-Zn distance of 3.16 +/- 0.02 angstrom, and a linear multiple-scattering feature at 6.12 +/- 0.06 angstrom. Formation of a Zn(OH)(2(am)) precipitate for the higher sorption density samples (Gamma +/- 3.38 mu mol/m(2)) is suggested on the basis of comparison of the EXAFS spectra of the sorption samples with that of synthetic Zn(OH)(2(am)). In contrast, EXAFS spectra of Zn(II) sorbed on hematite microparticles (HM) under similar experimental conditions showed no evidence of surface precipitates even at the same total [Zn(II)((aq))] that resulted in precipitate formation in the nanoparticle system. Instead, Zn(O,OH)(6) octahedra (d(Zn-O) = 2.10 +/- 0.02 angstrom) were found to sorb dominantly in an inner-sphere, bidentate, edge-sharing fashion on Fe3+ (O,OH)(6) octahedra at hematite microparticle surfaces, based on an EXAFS-derived Zn-Fe3+ distance of 3.44 +/- 0.02 angstrom. CaCl2 selective extraction experiments showed that 10-15% of the sorbed Zn(II) was released from Zn/HN sorption samples, and about 40% was released from a Zn/HM sorption sample. These fractions of Zn(II) are interpreted as weakly bound, outer-sphere adsorption complexes. The combined EXAFS and selective chemical extraction results indicate that (1) both Zn(O,OH)(4) and Zn(O,OH)(6) adsorption complexes are present in the Zn/HN system, whereas dominantly Zn(O,OH)(6) adsorption complexes are present in the Zn/HM system; (2) a higher proportion of outer-sphere Zn(II) surface complexes is present in the Zn/HM system; and (3) Zn-containing precipitates similar to Zn(OH)(2(am)) form in the nanoparticle system but not in the microparticle system, suggesting a difference in reactivity of the hematite nanoparticles vs microparticles with respect to Zn(II)((aq)).