To investigate the effect of P surface loading on the structure of surface complexes formed at the goethite/water interface, goethite was reacted with orthophosphate at P concentrations of 0.1, 0.2, and 0.8 mmol L-1 at pH 4.5 for 5 days. The P concentrations were chosen to ensure that P loadings at the surface would allow one to follow the transition between adsorption and surface precipitation. Extended X-ray Absorption Fine Structure (EXAFS) spectra were collected in fluorescence mode at the P K-edge at 2150 eV. The structural parameters were obtained through the fits of the sorption data to single and multiple scattering paths using Artemis. EXAFS analysis revealed a continuum among the different surface complexes, with bidentate mononuclear (E-2), bidentate binuclear (C-2) and monodentate mononuclear (V-1) surface complexes forming at the goethite/water interface under the studied conditions. The distances for P-O (1.51-1.53 angstrom) and P-Fe (3.2-3.3 angstrom for bidentate binuclear and around 3.6 angstrom for mononuclear surface complexes) shells observed in our study were consistent with distances obtained via other spectroscopic techniques. The shortest P-Fe distance of 2.83-2.87 angstrom was indicative of a bidentate mononuclear bonding configuration. The coexistence of different surface complexes or the predominance of one sorption mechanism over others was directly related to surface loading. (c) 2014 Elsevier Inc. All rights reserved.