The adsorption of phosphate on goethite is generally modeled by assuming a simple ligand exchange reaction with surface hydroxyl groups. This study investigates the binding forms of phosphate on goethite by evaluating the proton interaction and surface charge change during phosphate adsorption. It is found that OH(-) release stoichiometry increases with phosphate coverage, which suggests that different mechanisms predominate at different phosphate loadings. It demonstrates that surface binding changes from monodentate complexation to bidentate complexation with increasing surface phosphate coverage. The net OH(-) release accompanying this transformation is best interpreted with a 2pK(a) multisite model.