LAUSR

A structural study of the surface complexation of Pb(II) on the (11¯02) surface of hematite was undertaken using crystal truncation rod (CTR) X-ray diffraction measurements under in situ conditions. The sorbed Pb was found to form inner sphere (IS) complexes at two types of edge-sharing sites on the half layer termination of the hematite (11¯02) surface. The best fit model contains Pb in distorted trigonal pyramids with an average PbO bond length of 2.27(4) Å and two characteristic Pb-Fe distances of 3.19(1) Å and 3.59(1) Å. In addition, a site coverage model was developed to simulate coverage as a function of sorbate-sorbate distance. The simulation results suggest a plausible Pb-Pb distance of 5.42 Å, which is slightly larger than the diameter of Pb's first hydration shell. This relates the best fit surface coverage of 0.59(4) Pb per unit cell at monolayer saturation to steric constraints as well as electrostatic repulsion imposed by the hydrated Pb complex. Based on the structural results we propose a stoichiometry of the surface complexation reaction of Pb(II) on the hematite (11¯02) surface and use bond valence analysis to assign the protonation schemes of surface oxygens. Surface reaction stoichiometry suggests that the proton release in the course of surface complexation occurs from the Pb-bound surface O atoms at pH 5.5.