Presorbed phosphate significantly increases Pb sorption on the phyllosilicate kaolinite in the pH range from 4to 8. The sorbed Pb-to-P molar ratios over this pH range stray little from the molar ratio found in the mineral pyromorphite, suggesting sorbed phosphate reacts with soluble Pb to form a surface precipitate similar to pyromorphite. X-ray absorption near edge structure (XANES) studies at the Pb L3-edge support this interpretation. In particular, the fine structure of first-derivative Pb L3-edge XANES spectra of Pb species sorbed to phosphate-treated kaolinite samples covering a pH range extending from 4 to 10 match the fine structure of the spectrum of pyromorphite. Although the productis structurally and compositionally similarto pyromorphite, the ion activity product in the pH range 4-6 was undersaturated with respect to the solubility product of pyromorphite.