The local atomic environment of lead (Pb) adsorbed to a CH3(CH2)(19)COOH Langmuir monolayer was investigated in situ using grazing-incidence X-ray absorption fine structure (GI-XAFS) spectroscopy at the Pb L-III edge. Measurements were performed at pH 6.5 of the 10(-5) M PbCl2 solution subphase, a condition under which grazing incidence diffraction (GID) revealed a large-area commensurate superstructure underneath the close-packed organic monolayer. The XAFS results indicate covalent binding of the Pb cations to the carboxyl headgroups, and the observed Pb-Pb coordination suggests that the metal is adsorbed as a hydrolysis polymer, rather than as individual Pb2+ ions. The data are consistent with a bidentate chelating mechanism and a one Pb atom to one carboxyl headgroup binding stoichiometry. We discuss how this adsorption model can explain the peculiarities observed with Ph in previous metal-Langmuir monolayer studies. A systematic study of lead perchlorate and lead acetate aqueous solutions is presented and used in the analysis. XAFS multiple scattering effects from alignment of the Pb-C-C atoms in the lead acetate solutions are reported.