A novel technique for examining metal-ion interactions at the solid-water interface is introduced. Planar oxides, flat, thin coatings of uniform thickness created on a metal support, have been constructed as useful analogs for investigating metal-solid interactions under a variety of conditions. XPS and ToF/SIMS results from sorption studies at pH 6.0 show that the sorption behavior of Pb on each phase is similar with Pb binding preferentially to the bulk gamma-Al2O3. This may be due to the presence of defect sites on the bulk oxides, the preferential exposure of a specific crystallographic plane in the planar oxides, or it may be an artifact of instrumental analysis. A second study examining Pb sorption to planar gamma-Al2O3 under a series of increasingly complex conditions shows that our methods are able to successfully characterize sorption complexes formed in the presence of environmentally derived complexants. Results suggest that Pb is more strongly complexed by aqueous phase organic matter than sediment-bound organic material, indicating a possible control on Pb sorption in natural environments. Overall, the use of planar oxides combined with a powerful suite of spectroscopic tools provides a promising approach to better understanding metal ion sorption to natural sediment surfaces in aquatic environments.