The distributions of Pb(II) and As(V)O-4(3-) ions in the interfacial region between thin poly(acrylic acid) (PAA) coatings and α-Al2O3(0001), α-Al2O3(1-102), and α-Fe2O3(0001) single-crystal substrates were studied using long-period X-ray standing wave fluorescent yield (XSW-FY) and X-ray reflectivity techniques. The PAA film serves as a simplified analogue of natural organic matter (NOM) coatings on mineral surfaces. Such coatings are often assumed to play an important role in the partitioning and speciation of trace heavy metals in soils and aquatic systems. On the α-Al2O3(1-102) surface, Pb(II) ions were found to preferentially bind to the PAA coating, even at sub-micromolar Pb(H) concentrations, and to partition increasingly onto the metal oxide surface as the Pb(II) concentration was increased ([Pb(II)] = 5 x 10(-8) to 2 x 10(-5) M, pH = 4.5; 0.01 M NaCl background electrolyte). This observation suggests that the binding sites in the PAA coating outcompete those on the α-Al2O3(1-102) surface for Pb(II) under these conditions. The As(V)O-4(3-) oxoanion partitions preferentially to the α-Al2O3(1-102) surface for the As(V)O-4(3-) concentrations examined (1 x 10(-7) to 5 x 10(-7) M, pH = 4.5; 0.01 M NaCl background electrolyte). Partitioning of Pb(H) (at 1 x 10(-7) M and pH 4.5) was also examined at PAA/α-Al2O3(0001), and PAA/α-Fe2O3(0001) interfaces using XSW-FY measurements. Our results show that the PAA coating was the dominant sink for Pb(II) in all three samples; however, the relative order of reactivity of these metal oxide surfaces with respect to Pb(II) sorption is α-Fe2O3(0001) > α-Al2O3(1-102) > α-Al2O3(0001). This order is consistent with that found in previous studies of the PAA-free surfaces. These XSW results strongly suggest that the characteristics of the organic film (i.e., binding affinity, type, and density of binding sites) as well as metal oxide substrate reactivity are key factors determining the distribution and speciation of Pb(II) and As(V)O-4(3-) at organic film/metal oxide interfaces.