The ability of bentonite and montmorillonite pillared by Al-oxide and mixed (Ln-Al)-oxides (Ln = La, Ce) to remove (239)plutonium solution species from water is comparatively investigated at pH 7 and pH 4. Small-angle scattering and neutron contrast variation with H2O/D2O mixtures is used to verify the ingress of water in the calcined products after hydrophilicity was introduced by an NH3-H2O vapor treatment. The size and shape of the (La/Ce)-Al oxo-hydroxy pillaring cations (2 nm spheres) is determined by small-angle x-ray scattering from the pillaring solutions. Not all of the oxide pillars improved Pu uptake compared with sodium montmorillonite. At neutral and acidic pH only (Ce-Al)-oxide pillared clays showed the ability to remove Pu over the concentration range studied (1.35 x 10(-8)-8 x 10(-8) mol dm(-3)) with distribution coefficient (K-D) values > 10(4). XPS analysis of the (Ce-Al)-oxide pillared days indicates the presence of Ce4+ as cerium dioxide. The progressive improvement in sorption performance in the order of pillar type Al2O3 < La2O3 center dot Al2O3 < < CeO2 center dot Al2O3 reflects the increasing access of Pu solution species to the clay mineral layers by changes to the basal spacing and specific surface area, and also to the higher stability of the (Ce-Al)-oxide pillars.