Formation of crystalline PuO2+x·nH2O nanoparticles upon sorption of Pu(V,VI) onto hematite

Abstract

It has been recognized that natural aquatic colloids can readily sorb actinide elements, including plutonium, whose behavior is complicated by its multiple valence states and the possibility of redox reactions under environmental conditions. In this paper, the sorption and surface-mediated redox transformations of hexavalent plutonium on synthetic well-characterized hematite colloids are studied in a series of batch sorption experiments. The variation in the kinetics of the Pu–hematite interactions, Pu-L3-XAFS, and HRTEM over a broad range of total concentrations of Pu have been studied in an attempt to define the molecular-level speciation of Pu. The surface-mediated slow reduction of Pu(V/VI) results in the formation of crystalline nanoparticles of PuO2+x·nH2O approximately 1.5nm in size at [Pu]tot⩾10−9M. This result is confirmed independently by HRTEM images of Pu-containing particles and through the identification in the EXAFS of a Pu neighbor shell at 3.8Å. The formation of such nanoparticles potentially influences the colloid-mediated transport of Pu in the subsurface environment because of the very slow leaching of Pu from the hematite colloids.