Biogenic nanoparticulate UO2: Synthesis, characterization, and factors affecting surface reactivity

The surface reactivity of biogenic, nanoparticulate UO₂ with respect to sorption of aqueous Zn(II) and particle annealing is different from that of bulk uraninite because of the presence of surface-associated organic matter on the biogenic UO₂. Synthesis of biogenic UO₂ was accomplished by reduction of aqueous uranyl ions, by Shewanella putrefaciens CN32, and the resulting nanoparticles were washed using one of two protocols: (1) to remove surface-associated organic matter and soluble uranyl species (NAUO2), or (2) to remove only soluble uranyl species (BIUO2). A suite of bulk and surface characterization techniques was used to examine bulk and biogenic, nanoparticulate UO₂ as a function of particle size and surface-associated organic matter. The N₂-BET surface areas of the two biogenic UO₂ samples following the washing procedures are 128.63 m² g⁻¹ (NAUO2) and 92.56 m² g⁻¹ (BIUO2), and the average particle sizes range from 5-10 nm based on TEM imaging. Electrophoretic mobility measurements indicate that the surface charge behavior of biogenic, nanoparticulate UO₂ (both NAUO2 and BIUO2) over the pH range 3-9 is the same as that of bulk. The U L_III-edge EXAFS spectra for biogenic UO₂ (both NAUO2 and BIUO2) were best fit with half the number of second-shell uranium neighbors compared to bulk uraninite, and no oxygen neighbors were detected beyond the first shell around U(IV) in the biogenic UO₂. At pH 7, sorption of Zn(II) onto both bulk uraninite and biogenic, nanoparticulate UO₂ is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. The maximum surface area-normalized Zn(II) sorption loadings for the three substrates were 3.00 ± 0.20 μmol m⁻² UO₂ (bulk uraninite), 2.34 ± 0.12 μmol m⁻² UO₂ (NAUO2), and 2.57 ± 0.10 μmol m⁻² UO₂ (BIUO2). Fits of Zn K-edge EXAFS spectra for biogenic, nanoparticulate UO₂ indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations were observed at 2.8 ± 0.1 Å for NAUO2 and bulk uraninite; however, they were not observed for sample BIUO2. The derived Zn-U distance, coupled with an average Zn-O distance of 2.09 ± 0.02 Å, indicates that Zn(O,OH)₆ sorbs as bidentate, edge-sharing complexes to UO₈ polyhedra at the surface of NAUO2 nanoparticles and bulk uraninite, which is consistent with a Pauling bond-valence analysis. The absence of Zn-U pair correlations in sample BIUO2 suggests that Zn(II) binds preferentially to the organic matter coating rather than the UO₂ surface. Surface-associated organic matter on the biogenic UO₂ particles also inhibited particle annealing at 90 °C under anaerobic conditions. These results suggest that surface-associated organic matter decreases the reactivity of biogenic, nanoparticulate UO₂ surfaces relative to aqueous Zn(II) and possibly other environmental contaminants.