title: Neptunium(V) coprecipitation with calcite.
abstract: Coprecipitation experiments of Np(V) and U(VI) with calcite were performed in mixed-flow reactors under steady state conditions at room temperature for up to 400 h at precipitation rates of 1.0 x 10(-8) to 6.8 x 10(-8) mol/(m2 s). The saturation index with respect to calcite varied between 0.04 and 0.95. Initial Np(V) or U(VI) concentrations were 1 micromol/L, 0.01 mol/L NaCl was used as background electrolyte, and pH ranged from 7.8 to 12.8. Partition coefficients for Np(V) were in the range of 0.5-10.3, compared to 0.02 for U(VI). Np L(III) and U L(III) EXAFS were used to characterize the local structural environment of the incorporated actinides. In the case of U(VI), the structural environment is not unambiguously characterized. Our data suggest that Np(V) ions occupy calcium lattice sites. The two axial oxygen atoms of the linear neptunyl moiety substitute two calcite carbonate groups in the first coordination sphere. Thus, four carbonate groups coordinate the neptunyl-ion in a monodentate fashion with four equatorial oxygen atoms (Oeq) at 2.4 A and associated carbon atoms (C) at 3.2 A. The interatomic distances indicate slight structural relaxation of the carbonate groups from their ideal sites. A similar structural model has been reported for U(VI) incorporated into natural calcite.
authors.affiliation: Institut für Nukleare Entsorgung, Forschungszentrum Karlsruhe, P.O. Box 3640, 76021 Karlsruhe, Germany. Frank.Heberling@ine.fzk.de
authors.forename: Frank
authors.initials: F
authors.lastname: Heberling
authors.forename: Melissa A
authors.initials: MA
authors.lastname: Denecke
authors.forename: Dirk
authors.initials: D
authors.lastname: Bosbach
mesh_terms: D000327:Adsorption; D002119:Calcium Carbonate / Q000737:chemistry*; D011232:Chemical Precipitation; D006863:Hydrogen-Ion Concentration; D009405:Neptunium / Q000737:chemistry*; D013057:Spectrum Analysis; D014501:Uranium / Q000737:chemistry; D014875:Water Pollutants, Radioactive / Q000737:chemistry; D014965:X-Rays
chemical_list: D014875:Water Pollutants, Radioactive; D014501:Uranium; D009405:Neptunium; D002119:Calcium Carbonate