NeptuniumV retention by siderite under anoxic conditions: Precipitation of NpO2–like nanoparticles and of NpIV pentacarbonate
NeptuniumV retention by siderite under anoxic conditions: Precipitation of NpO2–like nanoparticles and of NpIV pentacarbonate
Scheinost, A. C.; Steudtner, R.; Hübner, R.; Weiss, S.; Bok, F.
The NpV retention by siderite, an FeII carbonate mineral with relevance for the near-field of high-level radioactive waste repositories, was investigated under anoxic conditions. Batch sorption experiments show that siderite has a high affinity for aqueous NpVO2+ across pH 7 to 13 as expressed by solid-water distribution coefficients, log Rd, >5, similar to the log Rd determined for the (solely) tetravalent actinide Th on calcite, suggesting reduction of NpV to NpIV by siderite. Np L3-edge X-ray absorption near edge (XANES) spectroscopy conducted in a pH range typical for siderite-containing host rocks (7 - 8), confirmed the tetravalent Np oxidation state. Extended X-ray absorption fine-structure (EXAFS) spectroscopy revealed a local structure in line with NpO2–like nanoparticles with diameter < 1 nm, a result further corroborated by high-resolution transmission electron microscopy (HRTEM). The low solubility of these NpO2–like nanoparticles (10-9 M), along with their negligible surface charge at neutral pH conditions which favors particle aggregation, suggest an efficient retention of Np in the near-field of radioactive waste repositories. When NpV was added to ferrous carbonate solution, the subsequent precipitation of siderite did not lead to a structural incorporation of NpIV by siderite, but caused precipitation of a NpIV pentacarbonate phase.
Keywords: neptunium; siderite; carbonate; radioactive waste respository; XAFS; XANES
Involved research facilities
- Ion Beam Center DOI: 10.17815/jlsrf-3-159
- Rossendorf Beamline at ESRF DOI: 10.1107/S1600577520014265
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- DOI: 10.1107/S1600577520014265 is cited by this (Id 23676) publication
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Environmental Science & Technology 50(2016)19, 10413-10420
Online First (2016) DOI: 10.1021/acs.est.6b02399
Cited 12 times in Scopus
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