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Neptunium Reactivity During Co-Precipitation and Oxidation of Fe(II)/Fe(III) (Oxyhydr)oxides

Research Centre for Radwaste Disposal and Williamson Research Centre for Molecular Environmental Science, School of Earth, and Environmental Sciences, The University of Manchester, Manchester M13 9PL, UK
Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, UK
Radiochemistry Unit, Department of Chemistry, The University of Helsinki, A.I. Virtasen Aukio 1 (PL 55), 00014 Helsinki, Finland
Author to whom correspondence should be addressed.
Geosciences 2019, 9(1), 27;
Received: 23 November 2018 / Revised: 14 December 2018 / Accepted: 14 December 2018 / Published: 8 January 2019
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Fe(II) bearing iron (oxyhydr)oxides were directly co-precipitated with Np(V)O2+ under anaerobic conditions to form Np doped magnetite and green rust. These environmentally relevant mineral phases were then characterised using geochemical and spectroscopic analyses. The Np doped mineral phases were then oxidised in air over 224 days with solution chemistry and end-point oxidation solid samples collected for further characterisation. Analysis using chemical extractions and X-ray absorption spectroscopy (XAS) techniques confirmed that Np(V) was initially reduced to Np(IV) during co-precipitation of both magnetite and green rust. Extended X-Ray Absorption Fine Structure (EXAFS) modelling suggested the Np(IV) formed a bidentate binuclear sorption complex to both minerals. Furthermore, following oxidation in air over several months, the sorbed Np(IV) was partially oxidised to Np(V), but very little remobilisation to solution occurred during oxidation. Here, linear combination fitting of the X-Ray Absorption Near Edge Structure (XANES) for the end-point oxidation samples for both mineral phases suggested approximately 50% oxidation to Np(V) had occurred over 7 months of oxidation in air. Both the reduction of Np(V) to Np(IV) and inner sphere sorption in association with iron (oxyhydr)oxides, and the strong retention of Np(IV) and Np(V) species with these phases under robust oxidation conditions, have important implications in understanding the mobility of neptunium in a range of engineered and natural environments. View Full-Text
Keywords: neptunium; magnetite; green rust; oxidation; XAS; XANES; EXAFS neptunium; magnetite; green rust; oxidation; XAS; XANES; EXAFS

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Roberts, H.E.; Morris, K.; Mosselmans, J.F.W.; Law, G.T.W.; Shaw, S. Neptunium Reactivity During Co-Precipitation and Oxidation of Fe(II)/Fe(III) (Oxyhydr)oxides. Geosciences 2019, 9, 27.

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