Controls on the fate and speciation of Np(V) during iron (oxyhydr)oxide crystallization
Bots, Pieter and Shaw, Samuel and Law, Gareth T.W. and Marshall, Timothy A. and Mosselmans, J. Frederick .W. and Morris, Katherine (2016) Controls on the fate and speciation of Np(V) during iron (oxyhydr)oxide crystallization. Environmental Science and Technology, 50 (7). pp. 3382-3390. ISSN 0013-936X (https://doi.org/10.1021/acs.est.5b05571)
Preview |
Text.
Filename: Bots_etal_EST2016_Controls_on_the_fate_and_speciation_of_Np_V_during_iron_oxyhydr_oxide_crystallization.pdf
Final Published Version License: Download (1MB)| Preview |
Abstract
The speciation and fate of neptunium as Np(V)O2+ during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2+ to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.
ORCID iDs
Bots, Pieter ORCID: https://orcid.org/0000-0001-6863-0648, Shaw, Samuel, Law, Gareth T.W., Marshall, Timothy A., Mosselmans, J. Frederick .W. and Morris, Katherine;-
-
Item type: Article ID code: 56550 Dates: DateEvent5 April 2016Published25 February 2016Published Online25 February 2016AcceptedSubjects: Science > Chemistry
Technology > Chemical engineeringDepartment: Faculty of Engineering > Civil and Environmental Engineering Depositing user: Pure Administrator Date deposited: 27 May 2016 11:40 Last modified: 27 Sep 2024 00:57 Related URLs: URI: https://strathprints.strath.ac.uk/id/eprint/56550