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Reactions of the feldspar surface with metal ions: Sorption of Pb(II), U(VI) and Np(V), and surface analytical studies of reaction with Pb(II) and U(VI) |
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| Authors: | Emmanuelle S Chardon Dirk Bosbach Ian C Lyon Jürgen Römer David J Vaughan Roy A Wogelius |
| Institution: | a Centre for Radiochemistry Research, School of Chemistry, The University of Manchester, Manchester M13 9PL, UK b School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, Manchester M13 9PL, UK c Forschungszentrum Karlsruhe, Institut für Nukleare Entsorgung (INE), Postfach 3640, D-76021 Karlsruhe, Germany |
| Abstract: | Feldspar minerals are thermodynamically unstable in the near-surface environment and their surfaces are well known to react readily with aqueous solutions, leading to incongruent dissolution at low pH values, but congruent dissolution at neutral and high pH values. Interactions with mineral surfaces are an important control on the environmental transport of trace elements and detrital feldspars are abundant in soils and sediments. However, the interactions of metal ions in solution with the reacting feldspar surface have not been widely explored. The interactions of Pb(II), U(VI) and Np(V) ions with the feldspar surface have therefore been studied. Lead is taken up by the microcline surface at pH 6 and 10, but no uptake could be measured at pH 2. There was measurable uptake of Pb(II) on the plagioclase surface at pH 2, 6 and 10. Uptake always increased with pH. In most conditions, Pb(II) reacts through cation exchange process although, at high pH, a discrete phase, probably hydrocerrusite, is observed by atomic force microscopy (AFM) to precipitate on the plagioclase surface. Supersaturation with hydrocerrusite in these conditions is expected from thermodynamic calculations. Uptake of uranyl ion  , generally through surface complex formation, could only be measured at pH 6 and 10. At pH 6 and an initial U(VI) concentration above 21.0 μM, precipitation of becquerelite (Ca(UO2)3O2(OH)3]2·8H2O), identified by AFM and characterised by grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy, is observed on plagioclase. The U(VI) concentration range in which becquerelite precipitation begins (dissolved U(VI) 1-5 μM) is consistent with that predicted from thermodynamic modelling. On plagioclase feldspar, secondary ion mass spectrometry showed diffusion of uranium into the altered surface layer. Uptake of the neptunyl ion (Np(V)) was found at pH 6 and 10 for microcline and at pH 2, 6 and 10 for plagioclase, and was generally lower than uptake of U(VI). By combining batch sorption experiments with imaging and surface analysis, and thermodynamic modelling, it has been possible to gain a mechanistic insight into the reactions of the feldspar surface with metal ions in solution. |
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