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AbstractAbstract
[en] The migration of radio-toxic elements in the geosphere is mainly regulated by chemical parameters which control the partitioning of the elements between mineral phases and aqueous solutions. Variation in temperature may affect the retention properties of a mineral surface and requires a careful investigation in order to understand the radionuclides behavior in the geosphere. In this way, the interaction mechanisms between uranium(VI) and two minerals (LaPO4 and Fe3O4) have been studied. In a first step, the monazite (LaPO4) has been chosen as methodological solid in order to clearly define all the different stages needed to completely characterize the influence of temperature on the sorption phenomena. To reach that goal, three media, more or less complexants towards aqueous uranyl and the mineral surface, have been considered. Physico-chemical as well as surface acid-base properties of the solid surface have been studied by considering three electrolytes (NaClO4, NaNO3 and Na2SO4) and temperatures ranged from 25 C to 95 C. The point of zero charge has been found to be identical for perchlorate and nitrate media (pHPZC=2.1) but it was found to be one pK unit higher for the sulfate medium indicating a sorption of the background electrolyte ions. The reaction heats associated to the hydration of the solid have been measured by using microcalorimetry and the nature of the reactive surface sites has been determined by carrying out Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS). On the basis of these experimental constraints, the titration curves obtained for the monazite suspensions were fitted by using the Constant Capacitance Model and the 1-pK model was preferred to characterize the surface charge evolution, due to the limited number of adjustable parameters. The surface protonation constants being determined, the behavior of U(VI) towards the monazite surface in the three electrolytes has been investigated. On the basis of both U(VI) speciation in solution and the results of a structural study carrying out by using TRLFS together with calorimetric measurements, the sorption edges have been modeled and the corresponding sorption constants determined. Since these values take into account a wide number of experimental results (both structural and thermodynamical ones) they appear to be accurate and could be extrapolated more confidently to other physico-chemical conditions. The experimental approach being validated with the methodological solid, preliminary tests have been carried out to study uranyl sorption onto a second substrate, the magnetite, more relevant than monazite in the field of radionuclides migration in the geosphere. (author)
Original Title
Etude thermodynamique de la sorption de l'uranyle sur la monazite et la magnetite
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Secondary Subject
Source
10 Jul 2012; 236 p; 236 refs.; Available from the INIS Liaison Officer for France, see the 'INIS contacts' section of the INIS website for current contact and E-mail addresses: http://www.iaea.org/inis/Contacts/; Also available from Service Commun de la Documentation Direction, Domaine universitaire de Paris-Sud, Bat. 407, Rue du Doyen-Poitou, 91405 ORSAY cedex, (France); These de Physique Nucleaire
Record Type
Report
Literature Type
Thesis/Dissertation
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Country of publication
CALORIMETRY, CHEMICAL PREPARATION, CHEMICAL STATE, COMPUTERIZED SIMULATION, CORROSION, CRYSTAL STRUCTURE, DISSOLUTION, INTERFACES, LANTHANUM PHOSPHATES, MAGNETITE, MONAZITES, RADIOACTIVE WASTE STORAGE, RADIONUCLIDE MIGRATION, SORPTION, SPECIFIC SURFACE AREA, TEMPERATURE DEPENDENCE, THERMODYNAMICS, UNDERGROUND STORAGE
CHEMICAL REACTIONS, ENVIRONMENTAL TRANSPORT, IRON ORES, LANTHANUM COMPOUNDS, MANAGEMENT, MASS TRANSFER, MATERIALS, MINERALS, ORES, OXIDE MINERALS, OXYGEN COMPOUNDS, PHOSPHATE MINERALS, PHOSPHATES, PHOSPHORUS COMPOUNDS, PHYSICAL PROPERTIES, RADIOACTIVE MATERIALS, RADIOACTIVE MINERALS, RADIOACTIVE WASTE MANAGEMENT, RARE EARTH COMPOUNDS, SIMULATION, STORAGE, SYNTHESIS, THORIUM MINERALS, WASTE MANAGEMENT, WASTE STORAGE
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