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Alexandre, Jean-Charles
Ecole Nationale Superieure de Chimie de Montpellier, 240 Avenue du Professeur Emile Jeanbrau, 34090 Montpellier (France); Institut de Chimie Separative de Marcoule, Centre de Marcoule, 30207 Bagnols-sur-Ceze (France); CEA, DAM-DASE (France)2018
Ecole Nationale Superieure de Chimie de Montpellier, 240 Avenue du Professeur Emile Jeanbrau, 34090 Montpellier (France); Institut de Chimie Separative de Marcoule, Centre de Marcoule, 30207 Bagnols-sur-Ceze (France); CEA, DAM-DASE (France)2018
AbstractAbstract
[en] In the field of environmental control, the behavior of plutonium in various media and particularly in surface waters is relevant taking into account its radiotoxicity. Carbonate ions widely present in these media mainly complex pentavalent plutonium. In this field, CE-ICP-MS coupling, which was already used for actinides speciation, has been considered for the determination of thermodynamic constants associated to plutonium carbonate complexes. The study developed on plutonium (VI) allowed determining the stability constants at 25 C. From these values, the specific interaction coefficients based on the values recommended by the NEA have been reevaluated. The speciation diagram of Pu(VI) in aqueous carbonate solution has been established and shows the complexation of the plutonyl form by carbonates complex beyond pH=3. The works realized on the complexation of actinides (V) (Np and Pu) by carbonate ions at different temperatures allowed determining both the stability constants and the molar enthalpies and entropies of reaction. Experimentally, the analogy between neptunium and plutonium has been observed and allowed the determination of values which are more precise and consistent with those of the literature. For a better understanding of the plutonium behavior in surface waters, the determination of enthalpies and entropies has been necessary. The speciation diagrams established from these values show a near similarity in the chemical distribution of plutonium species without any further consideration of the analyzed surface water location. (author)
[fr]
Dans le cadre de la surveillance environnementale, le devenir du plutonium au sein des differents milieux et en particulier au sein des eaux de surface est important notamment en raison de sa radiotoxicite. Dans ces milieux, la forme pentavalente du plutonium est predominante et est fortement complexee par les carbonates. Le couplage EC-ICP-MS, technique ayant deja ete eprouvee pour la speciation des actinides, a ete retenu pour determiner les constantes thermodynamiques associees a la formation de ces complexes. L'etude menee sur le plutonium (VI) a permis d'obtenir des constantes de stabilite a 25 C. A partir de ces valeurs, les coefficients d'interaction specifique ont ete re-evalues par rapport a celles reportees par l'AEN. Le diagramme de speciation en solution du Pu(VI) en presence d'ions carbonate a ete etabli. Il suggere la complexation de la forme plutonyle par les ions carbonate des pH=3. Les travaux realises sur les actinides (V) (Np et Pu) ont permis de determiner a la fois les constantes de stabilite des complexes carbonates puis les enthalpies et entropies molaires de reaction a partir de l'etude menee en temperature. Experimentalement, l'analogie entre le neptunium et le plutonium a ete confirmee. Afin de mieux comprendre le comportement du plutonium au sein d'eaux de surface, la determination des enthalpies et entropies a ete necessaire. Les diagrammes de speciation etablis a partir de ces donnees montrent une quasi similarite dans la repartition chimique des especes du plutonium pentavalent sans consideration de la localisation de l'eau de surface analysee.Original Title
Etablissement des diagrammes de speciation a plusieurs temperatures du plutonium (V) pour predire son comportement dans les eaux de surface
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21 Nov 2018; 156 p; 153 refs.; Available from the INIS Liaison Officer for France, see the INIS website for current contact and E-mail addresses; Chimie Separative, Materiaux et Procedes
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