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Thesis--University of California, Berkeley, 1960. / "UC-4 Chemistry General" -t.p. "TID-4500 (15th Ed.)" -t.p. Includes bibliographical references (p. 141-149).

Le combustible nucléaire usé, après avoir été débarrassé de l'uranium, du plutonium et potentiellement du neptunium par le procédé PUREX, est encore constitué d'environ la moitié des éléments du tableau périodique. Au sein de ceux-ci, l'américium est majoritairement responsable des émissions thermiques à long terme des colis de déchets. En le recyclant, la compacité des sites de stockage pourrait être significativement améliorée. Le procédé d'extraction liquide-liquide EXAm, dont l'étape clé est la séparation Am/Cm, a donc été développé afin de séparer l'Am seul. Pour ce faire, un mélange d'extractants est utilisé conjointement au TEDGA (N,N',N,N'-tétraéthyl-diglycolamide), un complexant aqueux. Ce dernier permet en effet d'améliorer la séparation Am/Cm en maintenant préférentiellement le curium en phase aqueuse, mais sa relation structure sélectivité est encore mal comprise. Ces travaux de thèse concernent donc la synthèse et l'évaluation d'analogues structuraux du TEDGA afin de mieux comprendre l'influence de sa structure sur la sélectivité Am/Cm dans le procédé EXAm. Durant cette étude, 14 analogues du TEDGA ont été synthétisés et 17 molécules ont été évaluées en extraction liquide-liquide. Plusieurs modifications structurales ont été étudiées : la longueur et l'encombrement stérique des chaines alkyle portées par les azotes, la taille de l'espaceur, ainsi que l'utilisation d'amides secondaires. Ainsi, ces travaux ont montré qu'à partir des chaines tétrabutyle, il n'est plus possible de maintenir les molécules en phase aqueuse et que l'ajout d'encombrement stérique sur les chaines alkyles ou la modification de la balance hydrophilie/lipophilie diminue systématiquement la sélectivité des ligands. L'introduction d'amides secondaires (-CONHR) donne des ligands extractibles par le solvant (formation de liaison hydrogène avec les extractants) ce qui les rend inutilisables dans le procédé EXAm. Quant à l'espaceur, il joue un rôle prépondérant sur la sélectivité : le raccourcir (malonamides) entraine la disparition du caractère complexant de la molécule à forte acidité, et l'allonger entraine une préférence du ligand pour l'Am au lieu du Cm (inversion de sélectivité). L'ensemble de l'étude met en lumière la particularité de la sélectivité apportée par le TEDGA face aux autres diglycolamides ainsi que la difficulté d'améliorer le procédé en utilisant cette famille de molécules. Néanmoins la meilleure compréhension de sa chimie a permis d'affiner sa modélisation dans le procédé et l'étude de sa relation structure sélectivité montre qu'une amélioration de la sélectivité des ligands pourrait encore être envisagée en rigidifiant l'espaceur. / After the reprocessing of uranium, plutonium and eventually neptunium by the PUREX process, the spent fuel is still composed of half of the periodic table. Among these elements, the main responsible for the heat of the wastes is americium. Its reprocessing could allow improving the compactness of deep geological storage of the wastes. Thus the liquid-liquid extraction process called EXAm was developed in order to recover the americium alone. The key step of the process is the Am/Cm separation. An extractant mixture is used with an aqueous complexing agent: TEDGA (N,N',N,N'-tetraethyl-diglycolamide). It allows to enhance the Am/Cm separation by keeping preferentially curium in the aqueous phase, but its structure selectivity relationship is not well known yet. Therefore, the purpose of this thesis is to synthesize and evaluate some structural analogues of TEDGA, in order to better understand the impact of its structure on the Am/Cm selectivity in the EXAm process.During this study, 14 analogues of TEDGA were synthesized and 17 molecules were evaluated in liquid-liquid extraction. Several structural modifications were studied: length and steric hindrance of the N-alkyl chains, size of the spacer, and the introduction of secondary amide functions. This work shows that it is not possible to maintain the ligand in the aqueous phase from tetrabutyl derivatives, and the addition of steric hindrance, or modification of hydrophilicity/lipophilicity balance, systematically decreases the selectivity of ligands. The addition of secondary amide functions (-CONHR) makes the molecules extractible by the solvent (formation of hydrogen bonds with the extractants), therefore they are unsuitable to be used in the EXAm process. The spacer has the main impact on the selectivity: the complexation capacity in high acid medium disappears when it is shortened (malonamide), whereas the ligand has a preference for Am instead of Cm (inversion of selectivity) when it is lengthen (TEDOODA and TETOUDA derivatives).This whole study shows the peculiar selectivity given by the TEDGA in comparison with other diglycolamides, and the difficulties to enhance the process using this family of ligands. Nevertheless, a better understanding of its chemistry has allowed to define more clearly its modeling in the process and the studying of its structure/selectivity relationship has shown that the enhancing of the ligands selectivity probably requires spacer preorganization.

For the first time microbial tDNA could be isolated from 50 g unperturbed Mont Terri Opalinus Clay. Based on the analysis of the tDNA the bacterial diversity of the unperturbed clay is dominated by representatives of Firmicutes, Betaproteobacteria, and Bacteriodetes. Firmicutes also dominate after treatment of the clay with R2A medium. Bacteria isolated from Mont Terri Opalinus Clay on R2A medium were related to Sporomusa spp., Paenibacillus spp., and Clostridium spp.. All further investigations are concentrated on the unique isolates Sporomusa sp. MT-2 and Paenibacillus sp. MT-2. Cells of the type Sporomusa sp. MT-2 and Paenibacillus sp. MT-2 were comprehensively analyzed in terms of growing, morphology, functional groups of the cell envelope, and cell membrane structure. Strong actinide(An)/lanthanide(Ln)-interactions with the Opalinus Clay isolates and the Äspö-strain Pseudomonas fluorescens (CCUG 32456) could be determined within a broad pH range (2-8). The metals bind as a function of pH on protonated phosphoryl, carboxyl and deprotonated phosphoryl sites of the respective cell membrane. The thermodynamic surface complexation constants of bacterial An/Ln-species were determined and can be used in modeling programs. Depending on the used An different interaction mechanisms were found (U(VI): biosorption, partly biomineralisation; Cm(III): biosorption, indications for embedded Cm(III); Pu: biosorption, bioreduction and indications for embedded Pu). Different strategies of coping with U(VI) were observed comparing P. fluorescens planktonic cells and biofilms under the chosen experimental conditions. An enhanced capability of the biofilm to form meta-autunite in comparison to the planktonic cells was proven. Conclusively, the P. fluorescens biofilm is more efficient in U(VI) detoxification. In conclusion, Mont Terri Opalinus Clay contains bacterial communities, that may influence the speciation and hence the migration behavior of selected An/Ln under environmental conditions.

For the first time microbial tDNA could be isolated from 50 g unperturbed Mont Terri Opalinus Clay. Based on the analysis of the tDNA the bacterial diversity of the unperturbed clay is dominated by representatives of Firmicutes, Betaproteobacteria, and Bacteriodetes. Firmicutes also dominate after treatment of the clay with R2A medium. Bacteria isolated from Mont Terri Opalinus Clay on R2A medium were related to Sporomusa spp., Paenibacillus spp., and Clostridium spp.. All further investigations are concentrated on the unique isolates Sporomusa sp. MT-2 and Paenibacillus sp. MT-2. Cells of the type Sporomusa sp. MT-2 and Paenibacillus sp. MT-2 were comprehensively analyzed in terms of growing, morphology, functional groups of the cell envelope, and cell membrane structure. Strong actinide(An)/lanthanide(Ln)-interactions with the Opalinus Clay isolates and the Äspö-strain Pseudomonas fluorescens (CCUG 32456) could be determined within a broad pH range (2-8). The metals bind as a function of pH on protonated phosphoryl, carboxyl and deprotonated phosphoryl sites of the respective cell membrane. The thermodynamic surface complexation constants of bacterial An/Ln-species were determined and can be used in modeling programs. Depending on the used An different interaction mechanisms were found (U(VI): biosorption, partly biomineralisation; Cm(III): biosorption, indications for embedded Cm(III); Pu: biosorption, bioreduction and indications for embedded Pu). Different strategies of coping with U(VI) were observed comparing P. fluorescens planktonic cells and biofilms under the chosen experimental conditions. An enhanced capability of the biofilm to form meta-autunite in comparison to the planktonic cells was proven. Conclusively, the P. fluorescens biofilm is more efficient in U(VI) detoxification. In conclusion, Mont Terri Opalinus Clay contains bacterial communities, that may influence the speciation and hence the migration behavior of selected An/Ln under environmental conditions.

L’acquisition de données structurales et thermodynamiques relatives à des systèmes actinides (An(III), Pu(IV) Pa(V))–acides organiques polyfonctionnels (citrique, NTA, DTPA), en solution aqueuse, vise à une meilleure compréhension des interactions actinides-ligands essentielle à l’optimisation de procédés de séparation, de décorporation, et également à l’évaluation de la sûreté des sites de stockage de déchets radioactifs. Le comportement du protactinium pentavalent à l’échelle des traces en présence des anions citrates et NTA a fait l’objet d’études systématiques par extraction liquide-liquide dans le système TTA/Toluène/HClO₄/NaClO₄/Pa(V)/ligands. Après avoir déterminé l’ordre limite des complexes (3 pour Pa(V)-Cit et 2 pour Pa(V)-NTA), les constantes de formation associées à chaque espèce ont pu être calculées. L’étude multi-technique (électrophorèse capillaire et spectrofluométrie laser) sur la complexation des An(III) par le DTPA, réalisée à plusieurs pH, a permis de mettre en évidence la coexistence des complexes mono-protoné (AnHDTPA–) et déprotoné. (AnDTPA²–) pour des solutions acides et faiblement acides. Une réinterprétation des données de la littérature, en considérant les deux complexes, a permis de faire converger les valeurs des constantes de complexation des espèces qui étaient jusqu’à maintenant dispersées. L’étude thermodynamique a ensuite été complétée par une étude théorique (calculs DFT). La structure des complexes protoné et non protoné et le mode de coordination du Curium ont ainsi été établis. L’étude exploratoire sur la complexation du Pu(IV) par le DTPA dans des conditions de pH proches du milieu biologique a nécessité le développement d’un protocole expérimental en trois étapes : protection de Pu(IV) contre l’hydrolyse avec NTA (pH faible), augmentation du pH vers des conditions neutres, compétition entre la complexation de Pu(IV) par le NTA et le DTPA. Les expériences préliminaires réalisées entre pH 1,5 et 3,5 par électrophorèse capillaire (EC-ICP-MS), semblent indiquer l’existence d’effet cinétique ou/et l’existence d’un complexe mixte. Les interprétations faites lors de cette étude exploratoire sont à confirmer. / A thorough knowledge of the chemical properties of actinides is now required in a wide variety of fields: extraction processes involved in spent fuel reprocessing, groundwater in the vicinity of radioactive waste packages, environmental and biological media in the case of accidental release of radionuclides. In this context, the present work has been focused on the complexation of Am(III), Cm(III), Cf(III), Pu(IV) and Pa(V) with organic ligands: DTPA, NTA and citric acid. The complexation of pentavalent protactinium with citric and nitrilotriacetic acids was studied using liquid-liquid extraction with the element at tracer scale (CPa < 10-10M). The order and the mean charge of each complex were determined from the analysis of the systematic variations of the distribution coefficient of Pa(V) as function of ligand and proton concentration. Then, the apparent formation constants related of the so-identified complexes were calculated. The complexation of trivalent actinides with DTPA was studied by fluorescence spectroscopy (TRLFS) and capillary electrophoresis (CE-ICP-MS). The coexistence of the mono-protonated and non-protonated complexes (AnHDTPA– and AnDTPA²–) in acidic media (1.5 ≤ pH ≤ 3.5) was shown unambiguously. Literature data have been reinterpreted by taking into account both complexes and a consistent set of formation constants of An(III)-DTPA has been obtained. The experimental study was completed by theoretical calculations (DFT) on Cm-DTPA system. The coordination geometry of Cm in CmDTPA²- and CmHDTPA- including water molecules in the first coordination sphere has been determined as well as interatomic distances. Finally, a study on the complexation of Pu(IV) with DTPA was initiated in order to more closely mimic physiological conditions. A three-step approach was proposed to avoid plutonium hydrolysis: i/ complexation of Pu(IV) with (NTA) in order to protect Pu(IV) from hydrolysis (at low pH) ii/ increase of pH toward neutral conditions and iii/ competition between the complexation of Pu with NTA and with DTPA. The preliminary experiments performed with CE-ICP-MS in the pH range 1.5 - 3.5 tend to indicate kinetic effect or/and the presence of mixed complex.

L'acquisition de données structurales et thermodynamiques relatives à des systèmes actinides (An(III), Pu(IV) Pa(V))-acides organiques polyfonctionnels (citrique, NTA, DTPA), en solution aqueuse, vise à une meilleure compréhension des interactions actinides-ligands essentielle à l'optimisation de procédés de séparation, de décorporation, et également à l'évaluation de la sûreté des sites de stockage de déchets radioactifs. Le comportement du protactinium pentavalent à l'échelle des traces en présence des anions citrates et NTA a fait l'objet d'études systématiques par extraction liquide-liquide dans le système TTA/Toluène/HClO₄/NaClO₄/Pa(V)/ligands. Après avoir déterminé l'ordre limite des complexes (3 pour Pa(V)-Cit et 2 pour Pa(V)-NTA), les constantes de formation associées à chaque espèce ont pu être calculées. L'étude multi-technique (électrophorèse capillaire et spectrofluométrie laser) sur la complexation des An(III) par le DTPA, réalisée à plusieurs pH, a permis de mettre en évidence la coexistence des complexes mono-protoné (AnHDTPA-) et déprotoné. (AnDTPA²-) pour des solutions acides et faiblement acides. Une réinterprétation des données de la littérature, en considérant les deux complexes, a permis de faire converger les valeurs des constantes de complexation des espèces qui étaient jusqu'à maintenant dispersées. L'étude thermodynamique a ensuite été complétée par une étude théorique (calculs DFT). La structure des complexes protoné et non protoné et le mode de coordination du Curium ont ainsi été établis. L'étude exploratoire sur la complexation du Pu(IV) par le DTPA dans des conditions de pH proches du milieu biologique a nécessité le développement d'un protocole expérimental en trois étapes : protection de Pu(IV) contre l'hydrolyse avec NTA (pH faible), augmentation du pH vers des conditions neutres, compétition entre la complexation de Pu(IV) par le NTA et le DTPA. Les expériences préliminaires réalisées entre pH 1,5 et 3,5 par électrophorèse capillaire (EC-ICP-MS), semblent indiquer l'existence d'effet cinétique ou/et l'existence d'un complexe mixte. Les interprétations faites lors de cette étude exploratoire sont à confirmer.

The groundwater bacterium Pseudomonas fluorescens (CCUG 32456) isolated at a depth of 70 m in the Äspö Hard Rock Laboratory secretes a pyoverdin-mixture with four main components (two pyoverdins and two ferribactins). The dominant influence of the pyoverdins of this mixture could be demonstrated by an absorption spectroscopy study. The comparison of the stability constants of U(VI), Cm(III), and Np(V) species with ligands simulating the functional groups of the pyoverdins results in the following order of complex strength: pyoverdins (PYO) > trihydroxamate (DFO) > catecholates (NAP, 6­HQ) > simple hydroxamates (SHA, BHA). The pyoverdin chromophore functionality shows a large affinity to bind actinides. As a result, pyoverdins are also able to complex and to mobilize elements other than Fe(III) at a considerably high efficiency. It is known that EDTA may form the strongest actinide complexes among the various organic components in nuclear wastes. The stability constants of 1:1 species formed between Cm(III) and U(VI) and pyoverdins are by a factor of 1.05 and 1.3, respectively, larger compared to the corresponding EDTA stability constants. The Np(V)-PYO stability constant is even by a factor of 1.83 greater than the EDTA stability constant. The identified Np(V)-PYO species belong to the strongest Np(V) species with organic material reported so far. All identified species influence the actinide speciation within the biologically relevant pH range. The metal binding properties of microbes are mainly determined by functional groups of their cell wall (LPS: Gram-negative bacteria and PG: Gram-positive bacteria). On the basis of the determined stability constants raw estimates are possible, if actinides prefer to interact with the microbial cell wall components or with the secreted pyoverdin bioligands. By taking pH 5 as an example, U(VI)-PYO interactions are slightly stronger than those observed with LPS and PG. For Cm(III) we found a much stronger affinity to aqueous pyoverdin species than to functional groups of the cell wall compartments. A similar behavior was observed for Np(V). This shows the importance of indirect interaction processes between actinides and bioligands secreted by resident microbes.

Made available in DSpace on 2014-10-09T12:33:04Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:06Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:33:04Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:06Z (GMT). No. of bitstreams: 0 / O carvão ativado é um tipo comum de rejeito radioativo que contém elevada concentração de produtos de ativação e fissão. O gerenciamento deste rejeito inclui a sua caracterização, visando à determinação e quantificação dos radionuclídeos específicos, incluindo aqueles conhecidos como Radionuclídeos de Difícil Medição (RDM). A análise dos RDMs geralmente envolve análises radioquímicas complexas para purificação e separação dos radionuclídeos, as quais são caras e demandam muito tempo. O objetivo deste trabalho foi definir uma metodologia de análise sequencial de isótopos de urânio, netúnio, plutônio, amerício e cúrio, presentes em um tipo de rejeito radioativo, avaliando-se rendimento químico, tempo de análise, quantidade de rejeito secundário gerado e custo. Foram comparadas e validadas três metodologias que empregam a troca iônica (TI + EC), extração cromatográfica (EC) e extração com polímeros (ECP). O rejeito estudado foi o carvão ativado, proveniente do sistema de purificação de água do circuito primário de refrigeração do reator IEA-R1. As amostras de carvão foram dissolvidas por digestão ácida, seguida de purificação e separação dos isótopos com resinas de troca iônica, extração cromatográfica e extração com polímeros. Os isótopos foram analisados em um espectrômetro alfa, equipado com detectores de barreira de superfície. O rendimento químico de todos os elementos foi satisfatório para os métodos TI + EC e EC. Para o método ECP, apenas o rendimento químico do U foi comparável aos outros métodos. As análises estatísticas dos resultados bem como a análise de custo e volume de rejeito secundário gerado demonstraram que o método EC é o mais adequado para a identificação e quantificação dos isótopos estudados em carvão ativado. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP