Dans le contexte de l’évaluation de la sûreté d’un stockage de déchets radioactifs en site géologique profond, les réactions de sorption sont un des principaux processus à prendre en compte pour prédire la migration des radionucléides. Ce travail est axé sur deux éléments: l´Eu(III) comme analogue des certains actinides trivalents et le Ni(II) en tant que produit d’activation. La calcite a été choisie comme solide d´étude en tant que composant des argilites du Callovo-Oxfordien. Notre étude combine des expériences de type batch avec des techniques spectroscopiques (SLRT, RBS et MEB-EDXS) pour élucider les mécanismes qui se produisent à l’interface Eu(III) / Ni(II) – calcite. Pour obtenir une meilleure compréhension des systèmes, avant de commencer les expériences de sorption, la chimie en solution de l’Eu(III) et du Ni(II) a été systématiquement étudiée. La calcite a montré une forte rétention de l'Eu(III), quelle que soit la concentration initiale, le temps de contact et la pression partielle de CO2. Ni(II) est également aisément retenu par la calcite, mais la rétention est dépendante de ces deux paramètres. Les résultats de désorption indiquent une réversibilité partielle pour Ni(II). La SLRT a montré l’influence de la concentration et du temps de contact sur l’interaction de l’Eu(III) avec la calcite. Avec l’aide de la RBS et de la MEB/EDX, elle a permis de discriminer entre différents mécanismes tels que la précipitation de surface, la formation de complexes de surface de sphère interne et l'incorporation. La RBS a démontré l'incorporation de l'Eu(III) dans la calcite jusqu’à une profondeur de 250 nm, contrairement au Ni(II) qui lui reste situé en surface. / In the context of the safety assessment of an underground repository for nuclear waste, sorption reactions are one of the main processes to take into account to predict the migration of the radionuclides. This work is focused on two elements: Eu(III) as an analogue of trivalent actinides and Ni(II) as activation product. Calcite was chosen as adsorbent due to its presence in Callovian-Oxfordian argillites. Our study combines batch experiments with spectroscopic techniques (TRLFS, RBS and SEM-EDXS) to elucidate the mechanisms occurring at Eu(III)/Ni(II) calcite interface. To obtain a better understanding on the systems, before starting sorption experiments, aqueous chemistry of Eu(III) and Ni(II) was carefully investigated. Macroscopic results showed a strong retention of Eu(III) on calcite, no matter the initial concentration, contact time and CO2 partial pressure. Ni(II) was also readily sorbed by calcite, but the retention was influenced by contact time and concentration. Time-dependent sorption experiments showed a marked and slow increase of retention upon a long time range (up to 4 months).Desorption results indicated a partly reversible sorption for Ni(II). TRLFS highlighted the influence of initial concentration and contact time on the interaction of Eu(III) with calcite. With the help of RBS and SEM-EDXS, it enabled to discriminate between different mechanisms like surface precipitation, inner-sphere complexation and incorporation. RBS showed incorporation of Eu(III) into calcite up to 250 nm, contrary to Ni(II) which was located at the surface.

The first 40Ar/39Ar ages of the Middle Jurassic Entrada Sandstone were derived from tephra beds found in central Utah. Eight air fall ash beds in the Entrada Sandstone, with 40Ar/39Ar biotite ages ranging from 168.1 ± 0.2 to 160.8 ± 0.2 Ma, help to establish the age of Entrada deposition. They were also used to create the first chronostratigraphic divisions within the mudstone-dominated Entrada Sandstone. Statistical cluster analysis of chemical data from electron microprobe analyses of phenocrysts were used as a second line of evidence to test absolute age and stratigraphic correlations. The first direct correlations of two distinct air fall ash beds within Jurassic rocks were correlated using three criteria: (1) stratigraphic position, (2) absolute ages, and (3) mineral chemistry. These tephra beds were identified and correlated across significant lateral distances (~40 km) of the San Rafael Swell in central Utah, and one can be correlated farther southwest to Cannonville, Utah (~160 km) using absolute age relationships. This latter tephra bed allows for stratigraphic correlation across significant facies and thickness changes thereby establishing a regional framework that future studies can use to make more accurate and precise litho- and sequence stratigraphic correlations. Absolute ages from a tephra bed ~20 m below the J-3 unconformity provide a lower age boundary for formation of the J-3 surface. Mega- and microfossil assemblages in the overlying Curtis Formation together with the radiometric ages reported in this study indicate that the age of the Callovian-Oxfordian boundary in the 2004 geologic time scale (161.2 ± 4.0 Ma) is more correct than the current boundary age (163.5 ± 1.1 Ma) in the 2012 geologic time scale.