Time-resolved laser-fluorescence spectroscopy (TRLFS) – A spectroscopic tool to investigate f-element interactions in solids and solutions on the molecular level

Time-resolved laser-fluorescence spectroscopy (TRLFS) is a spectroscopic technique with outstanding sensitivity, based on the spontaneous emission of light. Spontaneous emission of light or luminescence describes the process of radiative decay where an excited substance emits electromagnetic radiation upon relaxation. Some f-elements, such as the actinides U4+, and Cm3+, and the lanthanide Eu3+, relax through intense luminescence emission from an excited f-state to the ground f-level. These f-f transitions are sensitive to changes in the ligand field, thus, making TRLFS an extremely useful tool to account for the complex speciation of these elements. Depending on the f-element, the recorded emission spectra can provide information on e.g. the complexation mechanism of the ion on a solid surface or the symmetry of the adsorption/incorporation site of the metal. Information about the hydration state of the f-element cation can be gained from the fluorescence lifetime, i.e. the residence time in the excited state. In aquatic environments f-element spectroscopy is characterized by relatively short fluorescence lifetimes due to the transfer of electronic energy from an excited f-level to the vibrational levels of water molecules in the first coordination sphere of the metal. When some of these quenching entities are lost upon inner sphere surface complexation a longer lifetime is acquired, thus, providing information on the sorption mechanism. If incorporation occurs, the complete hydration sphere is replaced by the ligands of the crystal lattice and the lifetimes become very long.

In the present work we have used site-selective TRLFS to investigate the structural incorporation of Eu3+, as an analogue for Pu3+, Am3+ and Cm3+ found in spent nuclear fuel, in rare earth phosphate ceramics. These crystalline ceramic materials show promise as potential waste forms for immobilization of high-level radioactive wastes due to their stability over geological time scales [1] and their tolerance to high radiation doses [2]. The REPO4 crystallize in two distinct structures, depending on the ionic radius of the cation: the larger lanthanides (La3+ to Gd3+) crystallize in the nine-fold coordinated monazite structure, the smaller ones as Lu3+ form eight-fold coordinated xenotime structures. Here, we present results on the influence of the ionic radius of the host cation and the crystalline structure of the REPO4 on Eu3+ substitution in the ceramic.