Curium(III) and europium(III) incorporation in lanthanide phosphate ceramics for conditioning of radioactive wastes

The high-level radioactive waste (HLW) from spent nuclear fuel reprocessing facilities is currently immobilized in borosilicate glass. The vitrification process is well established and the flexible glass matrix is able to incorporate a very large range of elements present in the waste solution [1]. With the development of partitioning strategies, enabling the extraction of long-lived fission products and minor actinides (MA) from the PUREX raffinate, specific waste streams will be created that may require durable host matrices for their safe disposal. Especially for MA immobilization, some ceramic materials have been envisioned as host materials due to their thermal stability, high radiation tolerance, and chemical durability [2].
Lanthanide phosphate ceramics (LnPO4) are able to incorporate radionuclides in well-defined atomic positions within the crystal lattice [3] up to high (27 %) loadings [2]. The existence of very old natural analogues containing high concentrations of uranium and thorium shows that the crystalline phosphate structure is very tolerant towards self-irradiation damages as well as chemical weathering [4]. The dehydrated, high-temperature LnPO4 phases are known to crystallize in two distinct structures, depending on the ionic radius of the lanthanide cation: the larger lanthanides from La3+ to Gd3+ crystallize in the nine-fold coordinated monazite structure with a low symmetry, while the smaller lanthanides Tb3+ to Lu3+ form tetragonal, eight-fold coordinated xenotime structures.
In the present study we have used site-selective time-resolved laser fluorescence spectroscopy (TRLFS) to investigate the influence of the host cation radius as well as the crystal structure of the ceramic (monazite vs. xenotime) on the incorporation of the trivalent metal ions Eu3+ and Cm3+. We have synthesized pure monazites and xenotimes doped with 500 ppm Eu3+ or 50 ppm Cm3+ by precipitation of LnPO4 from a 0.3-0.5 M lanthanide nitrate solution with phosphoric acid followed by sintering of the precipitate at 1450°C to obtain the crystalline ceramic. The laser spectroscopy was performed either with a pulsed Nd:YAG-pumped tunable optical parametric oscillator or dye laser setup at cryogenic temperatures (~ 10 K). Excitation and emission spectra as well as luminescence lifetimes were collected for all measured samples.
Results on Eu3+-doped monazites show very narrow excitation spectra (Figure 1, left) for all investigated phases (LaPO4, SmPO4, GdPO4), indicating a complete incorporation of the dopant within the monazite crystal structure independent of the host cation radius. The emission spectra show a maximum splitting of the 7F1 and 7F2 bands (Figure 1, right), confirming the incorporation of Eu3+ on the low symmetry cation sites in the monazites.
The xenotime structure is not able to fully incorporate the europium ion within the crystal lattice. The excitation spectrum of Eu3+-doped LuPO4 in Figure 2 shows two regions of europium intensity that, upon excitation, decay with very different lifetimes. The broad signal in the wavelength region 575-580 nm corresponds to an ill-defined, partially hydrated europium species with a lifetime of approximately 580 µs (1.2 H2O). The species at 583.00 nm has a lifetime of 2700 µs indicating a full loss of the europium hydration sphere upon incorporation. The emission spectrum at this excitation wavelength shows a 2 and 4-fold splitting of the 7F1 and 7F2 bands, respectively, which is expected for an ion within the tetragonal cation site in the xenotime structure.
Our Eu3+ results demonstrate the importance of spectroscopic methods to probe the local environment of a guest cation within a solid matrix. According to our results, monazites can be considered as suitable host matrices for the immobilization of trivalent dopants. The xenotime structure on the other hand is not an ideal host for the larger lanthanide or actinide dopants due to the structure mismatch that does not allow for a complete guest ion substitution within the ceramic structure. Actinide (Cm3+)-doped LnPO4 samples have been synthesized similarly to the Eu3+ solids. The samples will be measured with TRLFS in the near future and results will be analyzed and compared to the existing Eu3+-data in order to confirm the incorporation behavior of trivalent dopants in the investigated solids. The results obtained for both dopants will be presented at the conference.