Determination of local structure in mixed lanthanoid phosphate solid solutions by X-ray absorption spectroscopy

In the 21st century, scientific challenges are required for the disposal of high-level nuclear waste in deep geological formations. Ceramic waste forms like monazite and xenotime, are natural lanthanoid phosphate minerals containing U and Th. When light lanthanoids are involved the monazite structure forms; when heavy lanthanoids are present, the xenotime structure predominates. X-ray absorption spectroscopy was carried out to elucidate the structural changes induced by different lanthanoids when mixed lanthanoids phosphates are formed. EXAFS measurements for La1-xEuxPO4 solid solutions around La and Eu, show the flexibility of the monazite structure when two light lanthanoids are hosted. The La-O distances in the first coordination shell and the first metal-metal distances decrease with increasing Eu content; while the Eu-O local coordination remains unchanged. Additionally, HR-XANES shows an increase on the white line in the absorption coefficient with increasing Eu content, suggesting a change in the valence electron distribution. However, EXAFS measurements of Sm1-xTbxPO4 solid solutions around the Sm, show significant differences between low and high Tb content.