Stabilization of divalent rare earth elements in natural fluorite

The occurrence of divalent rare earth elements (Sm2+, Yb2+, Tm2+, and Ho2+) in natural fluorite is evaluated using a suite of 37 samples deriving mainly from Sn-W deposits in the Erzgebirge (Germany), Central Kazakhstan, and the Mongolian Altai. Trace element composition was determined by ICP-AES and ICP-MS. The defect structure of the samples was studied by cathodoluminescence (CL), electron paramagnetic resonance EPR), and optical absorption spectroscopy. Reduction of cubic Sm3+, Yb3+, Tm3+, and Ho3+ under radioactive irradiation produces the corresponding divalent centers. Our data suggest a preferable formation of Sm2+ and Yb2+ under thorium and of Tm2+ and Ho2+ under uranium irradiation. Irradiation (indicated by intense brownish (thorium) and Jeep purple (uranium) coloration of fluorite) gives rise to a population of divalent centers in equilibrium with their decay. However, sporadic radioactive irradiation and stabilization of the divalent state of the REE by other electron defects were found in most cases. Three models of stabilization of Sm2+, Yb2+, Tm2+, and Ho2+ are discussed. The most effective mechanism for Sm, Yb, Tm, and Ho is coupling with Fe3+ centers (REE3++Fe2+ - > REE2++Fe3+). Accordingly, the occurrence of Fe3+ centers in natural fluorite is regarded to indicate not an oxidizing, but rather a reducing environment during fluorite precipitation. Originally incorporated in the divalent form, Fe2+ was converted to Fe3+ by radioactive irradiation. Such a conclusion is in agreement with the finding of high contents of interstitial fluorine providing tetragonal local compensation of divalent REE centers in crystals with high Fe3+. If Fe is not present, compensation of divalent Sm, Yb, and Tm is achieved by radiogenic oxidation of Ce(Pr, Tb)3+ accompanied by charge transfer (REE3++Ce(Pr, Tb)3+ -> REE2++ Ce(Pr, Tb)4+). Ho2+ is sometimes stabilized by a hole trapped by an electron localized on a F vacancy (Ho3++e- on and squ;F -> REE2++ self-trapped exciton). Because Sm2+ is optically active, the stabilization by Fe3+ (stable up to temperatures above 350 oC) or Ce(Pr, Tb)4+ (unstable even under visible light) in samples may be determined by careful observations in the field. (author)