Fluorescence emission spectra of three samples of fluorite containing 226-867 ppm total rare earth elements (REE) were excited by visible and ultraviolet wavelength lines of an argon ion laser and recorded with a Raman microprobe spectrometer system. Narrow emission lines (< 1 nm) due to 4f-4f electron transitions in individual trivalent REE (Pr, Nd, Sm, Eu?, Tb, Dy, Ho, Er, Tm) were observed in the wavelength range of 400-900 nm. Emission from individual REE occur in bands of overlapping lines in the wavelength intervals of 470-495 nm, 535-560 nm, 565-580 nm, 585-620 nm, 640-643 nm, 671.4 nm, and 758.2 nm. A broad band at 419 nm excited by the 363.8-nm ultraviolet line of the laser is due to a 4f-5d transition in Eu2+. Two bands of enigmatic origin are a narrow line at 682.8 nm present at all excitation wavelengths in only one sample and a broad band at 720 nm. We have tentatively assigned individual REE to specific lines in each emission band based on selection rules for strongly and weakly allowed 4f-4f transitions and the position of absorption and emission bands documented in the literature for REE in CaF2 and LaF3 host crystals. Working curves of integrated peak intensity of emission from Er3+ and Eu2, vs. ppm measured by ICP-MS give linear log-log fits with R2 > 0.9 for Eu2+, and 0.99 for Er3+. Detection limits for three micrometer spots are about 0.01 ppm Eu2+ and 0.07 ppm Er3+. These limits are less than chondrite abundance for Eu and Er, demonstrating the potential microprobe analytical applications of laser-excited fluorescence of REE in fluorite. However, application of this technique to common rock-forming minerals may be hampered by competition between fluorescence emission and radiationless energy transfer processes involving lattice phonons.
