Color Depth Gradient in Color-Change Fluorite from Brazil: A Multi-Spectroscopic Study on the Coloration Mechanism

This study investigated twelve gem-quality color-change fluorite specimens exhibiting a purple–blue gradient from Nova Era, Brazil, using colorimetry, Raman spectroscopy, UV-Vis spectroscopy, photoluminescence spectroscopy, EDXRF, and DiamondView imaging to explore the relationship between color depth and coloration mechanism. Raman spectroscopy further revealed enhanced defect-related peaks in dark samples, indicating cumulative irradiation-induced lattice damage. EDXRF analysis revealed that the radioactive element Th was detected exclusively in dark samples, with the darkest specimen reaching 0.184 wt.% Th, confirming that long-term Th-induced irradiation is the primary driver of color deepening. In UV-Vis spectra, the ~583 nm plasmon resonance absorption band of calcium colloids progressively red-shifted and broadened with increasing color depth, indicating elevated colloid concentrations and enhanced aggregation that directly intensify body color. DiamondView fluorescence weakened with deepening color, attributed to the quenching effect of calcium colloids. Photoluminescence spectra showed that the Eu2+ emission peak intensified in dark samples, while the broad 700–900 nm emission band systematically blue-shifted, reflecting differential responses of luminescence centers to radiation damage. This study provides non-destructive spectroscopic criteria for the fluorite color-change mechanism without relying on micro-area compositional analysis, establishing an analytical paradigm linking color gradients with spectral characteristics.