Spectroscopic Characteristics of Blue Calcite and the Origin of Its Coloration and Luminescence

Natural blue calcite is relatively rare, and its coloration and luminescence mechanisms have not been systematically established. In this study, four natural blue calcite samples from China were comprehensively characterized using mineralogical testing, X-ray diffraction (XRD), electron probe microanalysis (EPMA), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, ultraviolet–visible spectroscopy (UV-Vis), photoluminescence (PL), and electron paramagnetic resonance (EPR). XRD confirms single-phase trigonal calcite (space group R-3c). EPMA detects minor Mg, Fe, Cu, and Sr, with smaller-radius Mg2+, Fe2+, and Cu2+ being the main contributors to the contraction through isomorphous substitution for Ca2+. UV-Vis spectra show characteristic absorptions at 270 nm and 340 nm related to lattice defects with a broad emission band centered at 480 nm in the PL spectra. EPR detects a CO2− radical center (g = 2.003), and the same signal is also observed in the colorless sample. The colorless sample also contains the same CO2− radicals, indicating that these radicals alone do not account for the blue coloration. A broad 480 nm blue-violet fluorescence band is observed in the four blue samples under 405 nm excitation. These findings provide a spectroscopic and crystallographic basis for distinguishing natural blue calcite from analogous materials and for understanding the origin of its color and luminescence.