An electron microprobe analysis, secondary ion mass spectrometry, and single-crystal X-ray diffraction study of phlogopites from Mt. Vulture, Potenza, Italy: Consideration of cation partitioning

Abstract

Mt. Vulture trioctahedral micas-1M mainly consist of phlogopite-annite solid solutions with a minor component of brittle micas. However, both Li-free and Li- and F-rich compositions may coexist in the same volcano-stratigraphic level. We report the results of electron microprobe analysis (EMPA), secondary ion mass spectrometry (SIMS), and single-crystal X-ray diffraction (SCXRD) for three crystals (LC7-27Go, LC7-3Go, and LC7-1R) that are representative of both compositions. EMPA and SIMS showed that sample LC7-1R is richer in TiO2 , Li2O, and F and poorer in H2O than the other samples. Structure reÞ nements using anisotropic displacement parameters for the three samples, performed in space group C2/m, converged at 3.46 ≤ R ≤ 4.34, 3.89 ≤ Rw ≤ 4.39. When considering bond distances, the three samples can be described as homo-octahedral whereas mean atomic numbers suggest that only LC7-1R is meso-octahedral. SigniÞ cant differences occur among the samples for some distortion parameters commonly used for micas. In particular, LC7-1R displays higher values of BLDM2, shiftM2 and lower values of ΔK-O4 and tK-O4 than those of samples LC7-3Go and LC7-27Go. These differences are ascribed to F- and Ti-substitutions. Cation distributions were obtained by combining EMPA, SIMS, and SCXRD data after analysis of the effect of normalization schemes commonly used in mica formula recalculation. In LC7-3Go and LC7-27Go, Ti is incorporated according to the Ti-Tschermak mechanism, whereas more than one Ti-substitution mechanism occurs in LC7-1R. For the latter sample, octahedral vacancies are present leading to a complex substitution pattern and complex structural distortions related to the special octahedral compositions that were determined. Keywords: Analysis, chemical (mineral), EPMA and SIMS investigation, crystal structure, trioc- tahedral micas -1M, major and minor elements, Ti-F-bearing phlogopites, trace elements and REE, Li-bearing micas, XRD data, single-crystal structure reÞ nement