Volcanic activity at Mt Vulture lasted throughout the Middle Pleistocene and produced SiO2-undersaturated volcanics. Deposits from the Monte Vulture stratovolcano have been classified into four subsynthems and clustered into the Barile Synthem. In the present investigation, trioctahedral micas from the uppermost units (the Ventaruolo Subsynthem) of the Barile Synthem are considered. The samples are labelled VUT187. The phlogopitic micas were separated from the host rock (an olivine-foidite) and underwent chemical (electron microprobe analysis - EMPA and C-H-N), structural (single-crystal X-ray diffraction) and spectroscopic (Mössbauer) investigations.

The EMPA yielded: MgO (17.62–21.89 wt.%), FeOtot (5.98–9.78 wt.%), TiO2 (1.81–3.92 wt.%) and Al2O3 (14.47–17.98 wt.%), with H2O contents = 2.86 (±0.42) wt.% determined by C-H-N analyses. Mössbauer investigation provided [VI]Fe2+ = 12.6%, [VI]Fe3+ = 87.4%. The chemical and structural data are consistent with the occurrence of Ti-oxy, [VI]M2+ + 2(OH)[VI]Ti4+ + 2O2− + H2, and M3+-oxy substitutions, [VI]M2+ + (OH)[VI]M3+ + O2− + ½H2, with M3+ = Fe3+, Al3+. In particular, Fe3+-oxy substitution has affected the Fe2+/Fe3+ ratio in the studied sample. This is probably due to the fact that interaction with underground water or a hydrothermal system may have altered the oxygen fugacity and raised the Fe3+ content of VUT187 phlogopite with respect to magmatic values.

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