Tracking the Ti⁴⁺ substitution in phlogopite by spectroscopic imaging: A tool for unravelling the growth of micas at HP-HT conditions

Phlogopite solid-solutions have a wide pressure-temperature (P-T) stability field and are ubiquitous in a wide variety of geological settings, from deep lithosphere magmatic environments to upper crust metamorphic domains. Phlogopite composition represents therefore a valuable physical-chemical archive and may provide important information regarding its crystallization and the petrogenesis of the host-rock. In this paper we examine the phlogopite phenocrysts from the well-known Fort Regent mica-bearing lamprophyre minette from St. Helier (Island of Jersey, UK). Phlogopite phenocrystals from lamprophyres generally show normal-step and continuous compositional zoning, however those from the Fort Regent minette show a peculiar texture characterized by dark brown high-Ti (average TiO₂ ≈ 8.5 wt.%) cores enveloped by euhedral low- to mid-amplitude zonation due to oscillatory contents in Ti, Fe and Mg. Thermo-barometry modelling based on biotite-only composition yields relatively high P-T estimates (T ≈ 970 ± 54 °C at P ≈ 0.73 ± 0.13 GPa) for cores whereas lower values (T ≈ 790 ± 54 °C at P ≈ 0.29 ± 0.13 GPa) are obtained for the outer rims. Comparable temperatures (T ≈ 1075 ± 54 °C) but extremely high and anomalous pressure values (P ≈ 1.82 ± 0.13 GPa) are obtained for the yellowish inner rims. The combination of electron micro probe (EMP) analysis and single-crystal infra-red (FTIR) imaging in the OH-stretching region shows that the exceptional and oscillatory Ti contents are due to the Ti-vacancy substitution, typical of crystallization and growth processes of HP/HT environments. Raman imaging provides additional insight for this process, confirming the dominant dioctahedral nature for the Ti-Fe-rich cores and outer rims. Interpretation of thermobaric estimates obtained from the phlogopite composition-only model, based on the fine-scale compositional evolution, shows that pressure-temperature values from low-Ti high-Mg domains should be carefully evaluated because the substitution mechanisms during the dark mica growth are not univocally related to pressure-temperature variation of the crystallizing environment. Our results demonstrate how a multidisciplinary approach based on the combination of chemical investigations and vibrational spectroscopies could represent a valuable tool to evaluate pressure-temperature estimates from biotite composition-only thermo-barometry models and therefore to correctly unravel HP/HT petrogenetic processes at a very fine scale.