Precise chemical composition, including Fe3+ and H, of biotite from a pegmatite dike and its host granulite from the Kerala Khondalite Belt of SE India has been determined using a multi-technique approach involving EMP, SIMS, Mössbauer, and C-H-N elemental analysis. Biotite in these rocks formed at T > 800–850 °C and P = 5 ± 1 kbar.
The full analyses were normalized on the basis of [O12−(x+y+z)(OH)xClyFz]. Biotite in the pegmatite is Ti-, F-, and Cl-rich (0.33, 0.46, and 0.16 apfu, respectively), H2O-poor (OH = 0.86 pfu), has XMg = 0.49 and Fe3+/Fetot ≤3%. The low octahedral vacancies (0.06 pfu) and the high oxygen content in the hydroxyl site (OH + F + Cl = 1.49 pfu) confirm the role of the Ti-oxy substitution as a major exchange vector in these high-T biotites.
In the host granulite, fine-grained biotite is Fe3+-free, has low Cl (0.03 apfu), and more variable composition, with Ti, F, and XMg in the ranges 0.26–0.36, 0.52–0.67, and 0.67–0.77, respectively. The number of octahedral vacancies is relatively large (0.10–0.18 pfu) and the sum of volatiles (OH + F + Cl) varies from 1.71 to 2.06 pfu. Systematic variations of XMg are a function of the microstructural position and are in agreement with retrograde exchange reactions: biotite included in or in contact with garnet has the maximum values, whereas crystals in the matrix have the minima. Titanium has systematic negative correlations with F, XMg, and (OH + F + Cl), whereas Al and octahedral vacancies are virtually constant.
These trends indicate that the Ti-vacancy, along with substitutions involving Al, cannot explain the observed short-scale variations. Conversely, the Ti-oxy exchange appears to be active, resulting from combination of two vectors: the more conventional hydroxylation Ti4+ + 2O2− = (Fe,Mg)2+ + 2OH− and the “fluorination” Ti4+ + 2O2− = (Fe,Mg)2+ + 2F−. The systematic retrograde redistribution involves not only Fe and Mg as commonly observed, but also Ti, F, and H, in a way such to eliminate the primary Ti-oxy component of biotite.