A new activity model for Fe–Mg–Al biotites: II—Applications in the K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH) system

Abstract The new biotite activity model and standard-state thermodynamic properties of Ann, Phl, and Eas presented in part-I were used to make pseudosections of bulk compositions representing experimental Fe–Mg exchange equilibria and (model) pelitic bulk rock compositions in the system K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH), using mainly the software Perple_X. These pseudosection calculations (termed ‘our calculation(s)’ in the following) were compared to analogous ones performed with the solution model of biotite and thermodynamic data cited in White et al. (J Metamorph Geol 32:261–286, 2014, 10.1111/jmg.12071), termed ‘W14 calculation’. Our calculations with the experimental bulk composition used by Zhou (Ti–Mg–Fe biotites: formation, substitution, and thermodynamic properties at 650 to 900 °C and 1.1 Kb with fO2 defined by the CH4–graphite buffer. PhD thesis, State University of New York, 1994) in his experimental study of the Fe–Mg exchange between biotite (Bt) and olivine (Ol) confirm that biotite had no or only minimal octahedral Al (AlVI) in these experiments. The experimental data of Ferry and Spear (—FS78, Contrib Mineral Petrol 66:113–117, 1978, 10.1007/BF00372150) on the Fe–Mg distribution between biotite and garnet (Grt) are well reproduced by our calculations. The computed composition of biotite (XFe) in equilibrium with garnet of Alm90Py10 composition and the resulting lnKD values as a function of temperature are in good agreement with the experimental brackets. An analogous W14 calculation on the same Fe-rich bulk composition predicts too high XFeBt in order of 0.1 mol fraction. The AlVI contents of biotite of about 0.3–0.45 apfu, as measured by Gessman et al. (Am Mineral 82:1225–1240, 1997, 10.2138/am-1997-11-1218) in similar biotite–garnet exchange experiments performed with Alm80Py20 and Alm70Py30 garnets, are well reproduced by our, as well as by W14 calculations. The extent of Tschermak substitution in biotite in the FS78 experiments, which had Fe-richer bulk compositions, has not been measured. Comparing the FS78 biotites with the ones from Gessman et al. (Am Mineral 82:1225–1240, 1997, 10.2138/am-1997-11-1218), it is very likely that the biotites reported in FS78 contained AlVI in the same order of ca. 0.3–0.4 apfu. A T–XFe (= molar FeO/(FeO + MgO) pseudosection demonstrates the bulk composition dependence of lnKD of the Mg/FeGrt/Bt exchange reaction in high-variance fields. Further comparisons, demonstrating the application of the new biotite solution model in the KFMASH system, are presented in pseudosections constructed for an average model pelite, as well as for a natural high-T/low-P and a natural high-P metapelite. The pseudosections show that biotite according to our biotite model breaks down at lower temperatures and pressures than predicted from the W14 biotite model in the KFMASH system. This means that KFMASH biotite can break down before the wet solidus is reached, which can explain the existence of dry high-T/low-P metapelites. At higher pressures, biotite according to our calculations breaks down at lower pressures than computed with the W14 biotite model. Before biotite breaks down, however, its AlVI content based on our calculations could potentially be used for pseudosection barometry, similarly as the Si-in-phengite barometer. These trends need to be confirmed by a future extension of our model which incorporates Ti, Fe3+ and a di–tri-octahedral substitution.

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