The method for prediction of Gibbs free energies of formation, based on the parameter ΔGO=Mz+(clay) characterizing the oxygen affinity of the cation Mz+, on the smectites, considered as hydrated clay minerals, has been used for micas and brittle micas, and yielded underestimated values. This method of prediction can be improved by a new set of parameters ΔGO=Mz+(clay), characterizing the electronegativity of a cation in a specific site (interlayer, octahedral, tetrahedral in the 10 Å minerals), determined by minimizing the difference between experimental Gibbs free energies and calculated Gibbs free energies of formation from constituent oxides. By considering the crystal structure of 10 Å and 14 Å minerals, and assuming the same electronegativity of cations, ΔGO=Mz+(o), in the octahedral sheets, an attempt is made to determine the electronegativity of cations in the brucitic sheet, ΔGO=Mz+(b). The results indicate that this prediction method compared to other determinations, gives values within 0.25% of the experimentally-estim ated values. The relationships between ΔGO=Mz+(clay) corresponding to the electronegativity of a cation in the interlayer, octahedral, tetrahedral or brucitic sites and known ΔGO=Mz+(aq) were thus determined, allowing the determination of the electronegativity of transition metal ions and trivalent ions in each of the four sites and consequently contribute to the prediction of Gibbs free energies of formation of different micas and chlorites. Examples are given for low-Fe clinochlore whose solubility is measured experimentally and the results appear excellent when compared with experimental values.

This paper presents the results of an experimental study of the miscibility gap between trioctahedral and dioctahedral micas in the system K2O Li2O-MgO-FeO-Al2O3-SiO2-H2O-HF at 600°C under 2 kbar PH2O. The existence of this miscibility gap is known from previous experimental studies. The gap is large in the lithium-free system; its width reduces progressively with increasing Li content; for sufficient Li contents (Li > 0.6 atom per formula unit, based on 11 oxygens), a single Li-mica phase is obtained, intermediate between trioctahedral and dioctahedral micas. Any bulk composition located inside the miscibility gap gives an assemblage of two micas, one of the biotite-type and one of the muscovite-type. All the compositions located outside the gap, and, in particular, those belonging to the joins phlogopite-trilithionite and muscovite-zinnwaldite (or its magnesian equivalent) give a single mica phase, provided that the fluorine content is sufficient. The ratio Li/F ≈ 1 is a convenient suitable value. The types of micas and the evolutions of their compositions are well characterized by their interplanar distance d060. These experimental results allow the interpretation of most compositions of naturally occurring lithium micas, in the range 0 ⩽ Li ⩽ 1 a./f.u. Natural micas of biotite-type and muscovite-type are located on both sides of the miscibility gap and their compositions get closer with increasing Li content.

Primary almandine and spessartine-rich garnet and zinnwaldite phenocrysts occur along with feldspar (plagioclase and sanidine) phenocrysts, in the rhyolite of Profitis Ilias, which is located on the SE coast of the island of Chios, Greece. The distinctive mineralogical composition of this rhyolite is described. Although formed in the back-arc tectonic environment of the Aegean volcanic arc, the Profitis llias rhyolite shows significant trace element compositional differences when compared with typical arc or back-arc volcanic rocks of the area. It shows extreme depletion in Sr and Ba and enrichment in Nb and Mn, and has much more affinity with A-type granites and particularly Li-mica granites.

Apparently, both zinnwaldite and spessartine-rich garnet can be generated as primary phases from a granite melt enriched in volatile constituents at low P–T. This granite melt could be the residual product of an un-exposed, earlier formed, typical back-arc granite of the area, enriched in volatile constituents from a subcrustal source above the active mantle of the eastern Aegean area.

The extensive and deep faulting in the broad eastern Aegean lithosphere section would have facilitated the rapid ascent of that volatile-enriched granite melt, the parent of the Profitis Ilias rhyolite.

Li-mica (zinnwaldite and/or lepidolite)—topaz—albite granites in the Tregonning—Godolphin pluton and similar rocks in the St. Austell pluton appear to be petrogenetically unrelated to the spatially associated biotite granites. Evidence is provided by lack of development of Li-mica granites at roof zones of biotite granites and markedly different trends and composition fields in bivariate plots such as Li vs. Cs, Rb vs. Sr and Nb vs. Zr. Thus, differentiation of biotite granite magma is unlikely to have generated Li-mica granite magma, as also, on its own, is partial melting of biotite granite or biotiteabsent residual lower crust. However, partial melting of biotite-rich residual rocks involving biotite breakdown could yield a trace alkali- and F-enriched melt, although this would require marked femic mineral, K-feldspar and anorthite fractionation, and Na-enrichment. It is proposed that volatiles derwed from either a mantle source or the crust/mantle interface have aided metasomatism of either residual S-type crust that earlier provided S-type biotite granite magma, or basic (biotite-rich) granitoid, to produce a low-temperature, low-viscosity Li-mica granite melt that rose rapidly in the crust soon after the emplacement of associated biotite granites.

Physical and chemical properties of lustrous black mica from greisen veins at the Bom Futuro tin mine indicate that it is a relatively Fe-F-rich, Li-poor zinnwaldite with a composition near the midpoint of the polylithionite-siderophyllite join. On the basis of 22 oxygens, the mica contains 1.28–1.73 atoms of Li with an average octahedral occupancy of 5.61 and a filled interlayer site. Compositional variation reflects the net effects of alteration, coupled tetrahedral-octahedral substitutions, and petrogenetic factors related to vein fluid chemistry. Geological constraints and compositional data suggest the Bom Futuro zinnwaldite crystallized at T ≈ 500°, P ≈ 1–500 bar, and fO2 ≈ 10−23. High Mn-Zn concentrations in the Bom Futuro mica appear to be a feature of Fe-Li micas from evolved anorogenic granitic systems not shared by orogenic counterparts.

Lithium micas of the zinnwaldite and phengite–Li-phengite series occur as characteristic minerals in Permian Li-F-(P) granites of the western Gemeric unit (Western Carpathians) accompanied by topaz, tourmaline, Nb, Ta, Ti, Sn oxides and aluminophosphates. The calculated Li2O contents of all the mica analysed, together with Rb2O and Cs2O were confirmed by LA-ICP-MS analyses for all the identified micas. Samples from three localities were investigated: two surficial (Surovec, Vrchsúl’ová); and one drill hole (Dlhá dolina). Zinnwaldite (polylithionite) occurs in the upper level of the Dlhá dolina granitic intrusion and in the nearby shallow satellite body of Surovec. The lower level porphyritic granites contain only siderophyllite. The Vrchsúl’ ová micas are closer in composition to Li-annite and siderophyllite. Dioctahedral micas are mostly phengites, although zinnwaldite-bearing granites are rich in late-crystallizing Li-phengite, which extensively replaces earlier zinnwaldite. The secondary Liphengite and phengite are interpreted as products of Alpine metamorphism during Cretaceous burial and subsequent exhumation of the Gemeric unit. Reactions are suggested explaining the formation of Li-phengite by reaction of zinnwaldite with phengite or with muscovite. All mica types were investigated by Mössbauer spectroscopy, which showed high degrees of oxidation (25–50% Fe3+ of total Fe) with the exception of zinnwaldite from Vrchsúl’ová, which may have preserved an original, reduced value of 10%. The metamorphic assemblage present permitted calculation of P-T-X conditions: T = 184°C, P = 320 MPa, with oxidation of siderophyllite to phengite + goethite and fO2 at ΔNN = 4.7, confirming the low-grade conditions of the Alpine metamorphism in agreement with previous estimates.