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.

A unique hybrid natrocarbonatite, collected from the new ash cone of the volcano Oldoinyo Lengai. Tanzania in July 2008, consists of phenocrysts of nyerereite and gregoryite together with xenocrysts of clinopyroxene, nepheline and Ti-andradite set in a groundmass of cuspidine, sodalite, ferroan manganoan monticellite, K-Fe sulphide and manganoan titanian magnetite and gregoryite. The xenocrysts were not in equilibrium with the melt which formed their current host, as clinopyroxenes and Ti-andradite are mantled by cuspidine, and nepheline by sodalite and phlogopite—potassian kinoshitalite solid solutions. A microxenolith of ijolite exhibits similar reaction phenomena. The minerals of the xenocryst suite have similar compositions to plutonic ijolites found at Oldoinyo Lengai, and are thus considered to be derived by the fragmentation of such material in a previously contaminated natrocarbonatite melt. The latter, which has cuspidine, sodalite and monticellite as primary liquidus phases, is considered to have been formed by the complete assimilation of ijolitic material in a natrocarbonatite magma at depth in the volcano conduit. The occurrence of trace amounts of cuspidine, Fe-Mn-monticellite, K-Fe sulphide and Mn-Ti-spinel in recently erupted natrocarbonatites is ascribed to similar, but less extensive, assimilation of silicate material prior to their eruption.

Ba-rich and Si-rich phlogopites occur in the talc-bearing rocks of the La Creuse sulfide ore deposit in Beaujolais, France. They form a group of compositions completely separated from the common Al-rich phlogopites that occur in the surrounding talc-free metasiltites and metarhyolites, with higher Ba and Mg and lower Al contents. The Ba-rich phlogopites have a relatively narrow compositional range (0.24 to 0.80 Ba per formula unit, for 44 valencies) with high and constant Si (5.8 atoms per formula unit, apfu) and Mg + Fe (5.6 apfu), probably buffered by the presence of talc. Compared to low-Al phlogopites from talc-free rocks, the excess charge introduced by the BaK–1 substitution is compensated by interlayer vacancies. Such a high level of interlayer vacancy (0.56 pfu), related to the talc-producing metasomatic conditions, is essential for the stability of this special group of Ba-rich and Si-rich phlogopites.

Single crystal X-ray diffraction analyses were performed. Ba-rich and Si-rich phlogopite is monoclinic, space group C2/m, (R = 5.31%) with a = 5.3185(5), b = 9.2136(9), c = 10.1349(11) Å and β = 100.131(11)°. The occupancies of Mg/Fe and K/Ba were refined exploring different vacancies. The solutions giving the best R factor (4.77%) and goodness-of-fit (1.06) are obtained with 15% < vacancy < 40% at the interlayer site.