Sodium betpakdalite and conditions of its formation

Because orthopyroxenes do not occur in nephelinites, the widely used methods of calculating f(O₂) based on the olivine + orthopyroxene + spinel paragenesis are not applicable in this case. The authors present new methods of calculation, three of which are based on published data detailing exchange reactions between two pyroxenes and the melt. The activities of MgSiO₂ and FeSiO₂ are calculated from the composition of the groundmass of effusives in equilibrium with clinopyroxenes, making it possible (considering the activities of olivine and titanomagnetite components of the rocks) to normalize f(O₂) with regard to the quartz-fayalite-magnetite (QFM) buffer. In another version, the activities of enstatite are calculated considering the calcium content in rock olivines, using experimental data on the equilibrium of olivine with the two pyroxenes on which the well-known olivine geobarometer is based (Koehler and Brey, 1990). Still another method involves calculation of aFe.0 using the composition of the groundmass of nephelinites on the basis of equilibria of silicate melts with metallic iron (Ariskin et al., 1992), which then, in conjunction with magnetite, yields f (O₂).

The five methods of estimating f (O₂) by use of different sets of experimental data and thermodynamic constants for various solid phases yield a maximum spread that does not exceed 0.8 logarithmic units. The average value of log₁₀ f(O₂) for phenocryst and microphenocryst associations of nephelinites, obtained using all five methods, ranged from +1.6 to +1.8 above the level of the QFM buffer. These estimates support the conclusion that the mantle is in a relatively oxidized state in regions of intra-plate oceanic islands (Amundsen and Neumann, 1992). Coexisting microlites of titanomagnetite and ilmenite from the nephelinite groundmass point to an appreciably lower relative f(O₂) (below the QFM), which evidently is explained by a drop in the redox potential under the conditions of a relatively closed system, with intensive deposition of titanomagnetite.

The phenocryst associations of phonolites yield f(O₂) values normalized with respect to the QFM buffer that are close to analogous values for the phenocrysts and microphenocrysts of nephelinites (on average, 1.5 logarithmic units above the QFM on the basis of constants of the reaction between the components of titanomagnetite, clinopyroxene, nepheline, K-feldspar, and sphene). In all probability, differentiation in the magma chamber that led to the appearance of phonolite magmas in late stages occurred in a system that was open (with regard to oxygen). In this case, more intensive removal of magnetite resulted in silica activities in the residual magmas that were higher than in a closed system (phenocrysts of sphene are present in phonolites, but perovskite is observed in some cases in the groundmass of nephelinites, with sphene being absent).