Kinetic partitioning of major and trace cations between clinopyroxene and phonotephritic melt under convective stirring conditions. New insights into clinopyroxene sector zoning and concentric zoning

Within subvolcanic plumbing systems, along volcanic conduits and post-eruptive emplacement, mineral textures and compositions are governed by complex kinetic (undercooling) and dynamic (convective) processes that deviate from theoretical models and equilibrium criteria. In this perspective, we have investigated the partitioning of major and trace cations between clinopyroxene and phonotephritic melt under convective stirring conditions at high degrees of undercooling ( ΔTnominal = 30–60 ◦C) and atmospheric pressure. We have integrated this novel data set with conventional static (no physical perturbation) clinopyroxene-melt compositions obtained under interface- and diffusion-controlled growth regimes. Results show that clinopyroxene growth kinetics and diffusion boundary layers caused by melt supersaturation are partly mitigated by the homogenizing effects of stirring. Because of continuous supply of fresh melt to the advancing crystal surface, the partitioning of major and trace cations is governed by local equilibrium effects, which are interpreted as the extension of equilibrium thermodynamic principles to non-equilibrium bulk systems. Major cations are incorporated into the clinopyroxene structure via the coupled substitution [M1Mg, TSi] ↔ [M1Ti, TAl] and in conformity with the thermodynamic mixing properties of CaMgSiO2, CaAl2SiO6, and CaTiAl2O6 components. The complementary relationship between lattice strain (ΔGstrain) and electrostatic (ΔGelectrostatic) energies of heterovalent substitutions is the most appropriate thermodynamic description for the accommodation of trace cations in the clinopyroxene lattice site (i.e., ΔGpartitioning = ΔGstrain + ΔGelectrostatic). The excess energy of partitioning ΔGpartitioning changes principally with Al in tetrahedral coordination and determines the type and number of charge-balanced and -imbalanced configurations taking place in the structural sites of clinopyroxene. An important outcome from dynamic stirring experiments is that superimposition of convective mass transfer on melt supersaturation phenomena causes the formation of Cr-rich concentric zones under closed system crystallization conditions. However, these Cr-rich zones do not correlate with enrichment in other compatible elements and depletion in incompatible elements, as would be expected in natural open systems characterized by input of more primitive magmas. While the convective transport acts to reduce the diffusive length scale of chemical species in the experimental melt, fresh Cr cations are more easily incorporated into the concentric zones due to crystal field effects. Together, our findings reveal that during magma ascent and emplacement, convective stirring may promote clinopyroxene crystallization and minimize kinetic effects on clinopyroxene zoning