Clinopyroxene-melt element partitioning during interaction between trachybasaltic magma and siliceous crust: Clues from quartzite enclaves at Mt. Etna volcano

A peculiar characteristic of the paroxysmal sequence that occurred on March 16, 2013 at the New South East Crater of Mt. Etna volcano (eastern Sicily, Italy) was the eruption of siliceous crustal xenoliths representative of the sedimentary basement beneath the volcanic edifice. These xenoliths are quartzites that occur as subspherical bombs enclosed in a thin trachybasaltic lava envelope. At the quartzite-magma interface a reaction corona develops due to the interaction between the Etnean trachybasaltic magma and the partially melted quartzite. Three distinct domains are observed: (i) the trachybasaltic lava itself (Zone 1), including Al-rich clinopyroxene phenocrysts dispersed in a matrix glass, (ii) the hybrid melt (Zone 2), developing at the quartzite-magma interface and feeding the growth of newly-formed Al-poor clinopyroxenes, and (iii) the partially melted quartzite (Zone 3), producing abundant siliceous melt. These features makes it possible to quantify the effect of magma contamination by siliceous crust in terms of clinopyroxene-melt element partitioning. Major and trace element partition coefficients have been calculated using the compositions of clinopyroxene rims and glasses next to the crystal surface. Zone 1 and Zone 2 partition coefficients correspond to, respectively, the chemical analyses of Al-rich phenocrysts and matrix glasses, and the chemical analyses of newly-formed Al-poor crystals and hybrid glasses. For clinopyroxenes from both the hybrid layer and the lava flow expected relationships are observed between the partition coefficient, the valence of the element, and the ionic radius. However, with respect to Zone 1 partition coefficients, values of Zone 2 partition coefficients show a net decrease for transition metals (TE), high-field strength elements (HFSE) and rare earth elements including yttrium (REE + Y), and an increase for large ion lithophile elements (LILE). This variation is associated with coupled substitutions on the M1, M2 and T sites of the type M1(Al, Fe3 +) + TAl = M2(Mg, Fe2 +) + TSi. The different incorporation of trace elements into clinopyroxenes of hybrid origin is controlled by cation substitution reactions reflecting local charge-balance requirements. According to the lattice strain theory, simultaneous cation exchanges across the M1, M2, and T sites have profound effects on REE + Y and HFSE partitioning. Conversely, both temperature and melt composition have only a minor effect when the thermal path of magma is restricted to ~ 70 °C and the value of non-bridging oxygens per tetrahedral cations (NBO/T) shifts moderately from 0.31 to 0.43. As a consequence, Zone 2 partition coefficients for REE + Y and HFSE diverge significantly from those derived for Zone 1, accounting for limited cation incorporation into the newly-formed clinopyroxenes at the quartzite-magma interface.