Trace element partitioning in zoned clinopyroxene as a proxy for undercooling: Experimental constraints from trachybasaltic magmas

Abstract

Sector-zoned clinopyroxene records kinetic effects imposed by variable degrees of magma undercooling, ΔT, and can be utilised to track the dynamics of magmatic systems. The partitioning of trace elements into sectors grown in different crystallographic orientations can be used as a proxy for ΔT. However, an experimental assessment of the relationship between trace element zoning and ΔT has been lacking to date. Here we present trace element data from a series of undercooling crystallisation experiments on a primitive trachybasalt from Mt. Etna (Italy), at conditions of crustal storage (400 MPa, NNO + 2), and ΔT ranging from 23 to 173 °C. Changes in ΔT were modulated by varying both resting and liquidus temperatures, the latter via the melt-H2O content of the experiments. The resting temperature was retained for 24 h to ensure the attainment of near-equilibrium conditions.

High-resolution elemental mapping reveals the distribution of trace elements in individual clinopyroxene zones. Increasing ΔT drives a shift from polyhedral morphologies with Al-rich prism and Al-poor hourglass sectors (ΔT = 23–25 °C), to skeletal (ΔT = 75–123 °C) and dendritic (ΔT = 132–173 °C) crystals with Al-rich skeletons and Al-poor overgrowths. Aluminium-rich zones have higher concentrations of rare earth elements (REE) and high field strength elements (HFSE) than Al-poor zones across all investigated ΔT conditions, and overall, Al, REE and HFSE contents increase with ΔT. This indicates that tetrahedral aluminium (TAl) and associated charge-balancing mechanisms govern the incorporation of REE and HFSE within clinopyroxene. Lattice strain parameters for REE in the M2 site indicate the incorporation of light relative to heavy REE in clinopyroxene is controlled by competing effects between the strain-free partition coefficient, D0, and the optimum cation radius, r0. Critically, the middle and heavy REE switch from incompatible to compatible with increasing ΔT. Used to model fractional crystallisation, our data demonstrate that fractionation of clinopyroxene at low ΔT controls pre-eruptive melt evolution. Importantly, this indicates crystallisation of clinopyroxene in the deep portions of Mt. Etna’s plumbing system is not rapid and is unlikely to result in the early formation of dendrites.

We develop a parameterisation of ΔT based on REE partitioning between experimental clinopyroxene and coexisting melt, which can be applied to sector-zoned augite crystallising from mafic alkaline magmas, to reconstruct dynamic processes and thermal pathways during magma transport and storage. Applied to sector-zoned clinopyroxene microphenocrysts and groundmass microcrysts from the 1974 eccentric eruption at Mt. Etna, our parameterisation tracks an increase in ΔT with magma ascent and eruption, following recharge of Cr-rich mafic magma at depth. Sector-zoned clinopyroxene can track ΔT variations leading to volcanism at Mt. Etna and could be applied to quantify magma dynamics in other active volcanoes.