Sector-zoned clinopyroxene is common in igneous rocks, but has been overlooked in the study of magmatic processes. Whilst concentric zoning is commonly used as a record of physicochemical changes in the melt feeding crystal growth, clinopyroxene is also highly sensitive to crystallisation kinetics. In sector-zoned crystals, the fidelity of compositional changes as recorders of magma history is dubious and the interplay between thermodynamic and kinetic controls remains poorly understood. Here we combine electron probe and laser ablation micro-chemical maps of titanaugite crystals from Mt. Etna (Sicily, Italy) to explore the origin of sector zoning at the major and trace element levels, and its implications for the interpretation of magmatic histories. Elemental maps afford the possibility to revisit sector zoning from a spatially controlled perspective. The most striking observation is a clear decoupling of elements into sectors vs. concentric zones within single crystals. Most notably, Al-Ti enrichments and Si-Mg depletions in the prism sectors {1 0 0}, {1 1 0} and {0 1 0} relative to the hourglass (or basal) sectors {À1 1 1} correlate with enrichments in rare earth elements and highly charged high field strength elements due to cation exchanges driven by kinetic effects. In contrast, transition metals (Cr, Ni, Sc) show little partitioning into sectors and strong enrichments in concentric zones following resorbed surfaces, interpreted as evidence of mafic recharge and magma mixing. Our results document that kinetic partitioning has minor effects on the compositional variations of cations with low charge relative to the ideal charge/radius of the structural site they occupy in the clinopyroxene lattice. We suggest that this may be due to a lower efficiency in charge balance mechanisms compared to highly charged cations. It follows that compatible metals such as Cr can be considered trustworthy recorders of mafic intrusions and eruption triggers even in sector-zoned crystals. We also observe that in alkaline systems where clinopyroxene crystallisation takes place at nearequilibrium conditions, sector zoning should have little effect on Na-Ca partitioning and in turn, on the application of experimentally calibrated thermobarometers. Our data show that whilst non-sector-zoned crystals form under relatively stagnant conditions, sector zoning develops in response to low degrees of undercooling, such as during slow magma ascent. Thus, we propose that the chemistry of sector-zoned crystals can provide information on magma history, eruption triggers, and possibly ascent rates.
Crystals formed prior to a volcanic event can provide evidence of processes leading to and timing of eruptions. Clinopyroxene is common in basaltic to intermediate volcanoes, however, its ability as a recorder of pre-eruptive histories has remained comparatively underexplored. Here we show that novel high-resolution trace element images of clinopyroxene track eruption triggers and timescales at Mount Etna (Sicily, Italy). Chromium (Cr) distribution in clinopyroxene from 1974 to 2014 eruptions reveals punctuated episodes of intrusion of primitive magma at depth. Magma mixing efficiently triggered volcanism (success rate up to 90%), within only 2 weeks of arrival of mafic intrusions. Clinopyroxene zonations distinguish between injections of mafic magma and regular recharges with more evolved magma, which often fail to tip the system to erupt. High Cr zonations can therefore be used to reconstruct past eruptions and inform responses to geophysical signals of volcano unrest, potentially offering an additional approach to volcano hazard monitoring.
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