Nanoscale surface modification of Mt. Etna volcanic ash

Ashes emitted during volcanic explosive activity present peculiar surface chemical and mineralogical features related in literature to the interaction in the plume of solid particles with gases and aerosols. The compositional differences of magmas and gases, the magnitude, intensity and duration of the emission and the physical condition during the eruption, strongly influence the results of the modification processes. Here we report the characterization of the products emitted during the 2013 paroxysmal activity of Mt. Etna. The surface features of the ash particles were investigated through X-ray photoelectron spectroscopy (XPS) and Transmission electron microscopy (TEM) allowing the analysis at nanometer scale. TEM images showed on the surface the presence of composite structures formed by Ca, Mg and Na sulphates and halides and of droplets and crystals of chlorides; nanometric magnesioferrite and metallic iron dendrites are observable directly below the surface. From the chemical point of view, the most external layer of the volcanic glassy particles (<5nm), analysed by XPS, presents depletion in Si, Mg, Ca, Na and K and strong enrichment in volatile elements especially F and S, with respect to the inner zone, which represents the unaltered counterpart. Below this external layer, a transition glassy shell (thick 50-100nm) is characterized by Fe, Mg and Ca enrichments with respect to the inner zone. We propose that the ash particle surface composition is the result of a sequence of events which start at shallow depth, above the exsolution surface, where gas bubbles nucleate and the interfaces between bubbles and melt represent proto-surfaces of future ash particles. Enrichment of Ca, Mg and Fe and halides may be due to the early partition of F and Cl in the gas phase and their interaction with the melt layer located close to the bubbles. Furthermore the formation of volatile SiF4 and KF explain the observed depletion of Si and K. The F enrichment in the external ~50nm thick layer of the glassy particles suggests the resorption of this element during the rise from depth less than 400m below the summit vent. During the eruption, the gas/ash interaction persists inside the plume where further changes on the particle surface occurs. Gaseous S, Cl and F react causing the formation of solid Ca, Mg, Na and K compounds, while SiF4 was released as volatile phase and HF was physisorbed. Finally, in the low temperature plume zone, halides previously formed continuously react with gases producing sulfates.