Chalcophile element degassing at an active continental arc volcano

Arc volcanoes are significant natural sources of trace chalcophile elements to the atmosphere via gas and aerosol plumes. Villarrica volcano, part of the Andean arc, erupts basaltic magmas and is characterised by a persistent volcanic gas plume and therefore presents an opportunity to quantify volcanic chalcophile processing in a subduction zone from slab to surface. Here we present geochemical data for olivine-hosted melt inclusions, as well as for the gas and aerosol plume. We show that melts erupted at Villarrica are enriched (over mid-ocean ridge basalts) in a suite of fluid-mobile elements comprising the large ion lithophiles, including Cs, and chalcophile elements W, Tl, Pb and Sb. Volcanic gas and aerosol samples show that the chalcophile elements, and Cs, are strongly enriched in the gas phase over the silicate melt, 10(3) to 10(6) times more so than the non-volatile Rare Earth Elements. Volatilities (the percentage of an element that degasses from a melt on eruption) reach similar to 45 % for Tl, with Pb, Sn and Mo exhibiting volatilities of up to 0.3 % and Cu up to 0.08 %. Many of the chalcophile elements (e.g. Cu, Ag, Zn) have an affinity for chloride in the gas phase and we observe that the volatility of chloride-speciating trace metals is linked strongly to the availability of chlorine in volcanic plumes globally. Overall, we show that the trace element composition of the volcanic gas-and hence probably also the deeper, denser and more saline fluids in the subsurface-is sensitive to both the availability of chloride in the gas phase and the composition of the melt, which is controlled by the slab flux and may be variable between subduction zones.