Chalcophile element processing beneath a continental arc stratovolcano

The chalcophile elements are important both in terms of their economic value and as potential tracers of magmatic processes at convergent margins. However, because of analytical difficulties, comprehensive datasets of chalcophile element concentrations for volcanic rocks are rare. Here, we present analyses of a near complete suite of chalcophile elements (S, Cu, Ag, Se, As, Sb, Sn, W, Mo, Pb, Bi, Tl, Zn, Ga, Co) for volcanic rock samples collected from a typical continental arc stratovolcano in southern Chile (Antuco). Enrichment in Pb, Bi, W, Tl, Sb and As relative to Parental-MORB indicates that these elements have been mobilised from the subducting slab into the sub-arc mantle wedge, in contrast to Cu and Ag. Very low Se concentrations suggest that Se, like S, was lost during co-eruptive degassing of the Antuco magmas. Previous studies on oceanic arcs have demonstrated that as higher fO2 subduction-related magmas ascend through the overlying lithosphere, magnetite fractionation may trigger sulfide fractionation during crystallisation. If such a process is extensive and has a sharp onset, this would result in a plummet in the Cu, Se and Ag contents of the residual melt. At Antuco, although a decrease in the Fe2O3(T) and TiO2 concentrations at ∼55 wt.% SiO2 (∼3 wt.% MgO) indicates magnetite fractionation, this is not associated with a corresponding drop in Cu contents. Instead, we observe a general decrease in Cu and a decrease in Cu/Ag with increasing SiO2 and decreasing MgO. Furthermore, Cu/Ag in the most primitive Antuco rocks are lower than the global MORB array, indicating that the melts were sulfide saturated at an early stage in their crustal evolution. Through modelling fractional crystallisation, we show that only a minor volume (0.5–0.6 vol.%) of fractionating sulfide is needed to produce divergent trends in Cu and Ag, as observed in the Antuco samples. Our results show that sulfide