The oxidation state, and sulfur and Cu contents of arc magmas: implications for metallogeny

Abstract

Global data for measured Fe2O3/FeO ratios and Cu contents in unaltered volcanic and intrusive arc rocks indicate that, on average, they are slightly more oxidized than other magmas derived from depleted upper mantle (such as MORB), but contain similar Cu contents across their compositional ranges. Although Cu scatters to elevated values in some intermediate composition samples, the bulk of the data show a steady but gentle trend to lower concentrations with differentiation, reaching modal values of ~50–100ppm in andesitic rocks. These data suggest that Cu is mildly compatible during partial melting and fractionation processes, likely reflecting minor degrees of sulfide saturation throughout the magmatic cycle. However, the volume of sulfides must be small such that significant proportions of the metal content remain in the magma during fractionation to intermediate compositions. Previous studies have shown that andesitic magmas containing ~50ppm Cu can readily form large porphyry-type Cu deposits upon emplacement in the upper crust.A review of the literature suggests that the elevated oxidation state in the asthenospheric mantle wedge source of arc magmas (ΔFMQ≈+1±1) derives from the subduction of seawater-altered and oxidized oceanic crust, and is transmitted into the mantle wedge via prograde metamorphic dehydration fluids carrying sulfate and other oxidizing components. Progressive hydration and oxidation of the mantle wedge may take up to ~10m.y. to reach a steady state from the onset of subduction, explaining the rarity of porphyry deposits in primitive island arcs, and the late formation of porphyries in continental arc magmatic cycles. Magmas generated from this metasomatized and moderately oxidized mantle source will be hydrous basalts containing high concentrations of sulfur, mainly dissolved as sulfate or sulfite. Some condensed sulfides (melt or minerals) may be present due to the high overall fS2, despite the moderately high oxidation state. These sulfides may retain some highly siderophile elements in the source, but are unlikely to be sufficiently voluminous to significantly affect the budget of more modestly sulfide-compatible and more abundant elements such as Cu and Mo. These primary magmas can therefore be considered to be largely Cu-Mo-undepleted, although highly siderophile elements such as Au and platinum group elements (PGE) may be depleted unless no sulfides remain in the source. The latter condition seems unlikely during active subduction because of the continuous flux of fresh sulfur from the slab, but may occur during post-subduction re-melting (leading to potentially Au-rich post-subduction porphyry and alkalic-type epithermal systems).Lower crustal differentiation of main-stage arc magmas results in some loss of Cu to residual or cumulate sulfides, but again the amount appears to be minor, and does not drastically reduce the Cu content of derivative intermediate-composition melts. Fractionation and devolatilization affect the oxidation state of the magma in competing ways, but, while crystallization and segregation of Fe3+-rich magnetite can cause reduction in reduced to moderately oxidized evolved magmas, this effect appears to be outweighed by the oxidative effects of degassing reduced or weakly oxidized gaseous species such as H2, H2S, and SIVO2, and preferential solvation and removal of Fe2+ in saline hydrothermal fluids. Consequently, most arc magmatic suites show slight increases in oxidation state during differentiation, reaching typical values of ΔFMQ=+1 to +2.This oxidation state is significant, because it corresponds to the transition from dissolved sulfide to sulfate dominance in magmas. It has been shown that Cu and Au solubilities in silicate magma increase up to this level (ΔFMQ≈+1), but while Cu solubility continues to increase at higher oxidation states, Au shows a precipitous drop as sulfide, which solvates Au in the melt, is converted to sulfate. This may explain the somewhat restricted distribution of Au-rich porphyry Cu deposits, but the general association of porphyry Cu deposits with relatively oxidized magmas.Exsolution of a saline, high temperature aqueous fluid enables metals to partition from the magma into a highly mobile volatile phase. Sulfur also partitions strongly into this fluid phase, predominantly as SO2 at ΔFMQ=+1 to +2. However, as the fluid cools below ~400°C, SIVO2 disproportionates to form reduced H2S−II and oxidized H2SVIO4. The H2S bonds with metals in solution to precipitate as Cu- and Mo-sulfides, while the H2SO4 (and HCl) generates progressively acidic wallrock alteration (phyllic, argillic, advanced argillic). Gold may precipitate with early Cu/Mo-sulfides, but some may also stay in solution as bisulfide complexes, eventually reaching the epithermal environment.Thus, three components, [S], [H2O], and fO2 work together throughout subduction and arc magmatic processes to transport chalcophile and siderophile metals from the mantle into the upper crust, where they may be concentrated by hydrothermal processes to form ore deposits. These processes are far from 100% efficient, and metals (especially highly siderophile elements such as Au and PGE) may be left behind at various stages of the passage of arc magmas through the lithosphere, where they may form potentially metalliferous source rocks for partial melts and subsequent magmatic-hydrothermal ore deposits generated during later tectonomagmatic events.