Is gold solubility subject to pressure variations in ascending arc magmas?

Abstract

Magmas play a key role in the genesis of epithermal and porphyry ore deposits, notably by providing the bulk of ore metals to the hydrothermal fluid phase. It has been long shown that the formation of major deposits requires a multi-stage process, including the concentration of metals in silicate melts at depth and their transfer into the exsolved ore fluid in more superficial environments. Both aspects have been intensively studied for most of noble metals in subsurface conditions, whereas the effect of pressure on the concentration (i.e., solubility) of those metals in magmas ascending from the sublithospheric mantle to the shallow arc crust has been quite neglected. Here, we present new experimental data aiming to constrain the processes of gold (Au) dissolution in subduction-linked magmas along a range of depth. We have conducted hydrous melting experiments on two dacitic/adakitic magmas at 0.9 and 1.4GPa and ∼1000°C in an end-loaded piston cylinder apparatus, under fO2 conditions close to NNO as measured by solid Co–Pd–O sensors. Experimental charges were carried out in pure Au containers, the latter serving as the source of gold, in presence of variable amounts of H2O and, for half of the charges, with elemental sulfur (S) so as to reach sulfide saturation. Au concentrations in melt quenched to glass were determined by LA-ICPMS. When compared to previous data obtained at lower pressures and variable redox conditions, our results show that in both S-free and sulfide-saturated systems pressure has no direct, detectable effect on melt Au solubility. Nevertheless, pressure has a strong, negative effect on sulfur solubility. Since gold dissolution is closely related to the behavior of sulfur in reducing and moderately oxidizing conditions, pressure has therefore a significant but indirect effect on Au solubility. The present study confirms that Au dissolution is mainly controlled by fO2 in S-free melts and by a complex interplay of fO2 and melt S2− concentration in sulfide-saturated melts, at given temperature. In addition, we propose that the transition from sulfide (S2−) to sulfate (S6+) species in melt is shifted towards more oxidizing conditions when pressure and the degree of melt polymerization increase. If this is true, this may have important consequences during mantle melting and magma ascent. In particular, if mantle melting occurred in moderately oxidizing conditions, a small degree of partial melting would allow the primary melts to become Au-enriched but the relatively high pressure would move the sulfide-sulfate transition to more oxidizing conditions, making the primary melts saturated with sulfide phases that would sequester gold from the melt. During magma ascent, the decreasing pressure would favor the destabilization of sulfides and the release of gold to the silicate melt. However, at shallow levels, decreasing pressure, magma evolution, and varying redox conditions would be continuously competing to concentrate or fractionate gold.