Fluid density control on vapor-liquid partitioning of metals in hydrothermal systems

Hot aqueous fluids, both vapor and saline liquid, are primary transporting media for metals in hydrothermal-magmatic systems. Despite the growing geological evidence that the vapor phase, formed through boiling of magmatic ore-bearing fluids, can selectively concentrate and transport metals, the physical-chemical mechanisms that control the metal vapor-liquid fractionation remain poorly understood. We performed systematic experiments to investigate the metal vapor-liquid partitioning in model water-salt-gas systems H2O-NaCl-KCl-HCl at hydrothermal conditions. Measurements show that equilibrium vapor-liquid fractionation patterns of many metals are directly related to the densities of the coexisting vapor and liquid phases. Despite differences in the vapor-phase chemistry of various metals that form hydroxide, chloride, or sulfide gaseous molecules of contrasting volatile properties, water-solute interaction is a key factor that controls the metal transfer by vapor-like fluids in Earth's crust. These findings allow quantitative prediction of the vapor-liquid distribution patterns and vapor-phase metal transport in a wide range of conditions. Our density model accounts well for the vapor-brine distribution patterns of Na, Si, Fe, Zn, As, Sb, and Ag observed in fluid inclusions from magmatic-hydrothermal deposits. For An and Cu, the partitioning in favor of the liquid phase, predicted in a sulfur-free system, contrasts with the copper and gold enrichment observed in natural vapor-like inclusions. The formation of stable complexes of Cu and Au with reduced sulfur may allow for their enhanced transport by sulfur-enriched magmatic-hydrothermal vapors.