100th Anniversary Special Paper: Vapor Transport of Metals and the Formation of Magmatic-Hydrothermal Ore Deposits

      In most published hydrothermal ore deposit models, the main agent of metal transport is an aqueous liquid. However, there is increasing evidence from volcanic vapors, geothermal systems (continental and submarine), vapor-rich fluid inclusions, and experimental studies that the vapor phase may be an important and even dominant ore fluid in some hydrothermal systems. This paper reviews the evidence for the transport of metals by vapor (which we define as an aqueous fluid of any composition with a density lower than its critical density), clarifies some of the thermodynamic controls that may make such transport possible, and suggests a model for the formation of porphyry and epithermal deposits that involves precipitation of the ores from vapor or a vapor-derived fluid.
   Analyses of vapor (generally >90% water) released from volcanic fumaroles at temperatures from 500? to over 900?C and near-atmospheric pressure typically yield concentrations of ore metals in the parts per billion to parts per million range. These vapors also commonly deposit appreciable quantities of ore minerals as sublimates. Much higher metal concentrations (from ppm to wt %) are observed in vapor inclusions trapped at pressures of 200 to 1,000 bars in deeper veins at lower temperatures (400??650?C). Moreover, concentrations of some metals, notably Cu and Au, are commonly higher in vapor inclusions than they are in inclusions of coexisting hypersaline liquid (brine). Experiments designed to determine the concentration of Cu, Sn, Ag, and Au in HCl-bearing water vapor at variable although relatively low pressures (up to 180 bars) partly explain this difference. These experiments show that metal solubility is orders of magnitude higher than predicted by volatility data for water-free systems, and furthermore that it increases sharply with increasing water fugacity and correlates positively with the fugacity of HCl. Thermodynamic analysis shows that metal solubility is greatly enhanced by reaction of the metal with HCl and by hydration, which results in the formation of species such as MeClm.nH2O. Nonetheless, the concentrations measured by these experiments are considerably lower than those measured in experiments involving aqueous liquids or determined for vapor fluid inclusions. A possible explanation for this and for the apparent preference of metals such as Cu and Au for the vapor over the coexisting brine in some natural settings is suggested by limited experimental studies of metal partitioning between vapor and brine. These studies show that, whereas Cu, Fe, and Zn all partition strongly into the liquid in chloride-bearing sulfur-free systems, Cu partitions preferentially into the vapor in the presence of significant concentrations of sulfur. We therefore infer that high concentrations of Cu and Au in vapor inclusions reflect the strong preference of sulfur for Phase stability relationships in the system NaCl-H2O indicate how vapor transport of metals may occur in nature, by showing a range of possible vapor evolution paths for the conditions of porphyry-epithermal systems. At the world-class Bingham Canyon porphyry Cu-Au deposit, evidence from fluid inclusions supports a model in which a single-phase fluid of intermediate to vapor-like density ascends from a magma chamber. On cooling and decompression, this fluid condenses a small fraction of brine by intersecting the two-phase surface on the vapor side of the critical curve, without significantly changing the composition of the expanding vapor. Vapor and brine reach Cu-Fe sulfide saturation as both phases cool below 425?C. Vapor, which is the dominant fluid in terms of the total mass of H2O, Cu, and probably even Cl, is interpreted to be the main agent of metal transport. The evolution of fluids leading to high-grade epithermal gold mineralization is initiated by an H2S-, SO2-, Au-, and variably Cu- and As-rich vapor, which separates from an FeCl2-rich brine in a subjacent porphyry environment. In the early stages of the hydrothermal system, vapor expands rapidly and on reaching the epithermal environment, condenses, producing hypogene advanced argillic alteration and residual vuggy quartz and, in some cases, coeval high-sulfidation precious metal mineralization (e.g., Pascua). More commonly, the introduction of precious metals occurs somewhat later, after the site of magmatic fluid exsolution has receded to greater depth. Because of the relatively high pressure, the vapor separating from brine at this stage cools along a pressure-temperature path above the critical curve of the system, causing it to contract to a liquid capable of transporting several parts per million Au to temperatures as low as 150?C. the vapor phase and the formation of sulfur-bearing metallic gas species.

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