The partitioning behavior of silver in a vapor–brine–rhyolite melt assemblage

Abstract

The partitioning of silver in a sulfur-free rhyolite melt–vapor–brine assemblage has been quantified at 800 °C, pressures of 100 and 140 MPa and f O 2 ≈ NNO (nickel–nickel oxide). Silver solubility (±2 σ) in rhyolite increases 5-fold from 105 ± 21 to 675 ± 98 μg/g as pressure increases from 100 to 140 MPa. Nernst-type partition coefficients ( D Ag i , j ± 2 σ ) describing the mass transfer of silver at 100 MPa between vapor and melt, brine and melt and vapor and brine are 32 ± 30, 1151 ± 238 and 0.026 ± 0.004, respectively. At 140 MPa, values for D Ag i , j ( ± 2 σ ) for vapor and melt, brine and melt, and vapor and brine are 32 ± 10, 413 ± 172 and 0.06 ± 0.03, respectively. Apparent equilibrium constant values (±2 σ) describing the exchange of silver and sodium between vapor and melt, K Ag , Na v / m , at 100 and 140 MPa are 105 ± 68 and 14 ± 6. The average values (±2 σ) for silver and sodium exchange between brine and melt, K Ag , Na b / m , at 100 and 140 MPa are 313 ± 288 and 65 ± 12. These data indicate that the mass transfer of silver from rhyolite melt to an exsolved volatile phase(s) is enhanced at 100 MPa relative to 140 MPa, suggesting that decompression increases the silver ore-generative potential of an evolving silicate magma. Model calculations using the new data suggest that the evolution of low-density, aqueous fluid (i.e., vapor) may be responsible for the the silver tonnage of many porphyry-type and perhaps epithermal-type ore deposits. For example, Halter et al. (Halter W. E., Pettke T. and Heinrich C. A. (2002) The origin of Cu/Au ratios in porphyry-type ore deposits. Science 296, 1842–1844) used detailed silicate and sulfide melt inclusion and vapor and brine fluid inclusions analyses to estimate a melt volume on the order of 15 km 3 to satisfy the copper budget at the Bajo de la Alumbrera copper-, gold-, silver-ore deposit. Using their melt volume estimate with the data presented here, model calculations for a 15-km 3 felsic melt, saturated with pyrrhotite and magnetite, suggest that a low-salinity magmatic vapor may scavenge on the order of 7 × 10 12 g of silver from the melt. This quantity of silver exceeds the discovered 2 × 10 9 g of Ag at Alumbrera. Calculated tonnages for numerous other deposits yield similar results. The excess silver in the vapor, remaining after porphyry formation, is then available to precipitate at lower PTconditions in the stratigraphically higher epithermal environment. These data suggest that silver, and perhaps other ore metals, in the porphyry-epithermal continuum may be derived solely from the time-integrated flux of dominantly low-salinity vapor exsolved from a series of sequential magma batches.