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The physical and chemical evolution of low-salinity magmatic fluids at the porphyry to epithermal transition: a thermodynamic study
Authors:Christoph A Heinrich
Institution:(1) Isotope Geochemistry and Mineral Resources, Department of Earth Sciences, Swiss Federal Institute of Technology, ETH Zentrum NO, 8092 Zürich, Switzerland;(2) Faculty of Mathematics and Natural Sciences, University of Zürich, Zürich, Switzerland
Abstract:Fluid-phase relationships and thermodynamic reaction modelling based on published mineral solubility data are used to re-assess the Cu–Au-mineralising fluid processes related to calc-alkaline magmatism. Fluid inclusion microanalyses of porphyry ore samples have shown that vapour-like fluids of low to intermediate salinity and density (~2–10 wt% NaCl eq.; ~0.1–0.3 g cm–3) can carry percentage-level concentrations of copper and several ppm gold at high temperature and pressure. In epithermal deposits, aqueous fluids of similar low to intermediate salinity but liquid-like density are ubiquitous and commonly show a magmatic isotope signature. This paper explores the physical evolution of low-salinity to medium-salinity magmatic fluids of variable density, en route from their magmatic source through the porphyry regime to the near-surface epithermal environment, and investigates the chemical conditions required for effective transport of gold and other components from the magmatic to the epithermal domain. Multicomponent reaction modelling guided by observations of alteration zonation and vein overprinting relationships predicts that epithermal gold deposits are formed most efficiently by a specific succession of processes during the evolution of a gradually cooling magmatic–hydrothermal system. (1) The low-salinity to medium-salinity fluid, after separating from the magma and possibly condensing out some hypersaline liquid in the high-temperature porphyry environment, must physically separate from the denser and more viscous liquid, and then cool within the single-phase fluid stability field. By cooling under adequate confining pressure, such a vapour will evolve above the critical curve and contract, without any heterogeneous phase change, to an aqueous liquid of the same salinity. (2) High concentrations of gold, transported as stable Au bisulphide complexes supporting >1 ppm Au even at 200°C, can be maintained throughout cooling, provided that the fluid initially carries an excess of H2S over Cu+Fe on a molal scale. This condition is favoured by an initially high sulphide content in a particularly low-salinity magmatic fluid, or by preferential partitioning of sulphur into a low-salinity vapour and partial removal of Fe into a hypersaline liquid at high temperature. (3) Acid neutralisation further optimises gold transport by maximising the concentration of the HS ligand. This may occur by feldspar destructive alteration along pyrite±chalcopyrite±sulphate veins, in the transition zone between the porphyry and epithermal environments. An alternative acid/base control is the dissolution of calcite in sediments, which may enable long-distance gold transport to Carlin-type deposits, because of the positive feedback between acid neutralisation and permeability generation. The three physical and chemical transport requirements for high-grade epithermal gold mineralisation are suggested to be the common link of epithermal gold deposits to underlying magmatic–hydrothermal systems, including porphyry-Cu–Au deposits. Both mineralisation types are the result of gradual retraction of isotherms around cooling hydrous plutons in similar tectonic and hydrologic environments. As magmatic fluid is generated at increasing depths below the surface the importance of vapour contraction increases, leading to the typical overprinting of potassic, phyllic and advanced argillic alteration and their related ore styles.Editorial handling: B. Lehmann
Keywords:Gold  Copper  Arsenic solubility  Magmatic fluids  Vapour contraction  Hypersaline liquid  Condensation  Epithermal  Porphyry  Thermodynamic modelling
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