Platinum transport in chloride-bearing fluids and melts: Insights from in situ X-ray absorption spectroscopy and thermodynamic modeling

摘要

Hydrothermal chloride-rich fluids are identified at the late stages of the formation of platinum group element (PGE) deposits in giant layered intrusions, and are considered as the PGEs transport media in Cu(-Mo,Au) porphyry systems. In order to quantify the hydrothermal mobility of Pt we performed an investigation of the speciation of Pt in hydrothermal chloride-bearing fluids and dry melt by means of X-ray absorption spectroscopy (XAS). The experiments consisted in recording the Pt L-3-edge X-ray absorption near edge structure/extended X-ray absorption fine structure (XANES/EXAFS) spectra of Pt-bearing fluids obtained by dissolution of Pt metal in KCl/HCl and CsCl/HCl fluids in the temperature range from 450 to 575 degrees C at pressures from 0.5 to 5 kbar. A spectrum of Pt dissolved in dry CsCl/NaCl/KCl + K2S2O8 melt was recorded at 650 degrees C. The capillary method, when the experimental solution together with Pt((cr) )is sealed inside a silica glass capillary, was used. As was determined from the XANES spectra, in all the experimental systems Pt existed in the +2 oxidation state. Analysis of EXAFS spectra showed that Pt is coordinated by four Cl atoms with Rpt-cl = 2.31 +/- 0.01 angstrom independently of the T-P-compositional parameters. No evidence of the formation of complex with alkali metal cations in the second coordination sphere of Pt was found by the analysis of the EXAFS spectra of concentrated CsCl brines and melt. Our results imply that PtCl42- is the main Pt-Cl complex which predominates in hydrothermal fluids at t > 400 degrees C and fluid density d > 0.3 g.cm(-3). Experimental data obtained for dry melt of alkali metal chlorides suggest that Pt-Cl complexes can dominate Pt speciation in chloride-bearing aluminosilicate melts where Cl exhibits a salt-like atomic arrangement and ionic bonding. The literature data on the Pt solubility constant, Pt-(cr) + 2HCl((aq))degrees + 2Cl(-) = PtCl42- + H-2(aq), are compiled and fitted to the simple density m