Contributions to Mineralogy and Petrology

, Volume 109, Issue 2, pp 139–150 | Cite as

Partitioning of Cu, Sn, Mo, W, U, and Th between melt and aqueous fluid in the systems haplogranite-H2O−HCl and haplogranite-H2O−HF

  • Hans Keppler
  • Peter J. Wyllie


The partition coefficients KD=cfluid/cmelt of Cu, Sn, Mo, W, U, and Th between aqueous fluid and melt were measured in the systems haplogranite-H2O−HCl and haplogranite-H2O−HF at 2kbars, 750°C, and Ni−NiO buffer conditions using rapid-quench cold seal bombs, with many reversed runs. Concentrations of trace elements (1–1000 ppm) in the quenched aqueous fluid and in the glass were determined by plasma emission spectrometry (DCP). KD of F is close to 1 in the system studied. KD of Cu and Sn strongly increases with increasing Cl concentration due to the formation of chloride complexes in the aqueous fluid, while HF has no effect. However, in 2M HCl, KD of Cu approaches 100, while KD of Sn is below 0.1 under the same conditions. The partition coefficients of Mo and W are high if water is the only volatile present (Mo: 5.5, W: 3.5), but strongly decrease with increasing HCl and HF, due to the destabilization of hydroxy complexes. KD of U and Th is very low in the absence of complexing agents, but strongly increases with increasing HF concentration. KD of U also increases with increasing HCl concentration and with increasing CO2 concentration in the system haplogranite-H2O−CO2, indicating the stability of chloride and carbonate complexes of U at magmatic temperatures. The data suggest a stoichiometric ratio of Cl: U=3:1 and of F:U=2:1 in these complexes. Cl-rich fluids are responsible for the formation of porphyry Cu deposits, but are much less effective in the transport of Sn. F appears not to be essential for the concentration of Mo and W in fluids evolving from a granitic magma. The different complexing behavior of U and Th in aqueous fluids may account for their fractionation during magma genesis.


  1. Ashley PM (1984) Sodic granitoids and felsic gneisses associated with uranium-thorium mineralisation, Crockers Well, South Australia. Miner Deposita 19:7–18Google Scholar
  2. Barsukov VL, Durasova NA, Kovalenko NI, Ryabchikov ID, Ryzhenko BN (1987) Oxygen fugacity and tin behavior in metals and fluids. Geol Zb 38:723–733Google Scholar
  3. Calas G (1979) Etude expérimentale du comportement de l'uranium dans les magmas: états d'oxidation et coordinance. Geochim Cosmochim Acta 43:1521–1531Google Scholar
  4. Candela PA, Holland HD (1984) The partitioning of copper and molybdenum between silicate melts and aqueous fluids. Geochim Cosmochim Acta 48:373–380Google Scholar
  5. Chatterjee AK, Muecke GK (1982) Geochemistry and the distribution of uranium and throium in the granitoid rocks of the South Mountain Batholith, Nova Scotia: some genetic and exploration implications. Geol Surv Can Pap 81-23:11–17Google Scholar
  6. Congdon RD, Nash WP (1988) High-fluorine rhyolite: An eruptive pegmatite magma at the Honeycomb Hills, Utah. Geology 16:1018–1021Google Scholar
  7. Dingwell DB (1988) The structures and properties of fluorine-rich magmas: a review of experimental studies. In: Taylor RP, Strong DF (eds) Recent advances in the geology of granite-related mineral deposits. Canadian Institute of Mining and Metallurgy, Montreal, pp 1–12Google Scholar
  8. Dominé F, Velde B (1985) Preliminary investigation of the processes governing the solubility of uranium in silicate melts. Bull Minéral 108:755–765Google Scholar
  9. Ellis AJ (1963) The effect of temperature on the ionization of hydrofluoric acid. J Chem Soc 1963:4300–4304Google Scholar
  10. Eugster HP (1986) Minerals in hot water. Am Mineral 71:655–673Google Scholar
  11. Frantz JD, Marshall WL (1984) Electrical conductances and ionization constants of salts, acids, and bases in supercritical aqueous fluids: I. Hydrochloric acid from 100°C to 700°C and at pressures to 4000 bars. Am J Sci 284:651–667Google Scholar
  12. Holland HD (1972) Granites, solutions, and base metal deposits. Econ Geol 67:281–301.Google Scholar
  13. Holloway JR, Reese RL (1974) The generation of N2−CO2−H2O fluids for use in hydrothermal experimentation I. Experimental method and equilibrium calculations in the C−H−O−N system. Am Mineral 59:587–597Google Scholar
  14. Keppler H, Wyllie PJ (1989) Partitioning of Mo, W, U, Cu, and Sn between granitic melt and fluid phase. EOS Trans Am Geophys Union 70:1403Google Scholar
  15. Keppler H, Wyllie PJ (1990a) Experimental study of the partitioning of Cu, Sn, Mo, W, U, and Th between haplogranitic melt and aqueous fluid. Ber Dtsch Miner Ges (suppl to Eur J Mineral) 1, 1990:124Google Scholar
  16. Keppler H, Wyllie PJ (1990b) Role of fluids in transport and fractionation of uranium and thorium in magmatic processes. Nature 348:531–533Google Scholar
  17. Khitarov NI, Malinin SP, Lebedev YB, Shibayeva NP (1982) The distribution of Zn, Cu, Pb, and Mo between a fluid phase and a silicate melt of granitic composition at high temperatures and pressures. Geochem Int 19, 4: 123–136Google Scholar
  18. Kilinc IA, Burnham CW (1972) Partitioning of chloride between a silicate melt and coexisting aqueous phase from 2 to 8 kbars. Econ Geol 67:231–235Google Scholar
  19. Koster van Groos AF, Wyllie PJ (1968) Melting relationships in the system NaAlSi3O8−NaF−H2O to 4 kilobars pressure. J Geol 76:50–70Google Scholar
  20. Koster van Groos AF, Wyllie PJ (1969) Melting relationships in the system NaAlSi3O8−NaCl−H2O at 1 kilobar pressure, with petrological applications. J Geol 77:581–605Google Scholar
  21. Langmuir D (1978) Uranium solution-mineral equilibria at low temperatures with applications to sedimentary ore deposits. Geochim Cosmochim Acta 42:547–569Google Scholar
  22. Manning DAC, Henderson P (1984) The behaviour of tungsten in granitic melt-vapour systems. Contrib Mineral Petrol 86:286–293Google Scholar
  23. Nekrasov IY, Epel'baum MB, Sobolev VP (1980) Partition of tin between melt and chloride fluid in the granite-SnO−SnO2 fluid system. Doklady, Acad Sci USSR, Earth Sci Section, 252:165–168Google Scholar
  24. Pollard PJ, Pichavant M, Charoy B (1987) Contrasting evolution of fluorine and boron-rich tin systems. Miner Deposita 22:315–321Google Scholar
  25. Romberger SB (1984) Transport and deposition of uranium in hydrothermal systems at temperatures up to 300°C: geological applications. In: De Vivo B, Ippolito F, Capaldi G, Simpson PR (eds) Uranium geochemistry, mineralogy, geology, exploration and resources. Institution of Mining and Metallurgy, London, pp 12–17Google Scholar
  26. Ryabchikov ID, Orlova GP, Yefimov AS, Kalenchuk GY (1980) Copper in a granite-fluid system. Geochem Int 17, 5:29–34Google Scholar
  27. Ryabchikov ID, Rekharskiy VI, Kudrin AV (1981) Mobilization of molybdenum by fluids during the crystallization of granite melts. Geochem Int 18, 4: 183–186Google Scholar
  28. Stein H, Hannah JL (1985) Movement and origin of ore fluids in climax-type systems. Geology 13:469–474Google Scholar
  29. Štemprok M (1982) Tin-fluorine relationships in ore-bearing assemblages. In: Evans AM (ed) Metalization associated with acid magmatism. Wiley, New York, pp 321–337Google Scholar
  30. Štemprok M (1984) Alkaline trend in the differentiation of tinbearing granites. In: Janelidze TV, Tvalchrelidze AG (eds) Proceedings of the sixth quadrennial IAGOD symposium. Schweizerbarth, Stuttgart, pp 449–455Google Scholar
  31. Taylor JRP (1988) Experimental studies on tin in magmatic-hydrothermal systems. PhD thesis, Monash University, Melbourne, AustraliaGoogle Scholar
  32. Tuttle OF, Bowen NL (1958) Origin of granite in the light of experimental studies in the system NaAlSi3O8−KAlSi3O8−SiO2−H2O. Geol Soc Am Mem 74Google Scholar
  33. Urabe T (1985) Aluminous granite as a source magma of hydrothermal ore deposits: an experimental study. Econ Geol 80:148–157Google Scholar
  34. Webster JD (1990) Partitioning of F between H2O and CO2 fluids and topaz rhyolite melt. Contrib Mineral Petrol 104:424–438Google Scholar
  35. Webster JD, Holloway JR, Hervig RL (1989) Partitioning of lithophile trace elements between H2O and H2O+CO2 fluids and topaz rhyolite melt. Econ Geol 84:116–134Google Scholar
  36. Westra G, Keith SB (1981) Classification and genesis of stockwork molybdenum deposits. Econ Geol 76:844–873Google Scholar
  37. Wood SA, Vlassopoulos, D (1989) Experimental determination of the hydrothermal solubility and speciation of tungsten at 500°C and 1 kbar. Geochim Cosmochim Acta 53:303–312Google Scholar
  38. Wyllie PJ, Tuttle OF (1964) Experimental investigation of silicate systems containing two volatile components. Part III: The effects of SO3, P2O5, HCl and Li2O in addition to H2O, on the melting temperatures of albite and granite. Am J Sci 262:930–939Google Scholar

Copyright information

© Springer-Verlag 1991

Authors and Affiliations

  • Hans Keppler
    • 1
  • Peter J. Wyllie
    • 1
  1. 1.Division of Geological and Planetary Sciences 170-25California Institute of TechnologyPasadenaUSA
  2. 2.Bayerisches GeoinstitutUniversität BayreuthBayreuthFederal Republic of Germany

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