Geochemistry International

, Volume 48, Issue 5, pp 446–455 | Cite as

Ternary system H2O-CO2-NaCl at high T-P parameters: An empirical mixing model

  • L. Ya. Aranovich
  • I. V. Zakirov
  • N. G. Sretenskaya
  • T. V. Gerya


New experimental data on the solubility of NaCl in gaseous CO2 were obtained at pressures (P) of 30–70 MPa and temperatures of 623 and 673 K on experimental equipment making possible to sample a portion of the gas in the course of the experiment. The new measures have demonstrated that the NaCl solubility increases with increasing temperature (T) and pressure and is approximately four to five orders of magnitude higher than the saturated vapor pressure of NaCl at the corresponding temperature. The paper also reports newly obtained experimental data on the equilibrium conditions of the reaction of talc decomposition into enstatite and quartz at a variable H2O/NaCl ratio in the fluid. The results of the experiments validate the empirical equations previously suggested for H2O and NaCl activities in concentrated aqueous salt solutions that can be used in describing silica-saturated fluids at high T-P parameters. A new empirical equation is suggested for the Gibbs free mixing energy in the H2O-CO2-NaCl ternary system, with the parameters of the equation calibrated against experimental data on phase equilibria in marginal binary systems and on the location of the boundary of the region of homogeneous three-component fluid according to data on synthetic fluid inclusions in quartz.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    L. Y. Aranovich and R. C. Newton, “H2O Activity in Concentrated KCl and KCl-NaCl Solutions at High Temperatures and Pressures Measured by the Brucite-Periclase Equilibrium,” Contrib. Mineral. Petrol. 127, 261–271 (1997).CrossRefGoogle Scholar
  2. 2.
    D. S. Korzhinskii, “Principle of Alkali Mobility during Magmatic Phenomena,” in On the 70th Anniversary of the Academician D.S. Belyankin (Akad. Nauk SSSR, Moscow, 1946), pp. 134–152 [in Russian].Google Scholar
  3. 3.
    D. S. Korzhinskii, Physicochemical Principles of Paragenetic Analysis of Minerals (Akad. Nauk SSSR, Moscow, 1957) [in Russian].Google Scholar
  4. 4.
    L. Ya. Aranovich, K. I. Shmulovich, and V. V. Fed’kin, “H2O and CO2 Regime during Regional Metamorphism,” in Contributions to Physicochemical Petrology (Nauka, Moscow, 1987), No. 14, pp. 96–117 [in Russian].Google Scholar
  5. 5.
    L. L. Perchuk and T. V. Gerya, “Fluid Control of Charnockitization,” Chem. Geol. 108, 175–186 (1993).CrossRefGoogle Scholar
  6. 6.
    R. C. Newton, L. Y. Aranovich, E. C. Hansen, and B. A. Vandenheuvel, “Hypersaline Fluids in Precambrian Deep-Crustal Metamorphism,” Precambrian Res. 38, 21–34 (1998).Google Scholar
  7. 7.
    J. J. Ague, “Fluid Infiltration and Transport of Major, Minor and Trace Elements during Regional Metamorphism of Carbonate Rocks, Wepawaug Schist, Connecticut, USA,” Am. J. Sci. 303, 753–816 (2003).CrossRefGoogle Scholar
  8. 8.
    A. R. Kotel’nikov and Z. A. Kotel’nikova, “Experimental Study of the Phase State of the H2O-CO2-NaCl System by the Method of Synthetic Quartz Inclusions in Quartz,” Geokhimiya, No. 4, 526–537 (1990).Google Scholar
  9. 9.
    K. I. Shmulovich and C. M. Graham, “An Experimental Study of Phase Equilibria in the System H2O-CO2-NaCl at 800°C and 9 Kbar,” Contrib. Mineral. Petrol. 136, 247–257 (1999).CrossRefGoogle Scholar
  10. 10.
    K. I. Shmulovich and C. M. Graham, “An Experimental Study of Phase Equilibria in the Systems H2O-CO2-CaCl2 and H2O-CO2-NaCl at High Pressures and Temperatures (500–800°C, 0.5–0.9 GPa): Geological and Geophysical Applications,” Contrib. Mineral. Petrol. 146, 450–462 (2004).CrossRefGoogle Scholar
  11. 11.
    G. Skippen and V. Trommsdorf, “The Influence of NaCl and KCl on Phase Relations in Metamorphosed Carbonate Rocks,” Am. J. Sci. 286, 81–104 (1986).Google Scholar
  12. 12.
    W. Heinrich, S. S. Churakov, and M. Gottschalk, “Mineral-Fluid Equilibria in the System CaO-MgO-SiO2-H2O-CO2-NaCl and the Record of Reactive Fluid Flow in Contact Metamorphic Aureoles,” Contrib. Mineral. Petrol. 148, 131–149 (2004).CrossRefGoogle Scholar
  13. 13.
    V. Trommsdorff, G. Skippen, and P. Ulmer, “Halite and Sylvite as Solid Inclusions in High-Grade Metamorphic Rocks,” Contrib. Mineral. Petrol. 89, 24–29 (1985).CrossRefGoogle Scholar
  14. 14.
    G. Markl and K. Bucher, “Composition of Fluids in the Lower Crust Inferred from Metamorphic Salt in Lower Crustal Rocks,” Nature 391, 781–783 (1998).CrossRefGoogle Scholar
  15. 15.
    K.I. Shmulovich, Carbon Dioxide in High-Temperature Mineral-Forming Processes (Nauka, Moscow, 1988) [in Russian].Google Scholar
  16. 16.
    I. V. Zakirov and N. G. Sretenskaya, “Technique of Experimental Determination of Phase Composition under Heterogeneous Conditions,” in Experimental Problems of Geology (Nauka, Moscow, 1994), pp. 664–667 [in Russian].Google Scholar
  17. 17.
    Z. Duan, N. Moller, and J. H. Weare, “Equation of State for the NaCl-H2O-CO2 System: Prediction of Phase Equilibria and Volumetric Properties,” Geochim. Cosmochim. Acta 59, 2869–2882 (1995).CrossRefGoogle Scholar
  18. 18.
    K. Grjotheim, P. Heggelund, C. Krohn, and K. Motzfeldt, “On the Solubility of Carbon Dioxide in Molten Halides,” Acta Chem. Scandinav. 16, 689–694 (1962).CrossRefGoogle Scholar
  19. 19.
    I. M. Chou, “Halite Solubilities in Supercritical Carbon Dioxide-Water Fluids,” GSA Abstracts with Programs 20(7), 76 (1988).Google Scholar
  20. 20.
    T. S. Bowers and H. C. Helgeson, “Calculation of the Thermodynamic and Geochemical Consequences of Nonideal Mixing in the System H2O-CO2-NaCl on Phase Relations in Geologic Systems: Equation of State for H2O-CO2-NaCl Fluids at High Pressures and Temperatures,” Geochim. Cosmochim. Acta 47, 1247–1275 (1983).CrossRefGoogle Scholar
  21. 21.
    I. V. Zakirov, N. G. Sretenskaja, L. Y. Aranovich, and V. A. Volchenkova, “Solubility of NaCl in CO2 at High Pressure and Temperature: First Experimental Measurements,” Geochim. Cosmochim. Acta 71, 4251–4255 (2007).CrossRefGoogle Scholar
  22. 22.
    L. V. Gurvich, I. V. Veits, V. A. Medvedev, et al., Thermodynamic Properties of Substances (Nauka, Moscow, 1978), Vol. 1, Book 1.Google Scholar
  23. 23.
    I-M. Chou, S. M. Sterner, and K. S. Pitzer, “Phase Relations in the System NaCl-KCl-H2O: IV. Differential Thermal Analysis of the Sylvite Liquidus in the KCl-H2O Binary, the Liquidus in the NaCl-KCl-H2O Ternary, and the Solidus in the NaCl-KCl Binary to 2 Kb Pressure, and a Summary of Experimental Data for Thermodynamic PTX-Analysis of Solid-Liquid Equilibria at Elevated P-T Conditions,” Geochim. Cosmochim. Acta 56, 2281–2293 (1992).CrossRefGoogle Scholar
  24. 24.
    L. Y. Aranovich and R. C. Newton, “H2O Activity in Concentrated NaCl Solutions at High Pressures and Temperatures Measured by the Brucite-Periclase Equilibrium,” Contrib. Mineral. Petrol., 200–212 (1996).Google Scholar
  25. 25.
    T. J. B. Holland and R. Powell, “An Internally Consistent Thermodynamic Data Set for Phases of Petrological Interest,” J. Metamorph. Geol. 16, 309–343 (1998).CrossRefGoogle Scholar
  26. 26.
    L. S. Darken, “Thermodynamics of Binary Metallic Solutions,” Trans. Metal. Soc. AIME 239, 80–89 (1967).Google Scholar
  27. 27.
    V. V. Slavinskii, Candidate’s Dissertation in Geology and Mineralogy (Moscow, 1976).Google Scholar
  28. 28.
    L. Ya. Aranovich, Mineral Equilibria of Multicomponent Solutions (Nauka, Moscow, 1991) [in Russian].Google Scholar
  29. 29.
    R. C. Newton and C. E. Manning, “Quartz Solubility in H2O-NaCl and H2O-CO2 Solutions at Deep Crust-Upper Mantle Pressures and Temperatures: 2–15 Kbar and 500–900°C,” Geochim. Cosmochim. Acta 64, 2993–3005 (2000).CrossRefGoogle Scholar
  30. 30.
    K. I. Shmulovich, C. M. Graham, and B. Yardley, “Quartz, Albite and Diopside Solubilitites in H2O-NaCl and H2O-CO2 Fluids at 0.5–0.9 GPa,” Contrib. Mineral. Petrol. 141, 95–108 (2001).Google Scholar
  31. 31.
    L. Y. Aranovich and R. C. Newton, “Experimental Determination of CO2-H2O Activity-Composition Relations at 600–1000°C and 6–14 Kbar by Reversed Decarbonation and Dehydration Reactions,” Am. Mineral. 84, 1319–1332 (1999).Google Scholar
  32. 32.
    R. C. Newton and C. E. Manning, “Experimental Determination of Calcite Solubility in H2O-NaCl Solutions at Deep Crust/Upper Mantle Pressures and Temperatures: Implications for Metasomatic Processes in Shear Zones,” Am. Mineral. 87, 1401–1409 (2002).Google Scholar
  33. 33.
    T. J. B. Holland and R. Powell, “Activity-Composition Relations for Phases in Petrological Calculations: An Asymmetric Multicomponent Formulation,” Contrib. Mineral. Petrol. 145, 492–501 (2003).CrossRefGoogle Scholar
  34. 34.
    J. D. Frantz, R. K. Popp, and T. C. Hoering, “The Compositional Limits of Liquid Immiscibility in the System H2O-NaCl-CO2 as Determined with the Use of Synthetic Fluid Inclusions in Conjunction with Mass Spectrometry,” Chem. Geol. 98, 237–255 (1992).CrossRefGoogle Scholar

Copyright information

© Pleiades Publishing, Ltd. 2010

Authors and Affiliations

  • L. Ya. Aranovich
    • 1
    • 2
  • I. V. Zakirov
    • 2
  • N. G. Sretenskaya
    • 2
  • T. V. Gerya
    • 2
  1. 1.Institute of the Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry (IGEM)Russian Academy of SciencesMoscowRussia
  2. 2.Institute of Experimental MineralogyRussian Academy of SciencesChernogolovka, Moscow oblastRussia

Personalised recommendations