Advances in Earth Science ›› 2019, Vol. 34 ›› Issue (4): 414-423. doi: 10.11867/j.issn.1001-8166.2019.04.0414

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Thermodynamic Calculation of Solubility of Na 2SO 4/K 2SO 4 in Hydrothermal Fluids

Wei Zhang 1, 2( ),Li Zhou 2( ),Hongfeng Tang 2,Heping Li 2,Li Wang 2, 3   

  1. 1. Research Center of Karst Ecological Civilization, Guizhou Normal University, Guiyang 550025, China
    2. Key Laboratory of High-Temperature and High-Pressure Study of the Earth’s Interior, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, China
    3. University of Chinese Academy of Sciences, Beijing 100039, China
  • Received:2018-11-08 Revised:2019-03-19 Online:2019-04-10 Published:2019-05-27
  • Contact: Li Zhou E-mail:zhangwei@gznu.edu.cn;zhouli@vip.gyig.ac.cn
  • About author: Zhang Wei (1988-), male, Wuhan City, Hubei Province, Lecturer. Research areas include experimental and computational geochemistry on water-rock reactions. E-mail: zhangwei@gznu.edu.cn | Zhang Wei (1988-), male, Wuhan City, Hubei Province, Lecturer. Research areas include experimental and computational geochemistry on water-rock reactions. E-mail: zhangwei@gznu.edu.cn
  • Supported by:
    Project supported by the National Natural Science Foundation of China "Experimental study of the behavior of monazite and xenotime in hydrothermal fluids: Constraints on the usefulness of U-Th-Pb age and the mineralization of REE"(No. 41773058);The Joint Foundation of Guizhou Science and Technology Department and Guizhou Normal University “Study on sustainable utilization of geothermal resources in Shiqian County”(No. QIANKEHE LH [2017] 7339)

Wei Zhang,Li Zhou,Hongfeng Tang,Heping Li,Li Wang. Thermodynamic Calculation of Solubility of Na 2SO 4/K 2SO 4 in Hydrothermal Fluids[J]. Advances in Earth Science, 2019, 34(4): 414-423.

Sulfate fluids are common fluids in nature, and their salinity studies can provide important information for the evolution of ore-forming fluids, migration and enrichment of ore-forming elements, and the classification of deposit types. Considerable research has been carried out to investigate the solubility of Na2SO4 and K2SO4 in hydrothermal fluids, however most of the literature reported experimental data were under saturated vapor pressure or the water supercritical region. A few data have been reported for the low temperature hydrothermal mineralization region. Thermodynamic model is a useful method to study the properties of hydrothermal geofluids, especially for mineral solubility. Pitzer interaction model is one of the most widely used model to calculate the thermodynamic properties of hydrothermal fluids, but few work have ever been carried out to calculate the solubility of sulfate at high temperature and pressure. With Pitzer specific interaction model, using the literature reported density data of Na2SO4 and K2SO4 solutions at high temperature and pressure, the pressure effect on Pitzer activity coefficient of sulfate and the standard partial molar volume change during sulfate dissolution process were evaluated and related parameters were obtained. The standard partial molar volumes of Na2SO4 and K2SO4 calculated with these parameters agreed well with those reported in the literature. Combined with the relevant parameters in the literature under saturated vapor pressure, a thermodynamic model for Na2SO4 and K2SO4 solubility calculation with temperature up to 250 ℃ and pressure up to 40 MPa was developed. The model gave very good agreement with the experimental solubility data. With this model, Na2SO4 and K2SO4 solubility was calculated at high temperature and pressure. The calculation results showed that pressure had a positive effect on both the average activity coefficient and solubility product of Na2SO4 and K2SO4, but the solubility of Na2SO4 and K2SO4 decreased with pressure due to the larger change of the average activity coefficient with pressure. And as the temperature increased, the degree of such reduction became larger. The results herein can provide instructions for the compositional analysis of sulfate fluid inclusions.

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