Supporting Information

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1 Supporting Information Calcite and Barite Solubility Measurements in Mixed Electrolyte Solutions and The Development of A Comprehensive Model for Water-Mineral-Gas Equilibrium of the Na-K-Mg-Ca-Ba-Sr-Cl-SO 4 -CO 3 -HCO 3 -CO 2(Aq) -H 2 O System at Up To 250 o C and 1,500 Bars Zhaoyi Dai a*, Amy T. Kan a1, Wei Shi a, Fei Yan a, Fangfu Zhang a, Narayan Bhandari a, Gedeng Ruan a, Zhang Zhang a, Ya Liu a, Hamad A. Alsaiari a, Yi-Tsung Lu a, Guannan Deng a, Mason B. Tomson a a Department of Civil and Environmental Engineering, Rice University, 6100 Main Street, Houston, TX 77005, US * Corresponding Author contact information: address: Zhaoyi.Dai@rice.edu Tel: (713) Contributed equally to this work with the first author 1

2 Contents of Tables: Table S1. The sources of the virial coefficients and standard partial molar volume of neutral solutes adopted in this study Table S2. Sources of CO 2 and mineral solubility data adopted in this study and the ranges of temperature, pressure and background electrolyte Table S3. Sources of solution density data adopted in this study and the ranges of temperature, pressure and salt concentrations Table S4. The comparison of the standard partial molar volume among those listed in the Tables of the reference, those calculated using the original equation in the reference, and those calculated using the revised equation listed above Table S5. The compositions of synthetic brine III (mol/kg H 2 O). It is reproduced from the paper published by He and Morse (1993) Contents of Figures Figure S1. Schematic of the apparatus for testing barite solubility at high temperature and high pressure. It is reproduced from the paper published by Shi et al. (2013) Figure S2. Comparisons of the measured and predicted solution densities (g/cm 3 ) by this study for solutions of (a) KCl, (b) MgCl 2, (c) CaCl 2, (d) SrCl 2, (e) BaCl 2, (f) Na 2 SO 4, (g) K 2 SO 4, and (h) MgSO Figure S3. Comparison of the solubility products of halite from different sources Figure S4. Comparison of the change of standard molar compressibility of halite dissolution between Kaasa (1998) and this study versus that reported by Millero et al. (1987)

3 1. The sources of the virial coefficients, standard partial molar volume of neutral solutes, mineral solubility, and solution density adopted in this study Table S1. The sources of the virial coefficients and standard partial molar volume of neutral solutes adopted in this study. Species 0 Virial coefficients V * interactions H-Cl 1 1 Na-Cl 2 2 K-Cl 3 3 Ca-Cl 4 4 Mg/Ba-Cl 5 5 Sr-Cl 5 5 Na-SO K-SO Mg-SO Na-CO Na-HCO Na-CO Ca-CO Ca-HCO * 0 V represents the standard partial molar volume for the corresponding neutral solute of the species interactions, e.g., HCl, CaCl 2, K 2 SO 4, CaSO 4. It is always assumed that V 0. 0 H 3

4 Table S2. Sources of CO 2 and mineral solubility data adopted in this study and the ranges of temperature, pressure and background electrolyte. Mineral T ( o C) P (bar) Background electrolyte conc. * (m) Reference Psat Psat Psat halite Psat , , , anhydrite 50, Psat 1, Psat , gypsum , Psat Psat , , barite Psat 1, Psat Psat ,517 mixed electrolytes This study , , mixed electrolytes Psat ** calcite Psat 1, , , m NaCl and m Na 2 SO 4 This study Psat Psat celestite , 38, 39, 40 4

5 Psat CO , , CaCl 2 53 * If not specified, the background electrolyte is NaCl. ** References of the data adopted by De Visscher and Vanderdeelen (2012) are listed in their paper

6 Table S3. Sources of solution density data adopted in this study and the ranges of temperature, pressure and salt concentrations. Salt T ( o C) P (bar) Molality (m) References MgCl CaCl Psat Psat SrCl BaCl KCl Psat K 2 SO Na 2 SO MgSO Psat Psat Salt T ( o C) P (bar) Molality (m) References MgCl 2 CaCl 2 SrCl Psat Psat

7 BaCl KCl Psat K 2 SO Na 2 SO MgSO Psat Psat

8 2. Errors in the equation for molar volume calculations by Holmes et al. (1997) It is found that when using the parameters and the equations for molar volume calculation provided in the revision paper by Holmes and his co-authors, the calculated molar volumes are in error with those listed in the tables 66. After careful analysis and calculation, it is believed that the correct equation for molar volume calculation should be: V V 2 V ( P / P ) 3 V ( P / P ) The reproduced data are shown in the Table S4 below. Table S4. The comparison of the standard partial molar volume among those listed in the Tables of the reference, those calculated using the original equation in the reference, and those calculated using the revised equation listed above. T (K) P (MPa) 0 V listed in paper (J/bar/mol) 0 V before revision (J/bar/mol) 0 V after revision (J/bar/mol) MgCl Psat Psat Psat CaCl Psat Psat Psat SrCl Psat Psat Psat BaCl 2 8

9 Psat Psat Psat

10 3. Experimental apparatus used in this study and our previous publications Figure S1. Schematic of the apparatus for testing barite solubility at high temperature and high pressure. It is reproduced from the paper published by Shi et al. (2013)

11 4. Solution density predictions of this study 11

12 Figure S2. Comparisons of the measured and predicted solution densities (g/cm 3 ) by this study for solutions of (a) KCl, (b) MgCl 2, (c) CaCl 2, (d) SrCl 2, (e) BaCl 2, (f) Na 2 SO 4, (g) K 2 SO 4, and (h) MgSO 4. 12

13 5. Compositions of synthetic brine III. Table S5. The compositions of synthetic brine III (mol/kg H 2 O). It is reproduced from the paper published by He and Morse (1993) 67 Species Na + K + Ca 2+ Mg 2+ Cl - 2- SO 4 Colbey Colbey Kennedy

14 6. Comparison of halite solubility products and molar halite dissolution compressibility adopted in this study with literature data Figure S3. Comparison of the solubility products of halite from different sources. 14

15 Figure S4. Comparison of the change of standard molar compressibility of halite dissolution between Kaasa (1998) and this study versus that reported by Millero et al. (1987). 15

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