Modeling Reactive Multiphase Flow and Transport of Concentrated Solutions

Abstract A Pitzer ion-interaction model for concentrated aqueous solutions was added to the reactive multiphase flow and transport code TOUGHREACT. The model is described and verified against published experimental data and the geochemical code EQ3/6. The model is used to simulate water-rock-gas interactions caused by boiling and evaporation within and around nuclear waste emplacement tunnels at the proposed high-level waste repository at Yucca Mountain, Nevada. The coupled thermal, hydrological, and chemical processes considered consist of water and air/vapor flow, evaporation, boiling, condensation, solute and gas transport, formation of highly concentrated brines, precipitation of deliquescent salts, generation of acid gases, and vapor-pressure lowering caused by the high salinity of the concentrated brine.

[1]  W. Wagner,et al.  The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use , 2002 .

[2]  N. Møller,et al.  The prediction of mineral solubilities in natural waters: The Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic strengths at 25°C , 1984 .

[3]  John A. Cherry,et al.  The formation and potential importance of cemented layers in inactive sulfide mine tailings , 1991 .

[4]  J. Weare,et al.  A chemical equilibrium algorithm for highly non-ideal multiphase systems: Free energy minimization , 1987 .

[5]  N. Spycher,et al.  Fluid flow and reactive transport around potential nuclear waste emplacement tunnels at Yucca Mountain, Nevada. , 2003, Journal of contaminant hydrology.

[6]  E. C. Beahm,et al.  Modeling Thermodynamics and Phase Equilibria for Aqueous Solutions of Trisodium Phosphate , 1999 .

[7]  K. Pruess,et al.  TOUGH2 User's Guide Version 2 , 1999 .

[8]  Karsten Pruess,et al.  TOUGHREACT - A simulation program for non-isothermal multiphase reactive geochemical transport in variably saturated geologic media: Applications to geothermal injectivity and CO2 geological sequestration , 2006, Comput. Geosci..

[9]  Donald L. Suarez,et al.  Two-dimensional transport model for variably saturated porous media with major ion chemistry , 1994 .

[10]  Guoxiang Zhang Nonisothermal hydrobiogeochemical models in porous media , 2001 .

[11]  Jerry P. Greenberg,et al.  The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-K-Ca-Cl-SO4-H2O system to high concentration from 0 to 250°C , 1989 .

[12]  John H. Weare,et al.  The prediction of mineral solubilities in natural waters: the NaKMgCaClSO4H2O system from zero to high concentration at 25° C , 1980 .

[13]  H. Helgeson,et al.  Theoretical prediction of the thermodynamic behavior of aqueous electrolytes by high pressures and temperatures; IV, Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600 degrees C and 5kb , 1981 .

[14]  Eric L. Sonnenthal,et al.  Reactive Geochemical Transport Modeling of Concentrated AqueousSolutions: Supplement to TOUGHREACT User's Guide for the PitzerIon-Interaction Model , 2006 .

[15]  Changbing Yang,et al.  Biogeochemical Reactive Transport Model of the Redox Zone Experiment of the Äspö Hard Rock Laboratory in Sweden , 2004 .

[16]  Susan Carroll,et al.  Cesium migration in Hanford sediment: a multisite cation exchange model based on laboratory transport experiments. , 2003, Journal of contaminant hydrology.

[17]  Jiamin Wan,et al.  Modeling reactive geochemical transport of concentrated aqueous solutions , 2004 .

[18]  T. J. Wolery,et al.  EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 4 , 1992 .

[19]  S. Arnórsson,et al.  Precipitation of poorly crystalline antigorite under hydrothermal conditions , 2005 .

[20]  C. Monnin,et al.  Density calculation and concentration scale conversions for natural waters , 1994 .

[21]  C. R. Bryan Drift-Scale THC Seepage Model , 2005 .

[22]  Kenneth S. Pitzer,et al.  Thermodynamics of electrolytes. I. Theoretical basis and general equations , 1973 .

[23]  T. A. Buscheck MULTISCALE THERMOHYDROLOGIC MODEL , 2001 .

[24]  Sumit Mukhopadhyay,et al.  Modeling coupled thermal-hydrological-chemical processes in the unsaturated fractured rock of Yucca Mountain, Nevada: Heterogeneity and seepage , 2005 .

[25]  C. Monnin,et al.  A thermodynamic model for the solubility of barite and celestite in electrolyte solutions and seawater to 200°C and to 1 kbar , 1999 .

[26]  J. Samper,et al.  Coupled microbial and geochemical reactive transport models in porous media: Formulation and Application to Synthetic and In Situ Experiments , 2006 .

[27]  Karsten Pruess,et al.  Role of Competitive Cation Exchange on Chromatographic Displacement of Cesium in the Vadose Zone beneath the Hanford S/SX Tank Farm , 2004 .

[28]  Gordon Atkinson,et al.  Thermodynamics of concentrated electrolyte mixtures. 5. A review of the thermodynamic properties of aqueous calcium chloride in the temperature range 273.15-373.15 K , 1985 .

[29]  J. Nitao,et al.  Repository-Heat-Driven Hydrothermal Flow at Yucca Mountain, Part I: Modeling and Analysis , 1993 .

[30]  Susan Carroll,et al.  Evaporative evolution of a Na–Cl–NO3–K–Ca–SO4–Mg–Si brine at 95°C: Experiments and modeling relevant to Yucca Mountain, Nevada , 2005, Geochemical transactions.

[31]  E. Clarke,et al.  Evaluation of the Thermodynamic Functions for Aqueous Sodium Chloride from Equilibrium and Calorimetric Measurements below 154 °C , 1985 .

[32]  David L. Parkhurst,et al.  A computer program incorporating Pitzer's equations for calculation of geochemical reactions in brines , 1988 .

[33]  K. Knauss,et al.  Evaporative chemical evolution of natural waters at Yucca Mountain, Nevada , 2001 .

[34]  K. Pitzer,et al.  Thermodynamics of aqueous calcium chloride , 1983 .

[35]  J. A. Rard,et al.  Conversion and optimization of the parameters from an extended form of the ion-interaction model for Ca(NO3)2(aq) and NaNO3(aq) to those of the standard Pitzer model, and an assessment of the accuracy of the parameter temperature representations , 2005 .

[36]  N. Møller,et al.  The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-Ca-Cl-SO4-H2O system, to high temperature and concentration , 1988 .

[37]  B. Krumgalz,et al.  Application of the Pitzer ion interaction model to natural hypersaline brines , 2001 .