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Equilibrium Modeling of Clinoptilolite-Analcime Equilibria at Yucca Mountain, Nevada, USA

Published online by Cambridge University Press:  28 February 2024

Steve J. Chipera
Affiliation:
Earth and Enviromental Sciences, Los Alamos National Laboratory, Mail Stop D469, Los Alamos, New Mexico 87545
David L. Bish
Affiliation:
Earth and Enviromental Sciences, Los Alamos National Laboratory, Mail Stop D469, Los Alamos, New Mexico 87545
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Abstract

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Yucca Mountain, Nevada, is being investigated to determine its suitability to host a potential high-level radioactive waste respository. An important reason for its choice as a potential repository site was the presence of thick zeolite-rich horizons in the altered volcanic tufts that compose the mountain. Clinoptilolite is the most abundant zeolite at Yucca Mountain and may be important in radionuclide retardation and in determining hydrologic properties. Therefore, it is necessary to understand the geochemical conditions affecting its long-term stability. For example, it has been suggested that long-term, repository-induced heating of the rocks at Yucca Mountain may lead to the transformation of clinoptilolite to analcime, thereby significantly affecting the hydrologic properties and retardation capabilities of the rock.

Thermodynamic modeling of clinoptilolite-analcime equilibria was conducted with the program Ge0-Calc PTA-SYSTEM using estimated thermodynamic data for measured chemical compositions of clinoptilolite and analcime at Yucca Mountain. Log[aK+)2/aCa2+] versus log[aNa+)2/aCa2+] diagrams were calculated to model the conditions under which clinoptilolite may transform to analcime. Temperature, relative cation abundances and silica activity are all important factors in determining clinoptilolite-analcime equilibria. Increased Na+ concentrations in either clinoptilolite or the fluid phase, increased clinoptilolite K+ concentration, increased temperature and decreased aqueous silica activity all stabilize analcime relative to clinoptilolite, assuming present-day Yucca Mountain water compositions. However, increased Ca2+ concentrations in either clinoptilolite or the fluid phase, increased aqueous K+ concentration and increased Al:Si ratios in clinoptilolite (heulandite) all stabilize clinoptilolite with respect to analcime.

Assuming well J-13 water as the analog chemistry for Yucca Mountain water, clinoptilolite should remain stable with respect to analcime if temperatures in the clinoptilolite-bearing horizons do not significantly exceed 100 °C. Even if temperatures rise significantly (for example, to 150 °C not all clinoptilolite should alter to analcime. Perhaps more importantly, thermodynamic modeling suggests that some Yucca Mountain clinoptilolites, particularly those rich in Ca and Al, will remain stable at elevated temperatures, even with an aqueous silica activity at quartz saturation.

Type
Research Article
Copyright
Copyright © 1997, The Clay Minerals Society

References

Ames, L.L. Jr. 1964a. Some zeolite equilibria with alkali metal cations. Am Mineral 49: 127145.Google Scholar
Ames, L.L. Jr. 1964b. Some zeolite equilibria with alkaline earth metal cations. Am Mineral 49: 10991110.Google Scholar
Barrer, R.M. and Klinowski, J.. 1974. Ion-exchange selectivity and electrolyte concentration. J Chem Soc Faraday Trans 70: 20802091.CrossRefGoogle Scholar
Berman, R.G.. 1988. Internally consistent thermodynamic data for minerals in the system Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2. J Petrol 29: 445522.CrossRefGoogle Scholar
Berman, R.G. and Brown, T.H.. 1985. Heat capacity of minerals in the system Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2: Representation, estimation, and high temperature extrapolation. Contrib Mineral Petrol 89: 168183.CrossRefGoogle Scholar
Bish, D.L.. 1988. Effects of composition on the dehydration behavior of clinoptilolite and heulandite. In: Kallo, D., Sherry, H.S., editors. Occurrence, properties and utilization of natural zeolites. Budapest: Akademiai Kiado. p 565576.Google Scholar
Bish, D.L.. 1989. Evaluation of past and future alterations in tuff at Yucca Mountain, Nevada, based on the clay mineralogy of drill cores USW G-1, G-2, and G-3. Los Alamos National Laboratory Report LA-10667-MS. 40 p.CrossRefGoogle Scholar
Bish, D.L.. 1990. Long-term thermal stability of clinoptilolite: The development of a “B” phase. Eur J Mineral 2: 771777.CrossRefGoogle Scholar
Bish, D.L. and Aronson, J.L.. 1993. Paleogeothermal and paleohydrologic conditions in silicic tuff from Yucca Mountain, Nevada. Clays Clay Miner 41: 148161.CrossRefGoogle Scholar
Bish, D.L. and Chipera, S.J.. 1989. Revised mineralogic summary of Yucca Mountain, Nevada. Los Alamos National Laboratory Report LA-11497-MS. 68 p.CrossRefGoogle Scholar
Boles, J.R.. 1971. Synthesis of analcime from natural heulandite and clinoptilolite. Am Mineral 56: 17241734.Google Scholar
Bowers, T.S. and Burns, R.G.. 1990. Activity diagrams for clinoptilolite: Susceptibility of this zeolite to further diagenetic reactions. Am Mineral 75: 601619.Google Scholar
Brown, T.H., Berman, R.G. and Perkins, E.H.. 1989. PTA-SYSTEM: A GeO-Calc software package for the calculation and display of activity-temperature-pressure phase diagrams. Am Mineral 74: 485487.Google Scholar
Broxton, D.E., Bish, D.L. and Warren, R.G.. 1987. Distribution and chemistry of diagenetic minerals at Yucca Mountain, Nye County, Nevada. Clays Clay Miner 35: 89110.CrossRefGoogle Scholar
Broxton, D.E., Warren, R.G., Hagan, R.C. and Luedemann, G.. 1986. Chemistry of diagenetically altered tuffs at a potential nuclear waste repository, Yucca Mountain, Nye County, Nevada. Los Alamos National Laboratory Report LA-10802-MS. 160 p.CrossRefGoogle Scholar
Bruton, C., Glassley, W.E. and Viani, B.E.. 1993. Geochemistry. In: Wilder, D.G., editor. Preliminary near-field environment report, volume II: Scientific overview of near-field environment and phenomena. Lawrence Livermore National Laboratory Report UCRL-LR-107476 vol 2. 37: 122.Google Scholar
Buscheck, T.A., Nitao, J.J. and Saterlie, S.F.. 1994. Evaluation of thermo-hydrological performance in support of the thermal loading systems study. High Level Radioactive Waste Management, Proc 5th Annu Int Conf, vol 2; 22-26 May 1994; Las Vegas, NV. p 592610.Google Scholar
Carey, J.W. and Bish, D.L.. 1996. Equilibrium in the clinoptilolite-H2O system. Am Mineral 81: 952962.CrossRefGoogle Scholar
Chermak, J.A. and Rimstidt, J.D.. 1989. Estimating the thermodynamic properties (ΔGof and ΔHof) of silicate minerals at 298 K from the sum of polyhedral contributions. Am Mineral 74: 10231031.Google Scholar
Chipera, S.J. and Bish, D.L.. 1988. Mineralogy of drill hole UE-25p#1 at Yucca Mountain, Nevada. Los Alamos National Laboratory Report LA-11292-MS. 24 p.CrossRefGoogle Scholar
Chipera, S.J., Bish, D.L. and Carlos, B.A.. 1995. Equilibrium modeling of the formation of zeolites in fractures at Yucca Mountain, Nevada. In: Ming, D.W., Mumpton, F.A., editors. Natural zeolites '93: Occurrence, properties, use. Brockport, NY: Int Committee on Natural Zeolites. p 565577.Google Scholar
Codell, R.B. and Murphy, W.M.. 1992. Geochemical model for 14C transport in unsaturated rock. Proc 3rd Annu High Level Radioactive Waste Management Meeting; Las Vegas, NV. 19591965.Google Scholar
Delany, J.M.. 1985. Reactions of Topopah Spring Tuff with J-13 water: A geochemical modeling approach using the EQ3/6 reaction path code. Lawrence Livermore National Laboratory Report UCRL-53631. 46 p.CrossRefGoogle Scholar
Duffy, C.J.. 1993a. Preliminary conceptual model for mineral evolution in Yucca Mountain. Los Alamos National Laboratory Report LA-12708-MS. 46 p.CrossRefGoogle Scholar
Duffy, C.J.. 1993b. Kinetics of silica-phase transitions. Los Alamos National Laboratory Report LA-12564-MS. 22 p.CrossRefGoogle Scholar
Gottardi, G. and Galli, E.. 1985. Natural zeolites. New York: Springer-Verlag. 409 p.CrossRefGoogle Scholar
Hay, R.L.. 1966. Zeolites and zeolitic reactions in sedimentary rocks. Geol Soc Am Spec Pap 85. 130 p.CrossRefGoogle Scholar
Hay, R.L.. 1978. Geologic occurrence of zeolites. In: Sand, L.B., Mumpton, F.A., editors. Natural zeolites: Occurrence, properties, use. New York: Pergamon Pr. p 135143.Google Scholar
Hazen, R.M.. 1985. Comparative crystal chemistry and the polyhedral approach. In: Kieffer, S.W., Navrotsky, A., editors. Microscopic to macroscopic: Atomic environments to mineral thermodynamics. Rev Mineral 14. Washington DC: Mineral Soc Am. p 317345.CrossRefGoogle Scholar
Helgeson, H.C., Kirkham, D.H. and Flowers, G.C.. 1981. Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures: IV. Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600°C and 5kb. Am J Sci 281: 12491516.CrossRefGoogle Scholar
Hemingway, B.S. and Robie, R.A.. 1984. Thermodynamic properties of zeolites: Low-temperature heat capacities and thermodynamic functions for phillipsite and clinoptilolite. Estimates of the thermochemical properties of zeolitic water at low temperature. Am Mineral 69: 692700.Google Scholar
Holland, T.J.B.. 1989. Dependence of entropy on volume for silicate and oxide minerals: A review and a predictive model. Am Mineral 74: 513.Google Scholar
Honda, A. and Muffler, L.J.P.. 1970. Hydrothermal alteration in core from research drill hole Y-l, Upper Geyser Basin, Yellowstone National Park, Wyoming. Am Mineral 55: 17141737.Google Scholar
Howell, D.A., Johnson, G.K., Tasker, I.R., O'Hare, P.A.G. and Wise, W.S.. 1990. Thermodynamic properties of the zeolite stilbite. Zeolites 10: 525531.CrossRefGoogle Scholar
Iijima, A.. 1975. Effect of pore water to clinoptilolite-analcime-albite reaction series. J Fac Sci, Univ Tokyo, Sec II 19: 133147.Google Scholar
Iijima, A.. 1978. Geologic occurrences of zeolites in marine environments. In: Sand, L.B., Mumpton, F.A., editors. Natural zeolites: Occurrence, properties, use. New York: Pergamon Pr. p 175198.Google Scholar
Johnson, G.K., Flotow, H.E., O'Hare, P.A.G. and Wise, W.S.. 1982. Thermodynamic studies of zeolites: Analcime and dehydrated analcime. Am Mineral 67: 736748.Google Scholar
Johnson, G.K., Flotow, H.E., O'Hare, P.A.G. and Wise, W.S.. 1985. Thermodynamic studies of zeolites: Heulandite. Am Mineral 70: 10651071.Google Scholar
Johnson, G.K., Tasker, I.R., Jurgens, R. and O'Hare, P.A.G.. 1991. Thermodynamic studies of zeolites: Clinoptilolite. J Chem Thermodynamics 23: 475484.CrossRefGoogle Scholar
Johnson, G.K., Tasker, I.R., Flotow, H.E., O'Hare, P.A.G. and Wise, W.S.. 1992. Thermodynamic studies of mordenite, dehydrated mordenite, and gibbsite. Am Mineral 77: 8593.Google Scholar
Johnson, J.W., Oelkers, E.H. and Helgeson, H.C.. 1991. SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reaction from 1 to 5000 bars and 0° to 1000°C: Earth Sciences Dept, L-219, Lawrence Livermore National Laboratory, Livermore, CA. 80 p.Google Scholar
Johnstone, J.K., Peters, R.R. and Gnirk, P.R. 1984. Unit evaluation at Yucca Mountain, Nevada Test Site: Summary report and recommendations. Sandia National Laboratory Report SAND83-0372.Google Scholar
Jones, B.F., Rettig, S.L. and Eugster, H.P.. 1967. Silica in alkaline brines. Science 158: 13101314.CrossRefGoogle ScholarPubMed
Keith, T.E.C., White, D.E. and Beeson, M.H.. 1978. Hydrothermal alteration and self-sealing in Y-7 and Y-8 in northern part of Upper Geyser Basin, Yellowstone National Park, Wyoming. USGS Prof Paper 1054-A. 26 p.CrossRefGoogle Scholar
Kerrisk, J.E. 1983. Reaction-path calculations of groundwater chemistry and mineral formation at Rainier Mesa, Nevada. Los Alamos National Laboratory Report LA-9912-MS. 41 p.CrossRefGoogle Scholar
Kerrisk, J.F.. 1987. Groundwater chemistry at Yucca Mountain, Nevada, and vicinity. Los Alamos National Laboratory Report LA-10929-MS. 118 p.CrossRefGoogle Scholar
Knauss, K.G., Beiriger, W.J. and Peifer, D.W.. 1985. Hydrothermal interaction of crushed Topopah Spring Tuff and J-13 water at 90, 150, and 250°C using Dickson-type, gold-bag rocking autoclaves. Lawrence Livermore National Laboratory Report UCRL-53630. 27 p.Google Scholar
Knauss, K.G., Beiriger, W.J. and Peifer, D.W.. 1987. Hydrothermal interaction of solid wafers of Topopah Spring Tuff with J-13 water at 90 and 150°C using Dickson-type, gold-bag rocking autoclaves: Long-term experiments. Lawrence Livermore National Laboratory Report UCRL-53722. 21 p.Google Scholar
Knauss, K.G., Beiriger, W.J., Peifer, D.W. and Piwinskii, A.J.. 1985. Hydrothermal interaction of solid wafers of Topopah Spring Tuff with J-13 and distilled water at 90, 150, and 250°C, using Dickson-type, gold-bag rocking autoclaves. Lawrence Livermore National Laboratory Report UCRL-53645. 55 p.Google Scholar
Knauss, K.G. and Peifer, D.W.. 1986. Reaction of vitric Topopah Spring Tuff and J-13 ground water under hydrothermal conditions using Dickson-type, gold-bag rocking autoclaves. Lawrence Livermore National Laboratory Report UCRL-53795. 39 p.Google Scholar
Mumpton, F.A.. 1960. Clinoptilolite redefined. Am Mineral 45: 351369.Google Scholar
Murphy, W.M.. 1994. Geochemical models for gas-water-rock interactions in a proposed nuclear waste repository at Yucca Mountain, Nevada. Proc Site Characterization and Model Validation Focus '93: American Nuclear Society. p 115121.Google Scholar
Murphy, W.M. and Pabalan, R.T.. 1994. Geochemical investigations related to the Yucca Mountain environment and potential nuclear waste repository. US Nuclear Regulatory Commission Report NUREG/CR-6288. 190 p.CrossRefGoogle Scholar
Pabalan, R.T. and Bertetti, F.P.. 1994. Thermodynamics of ion-exchange between Na+/Sr2+ solutions and the zeolite mineral clinoptilolite. Mat Res Soc Symp Proc 333: 731738.CrossRefGoogle Scholar
Pabalan, R.T. and Murphy, W.M.. 1990. Progress in experimental studies on the thermodynamic and ion exchange properties of clinoptilolite. Center for Nuclear Waste Regulatory Analyses, CNWRA 89-006, San Antonio, TX. 39 p.Google Scholar
Perry, E. and Hower, J.. 1970. Burial diagenesis in Gulf Coast pelitic sediments. Clays Clay Miner 18: 165177.CrossRefGoogle Scholar
Perfect, D.L., Faunt, C.C., Steinkampf, W.C. and Turner, A.K.. 1995. Hydrochemical data base for the Death Valley Region, California and Nevada. USGS Open File Report 94-305. 10 p.CrossRefGoogle Scholar
Robinson, G.R. Jr and Haas, J.L. Jr. 1983. Heat capacity, relative enthalpy, and calorimetric entropy of silicate minerals: An empirical method of prediction. Am Mineral 68: 541553.Google Scholar
Sheppard, R.A. and Gude, A.J. 3rd. 1968. Distribution and genesis of authigenic silicate minerals in tuffs of Pleistocene Lake Tecopa, Inyo County, California. USGS Prof Pap 597. 38 p.CrossRefGoogle Scholar
Sheppard, R.A. and Gude, A.J. 3rd. 1969. Diagenesis of tuffs in the Barstow Formation, Mud Hills, San Bernardino County, California. USGS Prof Pap 634. 35 p.CrossRefGoogle Scholar
Sheppard, R.A. and Gude, A.J. 3rd. 1973. Zeolites and associated authigenic silicate minerals in tuffaceous rocks of the Big Sandy Formation, Mohave County, Arizona. USGS Prof Pap 830. 36 p.CrossRefGoogle Scholar
Smyth, J.R.. 1982. Zeolite stability constraints on radioactive waste isolation in zeolite-bearing volcanic rocks. J Geol 90: 195202.CrossRefGoogle Scholar
Smyth, J.R. and Caporuscio, F.A.. 1981. Review of the thermal stability and cation exchange properties of the zeolite minerals clinoptilolite, mordenite, and analcime: Applications to radioactive waste isolation in silicic tuff. Los Alamos National Laboratory Report LA-8841-MS. 30 p.CrossRefGoogle Scholar
Surdam, R.C. and Sheppard, R.A.. 1978. Zeolites in saline, alkaline-lake deposits. In: Sand, L.B., Mumpton, F.A., editors. Natural zeolites: Occurrence, properties, use. New York: Pergamon Pr. p 145174.Google Scholar
Vaughan, D.E.W.. 1978. Properties of natural zeolites. In: Sand, L.B., Mumpton, F.A., editors. Natural zeolites: Occurrence, properties, use. New York: Pergamon Pr. p 353371.Google Scholar
White, A.F., Claassen, H.C. and Benson, L.V.. 1980. The effect of dissolution of volcanic glass on the water chemistry in a tuffaceous aquifer, Rainier Mesa, Nevada. USGS Geol Survey Water-Supply Pap 1535-Q. 34 p.Google Scholar
Wilkin, R.T. and Barnes, H.L.. 1995. Solubilities of the zeolites analcime and Na-clinoptilolite in hydrothermal solutions. In: Barnes, H.L., editor. V. M. Goldschmidt Conf, Program and Abstracts. 97 p.Google Scholar
Yang, I.C.. 1992. Flow and transport through unsaturated rock—data from two test holes, Yucca Mountain, Nevada. Proc 3rd Annu High Level Radioactive Waste Management Meeting; Las Vegas, NV. p 732737.Google Scholar