Overview of chemical modeling of nuclear waste glass dissolution

Glass dissolution takes place through metal leaching and hydration of the glass surface accompanied by development of alternation layers of varying crystallinity. The reaction which controls the long-term glass dissolution rate appears to be surface layer dissolution. This reaction is reversible because the buildup of dissolved species in solution slows the dissolution rate due to a decreased dissolution affinity. Glass dissolution rates are therefore highly dependent on silica concentrations in solution because silica is the major component of the alteration layer. Chemical modeling of glass dissolution using reaction path computer codes has successfully been applied to short term experimental tests and used to predict long-term repository performance. Current problems and limitations of the models include a poorly defined long-term glass dissolution mechanism, the use of model parameters determined from the same experiments that the model is used to predict, and the lack of sufficient validation of key assumptions in the modeling approach. Work is in progress that addresses these issues. 41 refs., 7 figs., 2 tabs.

[1]  D. K. Smith,et al.  A Kinetic Model for Borosilicate Glass Dissolution Based on the Dissolution Affinity of a Surface Alteration Layer , 1989 .

[2]  L. Pederson,et al.  Inhibition of Nuclear Waste Glass Leaching by Chemisorption , 1982 .

[3]  W. Lanford,et al.  Hydration of soda-lime glass , 1979 .

[4]  K. Knauss,et al.  Dependence of albite dissolution kinetics on ph and time at 25°c and 70°c , 1986 .

[5]  A. Moghissi Radioactive waste forms for the future: edited by W. Lutze and R. C. Ewing. Elsevier Science Publishers: North-Holland, Amsterdam 1988, (712 pp., $247.25/Dfl. 470.00) , 1990 .

[6]  R. Doremus Diffusion-controlled reaction of water with glass , 1983 .

[7]  J. Crovisier,et al.  Dissolution of basaltic glass in seawater: Mechanism and rate , 1987 .

[8]  G. Greaves Exafs for studying corrosion of glass surfaces , 1990 .

[9]  Takashi Murakami,et al.  Analytical electron microscopy of leached layers on synthetic basalt glass , 1987 .

[10]  Rodney C. Ewing,et al.  Radioactive Waste Forms for the Future , 1988 .

[11]  B. Bunker,et al.  CHAPTER 10. LEACHING OF MINERAL AND GLASS SURFACES DURING DISSOLUTION , 1990 .

[12]  Aqueous Corrosion of the French LWR Solution Reference Glass First Generation Model , 1987 .

[13]  Thierry Advocat,et al.  Thermokinetic Model of Borosilicate Glass Dissolution: Contextual Affinity , 1989 .

[14]  B. Grambow,et al.  A comparison of the performance of nuclear waste glasses by modeling , 1987 .

[15]  A. Paccagnella,et al.  Hydrated-layer formation during dissolution of complex silicate glasses and minerals , 1990 .

[16]  Moving Boundary Model for Leaching of Nuclear Waste Glass , 1984 .

[17]  A. Paccagnella,et al.  Structural dependence of crystalline silicate hydration during aqueous dissolution , 1989 .

[18]  B. Smets,et al.  The effect of divalent cations on the leaching kinetics of glass , 1984 .

[19]  L. Pederson,et al.  The Relationship Between Reaction Layer Thickness and Leach Rate For Nuclear Waste Glasses , 1983 .

[20]  Stephen H. Garofalini,et al.  Molecular dynamics computer simulations of silica surface structure and adsorption of water molecules , 1990 .

[21]  R. H. Doremus,et al.  INTERDIFFUSION OF HYDROGEN AND ALKALI IONS IN A GLASS SURFACE , 1975 .

[22]  Richard M. Wallace,et al.  Leaching chemistry of defense borosilicate glass , 1982 .

[23]  B. Wood,et al.  Rates of Hydrothermal Reactions , 1983, Science.

[24]  H. Helgeson,et al.  Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions; IV, Retrieval of rate constants and activation parameters for the hydrolysis of pyroxene, wollastonite, olivine, andalusite, quartz, and nepheline , 1989 .