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Dissolution of Borosilicate Waste Glass: Effect of Al and B Coordination on Alkali Ion Exchange


EMSL Project ID
14592

Abstract

Borosilicate glass will be used to immobilize nuclear waste located at several U. S. Department of Energy sites. Currently at Hanford, immobilized low-activity waste (ILAW) will be produced using the Waste Treatment Plant (WTP) and placed into a near-surface disposal system located on the Hanford Site. Before the ILAW can be placed into the disposal system, DOE must approve a performance assessment (PA), which is a document that describes the long-term impact of the disposal facility on public health and environmental resources. A critical component of the PA will be to provide quantitative estimates of radionuclide release rates from the engineered portion of the disposal facilities (source term). Previous studies have illustrated a major factor controlling the radionuclide release rates is the dissolution rate of the vitrified matrix (McGrail et al. 2001a; Pierce et al. 2004). Therefore, to provide these estimates fundamental information on the reaction kinetics of glass is required.
The reaction kinetics of glass is controlled by matrix dissolution, and alkali-hydrogen ion exchange (IEX.
These processes are directly correlated to the structural characteristics of glass. Our discussion here will focus on one aspect of the glass/water interaction, IEX. The exchange of alkalis contained in glass for hydrogen contained in solution is a widely recognized process in the initial stages of the glass-water interactions. This process eventually causes the breakdown of the glass network and dissolution into the aqueous phase. The rate by which this process occurs has been directly correlated with non-bridging oxygen (NBO) sites using simple four component glasses (McGrail et al. 2001b). Non-bridging oxygen sites have also been observed in ILAW glass formulations. The presence of NBO sites causes network depolymerization and therefore decreases the overall glass durability. Therefore, to gain a more detailed understanding of the relationship between the local coordination geometry around aluminum, boron, and silicon atoms and the effect these network former element have on glass dissolution, magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy was collected for two prototypic LAW glass formulations; LAW-A44 and -B45.

Project Details

Project type
Capability Research
Start Date
2005-10-01
End Date
2007-07-18
Status
Closed

Team

Principal Investigator

Eric Pierce
Institution
Oak Ridge National Laboratory

Team Members

Wendy Shaw
Institution
Pacific Northwest National Laboratory

Related Publications

Icenhower JP, BP McGrail, WJ Shaw, EM Pierce, P Nachimuthu, DK Shuh, EA Rodriguez, and JL Steele. 2008. "Experimentally determined dissolution kinetics of Na-rich borosilicate glass at far from equilibrium conditions: Implications for Transition State Theory." Geochimica et Cosmochimica Acta 72(12):2767-2788. doi:10.1016/j.gca.2008.02.026
Pierce EM, BP McGrail, PPNNL Martin, JC Marra, BW Arey, and KN Geiszler. 2007. "Accelerated Weathering of High-Level and Plutonium-bearing Lanthanide Borosilicate Waste Glasses under Hydraulically Unsaturated Conditions." Applied Geochemistry 22(9):1841-1859. doi:10.1016/j.apgeochem.2007.03.056
Pierce EM, EA Cordova, LJ Calligan, WJ Shaw, and BP McGrail. 2008. "An Experimental Study of the Dissolution Rates of Simulated Aluminoborosilicate Waste Glasses as a Function of pH and Temperature under Dilute Conditions." Applied Geochemistry 23(9):2559-2573. doi:doi:10.1016/j.apgeochem.2008.05.006
Pierce EM, EL Richards, AM Davis, LR Reed, and EA Cordova. 2008. "Aluminoborosilicate Waste Glass Dissolution under Alkaline Conditions at 40°C: Implications for a Chemical Affinity-Based Rate Equation." Environmental Chemistry 5(1):73-85. doi:10.1071/EN07058
Pierce EM, LR Reed, WJ Shaw, SN Kerisit, BP McGrail, JP Icenhower, CF Windisch, Jr, EA Cordova, and JW Broady. 2008. "Experimental Determination of the Effect of the Ratio of B/Al on Glass 2 Dissolution along the Nepheline (NaAlSiO4) Malinkoite (NaBSiO4) 3 Join." PNNL-SA-61097
Pierce EM, LR Reed, WJ Shaw, SN Kerisit, BP McGrail, JP Icenhower, CF Windisch, Jr, EA Cordova, and JW Broady. 2008. "Experimental Determination of the Effect of the Ratio of B/Al on Glass 2 Dissolution along the Nepheline (NaAlSiO4) Malinkoite (NaBSiO4) 3 Join." PNNL-SA-61097
Richards EL, AM Davis, and EM Pierce. 2007. "Evaluation of Solution Composition Aluminoborosilicate Waste Glass Dissolution at 40°C." In Preprints of extended abstracts presented at the ACS National Meeting, American Chemical Society, Division of Environmental Chemistry, 2007, vol. 47, no. 1, pp. 125-134. American Chemical Society, Division of Environmental Chemistry, Washington, DC.