Development of a Geochemical Speciation Model for Use in Evaluating Leaching from a Cementitious Radioactive Waste Form

• Published in: Environmental science & technology Vol. 55; no. 13; pp. 8642 - 8653
• Main Authors: Chen, Zhiliang, Zhang, Peng, Brown, Kevin G, Branch, Janelle L, van der Sloot, Hans A, Meeussen, Johannes C. L, Delapp, Rossane C, Um, Wooyong, Kosson, David S
• Format: Journal Article
• Language: English
• Published: Easton American Chemical Society 06.07.2021
• Subjects: Aging; Blast furnace slags; Cast stone; Constituents; Contaminants in Aquatic and Terrestrial Environments; Diffusion; Geochemistry; Immobilization; Leaching; Pore water; Radioactive wastes; Slag; Speciation; chromium; grout; technetium; redox behavior; Cast Stone; monolithic diffusion
• ISSN: 0013-936X; 1520-5851
• DOI: 10.1021/acs.est.0c06227

Cast Stone has been developed to immobilize a fraction of radioactive waste at the Hanford Site; however, constituents of potential concern (COPCs) can be released when in contact with water during disposal. Herein, a representative mineral and parameter set for geochemical speciation modeling was developed for Cast Stone aged in inert and oxic environments, to simulate leaching concentrations of major and trace constituents. The geochemical speciation model was verified using a monolithic diffusion model in conjunction with independent monolithic diffusion test results. Eskolaite (Cr2O3) was confirmed as the dominant mineral retaining Cr in Cast Stone doped with 0.1 or 0.2 wt % Cr. The immobilization of Tc as a primary COPC in Cast Stone was evaluated, and the redox states of porewater within monolithic Cast Stone indicated by Cr are insufficient for the reduction of Tc. However, redox states provided by blast furnace slag (BFS) within the interior of Cast Stone are capable of reducing Tc for immobilization, with the immobilization reaction rate postulated to be controlled by the diffusive migration of soluble Tc in porewater to the surface of reducing BFS particles. Aging in oxic conditions increased the flux of Cr and Tc from monolithic Cast Stone.