Immobilizing Pertechnetate in Ettringite via Sulfate Substitution

• Published in: Environmental science & technology 2020-11, Vol.54 (21), p.13610-13618
• Main Authors: Saslow, Sarah A, Kerisit, Sebastien N, Varga, Tamas, Mergelsberg, Sebastian T, Corkhill, Claire L, Snyder, Michelle M. V, Avalos, Nancy M, Yorkshire, Antonia S, Bailey, Daniel J, Crum, Jarrod, Asmussen, R. Matthew
• Format: Article
• Language: English
• Subjects: Ab initio molecular dynamics; Additives; Anions; Calcium; Calcium ions; Contaminants in Aquatic and Terrestrial Environments; Crystal structure; Ettringite; Fluorescence; Gypsum; Immobilization; Lattices; Life cycles; Low temperature; MATERIALS SCIENCE; Minerals; Molecular dynamics; Physical and chemical processes; Radioactive Waste; Radioactive wastes; Sodium Pertechnetate Tc 99m; Solid phases; Substitutes; Sulfates; Synchrotron radiation; Synchrotrons; Technetium; Technetium isotopes; X ray absorption
• ISSN: 0013-936X; 1520-5851
• DOI: 10.1021/acs.est.0c03119

Technetium-99 immobilization in low-temperature nuclear waste forms often relies on additives that reduce environmentally mobile pertechnetate (TcO4 –) to insoluble Tc­(IV) species. However, this is a short-lived solution unless reducing conditions are maintained over the hazardous life cycle of radioactive wastes (some ∼10,000 years). Considering recent experimental observations, this work explores how rapid formation of ettringite [Ca6Al2(SO4)3(OH)12·26­(H2O)], a common mineral formed in cementitious waste forms, may be used to directly immobilize TcO4 –. Results from ab initio molecular dynamics (AIMD) simulations and solid-phase characterization techniques, including synchrotron X-ray absorption, fluorescence, and diffraction methods, support successful incorporation of TcO4 – into the ettringite crystal structure via sulfate substitution when synthesized by aqueous precipitation methods. One sulfate and one water are replaced with one TcO4 – and one OH– during substitution, where Ca2+-coordinated water near the substitution site is deprotonated to form OH– for charge compensation upon TcO4 – substitution. Furthermore, AIMD calculations support favorable TcO4 – substitution at the SO4 2– site in ettringite rather than gypsum (CaSO4·2H2O, formed as a secondary mineral phase) by at least 0.76 eV at 298 K. These results are the first of their kind to suggest that ettringite may contribute to TcO4 – immobilization and the overall lifetime performance of cementitious waste forms.