The evolution of hydrated lime-based cementitious waste forms during leach testing leading to enhanced technetium retention.

The interaction between radionuclides and cementitious material phases is crucial in the prediction of the long-term disposal behavior of cementitious waste forms. This work focuses on the behavior of technetium-99 (Tc) within a hydrated-lime based waste form developed as a candidate to immobilize high-sulphate containing liquid wastes known to inhibit cement solidification when using a fly ash based formulation. In leach testing, the hydrated-lime based formulation demonstrated improvement in Tc retention over a fly ash containing formulation beginning after 14 d leaching. The mineralogical evolution of the hydrated-lime samples during leach testing showed a decrease in portlandite content and reduction capacity at the onset of the Tc retention improvement. Leach testing upwards of 400 days showed the improved Tc retention was sustained. Samples cured for different lengths of time (28 days vs 60 days) confirmed that the improved Tc retention and mineralogic change was caused by cement - leachant interactions and not the sample curing time. The Tc observed diffusivities in the hydrated-lime samples are amongst the lowest measured in a cement waste form tested for development at the US Department of Energy Hanford site, leading to a possible pathway to improved cement conditioning where contaminants can be retained for long disposal times.

Competitive TcO4-, IO3-, and CrO42- Incorporation into Ettringite.

Ettringite is a naturally occurring mineral found in cementitious matrices that is known for its ability to incorporate environmentally mobile oxyanion contaminants. To better assess this immobilization mechanism for contaminants within cementitious waste forms intended for nuclear waste storage, this work explores how mixed oxyanion contaminants compete for ettringite incorporation and influence the evolving mineralogy. Ettringite was precipitated in the presence of TcO4-, IO3-, and/or CrO42-, known contaminants of concern to nuclear waste treatment, over pre-determined precipitation periods. Solution analyses quantified contaminant removal, and the collected solid was characterized using bulk and microprobe X-ray diffraction coupled with pair distribution function and microprobe X-ray fluorescence analyses. Results suggest that ≥96% IO3- is removed from solution, regardless of ettringite precipitation time or the presence of TcO4- or CrO42-. However, TcO4- removal remained <20%, was not significantly improved with longer ettringite precipitation times, and decreased to zero in the presence of IO3-. When IO3- is co-mingled with CrO42-, calcite and gypsum are formed as secondary mineral phases, which allows for oxyanion partitioning, e.g., IO3- incorporation into ettringite, and CrO42- incorporation into calcite. Results from this work exemplify the importance of competitive immobilization when assessing waste form performance and environmental risk of contaminant release.