Technetium oxidation in slag-based sodium salt waste forms exposed to water and moist Hanford soil - 15514

Several U.S. DOE sites use or plan to use waste forms and/or concrete containment structures for radioactive waste disposal that are designed to have a chemically reducing environment to immobilize selected contaminants such as Tc(VII)O₄^- and Cr(VI)O₄^2-. These waste forms and containment structures are typically deployed in near surface unsaturated oxidizing environments. Consequently, the effect of exposure to air (oxygen) and water containing dissolved oxygen during production, during the period of institutional control, and over the long term period of performance is important for predicting the speciation and mobility of the redox sensitive radioactive and stable contaminants. Both the SRS and Hanford waste streams contain soluble technetium which may require stabilization to meet disposal requirements. Technetium stabilization is a difficult problem because: 1) Tc is soluble and very mobile in the oxidized form typical of near surface environments, and 2) Tc-99 is a long-lived isotope with a half-life of 2.1 E+05 years which places demanding requirements on the engineered barriers and environment to meet current regulatory disposal requirements. A depth-discrete sampling and leaching method approach for measuring contaminant oxidation rate (effective contaminant specific oxidation rate) was used in this study. The method was modified by coating all sides of a cylindrical sample with an impermeable epoxy and cutting a fresh surface 2 to 2.5 cm from the original top surface eliminates sample inhomogeneity as the result of settling as a reason from observed results and provides 1-D soluble ion transport and gas transport information. Soluble Tc was leached from all of the depth-discrete sub-samples from both Tc2-9 and Tc2-10 which strongly suggests that oxygen was present in the entire length of both samples. About 24 mass percent of the Tc in the original sample, was leached (soluble) from sub-samples between 0.8 and 46 mm below the exposed surface of Tc2-9 (exposed to Hanford sediment). The same percent (24%) was leached from the sub-samples between 0.8 and 11 mm below the exposed surface of Tc2-10 (exposed to DI water). This suggests that the rate of oxygen migration into the sample exposed to soil was faster than the rate of migration into the sample exposed to water which is consistent with the more rapid transport of ions through a gas phase as compared to a liquid phase. It is assumed that moisture in the Hanford sediment was not sufficient to completely block the surface pores with respect to gas transport across the soil-waste form boundary. Based on nitrate leaching results for the depth- discrete sub-samples, regions depleted in nitrates were identified from the top surfaces to 9.5 and 3 mm into samples Tc2-9 (exposed to moist Hanford sediment) and Tc2-10 (DI water). Low mass fractions of nitrate were leached from these depth-discrete samples compared to samples further from the exposed surface presumably because a significant portion of the nitrate had already migrated into the soil or water, respectively. Depth-discrete sub-sample leaching results for Na can be interpreted in the same way over the same regions in the two samples tested. In conclusion, leaching monolithic porous cementitious waste forms in water appears to be conservative for non-redox sensitive contaminants. However, leaching data obtained under saturated exposure conditions do not appear to be conservative for redox sensitive contaminants which are easily oxidized. Leaching crushed samples in water still seems to be a conservative approach to estimating the concentrations of soluble contaminants in a waste form. (authors)