Getters for Tc and I Removal from Liquid Waste

Abstract:

<span">A cementitious waste form, Cast Stone, is being evaluated as a possible supplemental waste form for the low activity waste (LAW) at the Hanford Site, which contains significant amounts of radioactive ⁹⁹Tc and ¹²⁹I, as part of the tank waste cleanup mission. To improve the retention of Tc and/or I in Cast Stone, materials with a high affinity for Tc and/or I, termed “getters,” can be added to decrease the rate of contaminant release and diffusivity, and improve Cast Stone performance. A series of kinetic batch sorption experiments was performed to determine the effectiveness of the getter materials. Several Tc getters [blast furnace slag, Sn (II) apatite, SnCl₂, nanoporous Sn phosphate, KMS-2 (a potassium-metal-sulfide), and Sn(II) hydroxyapatite] and I getters [layered Bi hydroxide, natural argentite mineral, synthetic argentite, Ag-impregnated carbon, and Ag-exchanged zeolite] were tested in different solution media, 18.2 MΩ DI H₂O and a caustic LAW waste simulant containing 6.5 M Na or 7.8 M Na. The experiments were conducted at room temperature in the presence or absence of air. Results indicated that most Tc getters (with the exception of KMS-2) performed better in the DI H₂O solution than in the 6.5 and 7.8 M Na LAW simulant. In addition, Tc sequestration may be affected by the presence of other redox sensitive elements that were present in the LAW simulant, such as Cr. The Tc getter materials have been examined through various solid-state characterization techniques such as XRD, SEM/EDS, XANES and EXAFS which provided evidence for plausible mechanisms of aqueous Tc removal. The results indicated that the Tc precipitates differ depending on the getter material and that Tc(VII) is reduced to Tc(IV) in most of the getters but to a differing extents. For the I getters, Ag-exchanged zeolite and synthetic argentite were the most effective ones. The other I getters showed limited effectiveness for sorbing I under the high ionic strength and caustic conditions of the LAW simulant.