PNNL

Abstract

A sample of off-gas condensate produced during a demonstration test of the direct-feed low-activity waste (DFLAW) Radioactive Waste Test Platform using waste retrieved from Hanford storage tank AP-105 waste was analyzed for major cations, anions, total cyanide, Resource Conservation and Recovery Act (RCRA) metals, selected radionuclides, and selected organic compounds. The remaining off-gas condensate was concentrated through evaporation and then used to produce Cast Stone waste forms. After the solid waste forms cured for 28 days, U.S. Environmental Protection Agency (EPA) Method 1311 (EPA 1992) Toxicity Characteristic Leach Procedure (TCLP) tests were conducted on two samples. The TCLP leachates were analyzed for RCRA metals, fluoride, and total cyanide. These chemical analyses were conducted to collect data on the waste form performance and to determine if the waste form will meet the disposal requirements of the Waste Control Specialists LLC (WCS) Federal Waste Disposal Facility (FWF) in Texas (WCS 2015) and the Integrated Disposal Facility at Hanford. The radionuclide results in the off-gas condensate were used to estimate concentrations in the Cast Stone waste forms; these estimates were then compared to Class C limits (30 TAC 336.362 Appendix E). With the possible exception of U-232, all measured radionuclides were determined to be below their respective Class C limits. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to measure most of the radionuclides. It is not possible to differentiate the isotope measured at mass 232 between U 232 and Th-232 by mass spectroscopy. Class C limit comparisons were made by assuming two maximum possible scenarios; one in which all the isotope at mass 232 occurred as Th-232, and another assigning the entire mass contribution to U-232. If the isotope at mass 232 is all Th-232 then the waste form is well below its Class C limit; however, if the isotope at mass 232 is all U-232, then the Class C limit would be exceeded by more than a factor of 8. A chemical procedure to separate uranium from thorium followed by reanalysis by ICP-MS would be required to resolve this issue. A similar issue occurs at mass 238, which could be U-238 or Pu-238; however, in this case Pu-238 can be ruled out as a contributor to the isotope measured at mass 238 for the following reasons. Pu-238 has a half-life of 87.7 years and its daughter product (U-234) has a half-life of 2.5 × 105 years and a measured concentration of