Preliminary safety criteria for organic watch list tanks at the Hanford site

Condensed-phase, rapid reactions of organic salts with nitrates/nitrites in Hanford High Level Radioactive Waste single-shell tanks could lead to structural failure of the tanks resulting in significant releases of radionuclides and toxic materials. This report establishes appropriate preliminary safety criteria to ensure that tank wastes will be maintained safe. These criteria show that if actual dry wastes contain less than 1.2 MJ/kg of reactants reaction energy or less 4.5 wt % of total organic carbon, then the waste will be safe and will not propagate if ignited. Waste moisture helps to retard reactions; when waste moisture exceeds 20 wt %, rapid reactions are prevented, regardless of organic carbon concentrations. Aging and degradation of waste materials has been considered to predict the types and amounts to organic compounds present in the waste. Using measurements of 3 waste phases (liquid, salt cake, and sludge) obtained from tank waste samples analyzed in the laboratory, analysis of variance (ANOVA) models were used to estimate waste states for unmeasured tanks. The preliminary safety criteria are based upon calorimetry and propagation testing of likely organic compounds which represent actual tank wastes. These included sodium salts of citrate, formate, acetate and hydroxyethylethylenediaminetricetate (HEDTA). Hot cell tests of actual tank wastes are planned for the future to confirm propagation tests performed in the laboratory. The effects of draining liquids from the tanks which would remove liquids and moisture were considered because reactive waste which is too dry may propagate. Evaporation effects which could remove moisture from the tanks were also calculated. The various ways that the waste could be heated or ignited by equipment failures or tank operations activities were considered and appropriate monitoring and controls were recommended.