Studies of Mercury in High Level Waste Systems

During nuclear weapons production, nuclear reactor target and fuel rods were processed in F- and H-Canyons. For the target rods, a caustic dissolution of the aluminum cladding was performed prior to nitric acid dissolution of the uranium metal targets in the large canyon dissolvers. To dissolve the aluminum cladding and the U-Al fuel, mercury in the form of soluble mercury (II) nitrate was added as a catalyst to accelerate the dissolution of the aluminum. F-Canyon began to process plutonium-containing residues that were packaged in aluminum cans and thus required the use of mercury as a dissolution catalyst. Following processing to remove uranium and plutonium using the solvent extraction process termed the Plutonium-Uranium Recovery by Extraction (PUREX) process, the acidic waste solutions containing fission products and other radionuclides were neutralized with sodium hydroxide. The mercury used in canyon processing is fractionated between the sludge and supernate that is transferred from the canyons to the tank farm. The sludge component of the waste is currently vitrified in the Defense Waste Processing Facility (DWPF). The vitrified waste canisters are to be sent to the federal repository for High Level Waste. The mercury in the sludge, presumably in an oxide or hydroxide form is reduced to elemental mercury by the chemical additions and high temperatures, steam stripped and collected in the Mercury Collection Tank. The mercury in the dilute supernate is in the form of mercuric ion and is soluble. During evaporation, the mercuric ion is reduced to elemental mercury, vaporizes into the overheads system and is collected as a metallic liquid in the Mercury Removal Tank