Organic tanks safety program FY95 waste aging studies

This report gives the second year's findings of a study of how thermal and radiological processes may change the composition of organic compounds in the underground tanks at Hanford. Efforts were focused on the global reaction kinetics in a simulated waste exposed to γ rays and the reactions of organic radicals with nitrite ion. The gas production is predominantly radiolytic. Decarboxylation of carboxylates is probably an aging pathway. TBP was totaly consumed in almost every run. Radiation clearly accelerated consumption of the other compounds. EDTA is more reactive than citrate. Oximes and possibly organic nitro compounds are key intermediates in the radiolytic redox reactions of organic compounds with nitrate/nitrite. Observations are consistent with organic compounds being progressively degraded to compounds with greater numbers of C-O bonds and fewer C-H and C-C bonds, resulting in an overall lower energy content. If the radwaste tanks are adequately ventilated and continually dosed by radioactivity, their total energy content should have declined. Level of risk depends on how rapidly carboxylate salts of moderate energy content (including EDTA fragments) degrade to low energy oxalate and formate