A method has been developed for removing chromium from alkaline high-level radioactive tank waste. Removing chromium from these wastes is critical in reducing the volume of waste requiring expensive immobilization and deep geologic disposition. The method developed is based on the oxidation of insoluble chromium(III) compounds to soluble chromate using ferrate. This method could be generally applicable to removing chromium from chromium-contaminated solids, when coupled with a subsequent reduction of the separated chromate back to chromium(III). The tests conducted with a simulated Hanford tank sludge indicate that the chromium removal with ferrate is more efficient at 5 M NaOH than at 3 M NaOH. Chromium removal increases with increasing Fe(VI)/Cr(II) molar ratio, but the chromium removal tends to level out for Fe(VI)/ Cr(III) greaterthan 10. Increasingtemperature leadsto better chromium removal, but higher temperatures also led to more rapid ferrate decomposition. Tests with radioactive Hanford tank waste generally confirmed the simulant results. In all cases examined, ferrate enhanced the chromium removal, with a typical removal of around 60-70% of the total chromium present in the washed sludge solids. The ferrate leachate solutions did not contain significant concentrations of transuranic elements, so these solutions could be disposed as low-activity waste.

DISCLAIMERPortions of this document may be illegible in electronic image products. Images are produced from the best available original document. AbstractSludge washing and parametric caustic leaching tests were performed on sludge samples fiom five Hadord tanks: B-101, . These studies examined the effects of both dilute hydroxide washing and caustic leaching on the composition of the residual sludge solids.the P, and 63 to 99% of the Na from the H d o r d tank sludge samples examined. The partial removal of these elements was likely due to the presence of water-soluble sodium salts of aluminate, chromate, hydroxide, nitrate, nitrite, and phosphate, either in the interstitial liquid or as dried salts.The response of Al to caustic leaching was v~a b l e .When leached with 3 M NaOH for one week at 95 to 100°C, the cumulative Al removals were 62,99,61,95, and 89% for the B-101, BX-110, BX-112, (2-102, and S-101 samples, respectively. For the B-101 and the BX-110 samples, Al dissolution was rapid, with the AI concentrations reaching >SO% of their final values within the first 5 h of leaching.Interestingly, for the BX-112 sample, A I removal decreased with increasing leaching time and temperature-a trend contrary to what was expected. We hypothesize that this is due to the formation of aluminosilicate minerals. For the C-102 sludge, there was clearly a benefit in increasing the NaOH concentration from 1 M to 3 M. Leaching with 1 M NaOH removed -20 to 30% of the Al from the dilute hydroxide-washed solids while 3 M NaOH removed -95% of the Al. Aluminum dissolved slowly from the S-101 sample, which is consistent with boehmite being the predominant Al-containing phase.all the sludge samples examined, Cr removal during caustic leaching was highly time-dependent, but the Cr dissolution did not fit simple zero-, first-, or second-order kinetic models. Consistent trends in the effects of temperature and hydroxide concentration on Cr removal were difficult to discern. P from the sludge samples examined. Except for the Tank C-102 sample, cumulative P removals,were 285%. For C-102, the cumulative P removals were only -60%. Increasing temperature or hydroxide concentration generally did not result in large improvements in P removal; that is, relatively mild conditions tended to be adequate to remove P. 'The projected 137Cs content for the low-level waste (LLW) resulting fiom immobilizing the sludge washinglleaching solutions would range fiom -50 to -540 CVm3 for the samples examined. Although these concentrations are below the U.S. Nuclear Regulatory Commission Class C LLW limit of 4,600 Cum3, they are well above the proposed guideline of 3 Cum3 for the immobilized LLW product fiom the proposed private-processing facilities. Thu, it is likely that I3'Cs will need to be removed fiom the washing and leaching solutions. On the other hand, transuranic and Sr removal would likely not be required for the washing and leaching solutions fiom processing the sludges examined here. An estimate of high-level waste (HLW) glass produced in im...

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