Ferrocyanide safety project ferrocyanide aging studies FY 1995 annual report

This annual report gives the results of the work conducted by the Pacific Northwest Laboratory in FY 1995 on Task 3 of the Ferrocyanide Safety Project, Ferrocyanide Aging Studies. Aging refers to the dissolution and hydrolysis of simulated Hanford ferrocyanide waste in alkaline aqueous solutions by radiolytic and chemical means. The ferrocyanide simulant primarily used in these studies was dried In-Farm-1B, Rev. 7, prepared by Westinghouse Hanford Company to simulate the waste generated when the In-Farm flowsheet was used to remove radiocesium from waste supernates in single-shell tanks at the Hanford Site. In the In-Farm flowsheet, nickel ion and ferrocyanide anion were added to waste supernates to precipitate sodium nickel ferrocyanide, Na{sub 2}NiFe(CN){sub 6}, and co-precipitate radiocesium. Once the radiocesium was removed, supernates were pumped from the tanks, and new wastes from cladding removal processes or from evaporators were added. These new wastes were typically highly caustic, having hydroxide ion concentrations of over 1 M and as high as 4 M. The Aging Studies task is investigating reactions this caustic waste may have had with the precipitated ferrocyanide waste in a radiation field. In previous Aging Studies research, Na{sub 2}NiFe(CN){sub 6} in simulants was shown to dissolve in basic solutions, forming insoluble Ni(OH){sub 2} and soluble Na{sub 4}Fe(CN){sub 6}. The influence on solubility of base strength, sodium ion concentration, anions, and temperature was previously investigated. The results may indicate that even ferrocyanide sludge that did not come into direct contact with highly basic wastes may also have aged significantly