EXECUTIVE SUMMARYThe noble metals Ru, Rh, Pd, and Ag were produced in the Savannah River Site (SRS) reactors as products of the fission of U-235. Consequently they are in the High Level Waste (HLW) sludges that are currently being immobilized into a borosilicate glass in the Defense Waste Processing Facility (DWPF). The noble metals are a concern in the DWPF because they catalyze the decomposition of formic acid used in the process to produce the flammable gas hydrogen. As the concentration of these noble metals in the sludge increases, more hydrogen will be produced when this sludge is processed.a In the SRS Tank Farm it takes approximately two years to prepare a sludge batch for processing in the DWPF. This length of time is necessary to mix the appropriate sludges, blend them to form a sludge batch and then wash it to enable processing in the DWPF. This means that the exact composition of a sludge batch is not known for ~two years. During this time, studies with simulated nonradioactive sludges must be performed to determine the desired DWPF processing parameters for the new sludge batch. Consequently, prediction of the noble metal concentrations is desirable to prepare appropriate simulated sludges for studies of the DWPF process for that sludge batch. These studies give a measure of the amount of hydrogen that will be produced when that sludge batch is processed. This report describes in detail the measurement of these noble metal concentrations in sludges and a way to predict their concentrations from an estimate of the lanthanum concentration in the sludge. Results for two sludges are presented in this report. These are Sludge Batch 3 (SB3) currently being processed by the DWPF and a sample of unwashed sludge from Tank 11 that will be

When immobilizing into borosilicate glass the radionuclides in the caustic high-level radioactive wastes stored in the USA, the soluble fission product Cs-137 has to be removed from supernates of the wastes. In the current processes zeolites or an organic precipitant will be used to remove the Cs. These are then treated further and mixed with the radioactive sludges and vitrified into a borosilicate glass. This paper describes the vitrification of a mixture resulting from using a new process to remove Cs from the caustic supernate. A resorcinol based organic ion exchange resin is used. This resin was then mixed with sludge and frit and vitrified. Using an organic ion exchange resin rather than zeolite or the organic precipitant has certain advantages. For example, use of the zeolite increases the amount of glass to be made and use of the organic precipitant produces benzene as a secondary waste stream. Results in the paper indicate that a mixture of the resin, sludge and frit can be successfully vitrified in a joule-heated, slurry fed melter. However, when resin is present in the feed, the glass becomes less durable due to the increased amount of Fe(II) caused by reduction of Fe(III) in the melt. Based on the durabilities of other waste glasses, this glass is still suitable as a canistered wasteform.

DE92 015893

iv 3. Glass S02244 contains a very high-temperature burning, carbon-based material which resulted in the following observations and data: a. The ground glass has secondary particles in the scanning electron microscopy (SEM) images which give x-ray fluorescence (XRF) spectra that are largely carbonbased and which are distinctly different from the glass particles. b. The thermal gravimetric analysis with mass spectroscopy (TGA-MS) data for the glass show the loss of CO 2 , NO 2 , and SO 2 at temperatures similar to that observed for anthracite coal. c. The glass density is slightly lower (7%) than observed for the second glass sample S02247.

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