CONSOLIDATION OF K BASIN SLUDGE DATA AND EXPERIENCES ON AGGLOMERATE FORMATION

The formation of high sludge strength agglomerates is a key concern to the Sludge Treatment Project (STP) to ensure the sludge can be retrieved after planned storage for up to 10 years in Sludge Transport and Storage Containers (STSC) at T Plant. This report addresses observations of agglomerate formation, conditions that the data shows lead to agglomeration, the frequency of agglomerate formation and postulated physiochemical mechanisms that may lead to agglomeration. Although the exact underlying chemistry of K Basin sludge agglomerate formation is not known, the factors that lead to agglomeration formation, based on observations, are as follows: (1) High Total Uranium Content (i.e., sample homogeneity and influence from other constituents); (2) Distribution of Uranium Phases (i.e., extent of conversion from uraninite to uranium oxide hydroxide compounds); (3) Sample Dry-out (loss of cover water); (4) Elevated temperature; (5) Solubility ofU(IV) phases vs. U(VI) phases; and (6) Long storage times. Agglomerated sludge has occurred infrequently and has only been observed in four laboratory samples, five samples subjected to hydrothermal testing (performed for 7 to 10 hours at {approx}185 C and 225 psig), and indirectly during six sampling events in the KE Basin. In the four laboratory samples where agglomerates were observed, the agglomerates exhibited high shear strength and the sample container typically had to be broken to remove the solids. The total uranium content (dry basis) for the four samples (KE Pit, KC-2/3 SS, KC-2/3 M250 and 96-13) were {approx}8 wt%, {approx}59.0 wt%, 68.3 wt% and 82 wt%. The agglomerates that were present during the six sampling events were undoubtedly disturbed and easily broken apart during sample collection, thus no agglomerates were observed in subsequent laboratory analyses. The highest shear strengths measured for K Basin sludge samples were obtained after hydrothermal treatment (7 to 10 hr at 185 C) of high-uranium-content KE canister sludge. The unconfined compressive strength of samples from this testing, measured by a pocket penetrometer, infers that their shear strength may be between 120 kPa and 170 kPa (PNNL-16496). These short-duration hydrothermal tests were conducted at temperatures much greater than the temperature of the T Plant canyon cells (-7 C to 33 C); however, the strength results provide an initial bounding target for sludge stored for many years, and an upper range for simulants (042910-53451-TP02 Rev 1). Sampling and characterization activities conducted in 2009 have measured the total uranium content and speciation for sludge stored in Engineered Containers SCS-CON-220, -240, -250, and -260 (PNNL-19035). Based on on-going testing that has measured the shear strength of uranium samples containing varying uranium (IV) to uranium (VI) ratios and the characterization of the Engineered Containers SCS-CON-220, -240, -250, and -260, it is unlikely that agglomerates will form on a large scale in this sludge. The highest measured total uranium concentration in the Engineered Container SCS-CON-220 sludge is 35.2 wt% and only 4 wt% to 6 wt% (dry) in Engineered Containers SCS-CON -240, -250, and -260. The uranium concentrations in Engineered Containers SCS-CON-220, -240, -250, and -260 sludge are below the threshold for agglomerate formation. Settler sludge however is estimated to contain {approx} 80 wt% (dry) total uranium, which could lead to the formation of high strength agglomerates depending on the relative concentrations of U(IV) and U(VI) compounds. One of the chief concerns of the STP is sludge dry-out. Samples archived in PNNL hot cells have been known to dry out and form hard clods of material, which are then difficult to reconstitute (HNF-6705). In 1996, all but one of the samples archived at the 222-S Laboratory dried out. These samples were composed of sludge collected from the KE Basin floor and Weasel Pit. However, in the STP's current design plans for sludge stored in STSCs at T Plant, there are provisions for continual water level observation and periodic water replenishment when needed, which dramatically lowers the risk of a dryout event. Recent 2009 KE Engineered Container sludge and KW Engineered Container sludge physical characterization lead to opportunistic data on the behavior of dried sludge. As shown in section 5 of this report, sludge core samples taken from Engineered Container 220 that have inadvertently dried after characterization activities indicate that the sludge is mostly composed of very 'weak' and friable solids. Since Engineered Container SCS-CON-220 sludge has the highest total uranium (uranium metal and uranium oxide) concentration of the four Engineered Containers sampled to date, if a dry-out event should occur in the STSC while stored at T Plant there is qualitative evidence to suggest that the solids would be 'weak' and friable in nature and thus easily mobilized