Glass corrosion data from the ALTGLASS™ database were used to determine if gel compositions, which evolve as glass systems corrode, are correlated with the generation of zeolites and subsequent increase in the glass dissolution rate at long times. The gel compositions were estimated based on the difference between the elemental glass starting compositions and the measured elemental leachate concentrations from the long‐term product consistency tests (ASTM C1285) at various stages of dissolution, ie, reaction progress. A well‐characterized subset of high level waste glasses from the database was selected: these glasses had been leached for 15‐20 years at reaction progresses up to ~80%. The gel composition data, at various reaction progresses, were subjected to a step‐wise regression, which demonstrated that hydrogel compositions with Si*/Al* ratios of <1.0 did not generate zeolites and maintained low dissolution rates for the duration of the experiments. Glasses that formed hydrogel compositions with Si^*/Al^* ratios ≥1, generated zeolites accompanied by a resumption in the glass dissolution rate. The role of the gel Si/Al ratio, and the interactions with the leachate, provides the fundamental understanding needed to predict if and when the glass dissolution rate will increase due to zeolitization.

The durability of high level nuclear waste glasses must be predicted on geological time scales. Waste glass surfaces form hydrogels when in contact with water for varying test durations. As the glass hydrogels age, some exhibit an undesirable resumption of dissolution at long times while others exhibit near steady‐state dissolution, that is, nonresumption of dissolution. Resumption of dissolution is associated with the formation of zeolitic phases while nonresumption of dissolution is associated with the formation of clay minerals. Hydrogels with a stoichiometry close to that of imogolite, (Al2O3·Si(OH)4), with ferrihydrite (Fe2O3·0.5H2O), have been shown to be associated with waste glasses that resume dissolution. Aluminosilicate hydrogels with a stoichiometry of allophane‐hisingerite ((Al,Fe)2O3·1.3‐2Si(OH)4) have been shown to be associated with waste glasses that exhibit near steady‐state dissolution at long times. These phases are all amorphous and poorly crystalline and are also found on natural weathered basalt glasses. Interaction of these hydrogels with excess alkali and OH− (strong base) in the leachates, causes the Al2O3·nSiO2 (where n=1‐2) hydrogels to mineralize to zeolites. Excess alkali in the leachate is generated by alkali in the glass. Preliminary rate‐determining leach layer forming exchange reactions are hypothesized based on these findings.

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Fluidized Bed Steam Reforming (FBSR) is being considered as a potential technology for the immobilization of a wide variety of high sodium aqueous radioactive wastes. The addition of clay and a catalyst as co-reactants converts high sodium aqueous low activity wastes (LAW) such as those existing at the Hanford and Idaho DOE sites to a granular "mineralized" waste form that may be made into a monolith form if necessary. Simulant Hanford and Idaho high sodium wastes were processed in a pilotscale FBSR at Science Applications International Corporation (SAIC) Science and Technology Applications Research (STAR) facility in Idaho Falls, ID. Granular mineral waste forms were made from (1) a basic Hanford Envelope A low-activity waste (LAW) simulant and (2) an acidic INL simulant commonly referred to as sodium-bearing waste (SBW). The FBSR waste forms were characterized and the durability tested via ASTM C1285 (Product Consistency Test, 10), the Environmental Protection Agency (EPA) Toxic Characteristic Leaching Procedure (TCLP), and the Single Pass Flow Through (SPFT) test. The durability of the FBSR waste form products was tested in order to compare the measured durability to previous FBSR waste form testing on Hanford Envelope C waste forms that were made by THOR sm Treatment Technologies (TTT) and to compare the FBSR durability to vitreous LAW waste forms, specifically the Hanford low activity waste (LAW) glass known as the Low-activity Reference Material (LRM). The durability of the FBSR waste form is comparable to that of the LRM glass for the test responses studied.

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EXECUTIVE SUMMARYTwo samples of fluidized-bed steam reforming (FBSR) mineral waste form product were subjected to single-pass flow-through (SPFT) testing. Sample LAW 1123 resulted from pilot-scale FBSR processing with a Hanford Envelope A low-activity waste (LAW) simulant. Sample SBW 1173 resulted from pilot-scale FBSR processing with an Idaho National Laboratory (INL) simulant commonly referred to as sodium-bearing waste (SBW). The pilot-scale waste forms were made at the Science and Technology Applications Research (STAR) facility in Idaho Falls, Idaho. The durability of the two FBSR waste forms was assessed via the SPFT test in this study. Both samples were multiphase mineral waste forms, so the SPFT test results provide an overall release rate from the multiple mineral species in each sample and are dependent on the amount of each phase present and the mineralogy of the phases present. SPFT testing was performed at temperatures of 25°, 40°, 70°, and 90°C on LAW 1123, while SBW 1173 was only tested at 70° and 90°C. The 70° and 90°C data were compared to each other and the LAW-1123 results were compared to previous testing performed by the Pacific Northwest National Laboratory (PNNL) on a LAW Envelope C (high organic content) waste simulant.The objectives of this study were to obtain forward dissolution rate data for both STAR FBSR bed products (using SPFT tests). Also, a qualitative comparison of the FBSR bed products to a glass waste form (specifically the low-activity reference material (LRM) glass) was performed. For these comparisons, the relative surface areas of the FBSR and glass products had to be measured. Due to the more porous and irregular surface of FBSR bed products, the surface area of the bed products was determined using the Brunauer, Emmett, and Teller (BET) measurement method. The surface area of a glass is much smoother and the calculated geometric surface area is typically used for determining dissolution behavior.Presently there are no specifications or standard release rates that the FBSR tested materials have to meet, e.g. the data from the FBSR testing is normally used during subsequent Performance Assessment (PA) calculations. Since a PA calculation is not part of this study, the LAW and SBW steam reforming samples were compared to each other, to previous LAW FBSR SPFT results, and to the results from the LRM reference glass. The experimental durability data generated from this study suggests that an FBSR mineral waste form product would be an adequate alternative form to borosilicate glass. The tested FBSR mineral waste forms showed normalized release rates for matrix elements such as Si to be more than 200X slower than the LRM glass. However, further durability testing and mineral phase information is recommended to further substantiate these findings.