Using Polymerization, Glass Structure, and Quasicrystalline Theory to Produce High Level Radioactive Borosilicate Glass Remotely: A 20+ Year Legacy

Vitrification is currently the most widely used technology for the treatment of high level radioactive wastes (HLW) throughout the world. Most of the nations that have generated HLW are immobilizing in borosilicate glass. One of the primary reasons that glass has become the most widely used immobilization media is the relative simplicity of the vitrification process, e.g. melt a highly variable waste with some glass forming additives such as SiO2 and B2O3 in the form of a premelted frit and pour the molten mixture into a stainless steel canister. Seal the canister before moisture can enter the canister (10’ tall by 2’ in diameter) so the canister does not corrode from the inside out. Glass has also become widely used for HLW is that due to the fact that the short range order (SRO) and medium range order (MRO) found in the structure of glass atomistically bonds the radionuclides and hazardous species in the waste. The SRO and MRO have also been found to govern the melt properties such as viscosity and resistivity of the melt and the crystallization potential and solubility of certain species. The molecular structure of the glass also controls the glass durability, i.e. the contaminant/radionuclide release, by establishing the distribution of ion exchange sites, hydrolysis sites, and the access of water to those sites. The molecular structure is flexible and hence accounts for the flexibility of glass formulations to HLW waste variability. Nuclear waste glasses melt between 1050-1150°C which minimizes the volatility of radioactive components such as 99Tc, 137Cs, and 129I. Nuclear waste glasses have good long term stability including irradiation resistance. Process control models were developed based on the molecular structure of glass, polymerization theory of glass, and quasicrystalline theory of glass crystallization. These models create a glass which is durable, pourable, and processable with 95% accuracy without knowing from batch to batch what the composition of the waste coming out of the storage tanks will be. These models have operated the Savannah River Site Defense Waste Processing Facility (SRS DWPF), which is the world’s largest HLW Joule heated ceramic melter, since 1996. This unique “feed forward” process control, which qualifies the durability, pourability, and processability of the waste plus glass additive mixture before it enters the melter, has enabled ~8000 tons of HLW glass and 4242 canisters to be produced since 1996 with only one melter replacement

Mineralization of Radioactive Wastes by Fluidized Bed Steam Reforming (FBSR): Comparisons to Vitreous Waste Forms, and Pertinent Durability Testing

The Savannah River National Laboratory (SRNL) was requested to generate a document for the Washington State Department of Ecology and the U.S. Environmental Protection Agency that would cover the following topics: (1) A description of the mineral structures produced by Fluidized Bed Steam Reforming (FBSR) of Hanford type Low Activity Waste (LAW including LAWR which is LAW melter recycle waste) waste, especially the cage structured minerals and how they are formed. (2) How the cage structured minerals contain some contaminants, while others become part of the mineral structure (Note that all contaminants become part of the mineral structure and this will be described in the subsequent sections of this report). (3) Possible contaminant release mechanisms from the mineral structures. (4) Appropriate analyses to evaluate these release mechanisms. (5) Why the appropriate analyses are comparable to the existing Hanford glass dataset. In order to discuss the mineral structures and how they bond contaminants a brief description of the structures of both mineral (ceramic) and vitreous waste forms will be given to show their similarities. By demonstrating the similarities of mineral and vitreous waste forms on atomic level, the contaminant release mechanisms of the crystalline (mineral) and amorphous (glass) waste forms can be compared. This will then logically lead to the discussion of why many of the analyses used to evaluate vitreous waste forms and glass-ceramics (also known as glass composite materials) are appropriate for determining the release mechanisms of LAW/LAWR mineral waste forms and how the durability data on LAW/LAWR mineral waste forms relate to the durability data for LAW/LAWR glasses. The text will discuss the LAW mineral waste form made by FBSR. The nanoscale mechanism by which the minerals form will be also be described in the text. The appropriate analyses to evaluate contaminant release mechanisms will be discussed, as will the FBSR test results to date and how they compare to testing performed on LAW glasses. Other details about vitreous waste form durability and impacts of REDuction/OXidation (REDOX) on durability are given in Appendix A. Details about the FBSR process, various pilot scale demonstrations, and applications are given in Appendix B. Details describing all the different leach tests that need to be used jointly to determine the leaching mechanisms of a waste form are given in Appendix C. Cautions regarding the way in which the waste form surface area is measured and in the choice of leachant buffers (if used) are given in Appendix D

Durability of glasses from the Hg-doped Integrated DWPF Melter System (IDMS) campaign

The Integrated DWPF Melter System (IDMS) for the vitrification of high-level radioactive wastes is designed and constructed to be a 1/9th scale prototype of the full scale Defense Waste Processing Facility (DWPF) melter. The IDMS facility is the first engineering scale melter system capable of processing mercury, and flowsheet levels of halides and noble metals. In order to determine the effects of mercury on the feed preparation process, the off-gas chemistry, glass melting behavior, and glass durability, a three-run mercury (Hg) campaign was conducted. The glasses produced during the Hg campaign were composed of Batch 1 sludge, simulated precipitate hydrolysis aqueous product (PHA) from the Precipitate Hydrolysis Experimental Facility (PHEF), and Frit 202. The glasses were produced using the DWPF process/product models for glass durability, viscosity, and liquidus. The durability model indicated that the glasses would all be more durable than the glass qualified in the DWPF Environmental Assessment (EA). The glass quality was verified by performing the Product Consistency Test (PCT) which was designed for glass durability testing in the DWPF

Prediction of glass durability as a function of glass composition and test conditions: Thermodynamics and kinetics

The long-term durability of nuclear waste glasses can be predicted by comparing their performance to natural and ancient glasses. Glass durability is a function of the kinetic and thermodynamic stability of glass in solution. The relationship between the kinetic and thermodynamic aspects of glass durability can be understood when the relative contributions of glass composition and imposed test conditions are delineated. Glass durability has been shown to be a function of the thermodynamic hydration free energy which can be calculated from the glass composition. Hydration thermodynamics also furnishes a quantitative frame of reference to understand how various test parameters affect glass durability. Linear relationships have been determined between the logarithmic extent of hydration and the calculated hydration free energy for several different test geometries. Different test conditions result in different kinetic reactivity parameters such as the exposed glass surface area (SA), the leachant solution volume (V), and the length of time that the glass is in the leachant (t). Leachate concentrations are known to be a function of the kinetic test parameter (SAV)t. The relative durabilities of glasses, including pure silica, obsidians, nuclear waste glasses, medieval window glasses, and frit glasses define a plane in three dimensional ..delta..G/sub hyd/-concentration-(SAV)t space. At constant kinetic conditions, e.g., test geometry and test duration, the three dimensional plane is intersected at constant (SAV)t and the ..delta..G/sub hyd/-concentration plots have similar slopes. The slope represents the natural logarithm of the theoretical slope, (12.303 RT), for the rate of glass dissolution. 53 refs., 4 figs

Equilibration of Leachants with Basalt Rock for Repository Simulation Tests

In a nuclear waste repository in basalt, the groundwater will have a low redox potential (Eh) which may affect the leach rate of SRP waste glass. Accurate laboratory simulations of conditions in a basalt reposition must maintain low Eh values throughout the course of the experiment. In this report, important parameters affecting the ability of basalt to maintain appropriate Eh-pH conditions are examined, in particular basalt type and groundwater simulation

Waste vitrification: prediction of acceptable compositions in a lime-soda-silica glass-forming system

A model is presented based upon calculated bridging oxygens which allows the prediction of the region of acceptable glass compositions for a lime-soda-silica glass-forming system containing mixed waste. The model can be used to guide glass formulation studies (e.g., treatability studies) or assess the applicability of vitrification to candidate waste streams

Role of Manganese Reduction/Oxidation (REDOX) on Foaming and Melt Rate in High Level Waste (HLW) Melters (U)

High-level nuclear waste is being immobilized at the Savannah River Site (SRS) by vitrification into borosilicate glass at the Defense Waste Processing Facility (DWPF). Control of the Reduction/Oxidation (REDOX) equilibrium in the DWPF melter is critical for processing high level liquid wastes. Foaming, cold cap roll-overs, and off-gas surges all have an impact on pouring and melt rate during processing of high-level waste (HLW) glass. All of these phenomena can impact waste throughput and attainment in Joule heated melters such as the DWPF. These phenomena are caused by gas-glass disequilibrium when components in the melter feeds convert to glass and liberate gases such as H{sub 2}O vapor (steam), CO{sub 2}, O{sub 2}, H{sub 2}, NO{sub x}, and/or N{sub 2}. During the feed-to-glass conversion in the DWPF melter, multiple types of reactions occur in the cold cap and in the melt pool that release gaseous products. The various gaseous products can cause foaming at the melt pool surface. Foaming should be avoided as much as possible because an insulative layer of foam on the melt surface retards heat transfer to the cold cap and results in low melt rates. Uncontrolled foaming can also result in a blockage of critical melter or melter off-gas components. Foaming can also increase the potential for melter pressure surges, which would then make it difficult to maintain a constant pressure differential between the DWPF melter and the pour spout. Pressure surges can cause erratic pour streams and possible pluggage of the bellows as well. For these reasons, the DWPF uses a REDOX strategy and controls the melt REDOX between 0.09 {le} Fe{sup 2+}/{summation}Fe {le} 0.33. Controlling the DWPF melter at an equilibrium of Fe{sup +2}/{summation}Fe {le} 0.33 prevents metallic and sulfide rich species from forming nodules that can accumulate on the floor of the melter. Control of foaming, due to deoxygenation of manganic species, is achieved by converting oxidized MnO{sub 2} or Mn{sub 2}O{sub 3} species to MnO during melter preprocessing. At the lower redox limit of Fe{sup +2}/{summation}Fe {approx} 0.09 about 99% of the Mn{sup +4}/Mn{sup +3} is converted to Mn{sup +2}. Therefore, the lower REDOX limits eliminates melter foaming from deoxygenation

Fluidized Bed Steam Reforming Mineralization for High Organic and Nitrate Waste Streams for the Global Nuclear Energy Partnership

Waste streams that may be generated by the Global Nuclear Energy Partnership (GNEP) Advanced Energy Initiative may contain significant quantities of organics (0-53 wt%) and/or nitrates (0-56 wt%). Decomposition of high nitrate streams requires reducing conditions, e.g. organic additives such as sugar or coal, to reduce the NO{sub x} in the off-gas to N{sub 2} to meet the Clean Air Act (CAA) standards during processing. Thus, organics will be present during waste form stabilization regardless of which GNEP processes are chosen, e.g. organics in the feed or organics for nitrate destruction. High organic containing wastes cannot be stabilized with the existing HLW Best Developed Available Technology (BDAT) which is HLW vitrification (HLVIT) unless the organics are removed by preprocessing. Alternative waste stabilization processes such as Fluidized Bed Steam Reforming (FBSR) operate at moderate temperatures (650-750 C) compared to vitrification (1150-1300 C). FBSR converts organics to CAA compliant gases, creates no secondary liquid waste streams, and creates a stable mineral waste form that is as durable as glass. For application to the high Cs-137 and Sr-90 containing GNEP waste streams a single phase mineralized Cs-mica phase was made by co-reacting illite clay and GNEP simulated waste. The Cs-mica accommodates up to 30% wt% Cs{sub 2}O and all the GNEP waste species, Ba, Sr, Rb including the Cs-137 transmutation to Ba-137. For reference, the cesium mineral pollucite (CsAlSi{sub 2}O{sub 6}), currently being studied for GNEP applications, can only be fabricated at {ge} 1000 C. Pollucite mineralization creates secondary aqueous waste streams and NO{sub x}. Pollucite is not tolerant of high concentrations of Ba, Sr or Rb and forces the divalent species into different mineral host phases. The pollucite can accommodate up to 33% wt% Cs{sub 2}O

EVALUATION OF THE IMPACT OF THE DEFENSE WASTE PROCESSING FACILITY (DWPF) LABORATORY GERMANIUM OXIDE USE ON RECYCLE TRANSFERS TO THE H-TANK FARM

When processing High Level Waste (HLW) glass, the Defense Waste Processing Facility (DWPF) cannot wait until the melt or waste glass has been made to assess its acceptability, since by then no further changes to the glass composition and acceptability are possible. Therefore, the acceptability decision is made on the upstream feed stream, rather than on the downstream melt or glass product. This strategy is known as 'feed forward statistical process control.' The DWPF depends on chemical analysis of the feed streams from the Sludge Receipt and Adjustment Tank (SRAT) and the Slurry Mix Evaporator (SME) where the frit plus adjusted sludge from the SRAT are mixed. The SME is the last vessel in which any chemical adjustments or frit additions can be made. Once the analyses of the SME product are deemed acceptable, the SME product is transferred to the Melter Feed Tank (MFT) and onto the melter. The SRAT and SME analyses have been analyzed by the DWPF laboratory using a 'Cold Chemical' method but this dissolution did not adequately dissolve all the elemental components. A new dissolution method which fuses the SRAT or SME product with cesium nitrate (CsNO{sub 3}), germanium (IV) oxide (GeO{sub 2}) and cesium carbonate (Cs{sub 2}CO{sub 3}) into a cesium germanate glass at 1050 C in platinum crucibles has been developed. Once the germanium glass is formed in that fusion, it is readily dissolved by concentrated nitric acid (about 1M) to solubilize all the elements in the SRAT and/or SME product for elemental analysis. When the chemical analyses are completed the acidic cesium-germanate solution is transferred from the DWPF analytic laboratory to the Recycle Collection Tank (RCT) where the pH is increased to {approx}12 M to be released back to the tank farm and the 2H evaporator. Therefore, about 2.5 kg/yr of GeO{sub 2}/year will be diluted into 1.4 million gallons of recycle. This 2.5 kg/yr of GeO{sub 2} may increase to 4 kg/yr when improvements are implemented to attain an annual canister production goal of 400 canisters. Since no Waste Acceptance Criteria (WAC) exists for germanium in the Tank Farm, the Effluent Treatment Project, or the Saltstone Production Facility, DWPF has requested an evaluation of the fate of the germanium in the caustic environment of the RCT, the 2H evaporator, and the tank farm. This report evaluates the effect of the addition of germanium to the tank farm based on: (1) the large dilution of Ge in the RCT and tank farm; (2) the solubility of germanium in caustic solutions (pH 12-13); (3) the potential of germanium to precipitate as germanium sodalites in the 2H Evaporator; and (4) the potential of germanium compounds to precipitate in the evaporator feed tank. This study concludes that the impacts of transferring up to 4 kg/yr germanium to the RCT (and subsequently the 2H evaporator feed tank and the 2H evaporator) results in <2 ppm per year (1.834 mg/L) which is the maximum instantaneous concentration expected from DWPF. This concentration is insignificant as most sodium germanates are soluble at the high pH of the feed tank and evaporator solutions. Even if sodium aluminosilicates form in the 2H evaporator, the Ge will likely substitute for some small amount of the Si in these structures and will be insignificant. It is recommended that the DWPF continue with their strategy to add germanium as a laboratory chemical to Attachment 8.2 of the DWPF Waste Compliance Plan (WCP)

Quasicrystalline Approach to Predicting the Spinel-Nepheline Liquidus: Application to Nuclear Waste Glass Processing

The crystal-melt equilibria in complex fifteen component melts are modeled based on quasicrystalline concepts. A pseudobinary phase diagram between acmite (which melts incongruently to a transition metal ferrite spinel) and nepheline is defined. The pseudobinary lies within the Al{sub 2}O{sub 3}-Fe{sub 2}O{sub 3}-Na{sub 2}O-SiO{sub 2} quaternary system that defines the crystallization of basalt glass melts. The pseudobinary provides the partitioning of species between the melt and the primary liquidus phases. The medium range order of the melt and the melt-crystal exchange equilibria are defined based on a constrained mathematical treatment that considers the crystallochemical coordination of the elemental species in acmite and nepheline. The liquidus phases that form are shown to be governed by the melt polymerization and the octahedral site preference energies. This quasicrystalline liquidus model has been used to prevent unwanted crystallization in the world's largest high level waste (HLW) melter for the past three years while allowing >10 wt% higher waste loadings to be processed