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Modeling and Analysis of the Transport and Disposal of Beryllium Moderator Blocks and Greater than Class C (GTCC) Waste

Radioactive waste in the United states is categorized based on its source, radioactivity, and security risk. The categorization method employed by the Nuclear Regulatory Committee (NRC) for low-level radioactive waste is not currently applied to any waste generated by the Department of Energy (DOE) or disposed of in DOE facilities. As a result, there is a large volume of DOE-generated waste with characteristics similar to the NRC’s “Greater than Class C” (GTCC) waste category which presently do not have a path for long-term disposal. Much of this waste cannot undergo the standard commercial disposition process due to it being categorized as Transuranic (TRU) waste under DOE guidelines, due to elevated concentrations of key fission products. Possible solutions to this dilemma are explored in the Environmental Impact Statement for the “Disposal of Greater-Than-Class-C Low Level Radioactive Wave” (EIS-0375). This paper analyzes several EIS possible paths for disposal for this “orphaned” waste. One example that highlights this categorization issue is the spent beryllium cladding that has been extracted from the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL) throughout its operational lifetime. These beryllium blocks surround the reactor’s main chambers and components and serve as neutron moderators. This paper will use this particular waste form to analyze the economic and technological viability of transporting and storing this material under the storage and transportation criteria of the Waste isolation Pilot Plant (WIPP), which was deemed the most feasible disposition path according to the EIS. The example of this waste form used in this paper that highlights this categorization issue is the spent beryllium cladding extracted from Idaho National Laboratory’s (INL) Advanced Test Reactor (ATR). These beryllium blocks surround the reactor’s components and serve as neutron moderators, and thus have accumulated high concentration of high-activity transuranic isotopes. This paper analyzed the viability of transporting and storing this material under the storage and transportation criteria of the five primary disposition paths covered in EIS-0375. An array of calculations was carried out to assess the viability of the various disposition paths for the beryllium shipments as well as other waste shipments that fall within the GTCC category. Modeling with MCNP 6.2 was conducted to determine whether the beryllium blocks could be safely stored and transported within a 72-B cask; the standard shipping container for remote-handled, transuranic waste, while also meeting regulatory limits at various disposition paths. A cost analysis of the transportation and long-term disposal paths mentioned in the EIS was also carried out using available data and information from similar waste shipments. Lastly, a geochemical analysis of the various geological repository discussed in the EIS was also carried out using the Geochemists Workbench Release 14. Long-term disposal of the beryllium blocks at the Waste Isolation Pilot Plant (WIPP) proved to be the most cost-effective long-term disposition option of the ones considered in the EIS. A dose rate calculation at both contact and remote-handling distances indicate that the analyzed beryllium shipments should not exceed the exposure limits at any of the considered locations. Greater-than-class-C waste has been left in a regulatory state of limbo for years, resulting in backlogs of inventory across several research sites in the United States. Due to its high activity and presence of transuranic isotopes, it is imperative to ensure that it remains inaccessible and sequestered both in its short-term interim as well as a long-term geologic time scale. The information and assessments done in the paper could potentially serve as a reference for any future shipments of this waste form at the WIPP facility as well as other disposition paths that may be considered in the future.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

SNL Sigma Off-Gas Team Contribution to the FY15 DOE/NE-MRWFD Campaign Accomplishments Report

This program at Sandia is focused on Iodine waste form development for Fuel Cycle R&D needs. Our research has a general theme of “Capture and Storage of Iodine Fission Gas “ in which we are focused on silver loaded zeolite waste forms, evaluation of iodine loaded getter materials (eg., mordenite zeolite), and the development of low temperature glass waste forms that successfully incorporate iodine loaded getter materials from I 2 , organic iodide, etc. containing off-gas streams.

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Hydraulic Properties of Grout Monoliths Containing Organic Ion Exchange Resin - 18369

The Waste Treatment and Immobilization Plant (WTP) at Hanford is being constructed to treat 56 million gallons of radioactive waste currently stored in underground tanks at the Hanford site. Operation of the WTP will generate several solid secondary waste (SSW) streams including spent spherical resorcinol formaldehyde cation exchange resin (IXr). The current plan for safe disposal of IXr is solidification in cementitious material (CM) typically comprised of cement, fly ash and blast furnace slag. Three CM formulations were tested to stabilize IXr for long-term land disposal. Two IXr loading rates, 0.1 and 0.3 v/v IXr:grout were used with the three CM formulations to prepare simulated waste form monoliths for hydraulic property testing. Following curing, the monoliths were removed from molds and tested to determine saturated hydraulic conductivity (K{sub sat}) and water retention properties. K{sub sat} was measured using a standard flexible permeameter method ASTM D-5084-10. A constant vapor pressure (CVP) method was used to determine van Genuchten parameters for desorption moisture retention curves for each of the SSW grout formulations. For the CVP method, vacuum saturated, intact wafers approximately 1.25 cm thick were placed above a saturated salt solution inside a sealed container for equilibration. Each saturated salt solution has an associated vapor pressure related to relative humidity in the container. Visual examination and three-dimensional x-ray micro computed tomography (μCT) indicated that the IXr was uniformly distributed in the cured waste form. Saturated hydraulic conductivity was within the range previously reported by Flach et al. in a study of the hydraulic properties of 98 pastes and grouts. The solidification of IXr in CM resulted in a waste form with water retention properties similar to cementitious pastes. (authors)

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Separated waste stream immobilization of iodine and off-gas caustic scrubber solution (Final Report)

In this work, the approach was to immobilize the CS solution in a glass-bonded composite of cancrinite/sodalite. The synthesis of ceramic waste forms was accomplished by low-temperature (~90°C) processes developed by the team in the framework of a previous NEUP project. By building on our earlier efforts for iodine waste forms, we minimized the schedule and technical risk while still providing novel process demonstrations for the off-gas waste forms. In the case of AgI-based sorbents, a proof-of-concept stripping process was shown to remove iodine from AgI by converting it to NaI(aq) followed by immobilization of these ions in iodosodalite (ISOD), which could be glass-bonded in the same way as for the CS solution cancrinite/sodalite powders.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Microstructure and Cs Behavior of Ba-Doped Aluminosilicate Pollucite Irradiated with F+ Ions

Radionuclide 137Cs is one of the major fission products that dominate heat generation in spent fuels over the first 300 hundred years. A durable waste form for 137Cs that decays to 137Ba is needed to minimize its environmental impact. Aluminosilicate pollucite CsAlSi2O6 is selected as a model waste form to study the decay-induced structural effects. While Ba-containing precipitates are not present in charge-balanced Cs0.9Ba0.05AlSi2O6, they are found in Cs0.9Ba0.1AlSi2O6 and identified as monoclinic Ba2Si3O8. Pollucite is susceptible to electron irradiation induced amorphization. The threshold density of the electronic energy deposition for amorphization is determined to be ~235 keV/nm3. Pollucite can be readily amorphized under F+ ion irradiation at 673 K. A significant amount of Cs diffusion and release from the amorphized pollucite is observed during the irradiation. However, cesium is immobile in the crystalline structure under He+ ion irradiation at room temperature. The critical temperature for amorphization is not higher than 873 K under F+ ion irradiation. If kept at or above 873 K all the time, the pollucite structure is unlikely to be amorphized; Cs diffusion and release are improbable. A general discussion regarding pollucite as a potential waste form is provided in this report.

aluminosilicate pollucite↗

Iodine solid sorbent design: a literature review of the critical criteria for consideration

Designing sorbents for iodine capture in different conditions requires selection and optimization of a large and diverse range of variables. These variables fall into general categories (or features) of sorbent activity, sorbent stability, and the fate of the loaded material in terms of the disposal (waste form) options available. To illustrate, silver-loaded, high-porosity sorbents make for maximized iodine capture and less pressure drop in a column-based sorption system approach, however, this high porosity can lead to less mechanically stable sorbents. Additionally, waste forms containing silver must also be compliant with additional criteria for hazardous waste disposal. Thus, all these aspects must be considered simultaneously when selecting a sorbent for utilization under specific conditions. Information is given for different types of sorbent design considerations for different operating conditions and some emphasis is also given on promising alternatives for silver as the active (chemisorption-based) getter metal. Discussion is given around demonstrated options for waste forms for different metal-iodide compounds.

36 MATERIALS SCIENCE↗

Bubble Formation and Lattice Parameter Changes Resulting from He Irradiation of Defect-Fluorite Gd2Zr2O7

Pyrochlores have long been considered as potential candidates for advanced ceramic waste-forms for the immobilization of radioactive waste nuclides. This work provides evidence that Gd2Zr2O7, often considered the most radiation tolerant pyrochlore, could be susceptible to radiation damage in the form of bubble nucleation at the highest He doses expected over geological time. Ion irradiations were utilized to experimentally simulate the radiation damage and He accumulation produced by ..alpha..-decay. Samples were pre-damaged using 7 MeV Au3+ to induce the pyrochlore to defect-fluorite phase transformation, which would occur due to ..alpha..-recoil damage within several hundred years of storage in a Gd2Zr2O7 waste-form. These samples were then implanted to various He concentrations in order to study the long-term effects of He accumulation. Helium bubbles 1-3 nm in diameter were observed in TEM at a concentration of 4.6 at.% He. Some bubbles remained isolated, while others formed chains 10-30 nm in length parallel to the surface. GIXRD measurements showed lattice swelling after irradiating pristine Gd2Zr2O7 with 7 MeV Au3+ to a fluence of 2.2 x 1015 Au/cm2. An increase in lattice swelling was also measured after 2.2 x 1015 Au/cm2 + 2 x 1015 He/cm2 and 2.2 x 1015 Au/cm2 + 2 x 1016 He/cm2. A decrease in lattice swelling was measured after irradiation with 2.2 x 1015 Au/cm2 + 2 x 1017 He/cm2, the fluence where bubbles and bubble chains were observed in TEM. Bubble chains are thought to form in order to reduce lattice strain normal to the surface, which is produced by the Au and He irradiation damage.

36 MATERIALS SCIENCE↗

ETF Grout Expansion: Effects of Different Slags and Struvite Precipitation Protocols (Stirring Time)

The ETF ammonia tolerant grout waste form was developed by the Vitreous State Laboratory (VSL) to stabilize ammonium and thereby prevent emission of ammonia vapor during solidification of an ammonium-rich, concentrated sodium sulfate aqueous waste stream generated at the Hanford Effluent Treatment Facility (ETF). VSL personnel did not observe expansion in samples prepared during the waste form development work. However, Savannah River National Laboratory (SRNL) personnel detected expansion, in a few ETF grout samples, up to ~ 20 percent vertical expansion, while preforming work scope to evaluate the effect of ETF brine compositional ranges on the precipitation and solidification processes. The initial work requests can be found in Washington River Protection Services (WRPS) Statement of Work (SOW, Requisitions #: 339922 Revisions 0 and 1, March 11, 2021, and November 2021, respectively. As a result of the waste form expansion observed by SRNL, additional evaluation was requested by WRPS SOW Requisitions #: 356730 Revision 0 and Revision 1, February 1, 2022, and July 11, 2022, respectively. The goal of these requests was to determine whether differences in the slags and / or in sample preparation protocols used by VSL and SRNL were the cause of the expansion observed in the SRNL samples. G. Chen, WRPS, arranged a materials exchange between VSL and SRNL and coordinated the VSL protocol(s) for grouting and curing 1L batches of Base Case ETF base case simulant. Materials were exchanged between VSL and SRNL. Both laboratories performed the VSL struvite precipitation-solidification protocol and cured samples for at least 28 days. Differences in VSL and SRNL slag compositions, mineralogy and particle size results in themselves or combined were determined to not be the cause of the expansion because all samples expanded regardless of whether the VSL or SRNL slags were used. The fundamental cause of the observed expansion could not be attributed to minor variations in the following: 1) chemistry of the slag and other reagents, 2) container wall thickness, 3) ambient bench top curing conditions at VSL and SRNL, 4) pH adjustments to 7 ± a few tenths of unit, nor 5) stirring time between the precipitation and solidification process steps. Additional observations include: grout samples prepared with VSL slag expanded less than those prepared with the SRNL slag and, based on a very limited sample set, some samples stirred for longer times expanded less than those stirred for 20 minutes.

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Support of SRS salt-stone regulatory compliance - 15586

The SRS salt-stone Facility is designed and permitted to immobilize and dispose of low-level radioactive and hazardous liquid waste (salt solution) remaining from the processing of radioactive material at the Savannah River Site. The salt-stone Processing Facility (SPF) is permitted as a wastewater treatment facility per the South Carolina Department of Health and Environmental Control Regulations (SCDHEC) South Carolina Hazardous Waste Management Regulations (SCHWMR) R.61-67. The salt-stone Disposal Facility is permitted as a solid waste landfill site, as defined by SCDHEC Regulations R61-107.19. The salt-stone Sampling and Analysis Plan provides the SCDHEC with the chemical and physical characterization strategy for the salt solution and salt-stone waste form. During operation, samples are collected from Tank 50H on a quarterly basis and are analyzed by the Savannah River National Laboratory (SRNL) for over chemical and radioactive components. The analytical results are compared to the salt-stone waste acceptance criteria in a technical report. SRNL also prepares salt-stone samples from the quarterly sample and premix binder materials provided by the SPF to determine the non-hazardous nature of the grout to meet the requirements of the SCDHEC regulation for the 'Characteristic of Toxicity', R.61-79.261.24(b) and the 'Universal Treatment Standards', R.61-79.268.48.4. salt-stone samples are collected, size reduced, packaged, and shipped to an independent United States EPA certified laboratory, or a laboratory that holds an equivalent certification such as one from the National Environmental Laboratory Accreditation Program to perform the EPA Toxicity Characteristic Leaching Procedure (TCLP) extraction of the salt-stone sample. SRNL reviews the results of the TCLP analysis and prepares a report detailing the sample preparation and analysis that is used by the salt-stone Facility to demonstrate the nonhazardous nature of the salt-stone waste form. (authors)

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Saltstone 1QCY15 TCLP Toxicity and UTS Results

A Saltstone Disposal Facility (SDF) waste form was prepared in the Savannah River National Laboratory (SRNL) from a Tank 50H sample and Z-Area premix material for the first quarter of calendar year 2015 (1QCY15). After a 28 day cure, a sample of the SDF waste form was collected, and shipped to a certified laboratory for Toxic Characteristic and Universal Treatment Standards (UTS) analysis. The metals analysis is performed using the Toxic Characteristic Leaching Procedure (TCLP). The 1QCY15 saltstone sample results meet South Carolina Hazardous Waste Management Regulations (SCHWMR) R.61-79.261.24 and R.61-79.268.48(a) requirements for a nonhazardous waste form with respect to RCRA metals and underlying hazardous constituents (UHC).

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Saltstone 2QCY15 TCLP Toxicity and UTS Results

A Saltstone Disposal Facility (SDF) waste form was prepared in the Savannah River National Laboratory (SRNL) from a Tank 50H sample and Z-Area premix material for the second quarter of calendar year 2015 (2QCY15). After a 28 day cure, a sample of the SDF waste form was collected, and shipped to a certified laboratory for Toxic Characteristic and Universal Treatment Standards (UTS) analysis. The metals analysis is performed using the Toxic Characteristic Leaching Procedure (TCLP). The 2QCY15 saltstone sample results meet South Carolina Hazardous Waste Management Regulations (SCHWMR) R.61-79.261.24 and R.61-79.268.48(a) requirements for a nonhazardous waste form with respect to RCRA metals and underlying hazardous constituents (UHC).

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Saltstone 3QCY15 TCLP Toxicity and UTS Results

A Saltstone Disposal Facility (SDF) waste form was prepared in the Savannah River National Laboratory (SRNL) from a Tank 50H sample and Z-Area premix material for the third quarter of calendar year 2015 (3QCY15). After a 28 day cure, a sample of the SDF waste form was collected, and shipped to a certified laboratory for Toxic Characteristic and Universal Treatment Standards (UTS) analysis. The metals analysis is performed using the Toxic Characteristic Leaching Procedure (TCLP).1 The 3QCY15 saltstone sample results meet South Carolina Hazardous Waste Management Regulations (SCHWMR) R.61-79.261.24 and R.61-79.268.48(a) requirements for a nonhazardous waste form with respect to RCRA metals and underlying hazardous constituents (UHC).

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Saltstone 2QCY15 TCLP Toxicity and UTS Results

A Saltstone Disposal Facility (SDF) waste form was prepared in the Savannah River National Laboratory (SRNL) from a Tank 50H sample and Z-Area premix material for the second quarter of calendar year 2015 (2QCY15). After a 28 day cure, a sample of the SDF waste form was collected, and shipped to a certified laboratory for Toxic Characteristic and Universal Treatment Standards (UTS) analysis. The metals analysis is performed using the Toxic Characteristic Leaching Procedure (TCLP) 1 . The 2QCY15 saltstone sample results meet South Carolina Hazardous Waste Management Regulations (SCHWMR) R.61-79.261.24 and R.61-79.268.48(a) requirements for a nonhazardous waste form with respect to RCRA metals and underlying hazardous constituents (UHC).

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Pelletization with Spark Plasma Sintering and Characterization of Metal Iodides: An Assessment of Long-Term Radioiodine Immobilization Options

Four promising iodine “getter” materials (Ag, Cu, Bi, and Sn) for radioiodine capture were assessed in their pure metal-iodide (MI x ) pelletized forms to compare relative chemical durabilities. To study chemical durability, commercial MI x compounds of AgI, BiI 3 , BiOI, CuI, and SnI 4 were converted to dense monolithic pellets using spark plasma sintering. Semidynamic leach testing in the form of modified ASTM C1308 tests was then performed on the pellets in two different forms including unmounted (as-pressed) specimens (i.e., “U”) and epoxy-mounted specimens (i.e., “M”) with polished surfaces. The chemical durability results and sample characterizations showed that three of the five MI x compounds tested (i.e., AgI, CuI, and BiOI) displayed moderate to high leach resistances. Further, the remaining two MI x compounds (i.e., BiI 3 and SnI 4 ), which are both desirable iodine waste forms due to their high iodine loading capacities, readily decomposed during leach testing, indicated by crystallographic changes in the specimens as well as large amounts of iodine detected in the leachate solutions. The instabilities of BiI 3 and SnI 4 raise uncertainties for using the base metals/cations (i.e., Bi 0 /Bi 3+ and Sn 0 /Sn 4+ , respectively) as viable getters for radioiodine capture due to likely poor waste form chemical durabilities after capture and consolidation into waste forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scientific Solutions to Nuclear Waste Environmental Challenges

The Hidden Cost of Nuclear Weapons The Cold War arms race drove an intense plutonium production program in the U.S. This campaign produced approximately 100 tons of plutonium over 40 years. The epicenter of plutonium production in the United States was the Hanford site, a 586 square mile reservation owned by the Department of Energy and located on the Colombia River in Southeastern Washington. Plutonium synthesis relied on nuclear reactors to convert uranium to plutonium within the reactor fuel rods. After a sufficient amount of conversion occurred, the rods were removed from the reactor and allowed to cool. They were then dissolved in an acid bath and chemically processed to separate and purify plutonium from the rest of the constituents in the used reactor fuel. The acidic waste was then neutralized using sodium hydroxide and the resulting mixture of liquids and precipitates (small insoluble particles) was stored in huge underground waste tanks. The byproducts of the U.S. plutonium production campaign include over 53 million gallons of high-level radioactive waste stored in 177 large underground tanks at Hanford and another 34 million gallons stored at the Savannah River Site in South Carolina. This legacy nuclear waste represents one of the largest environmental clean-up challenges facing the world today. The nuclear waste in the Hanford tanks is a mixture of liquids and precipitates that have settled into sludge. Some of these tanks are now over 60 years old and a small number of them are leaking radioactive waste into the ground and contaminating the environment. The solution to this nuclear waste challenge is to convert the mixture of solids and liquids into a durable material that won't disperse into the environment and create hazards to the biosphere. What makes this difficult is the fact that the radioactive half-lives of some of the radionuclides in the waste are thousands to millions of years long. (The half-life of a radioactive substance is the amount of time it takes for one-half of the material to undergo radioactive decay.) In general, the ideal material would need to be durable for approximately 10 half-lives to allow the activity to decay to negligible levels. However, the potential health effects of each radionuclide vary depending on what type of radiation is emitted, the energy of that emission, and the susceptibility for the human body to accumulate and concentrate that particular element. Consequently, actual standards tend to be based on limiting the dose (energy deposited per unit mass) that is introduced into the environment. The Environmental Protection Agency (EPA) has the responsibility to establish standards for nuclear waste disposal to protect the health and safety of the public. For example, the Energy Policy Act of 1992 directed the EPA to establish radiation protection standards for the Yucca Mountain geologic repository for nuclear wastes. The standards for Yucca Mountain were promulgated in 2008, and limit the dose to 15 millirem per year for the first 10,000 years, and 100 milirem per year between 10,000 years and 1 million years (40 CFR Part 197; http://www.epa.gov/radiation/yucca/2008factsheet.html). So, the challenge is two-fold: (1) develop a material (a waste form) that is capable of immobilizing the waste over geologic time scales, and (2) develop a process to convert the radioactive sludge in the tanks into this durable waste form material. Glass: Hard, durable, inert, and with infinite chemical versatility Molten glass is a powerful solvent liquid, which can be designed to dissolve almost anything. When solidified, it can be one of the most chemically inert substances known to man. Nature's most famous analogue to glass is obsidian, a vitreous product of volcanic activity; formations over 17 million years old have been found. Archaeologists have found man-made glass specimens that are five thousand years old.

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Update on SRNL Support of Saltstone Sampling and Analysis - 16325

At the Savannah River Site, low-level waste is immobilized in cementitious waste form known as saltstone. The saltstone Performance Assessment models the performance of the waste form and other aspects of the Saltstone Disposal Facility over ten thousand years after closure to determine the transport history of radionuclides and other hazardous constituents in low-level waste. As part of an ongoing Performance Assessment Maintenance Plan, Savannah River Remediation with Savannah River National Laboratory, has designed a sampling and analyses plan to correlate the properties of field-emplaced samples and samples processed and cured in the laboratory. As part of the plan, SRR has retrieved field-emplaced samples from SDU 2A. Prior to analyzing the field emplaced samples, SRNL is developing the strategy, protocols and equipment necessary to retrieve, store in an inert environment, and analyze the three sample sets of interest outlined in the analysis plan. To date, the simulant saltstone samples have been analyzed for hydraulic conductivity, porosity, density, and other properties. This paper will give an update to the current protocols and equipment being utilized at Savannah River National Laboratory for storing and analyzing the field-emplaced and simulant samples, results from the simulant saltstone analyses, as well as analysis plans for the samples retrieved from the Saltstone Processing Facility and the field-emplaced samples. (authors)

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Analysis of Saltstone Cores Taken from Saltstone Disposal Unit Cell 2A - 17350

At the Savannah River Site, low-level waste is immobilized in cementitious waste form known as saltstone. The saltstone Performance Assessment models the performance of the waste form and other aspects of the Saltstone Disposal Facility over ten thousand years after closure to better understand the transport history of radionuclides and other hazardous constituents in low-level waste. As part of ongoing Performance Assessment Maintenance, Savannah River Remediation (SRR), with Savannah River National Laboratory (SRNL), designed a sampling and analyses plan to correlate the properties of field-emplaced samples and samples processed and cured in the laboratory. The primary objectives of the Sampling and Analyses Plan are; (1) to demonstrate a correlation between the measured properties of laboratory-prepared, simulant samples (termed Sample Set 3), and the field-emplaced saltstone samples (termed Sample Set 9), and (2) to validate property values assumed for the Saltstone Disposal Facility (SDF) Performance Assessment modeling. The analysis and property data for Sample Set 9 (i.e. core samples extracted from Saltstone Disposal Unit Cell 2A (SDU2A)) are documented, and where applicable, the results are compared to the results for Sample Set 3. SRNL received, stored and analyzed the samples cored from SDU2A. This paper discusses the results of the SRNL analysis of the SDU2A samples as well as the simulant saltstone samples. (authors)

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