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DOE OSTI2016

Impact of axial velocity and transmembrane pressure (TMP) on ARP filter performance

The Savannah River Site (SRS) is currently treating radioactive liquid waste with the Actinide Removal Process (ARP) and the Modular Caustic Side Solvent Extraction Unit (MCU). Recently, the low filter flux through the ARP of approximately 5 gallons per minute has limited the rate at which radioactive liquid waste can be treated. Salt Batch 6 had a lower processing rate and required frequent filter cleaning. Savannah River Remediation (SRR) has a desire to understand the causes of the low filter flux and to increase ARP/MCU throughput. One potential method for increasing filter flux is to adjust the axial velocity and transmembrane pressure (TMP). SRR requested SRNL to conduct bench-scale filter tests to evaluate the effects of axial velocity and transmembrane pressure on crossflow filter flux. The objective of the testing was to determine whether increasing the axial velocity at the ARP could produce a significant increase in filter flux. The authors conducted the tests by preparing slurries containing 6.6 M sodium Salt Batch 6 supernate and 2.5 g MST/L, processing the slurry through a bench-scale crossflow filter unit at varying axial velocity and TMP, and measuring filter flux as a function of time.

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DOE OSTI2012

Sample Results from the Integrated Salt Disposition Program Macrobatch 5 Tank 21H Qualification MST, ESS and PODD Samples

Savannah River National Laboratory (SRNL) performed experiments on qualification material for use in the Integrated Salt Disposition Program (ISDP) Batch 5 processing. This qualification material was a composite created from recent samples from Tank 21H and archived samples from Tank 49H to match the projected blend from these two tanks. Additionally, samples of the composite were used in the Actinide Removal Process (ARP) and extraction-scrub-strip (ESS) tests. ARP and ESS test results met expectations. A sample from Tank 21H was also analyzed for the Performance Objectives Demonstration Document (PODD) requirements. SRNL was able to meet all of the requirements, including the desired detection limits for all the PODD analytes. This report details the results of the Actinide Removal Process (ARP), Extraction-Scrub-Strip (ESS) and Performance Objectives Demonstration Document (PODD) samples of Macrobatch (Salt Batch) 5 of the Integrated Salt Disposition Program (ISDP).

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DOE OSTI2015

Integration of performance assessments and 3116 basis documents within the Savannah River Site liquid waste facilities - 15375

The end of the Cold War has left a legacy of over 136 million liters (36 million gallons) of radioactive waste in the aging waste tanks at the Department of Energy's Savannah River Site (SRS). A robust program is in place to remove waste from these tanks, treat the waste to separate it into a relatively small volume of high-level waste and a large volume of low-level waste, and to actively dispose of the low-level waste on-site. This process allows the US Department of Energy (DOE) to move forward with closure of the cleaned waste tanks and associated ancillary structures. To support performance-based, risk decision making for closure and disposal activities, three individual performance assessments (PAs) have been developed - salt-stone Disposal Facility, F-Tank Farm and H-Tank Farm. In addition, three Waste Determinations (WDs) have been made by the Secretary of Energy, in consultation with the Nuclear Regulatory Commission (NRC), under the authority of Section 3116 of the Ronald W. Reagan National Defense Authorization Act for Fiscal Year 2005 (NDAA Section 3116). To support these waste determination decisions, individual '3116 Basis Documents' were developed that describe the assumptions and conditions under which the criteria outlined in NDAA Section 3116 are met. The development of each of the PAs represented a long and arduous effort that involved the development of both deterministic and probabilistic conceptual models of the facilities, the development of assumptions and associated ranges, uncertainty and sensitivity analyses, model data collection and analyses, writing of the actual performance assessment, internal and external peer reviews, and ultimately approval by DOE. Similarly, the development of the 3116 Basis Documents represents similar time and financial commitments. At the end of these efforts, after years of preparation and millions of dollars in investment, we have thousands of pages of highly technical text, tables of data and hundreds of graphs and charts all contained in a series of thick binders that fit neatly on the shelf of a bookcase. We were done - right? Actually, we were just getting started. Performance Assessments and 3116 Basis Documents are living documents that shape day-to-day and long-term decision making in the operation of a low-level waste disposal facility (e.g., salt-stone Disposal Facility) or in area closure activities (e.g., F-Tank Farm or H-Tank Farm). Although these documents do not contain specifically described requirements per se, they do utilize specific assumptions that, if changed significantly, could result in no longer being able to demonstrate that there is reasonable assurance that the required performance objectives or the criteria from NDAA Section 3116 can be met. Savannah River Remediation LLC (SRR), the contractor responsible for Liquid Waste operations at SRS, has not only developed the PAs and 3116 Basis Documents to support this work and shepherded these documents through the DOE approval process, but has also developed the processes and procedures to ensure the successful implementation and integration of these documents into day-to-day decision making within the associated facilities. This paper describes these processes, including the Un-reviewed Waste Management Question process and the PA Maintenance process, and provides specific examples of their successful implementation. (authors)

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DOE OSTI2016

Utilization and Application of Kurion Mobile Processing System in Remediation of Radioactively Contaminated Water - 16370

Kurion{sup R} Mobile Processing Systems (KMPS) were deployed in Fukushima as first-of-a- kind at-tank isotope removal systems to remediate Sr from reverse osmosis concentrated salt water. The systems were successful in their efforts and achieved their decontamination and availability goals. The use of KMPS has been considered for other applications where a modular system is of benefit. The use of different Kurion Ion Specific Media (ISM) allows for precision removal of hazardous ions from a variety of waste streams. This paper describes a range of projects in which KMPS modularity will benefit the nuclear industry. The KMPS is a flexible system that can be deployed quickly and efficiently. One treatment system option being considered is the utilization of a KMPS for the removal of contamination from groundwater. Similar to its use in Japan, the KMPS can be sent to remote locations for the direct treatment of ground water. In particular, there are several sites across the world where uranium contamination is a problem. Uranium treatability testing was performed on collected groundwater samples from a radiologically contaminated site. The tests were used to help provide designs for KMPS modifications. These designs included the addition of chemical treatment module for the control of pH and other chemistry, the addition of an ultraviolet module for the destruction of biological material, among others. The tests determined the loading capacities of uranium capture resins (UCR) and media (UCM) for this specific waste stream. Based on uranium loading capacities of 37.3 mg/L (end of test C/C{sub 0} = 0.5) and 54.6 mg/L (extrapolated to C/C{sub 0} = 0.98), and the longevity of the resin (45,911 BV for C/C{sub 0} = 0.5, and 80,556 BV for C/C{sub 0} = 0.98) UCR-1 was selected as the media/resin to be proposed for a uranium treatment system. (authors)

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DOE OSTI2017

Decontamination of Irradiated Nuclear Graphite Using High Temperature Molten Salt - 17447

Irradiated graphite is one of the most significant, large volume waste streams in the UK. After shut down of gas cooled reactors there will be ∼96,000 tonnes of nuclear graphite arising from pressure vessels, sealed or unsealed stacks, temporary surface storage and in silos, which may account for up to 30% by ILW volume of any future UK geological disposal facility. High temperature molten salt treatment (HMST) could be considered as a partitioning process of the activation and fission products from irradiated graphite. The main objective of the research is to optimize a specific graphite treatment technology compatible with older, current and future reactors to provide a safe and effective process to decontaminate graphite and reduce the waste inventory. In order to reach that purpose principal radionuclides contained in irradiated samples from Magnox reactors were investigated by germanium (Ge) gamma spectrometry. The next key tasks were to employ treatment at 450 deg. C in LiCl-KCl eutectic which included the following procedures: electrochemical cleaning of the salt, initial cyclic voltammetry (CV) of graphite followed by several steps of chrono-potentiometry (CP) with different current applied and CV was taken after each step. Once the treatment was established, experiments investigating the electro-refinement of the resultant salt mixtures were conducted as well as the comparison of gamma spectroscopy results of graphite before and after the treatment providing the result of total activity reduction of around 60%. (authors)

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DOE OSTI2015

Characterization of DWPF Recycle Condensate Tank Materials (Revision 1)

A Defense Waste Processing Facility (DWPF) Recycle Condensate Tank (RCT) sample was delivered to the Savannah River National Laboratory (SRNL) for characterization with particular interest in the concentration of I-129, U-233, U-235, total U, and total Pu. Since a portion of Salt Batch 8 will contain DWPF recycle materials, the concentration of I-129 is important to understand for salt batch planning purposes. The chemical and physical characterizations are also needed as input to the interpretation of future work aimed at determining the propensity of the RCT material to foam, and methods to remediate any foaming potential. According to DWPF the Tank Farm 2H evaporator has experienced foaming while processing DWPF recycle materials. The characterization work on the RCT samples has been completed and is reported here.

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DOE OSTI2019

Characterization and CST Batch Contact Equilibrium Testing of Aged TCCR Tank 10H Batch 1A and 2 Process Supernate Samples

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DOE OSTI2020

Characterization and CST Batch Contact Equilibrium Testing of Modified Tank 9H Process Supernate Samples in Support of TCCR

The Tank Closure Cesium Removal (TCCR) system uses ion exchange columns filled with crystalline silicotitanate (CST) media to process radioactive waste solutions for the removal of ¹³⁷Cs. TCCR currently focuses on dissolving Savannah River Site (SRS) radioactive tank waste (primarily sodium saltcake solids) within Tank 10H followed by at-tank ion exchange column treatment. Two supernate batches from Tank 10H have been processed through the TCCR unit and processing of a third batch is expected soon. After processing of this supernate batch, plans are to replace the CST columns and process dissolved salt solution from Tank 9H through Tank 10H and then through the new CST columns installed in the TCCR unit. The new columns are expected to contain either a media similar to an archived CST batch (IE-911) or the R9120-B CST media used in the current TCCR columns (the two materials are fundamentally the same; just different specifications, product names, and preconditioning steps). Samples of Tank 9H dissolved saltcake were received at the Savannah River National Laboratory (SRNL) and characterized. The Tank 9H supernate contained a high sodium concentration (~9.6 M Na⁺) and will require dilution to near 6 M [Na⁺] prior to processing through the TCCR unit. The cesium concentration in Tank 9H is currently significantly higher than was observed with Tank 10H. Three dilutions of the Tank 9H supernate were conducted to mimic possible dilutions that could be conducted in the tank farm prior to TCCR processing using inhibited water, sodium hydroxide, and sodium nitrate solutions. Dilution #1 was prepared by diluting the Tank 9H supernate by a factor of 1.6 with inhibited water, Dilution #2 was prepared by diluting the Tank 9H supernate by a factor of 3.7 with a mixed sodium hydroxide/sodium nitrate diluent, and Dilution #3 was prepared by also diluting by a factor of 3.7 but with sodium hydroxide only. All three dilutions have similar Na⁺ concentrations (~6 M), but Dilutions #2 and #3 contain significantly less cesium. Major and key minor components of the diluted Tank 9H supernate samples are provided in Table ES-1. Batch contact equilibrium tests were conducted with the Tank 9H dilutions and the two different CST media batches being considered for use in the new TCCR columns. Results are summarized in Table ES-2 and compared to ZAM model predictions. The highest cesium distribution coefficient and percent removal were observed with Dilution #3. IE-911 CST (an archived CST media batch) was more effective at removing cesium than the more recently prepared R9120-B CST media, though both media samples removed >88% of the cesium and the differences may not be statistically different considering the overall uncertainty. Based on the results, maximum cesium loadings were calculated for each CST media type and Tank 9H dilution. In general, maximum cesium loadings from dilutions of this supernate batch are quite high (approaching 0.1 mmol total Cs⁺/g CST for Dilution #1). The highest calculated maximum ¹³⁷Cs loading for the Tank 9H dilutions using the ZAM model with input of the tank compositions and batch contact results was 207 Ci/kg CST (Dilution #1 with IE-911 CST). In all cases, higher maximum cesium loading values were predicted for IE-911 CST versus R9120-B, although the differences varied considerably between the dilutions. The maximum loading value for IE-911 CST with Tank 9H Dilution #1 was only 7% higher than the maximum loading for R9120-B. The maximum loading value for IE-911 CST with Dilution #3 was 24% higher than the maximum loading for R9120-B. Dilution #2 was intermediate between these values. Note that these maximum loading values are the theoretical calculated values, and actual operating conditions will cause differences. A CST binder dilution (correction) factor near 0.7 (relative to pure powder CST) was required for each batch contact test with IE-911 engineered CST using the three Tank 9H dilutions. Correction factors calculated for R9120-B CST ranged from 0.56 to 0.66 for the three dilutions. Following the batch contact tests, the CST samples were isolated from the Tank 9H solution, washed, dried, and digested in acid following established procedures. The analysis results are provided in Table ES-3. Total cesium loading values determined by CST digestion were similar to the calculated loading values based on solution analysis (Table ES-2) for all samples. In addition, the CST was observed to load calcium (R9120-B sample only), iron, strontium, lead, uranium, and plutonium after contact with the waste supernate, as has been observed previously.

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DOE OSTI2013

In-Situ Testing and Performance Assessment of a Redesigned WIPP Panel Closure - 13192

There are two primary regulatory requirements for Panel Closures at the Waste Isolation Pilot Plant (WIPP), the nation's only deep geologic repository for defense related Transuranic (TRU) and Mixed TRU waste. The Federal requirement is through 40 CFR 191 and 194, promulgated by the U.S. Environmental Protection Agency (EPA). The state requirement is regulated through the authority of the Secretary of the New Mexico Environment Department (NMED) under the New Mexico Hazardous Waste Act (HWA), New Mexico Statutes Annotated (NMSA) 1978, chap. 74-4-1 through 74-4-14, in accordance with the New Mexico Hazardous Waste Management Regulations (HWMR), 20.4.1 New Mexico Annotated Code (NMAC). The state regulations are implemented for the operational period of waste emplacement plus 30 years whereas the federal requirements are implemented from the operational period through 10,000 years. The 10,000 year federal requirement is related to the adequate representation of the panel closures in determining long-term performance of the repository. In Condition 1 of the Final Certification Rulemaking for 40 CFR Part 194, the EPA required a specific design for the panel closure system. The U.S. Department of Energy (DOE) Carlsbad Field Office (CBFO) has requested, through the Planned Change Request (PCR) process, that the EPA modify Condition 1 via its rulemaking process. The DOE has also requested, through the Permit Modification Request (PMR) process, that the NMED modify the approved panel closure system specified in Permit Attachment G1. The WIPP facility is carved out of a bedded salt formation 655 meters below the surface of southeast New Mexico. Condition 1 of the Final Certification Rulemaking specifies that the waste panels be closed using Option D which is a combination of a Salado mass concrete (SMC) monolith and an isolation/explosion block wall. The Option D design was also accepted as the panel closure of choice by the NMED. After twelve years of waste handling operations and a greater understanding of the waste and the behavior of the underground salt formation, the DOE has established a revised panel closure design. This revised design meets both the short-term NMED Permit requirements for the operational period, and also the Federal requirements for long-term repository performance. This new design is simpler, easier to construct and has less of an adverse impact on waste disposal operations than the originally approved Option D design. The Panel Closure Redesign is based on: (1) the results of in-situ constructability testing performed to determine run-of-mine salt reconsolidation parameters and how the characteristics of the bedded salt formation affect these parameters and, (2) the results of air flow analysis of the new design to determine that the limit for the migration of Volatile Organic Compounds (VOCs) will be met at the compliance point. Waste panel closures comprise a repository feature that has been represented in WIPP performance assessment (PA) since the original Compliance Certification Application of 1996. Panel closures are included in WIPP PA models principally because they are a part of the disposal system, not because they play a substantive role in inhibiting the release of radionuclides to the outside environment. The 1998 rulemaking that certified WIPP to receive transuranic waste placed conditions on the panel closure design to be implemented in the repository. The revised panel closure design, termed the Run-of-Mine (ROM) Panel Closure System (ROMPCS), is comprised of 30.48 meters of ROM salt with barriers at each end. The ROM salt is generated from ongoing mining operations at the WIPP and may be compacted and/or moistened as it is emplaced in a panel entry. The barriers consist of bulkheads, similar to those currently used in the panels as room closures. A WIPP performance assessment has been completed that incorporates the ROMPCS design into the representation of the repository, and compares repository performance to that achieved with the approved Option D design. Several key physical processes and rock mechanics principles are incorporated into the performance assessment. First, creep closure of the salt rock surrounding a panel entry results in consolidation of the ROM salt emplaced in the entry. Eventually, the ROM salt comprising the ROMPCS will approach a condition similar to intact salt. As the ROM salt reaches higher fractional densities during consolidation, back stress will be imposed on the surrounding rock mass leading to eventual healing of the disturbed rock zone above and below the panel closure. Healing of the disturbed rock zone above and below the ROMPCS reduces the porosity and permeability in those areas. Analysis of the new design demonstrates that: (1) the WIPP continues to meet regulatory compliance requirements when the ROMPCS design is implemented instead of Option D, and (2) there is no impact on the short-term effectiveness of the panel closure to limit the concentration of VOCs at the WIPP site boundary to a fraction of the health-based exposure limits (HBLs) during the operational period. (authors)

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DOE OSTI2019

Solid-liquid Separation Testing for the Remediation of Hanford Waste Treatment Plant Low Activity Waste Melter Off-Gas Condensate

The Low Activity Waste (LAW) vitrification facility at the Hanford Waste Treatment and Immobilization Plant (WTP) will generate an aqueous condensate stream (LAW Off-Gas Condensate) from the off-gas system. The plan for disposition of this stream during Direct Feed LAW operations is to transfer it to the Effluent Management Facility (EMF), where it will be concentrated by evaporation and recycled to the LAW vitrification facility again. The primary reason to recycle this stream is so that the semi-volatile 99Tc isotope eventually becomes incorporated into the glass. However, this stream also contains non-radioactive salt components that are problematic in the melter, so diversion of this stream to another process would eliminate recycling of these salts and would enable simplified operation of the LAW melter and the Pretreatment Facilities. This diversion from recycling this stream within WTP would have the effect of decreasing the quantity of glass waste produced by allowing further increases in waste loading, resulting in a shortened LAW vitrification mission duration. The concept being tested here involves selectively removing the 99 Tc so that the decontaminated aqueous stream, with the problematic salts, can be disposed as a different waste form and avoid reprocessing through vitrification.

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DOE OSTI2020

Cesium Removal Performance Comparisons of Crystalline Silicotitanate Media Batches with Savannah River Site Waste Simulant

The Tank Closure Cesium Removal (TCCR) system uses ion exchange columns filled with Crystalline Silicotitanate (CST) media to process radioactive waste solutions for the removal of Cs137. TCCR currently focuses on dissolving Savannah River Site (SRS) Tank 10H waste (primarily sodium salt cake solids) within the tank followed by at-tank ion exchange column treatment. Plans are underway to prepare and install a second TCCR unit at SRS. Capacity and particle size differences exist between archived (IE-911) and more recently-prepared CST media batches (9120- B and 9140-B). Side-by-side comparison testing was performed to evaluate the cesium removal performance of each batch to aid in selecting the preferred CST batch and media characteristics to load into the second TCCR unit. Batch contact equilibrium and flow-through column tests have been conducted with three CST batches using an SRS Average Simulant. Simulant batch contact equilibrium cesium loading results for the three CST batches (including two lots of one batch) are provided in Table ES-1. The 35 °C data indicates that the archived IE-911 batch has a higher cesium capacity than recently-prepared CST media and that the minor TCCR CST 9120-B media lot (2099000035) has similar cesium removal performance to the major TCCR lot (2099000034). Tests conducted at 25 ºC for the archived IE-911 CST batch indicated lower cesium removal performance with this simulant batch than was observed recently with a different SRS Average Simulant batch. A dilution factor (DF) is typically utilized when modeling engineered CST media cesium loading performance to account for mass contributions from the binder material. In cases where CST performance is lower than expected, this factor includes corrections for the binder and for low performance. The ZAM (Zheng, Anthony, and Miller) Isotherm Model DF values are provided in Table ES-1 for each simulant batch contact result. DF values near 0.5 were determined for the 9120-B and 9140-B CST batch contact tests while DF values near 0.6 (20% higher) were determined for the tests with IE-911. These dilution factors are lower than recently observed with a different SRS Average Simulant batch (9140-B DF = 0.68; IE-911 DF = 1.0). Based on these results, it appears that some component in the simulant solution used for equilibrium testing may have resulted in reduced cesium loading on the CST media.

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DOE OSTI2016

Developing a Signature Based Safeguards Approach for the Electrorefiner and Salt Cleanup Unit Operations in Pyroprocessing Facilities

Traditional nuclear materials accounting does not work well for safeguards when applied to pyroprocessing. Alternate methods such as Signature Based Safeguards (SBS) are being investigated. The goal of SBS is real-time/near-real-time detection of anomalous events in the pyroprocessing facility as they could indicate loss of special nuclear material. In high-throughput reprocessing facilities, metric tons of separated material are processed that must be accounted for. Even with very low uncertainties of accountancy measurements (<0.1%) the uncertainty of the material balances is still greater than the desired level. Novel contributions of this work are as follows: (1) significant enhancement of SBS development for the salt cleanup process by creating a new gas sparging process model, selecting sensors to monitor normal operation, identifying safeguards-significant off-normal scenarios, and simulating those off-normal events and generating sensor output; (2) further enhancement of SBS development for the electrorefiner by simulating off-normal events caused by changes in salt concentration and identifying which conditions lead to Pu and Cm not tracking throughout the rest of the system; and (3) new contribution in applying statistical techniques to analyze the signatures gained from these two models to help draw real-time conclusions on anomalous events.

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DOE OSTI2015

Leaning the tank closure process at the Savannah River Site - 15515

The Savannah River Site liquid waste system consists of multiple facilities that safely receive and store legacy radioactive waste prior to treatment and disposition. The liquid radioactive waste is stored in large underground tanks. The waste inventory currently stored in these tanks is a complex mixture of insoluble metal hydroxide solids and soluble salt supernate. The high-level (radioactive) portion of the waste is vitrified into a glass waste form, while the low-level waste is immobilized into a cementitious grout waste form called salt-stone. Once the waste is retrieved and processed, the tanks are closed. The closure process includes; waste removal, characterizing residuals, isolating the tank systems, and stabilizing the tank with tailored grout formulations. The core of Lean is to eliminate waste or non-value added steps from processes to maximize customer value. From the perspective of the customer, 'value' is defined as any action or process for which a customer would willingly pay. In this case our product is to safely and efficiently remove waste from the underground storage tanks and demonstrate operational closure to the State of South Carolina. Savannah River Remediation (SRR) initiated the use of the Lean process in late 2013 and identified the Tank Closure process as one of the targeted areas to improve. The first step in the Lean process is to 'map' out the value stream and identify areas where non-value added steps are present and then prioritize Rapid Improvement Events (RIE). Based on this mapping process, there were a number of areas that SRR determined warranted further evaluation for improvements, including; standard equipment design, characterization, standard work packages, regulatory documentation, tank characterization, structural evaluations, engineering documentation and equipment re-use. This paper focuses on the application of the Lean process at SRR and more specifically, effective application to the Tank Closure Process. This paper discusses the value stream mapping process for Tank Closures, as well as, summarizes the RIEs and demonstrate the realized benefits. Benefits can come in a variety of forms, from schedule compression to decreased costs. Through the Lean process we have been able to identify close to $10 M in savings over the life cycle of the tank closure process and a 4 year schedule compression. Cost and schedule savings are used to accomplish further risk reduction efforts. In addition to hard benefits, there are also soft benefits. These soft benefits are a result of the process itself and help drive improved efficiencies through better communication with key stakeholders, such as regulators and customers. (authors)

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DOE OSTI2013

Management of salt waste from electrochemical processing of used nuclear fuel

Electrochemical processing of used nuclear fuel involves operation of one or more cells containing molten salt electrolyte. Processing of the fuel results in contamination of the salt via accumulation of fission products and transuranic (TRU) actinides. Upon reaching contamination limits, the salt must be removed and either disposed or treated to remove the contaminants and recycled back to the process. During development of the Experimental Breeder Reactor-II spent fuel treatment process, waste salt from the electro-refiner was to be stabilized in a ceramic waste form and disposed of in a high-level waste repository. With the cancellation of the Yucca Mountain high-level waste repository, other options are now being considered. One approach that involves direct disposal of the salt in a geologic salt formation has been evaluated. While waste forms such as the ceramic provide near-term resistance to corrosion, they may not be necessary to ensure adequate performance of the repository. To improve the feasibility of direct disposal, recycling a substantial fraction of the useful salt back to the process equipment could minimize the volume of the waste. Experiments have been run in which a cold finger is used for this purpose to crystallize LiCl from LiCl/CsCl. If it is found to be unsuitable for transportation, the salt waste could also be immobilized in zeolite without conversion to the ceramic waste form. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2013

Assessment of the Impact of a New Guanidine Suppressor In NGS on F/H Laboratory Analyses For DWPF and Saltstone MCU Transfers

Implementation of the Next Generation Solvent (NGS) in the Modular Caustic-Side Solvent Extraction Unit (MCU) will now proceed with a new suppressor compound, 1,2,3-tris(3,7-dimethyloctyl)guanidine (TiDG), replacing the originally planned suppressor for NGS, 1,3-dicyclohexyl-2-(11-methyldodecyl) guanidine (DCiTG). The Savannah River National Laboratory (SRNL) was tasked with evaluating the potential impact to F/H Laboratory analyses supporting the Defense Waste Processing Facility (DWPF) Waste Acceptance Criteria (WAC) used to qualify transfers of MCU Strip Effluent (SE) into the facility and the Saltstone WAC used to qualify transfers of Tank 50 containing Decontaminated Salt Solution (DSS) from MCU into Saltstone. This assigned scope is covered by a Task Technical and Quality Assurance Plan (TTQAP). Previous impact evaluations were conducted when the DCiTG suppressor was planned for NGS and concluded that there was no impact to either the determination of MCU SE pH nor the analysis of Isopar ® L carryover in the MCU SE and DSS streams. SRNL reported on this series of cross-check studies between the SRNL and F/H Laboratories. The change in suppressor from DCiTG to TiDG in the NGS should not impact the measurement of Isopar ® L or pH in SE or DSS necessary to satisfy DWPF and Saltstone WAC (Tank 50) criteria, respectively. A statistical study of the low bias observed in Isopar ® L measurements in both SRNL and F/H Laboratories may be necessary now that the final NGS composition is fixed in order to quantify the low bias so that a proper correction can be applied to measurements critical to the DWPF and Saltstone WACs. Depending upon the final DWPF WAC requirement put in place for SE pH, it could become necessary to implement an alternative ICP-AES measurement of boron. The current blended solvent system testing in SRNL should address any impacts to Isopar ® L carryover into either the DSS or the SE. It is recommended that SRNL monitor the current blended solvent work underway with simulants in SRNL as well as any DWPF CPC testing done with the new SE stream to ascertain whether any need develops that could result in modification of any currently planned F/H Laboratory testing protocols.

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DOE OSTI2017

Investigation of variable compositions on the removal of technetium from Hanford Waste Treatment Plant low activity waste melter off-gas condensate simulant

The Low Activity Waste (LAW) vitrification facility at the Hanford Waste Treatment and Immobilization Plant (WTP) will generate an aqueous condensate recycle stream (LAW Off-Gas Condensate) from the offgas system. The plan for disposition of this stream during baseline operations is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility again. The primary reason to recycle this stream is so that the semi-volatile 99 Tc isotope eventually becomes incorporated into the glass. This stream also contains non-radioactive salt components that are problematic in the melter, so diversion of this stream to another process would eliminate recycling of these salts and would enable simplified operation of the LAW melter and the Pretreatment Facilities. This diversion from recycling this stream within WTP would have the effect of decreasing the LAW vitrification mission duration and quantity of glass waste. The concept being tested here involves removing the 99 Tc so that the decontaminated aqueous stream, with the problematic salts, can be disposed elsewhere.

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DOE OSTI2012

Impacts of Antifoam Additions and Argon Bubbling on Defense Waste Processing Facility (DWPF) REDuction/OXidation (REDOX)

Control of the REDuction/OXidation (REDOX) state of glass in High Level Waste (HLW) melters, such as the Defense Waste Processing Facility (DWPF), is critical in order to eliminate the formation of metallic species from overly reduced melts while minimizing foaming from overly oxidized melts. The REDOX control is normally a balance of the oxidants and reductants from the feed and from processing additives. However, after reflux in the Sludge Receipt and Adjustment Tank (SRAT) and the Slurry Mix Evaporator (SME), the balance between the oxidizing salts vs. reducing salts can be altered once the mixture is fed to the melter if the melt pool is bubbled with gaseous species that either oxidize or sparge the melt of oxygen. Hence, for a bubbled melt pool, the REDOX of the melt pool must be targeted based on the balance of the oxidizing and reducing salts from the feed and from the processing additives, as well as, accounting for the effects of any gas being bubbled through the melt to improve convection and mixing while also increasing melt rate. For example, one would not set a REDOX target of Fe 2+ /ΣFe of 0.20 based on chemical balancing and then bubble pure air through the melter as pure air would oxidize the melt pool to an Fe 2+ /ΣFe ~0. Some gases, such as argon, are inert but act as chemical sparging agents or “degassing” agents that can sparge out oxygen from the melt and cause the glass to become more reducing. This study examines DWPF flowsheets at various concentrations of antifoam (a reducing processing additive) in the absence of melt pool bubbling (crucible and production data) and in the presence of melt pool bubbling with argon (crucible and production data), a known sparging/degassing agent. In order to de-convolute the impacts of antifoam on the melt pool REDOX from the impacts of melt pool bubbling, crucible studies were performed with (1) varying antifoam concentrations without bubbling, and (2) minimal antifoam with Ar bubbling. This allowed an antifoam term to be added to the REDOX model and suggested that (1) more oxidizing Fe 2+ /ΣFe ratios could be targeted which would create more oxidizing species in the cold cap to offset the effects of Ar-sparging or (2) Ar-air gas mixtures could be blended with a mixing valve to control the melt pool REDOX at the same Fe 2+ /ΣFe ratios (same –log fO 2 ) as chosen for the chemical REDOX balancing. The 2006 EE REDOX model is an electron equivalents (EE) model that balances the electrons lost during oxidation of a reductant against the electrons gained during the reduction of an oxidant. The EE terms for the formates, nitrates, and oxalates in the REDOX model are based on the formatted salts like NaCOOH, the nitrated salts like NaNO 3 , and the oxalated salts like Na 2 C 2 O 4 that have higher decomposition temperatures than their acidic counterparts which flash off. Thus it is the higher decomposition salts that participate in the establishing the melt REDOX during their interactions in the melter cold cap.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Integrating the Safety Evaluation for a Molten Salt Reactor Operation and Fuel Cycle Facility Application

Molten salt reactor (MSR) sites may include additional elements of the nuclear fuel cycle beyond those of the existing fleet. In the existing fleet, the individual elements of the fuel cycle typically have been located on different sites and licensed separately. Providing robust separation between hazards remains a useful safety practice for MSRs. Although the different elements of the fuel cycle at a nuclear site that includes MSRs may transfer material between processes more frequently than prior practices, providing adequate separation between distinct facilities avoids the potential for adverse interactions. Additionally, some elements of the MSR fuel cycle, such as fuel salt preparation or waste stabilization, may be more efficient to share among multiple nearby reactors, and nuclear sites that include MSRs may also include other reactor classes. Hence, discrete MSR fuel cycle facilities located at a common site could be physically separated with robust barriers—albeit potentially connected by piping—and licensed individually. This report describes the hazards of individual elements of representative MSR fuel cycle facilities, including their relationship to overall site level hazards. The report maps the regulatory compliance aspects of the individual MSR fuel cycle elements (e.g., fuel salt preparation, reactor, waste stabilization) to existing and developing regulations, as well as describes current and developing site-level regulations from an MSR perspective.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗