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At least 199 records · Page 11

Building 100 Groundwater Bioremediation at the Former DOE Pinellas Plant, Florida: Review of Progress and Opportunities

Weapons research, development, and production operations at the former Pinellas Plant, which includes the Building 100 area, released chlorinated organic solvents into the subsurface, contaminating the underlying soil and groundwater. The site was sold to Pinellas County and is now home to a thriving industrial park known as the Young - Rainey Science, Technology, and Research (STAR) Center. The US Department of Energy (DOE) has applied bioremediation at the Building 100 Area as a key technology to clean up the chlorinated volatile organic compound (cVOC) contamination in soil and groundwater. The monitoring data indicate significant progress toward remedial objectives over the past two decades. Starting conditions in the 1980s-1990s included areas containing residual undissolved dense nonaqueous phase liquids (DNAPLs) and the associated presence of an extensive high concentration plume in the groundwater. The original parent cVOCs were primarily tetrachloroethene (PCE) and trichloroethene (TCE). After several informative pilot studies, bioremediation was implemented at the Building 100 Area of the site and relies on reductive biological pathways and the sequential removal of chlorine from the parent cVOCs forming dichloroethane (DCE) and chloroethene (vinyl chloride, VC). As bioremediation sites evolve toward cleanup, the trends in VC concentrations often serve as a critical indicator for progress and remediation timeframe because VC typically has a lower concentration target remedial objective (nominally 1 to 2 μg/L) compared to PCE and TCE (nominally 3 to 5 μg/L).

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Innovative Strategies for Long-Term Monitoring of Complex Groundwater Plumes at DOE’s Legacy Sites (Workshop Report)

Most remaining Department of Energy (DOE) sites will require extended periods of institutional control, especially at complex groundwater sites where attenuation-based strategies have been implemented to facilitate closure. The current practice of monitoring—obtaining and analyzing contaminant concentration in groundwater samples at numerous wells—will account for a large portion of the projected life-cycle at these DOE sites unless a new approach is adopted. State-of-the-art technologies are being developed, including in situ sensors, geophysics, radiation mapping, numerical modeling and AI/ML. These technologies can optimize monitoring strategies in space and time, provide spatially extensive information at vulnerable regions and/or provide more continuous monitoring at lower cost. As part of DOE’s Office of Environmental Management (DOE-EM’s) efforts to advance long-term monitoring systems, an in-person/virtual hybrid workshop was hosted by Savannah River National Laboratory (SRNL) on January 24 and 25, 2023, in Augusta, Georgia. Because DOE-EM’s complex sites will eventually be transferred to DOE’s Office of Legacy Management (DOE-LM), representatives of DOE-LM were important participants in the workshop. The purpose of the workshop was to identify challenges and opportunities for deploying advanced technologies for long-term monitoring at DOE sites. The key questions during the workshop were: 1) the regulatory acceptance of replacing a process that traditionally has used laboratory sampling and analysis of groundwater samples, and 2) the application of this strategy to the southwestern arid sites that include many of the remaining DOE-EM and DOE-LM complex groundwater plumes. Characteristics common to most arid sites present both limitations and opportunities for advanced technologies. DOE-EM has funded a National Laboratory team from SRNL, Lawrence Berkeley National Laboratory (LBNL), and Pacific Northwest National Laboratory (PNNL) to establish the overarching framework of long-term monitoring by systematically combining advanced hardware and software technologies. This project is titled “Advanced Long-Term Environmental Monitoring Systems (ALTEMIS)” and is sponsored by the DOE-EM Technology Development Program. The multi-laboratory team is currently developing and testing innovative monitoring strategies, including the use of in situ groundwater sensors, geophysics, drone/satellite-based remote sensing, reactive transport modeling, and artificial intelligence/machine learning (AI/ML). The project’s demonstration testbed is at the Savannah River Site (SRS) F-Area Seepage Basins, where a well-characterized complex groundwater plume composed of uranium and other radionuclides is in the latter stages of remediation. The workshop included more than 70 participants, presentations, a field visit to F-Area, breakout working groups, and large group discussion. Participants developed recommendations on five topics: in situ sensors, spatially integrative tools, challenges to regulatory acceptance, AI/ML strategies, and transitioning sites to DOE-LM.

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Coordination Chemistry in the Structural and Functional Exploration of Actinide-Based Metal-Organic Frameworks

The coordination chemistry between inorganic and organic species can be optimally exemplified by metal–organic frameworks (MOFs), whose structures and functionalities can be rationally designed from these highly tunable building blocks. The high porosity, stability, and versatile functionalities of MOFs have attracted wide-spread attention from energy-related research and pollution remediation to biomedical applications. A unique and underexplored subset of these materials are MOFs based on actinide nodes; these MOFs have distinguished themselves as a unique platform for investigating the versatile oxidation states, reactivity, and coordination chemistry of actinides. Herein, we will focus on the rational design and synthesis of actinide-based MOFs under the general guidelines of coordination chemistry for their structural and functional explorations. The dimensionality, topology, and structures of actinide-based MOFs can be controlled by selecting pre-designed building blocks of actinide-based nodes and organic linkers with certain desired coordination geometries and functionalities. Furthermore, these unique actinide-based MOFs have shown promise for applications in nuclear waste mitigation, pollution control, and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Functionalized Mesoporous Carbon and Silica for Effective Recovery of Rare Earth Elements from Magnet Scrap

The dependence on international supplies of rare earth elements (REEs) has prompted the US to explore alternative sources and sustainable technologies for domestic REE production. One potential source is the secondary electronic and industrial wastes across the US. These hazardous wastes require high costs for the maintenance and remediation, while their high-REE contents offer unique opportunities for REE recovery. However, current hydrometallurgical technologies for REE extraction are energy intensive and costly, with low REE recovery efficiency and the generation of hazardous secondary wastes. Thus, it is beneficial to develop environmentally friendly technologies for REE extraction from the secondary wastes. This project aims to develop novel functionalized mesoporous carbon fiber (MCF) and silica materials for effective recovery of REEs from NdFeB magnet scrap.

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Evaluation of Dose- and Risk-Based Groundwater Cleanup Levels for Low Energy Beta Radioisotopes

Low-energy beta-emitting radionuclides that were released historically during reactor operations and plutonium separations activities at some U.S. Department of Energy sites have migrated into the groundwater, forming contaminant plumes that are subject to federally regulated remediation actions. At the Hanford Site, the low-energy beta-emitting radionuclides include iodine-129, technetium-99, chlorine-36, carbon-14, and tritium (H-3). All are highly mobile in the subsurface, and except for tritium, and have very long half-lives—thousands to millions of years. The geochemistry and transport behavior of these contaminants in the subsurface present significant challenges for remediation of groundwater to federal drinking water standards (DWS)—the appropriate or relevant and applicable requirements (ARARs) for cleanup. For some of the low-energy beta-emitter contaminants, particularly iodine-129, cleanup and restoration of groundwater to DWS may not be attainable within a reasonable timeframe using currently available treatment technologies.

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Saltstone third quarter calendar year 2019 (3QCY19) toxicity characteristic leaching procedure (TCLP) results

The aqueous waste from Tank 50 (salt solution) is sampled quarterly for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TAR-Z-00008, Revision 01, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the third quarter of calendar year 2019 (3QCY19). One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample”. Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Remediation (SRR). After a 28 day cure, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The 3QCY19 saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC.

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Summary of Results from Batch 1 Qualification Samples for Tank Closure Cesium Removal 1A (TCCR 1A)

Savannah River Remediation (SRR) is currently operating the Tank Closure Cesium Removal 1A (TCCR 1A) process to remove 137 Cs from tank waste supernate using an ion exchange process. As part of that process, Savannah River National Laboratory (SRNL) receives and analyzes samples in support of the qualification of each waste supernate batch to be processed. SRNL recently received supernate samples retrieved from Tank 10H as well as in-tank batch contact samples for characterization in support of qualifying Batch 1 for processing through the TCCR 1A unit.

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Testing of Turner Manufacturing Wastewater Remediation Products in Advanced Bioreactor Systems

LANL received three types of simulated wastewater (oil-contaminated soil within a water matrix; commercial laundry; cheese production), which were treated with a corresponding biological agent (enzyme and/or microbial blend) provided by the company. Experiments were set up according to their instruction within an automated bioreactor/fermenter and monitored over time. Aliquots were obtained for total organic carbon (TOC), flow cytometry, Biological Oxygen Demand, Chemical Oxygen Demand.

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Additional Analysis of the 2H-Evaporator Wall Scale Sample HTF-17-57

Savannah River National Laboratory previously analyzed scale samples from both the wall and cone sections of the 242-16H Evaporator prior to chemical cleaning. The samples were analyzed for uranium and plutonium isotopes required for a Nuclear Criticality Safety Assessment of the scale removal process. The analysis of the scale samples found the material to contain crystalline nitrated cancrinite and clarkeite and significant amounts of mercury. Savannah River Remediation subsequently requested additional analyses on the samples. Inspection of the sample bottles revealed that no sample remained of the cone scale (HTF-17-56) while approximately 4 g of the wall scale sample (HTF-17-57) remained. The wall sample was subsequently ground with a mortar and pestle, at which time it was discovered that the sample contained a significant amount of liquid, metallic mercury. The portion of the sample that was not mercury was approximately 3 g. This portion of the sample was analyzed to determine the concentrations of selected radionuclides. The following radionuclide concentrations were measured: <9.6E+02 dpm/g H-3, 2.9E+02 dpm/g C-14, 5.6E+03 dpm/g Tc-99, and 1.6E+02 dpm/g I-129. Blank samples were also analyzed to evaluate sample contamination from the Shielded Cells environment. All blank sample results were below detectable limits. Due to the limited sample size and the anticipated low levels of the target radionuclides, no replicate sample analysis was conducted.

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Characterization of Tank 9H Salt Dissolution Batch 2A in Support of Tank Closure Cesium Removal (TCCR) 1A Batch 2 Preparations

Savannah River Remediation (SRR) is currently preparing the second batch of material to be processed through the Tank Closure Cesium Removal (TCCR) 1A system. The feed for TCCR 1A consists of dissolved saltcake from Tank 9H. The first batch of salt to make up Batch 2 (Batch 2A) has been dissolved in Tank 9H and will later be transferred to Tank 10H. Savannah River National Laboratory (SRNL) received samples from the batch of dissolved salt for characterization.

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Characterization of Americium and Curium Complexes with the Protein Lanmodulin: A Potential Macromolecular Mechanism for Actinide Mobility in the Environment

Anthropogenic radionuclides, including long-lived heavy actinides such as americium and curium, represent the primary long-term challenge for management of nuclear waste. The potential release of these wastes into the environment necessitates understanding their interactions with biogeochemical compounds present in nature. Here, we characterize the interactions between the heavy actinides, Am 3+ and Cm 3+ , and the natural lanthanide-binding protein, lanmodulin (LanM). LanM is produced abundantly by methylotrophic bacteria, including Methylorubrum extorquens, that are widespread in the environment. We determine the first stability constant for an Am 3+ -protein complex (Am 3 LanM) and confirm the results with Cm 3 LanM, indicating a ~5-fold higher affinity than that for lanthanides with most similar ionic radius, Nd 3+ and Sm 3+ , and making LanM the strongest known heavy actinide-binding protein. The protein’s high selectivity over 243 Am’s daughter nuclide 239 Np enables lab-scale actinide-actinide separations as well as provides insight into potential protein-driven mobilization for these actinides in the environment. The luminescence properties of the Cm 3+ -LanM complex, and NMR studies of Gd 3+ -LanM, reveal that lanmodulin-bound f-elements possess two coordinated solvent molecules across a range of metal ionic radii. Finally, we show under a wide range of environmentally relevant conditions that lanmodulin effectively outcompetes desferrioxamine B, a hydroxamate siderophore previously proposed to be important in trivalent actinide mobility. Overall, these results suggest that natural lanthanide-binding proteins such as lanmodulin may play important roles in speciation and mobility of actinides in the environment; it also suggests that protein-based biotechnologies may provide a new frontier in actinide remediation, detection, and separations.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Analysis of Defense Waste Processing Facility Sample: Off-Gas Condensate Tank Sample Batch 27862

The Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (now Savannah River Mission Completion (SRMC)), through a Technical Task Request (X-TTR-H-00107), to characterize the “as-received” Off-Gas Condensate Tank (OGCT) Sample identified as sample batch 27862, which was delivered to SRNL Shielded Cells on April 30, 2021. This OGCT report is the third of three sample characterization reports dealing with this Defense Waste Processing Facility (DWPF) Recycle Diversion Project. The other two recycling stream characterization reports are the Recycle Collection Tank (RCT) and the Slurry Mix Evaporator Condensate Tank (SMECT) sample report.

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Saltstone First Quarter Calendar Year 2021 (1QCY21) Toxicity Characteristic Leaching Procedure (TCLP) Results

The aqueous waste from Tank 50 (salt solution) is sampled quarterly for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TTR-Z00023, Revision 0, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the first quarter of calendar year 2021(1QCY21). One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample”. Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Remediation (SRR). After at least 28 days cured, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The 1QCY21 saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC that was in effect at the time of the tank sampling.

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Saltstone Third Quarter Calendar Year 2021 (3QCY21) Toxicity Characteristic Leading Procedure (TCLP) Results

The aqueous waste from Tank 50 (salt solution) is sampled quarterly for transfers to the Saltstone Production Facility (SPF). Salt solution is treated at SPF and disposed of in the Saltstone Disposal Facility (SDF). Per request of customer, X-TTR-Z-00023, Revision 0, two SDF waste form (saltstone) samples were prepared in the Savannah River National Laboratory (SRNL) from the Tank 50 Waste Acceptance Criteria (WAC) sample and Z-Area premix material for the third quarter of calendar year 2021(3QCY21). One sample contained a Full Premix which included 10:45:45 (by weight) of cement, slag and fly ash. The second sample contained 60:40 (by weight) of slag and fly ash only referred to as the “Cement-Free grout sample”. Results from this technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request (TTR) prepared by Savannah River Remediation (SRR). After at least 28 days cured, a sample of each of the SDF waste forms was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure (TCLP). The 3QCY21 saltstone (Full Premix) and the Cement-Free grout samples met the South Carolina (SC) Code of Regulations for Hazardous Waste Management Regulations (HWMR) 61-79.261.24 and 61-79-268.48 requirements for a non-hazardous waste form with respect to Resource Conservation and Recovery Act (RCRA) metals and Underlying Hazardous Constituents (UHCs), and also met the SPF WAC that was in effect at the time of the tank sampling.

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Geophysical Imaging of Flow and Transport (GIFT): FY24 Status Report

The GIFT (Geophysical Imaging of Flow and Transport) system will improve predictive capabilities as a platform for collecting multi-physical (MP) time-lapse datasets from well-controlled laboratory experiments. This will enable more accurate prediction of multi-phase fluid flow during delivery and transport of insitu remedial amendments as important components of the overall Hanford Site cleanup mission. Design and construction of the GIFT system, which consists of a meter-scale test cell and a network of custom gas circulation and analysis systems, was accomplished in fiscal year (FY) 2024, with plans to add liquid circulation to the system and use this new capability for multi-phase deep vadose experiments starting in FY25.

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Summary of Results from November 2021 Qualification Samples for Tank Closure Cesium Removal 1A (TCCR 1A)

Savannah River Remediation (SRR) is currently operating the Tank Closure Cesium Removal 1A (TCCR 1A) process to remove 137 Cs from tank waste supernate using an ion exchange process. As part of that process, Savannah River National Laboratory (SRNL) receives and analyzes samples in support of the qualification of each batch to be processed. SRNL recently received supernate samples retrieved from Tank 10H as well as in-tank batch contact samples for characterization in support of qualifying Batch 1 for processing through the TCCR 1A unit.

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Conceptual Model Update of Mercury Sources and Flux at Y-12 and Upper East Fork Poplar Creek, Oak Ridge,Tennessee

The interactions between the key processes that control the fate and transport of mercury (Hg) in the sediments, groundwater, and stream water within the Y-12 National Security Complex (Y-12) in Oak Ridge, Tennessee are complex, and many aspects are not well understood. In contaminated environments such as Y-12, conceptual models are frequently developed to aid in visualizing and understanding the dynamic nature of the hydrologic, geochemical, and physical environment. These conceptual models integrate data in an internally consistent manner to understand processes that control the fate and transport of contaminants. Over the past few decades of environmental investigation at Y-12, a number of conceptual models have been developed to identify and define various technical processes at various scales. The main purpose of the activities described in this report is to update the 2011 conceptual model for Upper East Fork Poplar Creek using the most recent Hg concentration and flux data and informed scientific interpretation. Emphasis was placed on improving the previous model by implementing a more detailed spatial and temporal approach to visualize transport pathways in the watershed and trends in flux and concentration over time, and to compare baseflow and stormflow system dynamics. Detailed descriptions of historical and current Hg sources and transport pathways are also provided for the east and west ends of the facility. This conceptual model will allow the US Department of Energy to evaluate past and present remedial activities and provide a strong technical basis for prioritizing and optimizing remedial responses in a cost-effective and efficient manner. Twenty years ago, Hg flux from Outfall (OF) 200 at the headwaters of East Fork Poplar Creek represented approximately 20% of the overall flux leaving Y-12. By the time of the 2011 conceptual model report, that percentage had increased to 70%–80%. Flux estimates compiled for this report using data from 2009 to 2018 show that OF200 accounted for roughly 60% of the flux leaving Y-12. The relative role of the four storm drain conduits to OF200 appeared similar to 2011, with OF163 being the greatest contributor to downstream flux. An increase in Hg concentrations and flux occurred throughout and downstream of west end storm drains in 2011 in response to a storm drain cleanout. Leading up to the 2011 storm drain cleanout, annual baseflow flux was higher at OF200A6 than at Station 17. From 2011 to 2018, the trend reversed with concentrations and flux being higher at Station 17 than at OF200A6. A spike in concentrations occurred in July 2018, potentially due to a one-time influx of Hg that occurred during COLEX decontamination and decommissioning activities at Y-12. This report includes recommendations for improving our conceptual understanding of Hg sources, transport pathways, and flux at Y-12. Important recommendations include further evaluation of transport pathways, concurrent measurement of Hg concentration and flux under baseflow and stormflow conditions at multiple sites, and research to understand the connections among periphyton and methylmercury concentration, bioavailability, and bioaccumulation. Ongoing facility decontamination and decommissioning efforts, site characterization, remedial actions, and research are facilitating the collection of new Hg data at Y-12. The conceptual model update provided herein takes advantage of the extensive recent Hg sampling to provide an updated assessment of Hg mass balance and support a refined understanding of Hg behavior at or near Y-12. This assessment should assist in future environmental management decisions and in mitigating the impacts of Hg on the surrounding environment.

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Results of Speciation Determination Measurements of Insulating Sulfur Hexafluoride Gas

Under the direction of the NNSA NA-231 Mo-99 Program, SRNL has provided technical assistance to U.S. companies under cooperative agreements. One such area of technical assistance has been for the recommendation for contamination management methods in the eventuality that tritium contaminates the insulating gas of a high-voltage ion source used in the accelerator-based process developed by SHINE Medical Technologies to produce Mo-99. The SHINE accelerator process uses tritium as the target of a deuterium ion beam, where the ion beam is produced within a high-voltage ion source insulated with sulfur hexafluoride (SF 6 ), and is separated from the tritium target by an extensive pump train. Normal operating conditions preclude the conditions necessary for contamination of the insulating gas, however certain atypical conditions could result in a tritium contamination event. Accelerator based processes for medical isotope production represent an anomalous tritium contamination challenge due to the presence of SF 6 . SF 6 decomposes through normal use as an insulator gas, and the exact speciation of the decomposition byproducts depends on a variety of factors. This creates a scenario where the anticipation of species present in the insulating gas mixture is difficult. In turn, the fate of tritium within such a chemical system is unclear. This document discusses the results of measurements made in-situ of the SF 6 insulating gas in use within a SHINE Medical Technology’s high-voltage ion source. This was done in an effort to determine the chemical speciation of the gas, allowing for the recommendation of management strategies in the event that tritium contaminates the insulating gas. The results of the measurements reported in this work suggest that tritium contamination in the insulating gas may result in two chemical forms of tritium in the system, tritiated water and molecular tritium. These two forms of tritium would be captured by two methods. Tritiated water may be captured and removed from the SF 6 by an adsorbent canister already present within the pressure vessel that houses the insulating gas while in use. It may also be separated from the SF 6 during routine purification of the SF 6 , which is performed by SHINE personnel routinely. The purification cart will perform all non-embedded systems cleanup necessary to remediate tritiated species in the system. The purification cart passes the insulating gas through several filters, followed by the liquefication of the SF 6 . The filters will separate tritiated water from the SF 6 at this stage. It is expected that molecular tritium will accumulate in the gas-phase during the liquification step, which is separated and stored. Tritium may be recovered from this mixture through more conventional hydrogen purification methods such as a palladium diffuser.

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