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At least 361 records · Page 20

Tank 48H Tetraphenylborate Mitigation: Simulant Studies using Sodium Permanganate

Tank 48H currently holds legacy material containing organic tetraphenylborate (TPB) compounds from the operation of the In-Tank Precipitation (ITP) process. TPB was added during the ITP process to precipitate the otherwise soluble cesium as insoluble cesium TPB (CsTPB), but excessive benzene generation from TPB degradation curtailed this treatment method. The contents of Tank 48H, which include approximately 26.000 kg of potassium TPB (KTPB) and trace CsTPB, are not compatible with the waste treatment facilities at the Savannah River Site (SRS) since the organic content and the associated flammability issues pose a challenge to the salt processing and sludge processing facilities within the liquid waste system. An in-tank process to remove (or decompose) TPB safely would be of great value. Previous testing at Savannah River National Laboratory (SRNL) demonstrated the destruction of glycolate via chemical oxidation using sodium permanganate with simulated and radioactive waste. Scoping tests were performed to study the destruction of TPB to determine if the contents of Tank 48H would be amenable to the same type of destruction. Partial destruction of TPB was observed in Tank 48H simulants under mild conditions (e g., pH 11, room temperature) with no definitive indication of benzene generation. To build upon the success of the scoping tests, an additional study was requested to provide a better understanding of the underlying chemistry for Tank 48H content destruction using sodium permanganate. Three experiments were performed with Tank 48H simulants at 40 °C to determine the efficacy of using sodium permanganate for TPB destruction. Three starting pH values were selected: 1) pH 11 for comparison with the previous work at room temperature, 2) pH 10 as the minimum pH recommended by the Corrosion Control Program (CCP) for in-tank processing, and 3) pH 8 to determine the effectiveness of TPB destruction at near neutral pH. While below the allowable pH for the CCP, the experiment at pH 8 was performed to study the TPB-Permanganate reaction under more extreme conditions and further verify the potential for out-of-tank processing.

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An Assessment of the Materials of Construction for the Transfer Lines and Unit Operations Equipment Associated with the Recycle Diversion Process

The Defense Waste Processing Facility (DWPF) processes and vitrifies radioactive waste that it receives from the Concentration, Storage, and Transfer Facility (CSTF) and Salt Waste Processing Facility (SWPF). As a result of the evaporation of water during both the melter feed preparation and the melter feed vitrification steps in DWPF, a recycle waste stream is generated, neutralized, and sent back to the CSTF. The recycle waste is a dilute water stream originating from the collection of condensate liquids containing some minor sludge and frit solids and other waste components primarily resulting from entrainment into the condensate during foam-over events. The recycle stream volume is significant and is expected to approach 3 million gallons per year once the SWPF reaches full operation. Diverting the bulk of the recycle waste stream from the CSTF is essential for the eventual closure of the waste tanks, and hence the completion of the SRS liquid waste mission.

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Radiological Impact of 2020 Operations at the Savannah River Site

This report presents environmental dose assessment methods and the estimated potential doses to the public from 2020 Savannah River Site (SRS) atmospheric and liquid radioactive releases. It also documents potential doses from special-case exposure scenarios, such as the consumption of wildlife and/or goat milk. Unless noted, the generic term “dose,” as used in this report, includes both the committed effective dose (50-year committed dose) from internal deposition of radionuclides and the effective dose attributable to sources external to the body. Using the effective dose allows doses from different types of radiation and to different parts of the body to be expressed on the same basis. Humans, plants, and animals potentially receive radiation doses from natural and man-made occurrences. The average annual “background” dose for all people living in the United States is 625 mrem. This includes an average background dose of 311 mrem from naturally occurring radionuclides (found in our bodies and in the earth) and from cosmic radiation. Man-made sources include medical procedures (300 mrem), consumer products (13 mrem), and industrial and occupational exposures (less than 1 mrem).

54 ENVIRONMENTAL SCIENCES↗

Alternative Liquid DSA Containers for Sludge Slurry Storage in the SRNL Shielded Cells

A pending revision of the Documented Safety Analysis (DSA) for the Savannah River National Laboratory (SRNL) defines “DSA containers” for liquid sludge slurries as containers not susceptible to a flashing spray release in a fire and requires that a list of DSA containers be maintained. High Level Waste (HLW) samples are typically received from the Savannah River Site (SRS) tank farm after retrieval from the storage tanks. Glass bottles are preferred for long-term storage of radioactive liquid sludge slurry samples but are not on the DSA container list. An evaluation has been conducted to identify vessel lids for the glass bottles that would vent prior to pressurization and liquid superheating in a fire event. Low melting Field’s Metal eutectic alloy with a melting point of 62 °C has been identified as a preferred material of construction for vessel lids for this application because the material is resistant to puncture and is expected to have good chemical compatibility and radiation stability in the shielded cells environment. A test vessel was designed to evaluate the alloy and confirm that it would melt before the water in the vessel reaches the boiling point. The tests confirmed: 1) that the reported melting point of the alloy was accurate, 2) that a top fashioned from this material will melt creating an open atmosphere in the vessel headspace prior to sample boiling under moderate and fast heating rates, and 3) that nonuniform heating of the bottle from the bottom also results in melting of the alloy prior to boiling. Based on the results, neither an engulfing fire with standing or toppled bottles or a fire producing localized heat at the vessel bottom would result in flashing spray conditions.

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Residual Insoluble Solids Expected from Saltcake Dissolution

A review of previous SRS saltcake dissolution and characterization studies was performed to inform the analysis of the amount of residual insoluble solids that may result from saltcake dissolution. A realistic value covering most cases for the maximum volume of a settled layer of residual insoluble solids that would result from dissolution of a volume of saltcake was calculated as 0.08 mL/mL (8 vol%). Applying factors to account for dissolution test uncertainty and differences between in-tank settling and laboratory testing, the recommended value for a settled layer of residual insoluble solids that would result from dissolution of a volume of saltcake is 0.16 mL/mL (16 vol%). This should apply to dissolution of saltcake with typical minimal amounts of entrained sludge but may not apply to saltcake with significant sludge. As it is composed of primarily non-radioactive isotopes, the precipitated aluminum hydroxide material does not contribute to the heat load.

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Installation of Lysimeters and Monitoring Wells in Support of the Revised Approach to E-Area Performance Monitoring

Savannah River Site (SRS) has developed a revised approach to performance monitoring of the E Area Low Level Waste Facility (ELLWF) that adds a saturated zone component to the existing vadose zone monitoring program (Kubilius, 2019). The revised approach specifies modifications to the vadose zone monitoring program, the addition of new lysimeters at Engineered Trench 3 (ET3), and the installation of water table monitoring wells to complement the existing well network surrounding the ELLWF. This project summary report is intended to provide the final construction details and layout for the new vadose zone lysimeters at ET3 and the water table monitoring wells installed as part of the new saturated zone component of the revised performance monitoring program.

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Modeling of Glycolate Destruction in the Recycle Collection Tank

The Savannah River Site’s DWPF is being upgraded with the introduction of the NG flowsheet. Glycolic acid has been shown to be a superior alternative to formic acid for sludge processing. The new flowsheet improves or maintains necessary parameters such as 1) reduction of mercury, 2) adjustment of feed rheology, 3) pH stability, and 4) adjustment of melter oxidation/reduction potential. Further, the use of glycolic acid virtually eliminates the potential for catalytic hydrogen generation in DWPF processing DWPF process condensates are collected and returned to the Savannah River Site (SRS) CSTF. The RCT collects off-gas condensate during chemical processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF. Each batch of recycle will have a small amount of glycolate from chemical processing and melter off-gas condensates. To avoid potential flammability issues due to thermolysis of glycolate in the CSTF, Savannah River National Laboratory (SRNL) provided to Savannah River Remediation (SRR) at their request a Task Technical and Quality Assurance Plan (TTQAP) to quantify and mitigate glycolate returns via DWPF’s recycle stream. The request included testing of a process to oxidize glycolate and other organic species that are responsible for hydrogen generation from thermolysis. Following that work SRR provided a Task Technical Request (TTR) that requested process modeling. In 2021 a TTQAP was issued to cover the modeling work. Modeling draws data from laboratory scale studies using chemical simulants and radioactive waste samples. Chemical kinetic modeling was performed to evaluate the feasibility of using sodium permanganate to destroy glycolate in the RCT. The results from the laboratory studies were summarized in a series of reports. Reference 9 is a report of lab scale processing of actual DWPF Slurry Mix Evaporate Condensate Tank (SMECT) and Offgas Condensate Tank (OGCT) samples in the SRNL Shielded Cells. Tests at caustic conditions demonstrated sodium permanganate was effective in converting glycolate to oxalate, and permanganate (Mn 7+ ) is reduced to manganate (Mn 6+ ) with no significant formation of carbon dioxide or carbonate. Equation (1) was found to best describe the observed reaction of glycolate with permanganate under nominal (60 to 145 mg/L in RCT) glycolate entrainment conditions.

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Appropriateness and Readiness of Cold Crucible Vitrification of Calcine Solids at the Idaho Site and H-Canyon Effluent at the Savannah River Site

This report summarizes the results from an assessment of the technology readiness and deployment of cold crucible induction melter (CCIM) technology to vitrify high level waste (HLW) calcine solids at the Idaho Site and H-Canyon liquid effluent at the Savannah River Site (SRS). The assessment was requested by the Department of Energy’s Office of Environmental Management (DOE-EM), but is not a DOE 413-3-4a assessment for technology deployment. A joint Savannah River National Laboratory (SRNL) and Fluor Idaho Cleanup Project (ICP) team with subject matter experts evaluated the existent literature and experience both within the DOE as well as relevant external experience. The technology assessment focused on the site-specific technology readiness and appropriateness based on a number of system factors including feasibility and appropriateness of the technology for the specific site application, the potential extent of the regulatory and design challenges, and evaluation of the ability to deploy within the treatment needs of each site. This initial assessment provides information to support DOE-EM in making a go/no-go decision to carry out additional work on the technology maturation for critical decisions and planning.

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Flowsheet for Conversion of Anion Resin from Nitrate to Sulfate Form for Disposal

Nitrate form anion exchange resins are specifically prohibited for disposal in TRU waste. At some DOE sites, spent resin was mixed with cement to immobilize the resin in a monolith with varying success. At SRS starting in the 1980s, spent anion resin has generally been converted to a more chemically stable form or it was digested with permanganate and transferred as a slurry to the HLW tank farm. In the early years of the site it is reported that over 20 metric tons of organic resin were transferred directly to the tank farm without any attempt to digest it. It appears that in the future conversion to a stable sulfate form could well be the favored disposal path for spent nitrate-form anion resin. This report will document the site history of converting between ionic forms (nitrate to sulfate) and will document process flowsheet conditions for performing that conversion.

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Molecular and Microstructural Bases for Understanding Microplastic Origin, Transport, and Fate

The formation of micro and nanoplastics from parent plastics is one of the most challenging ecological threats since plastic pollution reaches even the most desolate places on earth and is expected to double by 2030. The goal of this project is to understand physico-chemical properties on microplastics formation, transport, and fate by analyzing the microplastics found in environmentally collected samples at SRS, supported by lab-based experiments. An initial assessment found and identified microplastics and micronizing plastics in Fourmile Branch and the Savannah River. Fourmile Branch also carried trace-level radioactive contaminants associated with the Site’s legacy missions, which may incorporate into entrained microplastics.

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Small Reactors in Microgrids: Technical Studies Guidance

This report provides initial guidance for the technical studies that are needed for the integration of small reactors (SR)—i.e., small modular reactors (SMR) and microreactors—in microgrids. Power-system engineering issues related to the configuration of these microgrids and their interconnection and interaction with the grid are identified. This guidance applies microgrid concepts to the deployment of SRs for a range of use cases (scenarios). Further, it identifies issues and necessary studies related to laboratory testing and validation of various configurations of SR in microgrids.

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VERSE-LC TCCR Model Calibration using Batch 1A, Batch 2, and Batch 3 Column Data

The objective of this work is to utilize on-line gamma monitoring data collected during Tank Closure Cesium Removal (TCCR) Column Batch 3 operations to calibrate the parameters (essentially, the correction/dilution factors (CF or DF)) used in the VERSE-LC models for the prediction of cesium breakthrough while processing Savannah River Site (SRS) Tank 10H dissolved saltcake High-Level Waste through a packed cylindrical bed of Crystalline Silicotitanate (CST). Calibrated VERSE-LC models could be applied to aid in evaluating future TCCR operations.

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Characterization of Surface Water Dynamics within Fourmile Branch and its Linkages with Groundwater and I-129 Geochemistry

This research work has been supported by the DOE-FIU Science & Technology Workforce Development Initiative, an innovative program developed by the U.S. Department of Energy’s Environmental Management (DOE-EM) and Florida International University’s Applied Research Center (FIU-ARC). During the summer of 2021, DOE Fellow intern, Stevens Charles, spent 10 weeks doing a summer internship at Lawrence Berkley National Laboratory (LBNL) under the supervision and guidance of Dr. Haruko Wainwright from LBNL and Dr. Hansell GonzalezRaymat from Savannah River National Laboratory (SRNL). The intern’s project was initiated on June 1, 2020, and continued through August 6, 2020, with the objective of characterizing the surface water dynamics in the F-Area of Savannah River Site (SRS) and analyzing the surface water dynamics to find any linkages with groundwater and Iodine-129(I-129) geochemistry.

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SRNL EPC Installation Report

During the week of August 25th, 2021, three Electric Phenomenon Cluster (EPC) sensors were installed at the Savannah River Site (SRS) owned, Dominion Energy (DE) operated 504-2G substation.

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IC Report for project “Developing nonlinear laser-plasma instability models for high-fidelity, multi-physics simulation capability for ICF/HED” [Slides]

We’ve achieved our technical goals: (1) Perform large-scale kinetic simulations of SRS and CBET a range of plasma and laser conditions; (2) Develop a new $\delta f$-Gaussian-mixture algorithm to represent non-Maxwellian distribution functions from particle trapping and time-dependent plasma response; (3) Develop physics-based preliminary nonlinear LPI models for coupling to LRT/ Mazinisin and AMP; and (4) Begin implementation of LPI sub-grid models into Mazinisin.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Interactions between molecular-scale processes and hyporheic exchange for understanding Fe-S-C cycling in riparian wetlands (Final Report)

Wetlands represent some of the most productive ecosystems on the planet and critically influence global environmental health. Specifically, wetlands promote water quality by transforming nutrients and organic compounds and sequestering metals and contaminants. Riparian wetland hyporheic zones, where toxic surface water and anoxic groundwater mix, exhibit dynamic conditions that drive steep redox gradients and promote hotspots of diverse and fluctuating microbial activity. Changes in climate, water quality, and water quantity can disturb hydrologic flow and biogeochemical processing in these environments. Understanding how sulfate loading, impacted by hydrologic flux and anthropogenic inputs, influences iron and carbon cycling in wetlands will be crucial for predicting water quality issues driven by iron mineral precipitation and sorption, such as the release of heavy metals and other toxic elements. We used a fully integrated multi-scale and multi-method approach to develop a mechanistic understanding of how hydrologic flow influences coupled iron and sulfur cycles in riparian wetlands. This entailed hydrological, geochemical, and microbial observations at two locations: an anthropogenic sulfate-impacted riparian wetland in northern Minnesota, and a low-sulfate Fe-rich riparian wetland in Tims Branch at the Savannah River Site (SRS). These sites were characterized by hydrologically dynamic conditions where the stream and wetland systems oscillated between gaining (upward flow) and losing (downward flow) conditions that recharged the system occasionally with oxidants that fueled a variety of biogeochemical reactions. Aqueous geochemical measurements of surface water, groundwater, and porewater samples were made alongside solid-phase geochemical analyses of sediment gravity cores. Bulk X-ray absorption spectroscopy at the Advanced Photon Source (APS; Argonne) interrogated the speciation and distribution of Fe and S mineral phases of the sediments. Interestingly, it was discovered that, despite strongly reducing conditions, Fe(III) compounds and a variety of intermediate valence S compounds were stable in the subsurface. Indeed, compounds like thiosulfate, S(0), and intermediate valence organosulfur compounds were more prevalent than FeS and pyrite. The composition of the sediments did change with changes in hydrologic flow, showing their reactivity in changing redox conditions. The abundance of these intermediate S compounds was likely formed as a result of anaerobic oxidation by aqueous and solid-phase Fe(III) compounds, fueling a cryptic S cycle that is driving the breakdown of organic matter in the hyporheic zone. Microbiome surveys showed a core community that seemed stable across the landscape, but changed with increasing depth into the sediment. The community composition did not seem to change dramatically with changes in season or hydrologic flow, except for some organisms that have the potential to contribute to S cycling. More work is needed to confirm their functional activity. These fine process-scale analyses were placed within a dynamic field context using physical flow parameters from surface water and groundwater level measurements. These data helped shed light on sulfur-driven biogeochemical processes in hydrologically dynamic riparian wetlands, addressing a gap in our understanding about the impacts of pollution and other anthropogenic changes on ecologically sensitive environments.

54 ENVIRONMENTAL SCIENCES↗

IDP Analysis of Tank 9H Mined Well Samples

The Savannah River Site (SRS) Tank Farm Transfer Control Program Description Document (PDD) requires Inhalation Dose Potential (IDP) testing to determine whether a transfer qualifies as a “HIGH-REM” (> 2.08E+08 rem/gal) or a “LOW-REM” (≤ 2.08E+08 rem/gal) waste transfer. Due to the unexpected presence of solids in a variable depth sample taken from Tank 9H, transfers from salt tanks potentially containing insoluble solids are currently being assessed as sludge slurry transfers. The insoluble solids concentration of such samples were requested to be adjusted to 16.7 wt% for the results to be used to bound future transfers from that tank. Two samples, HTF-09-21-100 and -101, were received from Tank 9H for analysis to determine IDP. The initial percent insoluble solids concentrations of HTF-09-21-100 and -101 were measured at 4.04 wt% and 6.23 wt%, respectively. Sample HTF-09-21-101 was adjusted to a target of at least 16.7 wt% insoluble solids by removing supernate. Analysis measured the adjusted insoluble solids concentration at 19.0 wt%. A representative sample was obtained for analysis. Then, based on calculations, supernate was added back to HTF-09-21-101 to achieve a percent insoluble solids concentration of 17.1 wt%, and a representative sample was collected for analysis. Based on duplicate analyses at 17.1 wt% and 19.0 wt% insoluble solids, the samples contain less than 0.0012 Ci/L of gross alpha activity. Therefore, the Tank 9H material can be transferred as a “LOW REM” transfer.

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Results of the Analyses of the SRNL Solvent Components

At the request of the Savannah River Mission Completion (SRMC), personnel at Savannah River Site (SRS) performed analyses on the remaining solvent components that are being stored at the Savannah River National Laboratory (SRNL). This was done to determine if the remaining stock of materials were still suitable for use for the Salt Waste processing Facility (SWPF). Two drums of Modifier, two drums BOBCalix, four drums of MAXCalix, and four jars of TiDG*HCl were analyzed. All were found to be of acceptable purity for use.

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