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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Spent Crystalline Silicotitanate Storage Study

Washington River Protection Solutions is working to support initial production of immobilized low-activity waste (LAW) by feeding Hanford tank supernate from tank farms to the Hanford Waste Treatment and Immobilization Plant (WTP) LAW Facility. This goal incorporates the design of a Tank-Side Cesium Removal (TSCR) system, which filters tank waste supernate to remove suspended solids and then removes Cs by processing it through crystalline silicotitanate (CST) ion exchange media manufactured by Honeywell UOP, LLC. The 137 Cs-depleted product is intended to be sent to the WTP for vitrification. The Cs-loaded CST columns will be stored indefinitely, with a goal of eventual CST removal and treatment. Thus, the spent CST needs to be recoverable. The testing described herein looks to potential upset process conditions where CST storage may be required before various rinse steps are completed. This study evaluated upset conditions at three sequential processing steps envisioned for TSCR (feed, 0.1 M NaOH rinse, water rinse), and in-column drying with compressed air (normal end step) to assess impacts on the nature of the CST bed. Testing was conducted at the small scale (12-mL bed volume); simulated AP-105 tank waste was used as the feed. Following process disruption, the CST bed was dried in place at 70 °C. Post-dried CST bed physical properties (angle of repose, penetration depth, particle morphological changes) were measured to evaluate how CST moved and flowed. The testing is intended to provide a preliminary assessment of issues that may arise from desiccation of CST with the indicated salt solutions in place. Since these were small-scale tests, the processing conditions will not match full scale conditions exactly; however, the tests do provide insight into the impact of stopping processing at an earlier step than normal. Except for the feed that was dried in-place, all other process stop-conditions showed the CST bed flowed well after drying. At this small scale, CST beds would not present an issue for retrievability. The feed that was dried in place had solidified into a rock-hard monolith with no movement possible. Samples had to be chipped from the surface.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
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.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Organic Evaporation and Oxidation Testing in Support of Hanford Sample-and-Send

The Hanford site has approximately 56 million gallons of radioactive mixed waste stored in 177 underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the tank waste. The baseline method for immobilization of Low Activity Waste (LAW) through the WTP is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. An alternative cementitious waste form is being investigated for that future immobilization method to supplement vitrification. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste. This work evaluates potential avenues to eliminate that impediment to permit possible use of a cementitious waste form and work towards a decision whether additional LDR organic pretreatment would be required. Savannah River National Laboratory (SRNL) performed testing using simulants to examine evaporation as a method to remove some prevalent organics from LAW. Spiking the caustic LAW simulant with selected regulated organic chemicals found one that clearly decomposes because of caustic instability. Oxidation testing of other organic chemicals found some LDR organics degrade as desired and others are stable in the presence of peroxide and permanganate. In addition to studies with simulants, a literature review was performed to evaluate radiological stability of LDR organics. Descriptions of the experimental details, equipment, and results are included in this report. Evaporation testing consisted of preparing the LAW simulant, spiking that simulant with organic chemicals, and evaporating the mixture via differential distillation. The apparatus was a laboratory-scale vacuum evaporator operated at 60 ±5 torr absolute (vacuum evaporation) and also at atmospheric pressure. The LAW simulant represented the liquid expected to be retrieved from the Hanford tank farms at approximately 4.0 M [Na + ] total sodium ion concentration. The concentration of the organic chemicals added was significantly higher than typically found in the tank waste samples since the higher levels were necessary to assist in analytical measurement and tracking of the spiked species. Organic chemicals were chosen for the work with a consideration of how their volatility compares with that of methanol. This was done by comparing the ratio of the pure water Henry’s law coefficient (K h ) of methanol to that of the compound in question (hereafter termed the K h ratio), where ratios above unity indicated less volatility than methanol. Methanol was chosen because it is a common regulated chemical with relatively low volatility but which has been removed by evaporation in previous laboratory work. While organic separation results depend on evaporator design, laboratory experiments verified that organic partitioning to the overhead condensate stream by evaporation is a practical process. The work reported here found difficulties in quantitative analysis of the organic chemicals in aqueous samples. Most of the time there was insufficient analysis to close a mass balance for evaporator runs, but qualitative evidence of carryover was obtained. The methods were also able to show whether organic chemicals were susceptible or resistant to solution oxidation in permanganate or hydrogen peroxide tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Organic Evaporation, Oxidation, and Hydrolysis Testing in Support of Hanford Sample-and-Send

The Hanford site has approximately 54 to 56 million gallons of radioactive mixed waste stored in 156 unretrieved underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the tank waste. The baseline method for immobilization of Low Activity Waste (LAW) through the WTP is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. An alternative cementitious waste form is being investigated for that future immobilization method. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste, which are regulated on a concentration based standard in the final waste form. Hence, if the quantity of organics in LAW is high enough, they must be destroyed or removed to make a waste form compatible with disposal in a mixed low level waste landfill. This work evaluates potential avenues for treatment of LDR organics to eliminate the impediment and permit possible use of a cementitious waste form. Vacuum evaporation testing to remove LDR organics consisted of preparing a non-radioactive LAW simulant, spiking that simulant with organic chemicals, and evaporating the mixture via differential distillation. The apparatus was a laboratory-scale vacuum evaporator operated at 60 ±5 torr absolute (vacuum evaporation). The LAW simulant represented the liquid expected to be retrieved from the Hanford tank farms at approximately 4.0 M [Na+] total sodium ion concentration. The concentration of the organic chemicals added was significantly higher than typically found in the tank waste samples since the higher levels were necessary to assist in analytical measurement and tracking of the spiked species.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Evaluation of Sludge Solids Returns Impacts on Sludge Batch 10 Flammability, Glass Quality, and Glass Processability

The Savannah River National Laboratory (SRNL) is currently preparing to return ≤ 20 kgs of sludge solids collected over time from Tank Farm characterization activities and demonstrations of the Defense Waste Processing Facility (DWPF) flowsheets (nitric-formic and nitric-glycolic). These sludge solids will be transported and added to Tank 51 which is currently preparing Sludge Batch (SB) 10. DWPF plans to operate the under the nitric-glycolic flowsheet for the processing of SB10. The hydrogen generation rate for the nitric-glycolic flowsheet is 0.024 lb h -1 . The addition of ≤20 kg of sludge solids returns to SB 10 does not have an impact on flammability in the DWPF Chemical Process Cell (CPC) or glass quality and processability. The relatively low mass of the addition (≤20 kg) is insufficient to detect a significant analytical change to the expected SB 10 compositions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Online Alpha Monitoring of High Cs-137 Hanford and SRS High Level Waste with Tensioned Metastable Fluid Detectors

The Department of Energy’s Hanford and Savannah River Sites maintain millions of gallons of caustic supernate and salt high activity waste in their high-level waste (HLW) tank farm inventories. The Savannah River Site is currently treating this waste with a calixarene-based solvent extraction of Cs-137 to reduce these inventories. Hanford is employing an at-tank crystalline silico titanate (CST) based solid phase extraction methodology to reduce their liquid HLW inventories. Due to the high solubility of Cs-137 and the relative insolubility of the actinides in these caustic waste forms, the beta to alpha radioactivity ratio can often exceed six orders of magnitude in the feed solutions to these treatment processes. This unique characteristic leads to significant technical challenges in making rapid gross alpha measurements in the presence of the overwhelming beta, gamma, as well as dissolved sodium salt in these HLW matrices. Conventional radioanalytical techniques, such as liquid scintillation analysis or gas flow proportional counting require significant radiochemistry preparation prior to the radiometric measurements for gross alpha activity. These required pretreatments render these technologies untenable for rapid quantification of gross alpha activity that could be required to support on or at-line measurements ensuring a waste stream will meet regulatory requirements. The radiation measurement properties of Tensioned Metastable Fluid Detectors (TMFDs) have been studied by Purdue University’s Taleyarkhan research group for well over a decade. Fluids tensioned to the appropriate degree will rupture when struck by radiation, resulting in a measurable cavitation event. The negative pressure generating this tension can be adjusted by centrifugal rotation or by acoustic means in such a way that these cavitation events can be generated from alpha radiation but will not be generated by beta or gamma radiation. Purdue University and the Savannah River National Laboratory are currently collaborating to develop a gamma/beta blind, spectroscopic alpha measurement system based on the Tensioned Metastable Fluid Detector technology to provide a potential solution for performing rapid gross alpha measurements on these high gamma/beta sample matrices. Measurements using the Indirect Drive Acoustically Tensioned Metastable Fluid Detectors developed as part of this collaboration were performed with an alpha emitting radionuclide. Successful determination of gross alpha activity was observed, indicating a potential pathway for rapid gross alpha measurements in remote-handled shielded cells or in process situations requiring online alpha monitoring. Measurements using this system have been conducted on high beta activity solutions, demonstrating the beta blind capability of this system. Measurements are currently underway to test the system’s capability to measure gross alpha activity on Savannah River Site high level waste high Cs-137 samples that have been measured by the SRNL radiochemistry team. This work was supported by the DOE EM Technology Development program.

DiPrete, David [Savannah River National Laboratory↗
DOE OSTI2020

Testing of Crystalline Silicotitanate to Support Tank-Side Cesium Removal System Operations - 20458

The direct feed of waste from the Hanford tank farms to the Low-Activity Waste Facility at the Hanford Waste Treatment and Immobilization Plant requires an intermediate treatment step that prepares the waste for vitrification. Washington River Protection Solutions (WRPS) selected a near-tank treatment system known as the Tank-Side Cesium Removal (TSCR) system to perform the required intermediate treatment functions. The approach in the TSCR system is to filter waste supernatant with a sintered metal dead-end filter and then use a series of ion exchange columns to remove cesium; this system has several similarities to the Tank Closure Cesium Removal system that has been deployed on the Savannah River Site. The ion exchange media proposed for use is crystalline silicotitanate (CST), which is a non-elutable media with a high affinity for cesium. Because the media is non-elutable, loaded columns will be blown down with compressed air, moved into interim storage, and replaced with new columns when cesium capacity is reached. The assumed extent and rate of drying that could be achieved in the TSCR column geometry lacked confirmation by experimental data. In addition, once the columns are loaded with cesium, they generate flammable gases (primarily hydrogen) via radiolysis acting on any resident liquids, i.e., moisture, remaining in the media bed. An assessment of available information on CST concluded that gas generation data that bounds expected operational conditions were needed to support the TSCR system safety basis and planned operations. Working with WRPS, Pacific Northwest National Laboratory (PNNL) designed and conducted testing with CST media to address the need for (a) representative in-column drying data, and (b) bounding flammable gas generation data. Drying testing was performed using a full-height column with a diameter of approximately 2 inches with injected air at temperatures of 18 deg. C and 30 deg. C. Gas generation testing was conducted in an engineered bunker that allowed simultaneous irradiation of up to eight samples at a time. These two experimental approaches used at PNNL for the CST testing are summarized and the major outcomes are presented. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Advancements of On-Line Monitoring and Real-Time Characterization of Actual Low-Level Hanford Tank-Waste Samples

Waste and process stream characterization is essential to the safe, efficient, and cost-effective processing of Hanford Site materials. The demand for materials characterization including chemical, radionuclide, and physical attributes during waste management, transfer, and staging operations in the Hanford tank farms is expected to significantly increase as the U.S. Department of Energy River Protection Project progresses toward Hanford waste treatment and immobilization. Our past work has applied Raman on-line monitoring and chemometric modeling to the supernate of Hanford tank 241-AP-105 and has demonstrated the quantitative measurement of nine analytes within this waste. To demonstrate broader applicability, this method has now been expanded to waste from two additional Hanford tanks, AW-102 and AP-107, and the offgas condensate from lab-scale melter runs of actual-tank waste feeds. To enhance the performance of the Raman method, instruments with various excitation wavelengths were compared, since it is known that the Raman response is enhanced by shorter wavelength excitation. The laser excitations for the three systems tested were 404 nm, 532 nm, and 671 nm. In addition to laser wavelength selection, the laser power, measurement integration times, and signal averaging techniques were also investigated to determine their effect on detection limits for oxy-anion analytes within tank wastes. These advancements in Raman capability are compared with past standards and will be presented.

Bryan, Samuel A.↗
DOE OSTI2020

Overview of 2016 through 2018 Testing of Air-Purifying Respirator (APR) Cartridge Performance on Multiple Hanford Tank Headspaces and Exhausters

Between 2016 and 2018, 28 air purifying respirator (APR) cartridge tests were performed on headspace vapors from seven Hanford waste storage tanks (SY-102, A-101, BY-108, AX-101, BY-110, SX-101, and SX-104) and seven waste tank exhausters (AP in 2016, AP in 2018, 702-AZ, AN and AW in 2016, and AX and 702-AZ in 2017). All but two tests were conducted under static conditions absent waste-disturbing activities in the subject tanks or tank farms. The two exceptions were cartridges tested with vapors from 702-AZ in 2017 when samples were taken during waste-disturbing activities. Multipurpose APR cartridges, SCOTT 7422-SD1 and 7422-SC1, were tested on samples from each of the 14 tanks or exhausters. Out of 612 Chemicals of Potential Concern (COPCs), only ammonia, mercury, N-nitrosodimethylamine (NDMA), 2,5-dimethylfuran, 2,5-dihydrofuran, furan, and 1,3-butadiene exhibited breakthroughs with outlet concentrations that were >10% of their Occupational Exposure Limits (OEL).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

The Utility of Waste Tank Historical Reviews in Bulk Waste Removal Operations at the Savannah River Site – 25271

SRMC is actively working to remove, treat, and dispose radioactive waste generated by the separation facilities at SRS since their initial operations in the 1950s. The separation facilities at SRS have produced nuclear materials for a variety of purposes, particularly national defense, and continue to support the disposition of spent fuel through the Accelerated Basin Deinventory program. In almost 70 years of operation, nearly 625,000 m3 (165 million gallons) of radioactive waste have been generated and transferred to the tank farm facilities at SRS [1]. As a result of volume reduction (e.g., evaporation) and waste solidification (e.g., vitrification), approximately 127,000 m3 (33.5 million gallons) of material remain as of June 30, 2024 [2]. This liquid waste has since been stored in 51 large underground waste tanks present on the site. These waste tanks may contain up to 4,921 m3 (1.3 million gallons) of radioactive waste each in the form of saltcake or sludge. SRMC’s contract is to treat and dispose of this waste, clean the tanks, and operationally close them. To date, 8 of the 51 waste tanks have been operationally closed. Waste retrieval and tank closure activities are ongoing in an additional 17 tanks through either operations in the field or in design [3].

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

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.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Technology and Innovation Roadmap

This Technology and Innovation Roadmap outlines the Hanford Tank Waste Operations & Closure, LLC (H2C) strategic approach for advancing the Hanford Tank Waste Treatment Mission (HTWTM) through technology development. Our focus is on addressing technology needs that address risks, enhance efficiency, ensure worker safety, and uphold environmental standards. This Roadmap identifies key technology initiatives essential for the successful completion of the Hanford Site tank waste cleanup. Updated annually, it incorporates insights from the U.S. Department of Energy (DOE), the Integrated Tank Disposition Contractor (ITDC) H2C, recognized national lab experts, and fieldwork specialists. The Roadmap includes approximately 100 technology elements, each detailed in Technology Element Description Summaries (TEDS) and summarized in catalog sheets. These elements are crucial for aligning technology development activities with mission objectives across the HTWTM. With the initiation of the Direct-Feed Low-Activity Waste (DFLAW) program and the operation of the Tank Side Cesium Removal (TSCR) system, our focus now shifts to the support of scaled up production in East Area; applying similar and exploring new treatment alternatives to West Area Tank Waste; and advancing retrieval, delivery and treatment technologies for waste managed as high-level waste (HLW) across the Hanford tank farms. This transition is reflected in the technology and maturation (TM&E) charts, which highlight the evolving technology priorities. This document serves as a guide for navigating the challenges and opportunities in technology development at the Hanford Site.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Application of On-Line Monitoring and Real-Time Characterization of Low Level Waste Samples from Hanford Tanks

Waste and treatment stream characterization is an essential part of safe, efficient, and cost-effective processing of Hanford materials. The demand for materials characterization, including chemical, radionuclide, and physical attributes during waste management, transfer, and staging operations in the Hanford tank farms, is expected to significantly increase as the U.S. Department of Energy Office of River Protection (ORP) progresses toward Hanford waste treatment and immobilization. The application of on-line monitoring can greatly improve operation timeframes and reduce costs by providing real-time data and supporting the reduction of necessary grab sample collection. Recently, our team applied Raman online monitoring and chemometric modeling to the supernate of Hanford tank 241-AP-105, and demonstrated the quantitative measurement of nine analytes within this waste. Application of this method has been expanded to additional Hanford tank wastes, AW-102 and AP-107. The performance of the process monitoring instruments and the accuracy of the chemometric models will be assessed. On-line monitoring results will be compared to anion results determined from the current standard, ion-chromatographic and inductively coupled plasma mass spectrometry methods. Comparisons of both determined values and uncertainties of results will be presented. Results will be shared with personnel working on flowsheet interfaces for the Direct-Feed Low Activity Waste mission at Hanford.

Lines, Amanda M.↗
DOE OSTI2020

Application of On-Line Monitoring and Real-Time Characterization of Low Level Waste Samples from Hanford Tanks - 20380

Waste and treatment stream characterization is an essential part of safe, efficient, and cost-effective processing of Hanford materials. The demand for materials characterization, including chemical, radionuclide, and physical attributes during waste management, transfer, and staging operations in the Hanford tank farms, is expected to significantly increase as the U.S. Department of Energy Office of River Protection (ORP) progresses toward Hanford waste treatment and immobilization. The application of on-line monitoring can greatly improve operation time frames and reduce costs by providing real-time data and supporting the reduction of necessary grab sample collection. Recently, our team applied Raman online monitoring and chemometric modeling to the supernate of Hanford tank 241-AP-105, and demonstrated the quantitative measurement of nine analytes within this waste. Application of this method has been expanded to additional Hanford tank wastes, AW-102 and AP-107. The performance of the process monitoring instruments and the accuracy of the chemometric models will be assessed. On-line monitoring results will be compared to anion results determined from the current standard, ion-chromatographic and inductively coupled plasma mass spectrometry methods. Comparisons of both determined values and uncertainties of results will be presented. Results will be shared with personnel working on flowsheet interfaces for the Direct-Feed Low Activity Waste mission at Hanford. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

WRPS Hanford Update [Slides]

The purpose of this report is to coordinate with the staff from WRPS, the current contract holder for operations at the Hanford site to better inform design decisions for the Autonomous systems for Hanford waste tank handling project. The project goals are to support risk reduction associated with monitoring, inspection and mapping of Hanford tank underground pits and includes: 1. A pit mock-up demonstration of Idaho National Laboratory’s (INL) Autonomous Pit Exploration System (APES) technology, which has two configurations: A. The Autonomous Robotic Arm, which is a proposed collaboration with Florida International University (FIU) and has capabilities to visually inspect, monitor, map and conduct simple tool manipulation tasks in the tank pits, and B. The robotic crawler configuration, which has capabilities to deploy to the bottom of the pits and conduct closer and bottom-up visual inspections. 2. An Implementation Plan that identifies Hanford site-wide application of the INL remote robotics technologies to enhance the performance of the tank farm systems and the characterization of the waste they contain to mitigate risk and optimize the overall waste mission. 3. A first-of-a-kind environmental digital twin will be produced. Digital twins to date require permanently installed sensors in order to produce asset specific predictions. This project will use the intermittent signals during inspections from deployed sensors on robotic systems to produce the data sets used by AI/ML to enable predictions of issues on tanks.

42 - ENGINEERING↗
DOE OSTI2020

Panel Session 88: Waste Management from Remediation of Legacy Sites or Unplanned Releases

This panel focused on the progression of cleanup on the Hanford Site, Washington, USA, from establishing the regulatory framework necessary for cleanup, to understanding the risks and addressing near-term hazards, to moving to 24/7 operations as cleanup focuses on tank waste treatment and co-located risk reduction efforts as the active cleanup footprint shrinks. Panelists with presentations: Hanford: Past, Present, Future (Brian Vance); Protecting the River (L. Ty Blackford); Hanford Tank Farms (John Eschenberg Jr.); The Hanford Site (Robert Wilkinson); The Hanford Site (Valerie McCain)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

DOE Hanford Tank Side Cesium Removal System (TSCR) Update: Fabrication and Factory Acceptance Testing - 20300

The Tank Side Cesium Removal (TSCR) System is a modular, quickly-deployable, and passively safe system for efficiently removing solids and cesium from alkaline liquid waste raffinate created by fuel processing on the Hanford site. This paper provides an overview of the project with particular emphasis on completion of fabrication and factory acceptance testing (FAT). All TSCR System components are inside three enclosures known as the Process Enclosure, Ancillary Enclosure, and Control Enclosure. The Process Enclosure is seismic design category II (SDC-II) and built to withstand the rigors of transportation and lifting, high winds, volcanic ash fall, and heavy precipitation (snow) over a temperature range of -25 to 115 deg. F. The Process Enclosure and Control Enclosure were fabricated in AVANTech's Columbia, SC facility, while the Ancillary Enclosure was fabricated in AVANTech's Richland, WA facility. The design and preliminary documented safety analysis were completed in December 2019, with all work being performed in accordance with ASME NQA-1 quality assurance requirements. The Process Enclosure, Ion Exchange Columns (IXCs), and several other TSCR components have a nuclear safety function and are designated as safety significant structures, systems, and components (SS-SSCs). The NQA-1 Commercial Grade Dedication (CGD) process was used to identify critical characteristics in order to accept materials and items used for fabrication of several safety significant TSCR components. This paper also addresses unique aspects and challenges of implementing CGD in DOE facilities and systems. After fabrication and preliminary testing, the Process and Control Enclosures were shipped to AVANTech's Richland facility where the complete TSCR System was setup and connected in a represented layout and configuration that will be used on the Hanford site. Test tanks and pumps were put in place and connected to the TSCR Process Enclosure in a manner that mimicked interfacing Double Shell Tanks in the 241-AP Tank Farm. The TSCR System was then tested/operated under conditions equivalent to those planned for onsite operation. Testing was separated into five separate phases as defined below: - Phase 1: Confirmation of TSCR System readiness for the FAT; - Phase 2: Verification of TSCR System operation under standard conditions; - Phase 3: Demonstration of TSCR System operation under non-standard conditions; - Phase 4: Demonstration of ion exchange media removal from an IXC; and - Phase 5: Completion of TSCR System lift plans and site mobilization. The Hanford Tank Operations Contractor, Washington River Protection Solutions (WRPS), participated in all phases of testing. Testing at AVANTech's Richland Facility allowed WRPS personnel to familiarize themselves with TSCR operations in a radiologically clean facility prior to onsite mobilization. Engineering and operations personnel gained valuable experience that allowed them to better refine onsite operational protocols and procedures - including handling and movement of IXCs with a forklift. This paper describes the technologies used by the TSCR System as well as how these technologies are deployed and operated to advance the Hanford mission of safely, efficiently, and effectively treating tank waste. It also provides detailed information on fabrication and FAT, including operational data from simulated tank waste runs. A project schedule for WRPS' planned construction acceptance testing, operational acceptance testing, and actual tank waste treatment is provided. This presentation should be of great interest to parties responsible for the design, testing, and mobilization of modular NQA-1 technologies for the treatment of raffinate and similar liquid wastes containing high concentrations of radioactive cesium. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Assessment of Methane Generation from the Thermolysis of Organics in Caustic Waste

Methane generation has been detected during thermolytic Hydrogen Generation Rate (HGR) testing of SRS tank waste and in simulant samples. Simulant testing has shown methane generation in the presence of trimethylsilanol (TMS) and radioactive sample testing has shown methane generation in presence of methylmercury, both of which are found within SRS waste tanks. The 2019 report Evaluation of the Current State of Knowledge for Thermolysis of Organics within SRS Waste Forming Volatile Organic Compounds (VOCs) reviewed historical data and assessed literature pertaining to thermolytic methane generation. That review recommended undertaking thermolysis studies on simulated waste to detect and quantify VOCs. The purpose of this assessment is to review chemistry and current knowledge of organics in SRS waste to recommend which organics in SRS waste tanks, if any, should be tested for thermolytic methane generation. An evaluation of observed methane generation rates has been performed to assess the implication for current CSTF controls. Based on the inputs used in this report, it was concluded that no methane generation data observed to date has challenged the existing 5% organic contribution to the Composite Lower Flammability Limit (CLFL) assumption in the CSTF tank farm at temperatures below 100 °C. Evidence shows that thermolytic pathways to methane generation become significant at temperatures >100 °C in caustic waste. Currently, the influences of thermolytic methane production on the flammability of vessels at >100 °C (e.g., evaporators) is unclear. It is recommended that testing should be undertaken using the HGR experimental approach for methane generation. The initial simulant testing should obtain quantitative methane generation rates at elevated temperatures for methylated siloxanes/silanes and methylmercury with the goal of determining the current mechanism for thermolytic methane generation seen in SRS tank waste. The results of this testing should then be compiled and analyzed to ascertain the risk of challenging the current projected organic contribution of 5% to the CLFL at elevated temperatures. Following this testing, an evaluation of possible flammable gas generation in the 2H and 3H Evaporators should be performed to assess the risk of methane generation at the high temperatures employed by the evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗