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At least 127 records · Page 7

Analysis in Support of Disposition of Tank 48 Legacy Material

This report contains the characterization of six 200-mL Tank 48H samples: HTF-48-21-74, HTF-48-21-75, HTF-48-21-76, HTF-48-21-81, HTF-48-21-82, and HTF-48-21-83. The effort supports a Systems Engineering Evaluation (SEE) recommendation involving a Tank 48H decantation strategy that would remove liquid volume and grout the solids. The first three Tank 48H samples were surface samples taken after a quiescent period in the tank. The quiescent period allowed settling of the solids, these being mostly potassium tetraphenylborate. These three surface samples had no measurable solids, though a settling haze could be seen. The latter three samples were taken at 48, 25, and 10 inches from the bottom of Tank 48H immediately after tank mixing pumps had been run. Those samples contained measurable insoluble solids that were readily visible. All six samples were analyzed to provide chemical and radionuclide concentrations as defined as the "Limit" and "Target" in the Saltstone Production Facility (SPF) Waste Acceptance Criteria (WAC) and per the compliance strategy in the Tank Farm Waste Compliance Plan (WCP). Samples were analyzed by many methods to determine pH, density/specific gravity, radioactive isotopes, soluble and insoluble elements, total solids, total insoluble solids, organic and inorganic mercury, volatile and semi-volatile chemicals, and anions. Photographs of the settling of small samples were taken over time and are displayed in this report. The extent of settling was very significant, showing that surface sample liquids are similar to filtrates. However, Cs-137 measurements exceeded WAC limits in all surface samples (1.1E+07 vs. 1.3E+06). The solids were found to contain very high cesium activity, measured as high as 1.1E+10 dpm/gram. Sodium was in the range of 4.24 to 4.74 M for all samples, so the solids would tend to settle with time and would not be at risk of floating without air entrainment. No organic mercury was detected in this work.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of Tank 15H Sample in Support of Preliminary Cease Waste Removal and Closure Mode Determination

The Savannah River National Laboratory (SRNL) was requested by Savannah River Mission Completion (SRMC) to provide sample preparation and analysis of Tank 15H characterization samples. These samples follow an interest in exploring avenues to condense the extensive sampling of the Tank Closure process. One such pathway would be to collect a sample during an earlier waste removal campaign for analysis to determine comparability to the later residual tank inventory determined through Residual Material sampling and characterization prior to grouting. Six Tank 15H samples (HTF-15-24-9, HTF- HTF-15-24-10, HTF-15-24-11, HTF-15-24-12, HTF15-24-13, and HTF-15-24-14) were delivered to SRNL in May of 2024. These six Tank 15H samples were taken as close as possible to the solids layer of the Tank 15H. These six Tank 15H samples were combined to form one composite sample for characterization due to the lack of sufficient solids fraction.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Developing and Implementing New Waste Chemistry Controls for Hanford's Double-Shell Tanks - 20041

Waste chemistry controls for the Hanford double-shell tanks (DSTs) were established in the 1980's in response to tank failures caused by stress corrosion cracking (SCC) at the Savannah River Site (SRS). The controls were established based on a combination of SRS chemistry limits and corrosion testing results. Conditions in the Hanford DSTs have changed over time, with the temperature in the majority of the DSTs dropping below 50 deg. C. Testing indicated that the original chemistry control specification and SCC testing performed in 2010 did not protect against pitting corrosion mechanisms - what is believed to have caused the failure of tank 241-AY-102. New waste chemistry controls are necessary to protect the DSTs from both SCC and pitting corrosion. Savannah River National Laboratory (SRNL), with input from the Tank Integrity Expert Panel (TIEP) Corrosion Subgroup (CSG), performed a statistically based investigation of nitrate and halide ion induced pitting corrosion. The investigation was intended to develop a comprehensive waste chemistry envelope that minimizes the risk of both SCC and pitting caused by halide and nitrate ions. The waste chemistry envelope needed to be robust enough to address future waste retrieval and process changes which could significantly change the waste composition of the DSTs. The experimental design allowed the statistically significant ions and their effect on pitting corrosion to be determined. SRNL developed the 'pitting factor' which is an empirical relationship between the statistically significant inhibitive species (hydroxide, and nitrite), and pitting inducing species (nitrate, chloride, and fluoride). The coefficients are weighted factors that show the degree of influence the species have on the propensity for pitting. New waste chemistry control limits were recommended by SRNL, and concurred with by the TIEP CSG, that incorporated the pitting factor along with other limits. The controls developed to reduce the risk of pitting corrosion were evaluated to determine if they also protected against SCC. Hundreds of test results were reviewed and compared against the proposed limits. With the exception of one test result, instances where cracking was observed corresponded to chemistry that was outside of the proposed limits - indicating that the chemistry controls developed for pitting also adequately addressed SCC concerns. Existing tank composition estimates were evaluated against the new chemistry controls - three current tank chemistries are suspect, and may not meet the new chemistry control requirements. These included the interstitial liquid (liquid associated with solids) of DSTs 241-AN-102, 241-AN-106, 241-AN-107, and 241-AY-101. Measures are ongoing to evaluate the tanks with the suspect chemistry. These include varying combinations of: performing additional evaluations (history of use, modeling); DST specific laboratory testing; and, pursuing core samples of the DSTs. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solubility Predictions for Hanford Tank Concentrates with HSC - 20459

The commercially available Outotec HSC 9.9.0{sup R} provides excellent predictions for the solubilities of many species for Hanford waste tank concentrates. The HSC solubility predictions with a Harvie activity model agreed well with five boildowns that showed solubility limits for NaNO{sub 3}, NaNO{sub 2}, Na{sub 2}CO{sub 3}, NaF, Na{sub 2}SO{sub 4}, and Na{sub 3}PO{sub 4}. However, the HSC did not predict density and therefore water content very well and therefore we used the measured densities and derived water content from the difference between measured density and assays. Furthermore, we adjusted the HSC enthalpy for the minor species Na{sub 3}PO{sub 4}*NaF double salt in order to fit the five boildowns as well. Previous work has shown that gibbsite becomes and remains supersaturated in all of these boildowns and so there was no alumina precipitation despite supersaturation. Furthermore, an equilibrium model like HSC always shows complete oxidation of any TOC in the presence of nitrate and nitrite. We therefore suppressed the HSC oxidation of acetate and oxalate in order to fit measured acetate and oxalate solubilities as TOC. Space in Hanford waste tanks is very limited and therefore evaporator campaigns continue to recover needed tank space from dilute tank liquids. Prior to each evaporator campaign, a boildown of a sample of tank liquid for each campaign provides a basis for planning by measuring density, water activity, soluble species, and solids precipitation as a function of concentration at 18 deg. C. These boildowns then provide validations and calibrations for the HSC solubility prediction for Hanford wastes. Previous work has shown the solubilities of minor electrolytes in these five boildowns follow rather simple power law solubility products. Hanford's 222-S laboratory has reported each of five boildowns for concentrated liquids from five waste tanks and tank blends. All boildowns eventually showed the precipitation of the dominant electrolyte, NaNO{sub 3}, and overall solution activity largely drives all solubility. (authors)

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Methane Emissions Produced by Pneumatic Devices and Produced Water Tanks on Natural Gas Wellsites

In recent years, more scrutiny has been placed on the release of greenhouse gasses (GHGs) by the oil and gas industry in North America as climate concerns increase. In the coming years, stricter regulations proposed by the Environmental Protection Agency (EPA) concerning the release of GHGs will further direct attention to GHG emissions quantification, modeling, and overall reduction. Active natural gas wellsites employ production equipment that routinely emits methane during normal operation. Production equipment often includes, but is not limited to, gas production units (GPUs), pneumatic controllers (PCs) and actuators powered by produced natural gas, and produced water storage tanks. This work details direct methane emission measurements taken at active natural gas wellsites originating from intermittent pneumatic controllers and produced water storage tanks. Efforts to model methane flows originating from these sources are also detailed, and those results are compared to direct measurement. The direct methane emissions measurement campaign collected flow data from two active dry wellsites in the Marcellus shale region. These measurement campaigns captured, in total, several weeks of continuous data from these sites. Data included multiple pneumatic device vent flowrate channels, a single channel monitoring total emissions vented from the produced water storage tanks, and corresponding site weather data. Periodic composition measurements were taken from flows vented from produced water tanks. Computational modeling efforts attempted to mimic a given site’s methane emissions behavior given limited input parameters. Direct measurement data and simulation data yielded, through reduction and analysis, apparent methane emissions factors, statistics on pneumatic device actuation events, important relationships between GPU parameters and pneumatic device actuation events, produced water storage tank vent flows and flow compositions, and parameters most contributing to the magnitude and frequency of these fugitive methane emissions. Measurements, considering data from a 72hr period, produced PC emissions factors from 0.008 to 0.03 SCFH per device with an average device emitting 0.026 SCFH at the first site. The second site produced PC emissions factors spanning from 0.05 to 25.47 SCFH with an average device emitting 1.93 SCFH not including the 25.47 SCFH device, which was assumed to be malfunctioning. Two unique water tank emission measurements were made, 618 g CH4 per hour and 32.6 g CH4 per hour. On a water basis, the water tank emissions factors were 0.66 and 0.042 kg CH4 per bbl of water, respectively.

03 NATURAL GAS↗

Empirical characterization of vertical-tube inlets in hot-water storage tanks

Hot-water storage in residential and commercial tanks is of growing interest for peak-shifting the electrical demand associated with hot-water loads. How the water enters the tank can significantly affect the extraction efficiency of the storage. Vertical-tube inlets (VTIs) direct cold water into the tank. The VTI design influences whether large-scale mixing occurs, which can reduce the delivery capacity of the hot-water storage. In this work, the mixing at the VTI discharge was characterized by the eddy diffusivity factor (EDF) in an allometric curve fit to the ratio Re:Ri using inlet superficial velocities. The full experimental campaign tested VTI's with Re’s between 170 and 22,300 and Ri's between 0 and 376. Animated visualization of the experimentally measured data is provided, showing tank temperature evolution during inlet flows. The most predictive correlations for EDF are for VTI Re in the transition zone (i.e. ~2300 < Re < ~10,000) and at a Ri corresponding to a stably stratified tank (i.e. Ri > 5). For vertical-tubes that distribute cold water below the thermocline, increasing the EDF will decrease the stratification in a hot-water tank as EDF quantifies inlet mixing. Overall, the new correlations for VTIs can be used to design and model thermally-stratified storage tanks.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Summary of Expedited Results from Samples Supporting Tank Closure Cesium Removal (TCCR) Batch 3

Savannah River Remediation (SRR) is currently operating the Tank Closure Cesium Removal (TCCR) 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 3 for processing through the TCCR unit. SRNL received and characterized a set of dip samples collected from Tank 10H (one surface and one variable depth sample). No solids were observed in either sample and therefore the samples were combined, and a suite of analyses were performed on the composite sample. The density of the combined sample was 1.174 g/mL (0.18 %RSD), which was consistent with the measured sodium concentration of 3.54 M (0.08 %RSD). The 137Cs activity in the sample was 4.75E+07 dpm/mL (4.28 %RSD) and the total Cs concentration was calculated to be 1.54 mg/L (1.16E-05 M). The in-tank batch contact samples consist of 0.1 g of crystalline silicotitanate (CST) contained within a teabag device. Duplicate samples were submerged in Tank 10H supernate for a period of about 13 days, after which time they were retrieved and transferred to SRNL for analysis. At SRNL the CST was rinsed to remove excess salt solution and the CST was then air dried before being digested for analysis. Results of the analysis indicated a 137 Cs loading of 3.66E+10 ± 1.40E+09 dpm/g or 16.5 ± 0.63 Ci/kg CST . This value represents a bounding upper limit as it includes the addition of two sigma uncertainty from replicate analysis of the individual teabag samples as well as the addition of the small amount of 137 Cs activity measured in the rinse solutions. The above values are based on the air-dried mass of CST. Correcting to the true dry mass using a F-factor of 0.8191 results in a maximum loading of 20.2 ± 0.77 Ci/kg CST .

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cesium Ion Exchange Testing Using Crystalline Silicotitanate with Hanford Tank Waste 241-AP-107

At the time of this testing, the Low-Activity Waste Pretreatment System (LAWPS) was to provide for the initial production of immobilized low-activity waste by feeding Hanford tank supernate from tank farms to the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Facility for immobilization. Washington River Protection Solutions requested that Hanford tank waste collected from tank 241-AP-107 (hereafter called AP-107) be processed using conceived pretreatment steps (suspended solids removal by filtration, Cs removal by ion exchange) then vitrified. A small-scale test platform to demonstrate the solids filtration, Cs removal, and LAW vitrification was constructed and installed at Pacific Northwest National Laboratory. Bench-scale ion exchange testing with approximately 9 L of AP-107 supernate was conducted using crystalline silicotitanate (CST) ion exchange media. The IONSIV R9140-B CST was provided by Honeywell UOP, LLC in 2018 (Batch 2081000057). The ion exchange media was first tested with simulant and was previously described. This report describes the Cs ion exchange batch contact and column test results with the AP-107 tank waste. Batch contact testing helps to evaluate CST performance on tank waste supernate prior to processing it in the ion exchange columns. Batch contacts were performed with the waste at four Cs concentrations at a phase ratio of 200 (liquid volume to exchanger mass) with AP-107. The distribution coefficient (K d ) at the equilibrium condition of 8.57 µg Cs/mL (AP-107 feed condition) was determined to be 669 mL AP-107/g CST. With a CST bed density of 1.00 g/mL, this K d corresponded to a predicted 50% Cs breakthrough of 669 bed volumes (BVs). The Cs load capacity at the equilibrium feed condition was determined to be 7.5 mg Cs/g dry CST. The column testing was prototypic to the intended LAWPS operations in a lead-lag column format, although on a small-scale basis with 10-mL CST beds. The feed was processed downflow through the lead column and then through the lag column at ~2.2 BV/h. Loading continued until the lag column reached the WTP waste acceptance criteria (WAC) for receiving supernatant waste for vitrification (a function of the Na and 137 Cs concentrations). For AP-107, the WAC is 0.114% of the influent 137 Cs concentration; this required a Cs decontamination factor of 876. The Cs effluent from the lag column reached the WAC after processing ~410 BVs. To keep the subsequent product effluent below the WAC, a replacement lag column was prepared, the lead column was removed from service (after processing a total of 471 BVs), the lag column was put into the lead column position, and the replacement lag column was installed. Feed processing continued and after another ~290 BVs the Cs effluent from the lag column again exceeded the WAC. In both cases, the lead columns only reached 25% Cs breakthrough before removal. Although 50% Cs breakthrough was not reached, this value was estimated and averaged based on extrapolation of the loading curves (640 BVs) and agreed within 4% of the predicted 50% Cs breakthrough from batch contact test results (669 BVs). Table ES.1 summarizes the observed column performance and relevant Cs loading characteristics.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Subcriticality Measurements for a Changing Concentration Uranyl Nitrate Solution Tank by Californium Source-Driven Noise Analysis

Subcritical californium source-driven noise analysis (CSDNA) measurements were performed at the Oak Ridge Critical Experiments Facility in 1983 using a stainless-steel tank with an inside diameter of 76.2 cm and a height of 91.4 cm but only filled with a uranyl (93.16 wt.% 235 U) nitrate solution to a height of 76.2 cm for all measurements. The free acid content of the uranyl nitrate solution was less than 0.01 N to minimize hazards in handling. The total available highly enriched uranium for these measurements was 5,296 g. The concentration of the solution was varied from the highest density of 14.71 grams of uranium per liter (g U/L) initially in 16 steps, lowering the concentration to 0.3492 g U/L, and finally using a tank filled with only water. The tank had a Plexiglas lid to minimize evaporation. The Cf source was contained in a re-entrant Lexan tube which could be in the solution parallel to the axis of the cylindrical tank. The detectors were 3 He proportional counters in the solution in shrink-fit tubing to isolate the counters from the fissile solution and adjacent to the outside of the tank. In some cases, the detectors were scintillators adjacent to the outside of the tank. In other cases, the source was external to the tank. Some data presented in this report are from notes and are not in the logbook. The prompt neutron decay constant was obtained from fitting the date from the CSDNA measurements. The purpose of this report is to document the experimental information for the measurements performed so that later, researchers could perform the required uncertainty and calculational analyses and documentation to use these data for an International Nuclear Criticality Safety Benchmark Program (ICSBEP) or a Nuclear Energy Agency benchmark. The prompt neutron decay measurements could be the basis of as International Reactor Physic Benchmark Program. The data from these measurements are available from the Records Management Services Department of Oak Ridge National Laboratory, and the logbook is also available from the ICSBEP at Idaho National Laboratory. Preparation of the present report is part of a larger cooperative effort between Idaho National Laboratory (INL) and Oak Ridge National Laboratory (ORNL) to document more than 15 undocumented critical and subcritical experiments enumerated in ORNL/TM-2019/18 and performed by ORNL at ORCEF and other USDOE critical experiments facilities using more than 500 operational days of critical facility time.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Analysis of Air-Purifying Respirator (APR) Cartridge Performance Testing on Hanford Tanks SX-101 and SX-104: Volume 2 - Raw Analytical Data

As the Tank Operations Contractor for U.S. Department of Energy operations at the Hanford site in Washington State, Washington River Protection Solutions (WRPS) is responsible for managing highly radioactive wastes stored in tanks at Hanford. To protect workers at Hanford Tank Farms, WRPS tests air-purifying respirator (APR) and powered air-purifying respirator (PAPR) chemical cartridges commonly used at the tank farms. The tests were conducted to determine the period of time the cartridges would provide adequate performance for APRs and PAPRs when workers are exposed to a mixture of Chemicals of Potential Concern (COPC) from any vapors exiting headspaces in the storage tanks. Occupational Safety and Health Administration (OSHA) Standard 29 Code of the Federal Regulations (CFR) 1910.134(d)(3)(iii)(b)(2) specifies that for protection against gases and vapors, employers shall implement a schedule for cartridges to ensure that change-outs occur before the end of service life. The change schedule can be based on objective information or data that ensures cartridge change-outs occur before the end of their service life. The primary function of the WRPS Cartridge Test Program is to obtain objective data to determine service lives for the APR and PAPR cartridges used at Hanford Tank Farms. WRPS contracted with Pacific Northwest National Laboratory to analyze the test data and offer an independent analysis and any recommendations. This report summarizes data analysis of APR cartridge testing on headspace vapors from Hanford SX-101 and SX-104 single-shell tanks. Volume 1 of this report documents the testing, data analysis, results, conclusions, and recommendations resulting from the APR testing on SX-101 and SX-104 headspace vapors. Volume 2 provides an introduction to the raw data, including analytical laboratory analysis results that supported the analysis and conclusions documented in Volume 1.

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Analysis of Air-Purifying Respirator (APR) and Powered Air-Purifying Respirator (PAPR) Cartridge Performance Testing on a Hanford AX Tank Farm Exhauster Slipstream Volume 2: Raw Analytical Data

As the Tank Operations Contractor for U.S. Department of Energy operations at the Hanford site in Washington State, Washington River Protection Solutions (WRPS) is responsible for managing highly radioactive wastes stored in tanks at Hanford. To protect workers at Hanford Tank Farms, WRPS tests air-purifying respirator (APR) and powered air-purifying respirator (PAPR) chemical cartridges commonly used at the tank farms. The tests were conducted to determine the period of time the cartridges would provide adequate performance for APRs and PAPRs when workers are exposed to a mixture of Chemicals of Potential Concern (COPC) from any vapors exiting headspaces in the storage tanks. Occupational Safety and Health Administration (OSHA) Standard 29 Code of the Federal Regulations (CFR) 1910.134(d)(3)(iii)(b)(2) specifies that for protection against gases and vapors, employers shall implement a schedule for cartridges to ensure that change-outs occur before the end of service life. The change schedule can be based on objective information or data that ensures cartridge change-outs occur before the end of their service life. The primary function of the WRPS Cartridge Test Program is to obtain objective data to determine service lives for the APR and PAPR cartridges used at Hanford Tank Farms. WRPS contracted with Pacific Northwest National Laboratory to analyze the test data and offer an independent analysis and any recommendations. This report summarizes data analysis of APR and PAPR cartridge testing on a vapor slipstream from the Hanford AX tank farm exhauster. Volume 1 of this report documents the testing, data analysis, results, conclusions, and recommendations resulting from the cartridge testing on AX exhauster slipstream vapors. Volume 2 provides an introduction to the raw data, including analytical laboratory analysis results that supported the analysis and conclusions documented in Volume 1.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Powered Air-Purifying Respirator (PAPR) Cartridge Performance Testing on Hanford Tanks SX-101 and SX-104: Volume 2 Raw Analytical Data

As the Tank Operations Contractor for U.S. Department of Energy operations at the Hanford site in Washington State, Washington River Protection Solutions (WRPS) is responsible for managing highly radioactive wastes stored in tanks at Hanford. WRPS tests of cartridges used in air-purifying respirators (APR) and powered air-purifying respirators (PAPR) commonly used at Hanford Tank Farms. The tests are conducted to determine the period of time the cartridges would provide adequate performance for APRs and PAPRs used to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPC) from any vapors exiting headspaces in the storage tanks. Occupational Safety and Health Administration (OSHA) Standard 29 Code of the Federal Regulations (CFR) 1910.134(d)(3)(iii)(b)(2) specifies that for protection against gases and vapors, employers shall implement a schedule for cartridges to ensure that change-outs occur before the end of service life. The change schedule can be based on objective information or data that ensures cartridge change-outs occur before the end of their service life. The primary function of the WRPS Cartridge Test Program is to obtain objective data to determine service lives for the APR and PAPR cartridges used at Hanford Tank Farms. WRPS contracted with Pacific Northwest National Laboratory to analyze the test data and offer an independent analysis and any recommendations. This report summarizes data analysis of PAPR cartridge testing on headspace vapors from Hanford SX-101 and SX-104 single-shell tanks. Two different PAPR cartridges—one from MSA Safety Inc. (Pittsburgh, Pennsylvania) and another from 3M (Maplewood, Minnesota)—were assessed on each tank headspace source on separate days. These data represent the first PAPR cartridge testing under the recent WRPS program, as testing to date had been focused on APR cartridges. Volume 1 of this report documents the testing, data analysis, results, conclusions, and recommendations resulting from the PAPR testing on SX-101 and SX-104 headspace vapors. Volume 2 provides an introduction to the raw data, including analytical laboratory analysis results that supported the analysis and conclusions documented in Volume 1.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ion Exchange Processing of AN-107 Hanford Tank Waste through Crystalline Silicotitanate in a Staged 2- then 3-Column System

The Hanford Site stores an estimated 56 million gallons of mixed radioactive and chemically hazardous waste in large underground tanks. In support of the Direct Feed Low-Activity Waste (DFLAW) Program for expediting Hanford tank waste supernate treatment, laboratory-scale ion exchange processing using prototypic unit operations was conducted on AN-107 tank waste at the Pacific Northwest National Laboratory Radiochemical Processing Laboratory. This report describes the small-scale ion exchange testing with 13.7 L of diluted and filtered supernate from Tank 241-AN-107 (hereafter referred to as AN-107) at 16 °C (62 °F). One of the waste acceptance criteria (WAC) for the Waste Treatment Plant (WTP) Low-Activity Waste Facility is that the waste must contain less than 3.18×10 -5 Ci 137 Cs per mole of Na. For the AN-107 tank waste to meet this criterion, only 0.147% of the influent 137 Cs concentration may be delivered to the WTP; this requires a Cs decontamination factor of 678. Testing with AN-107 matched current Tank Side Cesium Removal (TSCR) facility prototypic operations where a lead-lag configuration was used until the lag column reached the WAC limit, then a polish column was brought online for continued processing in a lead-lag-polish column configuration. Feed was processed at 1.9 bed volumes (BVs) per hour; the flowrate, in terms of contact time with the crystalline silicotitanate (CST) bed, matched the expected flowrate at TSCR. The Cs-decontaminated product was retained for vitrification testing (to be reported separately). The lead column reached 40% Cs breakthrough after processing ~1700 BVs of feed; the 50% Cs breakthrough was extrapolated from the breakthrough data to occur at 1873 BVs. Testing compared to previous AP-101 and AP-107 testing at 16 °C showed ~300 BV increases in volume processed to reach the WAC limit for both lead and lag columns. The increase in capacity was determined to be due to the significantly lower K concentration in the AN-107 compared to the other tank waste matrices. A comparison in breakthrough curves for the three tests indicated slightly slower kinetic behavior in the AN-107, with variations in feed matrices (high organic complexants) likely responsible for the deviation. The Cs effluent from the lag column reached the WAC limit after processing 1097 BVs. Anticipating this breakthrough point, the polish column was preemptively installed around 900 BVs. Cs breakthrough from the lag column began at 500 BVs, reaching 3.06×10 0 µCi/mL, or 2.6 % Cs breakthrough, after processing all 1700 BVs of feed. Table S.1 and Figure S.1 summarize the observed column performance and relevant Cs loading characteristics.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Low-Cost, High-Performance Carbon Fiber for Compressed Natural Gas Storage Tanks (Final Technical Report – Down Select Report)

The aim of this project is to reduce the cost of Type IV, carbon fiber (CF) composite overwrap compressed gas storage tanks by reducing the cost of CF and CF composites. The project team worked to reduce the cost of CF by exploring and testing opportunities for a low-cost alternative precursor material for CF production to supplant market-dominant and costly polyacrylonitrile (PAN). Concurrently, the team aimed to reduce the cost of the tanks at the composite level by improving the interfacial adhesion between the fibers and the matrix resin through the incorporation of low-cost nanoparticles recycled from waste materials, which would reduce the volume of costly CF required to achieve the same tank performance. At the end of the first year, the project team selected mesophase pitch as the primary precursor candidate from a field of materials based on the superior mechanical performance and cost-saving potential. During the second year, the team produced CFs derived from mesophase pitch achieving an average tensile strength of 365.6 ksi and average tensile modulus of 40.74 Msi. Facility availability for spinning and converting these fibers at greater scale has hindered scale-up demonstration, but the team has identified opportunities to conduct this work in the near term. Cost modeling shows that these mesophase pitch-derived CFs can be up to 40% less expensive than PAN-derived CFs due to the lower cost of the feedstock material, higher throughput, greater conversion yield, and lower cost spinning method and compared to PAN. Additionally, the team has demonstrated at lab-scale that nanoparticle coating CFs can significantly increase the interfacial shear strength and load transfer efficiency of CFs in a matrix. Single filament pull-out testing showed a 27% average increase in max interfacial shear strength due to this coating. A continuous method of applying these coatings to a tow of CF has been developed for scale-up. 26 m tows of coated CFs were produced using this system and formed into composite ring samples for ASTM ring burst testing. Issues with the testing protocol have limited assessment of these results. A prototype Type IV tank was designed to meet ANSI HGV2 standards, and the design criteria set out by DOE, using the CF properties developed by the team paired with a proprietary resin matrix, a polyamide liner, and aluminum end bosses. The tank weighs 153.1 kg and with a total capacity of 5.8 kg H2 (5.6 kg usable), which yields a gravimetric capacity of 1.17 kWh/kg. Cost modeling predicts that the tank will have a projected cost of $15.73/kWh. Tank performance modeling does not include considerations for fiber-matrix load transfer efficiency improvements offered by nanoparticle coating method.

08 HYDROGEN↗

New Tank Mapping Method Improves Waste Removal Process

Savannah River Mission Completion is the Liquid Waste (LW) contractor at the Savannah River Site (SRS). The LW mission is tasked with treating and disposing of legacy nuclear waste. There are multiple facilities involved in this work, including the Concentration, Storage, and Transfer Facilities (CSTF), the Defense Waste Processing Facility (DWPF), the Salt Waste Processing Facility (SWPF), and the Saltstone Production Facility (SPF). The CSTF includes 43 underground waste tanks used to store and support processing of radioactive liquid waste. Waste removal activities, such as salt dissolution campaigns and sludge agitation, are conducted within the CSTF waste tanks to convert the waste into a form that allows for downstream processing at other LW facilities. While performing these waste removal campaigns, camera inspections are performed to assess the quantity and distribution of the remaining waste within the waste tank (i.e. saltcake or sludge). Understanding the quantity and distribution of the salt/sludge within the waste tanks allows for improved waste removal strategies (e.g. mixing pump operation) and refined safety controls. Typically, several camera inspections are performed during a waste removal transfer to verify the elevation of the visible salt/sludge mounds against the known elevation of the liquid surface. The camera inspection footage must then be interpreted by a trained engineer who will develop a 2-D map that depicts the waste distribution at various elevations within the waste tank. This tank mapping is then used in conjunction with conservative assumptions to evaluate the volume of saltcake or sludge that is present within the waste tank.

Mini, Melany↗

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].

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Polar Bear™ – Innovative Capture of Storage Tank Vapors

Polar Bear™ is a patented technology developed by the Energy & Environmental Research Center (EERC) to capture storage tank vapors and eliminate methane emissions from upstream oil- and gas-producing facilities. Sparked by early commercial investment, the EERC licensed the technology and extended the intellectual property to storage tanks. Polar Bear™ is uniquely engineered and adapted to individual lower-producing facilities where there is otherwise no economic alternative for capturing tank vapors. A high number of small producing oil and gas wells are distributed across the country. The aggregate contributes to a significant volume of emissions. Because of the lack of economy of scale, gas volumes from these facilities are typically not recovered and contribute to methane emissions. Polar Bear™ provides a fit-for-purpose compression solution that addresses cost by reducing complexity with respect to conventional vapor recovery units and eliminating oil changes. Unique to Polar Bear™ is the capability to separate oxygenated gas from storage tank vapors. Storage tanks are designed to “breathe,” allowing gas to enter and escape during internal level and temperature changes. This infiltration of air into the tank headspace imparts undesirable oxygen content with respect to pipeline gathering. Polar Bear™ separates the vapor stream, allowing oxygen-rich gas to be used as fuel on-site while recovering the liquids-rich portion of the gas where oxygen content is minimized. A prototype system was tested to verify process models, evaluate operational performance, and advance the technology readiness level from 5 to 6. Results provide a good match between experimental measurements and process models, indicating the models are useful for future scale-up and field design. Various mixtures of nitrogen and liquefied petroleum gas were tested to understand the mass balance of nitrogen and how it relates to the potential control of oxygen content. Findings indicate that less than 2000 ppm of oxygen is likely to remain in the liquid portion of the gas in field applications. The research and development prepare the technology for field implementation to eliminate routine and fugitive methane emissions from storage tanks.

02 PETROLEUM↗

Ion Exchange Processing of AW-105 Hanford Tank Waste through Crystalline Silicotitanate in a Staged 2- then 3-Column System

The Hanford Site stores an estimated 56 million gallons of mixed radioactive and chemically hazardous waste in large underground tanks. In support of the Direct Feed Low-Activity Waste (DFLAW) Program for expediting Hanford tank waste supernate treatment, laboratory-scale ion exchange processing using prototypic unit operations was conducted on AW-105 tank waste at the Pacific Northwest National Laboratory Radiochemical Processing Laboratory. This report describes the small-scale ion exchange testing with 9.2 L of diluted and filtered supernate from Tank 241-AW-105 (hereafter referred to as AW-105) at 16 °C (62 °F). One of the waste acceptance criteria (WAC) for the Waste Treatment Plant (WTP) Low-Activity Waste Facility is that the waste must contain less than 3.18×10 -5 Ci 137 Cs per mole of Na. For the AW-105 tank waste to meet this criterion, only 0.225% of the influent 137 Cs concentration may be delivered to the WTP; this requires a Cs decontamination factor of 445. Testing with AW-105 matched current Tank Side Cesium Removal (TSCR) facility prototypic operations where a lead-lag configuration was used until the lag column reached the WAC limit, then a polish column was brought online for continued processing in a lead-lag-polish column configuration. Feed was processed at 1.9 bed volumes (BVs) per hour; the flowrate, in terms of contact time with the crystalline silicotitanate (CST) bed, matched the expected flowrate at TSCR. The Cs-decontaminated product was retained for vitrification testing (to be reported separately). The lead column reached 83% Cs breakthrough after processing ~1500 BVs of feed; the 50% Cs breakthrough was interpolated from the breakthrough data and occurred at 1041 BVs. Despite the AW-105 having a significantly higher K concentration (0.55 M compared to 0.10 M), testing compared to previous AP-107 ion exchange column testing at 16 °C showed no difference in BVs processed to reach the WAC on the lead column and only an approximate ~20 BV decrease in volume processed to reach the WAC limit on the lag column. The negligible differences in capacity despite the 5x concentration differences in K was determined to be due to the significantly lower NO3 concentration in the AW-105 supernate compared to the AP-107 tank waste matrix. A comparison in breakthrough curves for the two tests also indicated slightly faster kinetic behavior in the AW-105, with the variations in feed matrices (lower NO3 concentration) likely responsible for the deviation. The Cs effluent from the lag column reached the WAC limit after processing 772 BVs. Anticipating this breakthrough point, the polish column was preemptively installed around 675 BVs. Cs breakthrough from the lag column began at 300 BVs, reaching 1.10×10 1 µCi/mL, or 14.13 % Cs breakthrough, after processing all 1500 BVs of feed. The polish column processed nominally 830 BVs and reached 2.10×10 -1 µCi/mL, or 0.27 % Cs breakthrough at the conclusion of the test. Table S.1 and Figure S.1 summarize the observed column performance and relevant Cs loading characteristics.

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