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Smoot, Margaret R.

Publications and source records attributed to Smoot, Margaret R..

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.

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Cesium Removal from AP-105 Hanford Tank Waste Using Spherical Resorcinol Formaldehyde Resin

Spherical resorcinol formaldehyde (SRF) resin is planned to be used to remove cesium (137Cs) from the aqueous phases of Hanford tank wastes in preparation for their vitrification at the Waste Treatment and Immobilization Plant. SRF is an elutable organic ion exchanger that is projected to be used in up to 30multiple process cycles (load/elute/regeneration) before being disposal . Only two full process cycles have been tested using SRF on Hanford tank waste. This paper describes the test results of six complete load/elute cycles using the SRF in a lead/lag column format with 12 liters of Hanford tank waste supernatant collected from Tank AP-105. The testing exposed the SRF to the combined sources of degradation: chemical attack from dissolved oxygen, nitric acid, and tank waste components; physical stress from resin expansion and contraction; and beta and gamma radiolytic exposure. Process conditions, dictated by Washington River Protection Solutions, featured loading until the lag column effluent reached 10% of the waste acceptance criteria (a Cs decontamination factor of 6,000). Under these conditions the lead column was nearly fully loaded and the lag column was loaded with about 20% of the input Cs. Variations in process flowrates and elution volumes were investigated as part of the testing. Characteristics examined included degradation with cycling, mass transfer zones as a function of flowrate, Cs leakage into the ensuing process cycle, and analyte mass fractionation.

spherical resorcincol formaldehyde, ion exchange, ↗

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

Pacific Northwest National Laboratory has been tasked with demonstrating the unit operations for the Low Activity Waste Pretreatment System with actual Hanford tank waste. Crystalline silicotitanate (CST) ion exchange media is planned to be used to remove cesium (137Cs) from the aqueous phases of the tank wastes. Washington River Protection Solutions requested that Hanford tank waste collected from tank 241-AP-107 be processed using conceived pretreatment steps (suspended solids removal by filtration, Cs removal by ion exchange), then vitrified. Removal of Cs from these wastes is an important processing step in preparing the waste for long-term safe storage. Bench-scale ion exchange testing with approximately 9 L of filtered AP-107 supernate was conducted using CST. Column testing was performed using prototypic LAWPS operations in a lead-lag column arrangement using 10-mL CST beds. Feed was processed until the lag column effluent reached the Hanford Tank Waste Treatment and Immobilization Plant waste acceptance criteria (WAC) for receiving supernatant waste for vitrification (a function of the Na and 137Cs concentrations), at which point, a new lag column was needed to continue processing and the original lag column was moved to the lead position. Greater than 99% of the Cs processed through the ion exchange system was collected on the CST in the columns. The AP-107 feed and column processing effluent underwent extensive characterization to better define waste characteristics and assess fractionation to the CST. Selected lead column samples were analyzed to assess particular metal analyte load characteristics. Results of these analyses will be discussed.

cesium exchange, Hanford tank waste, ion exchange↗

Cesium Removal from Tank Waste Simulants Using Crystalline Silicotitanate at 12% and 100% TSCR Bed Heights

The Direct Feed Low-Activity Waste flowsheet provides for the early production of immobilized low-activity waste (LAW) by feeding waste directly from Hanford tank farms to the Hanford Tank Waste Treatment and Immobilization Plant (WTP) for vitrification. Prior to the transfer of feed to the WTP LAW Vitrification Facility, tank waste supernatant will be pretreated by the Tank Side Cesium Removal (TSCR) system to meet the WTP LAW waste acceptance criteria (<3.18E-5 Ci 137 Cs/mole of Na). This pretreatment will remove cesium from the waste stream using ion exchange (IX). The selected media for IX is crystalline silicotitanate (CST), product number UOP-IONSIV-R9140-B, manufactured by Honeywell UOP LLC (Des Plaines, IL). Testing was requested by Washington River Protection Solutions to better define IX processing using Low-Activity Waste Pretreatment System (LAWPS) prototypic IX unit operation process steps at full height and medium height. The information is intended to significantly contribute towards establishing accurate process flowsheets for the individual feed campaigns planned for the LAWPS. Column testing at both the medium (12% of the full bed height) and full height scales was conducted to evaluate process variables and scale up performance of Cs exchange onto the CST, Lot 8056202-999. Nominal process conditions used 5.6 M Na simulant processed at 1.8 bed volumes per hour (BV/h) at 20 °C. Process variables included 1) increased process temperature to 35 °C, 2) increased Na concentration to 6.0 M, 3) added organics to the 5.6 M Na simulant, and 4) flowrate changes. The medium scale tests used single columns containing 44 mL of <25 mesh CST in a 1.44 cm diameter column, 27 cm tall CST bed. The full height columns used lead/lag columns containing 1.15 L unsieved (as-received) CST in 2.54-cm-diameter columns, 226 cm tall CST beds. Two process flowrates were tested at the full height: 1.30 and 1.82 BV/h. IX testing with simulant solutions was conducted using TSCR prototypic IX unit operations: feed processing, feed displacement with 0.1 M NaOH, water rinse, and solution expulsion with compressed air.

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

The Low-Activity Waste Pretreatment System (LAWPS) provides for the early 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 the 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.

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Cesium Ion Exchange Using Crystalline Silicotitanate with 5.6 M Sodium Simulant

The Low-Activity Waste Pretreatment System (LAWPS) facility is planned to pretreat Hanford tank waste supernate by filtering to remove solids and processing through ion exchange columns to remove cesium. The ion exchange media is currently (since 2018) targeted to be crystalline silicotitanate (CST). This material has been produced as an engineered form (generally spherical beads) by Honeywell UOP LLC (Des Plaines, IL). Previous forms of this media have been tested in a wide array of simulants and process scales, but column breakthrough and batch contact testing to date on actual tank waste has been limited to a few tank wastes. Washington River Protection Solutions requested a series of studies to demonstrate Cs load behavior in a small column format and determine if a simple batch contact test with CST can be used to qualify tank waste supernate prior to processing it in the LAWPS. The goal of the batch contact testing is to determine if there are any issues with the tank waste that would preclude Cs removal by the ion exchanger. Testing was conducted with IONSIV TM R9140-B CST provided by Honeywell UOP in 2018 (Batch 2081000057). The CST was received in the sodium (Na) form, so no pretreatment conditioning to convert to the Na form was required. Before use in testing, the CST was passed through a #25 sieve (710-micron openings) and collected on a #60 sieve (250-micron openings) with the intent of removing any large and fine particles. Physical properties were measured on the CST including particle size distribution (d50 = 570 microns) and scanning electron micrographic examination. The CST was rinsed with water until the contact solution was visually nearly clear. The CST bed density (1.00 g/mL) and CST bed void fraction (0.656) were measured on the sieved and rinsed CST. The batch contact testing varied Cs concentration in a 5.6 M Na simple simulant solution. Testing was conducted in a liquid volume to solids mass ratio of 200. The distribution coefficient (K d ) was determined to be 770 mL/g at the Cs equilibrium condition of 8.0 μg/mL; with a bed density of 1.00 g/mL, this corresponds to a predicted 50% Cs breakthrough of 770 bed volumes (BVs). The Cs load capacity at 8.0 μg/mL equilibrium condition was determined to be 6.16 mg Cs/g dry CST. The column testing was prototypic to the intended LAWPS operations in a lead-lag column format, albeit 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. Three flowrates were tested: 1.19, 1.99, and 4.56 BV/h. The feed was displaced with 0.1 M NaOH, and then the columns were rinsed with water sequentially through the lead then lag columns. One column system was evaluated top to bottom with a gamma scanner to assess the axial Cs loading. Table ES.1 summarizes the relevant Cs loading characteristics.

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Multi-Cycle Cesium Ion Exchange Testing Using Spherical Resorcinol-Formaldehyde Resin with Diluted Hanford Tank Waste 241-AP-105

Washington River Protection Solutions requested that at least 4 L of Hanford tank waste collected from tank 241-AP-105 and diluted to approximately 5.6 M Na (AP-105DF) be prepared for use in vitrification studies. Cesium removal was required to meet this objective and the waste pretreatment platform, established at Pacific Northwest National Laboratory, was used to create the vitrification feed. The Test Platform mimicked the Low-Activity Waste Pretreatment System (LAWPS) facility planned to pretreat Hanford tank waste supernate by removing solids in a cross flow filter apparatus and processing the supernate through ion exchange columns to remove cesium. At the time of testing, the ion exchange media was targeted to be spherical resorcinol-formaldehyde (SRF) resin. The SRF resin has been tested with a wide array of simulants and process scales, but column performance testing with actual tank waste had been somewhat limited to two Hanford tank wastes (AP-101 and AN-102) in up to two process cycles. This report describes testing conducted in a total of six load elute cycles with the AP-105DF tank waste. The column system was first tested with simulant and was previously described; this report describes the six process cycle results with the AP-105DF tank waste.

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Standard High Solids Vessel Design De-inventory Simulant Qualification

The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is working to develop a Standard High Solids Vessel Design (SHSVD) process vessel. To support testing of this new design, WTP engineering staff requested that a Newtonian simulant be developed that would represent the de-inventory (residual high-density tank solids cleanout) process. Its basis and target characteristics are defined in 24590-WTP-ES-ENG-16-021 and implemented through PNNL Test Plan TP-WTPSP-132 Rev. 1.0. This document describes the de-inventory Newtonian carrier fluid (DNCF) simulant composition that will satisfy the basis requirement to mimic the density (1.18 g/mL ± 0.1 g/mL) and viscosity (2.8 cP ± 0.5 cP) of 5 M NaOH at 25 °C.1 The simulant viscosity changes significantly with temperature. Therefore, various solution compositions may be required, dependent on the test stand process temperature range, to meet these requirements. Table ES.1 provides DNCF compositions at selected temperatures that will meet the density and viscosity specifications as well as the temperature range at which the solution will meet the acceptable viscosity tolerance.

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Cesium Ion Exchange Using Spherical Resorcinol-Formaldehyde Resin in Support of Waste Qualification Testing for LAWPS

The Low-Activity Waste Pretreatment System (LAWPS) facility is planned to pretreat Hanford tank waste supernate by filtering solids and processing through ion exchange columns to remove cesium. The ion exchange media is currently targeted to be spherical resorcinol-formaldehyde resin (SRF). This media has been tested in a wide array of simulants and process scales, but testing to date on actual tank waste has been limited to two tank wastes. Washington River Protection Solutions (WRPS) requested a study to determine if a simple batch contact test with SRF can be used to qualify tank waste supernate prior to processing it in the LAWPS. The goal of the batch contact testing would be to determine if there are any issues with the tank waste that would preclude Cs removal by the ion exchanger.

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Cesium Isotherm Testing with Spherical Resorcinol-Formaldehyde Resin at High Sodium Concentrations

Washington River Protection Solutions (WRPS) is developing a Low-Activity Waste Pretreatment System (LAWPS) to provide low-activity waste (LAW) directly to the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste Facility for immobilization. The pretreatment that will be conducted on tank waste supernate at the LAWPS facility entails filtration to remove entrained solids and cesium (Cs) ion exchange to remove Cs from the product sent to the WTP. Currently, spherical resorcinol-formaldehyde (sRF) resin (Microbeads AS, Skedsmokorset, Norway) is the Cs ion exchange resin of choice. Most work on Cs ion exchange efficacy in Hanford tank waste has been conducted at nominally 5 M sodium (Na). WRPS is examining the possibility of processing supernatant at high Na concentrations—up to 8 M Na—to maximize processing efficiency through the LAWPS. Minimal Cs ion exchange work has been conducted at 6 M and 8 M Na concentrations..

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K West Basin Sand Filter Backwash Sample Analysis

A sand filter is used to help maintain water clarity at the K West Basin where highly radioactive sludge is stored. Eventually that sand filter will require disposal. The radionuclide content of the solids trapped in the sand filter will affect the selection of the sand filter disposal pathway. The Pacific Northwest National Laboratory (PNNL) was contracted by the K Basin Operations & Plateau Remediation Project (operations contractor CH2M Hill) to analyze the radionuclide content of the solids collected from the backwash of the K West Basin sand filter. The radionuclide composition in the sand filter backwash solids will be used by CH2M Hill to determine if the sand filter media and retained sludge solids will be designated as transuranic waste for disposal purposes or can be processed through less expensive means. On October 19, 2015, K Basin Operations & Plateau Remediation Project staff backwashed the sand filter into the North Load-Out Pit (NLOP) and immediately collected sample slurry from a sampling tube positioned 24 in. above the NLOP floor. The 764 g sand filter backwash slurry sample, KW-105 SFBW-001, was submitted to PNNL for analysis on October 20, 2015. Solids from the slurry sample were consolidated into two samples (i.e., a primary and a duplicate sample) by centrifuging and measured for mass (0.82 g combined – wet centrifuged solids basis) and volume (0.80 mL combined). The solids were a dark brown/orange color, consistent with iron oxide/hydroxide. The solids were dried; the combined dry solids mass was 0.1113 g, corresponding to 0.0146 weight percent (wt%) solids in the original submitted sample slurry. The solids were acid-digested using nitric and hydrochloric acids. Insoluble solids developed upon dilution with 0.5 M HNO 3 , corresponding to an average 6.5 wt% of the initial dry solids content. The acid digestate and insoluble solids were analyzed separately by gamma spectrometry. Nominally, 7.7% of the 60 Co was present in the insoluble solids; less than 1% of other gamma-emitters (i.e., 137 Cs, 154/155 Eu, and 241 Am) were present in the insoluble solids. Aliquots of the acid digestate were analyzed directly using gamma energy analysis (GEA) and after separations for 238 Pu, 239+240 Pu, 237 Np, and 241 Am radioisotopes using alpha energy analysis (AEA). The 90 Sr was measured by liquid scintillation counting (LSC) on the Sr-separated fraction. The plutonium isotopic distribution of the acid digestate was analyzed following Pu separations by thermal ionization mass spectrometry (TIMS). A table summarizes the results for the primary and duplicate samples. The 239+240 Pu concentration (µCi/g dry) relative to 90 Sr and to 137 Cs concentrations (µCi/g dry) was examined. The K West Basin sludge has a 239+240 Pu/ 90 Sr ranging from 0.1 to 1.2 and the 239+240 Pu/ 137 Cs ratio ranging from 0.10 to 0.47. In contrast, the sand filter backwash solids 239+240 Pu/ 90 Sr ratio was 10.6 and the 239+240 Pu/ 137 Cs ratio was 2.0. The ratio differences indicate a relative enhancement of the Pu concentration in the sand filter solids relative to the 137 Cs and 90 Sr sludge concentrations currently in the K West Basin. A dose-to-curie radioisotope evaluation of the sand filter waste form may need to consider this dissimilarity.

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An Advanced TALSPEAK Concept Using 2-Ethylhexylphosphonic Acid Mono-2-Ethylhexyl Ester as the Extractant

A method for separating the trivalent actinides and lanthanides is being developed using 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) as the extractant. The method is based on the preferential binding of the actinides in the aqueous phase by N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA), which serves to keep the actinides in the aqueous phase while the lanthanides are extracted into an organic phase containing HEH[EHP]. The process is very robust, showing little dependence upon the pH or the HEH[EHP], HEDTA, and citrate concentrations over the ranges that might be expected in a nuclear fuel recycling plant. Single-stage runs with a 2-cm centrifugal contactor indicate that modifications to the process chemistry may be needed to increase the extraction rate for Sm, Eu, and Gd. The hydraulic properties of the system are favorable to application in centrifugal contactors.

actinide separation↗

STP K Basin Sludge Sample Archive at the Pacific Northwest National Laboratory FY2014

The Pacific Northwest National Laboratory (PNNL) currently houses 88 samples (~10.5 kg) of K Basin sludge (81 wet and seven dry samples) on behalf of the Sludge Treatment Project (STP), which is managed for the U.S. Department of Energy (DOE) by the CH2M Hill Plateau Remediation Company (CHPRC). Selected samples are intended to serve, in part, as sentinels to enhance understanding of sludge properties after long-term storage, and thus enhance understanding of sludge behavior following transfer to sludge transfer and storage containers (STSCs) and storage at the Hanford 200 Area central plateau. In addition, remaining samples serve in contingency for future testing requirements. At PNNL, the samples are tracked and maintained under a prescriptive and disciplined monthly sample-monitoring program implemented by PNNL staff. This report updates the status of the K Basin archive sludge sample inventory to April 2014. The previous inventory status report, PNNL 22245 (Fiskum et al. 2013, limited distribution report), was issued in February of 2013. This update incorporates changes in the inventory related to repackaging of 17 samples under test instructions 52578 TI052, K Basin Sludge Sample Repackaging for Continued Long Term Storage, and 52578 TI053, K Basin Sludge Sample Repackaging Post-2014 Shear Strength Measurements. Note that shear strength measurement results acquired in 2014 are provided separately. Specifically, this report provides the following: • a description of the K Basin sludge sample archive program and the sample inventory • a summary and images of the samples that were repackaged in April 2014 • up-to-date images and plots of the settled density and water loss from all applicable samples in the inventory • updated sample pedigree charts, which provide a roadmap of the genesis and processing history of each sample in the inventory • occurrence and deficiency reports associated with sample storage and repackaging

Archive↗

The Actinide-Lanthanide Separation Process

The Actinide-Lanthanide SEParation (ALSEP) process is described. The process uses an extractant phase consisting of either N,N,N',N'-tetraoctyldiglycolamide (TODGA) or N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). The neutral TODGA or T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid media. Switching the aqueous phase chemistry to a citrate buffered diethylenetriaminepentaacetic acid (DTPA) solution at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus resulting in separation of these two groups of elements.

actinide separation↗