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At least 19 records

Alternative Chemical Cleaning Methods for High Level Waste Tanks: Actual Waste Testing with SRS Tank 5F Sludge

Solubility testing with actual High Level Waste tank sludge has been conducted in order to evaluate several alternative chemical cleaning technologies for the dissolution of sludge residuals remaining in the tanks after the exhaustion of mechanical cleaning and sludge sluicing efforts. Tests were conducted with archived Savannah River Site (SRS) radioactive sludge solids that had been retrieved from Tank 5F in order to determine the effectiveness of an optimized, dilute oxalic/nitric acid cleaning reagent toward dissolving the bulk non-radioactive waste components. Solubility tests were performed by direct sludge contact with the oxalic/nitric acid reagent and with sludge that had been pretreated and acidified with dilute nitric acid. For comparison purposes, separate samples were also contacted with pure, concentrated oxalic acid following current baseline tank chemical cleaning methods. One goal of testing with the optimized reagent was to compare the total amounts of oxalic acid and water required for sludge dissolution using the baseline and optimized cleaning methods. A second objective was to compare the two methods with regard to the dissolution of actinide species known to be drivers for SRS tank closure Performance Assessments (PA). Additionally, solubility tests were conducted with Tank 5 sludge using acidic and caustic permanganate-based methods focused on the “targeted” dissolution of actinide species.

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Radioactive Demonstration Of Mineralized Waste Forms Made From Hanford Low Activity Waste (Tank Farm Blend) By Fluidized Bed Steam Reformation (FBSR)

The U.S. Department of Energy’s Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford’s tank waste. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in the time frame required by the Hanford Federal Facility Agreement and Consent Order, also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Supplemental Treatment is likely to be required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. The Supplemental Treatment chosen will immobilize that portion of the retrieved LAW that is not sent to the WTP’s LAW Vitrification facility into a solidified waste form. The solidified waste will then be disposed on the Hanford site in the Integrated Disposal Facility (IDF). Fluidized Bed Steam Reforming (FBSR) offers a moderate temperature (700-750°C) continuous method by which LAW can be processed irrespective of whether the waste contain organics, nitrates, sulfates/sulfides, chlorides, fluorides, volatile radionuclides or other aqueous components. The FBSR technology can process these wastes into a crystalline ceramic (mineral) waste form. The mineral waste form that is produced by co-processing waste with kaolin clay in an FBSR process has been shown to be comparable to LAW glass, i.e. leaches Tc-99, Re and Na at <2g/m 2 during ASTM C1285 (Product Consistency) durability testing. Monolithing of the granular FBSR product was investigated to prevent dispersion during transport or burial/storage. Monolithing in an inorganic geopolymer binder, which is amorphous, macro-encapsulates the granules, and the monoliths pass ANSI/ANS 16.1 and ASTM C1308 durability testing with Re achieving a Leach Index (LI) of 9 (the Hanford Integrated Disposal Facility, IDF, criteria for Tc-99) after a few days and Na achieving an LI of >6 (the Hanford IDF criteria for Na) in the first few hours. The granular and monolithic waste forms also pass the EPA Toxicity Characteristic Leaching Procedure (TCLP) for all Resource Conservation and Recovery Act (RCRA) components at the Universal Treatment Standards (UTS). Two identical Benchscale Steam Reformers (BSR) were designed and constructed at SRNL, one to treat non-radioactive simulants and the other to treat actual radioactive wastes. The results from the non-radioactive BSR were used to determine the parameters needed to operate the radioactive BSR in order to confirm the findings of non-radioactive FBSR pilot scale and engineering scale tests and to qualify an FBSR LAW waste form for applications at Hanford. Radioactive testing commenced using SRS LAW from Tank 50 chemically trimmed to look like Hanford’s blended LAW known as the Rassat simulant as this simulant composition had been tested in the non-radioactive BSR, the non-radioactive pilot scale FBSR at the Science Applications International Corporation-Science and Technology Applications Research (SAIC-STAR) facility in Idaho Falls, ID and in the TTT Engineering Scale Technology Demonstration (ESTD) at Hazen Research Inc. (HRI) in Denver, CO. This provided a “tie back” between radioactive BSR testing and non-radioactive BSR, pilot scale, and engineering scale testing. Approximately six hundred grams of non-radioactive and radioactive BSR product were made for extensive testing and comparison to the non-radioactive pilot scale tests performed in 2004 at SAIC-STAR and the engineering scale test performed in 2008 at HRI with the Rassat simulant. The same mineral phases and off-gas species were found in the radioactive and non-radioactive testing. The granular ESTD and BSR products (radioactive and non-radioactive) were analyzed for total constituents and durability tested as a granular waste form. A subset of the granular material was stabilized in a clay based geopolymer matrix at 42% and 65% FBSR loadings and durability tested as a monolith waste form. The 65 wt% FBSR loaded monolith made with clay (radioactive) was more durable than the 67-68 wt% FBSR loaded monoliths made from fly ash (non-radioactive) based on short term PCT testing. Long term, 90 to 107 day, ASTM C1308 testing (similar to ANSI/ANS 16.1 testing) was only performed on two fly ash geopolymer monoliths at 67-68 wt% FBSR loading and three clay geopolymer monoliths at 42 wt% FBSR loading. More clay geopolymers need to be made and tested at longer times at higher FBSR loadings for comparison to the fly ash monoliths. Monoliths made with metakaolin (heat treated) clay are of a more constant composition and are very reactive as the heat treated clay is amorphous and alkali activated. The monoliths made with fly ash are subject to the inherent compositional variation found in fly ash as it is a waste product from burning coal and it contains unreactive components such as mullite. However, both the fly ash and the clay based monoliths perform well in long term ASTM C1308 testing.

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Identification and Quantification of Technetium Species in Hanford Waste Tank AN-102

Technetium-99 (Tc) generated from the fission of 235U and 239Pu in high yields is one of the most difficult contaminants to be addressed at the U.S. Department of Energy Hanford Site. In strongly alkaline solutions typifying Hanford tank waste, Tc exists as pertechnetate (TcO4-) (oxidation state VII) as well as in reduced forms (oxidation state < VII) collectively known as non-pertechnetate species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non- pertechnetate species and their identification in the actual tank waste samples, which would facilitate development of new treatment technologies effective for dissimilar Tc species. Toward this objective, a spectroscopic library of the Tc(I) [fac-Tc(CO)3]+ and Tc(IV, VII) compounds was generated using a range of techniques and applied to the characterization of the actual tank waste supernatant collected from the tank 241-AN-102 at Hanford, WA. A sample of the 241-AN-102 tank waste supernatant was processed to adjust Na concentration to about 5.6 M and remove 137Cs by spherical resorcinol-formaldehyde (sRF) ion exchange resin. Cesium-loaded sRF column was eluted with 0.5 M HNO3. As received AN-102, Cs-depleted AN-102 effluent, and sRF eluate fractions were comprehensively characterized for chemical composition and speciation of Tc using 99Tc nuclear magnetic resonance spectroscopy and X-ray absorption spectroscopy. It was demonstrated for the first time that non-pertechnetate Tc present in the 241-AN-102 tank waste is composed of several low-valent Tc species, including the Tc(I) [fac-Tc(CO)3]+ and Tc(IV) compounds. This is the second experimental observation of the [fac-Tc(CO)3]+ species in the Hanford tank waste and the first demonstration of multiple forms of non-pertechnetate species existing simultaneously in the waste, cumulatively highlighting their importance for the waste processing.

Low Activity Waste (LAW), High Level Waste, nuclea↗

Enraf reference level updates for high-level nuclear waste tanks at Hanford site - 15705

The United States Department of Energy Hanford Site Tank Farm has implemented a system for monitoring tank waste levels in all single-shell tanks (SST), double-shell tanks (DST) and miscellaneous catch tanks using Enraf Series 854 level gauges. To ensure an accurate computation of the tank waste levels, a precise calculation of the tank reference level must be kept up to date. A system was developed where accurate waste tank reference levels are kept consistent with each Enraf assembly in the Tank Farms to ensure the continuation of accurate waste level monitoring. (authors)

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Cesium Exchange onto Crystalline Silicotitanate from Blended Hanford Tank Wastes

The Tank Side Cesium Removal (TSCR) system was developed to filter and remove cesium (Cs and 137 Cs) from Hanford tank waste supernate in preparation for vitrification. The Cs removal will be conducted with crystalline silicotitanate (CST) ion exchange media. Under the planned waste-processing strategy, the tank waste supernate will be queued for TSCR processing in tank 241-AP-107 (AP-107). Once AP-107 tank waste volume is sufficiently depleted, the waste supernate from tank 241-AP-105 (AP-105, the holding tank before transfer to AP-107) will be transferred to tank AP-107. Supernate from another tank will be transferred to the holding tank, AP-105, for eventual transfer to tank AP-107. These supernate streams will undergo blending in tanks AP-107 and AP-105; the volume blend ratios will be driven by how much the tank waste supernate volumes are depleted before the next tank waste is added. The consequence of tank waste blending on Cs uptake by CST was of interest and was tested via batch contacts; results are reported herein.

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Plutonium Particles in Samples Extracted from Hanford Tank Waste TX-118 and SY-102 (Interim Report)

This is an interim report on the characterization of plutonium particles from Hanford wastes. Plutonium-bearing particles were located in Hanford Waste Tank solids, SY-102 and TX-118. The particles in SY-102 were small, typically < 5 to 10 µm in length, and were crystalline plutonium oxide with an association of other elements at minor levels, including bismuth, phosphate, and iron based on Sanning Electron Microscopy (SEM) observations. Plutonium particles from SY-102 were extracted from the surface mount using the SEM-Focused Ion Beam (FIB) and prepared for Scanning Transmission Electron Microscopy (STEM). This was the first time that this type of analysis of Hanford tank waste solids has been attempted. The STEM analysis indicated a complex co-precipitation of plutonium oxide with bismuth and phosphate. Diffraction and imaging only partially matched with a PuO 2 phase. Pockets of phosphate and bismuth reside within the plutonium oxide suggesting that these phases formed at the same time. The SEM analysis indicated that the plutonium particles from TX-118 were a mixed bismuth-phosphate phase and plutonium oxide. These particles will be examined with SEM-FIB at a later time and then will undergo more detailed examination in the STEM.

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A History of Hanford Tank Waste, Implications for Waste Treatment and Disposal

More than 40 years of plutonium processing have left almost 56 million gallons of mixed radioactive waste sequestered in 177 underground tanks on the Hanford Site. Three different processing technologies were employed for plutonium purification in addition to uranium scavenging and fission product removal from the tank waste. All of these chemical processes have contributed to a complex waste stream that varies from tank to tank that presents downstream processing challenges to render the waste into a safe form for long-term storage. The current disposition pathway for Hanford tank waste is vitrification. To maximize waste loading and minimize the number of high-level waste canisters stored in a geologic repository, pretreatment of the waste is required. Both pretreatment and vitrification operations are impacted by the waste composition.

Separations, filtration, ion exchange↗

Aluminum Hydroxide Solubility in Sodium Hydroxide Solutions Containing Nitrite/Nitrate of Relevance to Hanford Tank Waste

The technical basis to support the One System River Protection Project Integrated Flowsheet assumption for diluting staged direct feed low-activity waste (DFLAW) from the Hanford waste tanks with raw river water must be assessed in light of the risk of aluminum hydroxide (gibbsite) precipitation prior to the subsequent transfer of tank contents into the low-activity waste pretreatment system (LAWPS) and/or the Tank Side Cesium Removal (TSCR) system from days to months after dilution. Aluminum solubility must be predicted as a function of the significant variables that influence gibbsite dissolution and precipitation. These variables include (i) other solution components that meaningfully affect the activity coefficient of either hydroxide or the aluminate ion, particularly nitrate and nitrite; and (ii) temperature. Based on a review of waste solubility data and the impact of dilution on solution stabilities with specific focus on aluminum hydroxide, data gaps associated with the impact of these variables on the prediction of gibbsite solubility with temperature were identified. An experimental program to aid in the prediction of gibbsite solubility in NaOH solutions containing a range of sodium nitrate and sodium nitrite concentrations up to the solubility limit at a range of temperatures has been conducted. The results of these investigations are summarized in this report.

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Determining the Release of Radionuclides from Tank Waste Residual Solids: FY2015 Report

Methodology development for pore water leaching studies has been continued to support Savannah River Site High Level Waste tank closure efforts. For FY2015, the primary goal of this testing was the achievement of target pH and Eh values for pore water solutions representative of local groundwater in the presence of grout or grout-representative (CaCO 3 or FeS) solids as well as waste surrogate solids representative of residual solids expected to be present in a closed tank. For oxidizing conditions representative of a closed tank after aging, a focus was placed on using solid phases believed to be controlling pH and E h at equilibrium conditions. For three pore water conditions (shown below), the target pH values were achieved to within 0.5 pH units. Tank 18 residual surrogate solids leaching studies were conducted over an E h range of approximately 630 mV. Significantly higher Eh values were achieved for the oxidizing conditions (ORII and ORIII) than were previously observed. For the ORII condition, the target Eh value was nearly achieved (within 50 mV). However, E h values observed for the ORIII condition were approximately 160 mV less positive than the target. E h values observed for the RRII condition were approximately 370 mV less negative than the target. Achievement of more positive and more negative E h values is believed to require the addition of non-representative oxidants and reductants, respectively. Plutonium and uranium concentrations measured during Tank 18 residual surrogate solids leaching studies under these conditions (shown below) followed the general trends predicted for plutonium and uranium oxide phases, assuming equilibrium with dissolved oxygen. The highest plutonium and uranium concentrations were observed for the ORIII condition and the lowest concentrations were observed for the RRII condition. Based on these results, it is recommended that these test methodologies be used to conduct leaching studies with actual Tank 18 residual solids material. Actual waste testing will include leaching evaluations of technetium and neptunium, as well as plutonium and uranium.

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Hanford Double Shell Waste Tank Corrosion Studies FY2020 (Final Report)

For fiscal year (FY) 2020, the Savannah River National Laboratory (SRNL) focused on three experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of deposits on the tanks’ inner sidewalls and bottoms. The second task studied vapor space corrosion (VSC) of the secondary liner using two commercially available vapor corrosion inhibitors (VCIs) at manufacturer recommended dosages. Finally, the third task investigated the long-term open circuit potential (OCP) drift for mill-scale coupons, coupons with polished surfaces, and partial mill-scale coupons that were exposed to tank waste simulants. Additional tests were performed to evaluate the OCP drift as a function of the quantity and composition of organic compounds added to the simulant. A test that was included in the matrix that established the new chemistry limits for tank corrosion, but was previously unreported, was presented and reviewed as well.

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Disposition of Hanford Tank Waste sludge from tank 241-AY-102 and the 241-Aa/241-AX farm tanks - 15298

WRPS must retrieve the waste from double-shell tank 241-AY-102 and the single-shell tanks in the 241A and -AX Tank Farms, while finishing the ongoing retrieval of tanks in the 241-C Tank Farm. Given the limited availability of double-shell tank space, the challenge is to identify an optimum combination of double-shell tanks that can safely and efficiently serve as receiver tanks for the combined inventory of sludge wastes from these source tanks. A multiple-criteria, weighted-sum decision-making process, in conjunction with sensitivity analysis and a Pareto evaluation, was used to determine the optimum set of receiver tanks. (authors)

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Critical Assumptions in the F-Tank Farm Operational Closure Documentation Regarding Waste Tank Internal Configurations

The intent of this document is to provide clarification of critical assumptions regarding the internal configurations of liquid waste tanks at operational closure, with respect to F-Tank Farm (FTF) closure documentation. For the purposes of this document, FTF closure documentation includes: (1) Performance Assessment for the F-Tank Farm at the Savannah River Site (hereafter referred to as the FTF PA) (SRS-REG-2007-00002), (2) Basis for Section 3116 Determination for Closure of F-Tank Farm at the Savannah River Site (DOE/SRS-WD-2012-001), (3) Tier 1 Closure Plan for the F-Area Waste Tank Systems at the Savannah River Site (SRR-CWDA-2010-00147), (4) F-Tank Farm Tanks 18 and 19 DOE Manual 435.1-1 Tier 2 Closure Plan Savannah River Site (SRR-CWDA-2011-00015), (5) Industrial Wastewater Closure Module for the Liquid Waste Tanks 18 and 19 (SRRCWDA-2010-00003), and (6) Tank 18/Tank 19 Special Analysis for the Performance Assessment for the F-Tank Farm at the Savannah River Site (hereafter referred to as the Tank 18/Tank 19 Special Analysis) (SRR-CWDA-2010-00124). Note that the first three FTF closure documents listed apply to the entire FTF, whereas the last three FTF closure documents listed are specific to Tanks 18 and 19. These two waste tanks are expected to be the first two tanks to be grouted and operationally closed under the current suite of FTF closure documents and many of the assumptions and approaches that apply to these two tanks are also applicable to the other FTF waste tanks and operational closure processes.

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The Continued Need for Modeling and Scaled Testing to Advance the Hanford Tank Waste Mission

Hanford tank wastes are chemically complex slurries of liquids and solids that can exhibit changes in rheological behavior during retrieval and processing. The Hanford Waste Treatment and Immobilization Plant (WTP) recently abandoned its planned approach to use computational fluid dynamics (CFD) supported by testing at less than full scale to verify the design of vessels that process these wastes within the plant. The commercial CFD tool selected was deemed too difficult to validate to the degree necessary for use in the design of a nuclear facility. Alternative, but somewhat immature, CFD tools are available that can simulate multiphase flow of non-Newtonian fluids. Yet both CFD and scaled testing can play an important role in advancing the Hanford tank waste mission—in supporting the new verification approach, which is to conduct testing in actual plant vessels; in supporting waste feed delivery, where scaled testing is ongoing; as a fallback approach to design verification if the Full Scale Vessel Testing Program is deemed too costly and time-consuming; to troubleshoot problems during commissioning and operation of the plant; and to evaluate the effects of any proposed changes in operating conditions in the future to optimize plant performance.

Fluid Dynamics↗

Evaluation of Technologies for Destruction of LDR Organics in Hanford Tank Waste

Aqueous Hanford tank wastes contain soluble organics and some tanks contain small amounts (<100 mg/L) of organics that are regulated under the Land Disposal Restrictions (LDR) portions of the Resource Conservation and Recovery Act (RCRA). Most of these organics can be removed by evaporation, but some are not. Methods to destroy/remove organics that are regulated by the LDR section of the RCRA and that are not removed by evaporation may be needed if ambient temperature waste treatment processes are used to immobilize aqueous Hanford tank wastes. To identify viable and compatible organic removal or destruction pretreatment methods an evaluation was performed by a team of researchers. The team utilized a Systems Engineering Approach that examines all aspects of the technology, based on information available in the literature and the experience of the team members. That evaluation led to recommendations by the team to perform testing on technologies to determine efficacy in destroying organics in Hanford tank waste liquids. The primary technologies recommended are chemical oxidants, including permanganate, peroxymonosulfate or peroxydisulfate (PMS/PDS), hydrogen peroxide, and ozone. Ultraviolet light irradiation of the stream with a solid catalyst sorbent is also recommended for testing. A generalized description of the test program is also included.

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Tank Inspection NDE Results for Waste Tanks 25, 26, 33, 34, 41 and 50 (FY2019)

In-service inspection is an essential element of a comprehensive structural integrity program for the carbon steel waste tanks at the Savannah River Site. Inspection confirms the effectiveness of corrosion controls used to preclude localized and general corrosion of the tanks. Ultrasonic inspection (UT) is used to detect general wall thinning, pitting and interface attack, as well as vertically oriented cracks through inspection of an 8.5 inch wide strip extending over the accessible height of the primary tank wall and knuckle regions. selected welds are also inspected for cracking parallel or perpendicular to the weld. The inspections were performed from the annular space of the Type III/IIIA waste storage tanks. The ISI Program calls for thickness mapping and crack detection scans on specified areas of the tank covering all present and historic waste interface levels and selected welds with particular emphasis on the highest stress region of the tank.

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Laboratory-Scale Melter Systems for Simulated and Real AP-105 Tank Waste - 19301

The Hanford Tank Waste Treatment and Immobilization Plant is being constructed to vitrify the nuclear waste stored in underground tanks on the Hanford Site. Through this conversion process, waste components become partitioned into one of two product streams: glass and off-gas, including condensate. A small-scale melter system is appropriate for analyzing the waste-to-glass process because it does not require the high volumes of input waste or resource commitment of a large-scale melter system while providing dynamic information that can be difficult to determine from batch reactions in a crucible system. A continuous laboratory-scale melter (CLSM) was sized to collect the relevant process and chemical information from obtainable volumes of Hanford tank waste and designed to operate with a continuous feeding process while periodically pouring glass product and collecting off-gas. Two CLSMs were constructed: one in a non-radioactive environment for processing waste simulants and another in a fume hood capable of handling radioactive material for processing actual Hanford tank waste. Multiple waste simulants were first tested in the non-radioactive CLSM to determine the processability and desired operating window for actual tank waste. About 12 liters of real waste from Hanford tank 241-AP-105 were received, filtered, and ion exchanged for removal of Cs-137. This quantity of waste was vitrified into 9.5 kg of glass product over the course of ∼15 hours of feeding to the CLSM. (authors)

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Gas Retention and Release from Hanford Site Sludge Waste Tanks

Radioactive wastes from nuclear fuel processing are stored in large underground storage tanks at the Hanford Site. Solid wastes can be divided into saltcake (mostly precipitated soluble sodium nitrate and nitrite salts with some interstitial liquid consisting of concentrated salt solutions) and sludge (mostly low solubility aluminum and iron compounds with relatively dilute interstitial liquid). Waste generates hydrogen through the radiolysis of water and organic compounds, radio-thermolytic decomposition of organic compounds, and corrosion of a tank’s carbon steel walls. Nonflammable gases, such as nitrous oxide and nitrogen, are also produced. Additional flammable gases (e.g., ammonia and methane) are generated by chemical reactions between various degradation products of organic chemicals present in the tanks.

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