Goethite Bench-scale and Large-scale Preparation Tests

The Hanford Waste Treatment and Immobilization Plant (WTP) is the keystone for cleanup of high-level radioactive waste from our nation's nuclear defense program. The WTP will process high-level waste from the Hanford tanks and produce immobilized high-level waste glass for disposal at a national repository, low activity waste (LAW) glass, and liquid effluent from the vitrification off-gas scrubbers. The liquid effluent will be stabilized into a secondary waste form (e.g. grout-like material) and disposed on the Hanford site in the Integrated Disposal Facility (IDF) along with the low-activity waste glass. The major long-term environmental impact at Hanford results from technetium that volatilizes from the WTP melters and finally resides in the secondary waste. Laboratory studies have indicated that pertechnetate ({sup 99}TcO{sub 4}{sup -}) can be reduced and captured into a solid solution of {alpha}-FeOOH, goethite (Um 2010). Goethite is a stable mineral and can significantly retard the release of technetium to the environment from the IDF. The laboratory studies were conducted using reaction times of many days, which is typical of environmental subsurface reactions that were the genesis of this new process. This study was the first step in considering adaptation of the slow laboratory steps to a larger-scale and faster process that could be conducted either within the WTP or within the effluent treatment facility (ETF). Two levels of scale-up tests were conducted (25x and 400x). The largest scale-up produced slurries of Fe-rich precipitates that contained rhenium as a nonradioactive surrogate for {sup 99}Tc. The slurries were used in melter tests at Vitreous State Laboratory (VSL) to determine whether captured rhenium was less volatile in the vitrification process than rhenium in an unmodified feed. A critical step in the technetium immobilization process is to chemically reduce Tc(VII) in the pertechnetate (TcO{sub 4}{sup -}) to Tc(Iv)by reaction with the ferrous ion, Fe{sup 2+}-Fe{sup 2+} is oxidized to Fe{sup 3+} - in the presence of goethite seed particles. Rhenium does not mimic that process; it is not a strong enough reducing agent to duplicate the TcO{sub 4}{sup -}/Fe{sup 2+} redox reactions. Laboratory tests conducted in parallel with these scaled tests identified modifications to the liquid chemistry necessary to reduce ReO{sub 4}{sup -} and capture rhenium in the solids at levels similar to those achieved by Um (2010) for inclusion of Tc into goethite. By implementing these changes, Re was incorporated into Fe-rich solids for testing at VSL. The changes also changed the phase of iron that was in the slurry product: rather than forming goethite ({alpha}-FeOOH), the process produced magnetite (Fe{sub 3}O{sub 4}). Magnetite was considered by Pacific Northwest National Laboratory (PNNL) and VSL to probably be a better product to improve Re retention in the melter because it decomposes at a higher temperature than goethite (1538 C vs. 136 C). The feasibility tests at VSL were conducted using Re-rich magnetite. The tests did not indicate an improved retention of Re in the glass during vitrification, but they did indicate an improved melting rate (+60%), which could have significant impact on HLW processing. It is still to be shown whether the Re is a solid solution in the magnetite as {sup 99}Tc was determined to be in goethite

Engineering-Scale Demonstration of DuraLith and Ceramicrete Waste Forms

To support the selection of a waste form for the liquid secondary wastes from the Hanford Waste Immobilization and Treatment Plant, Washington River Protection Solutions (WRPS) has initiated secondary waste form testing on four candidate waste forms. Two of the candidate waste forms have not been developed to scale as the more mature waste forms. This work describes engineering-scale demonstrations conducted on Ceramicrete and DuraLith candidate waste forms. Both candidate waste forms were successfully demonstrated at an engineering scale. A preliminary conceptual design could be prepared for full-scale production of the candidate waste forms. However, both waste forms are still too immature to support a detailed design. Formulations for each candidate waste form need to be developed so that the material has a longer working time after mixing the liquid and solid constituents together. Formulations optimized based on previous lab studies did not have sufficient working time to support large-scale testing. The engineering-scale testing was successfully completed using modified formulations. Further lab development and parametric studies are needed to optimize formulations with adequate working time and assess the effects of changes in raw materials and process parameters on the final product performance. Studies on effects of mixing intensity on the initial set time of the waste forms are also needed

Corrosion of Metal Inclusions In Bulk Vitrification Waste Packages

The primary purpose of the work reported here is to analyze the potential effect of the release of technetium (Tc) from metal inclusions in bulk vitrification waste packages once they are placed in the Integrated Disposal Facility (IDF). As part of the strategy for immobilizing waste from the underground tanks at Hanford, selected wastes will be immobilized using bulk vitrification. During analyses of the glass produced in engineering-scale tests, metal inclusions were found in the glass product. This report contains the results from experiments designed to quantify the corrosion rates of metal inclusions found in the glass product from AMEC Test ES-32B and simulations designed to compare the rate of Tc release from the metal inclusions to the release of Tc from glass produced with the bulk vitrification process. In the simulations, the Tc in the metal inclusions was assumed to be released congruently during metal corrosion as soluble TcO4-. The experimental results and modeling calculations show that the metal corrosion rate will, under all conceivable conditions at the IDF, be dominated by the presence of the passivating layer and corrosion products on the metal particles. As a result, the release of Tc from the metal particles at the surfaces of fractures in the glass releases at a rate similar to the Tc present as a soluble salt. The release of the remaining Tc in the metal is controlled by the dissolution of the glass matrix. To summarize, the release of 99Tc from the BV glass within precipitated Fe is directly proportional to the diameter of the Fe particles and to the amount of precipitated Fe. However, the main contribution to the Tc release from the iron particles is over the same time period as the release of the soluble Tc salt. For the base case used in this study (0.48 mass% of 0.5 mm diameter metal particles homogeneously distributed in the BV glass), the release of 99Tc from the metal is approximately the same as the release from 0.3 mass% soluble Tc salt in the castable refractory block and it is released over the same time period as the salt. Therefore, to limit the impact of precipitated Fe on the release of 99Tc, both the amount of precipitated Fe in the BV glass and the diameter of these particles should be minimized

PEP Integrated Test D Run Report Caustic and Oxidative Leaching in UFP-VSL-T02A

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed and operated as part of a plan to respond to issue M12, "Undemonstrated Leaching Processes" of the External Flowsheet Review Team (EFRT) issue response plan. The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario (Test B and D) has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario (Test A) has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP and vessels UFP VSL-00001A and B in the WTP PTF). In Test D, 19M sodium hydroxide (NaOH, caustic) was added to the waste slurry in the UFP VSL T02 vessel after the solids were concentrated to ~20% undissolved solids. The NaOH was added to leach solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by heating to 85°C using direct injection of steam to accelerate the leach process. The main difference of Test D compared to Test B is that the leach temperature is 85°C for 24 hrs as compared to 100°C for 12 hours. The other difference is the Test D simulant had Cr in the simulant from the start of processing and Test B had Cr added to adjust the simulant composition after aluminum leaching. Following the caustic leach, the UFP-VSL-T02A vessel contents are cooled using the vessel cooling jacket. The slurry was then concentrated to 17 wt% undissolved solids and washed with inhibited water to remove NaOH and other soluble salts. Next, the slurry was oxidatively leached using sodium permanganate to solubilize chrome. The slurry was then washed to remove the dissolved chrome and concentrated

PEP Run Report for Simulant Shakedown/Functional Testing

Pacific Northwest National Laboratory (PNNL) has been tasked by Bechtel National Inc. (BNI) on the River Protection Project-Waste Treatment Plant (RPP-WTP) project to perform research and development activities to resolve technical issues identified for the Pretreatment Facility (PTF). The Pretreatment Engineering Platform (PEP) was designed, constructed, and operated as part of a plan to respond to issue M12, "Undemonstrated Leaching Processes." The PEP is a 1/4.5-scale test platform designed to simulate the WTP pretreatment caustic leaching, oxidative leaching, ultrafiltration solids concentration, and slurry washing processes. The PEP replicates the WTP leaching processes using prototypic equipment and control strategies. The PEP also includes non-prototypic ancillary equipment to support the core processing. Two operating scenarios are currently being evaluated for the ultrafiltration process (UFP) and leaching operations. The first scenario has caustic leaching performed in the UFP-2 ultrafiltration feed vessels (i.e., vessel UFP-VSL-T02A in the PEP; and vessels UFP-VSL-00002A and B in the WTP PTF). The second scenario has caustic leaching conducted in the UFP-1 ultrafiltration feed preparation vessels (i.e., vessels UFP-VSL-T01A and B in the PEP; vessels UFP-VSL-00001A and B in the WTP PTF). In both scenarios, 19-M sodium hydroxide solution (NaOH, caustic) is added to the waste slurry in the vessels to leach solid aluminum compounds (e.g., gibbsite, boehmite). Caustic addition is followed by a heating step that uses direct injection of steam to accelerate the leach process. Following the caustic leach, the vessel contents are cooled using vessel cooling jackets and/or external heat exchangers. The main difference between the two scenarios is that for leaching in UFP-1, the 19-M NaOH is added to un-concentrated waste slurry (3-8 wt% solids), while for leaching in UFP-2, the slurry is concentrated to nominally 20 wt% solids using cross-flow ultrafiltration before the addition of caustic. In both scenarios, following the caustic leach, the slurry was then concentrated to 17 wt% and washed with inhibited water to remove NaOH and other soluble salts. Next, the slurry was oxidatively leached using sodium permanganate to solubilize chrome. The slurry was then washed to remove the dissolved chrome and concentrated

Letter Report: LAW Simulant Development for Cast Stone Screening Test

More than 56 million gallons of radioactive and hazardous waste are stored in 177 underground storage tanks at the U.S. Department of Energy’s (DOE’s) Hanford Site in southeastern Washington State. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the wastes and immobilize them in a glass waste form. The WTP includes a pretreatment facility to separate the wastes into a small volume of high-level waste (HLW) containing most of the radioactivity and a larger volume of low-activity waste (LAW) containing most of the nonradioactive chemicals. The HLW will be converted to glass in the HLW vitrification facility for ultimate disposal at an offsite federal repository. At least a portion (~35%) of the LAW will be converted to glass in the LAW vitrification facility and will be disposed of onsite at the Integrated Disposal Facility (IDF). The pretreatment and HLW vitrification facilities will have the capacity to treat and immobilize the wastes destined for each facility. However, a second facility will be needed for the expected volume of additional LAW requiring immobilization. A cementitious waste form known as Cast Stone is being considered to provide the required additional LAW immobilization capacity. The Cast Stone waste form must be acceptable for disposal in the IDF. The Cast Stone waste form and immobilization process must be tested to demonstrate that the final Cast Stone waste form can comply with waste acceptance criteria for the IDF disposal facility and that the immobilization processes can be controlled to consistently provide an acceptable waste form product. Further, the waste form must be tested to provide the technical basis for understanding the long term performance of the waste form in the IDF disposal environment. These waste form performance data are needed to support risk assessment and performance assessment (PA) analyses of the long-term environmental impact of the waste disposal in the IDF. A testing program was developed in fiscal year (FY) 2012 describing in some detail the work needed to develop and qualify Cast Stone as a waste form for the solidification of Hanford LAW (Westsik et al. 2012). Included within Westsik et al. (2012) is a section on the near-term needs to address Tri-Party Agreement Milestone M-062-40ZZ. The objectives of the testing program to be conducted in FY 2013 and FY 2014 are to: • Determine an acceptable formulation for the LAW Cast Stone waste form. • Evaluate sources of dry materials for preparing the LAW Cast Stone. • Demonstrate the robustness of the Cast Stone waste form for a range of LAW compositions. • Demonstrate the robustness of the formulation for variability in the Cast Stone process. • Provide Cast Stone contaminant release data for PA and risk assessment evaluations. The first step in determining an acceptable formulation for the LAW Cast Stone waste form is to conduct screening tests to examine expected ranges in pretreated LAW composition, waste stream concentrations, dry-materials sources, and mix ratios of waste feed to dry blend. A statistically designed test matrix will be used to evaluate the effects of these key parameters on the properties of the Cast Stone as it is initially prepared and after curing. The second phase of testing will focus on selection of a baseline Cast Stone formulation for LAW and demonstrating that Cast Stone can meet expected waste form requirements for disposal in the IDF. It is expected that this testing will use the results of the screening tests to define a smaller suite of tests to refine the composition of the baseline Cast Stone formulation (e.g. waste concentration, water to dry mix ratio, waste loading)

Pretreatment Engineering Platform Phase 1 Final Test Report

Pacific Northwest National Laboratory (PNNL) was tasked by Bechtel National Inc. (BNI) on the River Protection Project, Hanford Tank Waste Treatment and Immobilization Plant (RPP-WTP) project to conduct testing to demonstrate the performance of the WTP Pretreatment Facility (PTF) leaching and ultrafiltration processes at an engineering-scale. In addition to the demonstration, the testing was to address specific technical issues identified in Issue Response Plan for Implementation of External Flowsheet Review Team (EFRT) Recommendations - M12, Undemonstrated Leaching Processes.( ) Testing was conducted in a 1/4.5-scale mock-up of the PTF ultrafiltration system, the Pretreatment Engineering Platform (PEP). Parallel laboratory testing was conducted in various PNNL laboratories to allow direct comparison of process performance at an engineering-scale and a laboratory-scale. This report presents and discusses the results of those tests

Alternatives to Forest Gathering of Plant Materials for Hula Lei Adornment

With increasing interest in hula competitions in Hawaii, gathering of plant materials for adornment has begun to negatively impact some native forest ecosystems. A small survey explored conditions under which kumu hula (dance leaders) might consider alternatives to forest gathering. Growing plants in communal gardens or purchasing from commercial growers who might arise to service the need are suggested