Potential Waste Tank Headspace Concentrations of DDE and 1-Naphthylamine

Recent studies conducted for the Hanford Waste Treatment Plant (WTP) found that the centrifuged solids from tanks 241-AW-101, 241-AN-107, and 241-C-104 contained two carcinogenic chemicals, 1-naphthylamine and 2,2-bis(4-chlorophenyl)-1,1-dichloroethene (DDE), that had never been detected in tank headspaces. This report estimates the potential headspace concentrations associated with these two compounds. The calculation was based on a comparison of headspace concentrations and waste concentrations for sixteen other organic compounds in the passively-ventilated tank 241-C-104. An approximate relation was found between the compounds? solubilities in water and their headspace concentrations. The relation was used to estimate the 241-C-104 headspace concentration that would result from the maximum measured waste concentrations of DDE and 1-naphthylamine. On the basis of the assumptions made in this report about organic compound transport and equilibration, the DDE concentration was estimated at well below one part per trillion, below standard analytical detection limits. However, 1-naphthylamine could potentially be present in the headspace of a passively ventilated tank at the 30 ppb level

Assessment of New Calculation Method for Toxicological Sums-of-Fractions for Hanford Tank Wastes

The toxicological source terms used for potential accident assessment in the Tank Farms DSA are based on toxicological sums-of-fractions (SOFs) that were calculated in fiscal years 2002 and 2003 based on the Best Basis Inventory (BBI) from May 2002, using the method described by Cowley et al. (2003). The present report describes a modified SOF-calculation method that is to be used in future toxicological updates and assessments and compares its results (for the 2002 BBI) to those of the old method. The new method generally calculated different (usually larger) SOFs than the old. The dominant reason was the more conservative way in which the new method represents concentration variability, in that it uses the waste layer with the maximum SOF to represent the tank SOF. The old method had used a tank-average waste composition and SOF. Differences between thermodynamically modeled and BBI solubilities were the next most common reason for differences between old (modeled) and new (BBI) SOFs, particularly in the liquid phase. The solubility-related changes in SOF were roughly equally distributed between increases and decreases. Changes in the effective toxicities of TOC and lead, which resulted from changes in the compounds in which these analytes were considered to be present, were the third most common reason. These toxicity changes increased SOFs and therefore were in a conservative direction

Assessment of New Calculation Method for Toxicological Sums-of-Fractions for Hanford Tank Farm Wastes

The toxicological source terms used for potential accident assessment in the Hanford Tank Farms DSA are based on toxicological sums-of-fractions (SOFs) that were calculated based on the Best Basis Inventory (BBI) from May 2002, using a method that depended on thermodynamic equilibrium calculations of the compositions of liquid and solid phases. The present report describes a simplified SOF-calculation method that is to be used in future toxicological updates and assessments and compares its results (for the 2002 BBI) to those of the old method

Small-Scale Spray Releases: Orifice Plugging Test Results

One of the events postulated in the hazard analysis at the Waste Treatment and Immobilization Plant (WTP) and other U.S. Department of Energy (DOE) nuclear facilities, is a breach in process piping that produces aerosols with droplet sizes in the respirable range. The current approach for predicting the size and concentration of aerosols produced in a spray leak involves extrapolating from correlations published in the literature. These correlations are based on results obtained from small engineered spray nozzles using pure liquids with Newtonian fluid behavior. The narrow ranges of physical properties on which the correlations are based do not cover the wide range of slurries and viscous materials present in the WTP and across processing facilities in the DOE complex. Two key technical areas were identified where testing results were needed to improve the technical basis by reducing the uncertainty introduced by extrapolating existing literature results. The first technical need was to quantify the role of slurry particles in small breaches in which the slurry particles may plug and result in substantially reduced, or even negligible, respirable fraction formed by high pressure sprays. The second technical need was to determine the aerosol droplet size distribution and volume from prototypic breaches and fluids, specifically including sprays from larger breaches with slurries where data from the literature are largely absent. To address these technical areas, small- and large-scale test stands were constructed and operated with simulants to determine the aerosol release fractions and aerosol generation rates from a range of breach sizes and geometries. The properties of the simulants represented the range of properties expected in the WTP process streams and included water, sodium salt solutions, slurries containing boehmite or gibbsite, and a hazardous chemical simulant. The effect of anti-foam agents (AFA) was assessed with most of the simulants. Orifices included round holes and rectangular slots. Much of the testing was conducted at pressures of 200 and 380 psi, but some tests were conducted at 100 psi. Testing the largest postulated breaches was deemed impractical because of the large size of some of the WTP equipment. The purpose of the study described in this report is to provide experimental data for the first key technical area, potential plugging of small breaches, by performing small-scale tests with a range of orifice sizes and orientations representative of the WTP conditions. The simulants used were chosen to represent the range of process stream properties in the WTP. Testing conducted after the plugging tests in the small- and large-scale test stands addresses the second key technical area, aerosol generation. The results of the small-scale aerosol generation tests are included in Mahoney et al. 2012. The area of spray generation from large breaches is covered by large-scale testing in Schonewill et al. 2012

Large-Scale Spray Releases: Additional Aerosol Test Results

One of the events postulated in the hazard analysis for the Waste Treatment and Immobilization Plant (WTP) and other U.S. Department of Energy (DOE) nuclear facilities is a breach in process piping that produces aerosols with droplet sizes in the respirable range. The current approach for predicting the size and concentration of aerosols produced in a spray leak event involves extrapolating from correlations reported in the literature. These correlations are based on results obtained from small engineered spray nozzles using pure liquids that behave as a Newtonian fluid. The narrow ranges of physical properties on which the correlations are based do not cover the wide range of slurries and viscous materials that will be processed in the WTP and in processing facilities across the DOE complex. To expand the data set upon which the WTP accident and safety analyses were based, an aerosol spray leak testing program was conducted by Pacific Northwest National Laboratory (PNNL). PNNL’s test program addressed two key technical areas to improve the WTP methodology (Larson and Allen 2010). The first technical area was to quantify the role of slurry particles in small breaches where slurry particles may plug the hole and prevent high-pressure sprays. The results from an effort to address this first technical area can be found in Mahoney et al. (2012a). The second technical area was to determine aerosol droplet size distribution and total droplet volume from prototypic breaches and fluids, including sprays from larger breaches and sprays of slurries for which literature data are mostly absent. To address the second technical area, the testing program collected aerosol generation data at two scales, commonly referred to as small-scale and large-scale testing. The small-scale testing and resultant data are described in Mahoney et al. (2012b), and the large-scale testing and resultant data are presented in Schonewill et al. (2012). In tests at both scales, simulants were used to mimic the relevant physical properties projected for actual WTP process streams

Small-Scale Spray Releases: Initial Aerosol Test Results

One of the events postulated in the hazard analysis at the Waste Treatment and Immobilization Plant (WTP) and other U.S. Department of Energy (DOE) nuclear facilities is a breach in process piping that produces aerosols with droplet sizes in the respirable range. The current approach for predicting the size and concentration of aerosols produced in a spray leak involves extrapolating from correlations reported in the literature. These correlations are based on results obtained from small engineered spray nozzles using pure liquids with Newtonian fluid behavior. The narrow ranges of physical properties on which the correlations are based do not cover the wide range of slurries and viscous materials that will be processed in the WTP and across processing facilities in the DOE complex. Two key technical areas were identified where testing results were needed to improve the technical basis by reducing the uncertainty due to extrapolating existing literature results. The first technical need was to quantify the role of slurry particles in small breaches where the slurry particles may plug and result in substantially reduced, or even negligible, respirable fraction formed by high-pressure sprays. The second technical need was to determine the aerosol droplet size distribution and volume from prototypic breaches and fluids, specifically including sprays from larger breaches with slurries where data from the literature are scarce. To address these technical areas, small- and large-scale test stands were constructed and operated with simulants to determine aerosol release fractions and generation rates from a range of breach sizes and geometries. The properties of the simulants represented the range of properties expected in the WTP process streams and included water, sodium salt solutions, slurries containing boehmite or gibbsite, and a hazardous chemical simulant. The effect of anti-foam agents was assessed with most of the simulants. Orifices included round holes and rectangular slots. The round holes ranged in size from 0.2 to 4.46 mm. The slots ranged from (width × length) 0.3 × 5 to 2.74 × 76.2 mm. Most slots were oriented longitudinally along the pipe, but some were oriented circumferentially. In addition, a limited number of multi-hole test pieces were tested in an attempt to assess the impact of a more complex breach. Much of the testing was conducted at pressures of 200 and 380 psi, but some tests were conducted at 100 psi. Testing the largest postulated breaches was deemed impractical because of the large size of some of the WTP equipment. This report presents the experimental results and analyses for the aerosol measurements obtained in the small-scale test stand. It includes a description of the simulants used and their properties, equipment and operations, data analysis methodologies, and test results. The results of tests investigating the role of slurry particles in plugging small breaches are reported in Mahoney et al. (2012). The results of the aerosol measurements in the large-scale test stand are reported in Schonewill et al. (2012) along with an analysis of the combined results from both test scales

Hanford Waste Physical and Rheological Properties: Data and Gaps

The Hanford Site in Washington State manages 177 underground storage tanks containing approximately 250,000 m3 of waste generated during past defense reprocessing and waste management operations. These tanks contain a mixture of sludge, saltcake and supernatant liquids. The insoluble sludge fraction of the waste consists of metal oxides and hydroxides and contains the bulk of many radionuclides such as the transuranic components and 90Sr. The saltcake, generated by extensive evaporation of aqueous solutions, consists primarily of dried sodium salts. The supernates consist of concentrated (5-15 M) aqueous solutions of sodium and potassium salts. The 177 storage tanks include 149 single-shell tanks (SSTs) and 28 double -hell tanks (DSTs). Ultimately the wastes need to be retrieved from the tanks for treatment and disposal. The SSTs contain minimal amounts of liquid wastes, and the Tank Operations Contractor is continuing a program of moving solid wastes from SSTs to interim storage in the DSTs. The Hanford DST system provides the staging location for waste feed delivery to the Department of Energy (DOE) Office of River Protection’s (ORP) Hanford Tank Waste Treatment and Immobilization Plant (WTP). The WTP is being designed and constructed to pretreat and then vitrify a large portion of the wastes in Hanford’s 177 underground waste storage tanks

Estimate of Hanford Waste Rheology and Settling Behavior

The U.S. Department of Energy (DOE) Office of River Protection’s Waste Treatment and Immobilization Plant (WTP) will process and treat radioactive waste that is stored in tanks at the Hanford Site. Piping, pumps, and mixing vessels have been selected to transport, store, and mix the high-level waste slurries in the WTP. This report addresses the analyses performed by the Rheology Working Group (RWG) and Risk Assessment Working Group composed of Pacific Northwest National Laboratory (PNNL), Bechtel National Inc. (BNI), CH2M HILL, DOE Office of River Protection (ORP) and Yasuo Onishi Consulting, LLC staff on data obtained from documented Hanford waste analyses to determine a best-estimate of the rheology of the Hanford tank wastes and their settling behavior. The actual testing activities were performed and reported separately in referenced documentation. Because of this, many of the required topics below do not apply and are so noted

Results of Large-Scale Testing on Effects of Anti-Foam Agent on Gas Retention and Release

The U.S. Department of Energy (DOE) Office of River Protection’s Waste Treatment Plant (WTP) will process and treat radioactive waste that is stored in tanks at the Hanford Site. The waste treatment process in the pretreatment facility will mix both Newtonian and non-Newtonian slurries in large process tanks. Process vessels mixing non-Newtonian slurries will use pulse jet mixers (PJMs), air sparging, and recirculation pumps. An anti-foam agent (AFA) will be added to the process streams to prevent surface foaming, but may also increase gas holdup and retention within the slurry. The work described in this report addresses gas retention and release in simulants with AFA through testing and analytical studies. Gas holdup and release tests were conducted in a 1/4-scale replica of the lag storage vessel operated in the Pacific Northwest National Laboratory (PNNL) Applied Process Engineering Laboratory using a kaolin/bentonite clay and AZ-101 HLW chemical simulant with non-Newtonian rheological properties representative of actual waste slurries. Additional tests were performed in a small-scale mixing vessel in the PNNL Physical Sciences Building using liquids and slurries representing major components of typical WTP waste streams. Analytical studies were directed at discovering how the effect of AFA might depend on gas composition and predicting the effect of AFA on gas retention and release in the full-scale plant, including the effects of mass transfer to the sparge air. The work at PNNL was part of a larger program that included tests conducted at Savannah River National Laboratory (SRNL) that is being reported separately. SRNL conducted gas holdup tests in a small-scale mixing vessel using the AZ-101 high-level waste (HLW) chemical simulant to investigate the effects of different AFAs, their components, and of adding noble metals. Full-scale, single-sparger mass transfer tests were also conducted at SRNL in water and AZ-101 HLW simulant to provide data for PNNL’s WTP gas retention and release modeling

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