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Aerosol Formation from High-Pressure Sprays for Supporting the Safety Analysis for the Hanford Waste Treatment and Immobilization Plant

The Waste Treatment and Immobilization Plant (WTP) at Hanford is being designed and built to pretreat and vitrify waste currently stored in underground tanks at Hanford. One of the postulated events in the hazard analysis for the WTP is a breach in process piping that produces a pressurized spray with small droplets that can be transported into ventilation systems. Literature correlations are currently used for estimating the generation rate and size distribution of aerosol droplets in postulated spray releases. These correlations, however, are based on results obtained from small engineered nozzles using Newtonian liquids that do not contain slurry particles and thus do not accurately represent the fluids and breaches in the WTP. A test program was developed to measure the generation rate of droplets suspended in a test chamber and droplet size distribution from a range of prototypic sprays. A novel test method was developed to allow measurement of sprays from small to very large breaches and also includes the effect of aerosol generation from splatter when the spray impacts on walls. Results show that the aerosol generation rate increases with increasing the orifice area, though with a weaker dependence on orifice area than the currently-used correlation. A comparison of water sprays to slurry sprays with 8 to 20 wt% gibbsite or boehmite particles shows that the presence of slurry particles depresses the release fraction compared to water for droplets above 10 μm and increases the release fraction below this droplet size.

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Conservative Release Fraction Correlation for Spray Releases

Washington River Protection Solutions, LLC (WRPS) is planning to conduct repairs in the Liquid Effluent Retention Facility (LERF), and prior to conducting this work they will re-evaluate the hazard category designation for LERF. As part of this evaluation, WRPS needs estimates of the release fraction of potential accidental sprays, because a spray release is a potential bounding accident. Pacific Northwest National Laboratory previously developed a conservative correlation for the cumulative generation rate (volume per time) of aerosol droplets less than or equal to specific sizes from spray releases as a function of the spray pressure, orifice area, and droplet diameter. To obtain release fraction estimates from the conservative generation rate correlation, the correlation needs to be recast by dividing the aerosol generation rate by the flow rate of a spray. In the current study, a conservative release fraction correlation was developed from the conservative aerosol generation rate correlation developed previously by dividing the generation rate correlation by the flow rate of a spray using an orifice flow rate equation and then this correlation was adjusted to be conservative. Test data were also extrapolated to a lower pressure than the lowest pressure tested (100 psig) for the spray data used for developing the previous conservative generation rate correlation. The new conservative release fraction correlation was then used to predict release fractions of respirable droplets (droplets = 10 µm) for four specific pipes that are part of LERF.

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Technical Assessment of Internal Surface Smoothness and Particle Transmission to the American National Standard ANSI/HPS N13.1-2011

Clause 6.4.4 in the American National Standards Institute / Health Physics Society (ANSI/HPS) N13.1 standard, Sampling and Monitoring Releases of Airborne Radioactive Substances From the Stacks and Ducts of Nuclear Facilities, addresses the internal smoothness of sample transport lines present between the nozzle and the analyzer (or collector). This paper evaluates the appropriateness of this clause by comparing roughness length of various materials against the required relative roughness, and by conducting computational fluid dynamic modeling. The results indicate that the inclusion of numerical criteria for the relative roughness of pipe by the ANSI Standard N13.1 (Section 6.4.4) is not appropriate. Recommended alternatives would be elimination of the numerical criteria, or modification of the standard to include a variable criteria for relative roughness.

operational topics, aerosols, air sampling, atmosp↗

Decommissioning of the Reactor Pressure Vessels by Remote Controlled Thermal Cutting Segmentation Facilities of the ZION Nuclear Power Plant at ZION, USA - 16599

This paper presents the experiences for the segmentation of both reactor pressure vessels (RV) Units 1 and 2 at the ZION nuclear power plant. The Zion Station project was the first to use the large-scale application of thermal cutting (oxy-propane) technology in the USA. The elaborate planning and engineering was the basis for a quick, safe and flawless project execution without any aerosol migration or release of contamination. The used segmentation technology based on industry-tested methods with its big advantage of availability and spare parts inventory. For safeguarding Simulation (interfering edge analysis), animations and Trials with mock-ups dummies were executed prior. Also risk assessments and rescue concepts are part of the planning. Lean project organization for decommissioning and the flexibility, creativity, willingness to cooperate and willing for uninterrupted decisions of client and contractor are the essential basis for a successful project execution and a short project duration. The remote controlled segmentation of the RV of Unit 2 was performed in 3 month an in Unit 1 in less than 2 month.

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Reference document for LANL stack sampling and ANSI N13.1 (Article) Gielow RL and McNamee MR 1993. Numerical Flue Gas Flow Modeling for Continuous Emissions Monitoring Applications. EPRI CEM Users Group Meeting. Baltimore. RP1961-13

American National Standard N13.1 “sets forth guidelines and performance criteria for sampling the emissions of airborne radioactive substances in the air discharge ducts and stacks of nuclear facilities. Emphasis is on extractive sampling from a location in a stack or duct where the contaminant is well mixed. At such a location, sampling may be conducted at a single point. This standard provides performance-based criteria for the use of air sampling probes, transport lines, sample collectors, sample monitoring instruments, and gas flow measuring methods. This standard also covers sampling program objectives, quality assurance issues, developing air sampling action levels, system optimization, and system performance verification. Workplace, containment, and environmental air monitoring are not addressed. Specific sample analysis methods and the reporting or interpreting of results are also not addressed.” (HPS 2011).

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High-Precision Mass Measurements At TRIGA-TRAP

In order to study neutron-rich nuclides far from the valley of stability as well as long-lived actinoids the double Penning-trap mass spectrometer TRIGA-TRAP has been recently installed at the research reactor TRIGA Mainz. Short-lived neutron-rich fission products are produced by thermal neutron-induced fission of an actinoid target installed close to the reactor core. A helium gas-jet system with carbon aerosol particles is used to extract the fission products to the experiment. The Penning trap system has already been commissioned. Off-line mass measurements are routinely performed using a recently developed laser ablation ion source, and the gas-jet system has been tested. An overview of the experiment and current status will be given.

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Analysis of Dust Samples Collected from an In-Service Interim Storage System at the Maine Yankee Nuclear Site.

In July, 2016, the Electric Power Research Institute and industry partners performed a field test at the Maine Yankee Nuclear Site, located near Wiscasset, Maine. The primary goal of the field test was to evaluate the use of robots in surveying the surface of an in-service interim storage canister within an overpack; however, as part of the demonstration, dust and soluble salt samples were collected from horizontal surfaces within the interim storage system. The storage system is a vertical system made by NAC International, consisting of a steel-lined concrete overpack containing a 304 stainless steel (SS) welded storage canister. The canister did not contain spent fuel but rather greater-than-class-C waste, which did not generate significant heat, limiting airflow through the storage system. The surfaces that were sampled for deposits included the top of the shield plug, the side of the canister, and a shelf at the bottom of the overpack, just below the level of the pillar on which the canister sits. The samples were sent to Sandia National Laboratories for analysis. This report summarizes the results of those analyses. Because the primary goal of the field test was to evaluate the use of robots in surveying the surface of the canister within the overpack, collection of dust samples was carried out in a qualitative fashion, using paper filters and sponges as the sampling media. The sampling focused mostly on determining the composition of soluble salts present in the dust. It was anticipated that a wet substrate would more effectively extract soluble salts from the surface that was sampled, so both the sponges and the filter paper were wetted prior to being applied to the surface of the metal. Sampling was accomplished by simply pressing the damp substrate against the metal surface for two minutes, and then removing it. It is unlikely that the sampling method quantitatively collected dust or salts from the metal surface; however, both substrates did extract a significant amount of material. The paper filters collected both particles, trapped within the cellulose fibers of the filter, and salts, while the sponges collected only the soluble salts, with very few particles. Upon delivery to Sandia, both collection media were analyzed using the same methods. The soluble salts were leached from the substrates and analyzed via ion chromatography, and insoluble minerals were analyzed by scanning electron microscopy and energy dispersive X-ray spectroscopy. The insoluble minerals were found to consist largely of terrestrially-derived mineral fragments, dominantly quartz and biotite. Large (mm-sized) aggregates of calcium carbonate, calcium silicate, and calcium aluminum silicate were also present. The aggregates had one flat, smooth surface and one well crystallized surface, and were interpreted to be efflorescence on the inside of the overpack and in the vent, formed by seepage of cement pore fluids through joints in the steel liner of the overpack. Such efflorescence was commonly observed during the boroscope inspection of the storage system at the site. The material may have flaked off and fallen to the point where the dust was collected, or may have brushed off onto the sponges when the robot was retrieved through the inlet vent. Chemical analysis showed that the soluble salts on the shield plug were Ca- and Na-rich, with lesser K and minor Mg; the anionic component was dominated by SO 4 and Cl, with minor amounts of NO 3 . The cation composition of the soluble salts from the overpack shelf and the canister surface was similar to the filter samples, but the anions differed significantly, being dominantly NO 3 with lesser Cl and only trace SO 4 . The salts appear to represent a mixture of sea-salts (probably partially converted to nitrates and sulfates by particle-gas conversion reactions) and continental salt aerosols. Ammonium, a common component in continental aerosols, was not observed and may have been lost by degassing from the canister surface or after collection during sample storage and transportation. The demonstration at Maine Yankee has shown that the robot and sampling method used for the test can successfully be used to collect soluble salts from metal surfaces within an interim storage system overpack. The results were consistent from sample to sample, suggesting that a representative sample of the soluble salts was being collected. However, it is unlikely that the salt samples collected here represent quantitative sampling of the salts on the surfaces evaluated; for that reason, chloride densities per unit area are not presented here. It should also be noted that the relevance to storage systems at the site that contain SNF may be limited, because a heat- generating canister will result in greater airflow through the overpack, affecting dust deposition rates and possibly salt compositions.

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SRNL Review And Assessment Of WTP UFP-02 Sparger Design And Testing

During aerosol testing conducted by Parsons Constructors and Fabricators, Inc. (PCFI), air sparger plugging was observed in small-scale and medium-scale testing. Because of this observation, personnel identified a concern that the steam spargers in Pretreatment Facility vessel UFP-02 could plug during Waste Treatment and Immobilization Plant (WTP) operation. The U. S. Department of Energy (DOE) requested that Savannah River National Laboratory (SRNL) provide consultation on the evaluation of known WTP bubbler, and air and steam sparger issues. The authors used the following approach for this task: reviewed previous test reports (including smallscale testing, medium-scale testing, and Pretreatment Engineering Platform [PEP] testing), met with Bechtel National, Inc. (BNI) personnel to discuss sparger design, reviewed BNI documents supporting the sparger design, discussed sparger experience with Savannah River Site Defense Waste Processing Facility (DWPF) and Sellafield personnel, talked to sparger manufacturers about relevant operating experience and design issues, and reviewed UFP-02 vessel and sparger drawings.

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An environmental friendly animal waste disposal process with ammonia recovery and energy production: Experimental study and economic analysis

Highlights: • An environmental friendly animal manure waste treatment scheme was proposed. • Ammonia was removed and recovered from manure waste in the form of struvite. • Horse manure waste gasification was successfully conducted in a 10 kW gasifier. • Gasifier produces comparable or higher heating value of syngas as other feedstocks. • The proposed scheme is financially superior to pure gasification and incineration. - Abstract: Animal manure waste is considered as an environmental challenge especially in farming areas mainly because of gaseous emission and water pollution. Among all the pollutants emitted from manure waste, ammonia is of greatest concern as it could contribute to formation of aerosols in the air and could hardly be controlled by traditional disposal methods like landfill or composting. On the other hand, manure waste is also a renewable source for energy production. In this work, an environmental friendly animal waste disposal process with combined ammonia recovery and energy production was proposed and investigated both experimentally and economically. Lab-scale feasibility study results showed that 70% of ammonia in the manure waste could be converted to struvite as fertilizer, while solid manure waste was successfully gasified in a 10 kW downdraft fixed-bed gasifier producing syngas with the higher heating value of 4.9 MJ/(N m{sup 3}). Based on experimental results, economic study for the system was carried out using a cost-benefit analysis to investigate the financial feasibility based on a Singapore case study. In addition, for comparison, schemes of gasification without ammonia removal and incineration were also studied for manure waste disposal. The results showed that the proposed gasification-based manure waste treatment process integrated with ammonia recovery was most financially viable.

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MULTIPHYSICS-MODELING OF FIRE-INDUCED URANIUM AEROSOL FORMATION – A-POSTERIORI BENCHMARKING OF EXPERIMENTS

The formulation and solution of a model that properly described the temperature profiles of uranium in fire conditions was prepared, verified and validated, to support a-posteriori benchmarking of historical experiments. Data from the multi-physics model combined with data regression from the experiments provides a useful tool for exploring sources of potential bias in historical experiments. The approaches used are augmented by visual observations and photographic evidence allowing for correlations between various phenomena, independent of whether or not that specific phenomena are part of the validated model. In this manner, the validated model is a tool for a-posteriori benchmarking, and not a model designed to replicate the experimental output exactly for any specific experiment. For experiments like the Clark (2015) experiments, this integrated model (including chemistry) demonstrated that the largest bias was associated in the metallurgy of the coupons. The model developed does serve as a basis for defending which of the historical alloys tested are the most appropriate for any other alloy being considered (e.g., one that has not yet been tested). The model identifies key reactions that impact uranium chemistry and can significantly bias experimental results. Through use of the model and energy balances, data from historical experiments by Elder and Tinkle (1980) were regressed and benchmarked. This study identifies that all uranium alloys are not equal and that there are distinct differences between the dominant alloys representing distinct metallurgical phases.

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Airborne Release Fractions from Surrogate Nuclear Waste Fires Containing Lanthanide Nitrates and Depleted Uranium Nitrate in 30% Tributyl Phosphate in Kerosene

Airborne contaminants from fires containing nuclear waste represent significant health hazards and shape the design and operation of nuclear facilities. Much of the data used to formulate DOE-HDBK-3010-94, “Airborne Release Fractions/Rates and Respirable Fractions for Nonreactor Nuclear Facilities,” from the U.S. Department of Energy, were taken over 40 years ago. The objectives of this study were to reproduce experiments from Pacific Northwest Laboratories conducted in June 1973 employing current aerosol measurement methods and instrumentation, develop an enhanced understanding of particulate formation and transport from fires containing nuclear waste, and provide modeling and experimental capabilities for updating current standards and practices in nuclear facilities. A special chamber was designed to conduct small fires containing 25 mL of flammable waste containing lutetium nitrate, ytterbium nitrate, or depleted uranium nitrate. Carbon soot aerosols showed aggregates of primary particles ranging from 20 to 60 nm in diameter. In scanning electron microscopy, ~200-nm spheroidal particles were also observed dispersed among the fractal aggregates. The 200-nm spherical particles were composed of metal phosphates. Airborne release fractions (ARFs) were characterized by leaching filter deposits and quantifying metal concentrations with mass spectrometry. The average mass-based ARF for 238 U experiments was 1.0 × 10 -3 with a standard deviation of 7.5 × 10 -4 . For the original experiments, DOE-HDBK-3010-94 states, “Uranium ARFs range from 2 × 10 -4 to 3 × 10 -3 , an uncertainty of approximately an order of magnitude.” Therefore, current measurements were consistent with DOE-HDBK-3010-94 values. ARF values for lutetium and ytterbium were approximately one to two orders of magnitude lower than 238 U. Furthermore, metal nitrate solubility may have varied with elemental composition and temperature, thereby affecting ARF values for uranium surrogates (Yb and Lu). In addition to ARF data, solution boiling temperatures and evaporation rates can also be deduced from experimental data.

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Criticality Control Overpack Fire Testing (Phase III)

This report will describe the one test conducted during phase III of the Pipe Overpack Container (POC) test campaign, present preliminary results from these tests, and discuss implications for the Criticality Control Overpack (CCO). The goal of this test was to see if aerosol surrogate material inside the Criticality Control Container (CCC) gets released when the drum lid of the CCO comes off during a thirty-minute long, fully-engulfing, fire test. As expected from POC tests conducted in Phase I and II of this test campaign, the CCO drum lid is ejected about one minute after the drum is exposed to fully-engulfing flames. The remaining pressure inside the drum is high enough to eject the top plywood dunnage a considerable distance from the drum. Subsequently, most of the bottom plywood dunnage supporting the CCC burns off during and after the fire. High pressure buildup inside the CCC and inside two primary containers holding the surrogate powder also results in damage to the filter media of the CCC and the filter-house, thread attachment of the primary canisters. No discernable release of surrogate powder material was detected from the two primary containers when pre- and post-test average mass were compared. However, when the average masses are corrected to account for possible uncertainties in mass measurements, error overlap does not preclude the possibility that some surrogate powder mass may have been lost from these primary canisters. Still, post-test conditions of the secondary canisters enclosing these two primary canisters suggest it is very unlikely this mass loss would have escaped into the CCC.

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FY23 Update: Aerosol Sampling for the Canister Deposition Field Demonstration

This report describes the results of preliminary testing of aerosol monitoring equipment that will be used to continuously monitor the aerosol source term for the multi-year Canister Deposition Field Demonstration (CDFD). These data are required inputs for the development and validation of models for the deposition of dust and potentially corrosive salts on the surface of spent nuclear fuel (SNF) dry storage canisters. Surface salt loads correlate with the extent of corrosion damage on a metal surface, and potentially to the likelihood and timing of initiation of stress corrosion cracks. Aerosols will be monitored at the CDFD site using three instruments. A Dekati ® ELPI+ cascade impactor will be used for real-time monitoring of aerosol particle sizes. It will also collect dust in 14 size bins on impactor targets that can be chemically analyzed to determine the soluble salts present as a function of particle size. However, this instrument can only measure dried aerosols, with a diameter of <10 µm. The second instrument is a Topas laser particle size spectrometer, which provides real-time monitoring of aerosol particle sizes up to ~40 µm in size. It monitors both the ambient (potentially deliquesced) aerosol particle size distributions required for the dust deposition models and the distributions of the equivalent dried particles, allowing correlation with the Dekati ® data. However, it does not discriminate between inert dust particles and salt aerosols, and it does not retain samples of the different particle sizes for later analysis. The third instrument that will monitor aerosols at the CDFD site is a Clean Air Status and Trends Network (CASTNET) tower, which uses a multiple canister system to collect weekly samples for analysis to total suspended aerosol particle compositions and atmospheric gas concentrations. This status report describes work in FY23 to develop the capabilities for using these tools. In two training exercises, the cascade impactor and laser particle sizer were deployed in two different testing environments, one indoor and one outdoor. For the cascade impactor, the tests provided opportunities for the operators to familiarize themselves with impactor substrate preparation, and post-test sample removal and analysis. For the laser particle sizer, the tests were used to evaluate different instrument parameters, to determine the most appropriate settings for capturing transient events. Data and samples were collected for weeks to months for each test, and the results are presented here. In addition to the preliminary testing, contracts were developed with WSP Analytical Labs for sample preparation and analysis of the cascade impactor samples. The impactor tower from outdoor test was delivered to WSP and used to train the staff there in disassembly, sample extraction, sample analysis, and tower reassembly with new target substrates. These are tasks that WSP will be performing routinely for the CDFD project. The CASTNET system cannot be purchased or tested until an actual site has been selected for the CDFD test. Work for this FY has been restricted to preparation of contracts for purchasing the CASTNET tower, and for sample analysis, once the tower is in operation.

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A Predictive Model for Offgas Composition in Waste Glass Melters - Spring 2021 SULI General Audience Abstract

Approximately 56 million gallons of nuclear waste are currently stored in 177 underground storage tanks at the Hanford site in Washington state. A portion of the tank waste is targeted for immobilization by converting the nuclear waste to borosilicate glass through a process called vitrification. During vitrification, emissions are produced in addition to the intended glass product. These emissions, contained in a volume above the molten glass called the plenum, are composed of water vapor, air components, aerosols, particulates, and other gaseous species that result from evaporation, reactions, and air influx. The formation of these gasses causes the surface of the glass to foam. To reduce foaming, sucrose is added to the waste stream before the conversion to glass. Sucrose also reduces the formation of hazardous gasses in the plenum including nitrous oxides, NOx, and carboxides, COx. However, if excess sucrose is present, the reactions that produce the gasses in the plenum will be incomplete, and increased levels of NOx and COx can be observed. The Waste Treatment and Immobilization Plant at the Hanford site is equipped with the technology to treat the plenum emissions. Though many tests have been run to determine the presence of particulates in the plenum emissions, there is does not exist an established method to confidently predict the composition of the gaseous species in the plenum prior to treatment without physical testing. A model was created in the process modeling software Aspen Plus to predict the composition of NOx and COx in the plenum. The model employs a constant stirred tank reactor and user-defined reaction chemistry to determine the plenum composition. To verify the model, the offgas predicted by the model were compared to available offgas data for ten different feed compositions. It is demonstrated that the developed Aspen Plus model is capable of predicting the composition of NOx and COx in the plenum.

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Five Year Comparison of Mixing Height Determinations at the Savannah River Site

Air quality dispersion modeling is performed for the Savannah River Site (SRS) to demonstrate compliance with applicable regulations. The AMS/EPA Regulatory Model (AERMOD) modeling system is an EPA recommended model for air quality applications with a data preprocessor (AERMET) to incorporate meteorological data collected on site. AERMET parameterizes or calculates meteorological variables that are not directly measured onsite. One of the parameters estimated by AERMET is the atmospheric mixing height. While the mixing height is not currently a measurement input into AERMET, SRS has the capability to measure the local mixing height. The Savannah River National Laboratory (SRNL) operates a Vaisala CL31 Lidar Ceilometer which estimates mixing height from aerosol backscatter. This study compares the parameterized mixing height from AERMET to the ceilometer estimated mixing height for the current regulatory period at SRS incorporating data from 2015-2019. Results from this study showed the average daily minimum values (morning) from AERMET were an order of magnitude lower than the commonly used Holzworth (1972) method and the ceilometer estimated mixing heights. Additionally, on average, the ceilometer exhibited a daily maximum mixing height value that occurred 1-3 hours later than the AERMET estimated maximum. This difference is likely due to the nighttime atmospheric mixing height assumptions and calculations used by AERMET. The AERMET algorithm cuts off mixing height growth at sunset while the ceilometer data show ongoing evening convection typical of the southeastern United States. These results suggest that the AERMET parametrization scheme assumptions may not be representative of a forested landscape and evening convection which could account for more mixing overnight. The results obtained in this study are significant for air dispersion modeling applications for regulatory purposes and worker safety. Mixing height can impact model estimated pollutant concentrations. A greater mixing height will provide more volume for pollutant dispersion. This report documents efforts to quantify the dependence of mixing height inputs toward a conservative estimated pollutant concentration.

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Materials Identification System for 200 liter/55 gallon Waste Drums using Computer Tomographic Techniques - 17162

In 2014 a thermal runaway event within a drum in-situ at the Waste Isolation Pilot Plant (WIPP) facility near Carlsbad, NM, resulted in the drum being breached and activity released. This emphasized the need for a better determination of drum contents and identification of material combinations and in-drum conditions. Enhanced characterization is required to identify and quantify the presence of absorbent materials, determine whether they are organic or inorganic, locate their position in the drum with respect to other materials, and quantify how much liquid is being held in the absorbent material. As part of the waste characterization process to ensure compliance with the WIPP waste acceptance criteria, drums are currently inspected by Real Time Radioscopic (RTR) x-ray to identify prohibited items such as free liquids and un-punctured aerosol cans, but that technique cannot satisfy these newly identified requirements, and a new approach to non-destructive examination was required. This approach complements the current RTR inspection with Cone-Beam Area Detector Computed Tomography (CT) scanning of the whole drum, followed by more-quantitative CT scanning of specific areas of concern, using a highly collimated Linear Detector Array. The density of representative waste drums required x-ray energies of up to 9 MeV, which meant that sorting of materials by their photo-electric absorption is not viable as this occurs in the 80 - 180 keV range. However, a notable characteristic of higher energy imaging in this context is the general correspondence between material density and total attenuation in the 1.5-4.0 MeV range due to Compton Scatter. Development of the imaging chain, comprising the x-ray source and the detectors was critical to achieving the required system performance. Theoretical analysis of the energy spectra of the 9 MeV beam, and filtration of the beam to remove the lower energies which cause beam hardening artifacts in the image was required. Theoretical evaluation of the required efficiency and image acquisition performance of area detectors and linear array detectors, was carried out to complete the selection of equipment. A system of density calibration rods was designed and, together with the selected equipment, was configured and used to acquire cone-beam CT data and line-scan CT data by scanning a 55 gallon drum containing surrogate waste. From the acquired data, CT reconstruction was performed and the basis of algorithms to identify materials were developed. Following this, a series of blind tests were done using a range of surrogate materials the contents of which were unknown to the system operators. (authors)

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MODELING THE IMPACT OF ELEVATED MERCURY IN DEFENSE WASTE PROCESSING FACILITY MELTER FEED ON THE MELTER OFF-GAS SYSTEM-PRELIMINARY REPORT

The Defense Waste Processing Facility (DWPF) is currently evaluating an alternative Chemical Process Cell (CPC) flowsheet to increase throughput. It includes removal of the steam-stripping step, which would significantly reduce the CPC processing time and lessen the sampling needs. However, its downside would be to send 100% of the mercury that comes in with the sludge straight to the melter. For example, the new mercury content in the Sludge Batch 5 (SB5) melter feed is projected to be 25 times higher than that in the SB4 with nominal steam stripping of mercury. This task was initiated to study the impact of the worst-case scenario of zero-mercury-removal in the CPC on the DWPF melter offgas system. It is stressed that this study is intended to be scoping in nature, so the results presented in this report are preliminary. In order to study the impact of elevated mercury levels in the feed, it is necessary to be able to predict how mercury would speciate in the melter exhaust under varying melter operating conditions. A homogeneous gas-phase oxidation model of mercury by chloride was developed to do just that. The model contains two critical parameters pertaining to the partitioning of chloride among HCl, Cl, Cl{sub 2}, and chloride salts in the melter vapor space. The values for these parameters were determined at two different melter vapor space temperatures by matching the calculated molar ratio of HgCl (or Hg{sub 2}Cl{sub 2}) to HgCl{sub 2} with those measured during the Experimental-Scale Ceramic Melter (ESCM) tests run at the Pacific Northwest National Laboratory (PNNL). The calibrated model was then applied to the SB5 simulant used in the earlier flowsheet study with an assumed mercury stripping efficiency of zero; the molar ratio of Cl-to-Hg in the resulting melter feed was only 0.4, compared to 12 for the ESCM feeds. The results of the model run at the indicated melter vapor space temperature of 650 C (TI4085D) showed that due to excessive shortage of chloride, only 6% of the mercury fed is expected to get oxidized, mostly as HgCl, while the remaining mercury would exist either as elemental mercury vapor (90%) or HgO (4%). Noting that the measured chloride level in the SB5 qualification sample was an order of magnitude lower than that used in the SB5 simulant, the degree of chloride shortage will be even greater. As a result, the projected level of HgCl in the actual SB5 melter exhaust will be even lower than 6% of the total mercury fed, while that of elemental mercury is likely to be greater than 90%. The homogeneous oxidation of mercury in the off-gas was deemed to be of primary importance based on the postulation that mercury and other volatile salts form submicron sized aerosols upon condensation and thus remain largely in the gas stream downstream of the quencher where they can deposit in the off-gas lines, Steam-Atomized Scrubbers (SAS), and High-Efficiency Mist Eliminator (HEME). Formation of these submicron semi-volatile salts in the condensate liquid is considered to be unlikely, so the liquid phase reactions were considered to be less important. However, subsequent oxidation of mercury in the liquid phase in the off-gas system was examined in a simplified model of the off-gas condensate. It was found that the condensate chemistry was consistent with further oxidation of elemental mercury to Hg{sub 2}Cl{sub 2} and conversion of HgO to chlorides. The results were consistent with the available experimental data. It should also be noted that the model predictions presented in this report do not include any physically entrained solids, which typically account for much of the off-gas carryover on a mass basis. The high elemental mercury vapor content predicted at the DWPF Quencher inlet means that physically entrained solids could provide the necessary surface onto which elemental mercury vapor could condense, thereby coating the solids as well as the internal surfaces of the off-gas system with mercury. Clearly, there are many process benefits to be gained by removing the steam-stripping step from the CPC cycle. The goal of this task was to study what adverse impact the zero-mercury-removal scenario would have on the DWPF melter off-gas system operation. It is stressed again that this study was intended to be scoping in nature, so the results presented in this report are preliminary. Any further substantiation of these results for actual implementation into the DWPF flowsheet would require an in-depth modeling study of all three reaction zones, including the aqueous-phase reactions in the quencher, OGCT, Steam Atomized Scrubber (SAS), and off-gas condenser with recirculated condensate, and the proof-of-principle experiments.

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Processing Plan for Potentially Reactive/Ignitable Remote Handled Transuranic Waste at the Idaho Cleanup Project - 12090

Remote Handle Transuranic (RH-TRU) Waste generated at Argonne National Laboratory - East, from the examination of irradiated and un-irradiated fuel pins and other reactor materials requires a detailed processing plan to ensure reactive/ignitable material is absent to meet WIPP Waste Acceptance Criteria prior to shipping and disposal. The Idaho Cleanup Project (ICP) approach to repackaging Lot 2 waste and how we ensure prohibited materials are not present in waste intended for disposal at Waste Isolation Pilot Plant 'WIPP' uses an Argon Repackaging Station (ARS), which provides an inert gas blanket. Opening of the Lot 2 containers under an argon gas blanket is proposed to be completed in the ARS. The ARS is an interim transition repackaging station that provides a mitigation technique to reduce the chances of a reoccurrence of a thermal event prior to rendering the waste 'Safe'. The consequences, should another thermal event be encountered, (which is likely) is to package the waste, apply the reactive and or ignitable codes to the container, and store until the future treatment permit and process are available. This is the same disposition that the two earlier containers in the 'Thermal Events' were assigned. By performing the initial handling under an inert gas blanket, the waste can sorted and segregate the fines and add the Met-L-X to minimize risk before it is exposed to air. The 1-gal cans that are inside the ANL-E canister will be removed and each can is moved to the ARS for repackaging. In the ARS, the 1-gal can is opened in the inerted environment. The contained waste is sorted, weighed, and visually examined for non compliant items such as unvented aerosol cans and liquids. The contents of the paint cans are transferred into a sieve and manipulated to allow the fines, if any, to be separated into the tray below. The fines are weighed and then blended with a minimum 5:1 mix of Met-L-X. Other debris materials found are segregated from the cans into containers for later packaging. Recoverable fissile waste material (Fuel and fuel-like pieces) suspected of containing sodium bonded pieces) are segregated and will remain in the sieve or transferred to a similar immersion basket in the ARS. The fuel like pieces will be placed into a container with sufficient water to cover the recoverable fissile waste. If a 'reactive characteristic' is present the operator will be able to observe the formation of 'violent' hydrogen gas bubbles. When sodium bonded fuel-like pieces are placed in water the expected reaction is a non-violent reaction that does not meet the definition of reactivity. It is expected that there will be a visible small stream of bubbles present if there is any sodium-bonded fuel-like piece placed in the water. The test will be completed when there is no reaction or the expected reaction is observed..At that point, the fuel like pieces complete the processing cycle in preparation for characterization and shipment to WIPP. If a violent reaction occurs, the fuel-like pieces will be removed from the water, split into the required fissile material content, placed into a screened basket in a 1 gallon drum and drummed out of the hot cell with appropriate RCRA codes applied and placed into storage until sodium treatment is available. These 'violent' reactions will be evidenced by gas bubbles being evolved at the specimen surface where sodium metal is present. The operators will be trained to determine if the reaction is 'violent' or 'mild'. If a 'violent' reaction occurs, the sieve will be immediately removed from the water, placed in a 1 gallon paint can, canned in the argon cover gas and removed from the hot cell to await a future treatment. If the reaction is 'mild', the sieve will then be removed from the water; the material weighed for final packaging and allowed to dry by air exposure. Lot 2 waste cans can be opened, sorted, processed, and weighed while mitigating the potential of thermal events that could occur prior to exposing to air. Exposure to air is a WIPP compliance step demonstrating the absence of reactive or ignitable characteristics. (authors)

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