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At least 1,729 records · Page 96

Repackaging of High Fissile TRU Waste at the Transuranic Waste Processing Center - 13240

Twenty-six drums of high fissile transuranic (TRU) waste from Oak Ridge National Laboratory (ORNL) operations were declared waste in the mid-1980's and placed in storage with the legacy TRU waste inventory for future treatment and disposal at the Waste Isolation Pilot Plant (WIPP). Repackaging and treatment of the waste at the TRU Waste Packaging Center (TWPC) will require the installation of additional equipment and capabilities to address the hazards for handling and repackaging the waste compared to typical Contact Handled (CH) TRU waste that is processed at the TWPC, including potential hydrogen accumulation in legacy 6M/2R packaging configurations, potential presence of reactive plutonium hydrides, and significant low energy gamma radiation dose rates. All of the waste is anticipated to be repackaged at the TWPC and certified for disposal at WIPP. The waste is currently packaged in multiple layers of containers which presents additional challenges for repackaging activities due to the potential for the accumulation of hydrogen gas in the container headspace in quantities than could exceed the Lower Flammability Limit (LFL). The outer container for each waste package is a stainless steel 0.21 m{sup 3} (55-gal) drum which contains either a 0.04 m{sup 3} or 0.06 m{sup 3} (10-gal or 15-gal) 6M drum. The inner 2R container in each 6M drum is ∼12 cm (5 in) outside diameter x 30-36 cm (12-14 in) long and is considered to be a > 4 liter sealed container relative to TRU waste packaging criteria. Inside the 2R containers are multiple configurations of food pack cans, pipe nipples, and welded capsules. The waste contains significant quantities of high burn-up plutonium oxides and metals with a heavy weight percentage of higher atomic mass isotopes and the subsequent in-growth of significant quantities of americium. Significant low energy gamma radiation is expected to be present due to the americium in-growth. Radiation dose rates on inner containers are estimated to be 1-3 mSv/hr (100-300 mrem/hr) with an unshielded dose rate on the waste itself of over 10 mSv/hr (1 rem/hr). Additional equipment to be installed at the TWPC will include a new perma-con enclosure and a shielded/inert glovebox in the process building to repackage and stabilize the waste. All of the waste will be repackaged into Standard Pipe Overpacks. Most of the waste (21 of the 26 drums) is expected to be repackaged at the food-pack can level (i.e. the food-pack cans will not be opened). Five of the incoming waste containers are expected to be repackaged at the primary waste level. Three of the containers exceed the 200 gram Pu-239 Fissile Gram Equivalent (FGE) limit for the Standard Pipe Overpack. These three containers will be repackaged down to the primary waste level and divided into eight Standard Pipe Overpacks for shipment to WIPP. Two containers must be stabilized to eliminate any reactive plutonium hydrides that may be present. These containers will be opened in the inert, shielded glovebox, and the remaining corroded plutonium metal converted to a stable oxide form by using a 600 deg. C tube furnace with controlled oxygen feed in a helium carrier gas. The stabilized waste will then be packaged into two Standard Pipe Overpacks. Design and build out activities for the additional repackaging capabilities at the TWPC are scheduled to begin in Fiscal Year 2013 with repackaging, stabilization, and certification activities scheduled to begin in Fiscal Year 2014. Following repackaging and stabilization activities, the Standard Pipe Overpacks will be certified for disposal at WIPP utilizing Non-Destructive Examination (NDE) to verify the absence of prohibited items and Non-Destructive Assay (NDA) to verify the isotopic content under the TWPC WIPP certification program implemented by the Central Characterization Project (CCP). (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Monte Carlo Rectangle Packing Algorithm for Identifying Likely Spatial Distributions of Final Closure Cap Subsidence in the E-Area Low-Level Waste Facility

A Monte Carlo rectangle packing algorithm, summarized in Figure ES-1, has been developed to provide insights into the likely spatial distribution of subsided areas or holes in the final closure cap for the E-Area Low-Level Waste Facility (ELLWF) resulting from the placement of non-crushable waste containers within slit and engineered trench disposal units. Using historical records provided by Solid Waste Management as an indicator of future waste streams, a probability distribution of unique waste containers was constructed, and Monte Carlo sampling was used to sequentially select waste containers for placement in a rectangular region bounded by the disposal unit footprint. Within this Monte Carlo approach, the probability of any container type being selected is weighted by the fractional abundance relative to all other container types. For each Monte Carlo realization, the frequency of non-crushable waste containers appearing at each location on a spatially discretized mesh is updated. After many realizations, the location(s) with the highest frequencies of non-crushable waste containers are regarded as the most likely locations to experience subsidence (i.e., for a hole to form). Utilizing this approach has enabled the down-selection of a computationally intractable set of subsidence hole combinations to be explored in three-dimensional finite element groundwater flow and contaminant transport models. Such an approach can be applied to a number of different packaging problems.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cesium Ion Exchange Using Crystalline Silicotitanate with 5.6 M Sodium Simulant

The Low-Activity Waste Pretreatment System (LAWPS) facility is planned to pretreat Hanford tank waste supernate by filtering to remove solids and processing through ion exchange columns to remove cesium. The ion exchange media is currently (since 2018) targeted to be crystalline silicotitanate (CST). This material has been produced as an engineered form (generally spherical beads) by Honeywell UOP LLC (Des Plaines, IL). Previous forms of this media have been tested in a wide array of simulants and process scales, but column breakthrough and batch contact testing to date on actual tank waste has been limited to a few tank wastes. Washington River Protection Solutions requested a series of studies to demonstrate Cs load behavior in a small column format and determine if a simple batch contact test with CST can be used to qualify tank waste supernate prior to processing it in the LAWPS. The goal of the batch contact testing is to determine if there are any issues with the tank waste that would preclude Cs removal by the ion exchanger. Testing was conducted with IONSIV TM R9140-B CST provided by Honeywell UOP in 2018 (Batch 2081000057). The CST was received in the sodium (Na) form, so no pretreatment conditioning to convert to the Na form was required. Before use in testing, the CST was passed through a #25 sieve (710-micron openings) and collected on a #60 sieve (250-micron openings) with the intent of removing any large and fine particles. Physical properties were measured on the CST including particle size distribution (d50 = 570 microns) and scanning electron micrographic examination. The CST was rinsed with water until the contact solution was visually nearly clear. The CST bed density (1.00 g/mL) and CST bed void fraction (0.656) were measured on the sieved and rinsed CST. The batch contact testing varied Cs concentration in a 5.6 M Na simple simulant solution. Testing was conducted in a liquid volume to solids mass ratio of 200. The distribution coefficient (K d ) was determined to be 770 mL/g at the Cs equilibrium condition of 8.0 μg/mL; with a bed density of 1.00 g/mL, this corresponds to a predicted 50% Cs breakthrough of 770 bed volumes (BVs). The Cs load capacity at 8.0 μg/mL equilibrium condition was determined to be 6.16 mg Cs/g dry CST. The column testing was prototypic to the intended LAWPS operations in a lead-lag column format, albeit on a small-scale basis with 10-mL CST beds. The feed was processed downflow through the lead column and then through the lag column. Three flowrates were tested: 1.19, 1.99, and 4.56 BV/h. The feed was displaced with 0.1 M NaOH, and then the columns were rinsed with water sequentially through the lead then lag columns. One column system was evaluated top to bottom with a gamma scanner to assess the axial Cs loading. Table ES.1 summarizes the relevant Cs loading characteristics.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Airlock

An airlock for use in transferring waste objects from a positively pressurized enclosure aboard an operative space vehicle, to a waste receiver attached to the vehicle and maintained at the negative pressure of a celestial space environment. The airlock is characterized by a shell having an internal chamber and hermetically sealed within an opening formed in a bulkhead of the enclosure. The shell is provided with an insertion hatch adjacent to the enclosure, and an ejection hatch adjacent the waste receiver, each of the hatches being hermetically sealed by a hatch cover supported for deployment to a hatch-opening disposition through a manipulation of a hatch-deploying mechanism. A three-way selector valve is coupled with the deploying mechanism and ported to an internal chamber of the shell, the enclosure, and the environment and is provided for alternately coupling the chamber with the enclosure and the receiver, in direct communication, in response to a manipulation of the mechanism whereby a sequence is imposed on the operation of the airlock.

Linderfelt, H. R.↗

Conversion of Nuclear Waste into Nuclear Waste Glass: Experimental Investigation and Mathematical Modeling

The melter feed, slurry, or calcine charged on the top of a pool of molten glass forms a floating layer of reacting material called the cold cap. Between the cold-cap top, which is covered with boiling slurry, and its bottom, where bubbles separate it from molten glass, the temperature changes by up to 1000 K. The processes that occur over this temperature interval within the cold cap include liberation of gases, conduction and consumption of heat, dissolution of quartz particles, formation and dissolution of intermediate crystalline phases, and generation of foam and gas cavities. These processes have been investigated using thermal analyses, optical and electronic microscopies, x-ray diffraction, as well as other techniques. Properties of the reacting feed, such as heat conductivity and density, were measured as functions of temperature. Investigating the structure of quenched cold caps produced in a laboratory-scale melter complemented the crucible studies. The cold cap consists of two main layers. The top layer contains solid particles dissolving in the glass-forming melt and open pores through which gases are escaping. The bottom layer contains bubbly melt or foam where bubbles coalesce into larger cavities that move sideways and release the gas to the atmosphere. The feed-to-glass conversion became sufficiently understood for representing the cold-cap processes via mathematical models. These models, which comprise heat transfer, mass transfer, and reaction kinetics models, have been developed with the final goal to relate feed parameters to the rate of glass melting.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Road Map for Development of Crystal-Tolerant High Level Waste Glasses

The U.S. Department of Energy (DOE) is building a Tank Waste Treatment and Immobilization Plant (WTP) at the Hanford Site in Washington to remediate 55 million gallons of radioactive waste that is being temporarily stored in 177 underground tanks. Efforts are being made to increase the loading of Hanford tank wastes in glass while meeting melter lifetime expectancies and process, regulatory, and product quality requirements. This road map guides the research and development for formulation and processing of crystal-tolerant glasses, identifying near- and long-term activities that need to be completed over the period from 2014 to 2019. The primary objective is to maximize waste loading for Hanford waste glasses without jeopardizing melter operation by crystal accumulation in the melter or melter discharge riser. The potential applicability to the Savannah River Site (SRS) Defense Waste Processing Facility (DWPF) will also be addressed in this road map. The planned research described in this road map is motivated by the potential for substantial economic benefits (significant reductions in glass volumes) that will be realized if the current constraints (T 1% for WTP and T L for DWPF) are approached in an appropriate and technically defensible manner for defense waste and current melter designs. The basis of this alternative approach is an empirical model predicting the crystal accumulation in the WTP glass discharge riser and melter bottom as a function of glass composition, time, and temperature. When coupled with an associated operating limit (e.g., the maximum tolerable thickness of an accumulated layer of crystals), this model could then be integrated into the process control algorithms to formulate crystal-tolerant high-level waste (HLW) glasses targeting high waste loadings while still meeting process related limits and melter lifetime expectancies. The modeling effort will be an iterative process, where model form and a broader range of conditions, e.g., glass composition and temperature, will evolve as additional data on crystal accumulation are gathered. Model validation steps will be included to guide the development process and ensure the value of the effort (i.e., increased waste loading and waste throughput). A summary of the stages of the road map for developing the crystal-tolerant glass approach, their estimated durations, and deliverables is provided.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tank 11H Low Temperature Aluminum Dissolution and Inhalation Dose Potential Analyses at Savannah River Site – 26018

Currently, there is approximately 34 million gallons of high-level radioactive tank waste in the Tank Farm at the Savannah River Site (SRS). The ultimate goal of operations at the Tank Farm is to remove the high level waste (HLW) from the tanks followed by stabilization of the waste through vitrification of the HLW into glass or grouting the decontaminated waste into saltstone. After bulk removal of the HLW consisting of sludge, saltcake, and supernatant, further efforts are made to reduce the residual waste present in the tank in order to declare preliminary cease waste removal (PCWR) signifying completion of HLW removal. These reduction efforts can include tank washing to remove soluble salts and radioisotopes and dissolution of solids including aluminum. Aluminum in the form of gibbsite and boehmite is relatively insoluble in water. Through addition of aqueous sodium hydroxide, the aluminum can be dissolved at mild temperatures. In order for the waste tank to meet closure mode requirements of the Concentration, Storage, and Transfer Facilities (CSTF), which includes the Tank Farm, Documented Safety Analysis (DSA), a component of the safety basis, the inhalation dose potential (IDP) and the radiolytic hydrogen generation rate of the stored waste must be demonstrated to be lower than their respective designated limits. These parameters are calculated from measured radiochemical analyses of isotopes that emit a high amount of radioactivity including Cs-137, Sr-90, Pu-238, Pu-239, Pu-240, Pu-241, Am-241, and Cm-244. Following the low temperature aluminum dissolution (LTAD) process, Tank 11H slurry samples were pulled from the tank and sent to Savannah River National Laboratory (SRNL) to measure the extent of aluminum dissolution, hydroxide concentration, densities of slurry and supernatant, weight percent solids analyses, and radionuclide activities. The analyses of the composite sample found that approximately 90% of the total aluminum in the slurry was dissolved, indicating successful reduction of the insoluble aluminum in the waste tank. Additionally, the weight percent insoluble solids (slurry basis) measurement of the composite sample was found to be approximately 1%, demonstrating that minimal solids still remain in the tank. Finally, the radiochemical analyses of the composite sample determined that the waste contents of the tank met the IDP and radiolytic hydrogen generation rate requirements of the CSTF DSA. These measurements have shown that the LTAD process in Tank 11H was successful in waste reduction efforts and a positive step towards declaring PCWR and tank closure at SRS.

Dekarske, John [Savannah River National Laboratory↗

Mercury Phase II Study - Mercury Behavior in Salt Processing Flowsheet

Mercury (Hg) in the Savannah River Site Liquid Waste System (LWS) originated from decades of canyon processing where it was used as a catalyst for dissolving the aluminum cladding of reactor fuel. Approximately 60 metric tons of mercury is currently present throughout the LWS. Mercury has long been a consideration in the LWS, from both hazard and processing perspectives. In February 2015, a Mercury Program Team was established at the request of the Department of Energy to develop a comprehensive action plan for long-term management and removal of mercury. Evaluation was focused in two Phases. Phase I activities assessed the Liquid Waste inventory and chemical processing behavior using a system-by-system review methodology, and determined the speciation of the different mercury forms (Hg+, Hg++, elemental Hg, organomercury, and soluble versus insoluble mercury) within the LWS. Phase II activities are building on the Phase I activities, and results of the LWS flowsheet evaluations will be summarized in three reports: Mercury Behavior in the Salt Processing Flowsheet (i.e. this report); Mercury Behavior in the Defense Waste Processing Facility (DWPF) Flowsheet; and Mercury behavior in the Tank Farm Flowsheet (Evaporator Operations). The evaluation of the mercury behavior in the salt processing flowsheet indicates, inter alia, the following: (1) In the assembled Salt Batches 7, 8 and 9 in Tank 21, the total mercury is mostly soluble with methylmercury (MHg) contributing over 50% of the total mercury. Based on the analyses of samples from 2H Evaporator feed and drop tanks (Tanks 38/43), the source of MHg in Salt Batches 7, 8 and 9 can be attributed to the 2H evaporator concentrate used in assembling the salt batches. The 2H Evaporator is used to evaporate DWPF recycle water. (2) Comparison of data between Tank 21/49, Salt Solution Feed Tank (SSFT), Decontaminated Salt Solution Hold Tank (DSSHT), and Tank 50 samples suggests that the total mercury as well as speciated forms in the assembled salt batches in Tanks 21/49 pass through the Actinide Removal Process (ARP) / Modular Caustic Side Solvent Extraction Unit (MCU) process to Tank 50 with no significant change in the mercury chemistry. (3) In Tank 50, Decontaminated Salt Solution (DSS) from ARP/MCU is the major contributor to the total mercury including MHg. (4) Speciation analyses of TCLP leached solutions of the grout samples prepared from Tank 21, as well as Tank 50 samples, show the majority of the mercury released in the solution is MHg.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Valence Disproportionation of GeS in the PbS Matrix Forms Pb 5 Ge 5 S 12 Inclusions with Conduction Band Alignment Leading to High n-Type Thermoelectric Performance

Converting waste heat into useful electricity using solid-state thermoelectrics has a potential for enormous global energy savings. Lead chalcogenides are among the most prominent thermoelectric materials, whose performance decreases with an increase in chalcogen amounts (e.g., PbTe>PbSe>PbS). Herein, we demonstrate the simultaneous optimization of the electrical and thermal transport properties of PbS-based compounds by alloying with GeS. The addition of GeS triggers a complex cascade of beneficial events as follows: Ge 2+ substitution in Pb 2+ and discordant off-center behavior; formation of Pb 5 Ge 5 S 12 as stable second phase inclusions through valence disproportionation of Ge 2+ to Ge0 and Ge 4+ . PbS and Pb 5 Ge 5 S 12 exhibit good conduction band energy alignment that preserves the high electron mobility; the formation of Pb 5 Ge 5 S 12 increases the electron carrier concentration by introducing S vacancies. Sb doping as the electron donor produces a large power factor and low lattice thermal conductivity (κ lat ) of ~0.61 Wm -1 K -1 . The highest performance was obtained for the 14% GeS-alloyed samples, which exhibited an increased room temperature electron mobility of ~121 cm 2 V -1 s -1 for 3 × 10 19 cm -3 carrier density, and a ZT, of 1.32 at 923 K. This is ~ 55% greater that the corresponding Sb-doped PbS sample and is one of the highest reported for the n-type PbS system. Moreover, the average ZT (ZT avg ) of ~0.76 from 400 to 923 K is the highest for PbS-based systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preliminary Analysis of Advanced Reactor Spent Nuclear Fuel Storage, Transportation, and Disposal

Due to increased interest in advanced reactor deployment and their associated potential new fuel cycles, the U.S. Department of Energy (DOE) Spent Fuel and Waste Science and Technology (SFWST) program has begun to evaluate the possible implications of long term management and final disposition of the spent nuclear fuel (SNF) generated. Safely managing and dispositioning this SNF, along with any other associated radioactive waste, is the primary focus of this initial preliminary assessment. This paper summarizes efforts to evaluate the characteristics and packaging options for three types of advanced reactor SNF forms: (1) tristructural isotropic (TRISO), (2) metallic, and (3) irradiated fuel salt presented in the report titled “Storage, Transportation, and Disposal of Advanced Reactor Spent Nuclear Fuel and High-Level Waste”. TRISO and metallic SNF and their associated waste streams were emphasized because of the near-term anticipated demonstrations of X-energy’s Xe-100 and TerraPower and GE Hitachi’s Natrium advanced reactors. Preliminary information on spent fuel salts discharged from molten-salt reactors (MSRs) was also examined to provide a baseline for future efforts. All calculations and assumptions were based on publicly available information. This paper identifies several different reactors that produce either TRISO or metallic SNF as well as a few of the reactor and fuel characteristics used for the assessments. Based on these characteristics, calculations were performed to determine the applicability of packaging SNF into existing canister designs. The evaluations included geometric (e.g., dimension, volume) and mass/weight considerations, known operational approaches and loading procedures, physical and chemical considerations/conditions for storage environments, and as-loaded radiation, thermal, and criticality analyses to identify constraints on storage, transportation, and disposal. Gaps in publicly available data pertaining to reactor operation and/or fuel composition provide increased uncertainty in some evaluations. Additionally, uncertainty in packaging and SNF management operations provide additional uncertainty. However, preliminary conclusions can still be assessed through this work and are presented in this paper.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Comparison of waste combustion and waste electrolysis - A systems analysis

A steady state model of a closed environmental system has been developed which includes higher plant growth for food production, and is designed to allow wastes to be combusted or electrolyzed. The stoichiometric equations have been developed to evaluate various trash compositions, food items (both stored and produced), metabolic rates, and crew sizes. The advantages of waste electrolysis versus combustion are: (1) oxygen is not required (which reduces the load on the oxygen producing system); (2) the CO2 and H2 products are produced in pure form (reducing the load on the separators); and (3) nitrogen is converted to nitrate (which is directly usable by plants). Weight tradeoff studies performed using this model have shown that waste electrolysis reduces the life support weight of a 4-person crew by 1000 to 2000 kg.

Holtzapple, Mark T.↗

Vitrification of Hanford Tank 241-AP-105 Waste at 7 M Na and Equivalent Simulant

Hanford Site nuclear waste is to be vitrified at the Waste Treatment and Immobilization Plant (WTP), which is a part of the safe and efficient retrieval, treatment, and disposal mission of the U.S. Department of Energy Office of River Protection. Hanford tank 241-AP-105 (referred to herein as AP-105) is one of the initial Hanford radioactive tank wastes planned to be processed and vitrified. A portion of AP-105 waste was retrieved by Washington River Protection Solutions, LLC (WRPS) and transferred to Pacific Northwest National Laboratory (PNNL). The waste went through dilution by Columbia River water to reach a target sodium (Na) concentration of 7 M, solids filtration, and cesium removal by ion exchange. A glass composition was calculated from the Kim et al. glass models to satisfy the WTP baseline requirements based on the as-received sample and the target dilution to 7 M, from which a simulant was calculated and glass forming chemical (GFC) additions were determined to form a liquid/solids mixture called melter feed. To prepare for the processing of the 7 M Na AP-105 waste melter feed and learn about the production expectations, the melter feed simulant of 7 M Na AP-105 waste was processed in a non-radioactive, continuous laboratory-scale melter (CLSM) system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Processing liquid organic wastes at the NNL Preston laboratory

Organic compounds of various kinds have been used in the nuclear industry for numerous duties in uranium chemical, metal and ceramic processing plants. In the course of the various operations undertaken, these organic compounds have become contaminated with uranic material, either accidentally or as an inevitable part of the process. Typically, the chemical/physical form and/or concentration of the uranic content of the organics has prevented disposal. In order to address the issue of contaminated liquid organic wastes, the National Nuclear Laboratory (NNL) has developed a suite of treatments designed to recover uranium and to render the waste suitable for disposal. The developed processes are operated at industrial scale via the NNL Preston Laboratory Residue Processing Plant. The Oil Waste Leaching (OWL) Process is a fully industrialised process used for the treatment of contaminated oils with approximately 200 tonnes of uranium contaminated oil being treated to date. The process was originally developed for the treatment of contaminated tributyl phosphate and odourless kerosene which had been adsorbed onto sawdust. However, over the years, the OWL process has been refined for a range of oils including 'water emulsifiable' cutting oils, lubricating oils, hydraulic oils/fluids and 'Fomblin' (fully fluorinated) oils. Chemically, the OWL process has proved capable of treating solvents as well as oils but the highly volatile/flammable nature of many solvents has required additional precautions compared with those required for oil treatment. These additional precautions led to the development of the Solvent Treatment Advanced Rig (STAR), an installation operated under an inert atmosphere. STAR is a small 'module' (100 dm{sup 3} volume) which allows the treatment of both water miscible and immiscible solvents. This paper discusses the challenges associated with the treatment of liquid organic wastes and the process developments which have allowed a wide range of materials to be successfully treated. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of Bubbles and Silica Dissolution on Melter Feed Rheology during Conversion to Glass

As the nuclear waste glass melter feed is converted to molten glass, the feed becomes a continuous glass-forming melt where dissolving refractory constituents are suspended together with numerous gas bubbles. Knowledge of mechanical properties of the reacting melter feed is crucial for understanding the feed-to-glass conversion as it occurs during melting. We studied the melter feed viscosity during heating and correlated it with volume fractions of dissolving quartz particles and gas phase. The measurements were performed with a rotating spindle rheometer on the melter feed heated at 5 K/min, starting at several different temperatures. The effects of undissolved quartz particles, gas bubbles, and compositional inhomogeneity on the melter feed viscosity were determined by fitting a linear relationship between log viscosity and volume fractions of suspended phases.

Effect of solids and gases on viscosity↗

The formation of spinel-group minerals in contaminated soils: the sequestration of metal(loid)s by unexpected incidental nanoparticles

Mineralogical studies of contaminated soils affected by smelter emission and dust from mining activities indicate that minerals of the spinel group are one of the common hosts of metal-bearing contaminants. Spinel group minerals typically originate from high temperature processes, but an increasing number of studies indicate that metal-bearing spinel group minerals can also form under ambient Earth surface conditions in surficial soils. In this contribution to honor Donald Sparks, we show that the spinels Zn-bearing magnetite (Zn 0.5 Fe 2.5 O 4 ) and minium (Pb 3 O 4 ) form during low temperature alteration of Pb-bearing silica glass in surficial organic rich soils in proximity to a former Cu-smelter in Timmins, Ontario, Canada. The glass most likely formed during high-temperature processes and has been either emitted by the smelter or wind-blown from waste rock piles to near-by soils. The alteration of the glass by percolating pore solutions has resulted in the formation of large micrometer-size dendritic etch features and in nanometer-size dendritic alteration halos composed of nano-size prismatic crystals of Zn-rich magnetite and spherical nanoparticles of minium. Both spinel-type phases are embedded in an amorphous silica matrix which formed during the alteration of the glass at low temperature. A review on the occurrence of spinel-group minerals in smelter-affected soils or mine tailings indicates that the formation of these minerals under ambient Earth surface conditions is quite common and often results in the sequestration of contaminants such as Cu, Ni, Zn and Sb. The pedogenic spinels often occur as euhedral crystals in nano-size mineral assemblages within alteration features such as dendritic etch patterns, mineral surface coatings and mineralized organic matter. Their well-developed crystal forms indicate that (a) they have not formed during a rapid cooling process in a smelter or refinery which typically creates spherical particulate matter, and (b) they have not been part of particulate matter added via fluvial or Aeolian processes which most commonly yield anhedral morphologies. The formation of nano-size spinel-group minerals in low temperature environmental settings may lead to the long-term storage of metal(loid)s in mineral phases and their transport over vast distances via fluvial, alluvial and Aeolian processes.

58 GEOSCIENCES↗

Urine Pretreat Injection System

A new method of introducing the OXONE (Registered Trademark) Monopersulfate Compound for urine pretreat into a two-phase urine/air flow stream has been successfully tested and evaluated. The feasibility of this innovative method has been established for purposes of providing a simple, convenient, and safe method of handling a chemical pretreat required for urine processing in a microgravity space environment. Also, the Oxone portion of the urine pretreat has demonstrated the following advantages during real time collection of 750 pounds of urine in a Space Station design two-phase urine Fan/Separator: Eliminated urine precipitate buildup on internal hardware and plumbing; Minimized odor from collected urine; and Virtually eliminated airborne bacteria. The urine pretreat, as presently defined for the Space Station program for proper downstream processing of urine, is a two-part chemical treatment of 5.0 grams of Oxone and 2.3 ml of H2SO4 per liter of urine. This study program and test demonstrated only the addition of the proper ratio of Oxone into the urine collection system upstream of the Fan/Separator. This program was divided into the following three major tasks: (1) A trade study, to define and recommend the type of Oxone injection method to pursue further; (2) The design and fabrication of the selected method; and (3) A test program using high fidelity hardware and fresh urine to demonstrate the method feasibility. The trade study was conducted which included defining several methods for injecting Oxone in different forms into a urine system. Oxone was considered in a liquid, solid, paste and powered form. The trade study and the resulting recommendation were presented at a trade study review held at Hamilton Standard on 24-25 October 94. An agreement was reached at the meeting to continue the solid tablet in a bag concept which included a series of tablets suspended in the urine/air flow stream. These Oxone tablets would slowly dissolve at a controlled rate providing the proper concentration in the collected urine. To implement the solid tablet in a bag approach, a design concept was completed with prototype drawings of the complete urine pretreat prefilter assembly. A successful fabrication technique was developed for retaining the Oxone tablets in a fabric casing attached to the end of the existing Space Station Waste Collection System urine prefilter assembly. The final pretreat prefilter configuration held sufficient Oxone in a tablet form to allow normal scheduled daily (or twice daily) change out of the urine filter depending on the use rate of the Space Station urine collection system. The actual tests to prove the concept were conducted using the Urine Fan/Separator assembly that was originally used in the STS-52 Design Test Objective (DTO) urinal assembly. Other related tests were conducted to demonstrate the actual minimum ratio of Oxone to urine that will control microbial growth.

Source record↗

Development, Testing and Validation of a Waste Assay System for the Measurement and Characterisation of Active Spent Fuel Element Debris From UK Magnox Reactors - 12533

This paper describes the development, testing and validation of a waste measurement instrument for characterising active remote handled radioactive waste arising from the operation of Magnox reactors in the United Kingdom. Following operation in UK Magnox gas cooled reactors and a subsequent period of cooling, parts of the magnesium-aluminium alloy cladding were removed from spent fuel and the uranium fuel rods with the remaining cladding were removed to Sellafield for treatment. The resultant Magnox based spent fuel element debris (FED), which constitutes active intermediate level waste (ILW) has been stored in concrete vaults at the reactor sites. As part of the decommissioning of the FED vaults the FED must be removed, measured and characterised and placed in intermediate storage containers. The present system was developed for use at the Trawsfynydd nuclear power station (NPS), which is in the decommissioning phase, but the approach is potentially applicable to FED characterisation at all of the Magnox reactors. The measurement system consists of a heavily shielded and collimated high purity Germanium (HPGe) detector with electromechanical cooling and a high count-rate preamplifier and digital multichannel pulse height analyser. The HPGe based detector system is controlled by a software code, which stores the measurement result and allows a comprehensive analysis of the measured FED data. Fuel element debris is removed from the vault and placed on a tray to a uniform depth of typically 10 cm for measurement. The tray is positioned approximately 1.2 meters above the detector which views the FED through a tungsten collimator with an inverted pyramid shape. At other Magnox sites the positions may be reversed with the shielded and collimated HPGe detector located above the tray on which the FED is measured. A comprehensive Monte Carlo modelling and analysis of the measurement process has been performed in order to optimise the measurement geometry and eliminate interferences from radioactive sources and FED in the immediate vicinity of the measurement position. The detector system has been calibrated and high activity radioactive sources of Cs-137, Co-60 and Na-22 have been used to validate the measurement process. The data acquisition and analysis software code has been tested and validated in keeping with the software quality assurance requirements of both ISO:9001-2008 - TICK-IT in the UK and NQA-1. The measurement and analysis system has been comprehensively tested with high activity sources, is flexible and may be applicable to a wide range of remote handled radioactive waste measurement applications. It is due to be installed at Trawsfynydd NPS later this year. This paper describes the Waste Tray Assay System (WTAS) that has been developed for the measurement of Magnox FED waste. The WTAS has been tested with a range of radioactive sources and its operation has been simulated with benchmarked MCNP Monte Carlo calculations. The measurement software has been validated as has the operation of the system for a range of strong radioactive sources. A system based on the design is due for installation and operation in 2012. The system has application to the measurement of Magnox Fuel Element Debris (FED) waste at other Magnox reactor sites. The major design objective of the WTAS that has been achieved is the ability of the assay system to determine the content of Cs-137, and in turn to enable the fissile burden to be assessed using a radionuclide fingerprint, in the presence of higher and highly variable quantities of Co-60, typically from nimonic springs. The approach can be used in other Magnox FED waste configurations where the detector is located above the FED waste sorting tray and where the collimation is fixed below the detector and at a distance above the tray. In this case, which has also been investigated, there are different shielding problems and mechanical support issues. The extensive use of MCNP Monte Carlo modelling to simulate the geometry of the sorting cell and the distribution of radioactive sources has helped to ensure that all of the detector shielding requirements are addressed and suitable Cs-137 and Co-60 discrimination can be achieved. The WTAS in its present form or in other configurations has relevance to the measurement of other active ILW and highly active RH waste. Examples include high activity RH LLW and RH TRU (Transuranic) waste as defined in the United States arising from both commercial nuclear and Department of Energy (DOE) operations. The analysis is able to analyse a range of radionuclides beyong those expected in the Magnox FED cases. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A novel defoamer for processing nuclear waste: Testing and performance

Abstract Legacy radioactive waste from nuclear weapons material processing is the biggest environmental challenge in the state of South Carolina, and one of the biggest in the United States. Although substantial progress has been made in processing and vitrifying high‐level radioactive waste at the Savannah River site, approximately 35 million gallons remains to be treated and dispositioned. In this article, we show the development of a new defoamer for use in the processing of high‐level radioactive waste. The application of the new defoamer is not only more effective at controlling foam but will shorten the batch processing time leading to safer and more efficient processing. This has the potential to help shorten the overall site mission lifetime, saving the federal government hundreds of millions of dollars. The novel aspect of the new defoamer is its effectiveness and stability in the harsh conditions needed for processing high‐level radioactive waste: high temperatures, pH 4–13, strong oxidizing and reducing agents, and numerous metal catalysts. The defoamer will replace an existing antifoam agent that decomposes to form multiple flammable gases. Because the existing antifoam agent decomposes quickly, processing changes increased processing time. Statement of novelty We demonstrate that a new defoamer has been developed for use in processing high‐level radioactive waste. This novel defoamer is effective and stable in the harsh processing conditions with no detectable flammable by‐products. Because the existing antifoam agent decomposes quickly, processing changes, including lowering acid addition rates and evaporation rates, increased processing time. The new defoamer is not only more effective at controlling foam but will shorten the batch processing time and lead to safer and more efficient processing by eliminating the production of flammable gases. Statement of industrial relevance Foaming is of great concern in many industrial processes involving three‐phase gas/liquid/fine‐solids systems, like in water evaporation, mineral floatation, air sparging in situ remediation techniques, and in those found in the paper industry.

Lambert, Dan P.↗