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All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Khazar Iodine Production Plant Site Remediation in Turkmenistan. NORM Contaminated Waste Repository Establishment - 12398

Radiation safety provisions for NORM contaminated areas are in use in a number of the former Soviet republics. Some of these areas were formed by absorbed radionuclides at the iodine and bromine extraction sites. As a rule, there are not any plant radiation monitoring systems nor appropriate services to ensure personnel, population and environmental radiation safety. The most hazardous sites are those which are situated in the Caspian Sea coastal zone. The bulk of the accumulated waste is represented by a loose mixture of sand and charcoal, which was basically used as the iodine extraction sorbent. The amounts of these wastes were estimated to be approximately 20,000 metric tons. The waste contamination is mainly composed of Ra-226 (U-238 decay series) and Ra-224, Ra-228 (Th-232 decay series). In 2009, the 'ECOMET-S', a Closed Joint-Stock Company from St. Petersburg, Russian Federation, was authorized by the Turkmenistan government to launch the rehabilitation project. The project includes D and D activities, contaminated areas remediation, collected wastes safe transportation to the repository and its disposal following repository closure. The work at the Khazar chemical plant started in September, 2010. Comprehensive radiological surveys to estimate the waste quantities were carried out in advance. In course of the rehabilitation work at the site of the Khazar chemical plant additional waste quantities (5,000 MT, 10,000 m{sup 3}) were discovered after the sludge was dumped and drained. Disposal volumes for this waste was not provided initially. The additional volume of the construction wastes was required in order to accommodate all the waste to be disposed. For the larger disposal volume the project design enterprise VNIPIET, offered to erect a second wall outside the existing one and this solution was adopted. As of May, 2011, 40,575 m{sup 3} of contaminated waste were collected and disposed safely. This volume represents 96.6% of the initial repository volume. Now work is underway to erect the second repository wall, which will allow housing of the additional 16,800 m{sup 3} The Khazar chemical plant territory restoration work is underway as well. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Photooxidation of Polyolefins to Produce Materials with In-Chain Ketones and Improved Materials Properties

Herein, we report a selective photooxidation of commodity postconsumer polyolefins to produce polymers with in-chain ketones. The reaction does not involve the use of catalyst, metals, or expensive oxidants, and selectively introduces ketone functional groups. Under mild and operationally simple conditions, yields up to 1.23 mol % of in-chain ketones were achieved. Installation of in-chain ketones resulted in materials with improved adhesion of the materials and miscibility of mixed plastics relative to the unfunctionalized plastics. The introduction of ketone groups into the polymer backbone allows these materials to react with diamines, forming dynamic covalent polyolefin networks. This strategy allows for the upcycling of mixed plastic waste into reprocessable materials with enhanced performance properties compared to polyolefin blends. Mechanistic studies support the involvement of photoexcited nitroaromatics in consecutive hydrogen and oxygen atom transfer reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Three novel PHEX gene mutations in four Chinese families with X-linked dominant hypophosphatemic rickets

Highlights: Black-Right-Pointing-Pointer In our study, all of the patients were of Han Chinese ethnicity, which were rarely reported. Black-Right-Pointing-Pointer We identified three novel PHEX gene mutations in four unrelated families with XLH. Black-Right-Pointing-Pointer We found that the relationship between the phenotype and genotype of the PHEX gene was not invariant. Black-Right-Pointing-Pointer We found that two PHEX gene sites, p.534 and p.731, were conserved. -- Abstract: Background: X-linked hypophosphatemia (XLH), the most common form of inherited rickets, is a dominant disorder that is characterized by renal phosphate wasting with hypophosphatemia, abnormal bone mineralization, short stature, and rachitic manifestations. The related gene with inactivating mutations associated with XLH has been identified as PHEX, which is a phosphate-regulating gene with homologies to endopeptidases on the X chromosome. In this study, a variety of PHEX mutations were identified in four Chinese families with XLH. Methods: We investigated four unrelated Chinese families who exhibited typical features of XLH by using PCR to analyze mutations that were then sequenced. The laboratory and radiological investigations were conducted simultaneously. Results: Three novel mutations were found in these four families: one frameshift mutation, c.2033dupT in exon 20, resulting in p.T679H; one nonsense mutation, c.1294A > T in exon 11, resulting in p.K432X; and one missense mutation, c.2192T > C in exon 22, resulting in p.F731S. Conclusions: We found that the PHEX gene mutations were responsible for XLH in these Chinese families. Our findings are useful for understanding the genetic basis of Chinese patients with XLH.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Removal of TcO 4 - ions from solution: materials and future outlook

Technetium mainly forms during artificial nuclear fission; it exists primarily as TcO 4- in the nuclear waste, and is among the most hazardous radiation-derived contaminants because of its long half-life (t1/2 = 2.13 × 105 yrs) and environmental mobility. The high water solubility of TcO 4- (11.3 mol L -1 at 20°C) and its ability to readily migrate within the upper layer of Earth’s crust make it particularly hazardous. Several types of materials, namely resins, molecular complexes, layered double hydroxides, and pure inorganic and metal-organic materials, have been shown to be capable of capturing TcO 4- (or other oxoanions) from solution. In this review, we give a brief description about the types of materials that have been used to capture TcO 4- and closely related oxyanions so far and discuss the possibility of using metal-organic frameworks (MOFs) as next-generation ion-exchange materials for the stated application. In particular, with the advent of ultra-stable MOF materials, in conjunction with their chemical tunability, MOFs can be applied to capture these oxyanions under real-life conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Evaluation of Gas Retention in Waste Simulants: Intermediate-Scale Column and Open-Channel-Depth Tests

Gas generation in Hanford’s radioactive waste storage tanks can lead to gas accumulation within the layer of settled solids (sludge) at the tank bottom. The gas, which may be hazardous and/or flammable, is formed principally by radiation-driven chemical reactions. Accumulation of these gases within the sludge increases the sludge-layer volume, which decreases the available tank volume for waste storage. Further, accumulation of large amounts of gas in the sludge can potentially result in a relatively rapid release of the accumulated gas if the sludge-layer density is reduced to less than that of the overlying sludge or that of the supernatant liquid. The potential for rapid release of large amounts of hazardous and/or flammable gases is a safety hazard that needs to be managed. Accordingly, a thorough understanding is needed of the circumstances that can lead to problematic gas accumulation in sludge layers. The Deep-Sludge Gas Release Event Project (DSGREP) is tasked with developing an improved understanding of these gas release events.

Gas retention↗
DOE OSTI2020

Reconfiguring Plant Metabolism for Biodegradable Plastic Production

For decades, plants have been the subject of genetic engineering to synthesize novel, value-added compounds. Polyhydroxyalkanoates (PHAs), a large class of biodegradable biopolymers naturally synthesized in eubacteria, are among the novel products that have been introduced to make use of plant acetyl-CoA metabolic pathways. It was hoped that renewable PHA production would help address environmental issues associated with the accumulation of nondegradable plastic wastes. However, after three decades of effort synthesizing PHAs, and in particular the simplest form polyhydroxybutyrate (PHB), and seeking to improve their production in plants, it has proven very difficult to reach a commercially profitable rate in a normally growing plant. This seems to be due to the growth defects associated with PHA production and accumulation in plant cells. Here, we review major breakthroughs that have been made in plant-based PHA synthesis using traditional genetic engineering approaches and discuss challenges that have been encountered. Then, from the point of view of plant synthetic biology, we provide perspectives on reprograming plant acetyl-CoA pathways for PHA production, with the goal of maximizing PHA yield while minimizing growth inhibition. Specifically, we suggest genetic elements that can be considered in genetic circuit design, approaches for nuclear genome and plastome modification, and the use of multiomics and mathematical modeling in understanding and restructuring plant metabolic pathways.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1965

Cork is used to make tooling patterns and molds

Sheet and waste cork are cemented together to provide a tooling pattern or mold. The cork form withstands moderately high temperatures under vacuum or pressure with minimum expansion, shrinkage, or distortion.

Hoffman, F. J.↗
NASA NTRS1972

Fuel cell powerplant operation in Apollo spacecraft.

Primary electrical power for loads in the Apollo Command and Service Modules is furnished by a system of three fuel cell powerplants. The powerplants convert cryogenic hydrogen and oxygen into direct current. Water formed in the fuel cell reactions is supplied to the spacecraft for crew use. Waste heat is rejected through a coolant loop to a spacecraft radiator. The ability of the fuel cell to meet its voltage-power requirements and to control its own operating temperature under the environmental extremes of launch, ascent, earth orbit, translunar flight, and lunar orbit was demonstrated on successively more difficult missions leading up to the first lunar landing.

Ching, A. C.↗
DOE OSTI2011

Closure Report for Corrective Action Unit 539: Areas 25 and 26 Railroad Tracks Nevada National Security Site, Nevada with ROTCs 1-2, Revision 0

This Closure Report (CR) presents information supporting the closure of Corrective Action Unit (CAU) 539: Areas 25 and 26 Railroad Tracks, Nevada National Security Site, Nevada. This CR complies with the requirements of the Federal Facility Agreement and Consent Order (FFACO) that was agreed to by the State of Nevada; U.S. Department of Energy (DOE), Environmental Management; U.S. Department of Defense; and DOE, Legacy Management. The corrective action sites (CASs) within CAU 539 are located within Areas 25 and 26 of the Nevada National Security Site. Corrective Action Unit 539 comprises the following CASs: • 25-99-21, Area 25 Railroad Tracks • 26-99-05, Area 26 Railroad Tracks The purpose of this CR is to provide documentation supporting the completed corrective actions and provide data confirming that the closure objectives for CASs within CAU 539 were met. To achieve this, the following actions were performed: • Reviewed documentation on historical and current site conditions, including the concentration and extent of contamination. • Conducted radiological walkover surveys of railroad tracks in both Areas 25 and 26. • Collected ballast and soil samples and calculated internal dose estimates for radiological releases. • Collected in situ thermoluminescent dosimeter measurements and calculated external dose estimates for radiological releases. • Removed lead bricks as potential source material (PSM) and collected verification samples. • Implemented corrective actions as necessary to protect human health and the environment. • Properly disposed of corrective action and investigation wastes. • Implemented an FFACO use restriction (UR) for radiological contamination at CAS 25-99-21. The approved UR form and map are provided in Appendix F and will be filed in the DOE, National Nuclear Security Administration Nevada Site Office (NNSA/NSO), Facility Information Management System; the FFACO database; and the NNSA/NSO CAU/CAS files. From November 29, 2010, through May 2, 2011, closure activities were performed as set forth in the Streamlined Approach for Environmental Restoration (SAFER) Plan for Corrective Action Unit 539: Areas 25 and 26 Railroad Tracks, Nevada Test Site, Nevada. The purposes of the activities as defined during the data quality objectives process were as follows: • Determine whether contaminants of concern (COCs) are present. • If COCs are present, determine their nature and extent, implement appropriate corrective actions, and properly dispose of wastes. Analytes detected during the closure activities were evaluated against final action levels (FALs) to determine COCs for CAU 539. Assessment of the data generated from closure activities revealed the following: • At CAS 26-99-05, the total effective dose for radiological releases did not exceed the FAL of 25 millirem per Industrial Area year. Potential source material in the form of lead bricks was found at three locations. A corrective action of clean closure was implemented at these locations, and verification samples indicated that no further action is necessary. • At CAS 25-99-21, the total effective dose for radiological releases exceeds the FAL of 25 millirem per Industrial Area year. Potential source material in the form of lead bricks was found at eight locations. A corrective action was implemented by removing the lead bricks and soil above FALs at these locations, and verification samples indicated that no further action is necessary. Pieces of debris with high radioactivity were identified as PSM and remain within the CAS boundary. A corrective action of closure in place with a UR was implemented at this CAS because closure activities showed evidence of remaining soil contamination and radioactive PSM. Future land use will be restricted from surface and intrusive activities. Closure activities generated waste streams consisting of industrial solid waste, recyclable materials, low-level radioactive waste, and mixed low-level radioactive waste. Wastes were disposed of in the appropriate onsite landfills. The NNSA/NSO provides the following recommendations: • Clean closure is required at CAS 26-99-05. • Closure in place is required at CAS 25-99-21. • A UR is required at CAS 25-99-21. • A Notice of Completion to the NNSA/NSO is requested from the Nevada Division of Environmental Protection for closure of CAU 539. • Corrective Action Unit 539 should be moved from Appendix III to Appendix IV of the FFACO.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

The future of RADCALC- the radioactive material and waste transportation software program - 15154

This paper provides a thorough review of RADCALC, the U.S. Department of Energy (DOE)-developed software tool to assist DOE sites in making radioactive material and waste packaging and transportation determinations in compliance with applicable Federal regulations and DOE Orders and Standards. There are more than 400 registered users of the RADCALC tool across the DOE complex. DOE has also authorized a limited number of users from certain universities and foreign countries. DOE periodically upgrades the software consistent with changing domestic and international requirements, as well as needs unique to DOE. Due to recent changes in regulatory requirements by the Department of Transportation (DOT), it is necessary that the current version of RADCALC should be updated in a timely manner. Prior to investing funds in software upgrades, DOE decided to evaluate the nature of changes required and level of operational support and looked for alternatives for meeting sites' operational needs. DOE formed a joint review team consisting of experts from Energy Facility Contractors Group (EFCOG) sites, commercial waste treatment facilities and the National Laboratories. This team evaluated the RADCALC software, commercially available software packages, and internal DOE site-developed programs against an established set of criteria. The team also reviewed and prioritized regulatory changes and user-recommended enhancements. Based on extensive review, the team recommended that DOE continue to support RADCALC noting that RADCALC is a cost-effective, technically robust tool that can perform complicated radioactive material shipping determinations. The tool promotes accuracy, consistency, and completeness between shipments by a single shipper, between shippers at a given site, and between sites. The isotopic coverage, decay algorithm and the range of calculations are without compare either within DOE or in industry in a tool of this kind. The team also recommended that DOE should actively promote RADCALC use throughout the DOE complex and consider cooperative arrangements with the Department of Defense or other government entities that may have similar needs. (authors)

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DOE OSTI2013

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↗
DOE OSTI2019

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↗
DOE OSTI2018

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.

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NASA NTRS1974

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.↗
DOE OSTI2014

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↗
DOE OSTI2014

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↗
DOE OSTI2026

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↗
DOE OSTI2016

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.

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