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At least 1,171 records · Page 65

Mass Transfer And Hydraulic Testing Of The V-05 And V-10 Contactors With The Next Generation Solvent

The Modular Caustic Side Solvent Extraction (CSSX) Unit (MCU) facility is actively pursuing the transition from the current BOBCalixC6 based solvent to the Next Generation Solvent (NGS)-MCU solvent. To support this integration of NGS into the MCU facilities, Savannah River Remediation (SRR) requested that Savannah River National Laboratory (SRNL) perform testing of a blend of the NGS (MaxCalix based solvent) with the current solvent (BOBCalixC6 based solvent) for the removal of cesium (Cs) from the liquid salt waste stream. This testing differs from prior testing by utilizing a blend of BOBCalixC6 based solvent and the NGS with the full (0.05 M) concentration of the MaxCalix as well as a new suppressor, tris(3,7dimethyloctyl) guanidine. Single stage tests were conducted using the full size V-05 and V-10 centrifugal contactors installed at SRNL.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of the thermophilic xylanase Fsa02490Xyn from the hyperthermophile Fervidibacter sacchari belonging to glycoside hydrolase family 10

Fervidibacter sacchari is an aerobic hyperthermophile belonging to the phylum Armatimonadota that degrades a variety of polysaccharides. Its genome encodes 117 enzymes with one or more annotated glycoside hydrolase (GH) domain, but the roles of these putative GHs in polysaccharide catabolism are poorly defined. Here, we describe one F. sacchari enzyme encoding a GH10 domain, Fsa02490Xyn, that was previously shown to be active on Miscanthus, oat β-glucan, and beech-wood xylan, with optimal activity at 90-100 °C. We show that Fsa02490Xyn is also active on birch-wood xylan and gellan gum. The pH range on beech-wood xylan was 4.5 to 9.5 (pHopt 7.0-8.0). Fsa024940Xyn had a Km of 2.375 mm, Vmax of 1250 μm·min-1, and kcat/Km of 1.259 × 104 s-1·m-1 when using a para-nitrophenyl-?-xylobioside assay. A phylogenetic analysis of GH10 family enzymes revealed a large clade of enzymes from diverse members of the class Fervidibacteria, including Fsa02490Xyn and a second enzyme from F. sacchari, with apparent horizontal gene transfer within Fervidibacteria and between Fervidibacteria and thermophilic Bacillota. This study establishes Fsa02490Xyn as a hyperthermophilic GH10 enzyme with endo-β-1,4-xylanase activity and identifies a large clade of homologous GH10 enzymes within the class Fervidibacteria. Impact statement The depolymerization of xylan at high temperatures is important because this process limits the degradation of polysaccharides in nature and the synthesis of biofuels from plant wastes. Our study is also important because F. sacchari is one of only a few cultivated members of the Armatimonadota, which are polysaccharide-degradation specialists.

Armatimonadota↗

Thermal Conductivity of Thermal Interface Materials Evaluated By a Transient Plane Source Method

The thermal conductivity of thermal interface materials (TIMs) has been investigated using a transient plane source (TPS) method. In thermoelectric generators designed for vehicle waste heat recovery, high thermal conductivity materials are needed for the cold-side interface between a polyamide flexible circuit and an aluminum plate heat exchanger. The conventional heat flow method described by ASTM D5470 is often used to determine thermal contact resistance of an interface with a thin layer of interface material. The apparent thermal conductivity values provided by materials manufacturers are used to calculate heat transfer through the interface. Yet, estimated parameters based on the thermal conductivity of a TIM often do not agree with the actual heat transfer through the interface. Thermal conductivity of a series of 10 commercial TIMs were evaluated by applying a small quantity to an embedded TPS sensor. The 2-mm radius sensor was able to operate under standard bulk material measurement mode and produced consistent thermal conductivity measurements of the interface materials. The TPS method is demonstrated to be effective in ranking the available interface materials by thermal conductivity and to ensure that the material with consistent performance can be selected for the thermoelectric generator applications.

36 MATERIALS SCIENCE↗

Radiation-Induced Interfacial Hydroxyl Transformation on Boehmite and Gibbsite Basal Surfaces

Understanding the radiolytic reactivity of aluminum oxyhydroxide phases widely present in stored nuclear wastes is essential to develop reliable processing approaches. Recent experiments using vibrational sum frequency generation (VSFG), a surface sensitive technique, have shown that rehydration of γ-irradiated boehmite (010) and gibbsite (001) surfaces does not recover the initial hydroxyl density prior to irradiation. In this study, using density functional theory and nudged elastic band calculations, we examine dehydration and rehydration of these surfaces and attendant proton transfer mechanisms. While dehydration of both surfaces is predicted to be energetically unfavorable, rehydration of boehmite (010) is favorable after overcoming an energy barrier of 0.52 eV that relates to the orientation of surface hydroxyls controlling the hydrogen bonding network of adsorbed water. In the case of gibbsite (001), for which the experimental results suggest that rehydration mainly involves the reformation of interlayer hydroxyls, we found that a two-proton transfer mechanism is more likely than a one-proton transfer mechanism, and that it prevents the reorientation of interlayer hydroxyls into intralayer hydroxyls consistent with experimental VSFG findings. A detailed analysis of the effect of surface hydrogen vacancy on the strength of hydrogen bond interactions was performed, which indicates that H 2 and H 2 O are the energetically most favorable product species to form from radiation-induced surface H and/or OH defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fuel Pond Sludge - Lessons Learned from Initial De-sludging of Sellafield's Pile Fuel Storage Pond - 12066

The Pile Fuel Storage Pond (PFSP) at Sellafield was built and commissioned between the late 1940's and early 1950's as a storage and cooling facility for irradiated fuel and isotopes from the two Windscale Pile reactors. The pond was linked via submerged water ducts to each reactor, where fuel and isotopes were discharged into skips for transfer along the duct to the pond. In the pond the fuel was cooled then de-canned underwater prior to export for reprocessing. The plant operated successfully until it was taken out of operation in 1962 when the First Magnox Fuel Storage Pond took over fuel storage and de-canning operations on the site. The pond was then used for storage of miscellaneous Intermediate Level Waste (ILW) and fuel from the UK's Nuclear Programme for which no defined disposal route was available. By the mid 1970's the import of waste ceased and the plant, with its inventory, was placed into a passive care and maintenance regime. By the mid 1990s, driven by the age of the facility and concern over the potential challenge to dispose of the various wastes and fuels being stored, the plant operator initiated a programme of work to remediate the facility. This programme is split into a number of key phases targeted at sustained reduction in the hazard associated with the pond, these include: - Pond Preparation: Before any remediation work could start the condition of the pond had to be transformed from a passive store to a plant capable of complex retrieval operations. This work included plant and equipment upgrades, removal of redundant structures and the provision of a effluent treatment plant for removing particulate and dissolved activity from the pond water. - Canned Fuel Retrieval: Removal of canned fuel, including oxide and carbide fuels, is the highest priority within the programme. Handling and export equipment required to remove the canned fuel from the pond has been provided and treatment routes developed utilising existing site facilities to allow the fuel to be reprocessed or conditioned for long term storage. - Sludge Retrieval: In excess of 300 m{sup 3} of sludge has accumulated in the pond over many years and is made up of debris arising from fuel and metallic corrosion, wind blown debris and bio-organic materials. The Sludge Retrieval Project has provided the equipment necessary to retrieve the sludge, including skip washer and tipper machines for clearing sludge from the pond skips, equipment for clearing sludge from the pond floor and bays, along with an 'in pond' corral for interim storage of retrieved sludge. Two further projects are providing new plant processing routes, which will initially store and eventually passivate the sludge. - Metal Fuel Retrieval: Metal Fuel from early Windscale Pile operations and various other sources is stored within the pond; the fuel varies considerably in both form and condition. A retrieval project is planned which will provide fuel handling, conditioning, sentencing and export equipment required to remove the metal fuel from the pond for export to on site facilities for interim storage and disposal. - Solid Waste Retrieval: A final retrieval project will provide methods for handling, retrieval, packaging and export of the remaining solid Intermediate Level Waste within the pond. This includes residual metal fuel pieces, fuel cladding (Magnox, aluminium and zircaloy), isotope cartridges, reactor furniture, and miscellaneous activated and contaminated items. Each of the waste streams requires conditioning to allow it to be and disposed of via one of the site treatment plants. - Pond Dewatering and Dismantling: Delivery of the above projects will allow operations to progressively remove the radiological inventory, thereby reducing the hazard/risk posed by the plant. This will then allow subsequent dewatering of the pond and dismantling of the structure. (authors)

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Degradation of Polylactic Acid by Irradiation

Polylactic acid (PLA) waste has various treatment methods, such as natural decomposition, composting, incineration, and hydrolysis. Degradation of PLA waste by gamma ray and pulsed light irradiation is an efficient, safe and innovative method that also protects the environment. The focus of this study was on the development of an alternative, green technology for solving the PLA waste disposal problem of PLA, rather than using incineration or the landfill method. We used a novel approach to identify the thermal decomposition and heat properties of crystalline poly lactic acid, non-crystalline polylactic acid, and blend polylactic acid. The approach involved the degradation of the materials with gamma ray and pulsed light irradiation followed by thermogravimetric analysis (TGA). We also developed a novel approach to the heat effect, including heat reactivity properties by TGA tests and thermal mass loss simulation for proper application, processing, and waste treatment conditions. The data from this study can be used to improve the design of operation and waste treatment protocols for PLA, which will benefit the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent Hold Tank Sample Results For MCU-13-814, MCU-13-815, MCU-13-816, MCU-13,817, MCU-13-818 And MCU-13-819: Quarterly Sample From May 2013

Savannah River National Laboratory (SRNL) analyzed solvent samples from Modular Caustic-Side Solvent Extraction Unit (MCU) in support of continuing operations. A quarterly analysis of the solvent is required to maintain solvent composition within specifications. Analytical results of the analyses of Solvent Hold Tank (SHT) samples MCU-13-814, MCU-13-815, MCU-13-816, MCU-13-817, MCU-13-818 and MCU-13-819 received May 28, 2013 are reported. The results show that the solvent at MCU does not require an Isopar® L addition, but it will require addition of trioctylamine despite of the 272 g of TOA that was added to the solvent on June 5, 2013 based on the solvent containing a TOA level of 45% of nominal. A new TOA analysis method (HCl titration) has been used and its output was statistically similar to the results from the SVOA-TOA method. This method provides an independent method for measuring TOA and TiDG in MCU-NG solvent. An impurity containing a tert-butyl group was detected in the solvent and further analytical analysis is needed to identify it. SRNL recommends determining the impact of this impurity on the mass transfer ability of the solvent. SRNL also analyzed the SHT sample for 137 Cs content and determined the measured value is above the results observed from the January 2013.

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Rogers Quarry Special Studies Report 2023

Rogers Quarry (RQ) has a history of elevated Se concentrations in water and fish caused by inputs from the Y-12 National Security Complex Filled Coal Ash Pond (FCAP). Selenium is acutely toxic at high concentrations, and chronic toxicity occurs at low aqueous concentrations because Se bioaccumulates in fish tissues. The US Environmental Protection Agency (EPA) recently developed water quality criteria for Se that include fish tissue as well as aqueous Se concentrations. The water column concentration criterion is 1.5 µg L -1 for lentic ecosystems and 3.1 µg L -1 for lotic ecosystems. The fish tissue criteria include both an egg/ovary concentration (15.1 μg/g dry weight) and a concentration for whole-body (8.5 μg/g dry weight) or fish muscle (11.3 μg/g dry weight). The egg/ovary criterion supersedes the fillet and aqueous concentrations if measured because Se toxicity manifests via reproductive effects in birds and fish. It is maternally transferred through eggs, leading to teratogenicity (i.e., deformities, developmental effects) in young fish.

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How the NDA Provides Transparency and Visibility of the Technical Deliverability of the R and D Programme - 13303

The Nuclear Decommissioning Authority (NDA) was created under the UK Energy Act 2004 to ensure the UK historic civil public sector nuclear legacy sites are decommissioned safely, securely, cost effectively and in ways that protect the environment. The delivery will involve carrying out many unique projects within a high hazard environment requiring the very highest standards in safety, security and environmental management. Unique problems require unique solutions and there is a substantial amount of research and development required for each project. The NDA's R and D strategic objective is to ensure that delivery of the NDA's mission is technically underpinned by sufficient and appropriate research and development. This drives a requirement to provide transparency and visibility of the technical deliverability of the programme through the technical baseline and accompanying research and development requirements. The NDA need to have confidence in the technical deliverability of the Site License Companies (SLCs) plans, provide overall visibility of R and D across the NDA Estate and ensure that appropriate R and D is being carried out in a timely manner. They need to identify where coordinated R and D programmes may be advantageous as a result of common needs, risks and opportunities and ensure key R and D needs across NDA are identified, prioritised and work programmes are costed and scheduled in the Lifetime Plans for individual sites and SLCs. Evidence of the Site License Company's approach and their corresponding technical underpinning programmes is achieved through submission of a number of outputs collectively known as TBuRDs (Technical Baseline and Underpinning Research and Development Requirements). This paper is a summary of the information generated by an independent review of those TBuRDs. It highlights some of the key messages, synergies and common R and D activities across the estate. It demonstrates the value of a consistent approach to collecting R and D data across multiple Sites with a view to enhancing knowledge transfer and improving delivery efficiency. It will be of interest to all who are running R and D programmes where other programmes may be carrying out similar activities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Transitioning from Construction to Startup for the Waste Treatment and Immobilization Plant's Low-Activity Waste Facility - 17284

The original design of the Waste Treatment and Immobilization Plant (WTP) required all waste be processed through the Pretreatment (PT) Facility in order to separate the low-activity waste and high-level waste streams. The U.S. Department of Energy (DOE), Office of River Protection (ORP) has developed a sequenced approach to completing the WTP Project, beginning with delivering some liquid waste directly to the Low-Activity Waste (LAW) Facility, bypassing the PT Facility. This operating configuration is referred to as direct-feed LAW (DFLAW). The primary driver for the DFLAW approach is to enable startup and commissioning of the LAW Facility for low-activity waste processing prior to the completion and availability of the PT and High-Level Waste facilities. In March 2016, a federal judge amended the Consent Decree between DOE and the State of Washington to require completion of hot commissioning for the LAW Facility no later than December 31, 2023. During the next few years ORP and the WTP contractor will transition the project from completion of construction to the startup and commissioning phase for the LAW Facility and the associated support facilities. The WTP contractor has developed an integrated management process to successfully conduct facility startup testing for the WTP facilities required to support DFLAW. The WTP contractor will also develop a commissioning plan and facility transition plan. These plans will describe the strategy; schedule; and requirements for safe, efficient, and sequential startup, commissioning, and transfer of the WTP facilities to an operations contractor. The WTP contractor has also established a strategy to achieve operational readiness for the facilities required to support DFLAW consistent with DOE O 425.1D, Verification of Readiness to Start Up or Restart Nuclear Facilities and DOE O 413.3B, Program and Project Management for the Acquisition of Capital Assets. ORP has established a strategy for oversight of the WTP contractor's startup, commissioning, and readiness activities. The strategy also encompasses ORP's own activities to achieve readiness. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

First Road / River Barge Security Transport of SNF under the New German Transport Security Guidelines - 19102

A transfer of 342 spent fuel assemblies from NPP Obrigheim to NPP Neckarwestheim, both located alongside the river Neckar in the south of Germany, is required to promote the decommissioning process of NPP Obrigheim, which started in 2008 after the NPP had been shut down three years before. The spent fuel storage facility in Neckarwestheim offers sufficient storage space to accept the 342 SNF assemblies, stored in fifteen dry casks type CASTOR{sup R} 440/84 mvK. After several transport feasibility studies had been conducted, Daher Nuclear Technologies GmbH was awarded the commission to plan, prepare and conduct the SNF transport. Since the combined road / river barge transport promised to be the most suitable mode of transportation Daher Nuclear Technologies started to prepare its security concept, a prerequisite to apply for and attain the transport license mandatory for transporting spent nuclear fuel in Germany. In March 2014 the company applied for the transport license, which, after more than three years and numerous amendments to the security concept, was finally granted to Daher Nuclear Technologies on May 16, 2017 by the German Federal Office for the Safety of Nuclear Waste Management (successor organization of the BfS). Simultaneously to the license application phase the transport equipment - amongst others the heavy-duty trucks and trailers, the pusher tugs, the river barge and transport frames - had to be provided and modified to meet the intensified requirements of the New German Transport Security Guidelines Road / Rail as well as several other legal regulations referring to the transport of dangerous goods by road and inland waterways (e.g. ADR - European Agreement concerning the International Carriage of Dangerous Goods by Road and ADN - European Agreement concerning the International Carriage of Dangerous Goods by Inland Waterways). The planning process involved various meetings with representatives of different authorities and administrative bodies incl. accredited experts as well as subcontractors. Tremendous training efforts had to be undertaken to train more than 100 transport participants regarding security measures, health, safety and environmental measures, as well as the proper handling of radioactive material. This also included the training of the security staff, that had to be qualified in compliance with the new Transport Security Guidelines Road and Rail. Finally, in June 2017, when all preparations where complete, all requirements met, and all permits obtained, the first ever security SNF transport on a German river was performed. Three laden CASTOR{sup R} 440/84 mvK transport and storage casks were transported in one batch via heavy-duty truck-trailer from the NPP Obrigheim to the NPP's own harbor, to be rolled on to the river barge, that would carry the three casks upstream the river Neckar to the approx. fifty kilometer distant NPP Neckarwestheim. The journey on the river took about eleven hours, in which several bridges and locks had to be passed. The entire transport was escorted by qualified security staff and auxiliary police forces on waterways and alongside on roads. It attracted nationwide public attention, due to its pioneer status and the fact, that there hadn't been any SNF or HLW shipments in Germany since 2011. After the convoy safely arrived at NPP Neckarwestheim's pier the three laden CASTOR{sup R} 440/84 mvK casks were rolled off the river barge via heavy-duty truck-trailers to be stored in the on-site interim storage facility. This first transport was a success and was followed by four additionally successful security transports in September, October, November and December 2017. The public attention receded significantly during the transport campaign, which ended on December 19, 2017 with the transfer of the last three of fifteen casks to the on-site interim storage facility in Neckarwestheim. With the last cask safely transferred to the interim storage facility Daher Nuclear Technologies successfully completed the transport campaign on schedule, meeting one of EnBW's fundamental objectives to finish the transfer of the 342 SNF assemblies by the end of 2017. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Evaluation of Thermolytic Hydrogen Generation Rate Models at High-Temperature/High-Hydroxide Regimes

This report describes the results of testing performed to extend the applicable ranges of temperature and hydroxide concentration for use within the Glycolate and Global Total Organic Carbon (TOC) Hydrogen Generation Rate (HGR) expressions. Seven experimental conditions (six simulants of the 242-25H Evaporator system chosen as a D-optimal set of experiments and a single test conducted at an elevated boiling point of 170 °C) were investigated in the presence of sodium glycolate and Xiameter TM AFE-1010. Glycolate was employed to study the extension of the Glycolate Thermolytic HGR expression while Xiameter TM AFE-1010 was employed to study the extension of the Global TOC Thermolytic HGR expression. The following conclusions were derived from this testing: The Glycolate Thermolytic HGR expression may be confidently used to predict thermolytic HGRs from glycolate at temperatures as high as 170 °C and hydroxide concentrations as high as 23 M.; The hydroxide and temperature-dependence predicted by the Global TOC Thermolytic HGR expression has been confirmed at temperatures as high as 170 °C and hydroxide concentrations as high as 23 M, suggesting that the Global TOC Thermolytic HGR expression may be used at these ranges.; Methane was observed from tests with Xiameter TM AFE-1010 at production rates higher than those observed for hydrogen. These rates were observed at temperatures higher than 100 °C.; Preliminary models suggest that increasing hydroxide/temperature causes an increase in Methane Generation Rate (MGR) from Xiameter TM AFE-1010. The following recommendations are based on this testing: The existing equations for thermolytic HGR from glycolate and non-glycolate organics should be used at Concentration, Storage, and Transfer Facilities (CSTF) storage and evaporation conditions, including temperatures and hydroxide concentrations exhibited in the 242-25H Evaporator.; Further investigation should be made into the influence of methylsilanes on CSTF flammability. This investigation should include: determination of the types of methylsilanes historically added to the CSTF, determination of methane formation rates from each type of methylsilane, and determination of the extent of degradation of methylsilanes in CSTF waste.; Characterization techniques should be developed by Savannah River National Laboratory (SRNL) to assist in the speciation of methylsilane-containing waste in the CSTF.; Additional testing with radioactive waste should be performed to determine the MGRs possible in radioactive waste and better inform model predictions made from testing with simulants.

08 HYDROGEN↗

Troika partnership model for licensing NASA-LaRC technologies

The Technology Applications (TAG) Group at NASA Langley Research Center has currently more than 100 technologies that are ripe for commercialization. These technologies are categorized by various sectors including: Energy and the Environment; Materials and Structures; Manufacturing; Information and Communications; Transportation, and Medical/Sensor/ Instrumentation. A requirement that TAG has placed on all technologies ready for licensing is that there will be some university involvement in the technology transfer or knowledge transfer process. This model involves the troika of government (LaRC), industry and university. A number of variations on the Troika Partnership Model (TPM) were developed as a part of this ASEE Fellowship. Furthermore, five technologies were identified - three of which industrial interests have been matched: LaRC-SI, a thermoplastic that can be used as a coating; Variable Geometry Truss Manipulator Arm that can be used for nuclear waste clean -up and as scaffolding; and ADAPT (Approach to Data Management, Archive Protection, and Transmission) is a technology that could be used for a variety of multi-tasking operations over the Internet. The aim of this work was to initiate a Space Act Agreement (SAA) for at least one of these technologies using one of the options of the TPM. A preliminary partnership agreement using the SAA is currently being negotiated with NASA-LaRC, VPI and Virginia Power for the LaRC-SI thermoplastic that will be used as a coating.

Maclin, Arlene P.↗

Upcycling waste PET into functional multiblock copolymers through controlled macromolecular design

Poly(ethylene terephthalate) (PET) oligomers derived from glycolysis depolymerization were converted into multiblock copolymers through diisocyanate-mediated coupling with dihydroxy-terminated oligomers, enabling precise control over copolymer sequence distribution, connectivity, and mechanical performance. Here, we demonstrate that telechelic PET oligomers isolated directly from depolymerized consumer waste can serve as reactive building blocks for the formation of segmented multiblock copolymers, eliminating the need to revert to monomeric feedstocks. Dihydroxy-terminated PET oligomers (Mw ≈ 8 kg mol−1) were coupled with poly(ethylene oxide) (PEO, Mw ≈ 4 kg mol−1) to form PET-PEO multiblock copolymers with high molar mass (Mw ≈ 160 kg mol−1). We further show that the timing of end-capping reactions provides a key control parameter that governs the competition between chain extension and termination, thereby dictating the resulting multiblock architecture and molecular-weight evolution. Evaluation of their mechanical properties reveals that virgin PET exhibits high modulus (∼3 GPa) and strength (43 MPa) but limited ductility (<10% elongation). In contrast, PET–PEO multiblock copolymers retain comparable tensile strength (44 MPa), albeit while exhibiting dramatically enhanced ductility (>90% elongation), forming tougher materials with efficient stress transfer between the rigid PET domains and the flexible PEO segments. When incorporated into PET/PEO blends at low loadings, the multiblock copolymers serve as effective compatibilizers, yielding materials with an intermediate modulus (1.1–1.2 GPa) and improved elongation compared to uncompatibilized blends. Furthermore, the presence of PEO blocks increases water uptake and gas permeability relative to virgin PET, reflecting the tunability of molecular transport through the copolymeric blocks. To our knowledge, this represents the first report of PET–PEO multiblock copolymers derived from post-consumer PET for gas transport applications. These results demonstrate that multiblock copolymer formation from telechelic PET oligomers provides a versatile platform for tailoring the mechanical and transport behavior of polyester-based materials through controlled macromolecular design and establishes a generalizable strategy for transforming consumer plastic waste into functional segmented polymers without requiring complete depolymerization to monomers.

Watson-Sanders, Shelby [Department of Chemistry, U↗

Microalgae Biomass Production for Utilization of CO2 and Mitigation of Greenhouse Gas Emissions

Microalgal cultivation processes for production of foods, feeds, fuels, fertilizers and other bioproducts and wastewater treatment are being considered for reducing CO2 and other greenhouse gas emissions. Major differences between microalgae and higher plant biomass cultivation are include their potential for much higher productivities, their higher content of major (N-P-K) and minor nutrients, and the challenge of harvesting such microscopic plants. Most critical, microalgal mass cultures, unlike higher plants, currently require fertilization with concentrated sources of CO2. As practically all of the C fixed into algal biomass will be re-emitted into the atmosphere in short order, algae processes do not sequester carbon. Their potential for CO2 emissions reductions must thus be based on comparisons with current technologies for the production of competing products, such as biofuels or animal feeds, or in wastewater treatment. Further, due to economic limitations to flue gas transport (3 to 12 % CO2), as well as highly variable diurnal and seasonal CO2 utilization and limited land and water availability near most CO2 sources, only a small fraction of waste CO2 emissions will be directly utilizeable for microalgae biomass production. However, for long-distance transport, flue gas CO2 capture by chemical processes would greatly increase the costs of flue gas utilization. More concentrated, sources of CO2 from refineries, fertilizer, chemical plants, and fermentations are available, but are also very limited relative to the quantities required for commodity production. Microalgae can also be cultivated on organic wastes, which provide both nutrients (N, P, K, etc.) and organic and inorganic carbon for algal growth, reducing greenhouse gas emissions compared to conventional treatment processes. To maximize the potential for algae biomass production and CO2 utilization, direct capture of CO2 from air will be required. This could be accomplished with the algal cultivation process itself in large open-raceway ponds, through chemical and biological enhancements of CO2 transfer into algal cutures. The relative productivities, economics, greenhouse gas balances, and resource potentials of these alternative CO2 sources for large-scale production of microalgae will be reviewed.

09 BIOMASS FUELS↗

Thermal Analysis for SRS Saltstone Disposal Unit Facility

Saltstone Disposal Units (SDU) are long term disposal units for low activity grout produced from the solidification of decontaminated non-hazardous salt waste at SRS. The unit is a cylindrical disposal vault of 150 ft. in diameter and 23 ft. in height. The total volume the SDU can hold is 3 million gallons of grout. The hydration process of the grout material produces heat from an exothermic chemical reaction. If the grout reaches temperatures higher than the maximum safety temperature of 95 deg. C, cracks can start forming leading to contamination of the environment. The purpose of this study is to develop the optimal baseline domain boundary conditions and to perform a sensitivity analysis with respect to the baseline modeling conditions. The following assumptions were made for the modeling calculations: - The system geometry is axisymmetric; - The system was at steady state; - Ambient temperature was set to 100 deg. F; - Air was assumed to be an incompressible ideal gas; - Radiation was neglected for a conservative estimation; - Natural convection for the SDU vapor space is assumed to be turbulent because Rayleigh number based on typical operating conditions is higher than 10{sup 8}; - Water tables were not taken into consideration. The following sensitivity analyses were performed to find the optimal domain boundary: - Mesh size sensitivity; - Soil depth sensitivity - Soil depth varied from 30 ft to 250 ft with a soil thickness of 90 ft; - Soil thickness sensitivity - Soil thickness varied from 30 ft to 270 ft with a soil depth of 180 ft; - Soil conductivity sensitivity - Soil thermal conductivity varied from 0.25 W/m-K to 1 W/m-K; - Ambient Temperature Sensitivity - Ambient temperature varied from 70 deg. F to 110 deg. F. For the thermal calculations, the temperature of the bottom of the soil was set to 17.4 deg. C. The heat flux on the roof of the building and surface of the earth is 163.2 W/m{sup 2}. The soil sides are set to be adiabatic. The sensitivity analysis shows that the mesh size has no effect on the numerical results. This is mainly due to a small convection zone and large conduction zones in the modeling domain. The optimal domain boundary was found to be a soil thickness of 90 ft and a soil depth of 150 ft. The different sensitivity analysis performed here shows the optimal boundary domain to be used for thermal calculations is a soil depth of 150 ft beneath the SDU and a soil thickness of 90 ft. Anything larger would produce similar solutions but at a longer computational time to solve. The maximum temperature was more sensitive to soil properties as shown here. While the ambient temperature affected the max temperature linearly. Most of the heat transfer takes place downward vertically between the SDU and the soil beneath it. Using the optimal domain boundary determined by the sensitivity analyses, the maximum thermal loading to keep the maximum grout temperature below 95 deg. C is 1.646 W/m{sup 3}.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Lithium metal-mediated electrochemical reduction of per- and poly-fluoroalkyl substances

Per- and poly-fluoroalkyl substances (PFAS) have substantial environmental and health hazards. Unfortunately, current degradation routes require high temperatures or corrosive conditions and/or lead to incomplete defluorination and the generation of shorter alkyl chains. Inspired by the lithium-metal battery literature, here we develop an electrochemical degradation process that leverages reactive metals and highly reducing environments. Here, we show that electrodeposited lithium metal can enable 95% degradation and 94% defluorination of perfluorooctanoic acid to LiF without forming any shorter C 2 –C 6 PFAS as end products. Using computational simulations, we find that electron transfer from lithium to perfluorooctanoic acid leads to rapid C–F bond cleavage, fluoride formation and carbon chain fragmentation. We expand the scope to other PFAS compounds and demonstrate substantial degrees of degradation on over 22 different PFAS, plus complete mineralization to inorganic fluorides. Finally, we use the mineralized F − as a fluorine source for the synthesis of fluorinated non-PFAS compounds to complete a circular fluorine loop from waste to valuable product.

Sarkar, Bidushi [Univ. of Chicago, IL (United Stat↗

ILAW Container Cost Reduction and Optimization Study

This study, performed on behalf of Washington River Protection Solutions (WRPS), examines the potential for making cost savings for the Immobilized Low Active Waste (ILAW) containers over the mission life of the Waste Treatment and Immobilization Plant (WTP). it builds on earlier study assessments 24590-LAW-RPT-M-01-001 Rev 0 ILAW Product Container Specifications Optimization Study and DOE/ORP-2013-02 Rev 0 Decision Analysis of Low-Active Waste Container Finishing Handling System Alternatives. The WTP design and installed equipment has evolved over an extended period ~20 years. Consequently, some of the existing requirements relating the ILAW containers may no longer be applicable under current mission plans where the glass filled containers are placed into the Integrated Disposal Facility (IDF) rather than stacked in an engineered purpose-built ventilated store as originally envisioned. The study team reviewed available WTP project reference documents to establish the functions the container must perform and assign requirements against each of these functions. With the assumptions that some of the existing WTP contract restrictions would not necessarily apply to the subsequent facility operations contract the container requirements were reviewed to identify those which were ‘hard constraints‘, imposed by regulatory requirements. Initially each of these hard constraints were reviewed, evaluated and documented to see if they precluded the use of an alternate less expensive material of construction, carbon steel, to the existing 304 L stainless steel in the current container specification. That review did not generate any fatal flaws for a change in material of construction to carbon steel allowing the study team to examine the impacts of material cost savings, potential changes to the design and requirements and impacts on interfaces of the containers with the existing WTP process equipment from container receipt, transfers, glass filling, cooling and export. In addition, a change in container target fill level was evaluated and qualitative, and quantitative where feasible, impacts to the container fabrication process assessed. Lastly, additional follow on development or testing activities to support the use of carbon steel were assessed and a recommended path forward with a ROM cost and timescale developed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗