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At least 1,603 records · Page 89

Revised Guidelines for using Cellulose Degradation Product-Impacted Kd Values for Performance Assessments and Composite Analyses

Cellulosic materials include wood, paper, rags, and cardboard products. These materials are co-disposed with radiological waste at the Savannah River Site's (SRS) E-Area Low-Level Waste Facility (ELLWF). Cellulosic materials readily degrade in the environment to form cellulose degradation products (CDP) that will partition to the sediment or remain mobile in the groundwater. Savannah River National Lab (SRNL) has conducted studies to estimate the impact of CDP on radionuclide sorption to SRS sediments (Kd values). It was found that CDP impact on radionuclide sorption varies with radionuclide and CDP concentration. Furthermore, it was found that the amount of carbon (C) in the system could increase or decrease Kd values with respect to the base case of when no CDP was added. Throughout the expected pH range of the ELLWF, a low concentration of CDP in the system would increase Kd values (because C would sorb to the sediment and provide more exchange sites for radionuclides to sorb), whereas greater concentrations of CDP (≥20 mg/L C) would decrease Kd values (because C would remain in solution and complex the radionuclide and not permit the radionuclide to sorb to the sediment). A review of >230 dissolved organic carbon (DOC) groundwater concentrations in the Old Radioactive Waste Burial Ground (ORWBG) at the SRS indicated that the average DOC concentration, a gross measure of CDP, was 5 mg/L C. At approximately this DOC concentration, the laboratory studies demonstrated that no anions (Tc, I, or Se) or cations (Ni, Sr, Ce, Eu, Zr, or Th) have decreased sorption in the presence of carbon (an analogue for CDP).

09 BIOMASS FUELS↗

Capture of Organic Iodides from Vessel Off-Gas Streams

In nuclear waste reprocessing, radioactive iodine is released in both organic and inorganic forms into off-gas streams. Due to its properties of long half-life and potential accumulation in human bodies, radioactive iodine is required to be removed from off-gas streams by the Environmental Protection Agency (EPA) and Nuclear Regulatory Commission (NRC). In this study, the removal of organic iodides using two prototype silver (Ag) adsorbents, i.e., reduced Ag functionalized silica aerogel (Ag 0 -aerogel) and reduced Ag exchanged mordenite (Ag 0 Z), is investigated through a combination of experimental and modeling studies.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Transuranic Waste Processing Center (TWPC) Legacy Tank RH-TRU Sludge Processing and Compliance Strategy - 13255

The U.S. Department of Energy (DOE) needs to safely and efficiently treat its 'legacy' transuranic (TRU) waste and mixed low-level waste (LLW) from past research and defense activities at the Oak Ridge National Laboratory (ORNL) so that the waste is prepared for safe and secure disposal. The TWPC operates an Environmental Management (EM) waste processing facility on the Oak Ridge Reservation (ORR). The TWPC is classified as a Hazard Category 2, non-reactor nuclear facility. This facility receives, treats, and packages low-level waste and TRU waste stored at various facilities on the ORR for eventual off-site disposal at various DOE sites and commercial facilities. The Remote Handled TRU Waste Sludge held in the Melton Valley Storage Tanks (MVSTs) was produced as a result of the collection, treatment, and storage of liquid radioactive waste originating from the ORNL radiochemical processing and radioisotope production programs. The MVSTs contain most of the associated waste from the Gunite and Associated Tanks (GAAT) in the ORNL's Tank Farms in Bethel Valley and the sludge (SL) and associated waste from the Old Hydro-fracture Facility tanks and other Federal Facility Agreement (FFA) tanks. The SL Processing Facility Build-outs (SL-PFB) Project is integral to the EM cleanup mission at ORNL and is being accelerated by DOE to meet updated regulatory commitments in the Site Treatment Plan. To meet these commitments a Baseline (BL) Change Proposal (BCP) is being submitted to provide continued spending authority as the project re-initiation extends across fiscal year 2012 (FY2012) into fiscal year 2013. Future waste from the ORNL Building 3019 U-233 Disposition project, in the form of U-233 dissolved in nitric acid and water, down-blended with depleted uranyl nitrate solution is also expected to be transferred to the 7856 MVST Annex Facility (formally the Capacity Increase Project (CIP) Tanks) for co-processing with the SL. The SL-PFB project will construct and install the necessary integrated systems to process the accumulated MVST Facilities SL inventory at the TWPC thus enabling safe and effective disposal of the waste. This BCP does not include work to support current MVST Facility Surveillance and Maintenance programs or the ORNL Building 3019 U-233 Disposition project, since they are not currently part of the TWPC prime contract. The purpose of the environmental compliance strategy is to identify the environmental permits and other required regulatory documents necessary for the construction and operation of the SL- PFB at the TWPC, Oak Ridge, TN. The permits and other regulatory documents identified are necessary to comply with the environmental laws and regulations of DOE Orders, and other requirements documented in the SL-PFB, Safety Design Strategy (SDS), SL-A-AD-002, R0 draft, and the Systems, Function and Requirements Document (SFRD), SL-X-AD-002, R1 draft. This compliance strategy is considered a 'living strategy' and it is anticipated that it will be revised as design progresses and more detail is known. The design basis on which this environmental permitting and compliance strategy is based is the Wastren Advantage, Inc., (WAI), TWPC, SL-PFB (WAI-BL-B.01.06) baseline. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Production of Energy Efficient Preform Structures (PEEPS)

Due to its low density, good structural characteristics, excellent fabrication properties, and attractive appearance, aluminum metal and its alloys continue to be widely utilized. The transportation industry continues to be the largest consumer of aluminum products, with aerospace as the principal driver for this use. Boeing has long been the largest single company consumer of heat-treated aluminum in the U.S. The extensive use of aluminum to build aircraft and launch vehicles has been sustained, despite the growing reliance on more structurally efficient carbon fiber reinforced composite materials. The trend in the aerospace industry over the past several decades has been to rely extensively on large, complex, thin-walled, monolithic machined structural components, which are fabricated from heavy billets and thick plate using high speed machining. The use of these high buy-to-fly ratio starting product forms, while currently cost effective, is energy inefficient, with a high environmental impact. The widespread implementation of Solid State Joining (SSJ) technologies, to produce lower buy-to-fly ratio starting forms, tailored to each specific application, offers the potential for a more sustainable manufacturing strategy, which would consume less energy, require less material, and reduce material and manufacturing costs. One objective of this project was to project the energy benefits of using SSJ techniques to produce high-performance aluminum structures if implemented in the production of the world fleet of commercial aircraft. A further objective was to produce an energy consumption prediction model, capable of calculating the total energy consumption, solid waste burden, acidification potential, and CO2 burden in producing a starting product form - whether by conventional or SSJ processes - and machining that to a final part configuration. The model needed to be capable of computing and comparing, on an individual part/geometry basis, multiple possible manufacturing pathways, to identify the best balance of energy consumption and environmental impact. This model has been created and populated with energy consumption data for individual SSJ processes and process platforms. Technology feasibility cases studies were executed, to validate the model, and confirm the ability to create lower buy-to-fly ratio performs and machine these to final configuration aircraft components. This model can now be used as a tool to select manufacturing pathways that offer significant energy savings and, when coupled with a cost model, drive implementation of the SSJ processes.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Colorado State University Extension Industrial Assessment Center

Since its inception in 1984, the Colorado State University Industrial Assessment Center has performed industrial assessments at more than 720 manufacturing facilities in Colorado, Montana, Nebraska, Nevada, New Mexico, North Dakota, South Dakota, Utah, and Wyoming. From 2017 to 2019 there was a funding gap and the IAC shutdown. In 2020 through DOE extension funding the University relaunched the IAC as an extension center in order to provide assessments to underserved areas. Under this award, the CSU Industrial Assessment Center (IAC) was rebuilt with the help of student employees and the director. The CSU team experienced difficulty as the program was in the process of being restarted right as the 2020 pandemic hit. Nonetheless, the CSU IAC was instrumental in providing energy assessments to manufacturers in Colorado and Wyoming during the period of performance of 09/2019 – 12/2022. The Department of Energy's Industrial Assessment Centers (IACs) provide a valuable service to small and medium-sized manufacturers seeking to optimize their operations. These university-based centers offer no-cost, on-site assessments conducted by engineering faculty and students, analyzing energy consumption, production processes, and waste streams. They utilize advanced data acquisition systems to record operational data, and then use the data to create assessment recommendations. These recommendations form the foundation of the comprehensive energy report. The comprehensive report delivers actionable recommendations for enhancing energy efficiency, reducing waste, and reducing greenhouse gas emissions and improving productivity, often identifying significant cost savings. Furthermore, IACs facilitate access to implementation grants, enabling the businesses to readily adopt these improvements. This program not only strengthens individual businesses but also contributes to national goals of training the next generation of energy experts, as well as increasing industrial competitiveness and reduced environmental impact.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Special Analysis: 2017-001 Disposal of Drums Containing Enriched Uranium in Pit 38 at Technical Area 54, Area G

Los Alamos National Laboratory (LANL) generates radioactive waste as a result of various activities. Operational waste is generated from a wide variety of research and development activities including nuclear weapons development, energy production, and medical research. Environmental restoration (ER), and decontamination and decommissioning (D&D) waste is generated as contaminated sites and facilities at LANL undergo cleanup or remediation. The majority of this waste is low-level radioactive waste (LLW) and is disposed of at the Technical Area 54 (TA-54), Area G disposal facility. This special analysis, SA 2017-001, evaluates the potential impacts of disposing of this waste in Pit 38 at Area G based on the assumptions that form the basis of the Area G PA/CA. Section 2 describes the methods used to conduct the analysis; the results of the evaluation are provided in Section 3; and conclusions and recommendations are provided in Section 4.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Major Achievements of the Springfields Decommissioning Program - 16512

Since the 1940's, Springfields has manufactured fuel products for the UK's nuclear power stations and for international customers. The early operations were in support of the atomic weapons program, closely followed by fuel manufacture for electricity generation via the Magnox power stations commencing in the late 1950's. In 2005, responsibility for the assets and liabilities of Springfields was transferred to the Nuclear Decommissioning Authority (NDA). A new company, Springfields Fuels Limited, was created to run the site, which was managed and operated by Westinghouse Electric UK Ltd on the NDA's behalf. On April 1, 2010, Westinghouse entered into an agreement with the NDA for a long-term lease of the Springfields site, which transferred responsibility for the commercial fuel manufacturing business and Springfields Fuels Limited to Westinghouse. Today, the main Springfields activities include: - Oxide fuels for Advanced Gas-cooled and Light Water Reactors, as well as intermediate fuel products, such as powders, granules and pellets, - Manufacture of Uranium Hexafluoride (now in Care and Maintenance), - Processing and recovery of Uranium residues, - Decommissioning and demolition of redundant plants and buildings. Some 120 plant buildings and support facilities have been successfully decommissioned and demolished in the period 1996 to date. These range from 1940's buildings, subsequently converted for nuclear fuel manufacture, together with some of the formerly sealed chemical agent manufacture and storage facilities. Decommissioning of the now redundant Magnox manufacturing facilities is ongoing at Springfields without compromising the other site operations. Westinghouse is managing all activities related to the whole lifecycle, planning, design, safety case, radiation protection, Post Operational Clean Out (POCO), service diversions, characterization, decommissioning all phases through to ground remediation, waste disposal and agreed end states. Decommissioning of process plants starts with the removal of the majority of radiological activity or hazard contained within the plant. This is known as Post Operational Clean Out. Once this is complete, the plant may be dismantled. Work is scoped and defined within packages (at plant or cell level) to aid control and commercial monitoring as the decommissioning is progressed. This package approach also enables clean or lightly contaminated items to be removed separately to aid potential re-cycling and minimize decontamination and waste disposal costs. Westinghouse is further optimising work package delivery by planning parallel POCO and Decommissioning work phases within plant at a cell level to systematically remove redundant plant and reduce hazard earlier, whilst optimising use of both internal and external resources to reduce total project cost. Waste and Residues from all phases are disposed of via authorized disposal routes and in accordance with our environmental authorizations. On completion of decommissioning and removal of plant and equipment the building is re-assessed radiologically, categorized and appropriate remediation work progressed to render it safe for conventional demolition. The major elements of the success achieved to date can be attributed to the following elements: - Overall programme management with extensive experience of planning, cost, and risk management. Integration of the programme within a major commercial site without compromising safety or operations. - Complete site EHS management working within a complex regulatory framework including the Nuclear Site Licenses, Environmental Authorisations and Security requirements. - Avoiding safety complacency by use of rigorous and systematic process to emphasise safety over competing goals. Including structured use of Human Performance and Corrective Action and Learning processes. - Unique safety experiences attained through complex hazard reduction across a broad range of uranium manufacturing and chemical hazard/agent facilities. - Project leadership and excellence utilizing a core site team to deploy repeatable processes and safe practices to deliver complex scope within budget and schedule. - Optimised use of internal and external resources, with extensive use of Operating Experience to drive continuous improvement and problem resolution. - Management of Contractors from initial selection, pre-qualification, tender assessment and Performance using varied contract forms across delivery phases. - Use of Westinghouse expertise for safety case, waste management, uranium recovery, health physics and design. - Implementation of a work package to ensure gated discreet manageable packages. Underpinned by package specific method statements, with appropriate hold points to maintain management and control of the works. - Continuous local safety focus via safety planning, induction, plant specific training, proactive risk assessment, and a defined approach to decoupling operating plant safety cases enabling focussed and usable documentation. This paper will provide an overview of the latest decommissioning activities achieved on the Springfields site and will focus on best practices that allowed Westinghouse to maintain the program on time and on budget. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis Of Condensate Samples In Support Of The Antifoam Degradation Study

The degradation of Antifoam 747 to form flammable decomposition products has resulted in declaration of a Potential Inadequacy in the Safety Analysis (PISA) for the Defense Waste Processing Facility (DWPF). Savannah River National Laboratory (SRNL) testing with simulants showed that hexamethyldisiloxane (HMDSO), trimethylsilanol (TMS), and 1-propanal are formed in the offgas from the decomposition of the antifoam. A total of ten DWPF condensate samples from Batch 735 and 736 were analyzed by SRNL for three degradation products and additional analytes. All of the samples were analyzed to determine the concentrations of HMDSO, TMS, and propanal. The results of the organic analysis found concentrations for propanal and HMDSO near or below the detection limits for the analysis. The TMS concentrations ranged from below detection to 11 mg/L. The samples from Batch 736 were also analyzed for formate and oxalate anions, total organic carbon, and aluminum, iron, manganese, and silicon. Most of the samples contained low levels of formate and therefore low levels of organic carbon. These two values for each sample show reasonable agreement in most cases. Low levels of all the metals (Al, Fe, Mn, and Si) were present in most of the samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ANALYSIS OF CONDENSATE SAMPLES IN SUPPORT OF THE ANTIFOAM DEGRADATION STUDY

The degradation of Antifoam 747 to form flammable decomposition products has resulted in declaration of a Potential Inadequacy in the Safety Analysis (PISA) for the Defense Waste Processing Facility (DWPF). Savannah River National Laboratory (SRNL) testing with simulants showed that hexamethyldisiloxane (HMDSO), trimethylsilanol (TMS), and 1-propanal are formed in the offgas from the decomposition of the antifoam. A total of ten DWPF condensate samples from Batch 735 and 736 were analyzed by SRNL for three degradation products and additional analytes. All of the samples were analyzed to determine the concentrations of HMDSO, TMS, and propanal. The results of the organic analysis found concentrations for propanal and HMDSO near or below the detection limits for the analysis. The TMS concentrations ranged from below detection to 11 mg/L. The samples from Batch 736 were also analyzed for formate and oxalate anions, total organic carbon, and aluminum, iron, manganese, and silicon. Most of the samples contained low levels of formate and therefore low levels of organic carbon. These two values for each sample show reasonable agreement in most cases. Low levels of all the metals (Al, Fe, Mn, and Si) were present in most of the samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Process of forming catalytic surfaces for wet oxidation reactions

A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

Jagow, R. B.↗

Reforming of glucose and wood at the critical conditions of water

Reforming of organics in aqueous solutions is being investigated as a potential waste treatment process. Earlier studies showed that glucose in water reacts to form a gaseous mixture of CO, H2, CH4, CO2, C2H6, and C2H4 in the vicinity of the critical conditions of water (374 C, 22 MPa). The earlier work has been extended to determine the effect of variations in temperature and feed concentration on the extent of gasification. The percent gasification decreases with increasing feed concentration, indicating an overall kinetic order less than unity. Surprisingly, the percent gasification decreases with increasing temperature. A number of preliminary experiments were conducted with maple sawdust feed, which was thought to be representative of complex organic wastes from paper and vegetable matter. Once again, no solid products were found under the critical conditions; the percent gasification ranged from 16 to 88 percent, depending on the feed composition and residence time.

Modell, M.↗

Submixture model to predict nepheline precipitation in waste glasses

Abstract High‐alumina high‐level waste ( HLW ) glasses are prone to nepheline precipitation during canister‐centerline cooling ( CCC ). If sufficient nepheline forms, the chemical durability of the glass will be significantly impacted. Overly conservative constraints have been developed and used to avoid the deleterious effects of nepheline formation in U.S. HLW glasses. The constraints used have been shown to significantly limit the loading of waste in glass at Hanford and therefore the cost and schedule of cleanup. A 90‐glass study was performed to develop an improved understanding of the impacts of glass composition on the formation of nepheline during CCC . The CCC crystallinity data from these glasses were combined with 657 glasses found in the literature. The trends showed significant effects of Na 2 O, Al 2 O 3 , SiO 2 , B 2 O 3 , CaO, Li 2 O, and potentially K 2 O on the propensity for nepheline formation. A pseudo‐ternary submixture model was proposed to identify the glass composition region prone to nepheline precipitation. This pseudo‐ternary with axes of SiO 2 + 1.98B 2 O 3 , Na 2 O + 0.653Li 2 O + 0.158CaO, and Al 2 O 3 was found to divide glasses that precipitate nepheline during CCC from those that do not. Application of this constraint is anticipated to increase the loading of Hanford high‐alumina HLW s in glass by roughly one‐third.

Vienna, John D.↗

Improved third generation peristaltic crawler for removal of high-level waste plugs in United States department of energy Hanford site pipelines

There are approximately 56 million gallons (212 km{sup 3}) of high level waste (HLW) at the U.S. Department of Energy (DOE) Hanford Site. It is scheduled that by the year 2040, the HLW is to be completely transferred to secure double-shell tanks (DST) from the leaking single-tanks (SST) via transfer pipeline system. Blockages have formed inside the pipes during transport because of the variety in composition and characteristics of the waste. These full and partial plugs delay waste transfers and require manual intervention to repair, therefore are extremely expensive, consuming millions of dollars and further threatening the environment. To successfully continue the transfer of waste through the pipelines, DOE site engineers are in need of a technology that can accurately locate the blockages and unplug the pipelines. In this study, the proposed solution to remediate blockages formed in pipelines is the use of a peristaltic crawler: a pneumatically/hydraulically operated device that propels itself in a worm-like motion through sequential fluctuations of pressure in its air cavities. The crawler is also equipped with a high-pressure water nozzle used to clear blockages inside the pipelines. The crawler is now in its third generation. Previous generations showed limitations in its durability, speed, and maneuverability. Latest improvements include an automation of sequence that prevents kickback, a front-mounted inspection camera for visual feedback, and a thinner wall outer bellow for improved maneuverability. Different experimental tests were conducted to evaluate the improvements of crawler relative to its predecessors using a pipeline test-bed assembly. Anchor force tests, unplugging tests, and fatigue testing for both the bellow and rubber rims have yet to be conducted and thus results are not presented in this research. Experiments tested bellow force and response, cornering maneuverability, and straight line navigational speed. The design concept and experimental test results are reported. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

FY24 Task 5: Leachate Disposition

Directly feeding sludge solids to the high-level waste (HLW) Waste Treatment Plant represents an alternative flowsheet seeking to initiate sludge processing as soon as possible. Key processing functions previously captured during baseline pretreatment operations include leaching and washing prior to solids concentration. These operations should be considered in the potential direct feed flowsheets to maximize waste feed loading, minimize HLW volume, and mitigate corrosion challenges associated with vitrification of high phosphate and fluoride concentrations. Additionally, single-shell tank (SST) retrievals and waste transfers to double-shell tanks (DSTs) in a direct feed flowsheet would likely also benefit from some level of leaching, washing, and solids concentration in order to reduce DST space and mission duration. These operations could occur in a new facility or potentially in available DSTs. If washing and leaching are utilized, an effective disposition pathway for the wash water and leachate solutions are needed. Three target species that benefit significantly from leaching and washing are phosphate, fluoride and aluminum. Phosphate (PO 4 3- ) and fluoride (F - ) can contribute substantially to the amount of carrier fluid needed for dissolution, and the resulting volume of liquid generated. Disposition of this retrieval solution should be evaluated in order to prevent crystallization of these anions throughout system processing. Since there is a high probability that any retrieval solutions will be at or near their PO 4 3- and F - solubility limits, evaporation or blending with a high Na supernate (>3.5 M) is not recommended for the wash water streams without a method to remove precipitants prior to solution disposal. Additionally, aluminum present in the southeast quadrant of the Hanford site represents roughly 60% of the waste solids in the initial processing tanks. These aluminum solids are in the form of gibbsite (Al(OH) 3 ) and can pose significant challenges for processing due to the fast-settling times and high solids loading associated with these materials. Easily remediated by caustic addition to the solids, these wash solutions could be processed through crystalline silicotitanate (CST) ion exchange columns to prepare the supernate solutions for disposition. The current target for feed conditions to the Low Activity Waste (LAW) melter are waste streams that contain nominally 5-6 M Na. Fractions within the tanks contain upwards of 0.2 M phosphate and fluoride in solution at 3.5 M Na. Concentrating these solutions above 5 M Na would result in an exceedance of the solubility limits, and potential for uncontrolled precipitation of the phosphate and fluoride crystal material. The resulting crystalline salt material is typically sodium fluoride phosphate, also referred to as natrophosphate (Na 7 FPO 4 ·19H 2 O). Salt phases are of importance in tank waste due to their chemical reactivity, which can result in precipitation, dissolution, or transformation, impacting any downstream processes (Bolling et al. 2020, Russell, Snow, and Peterson 2010). Salt generation and precipitation could pose challenges by causing system plugging and melter corrosion if left in the supernate stream, or limit sodium molarity of the supernate that would be accepted without incident in waste operations. To understand the impact of this salt generation, the crystallization of natrophosphate in multiple simulant feed matrices was studied to understand the implications of various tank waste supernate chemistries. Three matrices were examined: high PO 4 3- /low F - , low PO 4 3- /high F - , and an average matrix. Subsequent testing was performed with the average matrix with the inclusion of CsNO 3 , and a final run with the average matrix including CsNO 3 and a 137 Cs spike for tracer purposes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Literature Review on the Sorption of Plutonium, Uranium, Neptunium, Americium and Technetium to Corrosion Products on Waste Tank Liners

The Savannah River Site (SRS) has conducted performance assessment (PA) calculations to determine the risk associated with closing liquid waste tanks. The PA estimates the risk associated with a number of scenarios, making various assumptions. Throughout all of these scenarios, it is assumed that the carbon-steel tank liners holding the liquid waste do not sorb the radionuclides. Tank liners have been shown to form corrosion products, such as Fe-oxyhydroxides (Wiersma and Subramanian 2002). Many corrosion products, including Fe-oxyhydroxides, at the high pH values of tank effluent, take on a very strong negative charge. Given that many radionuclides may have net positive charges, either as free ions or complexed species, it is expected that many radionuclides will sorb to corrosion products associated with tank liners.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Estimation of Sorption Behavior of Europium to Calcium Silicate Hydrate by Thermal Analysis - 20172

High-level radioactive waste generated from reprocessing processes will be disposed in a geological disposal that is deep underground. Calcium silicate hydrate is formed as a secondary mineral in the repository via the reaction of calcium ions leaching from the cement and the silicic acid dissolved from the host rocks. In this study, the sorption behavior of europium, which is also known as a chemical analog of americium, on calcium silicate hydrate was examined. The solid phase was analyzed via thermogravimetry- differential thermal analysis, differential scanning calorimetry, Raman spectroscopy, fluorescence spectroscopy, and fluorescence lifetime analysis. To understand the behavior of calcium silicate hydrate under conditions saturated with groundwater, the study samples were analyzed using the above methods, except for deferential scanning calorimetry, without a drying process. The results of the differential scanning calorimetry analyses showed that the temperatures for the endothermic peaks of calcium silicate hydrate for the lower Ca/Si ratios were larger than those for the higher Ca/Si ratios for coexistent conditions of europium ions. Hence, the relationships of the temperatures of the endothermic peaks and the Ca/Si ratios were reversed by the addition of europium ions. These study results suggest that calcium silicate hydrate can immobilize europium ions, thus preventing the production of colloidal forms. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Carbon polyaniline capacitive deionization electrodes with stable cycle life

Electrode materials for capacitive deionization (CDI), an energy efficient method for desalination, were developed in this work. Waste-tire derived carbon (TC) coated with polyaniline was used to form a carbon polymer composite (CPC). CPC was used as an electrode in CDI configurations to determine the salt adsorption capability of the material. Chemical treatment of TC with KOH led to an enhancement in surface area to 952 m 2 /g and microporosity in the sub-2-nm range. This unique microstructure is considered to be beneficial for effective ion uptake in CDI applications. The capacitance of the electrodes was further enhanced through surface coating with polyaniline, resulting in a specific capacitance of 168.2 F/g. In batch cell testing with 1.2 V applied potential, the salt adsorption capacity (SAC), measured in mg of salt adsorbed per gram of active material, in a 1500–1700 ppm KCl solution was measured at 14.2 mg/g. Scale-up of the process with ionic-membrane-assisted CDI (MCDI) led to improvement in SAC at 18.9 mg/g. Further, cycling tests revealed that the electrodes had comparable or better longevity compared to other CDI materials, retaining >92.8% charging capacity after 300 cycles. In conclusion, high adsorption capacities for other salts such as LiCl, NaCl, MgCl 2 and CaCl 2 have been found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atmospheric emission of nanoplastics from sewer pipe repairs

Nanoplastic particles are inadequately characterized environmental pollutants with significant adverse effects on aquatic and atmospheric systems, causing drastic impacts on human health through inhalation, ingestion, and skin penetration. At present, it is explicitly assumed that environmental nanoplastics (EnvNP) are weathering fragments of microplastic or larger plastic debris discharged into terrestrial and aquatic environments, while atmospheric occurrence of EnvNP is solely attributed to aerosolization by wind and other mechanical forces. However, sources and emissions of unintended EnvNP are poorly understood and are therefore largely unaccounted for in various risk assessments. In this work, we show that large quantities of EnvNP may be directly emitted into the atmosphere as steam laden waste components discharged from a commonly used technology to repair sewer pipes in urban areas. Comprehensive chemical analysis of the discharged waste condensate reveals abundant presence of insoluble colloids, which after drying form solid organic particles with composition and viscosity consistent with EnvNP. We suggest that airborne emissions of EnvNP from these globally used sewer repair practices may be prevalent in highly populated urban areas. Airborne emissions of these EnvNP particles may have important implications on air quality and toxicological levels in large urban areas that need to be mitigated.

77 NANOSCIENCE AND NANOTECHNOLOGY↗