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Niche Partitioning of Microbial Communities at an Ancient Vitrified Hillfort: Implications for Vitrified Radioactive Waste Disposal

A pre-Viking era vitrified hillfort, Broborg, provides a habitat analogue for disposed radioactive waste glass and shows strong niche partitioning among the organisms involved in glass alteration. Microbes cannot be eliminated from radioactive waste disposal facilities and the consequences of bio-colonization must be understood. We use Broborg as a model system to inform what microbial processes might influence long-term radioactive waste glass durability by examining anthropogenic glass that has been subjected to bio-colonization for over 1,500 years. Scanning electron microscopy (SEM) images reveal the surficial biofilm structure, and chemical/mineralogy analysis in combination with deoxyribonucleic acid (DNA) sequencing of samples from the vitrified substrate, the adjacent soil, and the general topsoil provide insight into niche partitioning. The ancient glass niche supports a unique microbial community of bacteria, fungi, and protists that manifests the species response to local geochemical and mineralogical conditions. Communities from the geochemical niche associated with the glass are distinct and less diverse than soil communities. The microbiome of the glass and adjacent soil are dominated by lichens, lichen-associated microorganisms, and other epilithic, endolithic, and epigeic organisms. Pseudomonads dominate the prokaryotic communities on the vitrified material, but not the adjacent soil. In contrast, the general topsoil communities are enriched in plant rhizosphere organisms. Taxa associated with vitrification have bio-corrosive properties that could be detrimental to glass durability, including silicate mineral dissolution, extraction of essential elements, secretion of geochemically reactive organic acids, and dissolution induced by improved water retention. However, these stable long-term biofilms also possess a homeostatic function that could limit glass alteration. Overall, this study demonstrates the potential impacts that microbial colonization and niche partitioning can have on glass alteration and subsequent release of radionuclides from a disposal facility for vitrified radioactive waste.

59 BASIC BIOLOGICAL SCIENCES↗

Nuclear Safety [Vol. 30, No. 1, January-March 1989]

Nuclear Safety is a review journal that covers significant developments in the field of nuclear safety. Its scope includes the analysis and control of hazards associated with nuclear energy, operations involving fissionable materials, and the products of nuclear fission and their effects on the environment. Primary emphasis is on safety in reactor design, construction, and operation; however, the safety aspects of the entire fuel cycle, including fuel fabrication, spent-fuel processing, nuclear waste disposal, handling of radioisotopes, and environmental effects of these operations, are also treated. Table of Contents for this issue follows. GENERAL SAFETY CONSIDERATIONS: 1 International Conference on Thermal Reactor Safety: NUCSAFE 88 by A. P. Malinauskas and J. G. Pruett; ACCIDENT ANALYSIS: 18 Chernobyl Today: State of Research by A. Yu. Gagarinskii; CONTROL AND INSTRUMENTATION: 23 Problems Associated with Routine In-Plant Radioactive Effluent Monitoring Systems at U.S. Light-Water Reactors by Barry G. Wahlig, David M. Walker, Mahmoud R. Ghavi, and John M. Palms; DESIGN FEATURES: 34 Twentieth DOE/NRC Nuclear Air-Cleaning Conference by R. R. Bellamy, D. W. Moeller, and M. W. First, 46 Design Options for the Core Support Structure for Liquid-Metal-Cooled Reactor Plants by J. P. Burelbach, W. J. Kann, J. G. Saiveau, and R. W. Seidensticker; ENVIRONMENTAL EFFECTS: 53 The Radiological Consequences of the Chernobyl Accident by L. V. Konstantinov and A. J. González; WASTE AND SPENT FUEL MANAGEMENT: 70 Activities Related to Waste Management Compiled by E. G. Silver; OPERATING EXPERIENCES: 80 Fuel Performance Annual Report for 1986 by W. J. Bailey, 103 Safety Considerations Related to 12-Hour Shift Schedules by S. Gould, 105 Reactor Shutdown Experience Compiled by J. W. Cletcher, 108 Operating U.S. Power Reactors Compiled by E. G. Silver; RECENT DEVELOPMENTS: 130 General Administrative Activities Compiled by E. G. Silver, 140 Reports, Standards, and Safety Guides by D. S. Queener, 145 Status of Power-Reactor Licensing Activities Compiled by E. G. Silver, 153 Proposed Rule Changes as of Sept. 30, 1988; ANNOUNCEMENTS: 69 Northwestern University Short Course on Radiation Safety, 79 International Seminar on Fission Product Transport Processes in Reactor Accidents, 129 Harvard School of Public Health Offers Short Courses, 152 MIT Offers Summer Short Courses on Reactor Safety and Nodal Analysis, 152 Seminar on Use of PCs in Probabilistic Safety Analysis, 157 The Authors, 160 Indexes to Nuclear Safety, Volume 29.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

WIPP Safety Significant Confinement Ventilation System (SSCVS) HEPA Filtration System - 20165

Construction and major equipment fabrication are underway for a new ventilation exhaust system at the Waste Isolation Pilot Plant (WIPP). The new system will provide continuous High Efficiency Particulate Air (HEPA) filtration of the exhaust from the WIPP underground while meeting the ventilation demands for expanded waste emplacement and mining operations over the next 40 years. The integrated system design provides for reducing the salt, clay and diesel particulates from the exhaust airflow from the mine, prior to full filtration using Nuclear Safety Significant HEPA filters. The SSCVS design and equipment provides for continuous HEPA filtration over a wide range of operating and environmental conditions. The new exhaust system connects to the existing underground exhaust shaft, and the exhaust air flows from the underground through Salt Reduction Units (SRUs) to protect the final filter banks from excessive moisture and rapid salt/dust buildup. Each of the six (6) SRUs consists of a demister to remove entrained moisture, a dry salt remover unit to filter approximately 90% of the entrained salt/dust, and an automated water treatment system to periodically clean the demisters and to remove salt from the SRU filters. At the maximum expected exhaust flowrate of 540,000 Cubic Feet per Minute (CFM) / 255 Cubic Meters per Second (m{sup 3}/s), five (5) salt removal units will be in operation with one unit in standby or maintenance. An in-line variable frequency drive booster fan will offset pressure losses through each SRU and reduce the relative humidity of the air exiting the SRUs. In the event of a high radiation alarm from the underground Continuous Air Monitors (CAMs), the SRUs will be automatically bypassed, which places the SRS and building outside of the Safety Significant confinement boundary. From the SRUs, the exhaust is directed to the HEPA filter banks located in the New Filter Building. The exhaust system is designed to provide continuous HEPA filtration prior to release to the exhaust stack. There are 22 HEPA filter banks rated at 27,000 CFM / 12.75 m{sup 3}/s each. Each filter bank has two stages of pre-filters and two stages of HEPA filters. The filtered air from each of the 22 filter banks discharges into a common concrete plenum, which is maintained under a negative pressure by the main exhaust fans. Six 1,000 HP variable frequency drive exhaust fans are provided on the south side of the plenum. At the maximum expected exhaust flow of 540,000 CFM, four exhaust fans and twenty filter banks will be in operation. The fans discharge vertically to a separate concrete exhaust plenum. The filtered exhaust is routed from the exhaust plenum to a 125-foot-tall exhaust stack via a 13-foot diameter duct. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ion Exchange Processes for CO 2 Mineralization Using Industrial Waste Streams: Pilot Plant Demonstration and Life Cycle Assessment

Abstract An attractive technique for removing CO 2 from the environment is sequestration within stable carbonate solids (e. g., calcite). However, continuous addition of alkalinity is required to achieve favorable conditions for carbonate precipitation (pH>8) from aqueous streams containing dissolved CO 2 (pH<4.5) and Ca 2+ ions. In this study, a pH‐swing process using ion exchange was demonstrated to process 300 L of produced water brine per day for CO 2 mineralization. Proton titration capacities were quantified for aqueous streams in equilibrium with gas streams at various concentrations of CO 2 (pCO 2 =0.03–0.20 atm) and at various flow rates (0.5–2.0 L min −1 ). Energy intensities for the process were determined to be between 30 and 65 kWh per tonne of CO 2 sequestered depending on the composition of the brine stream. A life cycle assessment was performed to analyze the net carbon emissions of the technology which indicated a net CO 2 reduction for pCO 2 ≥0.12 atm (−0.06–−0.39 kg CO 2 e per kg precipitated CaCO 3 ) utilizing calcium‐rich brines. The results from this study indicate the ion exchange process can be used as a scalable method to provide alkalinity necessary for the capture and storage of CO 2 in Ca‐rich waste streams.

Chemistry↗

Using Radioiodine Speciation to Address Environmental Remediation and Waste Stream Sequestration Problems at the Fukushima Daiichi Nuclear Power Plant and a DOE Site

Iodine-129 ( 129 I), with a half-life of half-life of 16 million years, is commonly considered the single greatest risk driver in high-level and low-level nuclear repositories. This risk stems from several basic properties of 129 I, and under many geochemical conditions, it can move as an anion at nearly the rate of water through the subsurface environment. 129 I is also extremely radiologically toxic because over 90% of body burden accumulates in the thyroid, which weighs only about 14g in an adult. There is also a large worldwide inventory of radioiodine as a result of its high fission yield and this inventory is rapidly increasing as a result of nuclear energy production. Radioiodine is produced at a rate of 40 GBq (1 Ci) per gigawatt of electricity produced by nuclear power. To illustrate how the properties of 129 I magnify its risk, 129 I accounts for only 0.00002% of the radiation released from the Savannah River Site in Aiken, South Carolina, but contributes 13% of the population dose, a six orders of magnitude magnification of risk with respect to its radioactivity. The currently favored solid phase for LLW immobilization is cement, while HLW immobilization is the incorporation of waste into glass (vitrification). However, so far, the incorporation into cement and subsequent leaching of only iodide has been seriously investigated. The major problem with this approach is that it ignores the complex speciation of iodine, i.e., it ignores iodate and organo-iodine which have different chemistries. Most of the past research was devoted to the mechanism of iodide uptake in cement hydrate phases that is sorption and/or incorporation. Very few data exist on iodate and organo-iodine incorporation in cement, even though large quantities of liquid waste containing also radioiodine have already been solidified in cement Iodine-129 from low-level waste is commonly disposed of in cementitious materials. Grout, a dense cementitious fluid, mixed with a reducing slag, is often used to immobilize radionuclides. However, the reducing environment might not be conducive to immobilize iodine. For example, the silver based immobilization technologies (e.g., AgCl, Ag-impregnated granular activated carbon, Ag-mordenite) remove iodine from the aqueous phase by promoting the formation of Ag-iodide precipitates. The solubility of AgI is eight orders of magnitude lower than it is for AgIO 3 . Similarly, coprecipitation of iodine into calcium carbonate phases occurs only with IO 3 - and not with I - and org-I. If one would want to immobilize iodine more effectively, different engineering approaches would need to be used to promote binding of I - , IO 3 - , or organo-I. Using laboratory experiments with grout, slag, and silver-based adsorbents, and GC-MS and I K-edge XANES and EXAFS and C K-edge XANES spectroscopy for identifying iodine speciation, the major problems with these methods have been identified as focused too much on just one of the iodine species for immobilization, while others, especially organo-I, remained mobile. Finally, we established that most of the adsorbents that are used contain sufficient amounts of organic matter to create organo-I . It is anticipated that increased attention directed at understanding and quantifying the speciation of radioiodine, as opposed to simply total radioiodine, will lead to improved remediation results to be used for long-term radioiodine disposal in cementitious waste forms.

129-Iodine↗

GDSA - Modeling and Integration – ORNL: PFLOTRAN modeling

This report summarizes work done at Oak Ridge National Laboratory (ORNL) related to post-closure criticality consequence analysis of dual-purpose canister (DPC) direct disposal in unsaturated alluvium. PFLOTRAN software was used to model the behavior of a breached DPC with low water infiltration rates and unsaturated conditions in alluvial deposits such that a low-power criticality event occurs with a focus on thermal hydrological constraints on criticality timing and power output. This summary describes initial exploration of those thermal hydrological processes and of the long-term average power output from a criticality event that could be sustained without driving water out of the DPC package and thereby terminating the criticality event. The objectives are (1) to identify, for different groundwater infiltration rates, the time at which the DPC fills with water sufficiently to potentially initiate criticality; (2) to bound the power output that could be produced by a criticality event that would thermally drive water out of the package at various percolation rates; and (3) provide an estimate of how the size of a package breach affects the water infiltration and therefore the possibility timing of criticality.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermal Integration of Advanced Nuclear Reactors with a Reference Refinery, Methanol Synthesis, and a Wood Pulp Plant (Rev.1)

The present report is intended to provide process flow diagrams (PFDs) and energy and mass balance data sheets for a U.S. industrial sector subset with which nuclear heat and power could be integrated—a subset that includes the oil refining, methanol and pulp and paper industries. Coupling options for integrating nuclear energy into these industries are quantitatively outlined for reference systems, and future work will extend this analysis in greater detail. Opportunities for integrating small modular nuclear reactors (SMNRs) were investigated for each of the industrial process configurations. Aspen HYSYS and Cycle-Tempo models for a high-temperature gas-cooled reactor were developed to evaluate the proposed integration. This introductory evaluation provides a general description and assessment of the operating principles, reactor coolant core outlet temperature, and reactor size to be integrated with industry. The industrial processes of oil refining and the production of methanol, pulp and paper were simulated by using Aspen HYSYS, Aspen Plus, and the PRELIM (Petroleum Refinery Life Cycle Inventory Model) tool to develop process details. Cycle-Tempo models then extend the process modeling results to obtain net energy demands (e.g., heat, steam, and electricity) when accounting for process steam and waste heat recovery. This information is intended to foster the analysis of integrating an SMNR to decarbonize industrial facilities. The SMNR would provide reliable, competitive, and sustainable clean energy while reducing carbon emissions and other environmental impacts, such as water withdrawals, consumption, and contamination. The refining industry, exhibited in Figure ES1, is a leading consumer of fossil -fuel-based heat, power, and hydrogen in the U.S. industrial sector, generating over 164 million metric tons (MMT) of CO 2 emissions in 2023. The overall mass and energy pertaining to a generalized complex refinery in the United States is reflected in Figure ES1, along with energy metrics regarding integration with a nuclear power plant (NPP). Data sheets were developed to indicate the energy requirements for the overall refinery and each refinery process. The data sheet for the overall refinery is shown in Table ES2.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Radiolytic and Thermolytic Bubble Gas Hydrogen Composition

The original version of this report described the development of a mathematical model for the estimation of the hydrogen composition of gas bubbles trapped in radioactive waste. The model described therein used a material balance approach to accurately incorporate the rates of hydrogen generation by several physical phenomena and scale the aforementioned rates in a manner that allows calculation of the final hydrogen composition. The proposed model accounted for the following physical phenomena: H 2 generation by primary radiolysis of water and salt solutions; H 2 generation by secondary radiolysis of formate and glycolate molecules in solution; Observation of negligible H 2 generation by thermolysis of formate at temperatures below 120 °C; H 2 generation by thermolysis of glycolate in caustic solutions; O 2 consumption by radiolysis and thermolysis of organic species. Additionally, the originally-proposed model conservatively excluded the following physical phenomena that are known to contribute slightly to the hydrogen composition in trapped gas bubbles: Equilibrium concentration of water vapor in trapped gas bubbles; Generation of N 2 O during radiolysis of nitrite solutions; Incomplete consumption of O 2 by organics. In this revision, the methodology for glycolate thermolysis has been improved to agree with recent findings published by Woodham and Martino. Furthermore, considerations for the thermolysis of organics other than glycolate have been made. In the case of non-glycolate organics, no evidence of non-flammable gas formation exists. Therefore, non-glycolate thermolysis is considered additive for conservatism.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Simple but tricky: Investigations of terephthalic acid purity obtained from mixed PET waste

In this study, we report for the first time, the basic depolymerization of mixed waste-polyethylene terephthalate (PET) by hydrolysis and subsequent terephthalic acid monomer recovery at high purity using benign reaction conditions. Several conditions were tested for depolymerization such as PET chips size, concentration of aqueous sodium hydroxide (20 or 30%), organic co-solvent (ethylene glycol or ethanol), temperature at which the reaction was run and duration of the heating. More importantly, several batches of PET were utilized as starting materials including a commercial PET, chopped PET obtained from clean bottles whose caps and labels were removed and the purity of the product from each condition was evaluated via nuclear magnetic resonance (1HNMR and 13CNMR), differential scanning calorimetry (DSC) and powder Xray diffraction (XRD). Unsurprisingly, the conversion of PET is dependent on the particle size varying from 100% conversion for fine powder to 73% conversion for (300 µm, mesh 6 – 20 or mesh 14-20). Ethanol appears to be more efficient as a co-solvent than ethylene glycol, with higher PET depolymerization conversions (94% versus 75-80%), shorter reaction times (2h versus 6h) and lower temperatures (80 °C versus 110 °C). The terephthalic acid (TPA) recovered appeared to have only subtle differences among the batches, most notably a pink color when the reaction was run in ethanol/base. The DSC of the compounds produced in ethylene glycol water appear to display a melting point (280-288 °C) while the samples prepared in ethanol as well as a commercial sample did not. Overall, the purity of the various TPA batches is comparable, and similar to commercial TPA, demonstrating the utility of the method to depolymerize realistic waste streams. The method is simple, demonstrated on multigram scale (15-30g) and allows for the complete removal of waste other than PET unaffected by alkaline conditions.

Cosimbescu, Lelia↗

Multimodal imaging of oil-in-water bilgewater emulsion and biofilms

Bilgewater emulsions, consisting of oil and surfactant mixtures in water, affect many aquatic species. Thus development of methods and techniques to treat or mitigate the formation and undesired consequences of shipboard emulsions are urgently needed. This work presents new results of the evolution of the bilgewaer chemical and physical properties using in situ imaging. A Navy O/W emulsion consisting of three oils and a detergent mixture was used as the synthetic bilgewater model [1, 2]. Synthetic oil-in-water (O/W) emulsion droplets were seled in a vacuum compatible microfluidic sample holder and imaged using a suite of tools including scanning electron microscopy (SEM), time-of-flight secondary ion mass spectrometry (ToF-SIMS), confocal laser scanning microscopy, and optical microscopy, highlighting the advantage of multiscale analysis and its applications in waste reduction and treatment in the environment. The transferrable and vacuum compatible microfluidic interface, System for Analysis at the Liquid Vacuum Interface (SALVI), was used in this study. SALVI enabled surface analysis of liquids and liquid-solid interactions using ToF-SIMS and SEM [3, 4]. Its detection window is an aperture of 2 ?m in diameter open to vacuum, permitting direct detection of the liquid surface. Liquid is withheld by surface tension within the aperture. The interface is composed of a silicon nitride membrane and polydimethylsiloxane microchannel [3, 4]. A variety of samples including complex liquid mixtures, ionic liquids, single mammalian cells, live biofilms, and solid-electrolyte interface have been analyzed using in situ imaging [5, 6]. The feasibility of using SALVI for in situ SEM imaging of nanoparticles and colloids in liquid was recently demonstrated [7]. This paper shows new findings of multimodal imaging and analysis of synthesized emulsion particles in water. Figure 1 depicts a schematic of multimodal in situ imaging of bilgewater emulsion using SEM and ToF-SIMS. Furthermore, we study the interactions of microbes and bilgewater emulsion. Microbes play an important role in the ocean. We hypothesize that microbes release organics that can act as surfactants that affect bilgewater formation or weakening. We present the first systematic study of emulsions and biofilms and investigate the effects of biofilms on bilgewater emulsions. Pseudomonas was selected as a model strain. Biofilms were cultured in a microchannel to allow culture [8]. Once a thick layer of biofilms was formed, the medium solution was changed to a mixture consisting of 50 % bilgewater emulsion. Dispersed biofilms were collected at 24 hrs. and 48 hrs. after emulsions were introduced into the channel. Bilgewater emulsions, biofilms, and mixtures of bilgewater emulsions and biofilms were analyzed using multiple in situ and ex situ techniques as described earlier. Our findings indicate that biofilms change the chemical makeup of the emulsion surface compositions and emulsion droplet size distribution, confirming the hypothesis that extracellular polymeric substance (EPS) related components released from biofilms can function as surfactants and change the oil-in-water interfaces.

bilgewater, multimodal imaging, biofilms↗

Development of the Underwater Disc Saw Used to Segment the Internals of Taiwan Research Reactor - 20038

Taiwan Research Reactor will be dismantled in the period of 2022 to 2027 according to the approved dismantling plan. Based on the sampling and analyzing results, some internals of Taiwan Research Reactor must be segmented under the water because of their higher radiation, and the calandria is one of them. To dismantle this calandria, Institute of Nuclear Energy Research develops an underwater disc saw that is driven by a hydraulic pump and will be used to segment the shell of the calandria. In this article, Taiwan Research Reactor and the structure of the calandria are briefly depicted, and the segmentation processes of this calandria and the design of this disc saw are also included. Besides, the trial of cutting the shell of the simplified full size calandria mockup is briefly demonstrated in this article. Further tests will be performed in the near future to figure out which parts or functions of this disc saw need to be modified to get better cutting performance. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Energy-efficient sorption-based gas clothes dryer systems

Standard electric resistance and fuel-driven dehydration technologies exhibit a maximum coefficient of performance of well below 1 mainly due to enthalpy losses associated with the air leaving the dehydration system. To improve energy efficiency, condensing dryer systems condense the moisture captured from a product in a closed-loop air circulation cycle. Existing condensing dehydration systems including heat pump dryers, however, need to significantly cool the air to achieve dehumidification. The added cooling and subsequent heating to return the air to a desired drying temperature consume substantial energy and thus reduce drying performance. Here, an innovative sorption-based gas dehydration system is proposed to overcome barriers deteriorating energy efficiency in existing gas, electric, or heat pump dryer systems. Decoupling latent and sensible loads, the system employs a liquid-desiccant solution to directly capture air humidity, thereby allowing circulation of the air in a closed loop to achieve high drying energy efficiency. In other words, the system captures waste latent heat from the moisture produced during the dehydration process and reuses it to improve energy efficiency. This study focuses on a comprehensive quasi-steady-state thermodynamic modeling of the proposed sorption-based dehydration concept employed for a gas clothes dryer application to predict transient response and overall drying performance (i.e., time and energy metrics). The analysis indicates the proposed sorption-based gas clothes dryer system can deliver a specific moisture extraction rate of 1.71 kg of water per kWh (i.e., a combined energy factor of 3.167 kg (6.98 lbm) of dry cloth per kWh) with a drying time of 44 min. This is a 112% energy improvement compared with state-of-the-art gas clothes dryers exhibiting a combined energy factor of 1.50 kg (3.3 lbm) of dry cloth per kWh. The technology pursued here can potentially be employed as a platform for many fuel-driven equipment to take advantage of available waste thermal energy in the environment instead of simply burning a fuel.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Hydrogen Sustainable Infrastructure Guidelines (H2SIG)

Infrastructure interacts with major global challenges inclusive of climate change, resilience, equity and social justice, environmental protection and biodiversity, public health, and economic recovery. This effort directly addresses how to apply sustainability assessments to the unique aspects of hydrogen (H2) infrastructure projects using the Envision® sustainability framework developed by the Institute for Sustainable Infrastructure (ISI). Envision is a flexible system of criteria and performance objectives to aid decision makers and help project teams identify sustainable approaches during planning, design and construction of infrastructure projects that will continue throughout the project’s operations, maintenance, and end-of-life phases. The goal of this work is to support those interested in conducting sustainability assessments for hydrogen infrastructure projects. Through this work the team has developed hydrogen-specific guidelines and best practices to assist project developers, investors and regulators in straightforward application of the Envision framework to systematically enhance clarity and increase objectivity across hydrogen projects. Subject matter experts from 20 different organizations (industry, non-profits, municipalities, emissions regulators, national labs) were engaged through 7 focus groups to discuss the H2-prioritized Envision requirements and elements to be included in the guidelines. In addition to these guidelines, the team conducted case studies as a way of demonstrating and informing the guidelines and providing examples or ideas for implementing sustainability in future projects. Through this study, the authors found that hydrogen infrastructure projects can incorporate many sustainable practices including reducing GHG emissions affecting climate change, reducing air pollutant emissions affecting the health of communities, synergistically handling waste byproducts, integrating into existing infrastructure, incorporating renewable energy, and addressing equity and environmental justice. Additionally, hydrogen infrastructure projects could benefit from 2-way communication engagement and collaborative planning with stakeholders, educational awareness of hydrogen technology, tracking and reporting on water use and water quality, and including monetized environmental and social benefits in life-cycle cost estimates. This document is the final technical report for the Hydrogen Sustainability Assessment Methods for Project Development project. While the main focus of the report is to provide guidelines for applying sustainability to hydrogen infrastructure, there are sections within the appendix providing completed project tasks and methodology.

08 HYDROGEN↗

Organic Evaporation and Oxidation Testing in Support of Hanford Sample-and-Send

The Hanford site has approximately 56 million gallons of radioactive mixed waste stored in 177 underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the tank waste. The baseline method for immobilization of Low Activity Waste (LAW) through the WTP is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. An alternative cementitious waste form is being investigated for that future immobilization method to supplement vitrification. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste. This work evaluates potential avenues to eliminate that impediment to permit possible use of a cementitious waste form and work towards a decision whether additional LDR organic pretreatment would be required. Savannah River National Laboratory (SRNL) performed testing using simulants to examine evaporation as a method to remove some prevalent organics from LAW. Spiking the caustic LAW simulant with selected regulated organic chemicals found one that clearly decomposes because of caustic instability. Oxidation testing of other organic chemicals found some LDR organics degrade as desired and others are stable in the presence of peroxide and permanganate. In addition to studies with simulants, a literature review was performed to evaluate radiological stability of LDR organics. Descriptions of the experimental details, equipment, and results are included in this report. Evaporation testing consisted of preparing the LAW simulant, spiking that simulant with organic chemicals, and evaporating the mixture via differential distillation. The apparatus was a laboratory-scale vacuum evaporator operated at 60 ±5 torr absolute (vacuum evaporation) and also at atmospheric pressure. The LAW simulant represented the liquid expected to be retrieved from the Hanford tank farms at approximately 4.0 M [Na + ] total sodium ion concentration. The concentration of the organic chemicals added was significantly higher than typically found in the tank waste samples since the higher levels were necessary to assist in analytical measurement and tracking of the spiked species. Organic chemicals were chosen for the work with a consideration of how their volatility compares with that of methanol. This was done by comparing the ratio of the pure water Henry’s law coefficient (K h ) of methanol to that of the compound in question (hereafter termed the K h ratio), where ratios above unity indicated less volatility than methanol. Methanol was chosen because it is a common regulated chemical with relatively low volatility but which has been removed by evaporation in previous laboratory work. While organic separation results depend on evaporator design, laboratory experiments verified that organic partitioning to the overhead condensate stream by evaporation is a practical process. The work reported here found difficulties in quantitative analysis of the organic chemicals in aqueous samples. Most of the time there was insufficient analysis to close a mass balance for evaporator runs, but qualitative evidence of carryover was obtained. The methods were also able to show whether organic chemicals were susceptible or resistant to solution oxidation in permanganate or hydrogen peroxide tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Comparing Critical Mass of Homogeneous and Heterogeneous Systems

The purpose of this project is to recreate a critical mass study comparing homogeneous and heterogeneous systems using a conservative modeling approach to expand upon historical experimental data. This project will help Nuclear Criticality Safety (NCS) engineers determine if modeling a heterogeneous system comprised of uranium and water as homogeneously mixed at a comparable density is a conservative method.

01 COAL, LIGNITE, AND PEAT↗

ALARA Review for Venting of Flanged Tritium Waste Containers (FTWCs) at TA-54

This project will vent headspace hydrogen and oxygen from specialized high-pressure storage vessels called flanged tritium waste containers (FTWCs). There are four of these containers located in Los Alamos National Laboratory’s (LANL’s) Technical Area 54 (TA-54), Building 1028. This building is in the southwest corner of LANL’s Material Disposal Area G. The vented headspace gas is expected to contain tritium in the form of water vapor, elemental hydrogen or a combination of both. The venting operation is expected to take place in 2025. There will be a series of operational readiness reviews prior to venting activities commencing. The FTWCs at TA-54 contain tritium-contaminated metal parts and molecular sieve media, which is a pebble-like material used to absorb water vapor from the air. This molecular sieve media inside the FTWCs is contained in metal canisters, along with some loose media material in bags. Over time, tritiated water vapor that had been adsorbed onto the media can become liberated into the FTWC headspace gas. Radiolysis can cause separation of the water vapor into its hydrogen and oxygen components, resulting in the potentially hazardous gas mixture within the FTWC. LANL has determined that continued tritium storage in these containers can pose an unsafe condition due to possible hydrogen and oxygen gas buildup within the FTWCs with a potential for explosion if sparks are generated within the FTWCs. To mitigate this hazard, the FTWCs will be stabilized by venting them in-place to remove hazardous gases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Structures and Free Energies of Cerium Ions in Acidic Electrolytes

The Ce 3+ /Ce 4+ redox potential changes with the electrolyte, which could be due to unequal anion complexation free energies between Ce 3+ and Ce 4+ or a change in the solvent electrostatic screening. Ce complexation with anions and solvent screening also affect the solubility of Ce and charge transfer kinetics for electrochemical reactions involving waste remediation and energy storage. Here, we report the structures and free energies of cerium complexes n seven acidic electrolytes based on Extended X-ray Absorption Fine Structure, LTV vis, and Density Functional Theory calculations. Ce 3+ coordinates with nine water molecules as [Ce(H 2 O) 9 ] 3+ in all studied electrolytes. However, Ce 4+ complexes with anions in all electrolytes except HClO 4 . Thus, our results suggest that Ce 4+ anion complexation leads to the large shifts in standard redox potential. Long range screening effects are smaller than the anion complexation energies but could be responsible for changes in the Ce solubility with acid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Brief Review of Technologies for Separating Tritium from the Aqueous Effluent of Reprocessing Plants

The scope of this letter report encompasses a review of technologies applicable to separating tritiated water from light and heavy water with a focus on wastewater arising from the reprocessing of UNF. Reports considering flowsheet options for tritium management are also reviewed. The main objective of this letter report is to support consideration of programmatic opportunities for the Materials Recovery and Waste Form Development (MRWFD) Campaign within the Department of Energy’s Office of Nuclear Energy.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗