Robust Imidazopyridinium Covalent Organic Framework as Efficient Iodine Capturing Materials in Gaseous and Aqueous Environment.

The development of a high-performing adsorbent that can capture both iodine vapor from volatile nuclear waste and traces of iodine species from water is an important challenge, especially in industrially relevant process conditions. This study introduces novel imidazopyridinium-based covalent organic frameworks (COFs) through post-modification of a picolinaldehyde-based imine COF. These COFs demonstrate excellent iodine adsorption capacity, adsorption kinetics, and a high stability/recyclability in both vapor and water phases. Notably, one imidazopyridinium COF exhibits gaseous iodine uptake of 21 wt.% under dynamic adsorption conditions at 150 °C and a relative humidity of 50%, surpassing the performance of the currently used silver-based zeolite adsorbents (Ag@MOR (17wt.%)). Additionally, the same imidazopyridinium COFs can efficiently remove iodine species at a low concentration from aqueous solution. Seawater containing triiodide ions treated under dynamic flow-through conditions resulted in decreased concentrations down to the ppb level. The adsorption mechanisms for iodine and polyiodide species are elucidated for the imine COF and imidazopyridinium COFs; involving halogen bonding, hydrogen bonding, and charge-transfer complexes.

Research progress on microbial adsorption of radioactive nuclides in deep geological environments.

Due to the development and utilization of nuclear energy, the safe disposal of nuclear waste needs to be urgently addressed. In recent years, the utilization of microorganisms' adsorption capacity to dispose of radioactive waste has received increasing attention. When compared with conventional disposal methods, microbial adsorption exhibits the characteristics of high efficiency, low cost, and no secondary pollution. In the long term, microbial biomass shows significant promise as specific chemical-binding agents. Optimization of biosorption conditions, identification of rare earth element binding sites, and studies on the sorption capacities of immobilized cells provide compelling reasons to consider biosorption for industrial applications in heavy metal removal from solutions. However, the interaction mechanism between microorganisms and radioactive nuclides is very complex. This mini-review briefly provides an overview of the preparation methods, factors affecting the adsorption capacity, and the mechanisms of microbial adsorbents.

High-pressure high-temperature synthesis of NdRe2.

In this study, we report the synthesis of a new cubic neodymium-rhenium metallic alloy NdRe2 through the utilization of high pressure and laser heating in a diamond anvil cell. NdRe2 crystallizes in the Fd3¯m space group with a lattice parameter equal to 7.486 (2) Å and Z = 8 at 24 (1) GPa and 2,200 (100) K. It was studied using high-pressure single-crystal X-ray diffraction. The compound crystallizes in the cubic MgCu2 structure type. Its successful synthesis further proves that high-pressure high-temperature conditions can be used to obtain alloys holding a Laves phase structure. Ab initio calculations were done to predict the mechanical properties of the material. We also discuss the usage of extreme conditions to synthesize and study materials present in the nuclear waste.

Insights into the Impact of Physicochemical and Microbiological Parameters on the Safety Performance of Deep Geological Repositories.

Currently, the production of radioactive waste from nuclear industries is increasing, leading to the development of reliable containment strategies. The deep geological repository (DGR) concept has emerged as a suitable storage solution, involving the underground emplacement of nuclear waste within stable geological formations. Bentonite clay, known for its exceptional properties, serves as a critical artificial barrier in the DGR system. Recent studies have suggested the stability of bentonite within DGR relevant conditions, indicating its potential to enhance the long-term safety performance of the repository. On the other hand, due to its high resistance to corrosion, copper is one of the most studied reference materials for canisters. This review provides a comprehensive perspective on the influence of nuclear waste conditions on the characteristics and properties of DGR engineered barriers. This paper outlines how evolving physico-chemical parameters (e.g., temperature, radiation) in a nuclear repository may impact these barriers over the lifespan of a repository and emphasizes the significance of understanding the impact of microbial processes, especially in the event of radionuclide leakage (e.g., U, Se) or canister corrosion. Therefore, this review aims to address the long-term safety of future DGRs, which is critical given the complexity of such future systems.

Energetics of water expulsion from intervening space between two particles during aggregation.

Solvent expulsion away from an intervening region between two approaching particles plays important roles in particle aggregation yet remains poorly understood. In this work, we use metadynamics molecular simulations to study the free energy landscape of removing water molecules from gibbsite and pyrophyllite slit pores representing the confined spaces between two approaching particles. For gibbsite, removing water from the intervening region is both entropically and enthalpically unfavorable. The closer the particles approach each other, the harder it is to expel water molecules. For pyrophyllite, water expulsion is spontaneous, which is different from the gibbsite system. A smaller pore makes the water removal more favorable. When water is being drained from the intervening region, single chains of water molecules are observed in gibbsite pore, while in pyrophyllite pore water cluster is usually observed. Water-gibbsite hydrogen bonds help stabilize water chains, while water forms clusters in pyrophyllite pore to maximize the number of hydrogen bonds among themselves. This work provides the first assessment into the energetics and structure of water being drained from the intervening region between two approaching particles during oriented attachment and aggregation.

Ultrafast Removal of Thorium and Uranium from Radioactive Waste and Groundwater Using Highly Efficient and Radiation-Resistant Functionalized Triptycene-Based Porous Organic Polymers.

Thorium (Th) and uranium (U) are important strategic resources in nuclear energy-based heavy industries such as energy and defense sectors that also generate significant radioactive waste in the process. The management of nuclear waste is therefore of paramount importance. Contamination of groundwater/surface water by Th/U is increasing at an alarming rate in certain geographical locations. This necessitates the development of strategic adsorbent materials with improved performance for capturing Th/U species from radioactive waste and groundwater. This report describes the design of a unique, robust, and radiation-resistant porous organic polymer (POP: TP-POP-SO3NH4), which demonstrates ultrafast removal of Th(IV) (<30 s)/U(VI) (<60 s) species present in simulated radioactive wastewater/groundwater samples. Thermal, chemical, and radiation stabilities of these POPs were studied in detail. The synthesized ammoniated POP revealed exceptional capture efficiency for trace-level Th (<4 ppb) and U (<3 ppb) metal ions through the cation-exchange mechanism. TP-POP-SO3NH4 shows a significant sorption capacity [Th (787 mg/g) and U (854 mg/g)] with an exceptionally high distribution coefficient (Kd) of 107 mL/g for Th. This work also demonstrates a facile protocol to convert a nonperforming POP, by simple chemical modifications, into a superfast adsorbent for efficient uptake/removal of U/Th.

Investigation of the leaching behavior of Na and Si in simulated HLW borosilicate glass obtained from the waste of a 1000 MWe class PWR reactor: using the response surface method.

The immobilization of high-level nuclear waste (HLW) in glass waste matrices provides the key safety function of slowing down radionuclide emissions from an underground disposal site. This study examines the leaching behavior of two major elements, Na and Si, in HLW borosilicate glass simulated from waste of a 1000 MWe class pressurized water reactor (PWR) using response surface methodology and Box-Behnken Design. The design of the experiment was carried out considering three independent variables: the pH of the solution, the contact time, and the leaching temperature, leading to 17 leaching runs performed using the static product consistency test (PCT). The results of statistical analysis (ANOVA: analysis of variance) indicated that the effects of the individual variables and the interactions between them were statistically significant, and the relative consistency of the data further confirmed the model's applicability. Data obtained from the PCT experiments revealed that the leaching behavior of Na and Si in the evaluated waste glass exhibited similar behavior to previously researched glasses for each condition tested.

Cement-based solidification of nuclear waste: Mechanisms, formulations and regulatory considerations.

This review paper provides a comprehensive analysis of cement-based solidification and immobilisation of nuclear waste. It covers various aspects including mechanisms, formulations, testing and regulatory considerations. The paper begins by emphasizing the importance of nuclear waste management and the associated challenges. It explores the mechanisms and principles in cement-based solidification, with a particular focus on the interaction between cement and nuclear waste components. Different formulation considerations are discussed, encompassing factors such as cement types, the role of additives and modifiers. The review paper also examines testing and characterisation methods used to assess the physical, chemical and mechanical properties of solidified waste forms. Then the paper addresses the regulatory considerations and compliance requirements for cement-based solidification. The paper concludes by critically elaborating on the current challenges, emerging trends and future research needs in the field. Overall, this review paper offers a comprehensive overview of cement-based solidification, providing valuable insights for researchers, practitioners and regulatory bodies involved in nuclear waste management.

Assessing Sensor Integrity for Nuclear Waste Monitoring Using Graph Neural Networks.

A deep geological repository for radioactive waste, such as Andra's Cigéo project, requires long-term (persistent) monitoring. To achieve this goal, data from a network of sensors are acquired. This network is subject to deterioration over time due to environmental effects (radioactivity, mechanical deterioration of the cell, etc.), and it is paramount to assess each sensor's integrity and ensure data consistency to enable the precise monitoring of the facilities. Graph neural networks (GNNs) are suitable for detecting faulty sensors in complex networks because they accurately depict physical phenomena that occur in a system and take the sensor network's local structure into consideration in the predictions. In this work, we leveraged the availability of the experimental data acquired in Andra's Underground Research Laboratory (URL) to train a graph neural network for the assessment of data integrity. The experiment considered in this work emulated the thermal loading of a high-level waste (HLW) demonstrator cell (i.e., the heating of the containment cell by nuclear waste). Using real experiment data acquired in Andra's URL in a deep geological layer was one of the novelties of this work. The used model was a GNN that inputted the temperature field from the sensors (at the current and past steps) and returned the state of each individual sensor, i.e., faulty or not. The other novelty of this work lay in the application of the GraphSAGE model which was modified with elements of the Graph Net framework to detect faulty sensors, with up to half of the sensors in the network being faulty at once. This proportion of faulty sensors was explained by the use of distributed sensors (optic fiber) and the environmental effects on the cell. The GNNs trained on the experimental data were ultimately compared against other standard classification methods (thresholding, artificial neural networks, etc.), which demonstrated their effectiveness in the assessment of data integrity.

Putting radioactive materials on the sustainability agenda: a report from a workshop on the sustainability of human-made radioactive materials held at the safeND Research Symposium 2023.

This report summarizes the findings of a workshop held at the safeND Research Symposium and hosted by the German Federal Office for the Safety of Radioactive Waste Management (BASE) in Berlin in September 2023. The workshop aimed to channel perspectives from various fields of expertise to discuss key sustainability concepts in terms of radioactive waste management. Therefore, the report highlights that current sustainability concepts, such as the United Nations' Sustainable Development Goals (SDG) as well as the concept of Planetary Boundaries, neglect challenges arising from the production and storage of human-made radioactive materials. The workshop consisted of three group tasks. The first attempted at identifying the interrelations between "sustainability" and radioactive waste management. The second was to map the global nature of the challenges. The third took first steps to determine a human-made radioactive material as a potential planetary sub-boundary for "novel entities". All three groups identified valuable knowledge gaps that should be addressed by future research and concluded that radioactive waste management is underrepresented in these sustainability concepts.

Saline groundwaters counteract up-flow of contaminants- implications for radionuclide repositories?

The high-level nuclear waste, HLW, from Swedish and Finnish reactors will be deposited in crystalline rock at depths around 500 m. The waste is enclosed in steel canisters protected against corrosion by a 5 cm thick copper shell, which ensures a lifetime far longer than 100 000 years. Should some canister be breached any leaking nuclides will have decayed to so low activity that even if they reached the biosphere, they would cause minimal risk to humans. The cost of the copper is significant. The dismantling of the nuclear reactors, with induced activity must also be disposed of and this waste volume is much larger than that of the HLW, which makes it impossible to protect it in the same way. This paper explores if by locating the waste at larger depth where the ground water is more saline, and where the hydraulic conductivity of the rock is lower up-flow of contaminated water can be ensured to be negligible because the denser water at larger depth counteracts up-flow due to negative buoyancy. Several processes that could cause local up-flow are addressed, such as infiltration of meteoric water, impact of surface topology, heat production of the waste, geothermal gradient, salinity gradient, hydraulic conductivity heterogeneities and salt migration between seeping water and salt in matrix pore water. Flow and transport simulations using data from extensive field investigations over more than ten years with scores of km deep boreholes suggest that a HLW repository at around one km depth may be sufficient to hinder up-flow to the biosphere.

Effect of Adsorbed Carboxylates on the Dissolution of Boehmite Nanoplates in Highly Alkaline Solutions.

Understanding the dissolution of boehmite in highly alkaline solutions is important to processing complex nuclear waste stored at the Hanford (WA) and Savannah River (SC) sites in the United States. Here, we report the adsorption of model carboxylates on boehmite nanoplates in alkaline solutions and their effects on boehmite dissolution in 3 M NaOH at 80 °C. Although expectedly lower than at circumneutral pH, adsorption of oxalate occurred at pH 13, with adsorption decreasing linearly to 3 M NaOH. Classical molecular dynamics simulations suggest that the adsorption of oxalate dianions onto the boehmite surface under high pH can occur through either inner- or outer-sphere complexation mechanisms depending on adsorption sites. However, both adsorption models indicate relatively weak binding, with an energy preference of 1.26 to 2.10 kcal/mol. By preloading boehmite nanoplates with oxalate or acetate, we observed suppression of dissolution rates by 23 or 10%, respectively, compared to pure solids. Scanning electron microscopy and transmission electron microscopy characterizations revealed no detectable difference in the morphologic evolution of the dissolving boehmite materials. We conclude that preadsorbed carboxylates can persist on boehmite surfaces, decreasing the density of dissolution-active sites and thereby adding extrinsic controls on dissolution rates.

Development of local-power-free, remote α-particle detection using optical fibers.

We demonstrate the application of fluorescence optical fiber coupled to a telecom grade fiber as a sensor for alpha particles using alpha-specific ZnS(Ag) scintillation materials whose wavelength is down-shifted into a low-loss region of the telecom grade fiber transmission band. Telecom-grade fiber optics offer a solution for sensing alpha radiation in deep repositories and cask storage for radioactive materials due to the stability of SiO2 under normal environmental conditions and its relative radiation hardness at low radiation doses. Long-term nuclear waste storage facilities require sensors for the detection of leakage of radioactive materials that are maintenance-free, do not require power and can survive with no 'wear out' mechanisms for decades. By accomplishing the wavelength transformation, we maximize efficiencies in the detection of α-particles and signal transport and can detect alpha scintillation at distances on the order of >1 km with a sensor that is ~3% efficient and can be easily scaled as a sensor array. This paper describes the construction and testing of the sensor including manufacture of the controlled thickness films, verification of the wavelength shift from 450 to 620 nm and optimization of the sensitivity as a function of thickness. We also model the relative sensitivity of the film as a function of film thickness, and we demonstrate a signal-to-noise ratio of 10 at a range of greater than 1 km.

A new research proposal to prevent hydrogen embrittlement for nuclear waste container by bacteria-a mini review.

A large amount of nuclear waste produced in the process of nuclear energy utilization has always been a key problem to be solved urgently for nuclear safety. At present, "deep geological disposal" is a feasible method and generally accepted by many countries. The oxygen content in the near field environment of the waste container will decrease to anaerobic conditions, and hydrogen will permeation into the internal materials of container for a long time. Hydrogen evolution corrosion may cause a risk of hydrogen embrittlement. The harm of hydrogen embrittlement in metal container is far more severe than predictable uniform corrosion. It is a research hotspot that the microorganisms impact on the corrosion behavior of container materials in the deep geological environment. Microbial corrosion in deep geological environments can be divided into two types: aerobic microbial corrosion and anaerobic microbial corrosion. There is a type of hydrogen consuming microorganism in the natural environment that uses the oxidation of hydrogen as the energy for its life activities. This provides a new approach for us to study reducing the hydrogen embrittlement sensitivity of nuclear waste container materials.

Enhanced Iodine Capture Using a Postsynthetically Modified Thione-Silver Zeolitic Imidazole Framework.

Efficient management of radionuclides that are released from various processes in the nuclear fuel cycle is of significant importance. Among these nuclides, radioactive iodine (mainly 129I and 131I) is a major concern due to the risk it poses to the environment and to human health; thus, the development of materials that can capture and safely store radioactive iodine is crucial. Herein, a novel silver-thione-functionalized zeolitic imidazole framework (ZIF) was synthesized via postsynthetic modification and assessed for its iodine uptake capabilities alongside the parent ZIF-8 and intermediate materials. A solvent-assisted ligand exchange procedure was used to replace the 2-methylimidazole linkers in ZIF-8 with 2-mercaptoimidazole, forming intermediate compound ZIF-8 = S, which was reacted with AgNO3 to yield the ZIF-8 = S-Ag+ composite for iodine uptake. Despite possessing the lowest BET surface area of the derivatives, the Ag-functionalized material demonstrated superior I2 adsorption in terms of both maximum capacity (550 g I2/mol) and rapid kinetics (50% loading achieved in 5 h, saturation in 50 h) compared to that of our pristine ZIF-8, which reached 450 g I2/mol after 150 h and 50% loading in 25 h. This improvement is attributed to the presence of the Ag+ ions, which provide a strong chemical driving force to form a stable Ag-I species. The results of this study contribute to a broader understanding of the strategies that can be employed to engineer adsorbents with robust iodine uptake behavior.

Decorating Channel Walls in Metal-Organic Frameworks with Crown Ethers for Efficient and Selective Separation of Radioactive Strontium(II).

Nuclear accidents and the improper disposal of nuclear wastes have led to serious environmental radioactive pollutions. The rational design of adsorbents for the highly efficient separation of strontium(II) is essential in treating nuclear waste and recovering radioactive strontium resources. Metal-organic frameworks (MOFs) are potential materials for the separation of aqueous metal ions owing to their designable structure and tunable functionality. Herein, a novel 3D MOF material MOF-18Cr6, in which 1D channels are formed using 18-crown-6-ether-containing ligands as channel walls, is fabricated for strontium(II) separation. In contrast to traditional MOFs designed by grafting functional groups in the framework pores, MOF-18Cr6 possesses regular 18-crown-6-ether cavities on the channel walls, which not only can transport and intake strontium(II) via the channels, but also prevent blockage of the channels after the binding of strontium(II). Consequently, the functional sites are fully utilized to achieve a high strontium(II) removal rate of 99.73 % in simulated nuclear wastewater. This study fabricates a highly promising adsorbent for the separation of aqueous radioactive strontium(II), and more importantly, can provide a new strategy for the rational design of high-performance MOF adsorbents for separating target substances from complex aqueous environments.

Stable microbial community in compacted bentonite after 5 years of exposure to natural granitic groundwater.

The Materials Corrosion Test (MaCoTe) at the Underground Research Laboratory in Grimsel, Switzerland, assesses the microbiology and corrosion behavior of engineered barrier components of a deep geological repository (DGR) for long-term disposal of high-level nuclear waste. Diversity and temporal changes of bentonite-associated microbial community profiles were assessed under DGR-like conditions for compacted Wyoming MX-80 bentonite (1.25 g/cm3 and 1.50 g/cm3 targeted dry densities) exposed to natural groundwater. Using culture-dependent and molecular techniques, samples taken from the outside layer of 5-year borehole modules revealed up to 66% and 23% of 16S rRNA gene sequences affiliated with Desulfosporosinus and Desulfovibrio, respectively. Putatively involved in sulfate reduction, these taxa were almost undetectable within the bentonite core. Instead, microbial profiles of the inner bentonite core were similar to uncompacted bentonite used to pack modules years earlier, and were consistent with a previously published 1-year time point, revealing no detectable microbial growth. Abundances of culturable aerobic and anaerobic heterotrophic bacteria in the uncompacted bentonite were relatively low, with less than 1,000 and 100 colony-forming units (CFUs) per gram dry weight, respectively. Nearly 5 years after emplacement, culturable heterotrophic bacterial CFUs and sulfate-reducing bacteria did not change significantly inside the bentonite core. Phospholipid fatty acid data indicated similar lipid abundance, and corresponding cell abundance estimates, for inner 5-year MaCoTe bentonite samples compared to those previously obtained for 1-year incubations. Collectively, our results provide complementary evidence for microbial stability inside highly compacted bentonite exposed to conditions that mimic engineered barrier components of a deep geological repository. IMPORTANCE The long-term safety of a deep geological repository for used nuclear fuel is dependent on the performance of the engineered and natural barriers. Microbial activity can produce chemical species that can influence the corrosion of the disposal containers for used nuclear fuel. Although previous studies have evaluated the microbiology of compacted bentonite clay within subsurface environments, these have been limited to relatively short incubations (i.e., 1 year). The current study provides a unique 5-year perspective that reinforces previous findings of growth inhibition for bentonite clay exposed to in situ subsurface conditions.

Nuclear waste Educator's workshop: What and how do we teach about nuclear waste?

A workshop was held at the Massachusetts Institute of Technology (MIT) on July 25th and 26th, 2022. The objective was to develop a blueprint for educating next-generation engineers and scientists about nuclear waste management and disposal, which requires knowledge from diverse disciplines, including nuclear, chemical, civil, environmental, and geological science and engineering. The 49 participants included university professors, researchers, industry experts, and government officials from different areas. First, we have developed a list of key fundamental knowledge on waste management and disposal across the nuclear fuel cycle. In addition, we discussed strategies on how to teach students with diverse backgrounds through innovative teaching strategies as well as how to attract students into this area. Through the workshop, we identified the critical needs to (1) develop community resources for nuclear waste education; (2) synthesize historical perspectives, including past contamination and the management of general hazardous waste; (3) emphasize a complete life-cycle perspective, including proper waste management as the key component for energy sustainability; (4) teach students how to communicate about the key facts and risks to technical and non-technical audiences; and (5) accelerate the use of the state-of-art-technologies to attract and retain a young workforce. Furthermore, we aim to build a diverse, inclusive community that supports students in developing their own narratives about nuclear waste, particularly in recognizing that antagonistic views have been important to improving safety and protecting public health and the environment.

Factors influencing acceptability of final disposal of incinerated ash and decontaminated soil from TEPCO's Fukushima Daiichi nuclear power plant accident.

TEPCO's Fukushima Daiichi nuclear power plant accident prompted extensive decontamination work. The decontaminated soil and incinerated ash generated by the process are scheduled for final disposal by March 2045 outside Fukushima Prefecture. The final disposal is unprecedented worldwide. Clarifying their acceptability will contribute to the final disposal of decontaminated soil and incinerated ash, as well as add knowledge about the perceived risk of low-concentration radioactive waste. A questionnaire survey was conducted to assess the psychological factors influencing final disposal acceptability. The results of the structural equation modeling demonstrated stable results, with risk perception decreasing acceptability, social benefits increasing acceptability, and personal benefits having limited impact. The initiative for the final disposal of decontaminated soil and incinerated ash can facilitate the reconstruction of Fukushima Prefecture after the disaster. Trust and intergenerational expectations are critical factors influencing the acceptability of this disposal. The responses were classified based on the relevance of moral norms using cluster analysis and moral foundations. The influence of each element on acceptability varied depending on the cluster. Trust was identified as the most influential factor in acceptability, regardless of the level of importance placed on moral norms.

Clay-associated microbial communities and their relevance for a nuclear waste repository in the Opalinus Clay rock formation.

Microorganisms are known to be natural agents of biocorrosion and mineral transformation, thereby potentially affecting the safety of deep geological repositories used for high-level nuclear waste storage. To better understand how resident microbial communities of the deep terrestrial biosphere may act on mineralogical and geochemical characteristics of insulating clays, we analyzed their structure and potential metabolic functions, as well as site-specific mineralogy and element composition from the dedicated Mont Terri underground research laboratory, Switzerland. We found that the Opalinus Clay formation is mainly colonized by Alphaproteobacteria, Firmicutes, and Bacteroidota, which are known for corrosive biofilm formation. Potential iron-reducing bacteria were predominant in comparison to methanogenic archaea and sulfate-reducing bacteria. Despite microbial communities in Opalinus Clay being in majority homogenous, site-specific mineralogy and geochemistry conditions have selected for subcommunities that display metabolic potential for mineral dissolution and transformation. Our findings indicate that the presence of a potentially low-active mineral-associated microbial community must be further studied to prevent effects on the repository's integrity over the long term.