3D Covalent Organic Framework with "the" Topology.

Discovery of new topology covalent organic frameworks (COFs) is a mainstay in reticular chemistry and materials research because it not only serves as a stepwise guide to the designed construction of covalent-organic architectures but also helps to comprehend function from structural design point-of-view. Proceeding on this track, the first 3D COF, TUS-38, with the topology is constructed by reticulating a planar triangular 3-c node of D3h symmetry with a tetragonal prism 8-c node of D2h symmetry via [3 + 8] reversible imine condensation reaction. TUS-38 represents a twofold interpenetrated multidirectional pore network with a high degree of crystallinity and structural integrity. Interestingly, stemming from the nitrogen-rich s-triazine rings with electron-deficient character and ─C â• N─ linkages composing the TUS-38 framework that benefit to the charge-transfer and hence dipole-dipole electrostatic interactions between the framework and iodine in addition to exclusive topological characteristics of the exotic the net, TUS-38 achieves an exemplary capacity for iodine vapor uptake reaching 6.3 g g-1. Recyclability studies evidence that TUS-38 can be reused at least five times retaining 95% of its initial adsorption capacity; while density functional theory (DFT) calculations have heightened the understanding of the interactions between iodine molecules and the framework.

Disentangling the History of Deep Ocean Disposal for DDT and Other Industrial Waste Off Southern California.

Ocean disposal of industrial waste from technical DDT [mainly 1,1'-(2,2,2-trichloroethane-1,1-diyl)bis(4-chlorobenzene), or 4,4'-DDT] manufacture occurred historically in the Southern California Bight. However, the paucity of historical records highlights uncertainties as to the mode, location, and timing of disposal or ongoing ecological effects of these wastes. This study combines sampling, chemical analysis, and numerical modeling of deep San Pedro Basin sediments revealing substantial DDT contamination that extends at least 25 km from the mainland. These findings narrate bulk DDT waste disposal to the offshore that peaked in the 1950s, prior to the onset of formal regulations; was agnostic to later-designated disposal sites; and has experienced sluggish transformation. Our findings further indicate an attenuating secondary source for the DDT daughter product, 1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene (4,4'-DDE), which still deposits into deep San Pedro Basin sediments. While demonstrating the severity of DDT contamination to the region, these findings further define the burial potential of DDT wastes and inform the past, present, and future contamination potential that is needed to understand and predict ecological consequences. This work also points firmly to bulk, not containerized, disposal of DDT waste and to potential alternative contents of collocated waste.

(Re)integrating radioactive materials and waste into a global sustainable development context.

The 17 Sustainable Development Goals (SDGs) of the United Nations, established in 2015, aim to achieve global sustainability by 2030 through the improvement of environmental, social, and economic parameters. However, unlike earlier concepts such as the Agenda 21 of 1992, the SDGs overlook radioactive waste management and related challenges of radiation itself. First, we investigate the historic consideration and unexplained disappearance of radioactive waste in earlier sustainability concepts. Then, we propose amending seven SDGs to address this gap. For SDGs 6 (Clean Water and Sanitation), 14 (Life Below Water), and 15 (Life on Land), new or revised indicators should monitor the release of hazardous materials. SDGs 9 (Industry, Innovation and Infrastructure), 16 (Peace, Justice and Strong Institutions), and 17 (Partnerships for the Goals) require additional targets and indicators to integrate international cooperation and social implications of nuclear facilities' operation. Redefining "hazardous waste" in SDG 12 (Responsible Consumption and Production) and "environmentally sound technologies" in SDG 17 is necessary to encompass radioactive waste. Implementing these changes demands statistical efforts, but the existing monitoring infrastructure, particularly in Europe and North America, can facilitate this. As 2030 approaches, it is crucial to reintroduce radioactive waste management into sustainability agendas, whether within the SDGs themselves or in a subsequent framework.

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.

Scenario development for safety assessment in deep geologic disposal of high-level radioactive waste and spent nuclear fuel: A review.

Radiation and radioactive substances result in the production of radioactive wastes which require safe management and disposal to avoid risks to human health and the environment. To ensure permanent safe disposal, the performance of a deep geological repository for radioactive waste is assessed against internationally agreed risk-based standards. Assessing postclosure safety of the future system's evolution includes screening of features, events, and processes (FEPs) relevant to the situation, their subsequent development into scenarios, and finally the development and execution of safety assessment (SA) models. Global FEP catalogs describe important natural and man-made repository system features and identify events and processes that may affect these features into the future. By combining FEPs, many of which are uncertain, different possible future system evolution scenarios are derived. Repository licensing should consider both the reference or "base" evolution as well as alternative futures that may lead to radiation release, pollution, or exposures. Scenarios are used to derive and consider both base and alternative evolutions, often through production of scenario-specific SA models and the recombination of their results into an assessment of the risk of harm. While the FEP-based scenario development process outlined here has evolved somewhat since its development in the 1980s, the fundamental ideas remain unchanged. A spectrum of common approaches is given here (e.g., bottom-up vs. top-down scenario development, probabilistic vs. bounding handling of uncertainty), related to how individual numerical models for possible futures are converted into a determination as to whether the system is safe (i.e., how aleatoric uncertainty and scenarios are integrated through bounding or Monte Carlo approaches).

Hybrid Twins Modeling of a High-Level Radioactive Waste Cell Demonstrator for Long-Term Temperature Monitoring and Forecasting.

Monitoring a deep geological repository for radioactive waste during the operational phases relies on a combination of fit-for-purpose numerical simulations and online sensor measurements, both producing complementary massive data, which can then be compared to predict reliable and integrated information (e.g., in a digital twin) reflecting the actual physical evolution of the installation over the long term (i.e., a century), the ultimate objective being to assess that the repository components/processes are effectively following the expected trajectory towards the closure phase. Data prediction involves using historical data and statistical methods to forecast future outcomes, but it faces challenges such as data quality issues, the complexity of real-world data, and the difficulty in balancing model complexity. Feature selection, overfitting, and the interpretability of complex models further contribute to the complexity. Data reconciliation involves aligning model with in situ data, but a major challenge is to create models capturing all the complexity of the real world, encompassing dynamic variables, as well as the residual and complex near-field effects on measurements (e.g., sensors coupling). This difficulty can result in residual discrepancies between simulated and real data, highlighting the challenge of accurately estimating real-world intricacies within predictive models during the reconciliation process. The paper delves into these challenges for complex and instrumented systems (multi-scale, multi-physics, and multi-media), discussing practical applications of machine and deep learning methods in the case study of thermal loading monitoring of a high-level waste (HLW) cell demonstrator (called ALC1605) implemented at Andra's underground research laboratory.

Radiological safety assessment for transportation of reactor pressure vessel during decommissioning of a nuclear power plant in Korea.

In Korea, decommissioning of nuclear power plants and transportation of the decommissioning waste are expected to expand in the near future. It is necessary to confirm that radiological risks to the public and workers are not significant through radiological safety assessment. The objective of this study is to assess the radiological safety for transportation of RPV waste, which is a major decommissioning waste with relatively high level of radioactivity. It was assumed that the waste would be transported to the Gyeongju disposal facility by land transportation. First, the source term and transportation method of the RPV waste were determined, and the external dose rates from the waste were calculated using MCNP. Then, transportation scenarios were assumed under both normal and accident conditions. Under the scenarios, radiation doses were calculated using the RADTRAN. Under normal operation scenarios without a transportation accident, assuming 40 shipments per year, the average individual doses for the public ranged from 6.56×10-6to 2.18×10-2mSv yr-1. The maximum individual doses for only a single shipment ranged from 2.43×10-6to 3.14×10-1mSv. For cargo handlers and vehicle crew members, the average doses were 2.26×101mSv yr-1and 2.95 mSv yr-1, respectively. Under transportation accident scenarios, average individual radiological risks which are product of the radiation doses and the annual accident rates ranged from 1.14×10-11to 1.61×10-10mSv yr-1by transportation route segment when considering the transportation accident rate. Average individual doses assuming transportation accident occurrence ranged from 2.62×10-4to 1.42×10-3mSv. The maximum individual dose under accident conditions was 7.99×10-2mSv. The calculated doses were below the regulatory limits in Korea. However, relatively high doses were observed for cargo handlers and vehicle crew members because of conservative assumptions. This study results can be used as basic data for the radiological safety assessment for the decommissioning waste transportation in the future.

Dramatic loss of microbial viability in bentonite exposed to heat and gamma radiation: implications for deep geological repository.

Bentonite is an integral part of the engineered barrier system (EBS) in deep geological repositories (DGR) for nuclear waste, but its indigenous microorganisms may jeopardize long-term EBS integrity. To predict microbial activity in DGRs, it is essential to understand microbial reactions to the early hot phase of DGR evolution. Two bentonites (BCV and MX-80) with varied bentonite/water ratios and saturation levels (compacted to 1600 kg.m- 3 dry density/powder/suspension), were subjected to heat (90-150 °C) and irradiation (0.4 Gy.h- 1) in the long-term experiments (up to 18 months). Molecular-genetic, microscopic, and cultivation-based techniques assessed microbial survivability. Exposure to 90 °C and 150 °C notably diminished microbial viability, irrespective of bentonite form, with negligible impacts from irradiation or sample type compared to temperature. Bentonite powder samples exhibited microbial recovery after 90 °C heating for up to 6 months but not 12 months in most cases; exposure to 150 °C had an even stronger effect. Further long-term experiments at additional temperatures combined with the mathematical prediction of temperature evolution in DGR are recommended to validate the possible evolution and spatial distribution of microbially depleted zones in bentonite buffer around the waste canisters and refine predictions of microbial effects over time in the DGR.

Extremophilic microbial metabolism and radioactive waste disposal.

Decades of nuclear activities have left a legacy of hazardous radioactive waste, which must be isolated from the biosphere for over 100,000 years. The preferred option for safe waste disposal is a deep subsurface geological disposal facility (GDF). Due to the very long geological timescales required, and the complexity of materials to be disposed of (including a wide range of nutrients and electron donors/acceptors) microbial activity will likely play a pivotal role in the safe operation of these mega-facilities. A GDF environment provides many metabolic challenges to microbes that may inhabit the facility, including high temperature, pressure, radiation, alkalinity, and salinity, depending on the specific disposal concept employed. However, as our understanding of the boundaries of life is continuously challenged and expanded by the discovery of novel extremophiles in Earth's most inhospitable environments, it is becoming clear that microorganisms must be considered in GDF safety cases to ensure accurate predictions of long-term performance. This review explores extremophilic adaptations and how this knowledge can be applied to challenge our current assumptions on microbial activity in GDF environments. We conclude that regardless of concept, a GDF will consist of multiple extremes and it is of high importance to understand the limits of polyextremophiles under realistic environmental conditions.

Mechanism of Cs Immobilization within a Sodalite Framework: The Role of Alkaline Cations and the Si/Al Ratio.

Conditioning of radioactive waste generated from the operation of medical institutions, nuclear cycle facilities, and nuclear facilities is important for the safety of the environment. One of the most hazardous radionuclides is radioactive cesium. There is a need for more effective solutions to contain radionuclides, especially cesium (Cs+). Geopolymers are promising inorganic materials that can provide a large active surface area with adjustable porosity and binding capacity. The existence of nanosized zeolite-like structures in aluminosilicate gels was shown earlier. These structures are candidates for immobilizing radioactive cesium (Cs+). However, the mechanisms of their interactions with the aluminosilicate framework related to radionuclide immobilization have not been well studied. In this work, the influence of alkaline cations (Na+ or K+) and the aluminosilicate framework structure on the binding capacity and mechanism of interaction of geopolymers with Cs+ is explored in the example of a sodalite framework. The local structure of the water molecules and alkaline ions in the equilibrium state and its behavior when the Si/Al ratio was changed were studied by DFT.