Machine learning molecular dynamics reveals the structural origin of the first sharp diffraction peak in high-density silica glasses.

The first sharp diffraction peak (FSDP) in the total structure factor has long been regarded as a characteristic feature of medium-range order (MRO) in amorphous materials with a polyhedron network, and its underlying structural origin is a subject of ongoing debate. In this study, we utilized machine learning molecular dynamics (MLMD) simulations to explore the origin of FSDP in two typical high-density silica glasses: silica glass under pressure and permanently densified glass. Our MLMD simulations accurately reproduce the structural properties of high-density silica glasses observed in experiments, including changes in the FSDP intensity depending on the compression temperature. By analyzing the simulated silica glass structures, we uncover the structural origin responsible for the changes in the MRO at high density in terms of the periodicity between the ring centers and the shape of the rings. The reduction or enhancement of MRO in the high-density silica glasses can be attributed to how the rings deform under compression.

Simulation study on 3H behavior in the Fukushima coastal region: Comparison of influences of discharges from the Fukushima Daiichi and rivers.

The release of tritium (3H) to the ocean is planned on the coastal environment in the Fukushima coastal region from Spring or Summer of 2023. Before its release, we evaluate the effect of 3H discharges from the port of Fukushima Daiichi and rivers in the Fukushima coastal region using a three-dimensional hydrodynamic model (3D-Sea-SPEC). The simulation results showed that discharges from the port of Fukushima Daiichi dominantly affected the 3H concentrations in monitoring points within approximately 1 km. Moreover, the results indicate that the effect of riverine 3H discharge was limited around the river mouth under base flow conditions. However, its impact on the Fukushima coastal regions under storm flow conditions was found, and the 3H concentrations in seawater in the Fukushima coastal region were formed around 0.1 Bq/L (mean 3H concentrations in seawater in the Fukushima coastal region) in the near shore.

Accumulation mechanisms of radiocaesium within lichen thallus tissues determined by means of in situ microscale localisation observation.

Many lichens are well known to accumulate radiocaesium and, thus acting as biomonitors of contamination levels. However, the actual localisation and chemical forms of radiocaesium in contaminated lichens have not yet been elucidated because, despite their high radioactivity, these forms are present in trace amounts as chemical entities. Here, we use autoradiography and demonstrate for the first time in situ microscale localisation of radiocaesium within thallus tissues to investigate the radiocaesium forms and their accumulation mechanism. Radiocaesium distributions showed similar trends in lichen tissues collected two and six years after the Fukushima nuclear accident. The radiocaesium was localised in the brown pigmented parts i.e., melanin-like substances, in the lower cortex of lichen thallus. Quantum chemical calculations showed that functional group of melanin-like substances can chelate Cs+ ion, which indicates that the Cs+ ions form complexes with the substances. Based on these findings, we suggest that radiocaesium ions may be retained stably in melanin-like substances for long periods (two to six years) due to steric factors, such as those seen in porphyrin-like structures and via multimer formation in the lower cortex. In addition, electron microscopy and autoradiography were used to observe radiocaesium-bearing microparticles (CsMPs) on/in the upper cortex and around the medullary layer. Micron-sized particles appeared to adhere to the surface tissue of the thallus, as shown by electron microscopy, suggesting that the particles were trapped by development of an adhesive layer; that is, CsMPs were trapped both physically and physiologically. These findings provide information on in situ localisation of two chemical forms of radiocaesium, cations and particles, in lichen thallus tissues and their accumulation mechanisms.

Machine learning molecular dynamics simulations toward exploration of high-temperature properties of nuclear fuel materials: case study of thorium dioxide.

Predicting materials properties of nuclear fuel compounds is a challenging task in materials science. Their thermodynamical behaviors around and above the operational temperature are essential for the design of nuclear reactors. However, they are not easy to measure, because the target temperature range is too high to perform various standard experiments safely and accurately. Moreover, theoretical methods such as first-principles calculations also suffer from the computational limitations in calculating thermodynamical properties due to their high calculation-costs and complicated electronic structures stemming from f-orbital occupations of valence electrons in actinide elements. Here, we demonstrate, for the first time, machine-learning molecular-dynamics to theoretically explore high-temperature thermodynamical properties of a nuclear fuel material, thorium dioxide. The target compound satisfies first-principles calculation accuracy because f-electron occupation coincidentally diminishes and the scheme meets sampling sufficiency because it works at the computational cost of classical molecular-dynamics levels. We prepare a set of training data using first-principles molecular dynamics with small number of atoms, which cannot directly evaluate thermodynamical properties but captures essential atomistic dynamics at the high temperature range. Then, we construct a machine-learning molecular-dynamics potential and carry out large-scale molecular-dynamics calculations. Consequently, we successfully access two kinds of thermodynamic phase transitions, namely the melting and the anomalous [Formula: see text] transition induced by large diffusions of oxygen atoms. Furthermore, we quantitatively reproduce various experimental data in the best agreement manner by selecting a density functional scheme known as SCAN. Our results suggest that the present scale-up simulation-scheme using machine-learning techniques opens up a new pathway on theoretical studies of not only nuclear fuel compounds, but also a variety of similar materials that contain both heavy and light elements, like thorium dioxide.

A modeling approach to estimate 3H discharge from rivers: Comparison of discharge from the Fukushima Dai-ichi and inventory in seawater in the Fukushima coastal region.

Estimation of 3H discharge from river catchments is important to evaluate the effect of Fukushima Dai-ichi discharge and future planned 3H release to the ocean on the coastal environment. Using a previously developed model based on the tank model and observed 3H concentration in river water, the 3H discharge from the Abukuma River and 13 other rivers in the Fukushima coastal region were estimated from June 2013 to March 2020. The 3H discharge from catchments of the Abukuma River and 13 other rivers in the Fukushima coastal region during 2014-2019 were estimated to be 1.2-4.0 TBq/y. These values were approximately 2-22 times larger than the annual 3H discharge from the Fukushima Dai-ichi after 2016, indicating the significance of 3H discharge from the catchments through the rivers. This estimation is expected to be useful to evaluate and predict 3H concentrations and inventories in the Fukushima coastal region for consideration of planned 3H release to the ocean.

Quantum chemical calculation studies toward microscopic understanding of retention mechanism of Cs radioisotopes and other alkali metals in lichens.

We evaluate stability of cesium (Cs) and other alkali-metal cation complexes of lichen metabolites in both gas and aqueous phases to discuss why lichens can retain radioactive Cs in the thalli over several years. We focus on oxalic acid, (+)-usnic acid, atranorin, lecanoric acid, and protocetraric acid, which are common metabolite substances in various lichens including, e.g., Flavoparmelia caperata and Parmotrema tinctorum retaining Cs in Fukushima, Japan. By performing quantum chemical calculations, their gas-phase complexation energies and aqueous-solution complexation free energies with alkali-metal cations are computed for their neutral and deprotonated cases. Consequently, all the molecules are found to energetically favor cation complexations and the preference order is Li[Formula: see text]Na[Formula: see text]K[Formula: see text]Rb[Formula: see text]Cs[Formula: see text] for all conditions, indicating no specific Cs selectivity but strong binding with all alkali cations. Comparing complexation stabilities among these metabolites, lecanoric and protocetraric acids seen in medullary layer are found to keep higher affinity in their neutral case, while (+)-usnic acid and atranorin in upper cortex exhibit rather strong affinity only in deprotonated cases through forming stable six atoms' ring containing alkali cation chelated by two oxygens. These results suggest that the medullary layer can catch all alkali cations in a wide pH range around the physiological one, while the upper cortex can effectively block penetration of metal ions when the metal stress grows. Such insights highlight a physiological role of metabolites like blocking of metal-cation migrations into intracellular tissues, and explain long-term retention of alkali cations including Cs in lichens containing enough such metabolites to bind them.

Calculations for ambient dose equivalent rates in nine forests in eastern Japan from 134Cs and 137Cs radioactivity measurements.

Understanding the relationship between the distribution of radioactive 134Cs and 137Cs in forests and ambient dose equivalent rates (H˙∗(10)) in the air is important for researching forests in eastern Japan affected by the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident. This study used a large number of measurements from forest samples, including 134Cs and 137Cs radioactivity concentrations, densities and moisture contents, to perform Monte Carlo radiation transport simulations for H˙∗(10) between 2011 and 2017. Calculated H˙∗(10) at 0.1 and 1 m above the ground had mean residual errors of 19% and 16%, respectively, from measurements taken with handheld NaI(Tl) scintillator survey meters. Setting aside the contributions from natural background radiation, 134Cs and 137Cs in the organic layer and the top 5 cm of forest soil generally made the largest contributions to calculated H˙∗(10). The contributions from 134Cs and 137Cs in the forest canopy were calculated to be largest in the first two years following the accident. Uncertainties were evaluated in the simulation results due to the measurement uncertainties in the model inputs by assuming Gaussian measurement errors. The mean uncertainty (relative standard deviation) of the simulated H˙∗(10) at 1 m height was 11%. The main contributors to the total uncertainty in the simulation results were the accuracies to which the 134Cs and 137Cs radioactivities of the organic layer and top 5 cm of soil, and the vertical distribution of 134Cs and 137Cs within the 5 cm soil layers, were known. Radioactive cesium located in the top 5 cm of soil was the main contributor to H˙∗(10) at 1 m by 2016 or 2017 in the calculation results for all sites. Studies on the 137Cs distribution within forest soil will therefore help explain radiation levels henceforth in forests affected by the FDNPP accident. The merits of this study are that it modelled multiple forests for a long time period, with the important model inputs being informed by field measurements, and it quantified how the measurement uncertainties in these inputs affected the calculation results.

Long-term simulations of radiocesium discharge in watershed with improved radioesium wash-off model: Applying the model to Abukuma River basin of Fukushima.

In order to simulate the long-term migration and distribution of radiocesium after the Fukushima accident, a numerical model, Soil and Cesium Transport (SACT) based on universal soil loss equation (USLE), has been developed in previous studies. Although the SACT model's results on radiocesium discharge in 2011 are in reasonable agreement with field measurements, it fails to capture the sharp decrease of radiocesium flux in subsequent years, especially in the case of Abukuma River. The present work aims to improve SACT by implementing new processes for radiocesium wash-off, in which the vertical migration, and long-term fixation of radiocesium in soil are taken in to account. To understand the vertical migration process, depth profile measurement results between 2011 and 2016 have been fitted by different distribution functions and analyzed statistically. A conceptual model has been developed to describe results from recent sorption experiments, which support long-term fixation of radiocesium in soil particles. For validation purpose, the annual average radiocesium concentration in sediments discharged from Abukuma river has been evaluated from measurement data. With these improvements, the new SACT model could achieve much better agreement with the measurement results without parameter tuning.

Development of the ReaxFF Methodology for Electrolyte-Water Systems.

A new ReaxFF reactive force field has been developed for water-electrolyte systems including cations Li+, Na+, K+, and Cs+ and anions F-, Cl-, and I-. The reactive force field parameters have been trained against quantum mechanical (QM) calculations related to water binding energies, hydration energies and energies of proton transfer. The new force field has been validated by applying it to molecular dynamics (MD) simulations of the ionization of different electrolytes in water and comparison of the results with experimental observations and thermodynamics. Radial distribution functions (RDF) determined for most of the atom pairs (cation or anion with oxygen and hydrogen of water) show a good agreement with the RDF values obtained from DFT calculations. On the basis of the applied force field, the ReaxFF simulations have described the diffusion constants for water and electrolyte ions in alkali metal hydroxide and chloride salt solutions as a function of composition and electrolyte concentration. The obtained results open opportunities to advance ReaxFF methodology to a wide range of applications involving electrolyte ions and solutions.

Understanding Competition of Polyalcohol Dehydration Reactions in Hot Water.

Dehydration of biomass-derived polyalcohols has recently drawn attention in green chemistry as a prototype of selective reactions controllable in hot water or hot carbonated water, without any use of organic solvents or metal catalysts. Here, we report a free-energy analysis based on first-principles metadynamics and blue-moon ensemble simulations to understand the mechanism of competing intramolecular dehydration reactions of 1,2,5-pentanetriol in hot acidic water. The simulations consistently predict that the most dominant mechanism is the proton-assisted SN2 process, where the protonation of the hydroxyl group by water and the C-O bond breaking and formation occur in a single step. However the free-energy barriers are different between the reaction paths: those leading to five-membered ether products, tetrahydrofurfuryl alcohol (THFA), are few kcal/mol lower than those leading to six-membered ether products, 3-hydroxytetrahydropyran (3-HTHP). A slight difference is seen in the timing of the protonation of the hydroxyl group of THFA and 3-HTHP on their reaction pathways. The detailed mechanism found from the simulations shows how the reaction paths are selective in hot water and why the reaction rates are accelerated in acidic environments, thus giving a clear explanation of experimental findings for a broad class of competing dehydration processes of polyalcohols.

Simulation study of the effects of buildings, trees and paved surfaces on ambient dose equivalent rates outdoors at three suburban sites near Fukushima Dai-ichi.

The influence of buildings, trees and paved surfaces on outdoor ambient dose equivalent rates (H˙∗(10)) in suburban areas near to the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) was investigated with Monte Carlo simulations. Simulation models of three un-decontaminated sites in Okuma and Tomioka were created with representations of individual buildings, trees and roads created using geographic information system (GIS) data. The 134Cs and 137Cs radioactivity distribution within each model was set using in-situ gamma spectroscopy measurements from December 2014 and literature values for the relative radioactive cesium concentration on paved surfaces, unpaved land, building outer surfaces, forest litter and soil layers, and different tree compartments. Reasonable correlation was obtained between the simulations and measurements for H˙∗(10) across the sites taken in January 2015. The effect of buildings and trees on H˙∗(10) was investigated by performing simulations removing these objects, and their associated 134Cs and 137Cs inventory, from the models. H˙∗(10) were on average 5.0% higher in the simulations without buildings and trees, even though the total 134Cs and 137Cs inventory within each model was slightly lower. The simulations without buildings and trees were then modified to include 134Cs and 137Cs in the ground beneath locations where buildings exist in reality, and the inventory of paved surfaces modelled as if they had high retention of 134Cs and 137Cs fallout like soil areas. H˙∗(10) increased more markedly in these cases than when considering the shielding effect of buildings and trees alone. These results help clarify the magnitude of the effect of buildings, trees and paved surfaces on H˙∗(10) at the un-decontaminated sites within Fukushima Prefecture.

Radiocesium interaction with clay minerals: Theory and simulation advances Post-Fukushima.

Insights at the microscopic level of the process of radiocesium adsorption and interaction with clay mineral particles have improved substantially over the past several years, triggered by pressing social issues such as management of huge amounts of waste soil accumulated after the Fukushima Dai-ichi nuclear power plant accident. In particular, computer-based molecular modeling supported by advanced hardware and algorithms has proven to be a powerful approach. Its application can now generally encompass the full complexity of clay particle adsorption sites from basal surfaces to interlayers with inserted water molecules, to edges including fresh and weathered frayed ones. On the other hand, its methodological schemes are now varied from traditional force-field molecular dynamics on large-scale realizations composed of many thousands of atoms including water molecules to first-principles methods on smaller models in rather exacting fashion. In this article, we overview new understanding enabled by simulations across methodological variations, focusing on recent insights that connect with experimental observations, namely: 1) the energy scale for cesium adsorption on the basal surface, 2) progress in understanding the structure of clay edges, which is difficult to probe experimentally, 3) cesium adsorption properties at hydrated interlayer sites, 4) the importance of the size relationship between the ionic radius of cesium and the interlayer distance at frayed edge sites, 5) the migration of cesium into deep interlayer sites, and 6) the effects of nuclear decay of radiocesium. Key experimental observations that motivate these simulation advances are also summarized. Furthermore, some directions toward future solutions of waste soil management are discussed based on the obtained microscopic insights.

Radiocesium interaction with clay minerals: Theory and simulation advances Post-Fukushima.

Insights at the microscopic level of the process of radiocesium adsorption and interaction with clay mineral particles have improved substantially over the past several years, triggered by pressing social issues such as management of huge amounts of waste soil accumulated after the Fukushima Dai-ichi nuclear power plant accident. In particular, computer-based molecular modeling supported by advanced hardware and algorithms has proven to be a powerful approach. Its application can now generally encompass the full complexity of clay particle adsorption sites from basal surfaces to interlayers with inserted water molecules, to edges including fresh and weathered frayed ones. On the other hand, its methodological schemes are now varied from traditional force-field molecular dynamics on large-scale realizations composed of many thousands of atoms including water molecules to first-principles methods on smaller models in rather exacting fashion. In this article, we overview new understanding enabled by simulations across methodological variations, focusing on recent insights that connect with experimental observations, namely: 1) the energy scale for cesium adsorption on the basal surface, 2) progress in understanding the structure of clay edges, which is difficult to probe experimentally, 3) cesium adsorption properties at hydrated interlayer sites, 4) the importance of the size relationship between the ionic radius of cesium and the interlayer distance at frayed edge sites, 5) the migration of cesium into deep interlayer sites, and 6) the effects of nuclear decay of radiocesium. Key experimental observations that motivate these simulation advances are also summarized. Furthermore, some directions toward future solutions of waste soil management are discussed based on the obtained microscopic insights.

Nuclear quantum effects of light and heavy water studied by all-electron first principles path integral simulations.

The isotopologs of liquid water, H2O, D2O, and T2O, are studied systematically by first principles PIMD simulations, in which the whole entity of the electrons and nuclei are treated quantum mechanically. The simulation results are in reasonable agreement with available experimental data on isotope effects, in particular, on the peak shift in the radial distributions of H2O and D2O and the shift in the evaporation energies. It is found that, due to differences in nuclear quantum effects, the H atoms in the OH bonds more easily access the dissociative region up to the hydrogen bond center than the D (T) atoms in the OD (OT) bonds. The accuracy and limitation in the use of the current density-functional-theory-based first principles PIMD simulations are also discussed. It is argued that the inclusion of the dispersion correction or relevant improvements in the density functionals are required for the quantitative estimation of isotope effects.

Transmutation effects on long-term Cs retention in phyllosilicate minerals from first principles.

The accidental release and incorporation of radiocesium into soil minerals represents a massive environmental, technical and social challenge. Accurately forecasting the evolving distribution and fate of long- and medium-lived isotopes such as 137Cs and 134Cs over decadal time scales is essential. The cesium cation has long been modeled as a strongly and selectively sorbed species into clay mineral interlayers; however, because of the time scales involved by the radioisotopes half-lives, the effects of radioactive decay on Cs retention have been unknown. We report density functional theory (DFT) simulations of transmutation effects of radiocesium on long-term Cs retention in phlogopite. The calculations show that the progressive appearance of daughter product Ba2+ is accompanied by a proportional increase in thermodynamic driving force to preferentially discharge remaining Cs, both radioactive and stable, back into aqueous solution. Based on thermodynamic analysis, the findings indicate that radiocesium transmutation provides a mean to weaken the binding of Cs in phyllosilicate minerals, therefore potentially involving a premature re-release of Cs back into the environment. In the case where radiogenic Ba2+ ions accumulate in the mineral, collateral effects would ultimately be an increase in the overall interlayer binding energy and a lower resorption capacity.

Characteristics of radio-cesium transport and discharge between different basins near to the Fukushima Dai-ichi Nuclear Power Plant after heavy rainfall events.

This paper describes watershed modeling of catchments surrounding the Fukushima Dai-ichi Nuclear Power Plant to understand radio-cesium redistribution by water flows and sediment transport. We extended our previously developed three-dimensional hydrogeological model of the catchments to calculate the migration of radio-cesium in both sediment-sorbed and dissolved forms. The simulations cover the entirety of 2013, including nine heavy rainfall events, as well as Typhoon Roke in September 2011. Typhoons Man-yi and Wipha were the strongest typhoons in 2013 and had the largest bearing on radio-cesium redistribution. The simulated 137Cs discharge quantities over the nine events in 2013 are in good agreement with field monitoring observations. Deposition mainly occurs on flood plains and points where the river beds broaden in the lower basins, and within dam reservoirs along the rivers. Differences in 137Cs discharge ratios between the five basins are explained by differences in the initial fallout distribution within the basins, the presence of dam reservoirs, and the input supply to watercourses. It is possible to use these simulation results to evaluate future radioactive material distributions in order to support remediation planning.

Molecular dynamics simulations of cesium adsorption on illite nanoparticles.

The charged surfaces of micaceous minerals, especially illite, regulate the mobility of the major radioisotopes of Cs (134Cs, 135Cs, 137Cs) in the geosphere. Despite the long history of Cs adsorption studies, the nature of the illite surface sites remains incompletely understood. To address this problem, we present atomistic simulations of Cs competition with Na for three candidate illite adsorption sites - edge, basal plane, and interlayer. Our simulation results are broadly consistent with affinities and selectivities that have been inferred from surface complexation models. Cation exchange on the basal planes is thermodynamically ideal, but exchange on edge surfaces and within interlayers shows complex, thermodynamically non-ideal behavior. The basal planes are weakly Cs-selective, while edges and interlayers have much higher affinity for Cs. The dynamics of NaCs exchange are rapid for both cations on the basal planes, but considerably slower for Cs localized on edge surfaces. In addition to new insights into Cs adsorption and exchange with Na on illite, we report the development of a methodology capable of simulating fully-flexible clay mineral nanoparticles with stable edge surfaces using a well-tested interatomic potential model.

Effect of Remediation Parameters on in-Air Ambient Dose Equivalent Rates When Remediating Open Sites with Radiocesium-contaminated Soil.

Calculations are reported for ambient dose equivalent rates [H˙*(10)] at 1 m height above the ground surface before and after remediating radiocesium-contaminated soil at wide and open sites. The results establish how the change in H˙*(10) upon remediation depends on the initial depth distribution of radiocesium within the ground, on the size of the remediated area, and on the mass per unit area of remediated soil. The remediation strategies considered were topsoil removal (with and without recovering with a clean soil layer), interchanging a topsoil layer with a subsoil layer, and in situ mixing of the topsoil. The results show the ratio of the radiocesium components of H˙*(10) post-remediation relative to their initial values (residual dose factors). It is possible to use the residual dose factors to gauge absolute changes in H˙*(10) upon remediation. The dependency of the residual dose factors on the number of years elapsed after fallout deposition is analyzed when remediation parameters remain fixed and radiocesium undergoes typical downward migration within the soil column.

Evaluation of ambient dose equivalent rates influenced by vertical and horizontal distribution of radioactive cesium in soil in Fukushima Prefecture.

The air dose rate in an environment contaminated with (134)Cs and (137)Cs depends on the amount, depth profile and horizontal distribution of these contaminants within the ground. This paper introduces and verifies a tool that models these variables and calculates ambient dose equivalent rates at 1 m above the ground. Good correlation is found between predicted dose rates and dose rates measured with survey meters in Fukushima Prefecture in areas contaminated with radiocesium from the Fukushima Dai-ichi Nuclear Power Plant accident. This finding is insensitive to the choice for modeling the activity depth distribution in the ground using activity measurements of collected soil layers, or by using exponential and hyperbolic secant fits to the measurement data. Better predictions are obtained by modeling the horizontal distribution of radioactive cesium across an area if multiple soil samples are available, as opposed to assuming a spatially homogeneous contamination distribution. Reductions seen in air dose rates above flat, undisturbed fields in Fukushima Prefecture are consistent with decrement by radioactive decay and downward migration of cesium into soil. Analysis of remediation strategies for farmland soils confirmed that topsoil removal and interchanging a topsoil layer with a subsoil layer result in similar reductions in the air dose rate. These two strategies are more effective than reverse tillage to invert and mix the topsoil.

Comment on 'Update of (40)K and (226)Ra and (232)Th series γ-to-dose conversion factors for soil'.

A comment on the recent Journal of Environmental Radioactivity article titled 'Update of (40)K and (226)Ra and (232)Th series γ-to-dose conversion factors for soil'.