Exploring simple ways to avoid collecting highly 137Cs-contaminated Aralia elata buds for the revival of local wild vegetable cultures.

Collection and cooking of wild vegetables have provided seasonal enjoyments for Japanese local people as provisioning and cultural ecosystem services. However, the Fukushima Daiichi Nuclear Power Plant accident in March 2011 caused extensive radiocesium contamination of wild vegetables. Restrictions on commercial shipments of wild vegetables have been in place for the last 10 years. Some species, including buds of Aralia elata, are currently showing radiocesium concentrations both above and below the Japanese reference level for food (100 Bq/kg), implying that there are factors decreasing and increasing the 137Cs concentration. Here, we evaluated easy-to-measure environmental variables (dose rate at the soil surface, organic soil layer thickness, slope steepness, and presence/absence of decontamination practices) and the 137Cs concentrations of 40 A. elata buds at 38 locations in Fukushima Prefecture to provide helpful information on avoiding collecting highly contaminated buds. The 137Cs concentrations in A. elata buds ranged from 1 to 6,280 Bq/kg fresh weight and increased significantly with increases in the dose rate at the soil surface (0.10-6.50 µSv/h). Meanwhile, the 137Cs concentration in A. elata buds were not reduced by decontamination practices. These findings suggest that measuring the latest dose rate at the soil surface at the base of A. elata plants is a helpful way to avoid collecting buds with higher 137Cs concentrations and aid in the management of species in polluted regions.

Coherent anti-Stokes Raman scattering spectroscopy system for observation of water molecules in anion exchange membrane.

Anion exchange membrane fuel cells (AEMFCs) provide one of the most feasible remedies to fuel cells' dependency on the dwindling Pt group catalysts. Nevertheless, AEMFCs still suffer reduced durability, which requires an in-depth understanding of their membranes. The low thermal endurance of the anion exchange membranes (AEMs) usually limits the direct application of powerful techniques, such as Raman spectroscopy. We sought to establish a system for coherent anti-Stokes Raman scattering (CARS) spectroscopy capable of taking measurements inside an AEM rapidly and accurately without photodamage. A 785 nm CARS system was newly developed to study the water species in an AEM (QPAF-4) located vertically in a fuel cell. From the results of water measurement in a QPAF-4 membrane, the OH-related region was deconvoluted into nine Gaussian peaks: Five H-bonded OH peaks, non-H-bonded OH, OH-, and two CH peaks. The H-bonded species increased with increasing relative humidity, but the other species remained constant. These results open unlimited possibilities for studying and comparing different AEMFCs, enabling more rapid technology optimization.

Influential factors of long-term and seasonal 137Cs change in agricultural and forested rivers: Temperature, water quality and an intense Typhoon Event.

In this study, the effect of temperature, water quality, and the impact of an intense typhoon event on change in 137Cs concentration in the water of agricultural and forested rivers near the Fukushima Daiichi nuclear power plant (Japan) was evaluated using monthly stationary observations obtained under baseflow conditions 2.8-10.6 years after the nuclear accident in 2011. The dissolved 137Cs concentration fluctuated seasonally with water temperature in all rivers, and the increase in dissolved 137Cs concentration for unit increase in temperature was higher in forested rivers than in agricultural rivers. The relationship between water temperature and the apparent distribution coefficient of 137Cs well followed the van 't Hoff equation in the two agricultural rivers, where the enthalpy of reaction was estimated as -15.6 and -19.6 kJ mol-1. The van 't Hoff equation was not well followed for a forested river, where the suspended solids mainly comprised organic matter, suggesting that the dominant process determining dissolved 137Cs concentrations in forested rivers is not only water temperature effect on ion exchange, but rather the input of 137Cs and K+ (competing with 137Cs for exchange sites on mineral particles) into the water phase via litter leaching. Suspended solids concentrations in agricultural rivers correlated negatively with 137Cs concentrations in suspended solids, suggesting an increased proportion of coarse particles or the input of soils with low 137Cs concentration from decontaminated agricultural land. At some sites, 137Cs concentrations in dissolved form and in suspended solids were reduced sharply in association with the passage of Typhoon Hagibis in October 2019, suggesting that Typhoon Hagibis caused large-scale surface erosion that removed the source of 137Cs.

Explaining the variation in 137Cs aggregated transfer factor for wild edible plants as a case study on Koshiabura (Eleutherococcus sciadophylloides) buds.

The aggregated transfer factor (Tag) is commonly used to represent the actual transfer of radiocesium from soil to wild edible plants, but the values have shown substantial variation since the Fukushima nuclear accident. To elucidate the factors causing this variation, we investigated the effects of spatial scale and vertical 137Cs distribution in the soil on the variation of Tag-137Cs values for one of the most severely contaminated wild edible plants, Eleutherococcus sciadophylloides Franch. et Sav. (Koshiabura). The variation in Tag-137Cs values was not reduced by direct measurement of 137Cs deposition in soil samples from the Koshiabura habitat, as a substitute for using spatially averaged airborne survey data at the administrative district scale. The 137Cs activity concentration in Koshiabura buds showed a significant positive correlation with the 137Cs inventories only in the organic horizon of soil from the Koshiabura habitat. The ratio of 137Cs inventories in the organic horizon to the total 137Cs deposition in soil exhibited substantial variation, especially in broad-leaved deciduous forests that Koshiabura primarily inhabits. This variation may be the cause of the wide range of Tag-137Cs values observed in Koshiabura buds when calculated from the total 137Cs deposition in soil.

Spatiotemporal patterns in differences between the 137Cs concentrations of forest and stream litters: effect of leaching.

Forest-stream ecotones possess prominent detritus-based food webs, and 137Cs-contaminated litter can influence the contamination levels of animals inhabiting such ecosystems. The effects of leaching on contaminated litter induce greater absolute differences between the 137Cs concentrations of forest and stream litter in more contaminated sites. Because 137Cs concentrations in litter can be attenuated temporally, spatiotemporal patterns in the differences in 137Cs concentrations between forest and stream litter may vary depending on both the amount of 137Cs deposition and the passage of time. To test this hypothesis, we sampled coniferous needle and broad-leaved deciduous litter in forests and streams at seven forested headwater sites affected by the Fukushima nuclear accident 3.24 and 11.24 years after the accident. We found that 137Cs concentrations in the two litter types were one order of magnitude lower 11.24 years after the accident than 3.24 years afterwards. The absolute difference in 137Cs activity concentrations of litter between forest and stream ecosystems was higher at more contaminated sites both 3.24 and 11.24 years after the accident. The spatiotemporal changes in litter contamination provide insight into 137Cs dynamics and complex transfer in the detritus-based food webs of forest-stream ecotones.

Contrasting seasonality of 137Cs concentrations in two stream animals that share a trophic niche.

Understanding the seasonality of 137Cs concentrations in aquatic animals is crucial for reviving local inland fisheries. The seasonality of 137Cs concentrations in animals is expected to vary, even if focal species consume similarly contaminated foods because the 137Cs excretion rate is species-specific, and 137Cs uptake by foraging autochthonous food resources also vary among seasons. Here, we conducted a seasonal monitoring survey of dissolved 137Cs concentrations as an indicator of the contamination level of food resources and measured 137Cs concentrations in two carnivorous aquatic animals (Palaemon paucidens and Rhinogobius sp.) that share a trophic niche in a stream connected to a dam reservoir. The dissolved 137Cs concentration had clear seasonality-high in summer and low in winter. The 137Cs concentrations in the animals revealed a different seasonal pattern-it peaked in October in P. paucidens and peaked in February in Rhinogobius. Overall, the 137Cs concentration was relatively higher in P. paucidens than in Rhinogobius, suggesting that P. paucidens has a lower excretion rate than Rhinogobius. Consequently, the seasonality of the 137Cs concentration in P. paucidens showed temporal changes similar to those of the dissolved 137Cs concentration, which were likely affected by 137Cs uptake through foraging, whereas that in Rhinogobius was controlled by 137Cs excretion. This study shows that the seasonality of 137Cs concentration can differ between sympatric animals that share a trophic niche. Accumulating knowledge and comparing the seasonality of 137Cs concentrations in fisheries species based on the balance between uptake and excretion will be valuable to determine the appropriate seasons to obtain less-contaminated products.

Scanning near-field optical spectroscopy and carrier transport based analysis in mesoscopic regions for two-dimensional semiconductors.

The measurements of photoexcited transport in mesoscopic regimes reveal the states and properties of mesoscopic systems. In this study, we focused on direct measurements of electromagnetic energy transports in the mesoscopic regions and constructed a scanning tunnelling microscope-assisted multi-probe scanning near-field optical microscope spectroscopy system. After producing an emission energy map through a single-probe measurement, two-probe measurement enables us to observe and analyse carrier transport characteristics. It suggests that exciton generation and transport in the mesoscopic region of semiconductors with quantum structure changes, such as the bias of dopant, affect the excited carrier emission recombination process. The measured probability density of the carrier transported with quantum effects can be used for applications in natural intelligence research by combining it with the analysis using tournament structures. Our developed measurement and analysis methods are expected to clarify the details of carrier's behaviour in the mesoscopic region in various materials and lead to applications for novel optoelectronic devices.

Untangling radiocesium dynamics of forest-stream ecosystems: A review of Fukushima studies in the decade after the accident.

Forest-stream ecosystems are widespread and biodiverse terrestrial landscapes with physical and social connections to downstream human activities. After radiocesium is introduced into these ecosystems, various material flows cause its accumulation or dispersal. We review studies conducted in the decade after the Fukushima nuclear accident to clarify the mechanisms of radiocesium transfer within ecosystems and to downstream areas through biological, hydrological, and geomorphological processes. After its introduction, radiocesium is heavily deposited in the organic soil layer, leading to persistent circulation due to biological activities in soils. Some radiocesium in soils, litter, and organisms is transported to stream ecosystems, forming contamination spots in depositional habitats. While reservoir dams function as effective traps, radiocesium leaching from sediments is a continual phenomenon causing re-contamination downstream. Integration of data regarding radiocesium dynamics and contamination sites, as proposed here, is essential for contamination management in societies depending on nuclear power to address the climate crisis.

Seasonal and annual fluctuations of deer populations estimated by a Bayesian state-space model.

Deer overabundance is a contributing factor in the degradation of plant communities and ecosystems worldwide. The management and conservation of the deer-affected ecosystems requires us to urgently grasp deer population trends and to identify the factors that affect them. In this study, we developed a Bayesian state-space model to estimate the population dynamics of sika deer (Cervus nippon) in a cool-temperate forest in Japan, where wolves (Canis lupus hodophilax) are extinct. The model was based on field data collected from block count surveys, road count surveys by vehicles, mortality surveys during the winter, and nuisance control for 12 years (2007-2018). We clarified the seasonal and annual fluctuation of the deer population. We found a peak of deer abundance (2010) over 12 years. In 2011 the estimated deer abundance decreased drastically and has remained at a low level then. The deer abundance gradually increased from April to December during 2013-2018. The seasonal fluctuation we detected could reflect the seasonal migration pattern of deer and the population recruitment through fawn births in early summer. In our model, snowfall accumulation, which can be a lethal factor for deer, may have slightly affected their mortality during the winter. Although we could not detect a direct effect of snow on population dynamics, snowfall decrease due to global warming may decelerate the winter migration of deer; subsequently, deer staying on-site may intensively forage evergreen perennial plants during the winter season. The nuisance control affected population dynamics. Even in wildlife protection areas and national parks where hunting is regulated, nuisance control could be effective in buffering the effect of deer browsing on forest ecosystems.

Microsensors based on a whispering gallery mode in AlGaN microdisks undercut by hydrogen-environment thermal etching.

AlGaN microdisks were fabricated via a top-down process using electron-beam lithography, inductively coupled plasma reactive-ion etching, and hydrogen-environment thermal etching from commercial epitaxial wafers with a 100-300 nm thick AlGaN layer grown on a c-plane GaN layer by metal-organic chemical vapor deposition. The hydrogen-environment thermal etching performed well in undercutting the AlGaN microdisks owing to the selective etching for the GaN layer. The AlGaN microdisks acted as the whispering gallery mode (WGM) optical microresonators, exhibiting sharp resonant peaks in room temperature photoluminescence spectra. The evanescent component of the whispering gallery mode (WGM) is influenced by the ambient condition of the microdisk, resulting in the shift of the resonant peaks. The phenomenon is considered to be used for microsensors. Using the WGM in the AlGaN microdisks, we demonstrated microsensors and a microsensor system, which can potentially be used to evaluate biological and chemical actions in a microscale area in real time.

Developing a food web-based transfer factor of radiocesium for fish, whitespotted char (Salvelinus leucomaenis) in headwater streams.

We developed a food web-based transfer factor (TFweb) to study contaminant movements from multiple prey items to a predator based on the dietary contributions of prey items with their respective contamination levels. TFweb was used to evaluate the transfer of 137Cs into whitespotted char (Salvelinus leucomaenis) from the trophic structure of a stream-riparian ecosystem in headwater streams draining a Japanese cedar forest. We also examined the applicability of this method by comparing sites with different contamination levels but similar surrounding environments in Fukushima and Gunma. All samples were collected from August 2012 to May 2013. The dietary contributions from both aquatic and terrestrial prey items to whitespotted char were analyzed using stable carbon and nitrogen isotope ratios. 137Cs activity concentrations in char ranged from 704 to 6082 Bq kg-1-dry in Fukushima and from 193 to 618 Bq kg-1-dry in Gunma. Dominant prey taxa such as mayflies (Ephemera japonica), spider crickets (Rhaphidosphoridae gen. spp.), and freshwater crabs (Geothelphusa dehaani), each of them accounted for 3-12% of the fish diet, based on lower and upper estimates, respectively. TFweb ranged from 1.12 to 3.79 in Fukushima and from 1.30 to 4.30 in Gunma, which suggested bioaccumulation from prey items to predator. Widely used ecological parameters TFs by media-char and TTF by single prey-char showed high variability with both dilution and accumulation. TFweb is applicable for 137Cs transfer in predator-prey systems with complex food web structures of stream-riparian ecosystems.

Fallout volume and litter type affect 137Cs concentration difference in litter between forest and stream environments.

It is important to understand the changes in the 137Cs concentration in litter through leaching when considering that 137Cs is transferred from basal food resources to animals in forested streams. We found that the difference of 137Cs activity concentration in litter between forest and stream was associated with both litter type and 137Cs fallout volume around Fukushima, Japan. The 137Cs activity concentrations in the litter of evergreen conifers tended to be greater than those in the litter of broad-leaved deciduous trees because of the absence of deciduous leaves during the fallout period in March 2011. Moreover, 137Cs activity concentrations in forest litter were greater with respect to the 137Cs fallout volume. The 137Cs activity concentrations in stream litter were much lower than those in forest litter when those in forest litter were higher. The 137Cs leaching patterns indicated that the differences in 137Cs activity concentration between forest and stream litter could change with changes in both fallout volume and litter type. Because litter is an important basal food resource in the food webs of both forests and streams, the 137Cs concentration gradient reflects to possible 137Cs transfer from lower to higher trophic animals. Our findings will improve our understanding of the spatial heterogeneity and variability of 137Cs concentrations in animals resident to the contaminated landscape.

Longitudinal Hierarchy Co3O4 Mesocrystals with High-dense Exposure Facets and Anisotropic Interfaces for Direct-Ethanol Fuel Cells.

Novel electrodes are needed for direct ethanol fuel cells with improved quality. Hierarchical engineering can produce catalysts composed of mesocrystals with many exposed active planes and multi-diffused voids. Here we report a simple, one-pot, hydrothermal method for fabricating Co3O4/carbon/substrate electrodes that provides control over the catalyst mesocrystal morphology (i.e., corn tubercle pellets or banana clusters oriented along nanotube domains, or layered lamina or multiple cantilevered sheets). These morphologies afforded catalysts with a high density of exposed active facets, a diverse range of mesopores in the cage interior, a window architecture, and vertical alignment to the substrate, which improved efficiency in an ethanol electrooxidation reaction compared with a conventional platinum/carbon electrode. On the atomic scale, the longitudinally aligned architecture of the Co3O4 mesocrystals resulted in exposed low- and high-index single and interface surfaces that had improved electron transport and diffusion compared with currently used electrodes.

Different cesium-137 transfers to forest and stream ecosystems.

Understanding the mechanisms of (137)Cs movement across different ecosystems is crucial for projecting the environmental impact and management of nuclear contamination events. Here, we report differential movement of (137)Cs in adjacent forest and stream ecosystems. The food webs of the forest and stream ecosystems in our study were similar, in that they were both dominated by detrital-based food webs and the basal energy source was terrestrial litter. However, the concentration of (137)Cs in stream litter was significantly lower than in forest litter, the result of (137)Cs leaching from litter in stream water. The difference in (137)Cs concentrations between the two types of litter was reflected in the (137)Cs concentrations in the animal community. While the importance of (137)Cs fallout and the associated transfer to food webs has been well studied, research has been primarily limited to cases in a single ecosystem. Our results indicate that there are differences in the flow of (137)Cs through terrestrial and aquatic ecosystems, and that (137)Cs concentrations are reduced in both basal food resources and higher trophic animals in aquatic systems, where primary production is subsidized by a neighboring terrestrial ecosystem.

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores.

Developing low-cost, efficient processes for recovering and recycling palladium, gold and cobalt metals from urban mine remains a significant challenge in industrialized countries. Here, the development of optical mesosensors/adsorbents (MSAs) for efficient recognition and selective recovery of Pd(II), Au(III), and Co(II) from urban mine was achieved. A simple, general method for preparing MSAs based on using high-order mesoporous monolithic scaffolds was described. Hierarchical cubic Ia3d wagon-wheel-shaped MSAs were fabricated by anchoring chelating agents (colorants) into three-dimensional pores and micrometric particle surfaces of the mesoporous monolithic scaffolds. Findings show, for the first time, evidence of controlled optical recognition of Pd(II), Au(III), and Co(II) ions and a highly selective system for recovery of Pd(II) ions (up to ~95%) in ores and industrial wastes. Furthermore, the controlled assessment processes described herein involve evaluation of intrinsic properties (e.g., visual signal change, long-term stability, adsorption efficiency, extraordinary sensitivity, selectivity, and reusability); thus, expensive, sophisticated instruments are not required. Results show evidence that MSAs will attract worldwide attention as a promising technological means of recovering and recycling palladium, gold and cobalt metals.

Sensing operations based on hexagonal GaN microdisks acting as whispering-gallery mode optical microcavities.

Using room temperature photoluminescence measurements, we have demonstrated a sensing operation based on hexagonal GaN microdisks with a side length of approximately 1.5 µm that acted as optical microcavities. In the experiment, the optical microresonant systems based on the whispering-gallery mode (WGM) in the microdisks were affected by their ambient conditions, resulting in shifts of the lasing wavelength by varying the mixing ratios of isopropanol and o-xylene. We also obtained such shifts for aqueous solutions with varying sucrose concentrations. In addition, we demonstrated that tiny waterborne particles can be detected using a microdisk. These results indicate that the WGM in the hexagonal GaN microdisks potentially can be used to develop optical microbiosensors that can evaluate a limited area with a radius of 1-2 µm.

Mesotubular-Structured Hybrid Membrane Nanocontainer for Periodical Monitoring, Separation, and Recovery of Cobalt Ions from Water.

Exposure to toxins can cause deleterious effects even at very low concentrations. We have developed an optical sensor, filter, and extractor (i.e., containerlike) in a nanoscale membrane (NSM) for the ultratrace sensing, separation, and recovery of Co(2+) ions from water. The design of the NSM is successfully controlled by dense decoration of a hydrophobic oil-hydrophilic receptor onto mesoscale tubular-structured silica nanochannels made of a hybrid anodic alumina membrane. The particular structure of the nanocontainer is ideal to control the multiple functions of the membrane, such as the optical detection/recognition, rejection/permeation, and recovery of Co(2+) species in a single step. A typical sensor, filter, and extractor assessment experiment was performed by using a benchtop contact time technique and a flow-through cell detector to allow for precise control of the optical detection and exclusive rejection of target ions and the permeation of nontarget metal ions in water. This nanocontainer membrane has great potential to meet the increasing needs of purification and separation of Co(2+) ions.

Mesosponge Optical Sinks for Multifunctional Mercury Ion Assessment and Recovery from Water Sources.

Using the newly developed organic-inorganic colorant membrane is an attractive approach for the optical detection, selective screening and removal, and waste management recovery of highly toxic elements, such as Hg(II) ions, from water sources. In the systematic mesosponge optical sinks (MOSs), anchoring organic colorants into 3D, well-defined cage cavities and interconnected tubular pores (10 nm) in the long microscale channels of membrane scaffolds enhances the requirements and intrinsic properties of the hierarchal membrane. This scalable design is the first to allow control of the multifunctional processes of a membrane in a one-step screening procedure, such as the detection/recognition, removal, and filtration of ultratrace Hg(II) ions, even from actual water sources (i.e., tap, underground). The selective recovery, detection, and extraction processes of Hg(II) ions in a heterogeneous mixture with inorganic cations and anions as well as organic molecules and surfactants are mainly dependent on the structure of the colorant agent, the pH conditions, competitive ion-system compositions and concentrations, and Hg-to-colorant binding events. Our result shows that the solid MOS membrane arrays can be repeatedly recycled and retain their hierarchal mesosponge sink character, avoiding fouling via the precipitation of metal salts as a result of the reuse cycle. The Hg(II) ion rejection and the permeation of nonselective elements based on the membrane filtration protocol may be key considerations in water purification and separation requirements. The selective recovery process of Hg(II) ions in actual contaminated samples collected from tap and underground water sources in Saudi Arabia indicates the practical feasibility of our designed MOS membrane arrays.

Export of radioactive cesium from agricultural fields under simulated rainfall in Fukushima.

In this study, we investigated the impact of rainfall on runoff, soil erosion and consequently on the discharge of radioactive cesium in agricultural fields in Fukushima prefecture using a rainfall simulator. Simulated heavy rainfalls (50 mm h(-1)) generated significant runoff and soil erosion. The average concentration of radioactive cesium (the sum of (134)Cs and (137)Cs) in the runoff sediments was ∼3500 Bq kg(-1) dry soil, more than double the concentrations measured in the field soils which should be considered in studies using the (137)Cs loss to estimate long-term soil erosion. However, the estimated mass of cesium discharged through one runoff event was less than 2% of the cesium inventory in the field. This suggested that cesium discharge via soil erosion is not a significant factor in reducing the radioactivity of contaminated soils in Fukushima prefecture. However, the eroded sediment carrying radioactive cesium will deposit into the river systems and potentially pose a radioactivity risk for aquatic living organisms.

Radiocesium leaching from contaminated litter in forest streams.

In Japanese forests suffering from the Fukushima Daiichi Nuclear Power Plant accident, litter fall provides a large amount of radiocesium from forests to streams. Submerged litter is processed to become a vital food resource for various stream organisms through initial leaching and subsequent decomposition. Although leaching from litter can detach radiocesium similarly to potassium, radiocesium leaching and its migration are poorly understood. We examined both radiocesium and potassium leaching to the water column and radiocesium allocation to minerals (glass beads, silica sand, and vermiculite) in the laboratory using soaked litter with and without minerals on a water column. The mineral types did not affect radiocesium leaching from litter, but soaking in water for 1, 7, and 30 days decreased the radiocesium concentration in litter by ×0.71, ×0.66, and ×0.56, respectively. Meanwhile, the 1-, 7-, and 30-day experiments decreased potassium concentration in litter by ×0.17, ×0.11, and ×0.09, respectively. Leached radiocesium remained in a dissolved form when there was no mineral phases present in the water, whereas there was sorption onto the minerals when they were present. In particular, vermiculite adsorbed radiocesium by two to three orders of magnitude more effectively than the other minerals. Because radiocesium forms (such as that dissolved or adsorbed to organic matter or minerals) can further mobilize to ecosystems, our findings will increase our understanding regarding the dynamics of radiocesium in stream ecosystems.