High-sensitive XANES analysis at Ce L2-edge for Ce in bauxites using transition-edge sensors: Implications for Ti-rich geological samples.

Accurate determination of cerium (Ce) valence state is important for interpreting the Ce anomaly in geological archives for (paleo)redox reconstruction. However, the routine application of Ce L3-edge X-ray absorption near-edge structure (XANES) spectroscopy for detecting trace Ce in geological samples can often be restricted by coexisting titanium (Ti) due to the proximity of their fluorescence emission lines. Therefore, the signal-to-noise ratio of Ce L3-edge XANES spectra may not be sufficiently high for high-quality spectroscopic analysis. This study introduces a semi-quantitative approach appropriate for Ti-rich, Ce-dilute geological materials by synchrotron-based X-ray measurement at the Ce L2-edge. First, the results confirm that Ce L2-edge XANES spectra are able to avoid overlapping Ti Kß emissions and provide more reliable information on the Ce valence state in Ti-rich materials relative to L3-edge XANES. Moreover, the application of transition-edge sensor (TES) could reach the higher sensitivity with better energy resolution than conventional silicon drift detector (SDD) to detect fluorescence X-ray (Ce Lß1). The investigation on bauxites developed from the Columbia River Basalts shows that combining Ce L2-edge XANES and TES allows for resolving weak Ce fluorescence lines at the L2-edge from Ti-rich, Ce-dilute samples (Ti/Ce mass ratio up to ∼6000, tens of ppm Ce). The outcome emphasizes the practical possibility of investigating Ce redox state in Ti-rich geological samples.

Radiocesium-bearing microparticles cause a large variation in 137Cs activity concentration in the aquatic insect Stenopsyche marmorata (Tricoptera: Stenopsychidae) in the Ota River, Fukushima, Japan.

After the Tokyo Electric Power Company Fukushima Daiichi Nuclear Power Plant accident in Japan, freshwater ecosystems near the site remained contaminated by radiocesium (RCs). Clarifying RCs concentrations in aquatic insects is crucial because fishes consume these insects that transfer RCs into freshwater ecosystems. As aquatic insects are usually measured for radioactivity in bulk samples of several tens of insects, variation in RCs concentration among individuals is not captured. In this study, we investigated the variability in 137Cs activity concentration in individual aquatic insects in detritivorous caddisfly (Stenopsyche marmorata) and carnivorous dobsonfly (Protohermes grandis) larvae from the Ota River, Fukushima. Caddisfly larvae showed sporadically higher radioactivity in 4 of the 46 caddisfly larvae, whereas no such outliers were observed in 45 dobsonfly larvae. Autoradiography and scanning electron microscopy analyses confirmed that these caddisfly larvae samples contained radiocesium-bearing microparticles (CsMPs), which are insoluble Cs-bearing silicate glass particles. CsMPs were also found in potential food sources of caddisfly larvae, such as periphyton and drifting particulate organic matter, indicating that larvae may ingest CsMPs along with food particles of similar size. Although CsMP distribution and uptake by organisms in freshwater ecosystems is relatively unknown, our study demonstrates that CsMPs can be taken up by aquatic insects.

Temporal variability of 137Cs concentrations in coastal sediments off Fukushima.

Large amounts of radiocesium were released into marine environments following the Fukushima Daiichi Nuclear Power Plant accident in March 2011. Released radiocesium influenced not only marine environment but also marine biota in Fukushima. Since marine biota as fisheries products is important for Japanese market, it is important to assess the distribution of radiocesium in coastal environment off Fukushima for safety concerns of radioactive contamination. Radiocesium concentrations in sediments are important for understanding fishing ground conditions and for proving the safety of fisheries products in Fukushima. In this study, monthly monitoring data collected from May 2011 to March 2020 were analyzed to describe the temporal variability of 137Cs concentrations in coastal sediments off Fukushima (total of 3647 samples from eight lines at depths of 7-125 m off Fukushima, and three sites in Matsukawa-ura Lagoon). The 137Cs concentration in sediment showed a decreasing trend, but our nonlinear model fitting suggested that this rate of decrease had slowed down. Additionally, 137Cs concentrations were up to 4.08 times greater in shallow sampling sites (7, 10, 20 m depth) following heavy rainfall events (before five months vs. after five months), such as typhoons. These observations were consistent with increasing input from particulate 137Cs fluxes from rivers and increasing dissolved 137Cs concentrations in seawater. Finally, our numerical modeling suggested that riverine 137Cs input could maintain 137Cs concentrations in coastal sediment. These results indicate that riverine 137Cs input following heavy rainfall events is the main factor for maintaining 137Cs concentrations in coastal sediments near the Fukushima Daiichi Nuclear Power Plant.

First isolation and analysis of caesium-bearing microparticles from marine samples in the Pacific coastal area near Fukushima Prefecture.

A part of the radiocaesium from the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident was emitted as glassy, water-resistant caesium-bearing microparticles (CsMPs). Here, we isolated and investigated seven CsMPs from marine particulate matter and sediment. From the elemental composition, the 134Cs/137Cs activity ratio, and the 137Cs activity per unit volume results, we inferred that the five CsMPs collected from particulate matter were emitted from Unit 2 of the FDNPP, whereas the two CsMPs collected from marine sediment were possibly emitted from Unit 3, as suggested by (i) the presence of calcium and absence of zinc and (ii) the direction of the atmospheric plume during the radionuclide emission event from Unit 3. The presence of CsMPs can cause overestimation of the solid-water distribution coefficient of Cs in marine sediments and particulate matter and a high apparent radiocaesium concentration factor for marine biota. CsMPs emitted from Unit 2, which were collected from the estuary of a river that flowed through a highly contaminated area, may have been deposited on land and then transported by the river. By contrast, CsMPs emitted from Unit 3 were possibly transported eastward by the wind and deposited directly onto the ocean surface.

Changes in radioactive cesium concentrations from 2011 to 2017 in Fukushima coastal sediments and relative contributions of radioactive cesium-bearing microparticles.

Sedimentary cesium-137 concentrations around the Fukushima Daiichi Nuclear Power Plant (FDNPP) were measured from 2011 to 2017 at eight stations. Although high values were observed until 2013, decreasing trends were observed at the surface sediments of seven stations. We isolated 25 radioactive Cs-bearing microparticles (CsMPs; 1.0-5385 Bq per particle). The contribution ratio of CsMPs to each sample ranged from 4.1% to 99.5% (median 58.8%), with the contribution ratio of the CsMPs in the southern part of the FDNPP was low compared to that from the northern part. In the southern part of the FDNPP, small CsMPs that could not be isolated in this study were present in large quantities immediately after the accident, and gradually diffused away and/or were dissolved over time. In contrast, the CsMPs in the northern part of the FDNPP have most likely accumulated over time, as suggested by the silty nature of the sediments there.

Characterization of two types of cesium-bearing microparticles emitted from the Fukushima accident via multiple synchrotron radiation analyses.

A part of radiocesium emitted during the Fukushima nuclear accident was incorporated in glassy water-resistant microparticles, called Type-A particles, which are spherical with ~ 0.1 to 10 µm diameter and ~ 10-2 to 102 Bq cesium-137 (137Cs) radioactivity; they were emitted from Unit 2 or 3 of the Fukushima Daiichi Nuclear Power Plant. Meanwhile, Type-B particles, having various shapes, 50-400 µm diameter, and 101-104 Bq 137Cs radioactivity, were emitted from Unit 1. The chemical properties of these radioactive particles have been reported in detail, but previous studies investigated only a small number of particles, especially Type-B particles. We tried to understand radioactive particles systematically by analyzing a large number of particles. Micro-X-ray computed tomography combined with X-ray fluorescence analysis revealed the presence of many voids and iron-rich part within Type-B particles. The 137Cs concentration (Bq mm-3) of Type-A particles was ~ 10,000 times higher than that of Type-B particles. Among the Type-B particles, the spherical ones had higher concentration of volatile elements than the non-spherical ones. These differences suggested that Type-A particles were formed through gas condensation, whereas Type-B particles were formed through melt solidification. These findings might contribute to the safe decommissioning of reactors and environmental impact assessment.

Isotopic ratios of uranium and caesium in spherical radioactive caesium-bearing microparticles derived from the Fukushima Dai-ichi Nuclear Power Plant.

Spherical radioactive caesium (Cs)-bearing microparticles (CsMPs) were emitted during the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident in March, 2011. The emission source (timing) and formation process of these particles remain unclear. In this study, the isotopic ratios of uranium (235U and 238U) and caesium (133Cs, 134Cs, 135Cs, and 137Cs) isotopes in the five spherical CsMPs (ca. 2 µm in size) sampled at 50 km west of the FDNPP were determined using secondary ion mass spectrometry and laser ablation-ICPMS, respectively. Results showed that the 235U/238U ratios of CsMPs were homogeneous (1.93 ± 0.03, N = 4) and close to those estimated for the fuel cores in units 2 and 3, and that the Cs isotopic ratios of CsMP were identical to those of units 2 and 3. These results indicated that U and Cs in the spherical CsMPs originated exclusively from the fuel melt in the reactors. Based on a thorough review of literatures related to the detailed atmospheric releases of radionuclides, the flow of plumes from the FDNPP reactor units during the accident and the U and Cs isotopic ratio results in this study, we hereby suggest that the spherical CsMPs originate only from the fuel in unit 2 on the night of 14 March to the morning of 15 March. The variation range of the analysed 235U/238U isotopic ratios for the four spherical particles was extremely narrow. Thus, U may have been homogenised in the source through the formation of fuel melt, which ultimately evaporating and taken into CsMPs in the reactor and was released from the unit 2.

A review of Cs-bearing microparticles in the environment emitted by the Fukushima Dai-ichi Nuclear Power Plant accident.

Scientists face challenge in identifying the radioactive materials which are found as dotted images on various imaging plate (IP) autoradiographic photos of radioactively contaminated materials by the Fukushima Dai-ichi Nuclear Power Plant (F1NPP, or FDNPP) accident, such as air filter, fugitive dust, surface soil, agricultural materials, and water-shed samples. It has been revealed that they are minute particles with distinct morphology and elemental composition with high specific radioactivity, and different from those of the so-called Chernobyl hot particles. Basically, they are glassy particles once molten, composed of Si, O, Fe, Zn etc. with highly concentrated radiocaesium, which can be called as radiocaesium-bearing microparticles (CsMP). At present, CsMP can be classified into two types, Types-A and -B, which are characterized by different specific radioactivity, 134Cs/137Cs ratio, size and morphology, and geographic distribution around F1NPP. Such studies on the CsMP from various aspects have provided valuable information about what happened in the nuclear reactors during the F1NPP accident and fates of the CsMP in the environment. This review first provides a retrospective view on the research history of the CsMP, which is helpful to understand the unique character of the CsMP. Subsequently, more details about the current understanding of the natures of these hot particles, such as origin, morphology, chemical compositions, thermal properties, water-solubility, and secondary migration of CsMP in river and ocean systems are described with future prospects.