"Invisible" radioactive cesium atoms revealed: Pollucite inclusion in cesium-rich microparticles (CsMPs) from the Fukushima Daiichi Nuclear Power Plant.

Understanding radioactive Cs contamination has been a central issue at Fukushima Daiichi and other nuclear legacy sites; however, atomic-scale characterization of radioactive Cs in environmental samples has never been achieved. Here we report, for the first time, the direct imaging of radioactive Cs atoms using high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). In Cs-rich microparticles collected from Japan, we document inclusions that contain 27 - 36 wt% of Cs (reported as Cs2O) in a zeolite: pollucite. The compositions of three pollucite inclusions are (Cs1.86K0.11Rb0.19Ba0.22)2.4(Fe0.85Zn0.84X0.31)2.0Si4.1O12, (Cs1.19K0.05Rb0.19Ba0.22)1.7(Fe0.66Zn0.32X0.41)1.4Si4.6O12, and (Cs1.27K0.21Rb0.29Ba0.15)1.9(Fe0.60Zn0.32X0.69)1.6Si4.4O12 (X includes other cations). HAADF-STEM imaging of pollucite, viewed along the [111] zone axis, revealed an array of Cs atoms, which is consistent with a simulated image using the multi-slice method. The occurrence of pollucite indicates that locally enriched Cs reacted with siliceous substances during the Fukushima meltdowns, presumably through volatilization and condensation. Beta radiation doses from the incorporated Cs are estimated to reach 106 - 107 Gy, which is more than three orders of magnitude less than typical amorphization dose of zeolite. The atomic-resolution imaging of radioactive Cs is an important advance for better understanding the fate of radioactive Cs inside and outside of nuclear reactors damaged by meltdown events.

Detecting radioactive particles in complex environmental samples using real-time autoradiography.

Radioactive particles often contain very high radioactivity concentrations and are widespread. They pose a potential risk to human health and the environment. Their detection, quantification, and characterization are crucial if we are to understand their impact. Here, we present the use of a real-time autoradiography gaseous detector (using parallel ionization multiplier) to expedite and improve the accuracy of radioactive particle screening in complex environmental samples. First, standard particles were used to assess the detector capabilities (spatial resolution, spectrometry, and artefact contributions), then, we applied the technique to more complex and environmentally relevant samples. The real-time autoradiography technique provides data with a spatial resolution (≲100 µm) suitable for particle analysis in complex samples. Further, it can differentiate between particles predominantly emitting alpha and beta radiation. Here, the technique is applied to radioactive cesium-rich microparticles collected from the Fukushima Daiichi nuclear exclusion zone, showing their accurate detection, and demonstrating the viability of real-time autoradiography in environmental scenarios. Indeed, for more complex samples (radioactive particles in a less radioactive heterogeneous background mix of minerals), the technique permits relatively high selectivity for radioactive particle screening (up to 61.2% success rate) with low false positive percentages (~ 1%).

Occurrence of radioactive cesium-rich micro-particles (CsMPs) in a school building located 2.8 km south-west of the Fukushima Daiichi Nuclear Power Plant.

Radioactive Cs-rich microparticles (CsMPs) released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) are a potential health risk through inhalation. Little has been documented on the occurrence of CsMPs, particularly their occurrence inside buildings. In this study, we quantitatively analyze the distribution and number of CsMPs in indoor dust samples collected from an elementary school located 2.8 km to the southwest of FDNPP. The school had remained deserted until 2016. Then, using a modified version of the autoradiography-based "quantifying CsMPs (mQCP) method," we collected samples and determined the number of CsMPs and Cs radioactive fraction (RF) values of the microparticles (defined as total Cs activity from CsMPs/bulk Cs activity of the entire sample). The numbers of CsMPs ranged from 653 to 2570 particles/(g dust) and 296-1273 particles/(g dust) on the first and second floors of the school, respectively. The corresponding RFs ranged between 6.85 - 38.9% and 4.48-6.61%, respectively. The number of CsMPs and RF values in additional outdoor samples collected near the school building were 23-63 particles/(g dust or soil) and 1.14-1.61%, respectively. The CsMPs were most abundant on the school's first floor near to the entrance, and the relative abundance was higher near the stairs on the second floor, indicating a likely CsMP dispersion path through the building. Additional wetting of the indoor samples combined with autoradiography revealed that indoor dusts had a distinct absence of intrinsic, soluble Cs species, such as CsOH. These combined observations indicate that a significant amount of poorly soluble CsMPs were likely contained in initial radioactive airmass plumes from the FDNPP and that the microparticles penetrated buildings. CsMPs could still be abundant at the location, with locally high Cs activity in indoor environments near to openings.

Volatilization of B4C control rods in Fukushima Daiichi nuclear reactors during meltdown: B-Li isotopic signatures in cesium-rich microparticles.

Boron carbide control rods remain in the fuel debris of the damaged reactors in the Fukushima Daiichi Nuclear Power Plant, potentially preventing re-criticality; however, the state and stability of the control rods remain unknown. Sensitive high-resolution ion microprobe analyses have revealed B-Li isotopic signatures in radioactive Cs-rich microparticles (CsMPs) that formed by volatilization and condensation of Si-oxides during the meltdowns. The CsMPs contain 1518-6733 mg kg-1 of 10+11B and 11.99-1213 mg kg-1 of 7Li. The 11B/10B (4.15-4.21) and 7Li/6Li (213-406) isotopic ratios are greater than natural abundances (~4.05 and ~12.5, respectively), indicating that 10B(n,α)7Li reactions occurred in B4C prior to the meltdowns. The total amount of B released with CsMPs was estimated to be 0.024-62 g, suggesting that essentially all B remains in reactor Units 2 and/or 3 and is enough to prevent re-criticality; however, the heterogeneous distribution of B needs to be considered during decommissioning.