"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%).

Improved Radio-Cesium Detection Using Quantitative Real-Time Autoradiography.

Cesium-134 and -137 are prevalent, long-lived, radio-toxic contaminants released into the environment during nuclear accidents. Large quantities of insoluble, respirable Cs-bearing microparticles (CsMPs) were released into the environment during the Fukushima Daiichi nuclear accident. Monitoring for CsMPs in environmental samples is essential to understand the impact of nuclear accidents. The current detection method used to screen for CsMPs (phosphor screen autoradiography) is slow and inefficient. We propose an improved method: real-time autoradiography that uses parallel ionization multiplier gaseous detectors. This technique permits spatially resolved measurement of radioactivity while providing spectrometric data from spatially heterogeneous samples-a potential step-change technique for use after nuclear accidents for forensic analysis. With our detector configuration, the minimum detectable activities are sufficiently low for detecting CsMPs. Further, for environmental samples, sample thickness does not detrimentally affect detector signal quality. The detector can measure and resolve individual radioactive particles ≥465 µm apart. Real-time autoradiography is a promising tool for radioactive particle detection.

Chemical species of cesium and iodine in condensed vaporized microparticles formed by melting nuclear fuel components with concrete materials.

In this study, we report chemical species of Cs and I in condensed vaporized particles (CVPs) produced by melting experiments using nuclear fuel components containing CsI with concrete. Analyses of CVPs by SEM with EDX showed the formation of many round particles containing Cs and I of diameters less than ∼20 µm. X-ray absorption near-edge-structure and SEM-EDX analyses showed two kinds of particles: one containing large amounts of Cs and I, suggesting the presence of CsI, and the other containing small amounts of Cs and I with large Si content. When CVSs were placed in contact with deionized water, most of the CsI from both particles was dissolved. In contrast, some fractions of Cs remained from the latter particles and possessed different chemical species from CsI. In addition, the remaining Cs was concomitantly present with Si, resembling chemical components in the highly radioactive cesium-rich microparticles (CsMPs) released by nuclear plant accidents into the surrounding environments. These results strongly suggest that Cs was incorporated in CVSs along with Si by melting nuclear fuel components to form sparingly-soluble CVMPs.

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.

Direct observation of Mn distribution/speciation within and surrounding a basidiomycete fungus in the production of Mn-oxides important in toxic element containment.

Biogenic manganese (Mn) oxides occur ubiquitously in the environment including the uranium (U) mill tailings at the Ningyo-toge U mine in Okayama, Japan, being important in the sequestration of radioactive radium. To understand the nanoscale processes in Mn oxides formation at the U mill tailings site, Mn2+ absorption by a basidiomycete fungus, Coprinopsis urticicola, isolated from Ningyo-toge mine water samples, was investigated in the laboratory under controlled conditions utilizing electron microscopy, synchrotron-based X-ray analysis, and fluorescence microscopy with a molecular pH probe. The fungus' growth was first investigated in an agar-solidified medium supplemented with 1.0 mmol/L Mn2+, and Cu2+ (0-200 µM), Zn2+ (0-200 µM), or diphenyleneiodonium (DPI) chloride (0-100 µM) at 25 °C. The results revealed that Zn2+ has no significant effects on Mn oxide formation, whereas Cu2+ and DPI significantly inhibit both fungal growth and Mn oxidation, indicating superoxide-mediated Mn oxidation. Indeed, nitroblue tetrazolium and diaminobenzidine assays on the growing fungus revealed the production of superoxide and peroxide. During the interaction of Mn2+ with the fungus in solution medium at the initial pH of 5.67, a small fraction of Mn2+ infiltrated the fungal hyphae within 8 h, forming a few tens of nm-sized concentrates of soluble Mn2+ in the intracellular pH of ∼6.5. After 1 day of incubation, Mn oxides began to precipitate on the hyphae, which were characterized as fibrous nanocrystals with a hexagonal birnessite-structure, these forming spherical aggregates with a diameter of ∼1.5 µm. These nanoscale processes associated with the fungal species derived from the Ningyo-toge mine area provide additional insights into the existing mechanisms of Mn oxidation by filamentous fungi at other U mill tailings sites under circumneutral pH conditions. Such processes add to the class of reactions important to the sequestration of toxic elements.

Gravitational separation of 137Cs contaminated soil in Fukushima environment: Density dependence of 137Cs activity and application to volume reduction.

Behavior of radiocesium in Fukushima after its deposition is mainly controlled by mobility of soil components, of which the density is one of the parameters governing the mobility; however, little information is available on the density of soil components associated with radiocesium in environment. Furthermore, the reduction of the volume of radiocesium-contaminated soil in the interim storage is highly demanded. In this study, we developed a gravitational separation method using a sodium polytungstate (SPT) solution combined with size fractionation to understand the relation between 137Cs activity and the density of surface soil components and evaluate the feasibility of the method for the volume reduction of the contaminated soil. In all soil samples examined, 137Cs concentration of the small size (<0.063 mm) and high-density (2.4-2.8 g cm-3) fraction was the highest among the separated fractions, whereas most of the radiocesium-rich micro-particles were distributed in the small size (<0.063 mm) and low density (<2.4 g cm-3) fraction. Although ultrasonication improved the size separation efficiency, a single-step gravitational separation method using an SPT solution with a density of 2.4 g cm-3 without size separation and ultrasonication revealed that the 137Cs concentration on 50°C-dry weight basis in the dense (>2.4 g cm-3) fraction was 25.6-82.7% lower than that of the bulk sample for all soil samples. In particular, for the samples with a bulk 137Cs concentration of 29.6 Bq g-1 50°C-dry weight, the 137Cs concentration in the fraction was below the safety treatment requirement (i.e., 8 Bq g-1). Therefore, single-step gravitational separation may be used for the volume reduction of contaminated soils.

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.

New highly radioactive particles derived from Fukushima Daiichi Reactor Unit 1: Properties and environmental impacts.

A contaminated zone elongated toward Futaba Town, north-northwest of the Fukushima Daiichi Nuclear Power Plant (FDNPP), contains highly radioactive particles released from reactor Unit 1. There are uncertainties associated with the physio-chemical properties and environmental impacts of these particles. In this study, 31 radioactive particles were isolated from surface soils collected 3.9 km north-northwest of the FDNPP. Two of these particles have the highest particle-associated 134+137Cs activity ever reported for Fukushima (6.1 × 105 and 2.5 × 106 Bq per particle after decay-correction to March 2011). The new, highly-radioactive particle labeled FTB1 is an aggregate of flaky silicate nanoparticles with an amorphous structure containing ~0.8 wt% Cs, occasionally associated with SiO2 and TiO2 inclusions. FTB1 likely originates from the reactor building, which was damaged by a H2 explosion, after adsorbing volatilized Cs. The 134+137Cs activity in the other highly radioactive particle labeled FTB26 exceeded 106 Bq. FTB26 has a glassy carbon core and a surface that is embedded with numerous micro-particles: Pb-Sn alloy, fibrous Al-silicate, Ca-carbonate or hydroxide, and quartz. The isotopic signatures of the micro-particles indicate neutron capture by B, Cs volatilization, and adsorption of natural Ba. The composition of the micro-particles on FTB26 reflects the composition of airborne particles at the moment of the H2 explosion. Owing to their large size, the health effects of the highly radioactive particles are likely limited to external radiation during static contact with skin; the highly radioactive particles are thus expected to have negligible health impacts for humans. By investigating the mobility of the highly radioactive particles, we can better understand how the radiation dose transfers through environments impacted by Unit 1. The highly radioactive particles also provide insights into the atmospheric conditions at the time of the Unit 1 explosion and the physio-chemical phenomena that occurred during reactor meltdown.

Occurrence of highly radioactive microparticles in the seafloor sediment from the pacific coast 35 km northeast of the Fukushima Daiichi nuclear power plant.

To understand the properties and significance of highly radioactive particles in the marine environment, we have examined seafloor sediment with a radioactivity of ∼1200 Bq/kg (dry weight; after decay correction to March 2011) collected 35 km northeast of the Fukushima Daiichi Nuclear Power Plant (FDNPP). Among the 697 highly radioactive particles separated from the sediment, two particles, D1-MAX and D1-MID, had a total Cs radioactivity of ∼56 and 0.67 Bq (after decay correction to March 2011), respectively. These particles were characterized with a variety of electron microscopic techniques, including transmission electron microscopy. The 134Cs/137Cs radioactivity ratio of D1-MAX, 1.04, was comparable to that calculated for Unit 2 or 3. D1-MAX consisted mainly of a Cs-rich microparticle (CsMP) with a silica glass matrix. The data clearly suggested that D1-MAX resulted from a molten core-concrete interaction during meltdowns. In contrast, D1-MID was an aggregate of plagioclase, quartz, anatase, and Fe-oxide nanoparticles as well as clay minerals, which had adsorbed soluble Cs. D1-MID was likely a terrestrial particle that had been transported by wind and/or ocean currents to a site 35 km from the FDNPP. The radioactive fractions of D1-MAX and D1-MID were 15% and 0.36%, respectively, of the total radioactivity in the bulk sediment. These highly radioactive particles have a great impact on the movement of radioactive Cs in the marine environment by carrying condensed Cs radioactivity with various colloidal and desorption properties depending on the host phase.

Organic complexation of U(VI) in reducing soils at a natural analogue site: Implications for uranium transport.

Understanding the long-term fate, stability, and bioavailability of uranium (U) in the environment is important for the management of nuclear legacy sites and radioactive wastes. Analysis of U behavior at natural analogue sites permits evaluation of U biogeochemistry under conditions more representative of long-term equilibrium. Here, we have used bulk geochemical and microbial community analysis of soils, coupled with X-ray absorption spectroscopy and µ-focus X-ray fluorescence mapping, to gain a mechanistic understanding of the fate of U transported into an organic-rich soil from a pitchblende vein at the UK Needle's Eye Natural Analogue site. U is highly enriched in the Needle's Eye soils (∼1600 mg kg-1). We show that this enrichment is largely controlled by U(VI) complexation with soil organic matter and not U(VI) bioreduction. Instead, organic-associated U(VI) seems to remain stable under microbially-mediated Fe(III)-reducing conditions. U(IV) (as non-crystalline U(IV)) was only observed at greater depths at the site (>25 cm); the soil here was comparatively mineral-rich, organic-poor, and sulfate-reducing/methanogenic. Furthermore, nanocrystalline UO2, an alternative product of U(VI) reduction in soils, was not observed at the site, and U did not appear to be associated with Fe-bearing minerals. Organic-rich soils appear to have the potential to impede U groundwater transport, irrespective of ambient redox conditions.

Particulate plutonium released from the Fukushima Daiichi meltdowns.

Traces of Pu have been detected in material released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) in March of 2011; however, to date the physical and chemical form of the Pu have remained unknown. Here we report the discovery of particulate Pu associated with cesium-rich microparticles (CsMPs) that formed in and were released from the reactors during the FDNPP meltdowns. The Cs-pollucite-based CsMP contained discrete U(IV)O2 nanoparticles, <~10 nm, one of which is enriched in Pu adjacent to fragments of Zr-cladding. The isotope ratios, 235U/238U, 240Pu/239Pu, and 242Pu/239Pu, of the CsMPs were determined to be ~0.0193, ~0.347, and ~0.065, respectively, which are consistent with the calculated isotopic ratios of irradiated-fuel fragments. Thus, considering the regional distribution of CsMPs, the long-distance dispersion of Pu from FNDPP is attributed to the transport by CsMPs that have incorporated nanoscale fuel fragments prior to their dispersion up to 230 km away from the Fukushima Daiichi reactor site.

Abundance and distribution of radioactive cesium-rich microparticles released from the Fukushima Daiichi Nuclear Power Plant into the environment.

The abundance and distribution of highly radioactive cesium-rich microparticles (CsMPs) that were released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) during the first stage of the nuclear disaster in March 2011 are described for 20 surface soils collected around the FDNPP. Based on the spatial distribution of the numbers (particles/g) and radioactive fraction (RF) of the CsMPs in surface soil, which is defined as the sum of the CsMP radioactivity (in Bq) divided by the total radioactivity (in Bq) of the soil sample, three regions of particular interest have been identified: i.) near-northwest (N-NW), ii.) far-northwest (F-NW), and iii.) southwest (SW). In these areas, the number and RF of CsMPs were determined to be 22.1-101 particles/g and 15.4-34.0%, 24.3-64.8 particles/g and 36.7-37.4%, and 0.869-8.00 particles/g and 27.6-80.2%, respectively. These distributions are consistent with the plume trajectories of material released from the FDNPP on March 14, 2011, in the late afternoon through to the late afternoon of March 15, 2011, indicating that the CsMPs formed only during this short period. Unit 3 is the most plausible source of the CsMPs at the beginning of the release based on an analysis of the sequence of release events. The lower RF values in the N-NW region indicate a larger influence from subsequent plumes that mainly consisted of soluble Cs species formed simultaneously with precipitation. The quantitative map of the distribution of CsMPs provides an important understanding of CsMP dispersion dynamics and can be used to assess risks in inhabited regions.

Metaschoepite Dissolution in Sediment Column Systems-Implications for Uranium Speciation and Transport.

Metaschoepite is commonly found in U-contaminated environments and metaschoepite-bearing wastes may be managed via shallow or deep disposal. Understanding metaschoepite dissolution and tracking the fate of any liberated U is thus important. Here, discrete horizons of metaschoepite (UO3·nH2O) particles were emplaced in flowing sediment/groundwater columns representative of the UK Sellafield Ltd. site. The column systems either remained oxic or became anoxic due to electron donor additions, and the columns were sacrificed after 6- and 12-months for analysis. Solution chemistry, extractions, and bulk and micro/nano-focus X-ray spectroscopies were used to track changes in U distribution and behavior. In the oxic columns, U migration was extensive, with UO22+ identified in effluents after 6-months of reaction using fluorescence spectroscopy. Unusually, in the electron-donor amended columns, during microbially mediated sulfate reduction, significant amounts of UO2-like colloids (>60% of the added U) were found in the effluents using TEM. XAS analysis of the U remaining associated with the reduced sediments confirmed the presence of trace U(VI), noncrystalline U(IV), and biogenic UO2, with UO2 becoming more dominant with time. This study highlights the potential for U(IV) colloid production from U(VI) solids under reducing conditions and the complexity of U biogeochemistry in dynamic systems.

Dissolution of radioactive, cesium-rich microparticles released from the Fukushima Daiichi Nuclear Power Plant in simulated lung fluid, pure-water, and seawater.

To understand the chemical durability of highly radioactive cesium-rich microparticles (CsMPs) released from the Fukushima Daiichi Nuclear Power Plant in March 2011, we have, for the first time, performed systematic dissolution experiments with CsMPs isolated from Fukushima soils (one sample with 108 Bq and one sample with 57.8 Bq of 137Cs) using three types of solutions: simulated lung fluid, ultrapure water, and artificial sea water, at 25 and 37 °C for 1-63 days. The 137Cs was released rapidly within three days and then steady-state dissolution was achieved for each solution type. The steady-state 137Cs release rate at 25 °C was determined to be 4.7 × 103, 1.3 × 103, and 1. 3 × 103 Bq·m-2 s-1 for simulated lung fluid, ultrapure water, and artificial sea water, respectively. This indicates that the simulated lung fluid promotes the dissolution of CsMPs. The dissolution of CsMPs is similar to that of Si-based glass and is affected by the surface moisture conditions. In addition, the Cs release from the CsMPs is constrained by the rate-limiting dissolution of silicate matrix. Based on our results, CsMPs with ∼2 Bq, which can be potentially inhaled and deposited in the alveolar region, are completely dissolved after >35 years. Further, CsMPs could remain in the environment for several decades; as such, CsMPs are important factors contributing to the long-term impacts of radioactive Cs in the environment.

Calcium molybdate nanoparticles formation in egg phosphatidyl choline based liposome caused by liposome fusion.

In order to achieve the highly efficient 99mTc production from 100MoO3 by the 100Mo(n, 2n)99Mo reaction, we have developed a new protocol to synthesize nano-sized Mo particles, of which the size was controlled by the inner space of the liposomes. Calcium and molybdate ions were encapsulated into ∼100 nm size liposomes. The liposome suspensions were then mixed and heated to promote the membrane fusion. As a result, the insoluble CaMoO4 nanoparticles precipitated inside the liposomes. The median particle diameter of 168 nm and average diameter of 169 ±â€¯56 nm (n = 109) were obtained from an SEM image, and the particles have a powellite-structure. The formation process of the particles was then examined. The formation of nano-sized CaMoO4 was observed by the high resolution TEM image and TEM image of negative-stained liposome. At the room temperature, the fusion of liposome did not occur significantly. These results suggest that nanocrystals of the CaMoO4 were likely formed in the liposomes because of the liposome fusion and aggregated during the drying processes of reaction solution.

Novel Method of Quantifying Radioactive Cesium-Rich Microparticles (CsMPs) in the Environment from the Fukushima Daiichi Nuclear Power Plant.

Highly radioactive cesium-rich microparticles (CsMPs) were released from the Fukushima Daiichi nuclear power plant (FDNPP) to the surrounding environment at an early stage of the nuclear disaster in March of 2011; however, the quantity of released CsMPs remains undetermined. Here, we report a novel method to quantify the number of CsMPs in surface soils at or around Fukushima and the fraction of radioactivity they contribute, which we call "quantification of CsMPs" (QCP) and is based on autoradiography. Here, photostimulated luminescence (PSL) is linearly correlated to the radioactivity of various microparticles, with a regression coefficient of 0.0523 becquerel/PSL/h (Bq/PSL/h). In soil collected from Nagadoro, Fukushima, Japan, CsMPs were detected in soil sieved with a 114 µm mesh. There was no overlap between the radioactivities of CsMPs and clay particles adsorbing Cs. Based on the distribution of radioactivity of CsMPs, the threshold radioactivity of CsMPs in the size fraction of <114 µm was determined to be 0.06 Bq. Based on this method, the number and radioactivity fraction of CsMPs in four surface soils collected from the vicinity of the FDNPP were determined to be 48-318 particles per gram and 8.53-31.8%, respectively. The QCP method is applicable to soils with a total radioactivity as high as ∼106 Bq/kg. This novel method is critically important and can be used to quantitatively understand the distribution and migration of the highly radioactive CsMPs in near-surface environments surrounding Fukushima.

The competing effects of microbially derived polymeric and low molecular-weight substances on the dispersibility of CeO2 nanoparticles.

To understand the competing effects of the components in extracellular substances (ES), polymeric substances (PS) and low-molecular-weight small substances (SS) <1 kDa derived from microorganisms, on the colloidal stability of cerium dioxide nanoparticles (CeNPs), we investigated their adsorption to sparingly soluble CeNPs at room temperature at pH 6.0. The ES was extracted from the fungus S. cerevisiae. The polypeptides and phosphates in all components preferentially adsorbed onto the CeNPs. The zeta potentials of ES + CeNPs, PS + CeNPs, and SS + CeNPs overlapped on the plot of PS itself, indicating the surface charge of the polymeric substances controls the zeta potentials. The sizes of the CeNP aggregates, 100-1300 nm, were constrained by the zeta potentials. The steric barrier derived from the polymers, even in SS, enhanced the CeNP dispersibility at pH 1.5-10. Consequently, the PS and SS had similar effects on modifying the CeNP surfaces. The adsorption of ES, which contains PS + SS, can suppress the aggregation of CeNPs over a wider pH range than that for PS only. The present study addresses the non-negligible effects of small-sized molecules derived from microbial activity on the migration of CeNP in aquatic environments, especially where bacterial consortia prevail.

Uranium Dioxides and Debris Fragments Released to the Environment with Cesium-Rich Microparticles from the Fukushima Daiichi Nuclear Power Plant.

Trace U was released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) during the meltdowns, but the speciation of the released components of the nuclear fuel remains unknown. We report, for the first time, the atomic-scale characteristics of nanofragments of the nuclear fuels that were released from the FDNPP into the environment. Nanofragments of an intrinsic U-phase were discovered to be closely associated with radioactive cesium-rich microparticles (CsMPs) in paddy soils collected ∼4 km from the FDNPP. The nanoscale fuel fragments were either encapsulated by or attached to CsMPs and occurred in two different forms: (i) UO2+X nanocrystals of ∼70 nm size, which are embedded into magnetite associated with Tc and Mo on the surface and (ii) Isometric (U,Zr)O2+X nanocrystals of ∼200 nm size, with the U/(U+Zr) molar ratio ranging from 0.14 to 0.91, with intrinsic pores (∼6 nm), indicating the entrapment of vapors or fission-product gases during crystallization. These results document the heterogeneous physical and chemical properties of debris at the nanoscale, which is a mixture of melted fuel and reactor materials, reflecting the complex thermal processes within the FDNPP reactor during meltdown. Still CsMPs are an important medium for the transport of debris fragments into the environment in a respirable form.

Removal of Soluble Strontium via Incorporation into Biogenic Carbonate Minerals by Halophilic Bacterium Bacillus sp. Strain TK2d in a Highly Saline Solution.

Radioactive strontium (90Sr) leaked into saline environments, including the ocean, from the Fukushima Daiichi Nuclear Power Plant after a nuclear accident. Since the removal of 90Sr using general adsorbents (e.g., zeolite) is not efficient at high salinity, a suitable alternative immobilization method is necessary. Therefore, we incorporated soluble Sr into biogenic carbonate minerals generated by urease-producing microorganisms from a saline solution. An isolate, Bacillus sp. strain TK2d, from marine sediment removed >99% of Sr after contact for 4 days in a saline solution (1.0 × 10-3 mol liter-1 of Sr, 10% marine broth, and 3% [wt/vol] NaCl). Transmission electron microscopy and energy-dispersive X-ray spectroscopy showed that Sr and Ca accumulated as phosphate minerals inside the cells and adsorbed at the cell surface at 2 days of cultivation, and then carbonate minerals containing Sr and Ca developed outside the cells after 2 days. Energy-dispersive spectroscopy revealed that Sr, but not Mg, was present in the carbonate minerals even after 8 days. X-ray absorption fine-structure analyses showed that a portion of the soluble Sr changed its chemical state to strontianite (SrCO3) in biogenic carbonate minerals. These results indicated that soluble Sr was selectively solidified into biogenic carbonate minerals by the TK2d strain in highly saline environments.IMPORTANCE Radioactive nuclides (134Cs, 137Cs, and 90Sr) leaked into saline environments, including the ocean, from the Fukushima Daiichi Nuclear Power Plant accident. Since the removal of 90Sr using general adsorbents, such as zeolite, is not efficient at high salinity, a suitable alternative immobilization method is necessary. Utilizing the known concept that radioactive 90Sr is incorporated into bones by biomineralization, we got the idea of removing 90Sr via incorporation into biominerals. In this study, we revealed the ability of the isolated ureolytic bacterium to remove Sr under high-salinity conditions and the mechanism of Sr incorporation into biogenic calcium carbonate over a longer duration. These findings indicated the mechanism of the biomineralization by the urease-producing bacterium and the possibility of the biomineralization application for a new purification method for 90Sr in highly saline environments.