Selective Separation of Radiocesium from Complex Aqueous Matrices Using Dual Solid-Phase Extraction Systems.

The release of radiocesium (r-Cs) into natural aqueous systems is of concern because of its extended solubility as an alkaline metal ion and its facile incorporation into living beings. A technique for the selective separation of Cs from an aqueous matrix using dual solid-phase extraction (SPE) systems in a series is proposed in this paper. The SPEs equipped with chelates (Nobias Chelate-PA1 and Nobias Chelate-PB1), an ion-exchange resin (Nobias Ion SC-1), or macrocycles (MetaSEP AnaLig Cs-01 and MetaSEP AnaLig Cs-02) were evaluated in terms of selectivity and retention/recovery behavior toward Cs and other potentially competing ions (Li, Na, K, Rb, Ba, Ca, Mg, and Sr). The simulated solution of 133Cs, a chemical analog of r-Cs, was used to optimize the separation process. Operating parameters such as pH (3-13), flow rate (0.2-5.0 mL min-1), and elution behavior (HCl, 0.1-5.0 mol L-1) were optimized to ensure maximum removal of Cs from the aqueous matrices. The dual SPE system comprised Nobias Chelate-PB1 that minimized the competing impact of ions, while selective Cs retention was attained with MetaSEP AnaLig Cs-02. The proposed process was verified using real r-Cs-contaminated water from Fukushima, Japan, to observe the quantitative separation and preconcentration of r-Cs from the complex matrices.

Radiocaesium accumulation capacity of epiphytic lichens and adjacent barks collected at the perimeter boundary site of the Fukushima Dai-ichi Nuclear Power Station.

We investigated the radiocaesium content of nine epiphytic foliose lichens species and the adjacent barks of Zelkova serrata (Ulmaceae, "Japanese elm") and Cerasus sp. (Rosaceae, "Cherry tree") at the boundary of the Fukushima Dai-ichi Nuclear Power Station six years after the accident in 2011. Caesium-137 activities per unit area (the 137Cs-inventory) were determined to compare radiocaesium retentions of lichens (65 specimens) and barks (44 specimens) under the same growth conditions. The 137Cs-inventory of lichens collected from Zelkova serrata and Cerasus sp. were respectively 7.9- and 3.8-times greater than the adjacent barks. Furthermore, we examined the radiocaesium distribution within these samples using autoradiography and on the surfaces with an electron probe micro analyzer (EPMA). Autoradiographic results showed strong local spotting and heterogeneous distributions of radioactivity in both the lichen and bark samples, although the intensities were lower in the barks. The electron microscopy analysis demonstrated that particulates with similar sizes and compositions were distributed on the surfaces of the samples. We therefore concluded that the lichens and barks could capture fine particles, including radiocaesium particles. In addition, radioactivity was distributed more towards the inwards of the lichen samples than the peripheries. This suggests that lichen can retain 137Cs that is chemically immobilised in particulates intracellularly, unlike bark.

Non-invasive imaging of radiocesium dynamics in a living animal using a positron-emitting 127Cs tracer.

Visualizing the dynamics of cesium (Cs) is desirable to understand the impact of radiocesium when accidentally ingested or inhaled by humans. However, visualization of radiocesium in vivo is currently limited to plants. Herein, we describe a method for the production and purification of 127Cs and its use in visualizing Cs dynamics in a living animal. The positron-emitting nuclide 127Cs was produced using the 127I (α, 4n) 127Cs reaction, which was induced by irradiation of sodium iodide with a 4He2+ beam from a cyclotron. We excluded sodium ions by using a material that specifically adsorbs Cs as a purification column and successfully eluted 127Cs by flowing a solution of ammonium sulfate into the column. We injected the purified 127Cs tracer solution into living rats and the dynamics of Cs were visualized using positron emission tomography; the distributional images showed the same tendency as the results of previous studies using disruptive methods. Thus, this method is useful for the non-invasive investigation of radiocesium in a living animal.

Radiocesium concentrations in mushrooms collected in Kawauchi Village five to eight years after the Fukushima Daiichi Nuclear Power Plant accident.

Following the Fukushima Daiichi Nuclear Power Plant accident in March 2011, radionuclides such as iodine-131, cesium-134 and cesium-137 were released into environment. In this study, we collected wild mushrooms from the Kawauchi Village of Fukushima Prefecture, located less than 30 km southwest of the Fukushima nuclear power plant, to evaluate their radiocesium (134Cs+137Cs) concentrations and the risk of internal radiation exposure in local residents. 342 mushroom samples were collected from 2016 to 2019. All samples were analysed for radiocesium content by a high-purity germanium detector. Among 342 mushroom samples, 260 mushroom samples (76%) were detected the radiocesium exceeding the regulatory limit of radiocesium (100 Bq/kg for general foods in Japan). The median of committed effective dose from ingestion of wild mushrooms was in the range of 0.015-0.053 mSv in 2016, 0.0025-0.0087 mSv in 2017, 0.029-0.110 mSv in 2018 and 0.011-0.036 mSv in 2019 based on the assumption that Japanese citizens consumed wild mushrooms for 1 year. Thus, our study showed that although radiocesium is still detected in mushrooms collected in Kawauchi village even after 5 to 9 years later, the committed effective dose due to consuming mushrooms was lower than 1 mSv per year. Long-term comprehensive follow-up should monitor radiocesium concentrations in wild mushrooms to support the recovery of the community after the nuclear disaster.

Removal of radioactive cesium from an aqueous solution via bioaccumulation by microalgae and magnetic separation.

We evaluated the potential sequestration of cesium (Cs+) by microalgae under heterotrophic growth conditions in an attempt to ultimately develop a system for treatment of radioactive wastewater. Thus, we examined the effects of initial Cs+ concentration (100-500 µM), pH (5-9), K+ and Na+ concentrations (0-20 mg/L), and different organic carbon sources (acetate, glycerol, glucose) on Cs+ removal. Our initial comparison of nine microalgae indicated that Desmodesmus armatus SCK had removed the most Cs+ under various environmental conditions. Addition of organic substrates significantly enhanced Cs+ uptake by D. armatus, even in the presence of a competitive cation (K+). We also applied magnetic nanoparticles coated with a cationic polymer (polyethylenimine) to separate 137Cs-containing microalgal biomass under a magnetic field. Our technique of combining bioaccumulation and magnetic separation successfully removed more than 90% of the radioactive 137Cs from an aqueous medium. These results clearly demonstrate that the method described here is a promising bioremediation technique for treatment of radioactive liquid waste.

Comparison of 0.1 M Stable CsCl and 1 M NH4NO3 as an Extraction Reagent to Evaluate Cs-137 Mobility in Soils.

To evaluate the mobility and bioavailability of 137Cs in soils, we compared the extraction of 137Cs with stable Cs and ammonium solutions from 137Cs-contaminated minerals and soils. The extraction yields of 137Cs with stable Cs were significantly lower than those with ammonium for minerals with frayed edge sites, but such differences were not observed for minerals without frayed edge sites. The amount of 137Cs extracted with stable Cs from soils was lower than, or equal to, that extracted with ammonium. The above results suggest that stable Cs extracted the 137Cs from easily accessible sites. Plant available 137Cs was assessed using Kochia (Bassia scoparia) cultivated in pots of contaminated soils, and compared with soil parameters including extractable 137Cs and K, and radiocesium intercept potential. The 137Cs/K ratio extracted with stable Cs solution was found to be a potential index for evaluation of the easily mobile and bioavailable fraction of 137Cs in soil.

Remediation of 137Cs-contaminated concrete rubble by supercritical CO2 extraction.

The removal of cesium contamination is a critical issue for the recycling of concrete rubble in most decommissioning operations. The high solvent strength and diffusivity of supercritical CO2 make it an attractive choice as vector for extractant system in this context. Experimental extraction runs have been carried out in a radioactive environment on rubble contaminated with 137Cs. The best extraction system was found to be CalixOctyl (25,27-Bis(1-octyloxy)calix[4]arene-crown-6, 1,3-alternate) with pentadecafluorooctanoic acid as a modifier. The effects of various operating parameters were investigated, namely the coarseness of rubble, the temperature of supercritical CO2, the residual water and initial cesium concentrations, and the amounts of extractant and modifier used. The yields from direct extraction were low (<30%), because of the virtually irreversible sorption of Cs in concrete. The best extraction yield of ∼55% was achieved by leaching concrete rubble with nitric acid prior to supercritical CO2 extraction.

Spatial variations of tritium concentrations in groundwater collected in the southern coastal region of Fukushima, Japan, after the nuclear accident.

Spatial variations in tritium concentrations in groundwater were identified in the southern part of the coastal region in Fukushima Prefecture, Japan. Higher tritium concentrations were measured at wells near the Fukushima Daiichi Nuclear Power Station (F1NPS). Mean tritium concentrations in precipitation in the 5 weeks after the F1NPS accident were estimated to be 433 and 139 TU at a distance of 25 and 50 km, respectively, from the F1NPS. The elevations of tritium concentrations in groundwater were calculated using a simple mixing model of the precipitation and groundwater. By assuming that these precipitation was mixed into groundwater with a background tritium concentration in a hypothetical well, concentrations of 13 and 7 TU at distances of 25 and 50 km from the F1NPS, respectively, were obtained. The calculated concentrations are consistent with those measured at the studied wells. Therefore, the spatial variation in tritium concentrations in groundwater was probably caused by precipitation with high tritium concentrations as a result of the F1NPS accident. However, the highest estimated tritium concentrations in precipitation for the study site were much lower than the WHO limits for drinking water, and the concentrations decreased to almost background level at the wells by mixing with groundwater.

Sodium-copper hexacyanoferrate-functionalized magnetic nanoclusters for the highly efficient magnetic removal of radioactive caesium from seawater.

Sodium-copper hexacyanoferrate (NaCuHCF)-functionalized magnetic nanoadsorbents were fabricated for the highly efficient magnetic removal of radioactive caesium from seawater. The magnetic nanoclusters (MNCs), composed of many individual Fe3O4 nanoparticles, were covalently coated with polyethyleneimine (PEI) to functionalize the MNC surfaces with NaCuHCF. After simple immobilization of Cu and Na ferrocyanide on the NC surface, the resulting NaCuHCF-functionalized MNCs showed good magnetic properties and a significant adsorption capacity for Cs+ with a high content of NaCuHCF (36.04%). The adsorption kinetics and isotherms were well fit to a pseudo-second-order model and Langmuir isotherm, respectively. The sorption of 97.35% Cs by the NaCuHCF-PEI-MNCs completed in less than 5 min, and the maximum adsorption capacity of the adsorbent was 166.67 mg/g. The NaCuHCF-PEI-MNCs selectively adsorbed Cs even in the presence of various competing ions, such as Na, K, Mg, and Ca, and the Cs removal mechanism was revealed as ion exchange between Cs in solution and Na in the NaCuHCF-PEI-MNCs. In radioactive tests, our adsorbent displayed excellent removal performance in real seawater with a high removal efficiency exceeding 99.73%, a decontamination factor exceeding 372, and a high stability in water over a wide pH range from 4 to 10 with negligible leaching of Fe.

Cesium-induced inhibition of bacterial growth of Pseudomonas aeruginosa PAO1 and their possible potential applications for bioremediation of wastewater.

Radioactive isotopes and fission products have attracted considerable attention because of their long lasting serious damage to the health of humans and other organisms. This study examined the toxicity and accumulation behavior of cesium towards P. aeruginosa PAO1 and its capacity to remove cesium from waste water. Interestingly, the programmed bacterial growth inhibition occurred according to the cesium environment. The influence of cesium was analyzed using several optical methods for quantitative evaluation. Cesium plays vital role in the growth of microorganisms and functions as an anti-microbial agent. The toxicity of Cs to P. aeruginosa PAO1 increases as the concentration of cesium is increased in concentration-dependent manner. P. aeruginosa PAO1 shows excellent Cs removal efficiency of 76.1% from the contaminated water. The toxicity of cesium on the cell wall and in the cytoplasm were studied by transmission electron microscopy and electron dispersive X-ray analysis. Finally, the removal of cesium from wastewater using P. aeruginosa PAO1 as a potential biosorbent and the blocking of competitive interactions of other monovalent cation, such as potassium, were assessed. Overall, P. aeruginosa PAO1 can be used as a high efficient biomaterial in the field of radioactive waste disposal and management.

No effect of digestate amendment on Cs-137 and Sr-90 translocation in lysimeter experiments.

The soil-plant transfer of Cs-137 and Sr-90 in different crops was determined with respect to the present-day amendment practice of using digestate from biogas fermenters. The studies were performed using large lysimeters filled with undisturbed luvisol monoliths. In contrast to the conservative tracer, Br-, neither of the studied radionuclides showed a significant vertical translocation nor effect of the applied digestate amendment compared to a non-amended control was found. Furthermore, no significant plant uptake was measured for both nuclides in wheat or oat as indicated by the low transfer factors between soil-shoot for Cs-137 (TF 0.001-0.010) and for Sr-90 (0.10-0.51). The transfer into nutritionally relevant plant parts was even lower with transfer factors for soil-grain for Cs-137 (TF 0.000-0.001) and for Sr-90 (0.01-0.06). Hence, the amendment with biogas digestate is unfortunately not an option to further reduce plant uptake of these radionuclides in agricultural crops, but it does not increase plant uptake either.

Chornobyl 30 years later: Radiation, pregnancies, and developmental anomalies in Rivne, Ukraine.

In the 30 years since the Chornobyl nuclear power plant disaster, there is evidence of persistent levels of incorporated ionizing radiation in adults, children and pregnant women in the surrounding area. Measured levels of Cesium-137 vary by region, and may be influenced by dietary and water sources as well as proximity to nuclear power plants. Since 2000, comprehensive, population-based birth defects monitoring has been performed in selected regions of Ukraine to evaluate trends and to generate hypotheses regarding potential causes of unexplained variations in defect rates. Significantly higher rates of microcephaly, neural tube defects, and microphthalmia have been identified in selected regions of Ukraine collectively known as Polissia compared to adjacent regions collectively termed non-Polissia, and these significantly higher rates were evident particularly in the years 2000-2009. The Polissia regions have also demonstrated higher mean whole body counts of Cesium-137 compared to values in individuals residing in other non-Polissia regions. The potential causal relationship between persistent ionizing radiation pollution and selected congenital anomaly rates supports the need for a more thorough, targeted investigation of the sources of persistent ionizing radiation and the biological plausibility of a potential teratogenic effect.

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.

Cadmium and other elements in tissues from four ungulate species from the Mackenzie Mountain region of the Northwest Territories, Canada.

Tissue samples from four ungulate species from the south Mackenzie Mountain region of the Northwest Territories (NT), Canada, were analysed for stable and radioactive elements and (15)N and (13)C stable isotopes. Elevated Cd concentrations in moose (Alces americanus) kidney have been observed in the region and are a health care concern for consumers of traditional foods. This study examined the factors associated with, and potential renal effects from, the accumulation of cadmium, and interactions with other elements in four sympatric ungulate species. Mean renal Cd concentration was highest in moose (48.3mg/kg ww), followed by mountain caribou (Rangifer tarandus caribou) (13.9mg/kg ww) and mountain goat (Oreamnos americanus) (5.78mg/kg ww). No local sources of Cd were evident and the elevated levels in moose are considered to be natural in origin. Conversely, total Hg concentration was significantly higher in mountain caribou kidney (0.21mg/kg ww) than in moose (0.011mg/kg ww). (134)Cs (t½=2.1 y) in mountain goat and Dall's sheep (Ovis dalli) muscle is evidence of deposition from the Fukushima reactor accident in 2011. (137)Cs (t½=30.2 y) in all four ungulates is primarily a remnant of the nuclear weapons tests of the 1960s. The levels of both nuclides are low and the risk to the animals and people consuming them is negligible. Stable isotope δ(15)N and δ(13)C signatures in muscle showed a separation between the mountain caribou, with a lichen-dominated diet, and moose, which browse shrubs and forbs. Isotope signatures for mountain goat and Dall's sheep showed generalist feeding patterns. Differences in elemental and radionuclide levels between species were attributed to relative levels of metal accumulation in the different food items in the diets of the respective species. Kidneys from each species showed minor histological changes in the proximal tubule and glomerulus, although glomerular changes were rare and all changes were rare in mountain goat kidney. Kidney function was not expected to be affected in any species. Provisional Monthly Intake recommendations from the WHO indicate that Cd in moose organs will continue to be a public health care concern. However, traditional foods continue to be an important nutritional component of northern diets, particularly in consideration of the shift towards store-bought food.

[Survey of Radioactive Cesium and Potassium Intake from Food Using Duplicate Diet (Fiscal Years 2011-2014)].

Dietary intake of radioactive substances ((134)Cs, (137)Cs, (40)K) from food in fiscal 2011--2014 was surveyed using the duplicate diet method. 1,612 diet samples were collected from general households of 18 prefectures. (134)Cs and (137)Cs were detected in samples from Fukushima Prefecture, Miyagi Prefecture and Tokyo Prefecture. (134)Cs and (137)Cs were detected in 11 samples in fiscal 2011, 12 samples in fiscal 2012, and 7 samples in fiscal 2013, but none was detected in fiscal 2014. The largest radioactivity in a sample was 12 Bq/kg in Fukushima Prefecture in fiscal 2011. The detected levels gradually decreased and were less than 1.0 Bq/kg in fiscal 2014. The maximum estimated dose of radioactive cecium was 0.14 mSv/year in fiscal 2011. Radioactive potassium was detected in every meal, and showed little change through the four years (median around 30 Bq/kg).

Multifunctional flexible free-standing titanate nanobelt membranes as efficient sorbents for the removal of radioactive (90)Sr(2+) and (137)Cs(+) ions and oils.

For the increasing attention focused on saving endangered environments, there is a growing need for developing membrane materials able to perform complex functions such as removing radioactive pollutants and oil spills from water. A major challenge is the scalable fabrication of membranes with good mechanical and thermal stability, superior resistance to radiation, and excellent recyclability. In this study, we constructed a multifunctional flexible free-standing sodium titanate nanobelt (Na-TNB) membrane that was assembled as advanced radiation-tainted water treatment and oil uptake. We compared the adsorption behavior of (137)Cs(+) and (90)Sr(2+) on Na-TNB membranes under various environmental conditions. The maximum adsorption coefficient value (Kd) for Sr(2+) reaches 10(7) mL g(-1). The structural collapse of the exchange materials were confirmed by XRD, FTIR and XPS spectroscopy as well as Raman analysis. The adsorption mechanism of Na-TNB membrane is clarified by forming a stable solid with the radioactive cations permanently trapped inside. Besides, the engineered multilayer membrane is exceptionally capable in selectively and rapidly adsorbing oils up to 23 times the adsorbent weight when coated with a thin layer of hydrophobic molecules. This multifunctional membrane has exceptional potential as a suitable material for next generation water treatment and separation technologies.

Effectiveness of Protective Activities for Rehabilitation of the Forage Lands in Russia and Belarus Contaminated as a Result of the Chernobyl Accident.

Regularities of changes in the content of (137)Cs in green fodder during the remote period after the CNPP accident depending on application of agro-technical and agrochemical activities are analyzed. It is revealed that the use of mineral fertilizers reduces receipt of (137)Cs from the soil to forage and further to a food chain. It is also established that agrochemical activities are more effective than agro-technical ones.

Copper Ferrocyanide-Functionalized Magnetic Nanoparticles for the Selective Removal of Radioactive Cesium.

Copper ferrocyanide-functionalized magnetite nanoparticles (Cu-FC-MNPs) were successfully synthesized by immobilizing copper and ferrocyanide on the surfaces of [1-(2 amino-ethyl)-3-aminopropyl] trimethoxysilane-modified magnetite nanoparticles. Radioactive cesium (Cs) adsorption tests were conducted to investigate the effectiveness of the Cu-FC-MNPS toward the removal of radioactive Cs. The Cu-FC-MNPs showed excellent separation properties using an external magnet in an aqueous solution.

[Dynamics of Radioecological State of the Fresh-Water Ecosystems Affected by a Long-Term Impact from Nuclear Power Plant in the Frontiers of the Zone under Observation].

The results of radioecological studies of six small rivers situated in the surveillance zone of the Beloyarskaya NPP (BNPP) and around the cooling pond of the power plant are presented. 21 radionuclides and the total α- and ß-activity were studied in the main components of the aquatic ecosystems. It is shown that after the 1st and 2nd BN PP blocks decommissioning the content of 60Co and 137Cs in the Beloyarskoye storage pond water, sediments, fish fauna and macrophytes dropped tens and hundreds of times. The fundamental importance of this fact is that in a large range of time the aquatic ecosystem mechanism of self-purification from radionuclides is working due to radioactive substances decay as well as redistribution of radionuclides from water to other components, primarily to the sediments. Of 6 small rivers the maximum levels of radioactive substances is found in the river Olkhovka, which for several years has been subjected to the low-level radioactive water discharges from Beloyarskaya NPP. The radionuclide content in the main components of the aquatic ecosystems of the other five rivers studied after BNPP 47-year operation period corresponds to the regional background.

Solvent-free synthesis and application of nano-Fe/Ca/CaO/[PO4] composite for dual separation and immobilization of stable and radioactive cesium in contaminated soils.

This study assessed the synthesis and application of nano-Fe/Ca/CaO-based composite material for use as a separation and immobilizing treatment of dry soil contaminated by stable ((133)Cs) and radioactive cesium species ((134)Cs and (137)Cs). After grinding with nano-Fe/CaO, nano-Fe/Ca/CaO, and nano-Fe/Ca/CaO/[PO4], approximately 31, 25, and 22 wt% of magnetic fraction soil was separated. Their resultant (133)Cs immobilization values were about 78, 81, and 100%, respectively. When real radioactive cesium contaminated soil obtained from Fukushima was treated with nano-Fe/Ca/CaO/[PO4], approximately 27.3 wt% of magnetic and 72.75% of non-magnetic soil fractions were separated. The highest amount of entrapped (134)Cs and (137)Cs was found in the lowest weight of the magnetically separated soil fraction (i.e., 80% in 27.3% of treated soil). Results show that (134)Cs and (137)Cs either in the magnetic or non-magnetic soil fractions was 100% immobilized. The morphology and mineral phases of the nano-Fe/Ca/CaO/[PO4] treated soil were characterized using SEM-EDS, EPMA, and XRD analysis. The EPMA and XRD patterns indicate that the main fraction of enclosed/bound materials on treated soil included Ca/PO4 associated crystalline complexes. These results suggest that simple grinding treatment with nano-Fe/Ca/CaO/[PO4] under dry conditions might be an extremely efficient separation and immobilization method for radioactive cesium contaminated soil.