Shiho Asai

Removal of Cesium Using Cobalt-Ferrocyanide-Impregnated Polymer-Chain-Grafted Fibers

Radioisotopes are currently being released by Fukushima Daiichi nuclear power plant, which was damaged by the magnitude 9.0 earthquake and the tsunami that followed. Cesium-137, cesium-134, and iodine-131 produced by the fission of nuclear fuels are expected to seriously contaminate the sea and ground. Cesium and iodine dissolve in water and seawater in ionic forms of Csþ and I or IO3 , respectively. Cesium-137, with a longer half-life (30 years) than iodine131 (8 days), should be removed and confined. Adsorption is a feasible method of removing radioactive species from water contaminated with radioisotopes. Zeolites and insoluble metal ferrocyanides are known as adsorbents capable of specifically capturing cesium-137 ions. Moreover, the insoluble metal ferrocyanides are loaded onto solid supports in bead or granule form such as porous anionexchange resins, silica gels, and zeolites. However, fibrous adsorbents are effective for easy operation at sites for processing water contaminated with radioisotopes. Here, we propose a novel fiber that can immobilize metal ferrocyanides for the removal of cesium ions using a commercially available 6-nylon fiber as a starting material. Precipitates of metal ferrocyanide (M-FC) were formed among the polymer chains grafted onto the 6-nylon fiber. Therefore, the M-FC-impregnated fibers with a small diameter enhance the mass transfer of cesium ions from the bulk of liquid to the M-FC particles, leading to the rapid removal of cesium ions. In addition, the M-FC-impregnated fibers can be fabricated into various fiber modules for easy operation at the sites. In this study, the cobalt ion was used as a metal ion that precipitates with potassium ferrocyanide. II. Experimental

Determination of 79Se and 135Cs in Spent Nuclear Fuel for Inventory Estimation of High-Level Radioactive Wastes

79Se and 135Cs are long-lived fission products and are found in high-level radioactive waste (HLW). The estimation of their inventories in HLW is essential for the safety assessment of geological disposal, owing to their mobility in the strata. In this study, the amounts of 79Se and 135Cs in a spent nuclear fuel solution were measured. About 5 g of irradiated UO2 fuel discharged from a commercial Japanese pressurized water reactor (PWR) with a burn-up of 44.9 GWd/t was sampled and dissolved with 50mL of 4M nitric acid in a hot cell for 2 h. After Se and Cs were chemically separated, the amounts of 79Se and 135Cs in the spent nuclear fuel solution were measured by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS). The amounts of 79Se and 135Cs were 5:2 ± 1:5 and 447 ± 40 g/MTU, respectively. The results presented in this study, which are the first postirradiation experimental data in Japan, showed good agreement with those obtained by the ORIGEN2 code using the data library of JENDL-3.3.

LA-ICP-MS of rare earth elements concentrated in cation-exchange resin particles for origin attribution of uranium ore concentrate

Rare earth elements (REE) concentrated on cation-exchange resin particles were measured with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to obtain chondrite-normalized REE plots. The sensitivity of REE increased in ascending order of the atomic number, according to the sensitivity trend in pneumatic nebulization ICP-MS (PN-ICP-MS). The signal intensities of REE were nearly proportional to the concentrations of REE in the immersion solution used for particle-preparation. Minimum measurable concentration calculated from the net signals of REE was approximately 1 ng/g corresponding to 0.1 ng in the particle-preparation solution. In LA analysis, formation of oxide and hydroxide of the light REE and Ba which causes spectral interferences in the heavy REE measurement was effectively attenuated due to the solvent-free measurement capability, compared to conventional PN-ICP-MS. To evaluate the applicability of the proposed method, the REE-adsorbed particles prepared by immersing them in a U-bearing solution (commercially available U standard solution) were measured with LA-ICP-MS. Aside from the LA analysis, each concentration of REE in the same U standard solution was determined with conventional PN-ICP-MS after separating REE by cation-exchange chromatography. The concentrations of REE were ranging from 0.04 (Pr) to 1.08 (Dy) μg/g-U. The chondrite-normalized plot obtained through LA-ICP-MS analysis of the U standard sample exhibited close agreement with that obtained through the PN-ICP-MS of the REE-separated solution within the uncertainties.

Highly sensitive detection of neodymium ion in small amount of spent nuclear fuel samples using novel fluorescent macrocyclic hexadentate polyaminocarboxylate probe in capillary electrophoresis-laser-induced fluorescence detection.

A rapid and high-sensitive detection method for the total concentration of Nd ion (total Nd) in a small amount of a spent nuclear fuel sample is urgently required since the precise quantification of total Nd ion makes it possible for burnup (degree of fuel consumption) to be determined. In this work, a capillary electrophoresis-laser-induced fluorescent detection method (CE-LIF) is proposed for the analysis of total Nd in a spent fuel sample solution, with the use of a newly synthesized metal fluorescent probe which has a fluorescein and a macrocylic hexadentate chelating group, FTC-ABNOTA, for lanthanide (Ln) ions. Ln ions were derivatized to form a strongly fluorescent complex with the probe to suppress the quenching of the ligand-centered emission. The detection of Ln complexes in the CE-LIF indicated that the interaction between Ln ions and the FTC-ABNOTA was strong enough not to dissociate during migration. The mutual separation among the Ln-FTC-ABNOTA complexes in CE-LIF was achieved by pH control providing a dynamic ternary complexation (DTC) with hydroxide ions. Using the DTC separation mode, a high resolution of Nd from other Ln ions with high resolution of 1.3-1.9 and a theoretical plate number of 68,000, and a very low detection limit of 22 pM (3.2 ppt, 0.11 attomole amount basis) were successfully obtained. A simulated spent fuel sample containing various metal ions was examined in this method with a good quantification result of 102.1% recovery obtained even with a large excess of U.

Dependence of Lanthanide-Ion Binding Performance on HDEHP Concentration in HDEHP Impregnation to Porous Sheet

An octadecylamino-group-introduced polymer chain grafted onto a porous sheet was impregnated with bis(2-ethylhexyl)hydrogen phosphate (HDEHP). A mixture of HDEHP and ethanol of various HDEHP concentrations was used for the impregnation. The porous sheet into which a C18H37NH group was introduced was immersed in HDEHP/ethanol solution before ethanol evaporation. The liquid permeability of a cartridge charged with the HDEHP-impregnated porous sheet in disk form prepared in 50 (v/v)% HDEHP/ethanol solution was 96% that of the starting-porous-disk-packed cartridge. The equilibrium binding capacity of the HDEHP-impregnated porous disk for yttrium ions was 0.32 mol per kg of the disk. In addition, the HDEHP-impregnated-porous-disc-packed cartridge was found to be applicable to the preconcentration of trace amounts of lanthanides in a multielement solution prior to their measurement by inductively coupled plasma mass spectrometry.

Interaction Between an Acidic Extractant and an Octadecylamino Group Introduced into a Grafted Polymer Chain

Abstract Poly‐glycidyl methacrylate (GMA) was appended onto a porous membrane of a hollow‐fiber form with an epoxy group density of 14 mol per kg of the starting porous membrane. Octadecylamine was added to the epoxy group of the polymer brush at a maximum molar conversion of the epoxy group into the octadecylamino group of 59%. An acidic extractant, bis(2,4,4,‐trimethylpentyl)phosphinic acid (Cyanex 272), was impregnated on the octadecylamino group by immersion of the octadecylamine‐added porous membrane in Cyanex 272/ethanol solution. The amount of impregnated extractant was 1.4 mol per kg of the GMA‐grafted porous membrane at a molar conversion of 59%. The phosphinic acid moiety of Cyanex 272 was attracted by the amino part of the octadecylamino group of the polymer brush to swell the entire volume of the porous membrane. This swelling compensated for the pore volume reduction caused by grafting the charged polymer brush to the pore surfaces of the porous membrane. The impregnated Cyanex 272 was repositioned on the charged polymer brush in response to the properties of surrounding liquids. The hydrophobic interaction enables the hydrophobic moiety of Cyanex 272 to associate with the octadecyl part of the octadecylamino group of the polymer brush to capture zinc ions. The binding efficiency of the Cyanex 272‐impregnated polymer brush for zinc ion was as high as 93%.

Preparation of Microvolume Anion-Exchange Cartridge for Inductively Coupled Plasma Mass Spectrometry-Based Determination of 237Np Content in Spent Nuclear Fuel

Microvolume anion-exchange porous polymer disk-packed cartridges were prepared for Am/Np separation, which is required prior to the measurement of Neptunium-237 ((237)Np) with inductively coupled plasma mass spectrometry (ICPMS). Disks with a volume of 0.08 cm(3) were cut out from porous sheets having anion-exchange-group-containing polymer chains densely attached on the pore surface. Four different amine-based groups, N,N-dimethylaminoethyl methacrylate, trimethylammonium, diethylamine, and triethylenediamine (TEDA), were selected as the anion-exchange groups to be introduced into the porous sheets. The separation performances of Am/Np were evaluated using a standard solution of (243)Am, which had the same activity as its daughter nuclide (239)Np in secular equilibrium. (239)Np recovery of close to 100% with practically no contamination of (243)Am was achieved using the TEDA-introduced disk-packed cartridge. The time to elute (239)Np from the cartridge was approximately 40 s. The TEDA-introduced disk-packed cartridge was applied to the separation of Np from a spent nuclear fuel sample to confirm its separation performance. A known amount of (243)Am ((239)Np) was added to the spent nuclear fuel sample solution to monitor the chemical yield of Np. The chemical yield of Np calculated from a measured concentration of (239)Np was 90.4%. Am leakage in the Np-eluted solution was less than 1 ppt, corresponding to 0.001% of the original Am concentration in the sample. This indicates that no additional (239)Np was produced by the decay of the (243)Am remaining in the Np-eluted solution, thus providing a reliable chemical yield. U, which can cause a serious spectral interference involving the peak tail from the mass spectrum of (238)U, was thoroughly removed with the TEDA cartridge, providing interference-free measurement of (237)Np. The concentration of (237)Np obtained by ICPMS was 718 ± 12 ng/mg-U, which agrees well with the theoretically calculated value. Compared with the conventional separation technique using commercially available anion-exchange resin columns, the time required to adsorb, wash, and elute Np using the TEDA- introduced disk-packed cartridge was reduced by 75%.

Crosslinked-Chelating Porous Sheet with High Dynamic Binding Capacity of Metal Ions

A crosslinked chelating porous sheet was prepared by cografting ethylene glycol dimethacrylate (EGDMA) with glycidyl methacrylate onto an electron-beam-irradiated porous polyethylene sheet, followed by the introduction of an iminodiacetate group. At a molar percentage of EGDMA of 1.0 mol%, the sheet exhibited a maximum dynamic binding capacity for copper ions of 0.93 mmol/g, while the equilibrium binding capacity remained the same (1.2 mmol/g) as that of a non-crosslinked chelating porous sheet. The crosslinking of the grafted chain causes copper ions to lower their diffusion rate along the sheet thickness driven by the gradient of the amount of copper ions adsorbed.

Isotope dilution inductively coupled plasma mass spectrometry for determination of 126Sn content in spent nuclear fuel sample

The 126Sn content in a spent nuclear fuel solution was determined by isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) for its inventory estimation in high-level radioactive waste. A well-characterized irradiated UO2 fuel sample dissolved in a hot cell was used as a sample to evaluate the reliability of the methodology. Prior to the ICP-MS measurement, Sn was separated from Te (126Te), which causes major isobaric interference in the determination of 126Sn content, along with highly radioactive coexisting elements, such as Sr (90Sr), Y (90Y), Cs (137Cs) and Ba (137m Ba), using an anion-exchange column. The absence of counts attributed to Te at m/z = 125, 128, and 130 in the Sn-containing effluent (Sn fraction) indicates that Te was completely removed from the anion-exchange column. After washing, Sn retained on the column was readily eluted with 1 M HNO3 accompanied with approximately 80% of the Cd and 0.03% of the U in the initial sample. Owing to the presences of Cd and U in Sn fraction, the measurements of 116Sn and 119Sn were affected by the isobaric 116Cd and the doubly charged 238U2+ion, resulting in the positive bias of the determined values. With the exception of the isotopic ratios including 116Sn and 119Sn, 117Sn/126Sn, 118Sn/126Sn, 120Sn/126Sn, 122Sn/126Sn and 124Sn/126Sn were successfully determined and showed good agreement with those obtained through ORIGEN2 calculations. The measured concentration of 126Sn in the spent nuclear fuel sample solution was 0.74 ± 0.14 ng/g, which corresponds to 23.0 ± 4.5 ng per gram of the irradiated UO2 fuel (excluding the presence of 126Sn in the insoluble residue). The results reported in this paper are the first experimental values of 126Sn content and isotope ratios in the spent nuclear fuel solution originating in spent nuclear fuel irradiated at a nuclear power plant in Japan.

Simple Method for High-Density Impregnation of Aliquat 336 onto Porous Sheet and Binding Performance of Resulting Sheet for Palladium Ions

Aliquat 336 was impregnated onto the polymer chain grafted onto a 2.0-mm-thick porous sheet with a porosity of 75% and a pore size of 1.2 µm via the graft polymerization of glycidyl methacrylate and the subsequent reaction of the epoxy group with mercaptoundecanoic acid. In a 2:1 ethanol/4M NaOH (v/v) mixture, Aliquat 336 was impregnated at a density of 0.85 mmol/g, which was comparable to that of conventional Aliquat-336-impregnated polymeric beads. The dynamic binding capacity for palladium was 0.60 mmol/g when 100 mg-Pd/L palladium chloride solution was forced to permeate at a space velocity of 3700 h−1.