Yutaka Kameo

Sequential inductively coupled plasma quadrupole mass-spectrometric quantification of radioactive strontium-90 incorporating cascade separation steps for radioactive contamination rapid survey

Radioactive strontium-90 scattered by a nuclear power plant accident was specifically quantified by conventional inductively coupled plasma quadrupole mass-spectrometry (ICP-QMS) preceded by on-line chelate column separation (based on lab-on-valve) and oxygen reaction (designated the cascade step). The proposed system overcomes the isobaric interference of 90Zr, whose soil concentration exceeds that of 90Sr by more than six orders of magnitude. In addition, the system requires no ultimate mass spectrometry or radioactive 90Sr standards. The radioactive 90Sr standard was replaced with the stable isotope 88Sr as a pseudo-standard. The modified ICP-QMS system yielded a precise, reproducible sharp 90Sr peak in the ICP-MS profile. The elution time of 90Sr was highly reproducible (RSD = 0.5%). After implementing the cascade-step, the detection limit (DL) was 2.3 Bq L−1 (equivalent to 0.46 ppq as 90Sr). Analysis of microwave-digested soil yielded a DL of 3.9 Bq kg−1 (equivalent to 0.77 ppq as 90Sr). The 90Sr from environmental contaminated soil samples collected from areas at a distance of 10 and 20 km from the Fukushima Daiichi nuclear power plant ranged from 52 Bq kg−1 to 73 Bq kg−1, with no statistical difference between the proposed and general methods at 95% confidence level. The proposed method offers an attractive alternative use for ICP-other ionization mass spectrometry as an enrichment or purification step, thereby expanding the scope of ICP-mass-spectrometric analysis.

Radiochemical analysis of rubble and trees collected from Fukushima Daiichi Nuclear Power Station

To characterize the rubble and trees contaminated by radionuclides released by the recent accident at the Fukushima Daiichi Nuclear Power Station, the radiochemical analysis protocols were modified using those developed by the Japan Atomic Energy Agency for the waste generated by research, industrial, and medical facilities. The radioactivity concentrations of gamma-ray-emitting nuclides 60Co, 94Nb, 152Eu, and 154Eu, and beta-particle-emitting nuclides 14C, 129I, 36Cl, 79Se, and 99Tc were successfully applied by the modified analytical method. In contrast, the radioactivity concentrations of 3H, 90Sr, 137Cs, and alpha-particle-emitting nuclides were applied by the conventional method. Unfortunately, 36Cl, 94Nb, 129I, 152Eu, 154Eu, and alpha-particle-emitting nuclides were below the detection limit of the conventional method. The measured radioactivity concentrations, except for that of 3H, were not uniform in the area but depended on the reactor unit. Although the radioactivity concentrations were varied widely, this analysis successfully clarified the characteristics of the radioactivity concentrations of the rubble and trees.

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.

Simple determination of 99Tc in radioactive waste using Tc extraction disk and imaging plates

A simple method was developed for determination of (99)Tc in low-level radioactive waste: Technetium-99 retained by a solid phase extraction disk was directly measured with imaging plates system. It was found that more than 97% of Tc were retained by the disk from a solution of pH 2 to 12, whereas depth profile of Tc in the disk, which greatly influences the counting efficiency, depended on solution pH. The present method was successfully applied to actual radioactive liquid waste samples arising from nuclear research facilities.

Influence of hydrofluoric acid on extraction of thorium using a commercially available extraction chromatographic resin

The dependence of Th recovery on hydrofluoric acid (HF) concentration in nitric acid (HNO(3)) solutions (1-5 mol/dm(3)) containing 1x10(-6) mol/dm(3) of Th and various concentrations of HF and the elution behavior were studied using a commercially available UTEVA (for uranium and tetravalent actinide) resin column. Thorium recovery decreased with an increase in HF concentration in the sample solutions. The concentration of HF at which Th recovery started to decrease was approximately 1x10(-4) mol/dm(3) in 1 mol/dm(3) HNO(3) solution, approximately 1x10(-3) mol/dm(3) in 3 mol/dm(3) HNO(3) solution, and approximately 1x10(-2) mol/dm(3) in 5 mol/dm(3) HNO(3) solution. When Al(NO(3))(3) (0.2 mol/dm(3)) or Fe(NO(3))(3) (0.6 mol/dm(3)) was added as a masking agent for F(-) to the Th solution containing 1x10(-1) mol/dm(3) HF and 1 mol/dm(3) HNO(3), Th recovery improved from 1.4+/-0.3% to 95+/-5% or 93+/-3%. Effective extraction of Th using UTEVA resin was achieved by selecting the concentration of HNO(3) and/or adding masking agents such as Al(NO(3))(3) according to the concentration of HF in the sample solution.

Development of a separation method for molybdenum from zirconium, niobium, and major elements of rubble samples.

A method for separation of Mo from Zr, Nb, and other major elements of rubble samples from the Fukushima Daiichi Nuclear Power Station (FDNPS) was developed to enable 93Mo assay of the rubble samples. Although (93)Mo analysis has been reported in a few studies, the known separation method is tedious and time consuming, or the target is a simple material. Therefore, a simple and rapid protocol for the separation of a complex material, i.e., the rubble sample, was developed in this study. Firstly, loss of Mo during the digestion of simulated rubble samples was evaluated. Next, weight distribution coefficients (Kds) of Zr, Nb, and Mo between an extraction chromatographic resin (tetra valent actinide resin, TEVA resin) and acid solutions (HF-HCl and HF-HNO3 solutions) were determined to obtain suitable solution conditions for the separation of Mo from Zr and Nb. Based on the obtained Kds, a chromatographic separation scheme was designed and applied to the digested solution of the simulated rubble sample. Consequently, Mo was successfully separated from Zr, Nb and other major metal ions of the simulated rubble sample.

Removal of Metal-Oxide Layers Formed on Stainless and Carbon Steel Surfaces by Excimer Laser Irradiation in Various Atmospheres

Abstract To apply the laser ablation technique for decontamination of metal wastes contaminated with radioactive nuclides, the effect of irradiation atmospheres on removal of oxide layers on steel surfaces by laser ablation was studied. Based on the assumption that the absorption of laser light follows the Lambert-Beer law, ablation parameters, such as absorption length and threshold fluence for ablation, of sintered Fe2O3 and stainless and carbon steels were measured in He, O2, Kr, or SF6 atmospheres. The results indicated that SF6 was the most effective gas of all irradiation atmospheres studied for the exclusive removal of oxide layers formed on stainless and carbon steel samples in high-temperature pressurized water. Secondary ion mass spectroscopic measurement and scanning electron microscopic observation confirmed that no oxide layer existed on the steel samples after the exclusive removal with laser irradiation.

Carbon-14 analysis in solidified product of non-metallic solid waste by a combination of alkaline fusion and gaseous CO2 trapping

In order to establish a simple and rapid analytical method for (14)C in solidified products made from non-metallic low-level radioactive solid wastes such as concrete, mortar and glass by melting treatment, a radiochemical analysis in combination with alkaline fusion as a sample decomposition method was examined. A simulated solidified product containing (14)C, which was prepared by using nuclear reaction (14)N(n, p)(14)C with thermal neutron irradiation, was analyzed by the present method to compare with a conventional radiochemical analysis using oxidizing combustion. The reproducible and quantitative recovery of (14)C from the simulated solidified product indicates that the present method is more efficient for (14)C analysis in solidified products than the conventional method using oxidizing combustion.

Effects of basicity and FeO concentration on the retention of 137Cs and 60Co in slag made from non-metallic radioactive wastes

Summary Simulated non-metallic wastes containing 60Co, 137Cs and 152Eu were melted to examine the effects of basicity and FeO concentration on the retention of the radioactive nuclides in a resulting solidified product (Al2O3-CaO-FeO-SiO2 quaternary slag). The retention of 60Co was almost independent of chemical composition of slag. On the other hand, the retention of 137Cs decreased with an increase of the basicity of slag, defined as a ratio of CaO to SiO2 in wt. independent of FeO concentration. Energy dispersive X-ray fluorescence spectroscopic analysis and Mössbauer spectroscopic measurement were also conducted for the solidified product. Mössbauer spectra indicated that Fe2+ ions as well as Ca2+ ions existed as network modifying cations in a silicate network structure of slag. Referring to a structure model of silicate glasses, it is inferred that the retention of 137Cs reflects differences in chemical properties between Ca2+ and Fe2+ in the internetwork region formed by modifying cations and anionic non-bridging oxygen.

A new method to analyze 242mAm in low-level radioactive waste based on extraction chromatography and β-ray spectrometry.

A new method for identifying (242m)Am in low-level radioactive waste (LLW) using β-ray spectrometry is proposed. First, (152)Eu, (241+242m+243)Am, and (244)Cm in a digested solution of simulated LLW were separated from the major components of the digested solution and Pu using a transuranium element resin (TRU resin). Next, Am and Cm were separated from Eu using a tetravalent actinide element resin (TEVA resin). A β-ray spectrum of the fraction containing Am and Cm was recorded and the contribution of (239)Np, which is a daughter nuclide of (243)Am, was subtracted to determine the radioactivity of (242m)Am. Also mutual separation of Am, Cm, and Eu was carried out using a tertiary pyridine resin to determine (242m)Am by analyzing the increase of (242)Cm in the Am fraction just after separation of Am from Cm, which is the traditional method. The isotope ratio of (242m)Am/(241)Am determined by β-ray spectrometry agreed with that obtained by analyzing the traditional method.