Bunseki, 2018(10), p.408 - 411, 2018/10
Recent development of analytical techniques for identification of particles containing nuclear materials, isotope ratio analysis of uranium and plutonium using mass spectrometry, and age determination is described in this paper. These techniques are successfully applied to the trace analysis for nuclear non-proliferation.
Yamada, Yoichi*; Kuklin, A. V.*; Sato, Sho*; Esaka, Fumitaka; Sumi, Naoya*; Zhang, C.*; Sasaki, Masahiro*; Kwon, E.*; Kasama, Yasuhiko*; Avramov, P. V.*; et al.
Carbon, 133, p.23 - 30, 2018/07
We report first STM observation of the Li ion endohedral C, which is of a new class of endohedral fullerenes, prepared by means of evaporation of high-purity Li@C[PF] salt in ultra-high vacuum. Prior to the STM measurements, the electronic structure of Li@C in the Li@C[PF] salt was also precisely determined. In the salt, it is shown that Li and PF have nearly single positive and negative charge, respectively, and the C cage is nearly neutral, suggesting that Li@C in the salt retains its original electronic state.
Yomogida, Takumi; Esaka, Fumitaka; Magara, Masaaki
Analytical Methods, 9(44), p.6261 - 6266, 2017/11
A combination of micro-sampling, micro-Raman spectroscopy (MRS), and secondary ion mass spectrometry (SIMS) was applied to the characterization of individual uranium particles. Reference particles with UO (NBL CRM U010) and UO were identified by scanning electron microscopy combined with energy dispersive X-ray detection (SEM-EDX) and transferred onto grassy carbon substrates by micro-sampling. The crystalline phases of the reference particles with diameters ranging from 1 m to 5 m were determined non-destructively by using MRS thanks to the optimization of laser power at the measurement. Isotope ratios were also determined with SIMS after the MRS analysis and were consistent with values in the literature. These results indicate that chemical forms and isotope ratios of individual uranium particles as small as 1 m can be analyzed efficiently by using the proposed method.
Miyamoto, Yutaka; Yasuda, Kenichiro; Suzuki, Daisuke; Esaka, Fumitaka; Magara, Masaaki
KEK Proceedings 2017-6, p.292 - 298, 2017/11
Our updated analytical techniques of ultra-trace plutonium in the IAEA environmental samples by ICP-MS were mentioned. Some careful techniques to accurately determine ultra-trace plutonium in the range of femto-grams to pico-grams were introduced. The uncertainties of analytical results were estimated according to the GUM concept. Our trials of determination of sub-femto grams americium in an environmental sample were also mentioned.
Analytical Sciences, 33(10), p.1097 - 1098, 2017/10
Inductively coupled plasma-mass spectrometry (ICP-MS) is widely used in various fields such as environmental, geological, and clinical sciences. In this report, recent advances of the ICP-MS analysis and expected applications are described.
Yomogida, Takumi; Asai, Shiho; Saeki, Morihisa*; Hanzawa, Yukiko; Horita, Takuma; Esaka, Fumitaka; Oba, Hironori*; Kitatsuji, Yoshihiro
Bunseki Kagaku, 66(9), p.647 - 652, 2017/09
Palladium-107 is a long-lived fission product, which can be found in high-level radioactive liquid wastes (HLLW). Determination of the Pd contents in HLLW is essential to evaluate the long-term safety of HLLW repositories. However, the Pd content in HLLW has not been reported because of difficulties in pretreatment for the measurement. In this study, we investigated applicability of laser-induced photoreduction to HLLW solution: it enables a simple and non-contact separation of Pd. The results showed the recovery of 60% was achieved at the conditions: 40% ethanol, 20 min irradiation, 100 mJ of pulse energy. Additionally, major radionuclides and potentially interfering components in ICP-MS were removed from the simulated HLLW over a wide concentration range of Pd from 0.24 to 24 mg L, showing the applicability of the proposed separation technique to HLLW samples.
Esaka, Fumitaka; Yasuda, Kenichiro; Suzuki, Daisuke; Miyamoto, Yutaka; Magara, Masaaki
Talanta, 165, p.122 - 127, 2017/04
The isotope ratios of Pu/Pu, Pu/Pu, Pu/Pu, and Pu/Pu were measured for individual Pu and U-Pu mixed oxide particles by a combination of alpha spectrometry and inductively coupled plasma mass spectrometry (ICP-MS). As a consequence, we were able to determine the Pu/Pu, Pu/Pu, and Pu/Pu isotope ratios with ICP-MS after particle dissolution and chemical separation of uranium, plutonium and americium with UTEVA resins. Furthermore, Pu/Pu isotope ratios were able to be calculated by using both the Pu/( Pu+Pu) activity ratios that had been measured through alpha spectrometry and the Pu/Pu isotope ratios determined through ICP-MS. Therefore, the combined use of alpha spectrometry and ICP-MS is useful in determining plutonium isotope ratios, including Pu/Pu, in individual U-Pu mixed oxide particles.
Esaka, Fumitaka; Nojima, Takehiro; Udono, Haruhiko*; Magara, Masaaki; Yamamoto, Hiroyuki
Surface and Interface Analysis, 48(7), p.432 - 435, 2016/07
XPS is widely used for non-destructive chemical state analysis of solid materials. In this method, depth profiling can be carried out by a combination with ion beam sputtering. However, the sputtering often causes segregation and preferential sputtering of atoms and gives inaccurate information. The use of energy-tunable X-rays from synchrotron radiation (SR) enables us to perform non-destructive depth profiling in XPS. Here, the analytical depth can be changed by changing excitation X-ray energy. In the present study, we examined methods to perform depth profiling with XPS by changing excitation energy and XAS by changing electron energy for detection. These methods were then applied to the analysis of native surface oxide layers on MgSi crystals. In this XAS analysis, the peak at 1843.4 eV becomes dominant when the electron energy for detection increases, which implies that Si-O or Si-O-Mg structure is formed as the surface oxide layer on the MgSi.
Esaka, Fumitaka; Magara, Masaaki
Mass Spectrometry Letters, 7(2), p.41 - 44, 2016/06
Secondary ion mass spectrometry (SIMS) is a promising tool to measure isotope ratios of individual uranium particles in environmental samples for nuclear safeguards. However, the analysis requires prior identification of a small number of uranium particles that coexist with a large number of other particles without uranium. In the present study, this identification was performed by scanning electron microscopy -energy dispersive X-ray analysis with automated particle search mode. The analytical results for an environmental sample taken at a nuclear facility indicated that the observation of backscattered electron images with 1000 magnification was appropriate to efficiently identify uranium particles. Lower magnification (less than 500) made it difficult to detect smaller particles of approximately 1 m diameter.
Esaka, Fumitaka; Suzuki, Daisuke; Yomogida, Takumi; Magara, Masaaki
Analytical Methods, 8(7), p.1543 - 1548, 2016/02
The isotope ratio analysis of individual uranium particles in environmental samples taken at nuclear facilities is important to clarify their origins for nuclear safeguards. In the present study, automated particle screening was used to select uranium particles prior to precise isotope ratio analysis by thermal ionization mass spectrometry (TIMS). As a result, molecular ion interferences on the uranium mass region were able to be almost completely avoided in the analysis of real inspection samples using APM-TIMS. Therefore, the performance of APM-TIMS was sufficient for obtaining isotope ratio data of individual particles without molecular ion interferences.
Esaka, Fumitaka; Suzuki, Daisuke; Miyamoto, Yutaka; Magara, Masaaki
Journal of Radioanalytical and Nuclear Chemistry, 306(2), p.393 - 399, 2015/11
An analytical technique was developed by a combination of single particle dissolution, chemical separation of uranium, plutonium and americium with extraction chromatography using UTEVA resins and measurement with inductively coupled plasma mass spectrometry (ICP-MS). This method was applied to plutonium isotope ratio analysis of individual U-Pu particles with U/Pu ratios ranging from 1 to 70. Consequently, Pu/Pu, Pu/Pu and Pu/Pu isotope ratios were successfully determined, while it was impossible to determine Pu/Pu ratios due to the high process blank values on m/z 238.
Miyamoto, Yutaka; Suzuki, Daisuke; Esaka, Fumitaka; Magara, Masaaki
Analytical and Bioanalytical Chemistry, 407(23), p.7165 - 7173, 2015/09
Age of individual uranium-plutonium mixed particles with various U/Pu atomic ratios were determined by inductively-coupled plasma mass spectrometry. Micron-sized particles were prepared from U and Pu certified reference materials. The Pu reference was stored for 4-6 years since the last purification. The Pu purification age was obtained from the Am/Pu ratio which was calculated from the product of three measured ratios of Pu and Am isotopes in the eluted fractions. Am, U and Pu in a sample solution were sequentially separated a small anion-exchange column. The Am/Pu ratio was accurately determined by spiking pure Am to the sample solution. The determined age of particles with various U/Pu ratios was in good agreement with the expected age with high accuracy and high precision.
Ekisupato Oyo Kagaku Sirizu; Kiki Bunseki, p.119 - 135, 2015/09
Bulk analysis has been conventionally used for measuring solid materials. In contrast, surface analysis is extensively used for analyzing chemical compositions and chemical states of solid surface. The surface compositions often differ from those of bulk materials. Recently, doping of impurity elements and deposition of thin films on the surface of the materials are key techniques to fabricate functional materials. Therefore, surface analysis becomes important to characterize such materials. In this paper, the principle and feature of some surface analytical techniques are described.
Lee, C.-G.*; Suzuki, Daisuke; Esaka, Fumitaka; Magara, Masaaki; Song, K.*
Talanta, 141, p.92 - 96, 2015/08
Thermal ionization mass spectrometry (TIMS) with a continuous heating technique is known as an effective method for measuring the isotope ratio in trace amounts of uranium. In this study, the analytical performance of thermal ionization mass spectrometry with a continuous heating technique was investigated using a standard plutonium solution (SRM 947). The influence of the heating rate of the evaporation filament on the precision and accuracy of the isotope ratios was examined using a plutonium solution sample at the fg level. Changing the heating rate of the evaporation filament on samples ranging from 0.1 fg to 1000 fg revealed that the influence of the heating rate on the precision and accuracy of the isotope ratios was slight around the heating rate range of 100 to 250 mA/min. All of the isotope ratios of plutonium (SRM 947), Pu/Pu, Pu/Pu, Pu/Pu and Pu/Pu, were measured down to sample amounts of 70 fg. The ratio of Pu/Pu was measured down to a sample amount of 0.1 fg, which corresponds to a PuO particle with a diameter of 0.2 m. Moreover, the signals of Pu could be detected with a sample amount of 0.03 fg, which corresponds to the detection limit of Pu of 0.006 fg as estimated by the 3 criterion. Pu and Am formed by the decay of Pu could be discriminated owing to the difference in the evaporation temperature. As a result, Pu/Pu as well as Pu/Pu and Pu/Pu in plutonium samples could be measured by TIMS with a continuous heating technique and without any chemical separation processes.
Esaka, Fumitaka; Suzuki, Daisuke; Magara, Masaaki
Analytical Chemistry, 87(5), p.3107 - 3113, 2015/03
The analysis of uranium particles in environmental samples taken from nuclear facilities is a useful tool to unveil undeclared nuclear activities related to the production of nuclear weapons. An efficient method to analyze isotope ratios of individual uranium particles is thermal ionization mass spectrometry (TIMS) combined with a fission track technique. A drawback in the fission track-TIMS technique is so-called particle-mixing. Here, some uranium particles are measured as a single particle and an averaged isotope ratio is obtained, which may lead to misunderstanding conclusions for source identification. In the present study, micro-sampling under a scanning electron microscope has been added to the procedure of the fission track-TIMS technique. The analysis of a mixed sample containing uranium particles in SRM 950a and CRM U100 materials indicated that the problem of particle mixing was almost avoidable with the proposed technique.
Suzuki, Daisuke; Esaka, Fumitaka; Miyamoto, Yutaka; Magara, Masaaki
Applied Radiation and Isotopes, 96, p.52 - 56, 2015/02
Isotope ratios of uranium and plutonium in individual U-Pu mixed particles with various U/Pu ratios were determined by thermal ionization mass spectrometry with a continuous heating method without chemical separation. Prior to the measurements, micron-sized U-Pu mixed particles with U/Pu ratios of 1, 5, 10, 18 and 70 were produced by using certified reference materials CRM U-010 (1%U enriched, NBL) and SRM 947 (NBS) solutions. As a result of isotope ratio analysis, accurate values for U and Pu ratios, except for Pu/Pu, were successfully determined for the particles with all U/Pu ratios. Although some pre-treatment such as chemical separation would need for accurate determination of Pu/Pu isotope analysis, it was shown that this analytical technique has a potential of powerful tool for nuclear safeguards and forensics.
Esaka, Fumitaka; Suzuki, Daisuke; Miyamoto, Yutaka; Magara, Masaaki
Microchemical Journal, 118, p.69 - 72, 2015/01
The determination of the time elapsed since the last purification of plutonium with chemical separation gives important information for monitoring nuclear activities related to reprocessing and nuclear weapon production. Although methods for the analysis of plutonium solutions have been extensively studied, few studies were conducted for the measurement of individual particles. In this work, a simple technique was developed for age determination of individual plutonium particles by a combination of single particle dissolution and measurement by inductively coupled plasma mass spectrometry (ICP-MS) without prior chemical separation. The analytical results of individual plutonium particles having an age of 5.98 y indicated that the use of Pu/U ratios allowed for the determination of accurate ages, though that of Pu/U and Pu/U ratios was not suitable because of the contamination of natural uranium during the process of sample preparation.
Yamamoto, Hiroyuki; Nojima, Takehiro; Esaka, Fumitaka
Photon Factory Activity Report 2014, Part B, P. 112, 2015/00
In order to develop silicon-based electronic devices, metal silicides are widely studied. Information of the surface chemical states of metal silicides is important to obtain homo-epitaxial films with excellent quality. In this work, depth analysis of surface chemical states of MgSi crystals is carried by XPS. Depth analysis is also performed in XAS measurement with a partial electron yield (PEY) mode. The Si 1s XPS spectra of the cleaved surface of the MgSi crystal indicates that SiO is formed on the surface of the MgSi crystal. Here, no peak assigned to SiO structure is observed. The Si K-edge XAS spectra obtained with the PEY mode show a peak at 1843.7 eV, which can be assigned to SiO structure.
Ozu, Akira; Esaka, Fumitaka; Yasuda, Kenichiro
Bunseki Kagaku, 63(7), p.609 - 617, 2014/07
Decay ratios of the laser-induced fluorescence emitted from five types of asbestos and six types of building materials in the broad wavelength region from 350 to 700 nm were investigated by using an ultraviolet laser pulse of 266 nm. Dependence of the decay ratios on the wavelength were compared, and evaluated in an attempt to numerically discriminate asbestos from the other building materials. It was observed that the decay ratios of each material were not constant over the wavelength region and varied in the wavelength over time. The fluorescence of asbestos and the building materials except for rock fiber at above 500 nm decayed faster than that at below 500 nm. The wavelength region from 405 to 420 nm was found optimum to identify types of asbestos and to discriminate asbestos from the building materials by comparing the decay ratio at the delay time of 10 ns after the incidence of laser pulse.
Ono, Masao; Okayasu, Satoru; Iguchi, Yusuke*; Esaka, Fumitaka; Bagum, R.*; Haruki, Rie; Mashimo, Tsutomu*
Transactions of the Japan Society for Aeronautical and Space Sciences, Aerospace Technology Japan (Internet), 12(ists29), p.Tq_1 - Tq_3, 2014/04
We had realized the composition gradient of elements or isotopes in some binary alloys or single element by solid-state centrifugation. While, it might difficult to realize graded structure of elements in binary ionic crystal by centrifugation as it strongly keeps their stoichiometry. However, isotope fractionation in binary ionic crystal by centrifugation might be expected as the self-diffusion of ions occurs. We have planed the ultracentrifuge experiments on -AgI superionic conductor to investigate the isotope effect in binary ionic crystal under a strong centrifugal acceleration field. -AgI superionic conductor is suitable for the confirmation experiment as it is an intrinsic ionic crystal and Ag ions have high diffusivity. For the first stage, we have experimentally searched the experimental conditions of magnitude of centrifugal acceleration and temperature that ensure the experiment without decomposition. It is confirmed that the combination of experimental conditions of up to 6.110 g, 350C, 24h ensure the experiment without decomposition at least.