Development of a quantification method for Zr isotopes in solid samples by LA-ICP-MS for rapid analysis of Zr-93 in high-level radioactive wastes

Morii, Shiori; Yomogida, Takumi; Asai, Shiho*; Ouchi, Kazuki; Oka, Toshitaka; Kitatsuji, Yoshihiro

Bunseki Kagaku, 72(10.11), p.441 - 448, 2023/10

https://doi.org/10.2116/bunsekikagaku.72.441

Rapid analytical method for the determination of Zr-93 in radioactive wastes has been developed. Laser ablation (LA)-ICP-MS was applied to the analysis of Zr isotopes in simulated high-level radioactive waste (HLW). Sample preparation time was dramatically reduced by using a DGA resin as the adsorbent for Zr. Direct quantification of Zr isotopes in this resin sample was carried out by LA-ICP-MS. Laser settings were optimized to obtain a reliable isotope ratio of the sample by LA-ICP-MS. Quantification of Zr isotopes in the simulated HLW solution by isotope dilution mass spectrometry (IDMS) was examined. The amount of Zr-90 in the sample obtained by IDMS corresponded to a value calculated from the given concentration of Zr in the sample within uncertainty. Thus, this method can be applied for the quantification of Zr-93 in radioactive wastes.

Outlining zircon growth in a granitic pluton using 3D cathodoluminescence patterns, U-Pb age, titanium concentration, and Th/U; Implications for the magma chamber process of Okueyama granite, Kyushu, Japan

Yuguchi, Takashi*; Ito, Daichi*; Yokoyama, Tatsunori; Sakata, Shuhei*; Suzuki, Satoshi*; Ogita, Yasuhiro; Yagi, Koshi*; Imura, Takumi*; Motai, Satoko*; Ono, Takeshi*

Lithos, 440-441, p.107026_1 - 107026_14, 2023/03

https://doi.org/10.1016/j.lithos.2023.107026

We propose a new method for elucidating zircon growth in granitic plutons, based on variations in three-dimensional 3D cathodoluminescence (CL) patterns, U-Pb ages, titanium concentration, and Th/U ratios. We focused on the zircon growth processes in the Okueyama granite (OKG) in central Kyushu, Japan, to obtain interpretations of magma chamber processes that result in the formation of granitic plutons. The OKG consists of three lithofacies: biotite granite (BG), hornblende granite (HG), and hornblende granodiorite (HGD). To determine the 3D internal structure and growth pattern of a zircon crystal, we performed CL observations for multi-sections of the samples. Simultaneously, we also determined the zircon U-Pb age and titanium concentration of the center sections of the samples. The 3D distribution of the oscillatory zoning can be used to determine the crystal nucleus. The simultaneous determination of zircon U-Pb ages and Ti concentrations of the granite samples indicates the time-temperature (t-T) history of granitic magma before its solidification. The t-T histories of the BG, HG, and HGD represented similar cooling behaviors within the magma chamber: rapid cooling from the zircon crystallization temperature to the closure temperature of the biotite K-Ar system between 16 Ma and 10 Ma. The variations in the Th/U ratios against temperature also demonstrate a different trend at the boundary of approximately 670 C. Fractional crystallization in the magma chamber progressed significantly at temperatures above 670 C; below 670 C, crystallization progressed slowly, indicating only minimal changes in the magma composition. The variations in the Th/U ratio against temperature in the BG, HG, and HGD portrayed common tendencies, indicating the same behavior in the progression of fractional crystallization among the three lithofacies, which in turn, represented the same behavior within the entire magma chamber.

Analytical method for chemical compositions of volcanic glasses in Tono Geoscience Center; Quantitative measurements of Major Elements by using EPMA and Minor Elements by LA-ICP-MS

Kagami, Saya; Yokoyama, Tatsunori; Umeda, Koji*

JAEA-Testing 2021-001, 49 Pages, 2021/08

JAEA-Testing-2021-001.pdf:3.86MB

To make a contribution to safety assessment for geological disposal of high level radioactive and/or TRU waste, we need to assess long-term stability of geological environment and predict long-term changes of geotectonic events that will occur in the future, especially for Quaternary period ( 2.6 million years ago-present). In the most case, we investigate chronological data of geological events by radiometric dating. When some geological samples have no objects to which radiometric dating method can be applied (e.g., zircon, biotite, wood fragments and plant residues), we can use tephrochronology, which is geological dating method using each layer of tephra (erupted volcanic ash), for dating of geological layers. This chronological method is essential in Japan, where volcanism is very active. Tephra is usually characterized by petrographic characteristics and/or chemical composition (mainly major elements) of volcanic glasses and/or minerals in tephra. In Tono Geoscience Center (Japan Atomic Energy Agency), we develop an analytical technique of chemical composition including trace elements of volcanic glasses for detailed tephra identification. In this paper, we report a sample preparation procedure and analytical methods of chemical compositions of individual volcanic glass shards by using an electron probe microanalyzer and a laser ablation-inductively coupled plasma-mass spectrometer.

Determination of Pd in Pd purified by selective precipitation from spent nuclear fuel by laser ablation ICP-MS

Asai, Shiho; Ohata, Masaki*; Yomogida, Takumi; Saeki, Morihisa*; Oba, Hironori*; Hanzawa, Yukiko; Horita, Takuma; Kitatsuji, Yoshihiro

Analytical and Bioanalytical Chemistry, 411(5), p.973 - 983, 2019/02

https://doi.org/10.1007/s00216-018-1527-3

Determination of radiopalladium Pd is required for ensuring the radiation safety of Pd extracted from spent nuclear fuel for recycling or disposal. We employed laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to simplify an analytical procedure of Pd. Pd was separated through selective Pd precipitation reaction from spent nuclear fuel. Laser ablation allows direct measurement of the Pd precipitates, skipping the dissolution and dilution procedure. In this study, Pd in natural Pd standard solution was used as an internal standard, taking advantage of its absence in spent nuclear fuel. The Pd precipitate was uniformly embedded on the surface of the centrifugal filter, forming a microscopically thin flat surface of Pd. The resulting homogeneous Pd layer is suitable for obtaining a stable signal ratio of Pd/Pd. The amount of Pd obtained by LA-ICP-MS corresponds to the values obtained by conventional solution nebulization measurement.

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

Asai, Shiho; Limbeck, A.*

Talanta, 135, p.41 - 49, 2015/04

https://doi.org/10.1016/j.talanta.2014.12.009

A new analytical method for chondrite-normalized Rare earth elements (REE) plot has been developed in this study. Cation-exchange resin particles were used as a substrate to retain REE for laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). 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, compared to conventional solution nebulization ICP-MS. To evaluate the applicability of the proposed method, the REE-adsorbed particles prepared by immersing them in a U-bearing solution were measured with LA-ICP-MS. Additionally, each concentration of REE in the U standard solution was determined with solution nebulization ICP-MS. The chondrite-normalized plot obtained through LA-ICP-MS analysis exhibited close agreement with that obtained through the solution nebulization ICP-MS of the REE-separated solution within the uncertainties.

Simultaneous determination of zircon U-Pb age and titanium concentration using LA-ICP-MS; A Case study of the Okueyama granite, Kyusyu, Japan

Ito, Daichi*; Ishibashi, Kozue*; Sakata, Shuhei*; Yokoyama, Tatsunori; Ogita, Yasuhiro; Yagi, Koshi*; Ono, Takeshi*; Yuguchi, Takashi*

no journal, , 

no abstracts in English

Direct mass-spectrometric imaging method for difficult-to-measure radioisotopes

Yanagisawa, Kayo; Matsueda, Makoto; Furukawa, Makoto*; Hirata, Takafumi*; Takagai, Yoshitaka*

no journal, , 

Determinations of radioisotopes in fuel debris and radioactive wastes are important for decommissioning of Fukushima Daiichi Nuclear Power Plant. Difficult-to-measure radioisotopes such as Sr-90 have been measured by radiometric analysis and inductively coupled plasma-mass spectrometry (ICP-MS), the methods have not achieved the distribution of the radioisotopes on the sample's surface due to its digestion process of the samples before measurements. Laser ablation (LA)-ICP-MS can obtain the distribution information of radionuclides directly on the surface of solid samples. In contrast, the quantification with the method is difficult caused by the spectral interferences and matrix effects from samples. In this study, a quantification method was developed combined with LA-ICP-MS and isotope dilution method. The proposed method was applied for Sr-90 quantification.

Age determination using tephra as indicator; Detailed identification by trace-element composition of volcanic glass shards

Kagami, Saya

no journal, , 

Tephrochronology, which uses tephra to determine the chronostratigraphy of strata is important to understand geotectonic events for the last few Myr. We used EPMA and LA-ICP-MS for major and trace element concentration of volcanic glass shards in Znp-Ohta tephra and Tng tephra, of which major elements are similar to that of Znp-Ohta. These two tephras could be distinguished by rare earth elements pattern, in addition to the conventional indices. Identification of tephras by more than one indicator could distinguish tephra with similar characteristics and prevent incorrect stratigraphic correlation. It is necessary to improve the chemical composition database of wide-spread tephras including trace element compositions, and we plan to measure various wide-spread tephras by the method in this study.

Development of software to support the efficiency of mass spectrometric imaging

Yanagisawa, Kayo; Yokota, Hiromi; Matsueda, Makoto; Ishiniwa, Hiroko*; Fujimoto, Katsushige*; Takagai, Yoshitaka*

no journal, , 

Fuel debris is considered a heterogeneous mixture of nuclear fuel, control rods and reactor structural materials that has cooled and solidified, and it is important to understand its composition (elements and isotopes) and distribution to formulate storage, treatment and disposal methods after fuel debris removal. Mass spectrometric imaging using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is useful for the aforementioned fuel debris analysis because it can visualise the distribution of elements and isotopes at the 10 - 10 g/g level with a spatial resolution of 10-100 m. However, the number of data is enormous when the number of measurement points is large. In this study, an automatic peak detection method using the asymmetric least squares method with a penalty term was developed, data processing for LA-ICP-MS was automated and an intuitive GUI was constructed.

A Survey on new standard materials for U-Pb dating of carbonate using LA-ICP-MS

Yokoyama, Tatsunori; Kokubu, Yoko; Murakami, Hiroaki; Watanabe, Takahiro; Hirata, Takafumi*; Sakata, Shuhei*; Danhara, Toru*; Iwano, Hideki*; Maruyama, Seiji*; Miyazaki, Takashi*; et al.

no journal, , 

Chronological and geochemical studies of carbonates, which are commonly found as fracture filling minerals in rocks, can provide information about geochemical conditions present during formation including in deep subsurface environments. A dating technique for the carbonates using laser ablation-multiple collector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is still immature partly because of a lack of a consensus international carbonate standard for the in-situ dating technique. In this study, we performed a survey on the carbonate standard materials that may be suitable for high precision U-Th-Pb dating using LA-MC-ICPMS. We examined carbonate standard materials JCp-1 and JCt-1 issued by the Geological Survey of Japan (GSJ). Based on solution-based bulk analysis using MC-ICP-MS, heterogeneities in Pb isotope compositions were confirmed. Nevertheless, the 206Pb-based isotopic compositions were all within 1.2 per mill variations acceptable for a standard used for age determination using LA-MC-ICPMS. Additional tests on the heterogenities in U-Th-Pb compositions of the carbonate standards along with determinations of other trace elements using a 2D imaging LA-ICP-MS are ongoing. Examinations on both natural standards and synthetic standards are ongoing for further efforts in determination of the standard suitable for U-Th-Pb dating of carbonates.