High-sensitive XANES analysis at Ce L2-edge for Ce in bauxites using transition-edge sensors: Implications for Ti-rich geological samples

Wenshuai Li; Shinya Yamada; Tadashi Hashimoto; Takuma Okumura; Ryota Hayakawa; Kiyofumi Nitta; Oki Sekizawa; Hiroki Suga; Tomoya Uruga; Yuto Ichinohe; Toshiki Sato; Yuichi Toyama; Hirofumi Noda; Tadaaki Isobe; Sayuri Takatori; Takahiro Hiraki; Hideyuki Tatsuno; Nao Kominato; Masaki Ito; Yusuke Sakai; Hajime Omamiuda; Akiko Yamaguchi; Takumi Yomogida; Hikaru Miura; Makoto Nagasawa; Shinji Okada; Yoshio Takahashi

doi:10.1016/j.aca.2022.340755

High-sensitive XANES analysis at Ce L₂-edge for Ce in bauxites using transition-edge sensors: Implications for Ti-rich geological samples

Anal Chim Acta. 2023 Feb 1:1240:340755. doi: 10.1016/j.aca.2022.340755. Epub 2022 Dec 29.

Authors

Wenshuai Li¹, Shinya Yamada², Tadashi Hashimoto³, Takuma Okumura⁴, Ryota Hayakawa², Kiyofumi Nitta⁵, Oki Sekizawa⁵, Hiroki Suga⁵, Tomoya Uruga⁵, Yuto Ichinohe², Toshiki Sato², Yuichi Toyama⁶, Hirofumi Noda⁷, Tadaaki Isobe⁸, Sayuri Takatori⁹, Takahiro Hiraki⁹, Hideyuki Tatsuno¹⁰, Nao Kominato², Masaki Ito², Yusuke Sakai², Hajime Omamiuda², Akiko Yamaguchi¹¹, Takumi Yomogida¹², Hikaru Miura¹³, Makoto Nagasawa¹⁴, Shinji Okada⁶, Yoshio Takahashi¹⁵

Affiliations

¹ Department of Earth and Planetary Science, The University of Tokyo, Hongo 7-3-1, Bunkyo, Tokyo, 113-0033, Japan. Electronic address: wenshuai0615@gmail.com.
² Department of Physics, Rikkyo University, Toshima-Ku, Tokyo, 171-8501, Japan.
³ Advanced Science Research Center (ASRC), Japan Atomic Energy Agency (JAEA), Tokai, 319-1184, Japan.
⁴ Department of Chemistry, Tokyo Metropolitan University, Hachioji, Tokyo, 192-0397, Japan.
⁵ Center for Synchrotron Radiation Research, Japan Synchrotron Radiation Research Institute (JASRI), Sayo, Hyogo, 679-5198, Japan.
⁶ Engineering Science Laboratory, Chubu University, Kasugai, 487-8501, Japan.
⁷ Department of Earth and Space Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan.
⁸ RIKEN Nishina Center, RIKEN, Wako, 351-0198, Japan.
⁹ Research Institute for Interdisciplinary Science, Okayama University, Okayama, Okayama, 700-8530, Japan.
¹⁰ Department of Physics, Tokyo Metropolitan University, Hachioji, Tokyo, 192-0397, Japan.
¹¹ Center for Computational Science and e-Systems, Japan Atomic Energy Agency, Kashiwa, Chiba, 277-0871, Japan.
¹² Nuclear Science and Engineering Center, Japan Atomic Energy Agency, Ibaraki, 319-1195, Japan.
¹³ Sustainable System Research Laboratory, Central Research Institute of Electric Power Industry, 1646 Abiko, Abiko, Chiba, 270-1194, Japan.
¹⁴ Department of Earth and Planetary Science, The University of Tokyo, Hongo 7-3-1, Bunkyo, Tokyo, 113-0033, Japan.
¹⁵ Department of Earth and Planetary Science, The University of Tokyo, Hongo 7-3-1, Bunkyo, Tokyo, 113-0033, Japan. Electronic address: ytakaha@eps.s.u-tokyo.ac.jp.

PMID: 36641142
DOI: 10.1016/j.aca.2022.340755

Abstract

Accurate determination of cerium (Ce) valence state is important for interpreting the Ce anomaly in geological archives for (paleo)redox reconstruction. However, the routine application of Ce L₃-edge X-ray absorption near-edge structure (XANES) spectroscopy for detecting trace Ce in geological samples can often be restricted by coexisting titanium (Ti) due to the proximity of their fluorescence emission lines. Therefore, the signal-to-noise ratio of Ce L₃-edge XANES spectra may not be sufficiently high for high-quality spectroscopic analysis. This study introduces a semi-quantitative approach appropriate for Ti-rich, Ce-dilute geological materials by synchrotron-based X-ray measurement at the Ce L₂-edge. First, the results confirm that Ce L₂-edge XANES spectra are able to avoid overlapping Ti K_β emissions and provide more reliable information on the Ce valence state in Ti-rich materials relative to L₃-edge XANES. Moreover, the application of transition-edge sensor (TES) could reach the higher sensitivity with better energy resolution than conventional silicon drift detector (SDD) to detect fluorescence X-ray (Ce L_β1). The investigation on bauxites developed from the Columbia River Basalts shows that combining Ce L₂-edge XANES and TES allows for resolving weak Ce fluorescence lines at the L₂-edge from Ti-rich, Ce-dilute samples (Ti/Ce mass ratio up to ∼6000, tens of ppm Ce). The outcome emphasizes the practical possibility of investigating Ce redox state in Ti-rich geological samples.

Keywords: Oxidation; Redox; SPring-8; Valence state; XANES.

MeSH terms

Aluminum Oxide
Cerium* / chemistry
Oxidation-Reduction
Titanium
X-Ray Absorption Spectroscopy

Substances

Cerium
Titanium
Aluminum Oxide