journal article·2016-10Open access

Chemical state analysis of trace-level alkali metals sorbed in micaceous oxide by total reflection X-ray photoelectron spectroscopy

Y. Baba, I. Shimoyama, N. Hirao

Abstract

Abstract In order to determine the chemical states of radioactive cesium ( 137 Cs or 134 Cs) sorbed in clay minerals, chemical states of cesium as well as the other alkali metals (sodium and rubidium) sorbed in micaceous oxides have been investigated by X-ray photoelectron spectroscopy (XPS). Since the number of atoms in radioactive cesium is extremely small, we specially focused on chemical states of trace-level alkali metals. For this purpose, we have measured XPS under X-ray total reflection (TR) condition. For cesium, it was shown that ultra-trace amount of cesium down to about 100 pg cm −2 can be detected by TR-XPS. This amount corresponds to about 200 Bq of 137 Cs (t 1/2 = 30.2 y). It was demonstrated that ultra-trace amount of cesium corresponding to radioactive cesium level can be measured by TR-XPS. As to the chemical states, it was found that core-level binding energy in TR-XPS for trace-level cesium shifted to lower-energy side compared with that for thicker layer. A reverse tendency is observed in sodium. Based on charge transfer within a simple point-charge model, it is concluded that chemical bond between alkali metal and micaceous oxide for ultra-thin layer is more polarized that for thick layer.
Source: openaire · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Radioactive element chemistry and processing · Nuclear materials and radiation effects · Nuclear Materials and Properties

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (29)

Show source-provided references
1. Wahlberg · 1962
2. Structural implications in cesium sorption10.1097/00004032-195910000-00009 ↗
3. Sorption of cesium on illite: none-equilibrium behaviour and reversibility10.1016/0016-7037(91)90002-M ↗
4. 133Cs NMR study of cesium on the surfaces of kaolinite and illite10.1016/S0016-7037(96)00257-8 ↗
5. Desorption of Cs+ ions intercalated in vermiculite clay through cation exchange with Mg2+ ions10.1246/cl.2012.1715 ↗
6. XRD and HRTEM evidence for fixation of cesium ions in vermiculite clay10.1246/cl.2012.380 ↗
7. Mechanism of strong affinity of clay minerals to radioactive cesium: first-principles calculation study for adsorption of cesium at frayed edge sites in muscovite10.7566/JPSJ.82.033802 ↗
8. Nature of the sites involved in the process of cesium desorption from vermiculite10.1016/j.jcis.2015.05.053 ↗
9. Caesium incorporation and retention in illite interlayers10.1016/j.clay.2015.02.008 ↗
10. Molecular models of cesium and rubidium adsorption on weathered micaceous minerals10.1021/jp512824k ↗
11. Determination of site specific binding environments of surface sorbed cesium on clay minerals by Cs-EXAFS10.1051/jp4:1997234 ↗
12. Cesium adsorption on clay minerals:An EXAFS spectroscopic investigation10.1021/es0156892 ↗
13. Investigation of cesium adsorption on soil and sediment samples from Fukushima Prefecture by sequential extraction and EXAFS technique10.2343/geochemj.2.0214 ↗
14. Real-time-resolved X-ray absorption fine structure spectroscopy for cesium adsorption on some clay minerals
15. 133Cs NMR and XPS investigation of cesium adsorbed on clay minerals and related phases10.1016/0016-7037(95)00452-1 ↗
16. A comparative study of DFT and XPS with reference to the adsorption of caesium ions in smectites10.1016/S0927-0256(98)00116-5 ↗
17. A combined X-ray photoelectron and Auger electron spectroscopic study of cesium in variable-charge montmorillonites10.1006/jcis.1999.6291 ↗
18. Interaction between ultra-trace amount of cesium and oxides studied by total-reflection X-ray photoelectron spectroscopy e-J10.1380/ejssnt.2015.417 ↗
19. Total reflection X-ray fluorescence and grazing incidence X-ray spectrometry — Tools for micro- and surface analysis. A review10.1016/j.sab.2009.06.012 ↗
20. The Center for X-Ray Optics, Lawrence Berkeley National Laboratory's (LBNL) Materials Sciences Division, Homepage http://henke.lbl.gov/optical_constants/.
21. Wagner · 1979
22. Scofield · 1973
23. Quantitative electron spectroscopy of surfaces: a standard data base for electron inelastic mean free paths in solids10.1002/sia.740010103 ↗
24. Sodium–oxygen graphite intercalation compound: XPS, UPS and STM study10.1080/10587259808045341 ↗
25. An XPS study of the adsorption of oxygen on silver and platinum surfaces covered with potassium or cesium10.1016/0039-6028(83)90017-1 ↗
26. XPS and TPD studies of C-O complexes on Ag surfaces: single crystal versus supported catalysts10.1016/S0169-4332(97)80196-1 ↗
27. XPS, TPD and TPR studies of Cs–O complexes on silver: their role in ethylene epoxidation10.1016/S1381-1169(00)00101-1 ↗
28. Low-temperature oxidation of alkali overlayers: ionic species and reaction kinetics10.1016/j.apsusc.2013.01.008 ↗
29. First-principles studies on cesium adsorption of clay minerals; Mechanism and chemical bonding (in Japanese)