Abstract
Vermiculite and micaceous minerals are relevant Cs+ sorbents in soils and sediments. To understand the bioavailability of Cs+ in soils resulting from multi-cation exchanges, sorption of Cs+ onto clay minerals was performed in batch experiments with solutions containing Ca2+, Mg2+, and K+. A sequence between a vermiculite and various micaceous structures has been carried out by conditioning a vermiculite at various amounts of K. Competing cation exchanges were investigated as function of Cs+ concentration. The contribution of K+ on trace Cs+ desorption is probed by applying different concentrations of K+ on Cs-doped vermiculite and micaceous structures. Cs sorption isotherms at chemical equilibrium were combined with elemental mass balances in solution and structural analyses. Cs+ replaces easily Mg2+ > Ca2+ and competes scarcely with K+. Cs+ is strongly adsorbed on the various matrix, and a K/Cs ratio of about a thousand is required to remobilize Cs+. Cs+ is exchangeable as long as the clay interlayer space remains open to Ca2+. However, an excess of K+, as well as Cs+, in solution leads to the collapse of the interlayer spaces that locks the Cs into the structure. Once K+ and/or Cs+ collapse the interlayer space, the external sorption sites are then particularly involved in Cs sorption. Subsequently, Cs+ preferentially exchanges with Ca2+ rather than Mg2+. Mg2+ is extruded from the interlayer space by Cs+ and K+ adsorption, excluded from short interlayer space and replaced by Ca2+ as Cs+ desorbs.
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The authors thank Hélène Isnard and Nathalie Coreau for their analytical support in ICP/MS and ion chromatography. Olivier Bildstein is acknowledged for his helpful discussion and English proofreading.
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The authors received financial support from the French “Programme Investissement d’Avenir” (ANR 11-RSNR-0005 DEMETERRES, https://anr.fr/ProjetIA-11-RSNR-0005) and the French Alternative Energies and Atomic Energy Commission.
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Conceptualization, Christelle Latrille. Literature search and data analysis, Christelle Latrille and Julien Dubus. Writing—original draft preparation, Christelle Latrille. Writing—review and editing, Christelle Latrille, Nathalie Prat-Léonhardt, and Julien Dubus. Supervision, Christelle Latrille and Nathalie Prat-Léonhardt.
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Dubus, J., Leonhardt, N. & Latrille, C. Multi-cation exchanges involved in cesium and potassium sorption mechanisms on vermiculite and micaceous structures. Environ Sci Pollut Res 30, 1579–1594 (2023). https://doi.org/10.1007/s11356-022-22321-4
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DOI: https://doi.org/10.1007/s11356-022-22321-4