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A comparative study on the Cs adsorption/desorption and structural changes in different clay minerals

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Abstract

We investigated the structural changes in clay minerals after Cs adsorption and understood their low desorption efficiency using an ion-exchanger. We focused on the role of interlayers in Cs adsorption and desorption in 2:1 clay minerals, namely illite, hydrobiotite, and montmorillonite, using batch experiments and XRD and EXAFS analyses. The adsorption characteristics of the clay minerals were analyzed using cation exchange capacity (CEC), maximum adsorption isotherms (Qmax), and radiocesium interception potential (RIP) experiments. Although illite showed a low CEC value, it exhibited high selectivity for Cs with a relatively high RIP/CEC ratio. The Cs desorption efficiency after treatment with a NaCl ion exchanger was the highest for illite (74.3%), followed by hydrobiotite (45.5%) and montmorillonite (30.3%); thus, Cs adsorbed onto planar sites, rather than on interlayers or frayed edge sites (FESs), is easily desorbed. After NaCl treatment, XRD analysis showed that the low desorption efficiency was due to the collapse of the interlayer-fixed Cs, which tightly narrowed the interlayers’ hydrobiotite due to the ion exchange of divalent cations (Mg2+ or Ca2+) into the monovalent cation (Na+). Moreover, EXAFS analysis showed that hydrobiotite formed inner-sphere structures after NaCl desorption, indicating that it was difficult to remove Cs from NaCl desorption due to the collapsed hydrobiotite and montmorillonite interlayers as well as the strong bonding in FESs of illite. In contrast, chelation desorption using oxalic acid effectively dissolved the narrowed interlayers of hydrobiotite (98%) and montmorillonite (85.26%), enhancing the desorption efficiency. Therefore, low desorption efficiency for Cs clays using an ion exchanger was caused by the collapsed interlayer due to the exchange between monovalent cation and divalent cation.

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Funding

This study was supported by grants from the National Research Foundation of Korea (NRF), funded by the Korean government, Ministry of Science, ICT and Future Planning (RS-2023–00243600 and 2022M2D2A1A02063569).

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Authors and Affiliations

  1. Decommissioning Technology Research Division, Korea Atomic Energy Research Institute, 989-111, Daedeok-Daero, Yuseong-Gu, Daejeon, 34057, Republic of Korea

    In-Ho Yoon, Ilgook Kim & Sung Man Kim

  2. Disposal Performance Demonstration Research Division, Korea Atomic Energy Research Institute, Daedeok-Daero 989-111, Yuseong-Gu, Daejeon, 305-353, Republic of Korea

    Sang-Ho Lee

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  1. In-Ho Yoon
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All authors contributed to the study’s conception and design. In-Ho Yoon is responsible for writing—original draft, conceptualization, methodology, software, data curation, visualization, and supervision. Sang-Ho Lee is assigned to the investigation, data curation, and writing—original draft. Ilgook Kim is responsible for the writing—review and editing, and validation. Sung Man Kim did the methodology, investigation, and data curation. All authors read and approved the final manuscript.

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Correspondence to In-Ho Yoon.

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Yoon, IH., Lee, SH., Kim, I. et al. A comparative study on the Cs adsorption/desorption and structural changes in different clay minerals. Environ Sci Pollut Res 31, 25342–25355 (2024). https://doi.org/10.1007/s11356-024-32826-9

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