Characteristics of Organobentonite and Study of Iodide Adsorption on Organobentonite using X-ray Absorption Spectroscopy

The adsorption of iodide on untreated bentonite and bentonites modified with organic cation (i.e., hexadecylpyridinium chloride monohydrate (HDP+)) was investigated, and the organobentonites were characterized using uptake measurements, micro X-ray diffraction (micro-XRD), and electrophoretic mobility measurements prior to reaction with KI solutions. Uptake measurements indicate that bentonite has a high affinity for HDP+. Increasing [HDP+](aq) results in an increase in HDP+ uptake on bentonite by up to 280% of the CEC equivalents of bentonite, and causes a concomitant increase in Na released as a result of the replacement of exchangeable inorganic cations in bentonite interlayers. Based micro-XRD, the d001 spacing of untreated bentonite was 1.22 nm whereas organobentonites modified with HDP+ at different equivalent amounts, corresponding to 100%, 200%, and 400% of the cation exchange capacity (CEC) of bentonite, showed d001 spacings of 1.96 nm, 3.77 nm, and 3.77 nm, respectively. Our micro-XRD study indicates that organobentonites significantly expanded in basal spacing and organic cations were substantially intercalated into the interlayer spaces of montmorillonite. The electrophoretic mobility indicates that the untreated bentonite had a negative surface charge over the entire pH range examined (pH 2-12) whereas the organobentonite at an equivalent amount corresponding to 200% of the CEC had a positive surface charge over this pH range. We found significant differences in adsorption capacities of iodide depending on the bentonite properties as follows: iodide adsorption capacities were 439 mmol/kg for the bentonite modified with HDP+ at an equivalent amount corresponding to 200% of the CEC of bentonite whereas no adsorption of iodide was observed for the untreated bentonite. The molecular environments of iodine adsorbed on organobentonites were further studied using I K-edge and LIII-edge x-ray absorption spectroscopy (XAS). The X-ray absorption near-edge structure (XANES) of iodine spectra from organobentonites was similar to that of KI reference solution. Quantitative analysis of EXAFS spectra of organobentonite samples indicates that iodine is bound to carbon and the coordination number and interatomic distances between I-C varied depending on the organic concentration on bentonite. Linear combination fitting of EXAFS data suggests the fraction of iodine reacted with the organic compound increased from 49% to 77% with increasing loading of the organic compound on organobentonites. In this study, we observed significant differences in the adsorption environments of iodide depending on the property of the bentonite, and suggest that these molecular-level differences result in an organobentonite that has potential as reactive barrier material around a nuclear waste repository containing radioactive iodide.