Journal of the Mineralogical Society of Korea (한국광물학회지)

The Mineralogical Society of Korea (한국광물학회)
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Study of Iodide Adsorption on Organobentonite using X-ray Absorption Spectroscopy

X-선 흡수분광기를 이용한 유기벤토나이트의 요오드 흡착연구

  • Yoon, Ji-Hae (Department of Geological & Environmental Science, Stanford University) ;
  • Ha, Ju-Young (Department of Geological & Environmental Science, Stanford University) ;
  • Hwang, Jin-Yeon (Division of Earth Environmental System, Pusan National University) ;
  • Hwang, Byoung-Hoon (Division of Earth Environmental System, Pusan National University) ;
  • Gordon E. Brown, Jr. (Department of Geological & Environmental Science, Stanford University)
  • 윤지해 (스탠포드대학교 지질환경과학과) ;
  • 하주영 (스탠포드대학교 지질환경과학과) ;
  • 황진연 (부산대학교 지구환경시스템학부) ;
  • 황병훈 (부산대학교 지구환경시스템학부) ;
  • Published : 2009.03.31
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Abstract

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, ${\mu}$-XRD, and electrophoretic mobilities measurement. Uptake measurements indicate that bentonite has a high affinity for $HDP^+$. Our ${\mu}$-XRD study indicates that organobentonites significantly expanded in basal spacing and organic cations were substantially intercalated into the interlayer spaces of bentonite. The electrophoretic mobility indicates that organobentonite tht is modified with organic cations in excess of the CEC of bentonite is completely different from untreated bentonite in the surface charge distribution. 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 $L_{III}$-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. Linear combination fitting of EXAFS data suggests the fraction of iodine reacted with the organic compound increased 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 modified property of bentonite and suggest that an organobentonite has potential as reactive barrier material around a nuclear waste repository containing anionic radioactive iodide.

유기양이온(hexadecylpyridinium chloride monohydrate ($HDP^+$))으로 개질시킨 유기벤토나이트의 특성을 유기탄소함량 측정, 마이크로-X 선회절 분석, 전기영동 이동성 측정을 이용하여 관찰하고, 무처리 벤토나이트와 유기벤토나이트의 요오드에 대한 흡착성을 비교 조사하였다. 벤토나이트는 유기양이온인 $HDP^+$에 대해서 높은 친화력을 보여주었다. 마이크로-X선 회절 분석 결과에 의하면 유기벤토나이트는 저면 간격에 있어서 현저하게 팽창을 하였고, 이는 유기 양이온이 벤토나이트의 층간에 충분히 삽입되었음을 의미한다. 전기영동 이동성 측정에 의하면벤토나이트의 양이온 교환 용량 이상의 유기 양이온으로 치환시킨 유기벤토나이트의 경우 무처리 벤토나이트와 전혀다른 표면 전하분포를 나타냄을 알 수 있다. 요오드의 흡착능에 있어서, 무처리 벤토나이트는 요오드를 전혀 흡착하지 못한 반면, 벤토나이트의 양이온 교환용량의 200% 양으로 개질 시킨 유기벤토나이트의 경우 요오드 439 mmol/kg를 흡착하였다. 유기 벤토나이트에 흡착된 요오드의 분자 환경은 요오드 K-edge와 $L_{III}$-edge X-선 흡수 분광을 이용하여 연구하였다. 유기벤토나이트의 요오드 X선 흡수 변연 구조를 통해 유기벤토나이트에 흡착된 요오드의 경우 KI 표준용액의 구조와 유사함을 알 수 있었다. 광범위 X-선 흡수 미세구조의 선형 결합 분석결과는 유기 복합체와 반응한 요오드의 비율이 벤토나이트에 흡착된 유기 복합체의 양이 증가함에 따라 같이 증가함을 나타냈다. 본 연구를 통해, 벤토나이트의 개질 특성에 의해 요오드의 흡착 환경이 현저하게 달라짐을 관찰할 수 있었으며, 음이온성 방사성 요오드를 포함하는 핵폐기물 저장소 주변의 방어벽 물질로 유기벤토나이트의 적용 가능성을 살펴 볼 수 있었다.

Keywords

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