Journal of Soil and Groundwater Environment (한국지하수토양환경학회지:지하수토양환경)

Korean Society of Soil and Groundwater Environment (한국지하수토양환경학회)
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Effects of Humic Acid on the pH-dependent Sorption of Europium (Eu) to Kaolinite

PH 변화에 따른 카올리나이트와 유로퓸(Eu)의 흡착에 대한 휴믹산의 영향

  • Harn, Yoon-I (Department of Environmental Energy Engineering, Seoul National University of Technology) ;
  • Shin, Hyun-Sang (Department of Environmental Energy Engineering, Seoul National University of Technology) ;
  • Rhee, Dong-Seok (Division of Environmental and Geosystem Engineering, Kangwon National University) ;
  • Lee, Myung-Ho (Nuclear Chemistry, Korea Atomic Energy Research Institute) ;
  • Chung, Euo-Cang (Nuclear Chemistry, Korea Atomic Energy Research Institute)
  • 한윤이 (서울산업대학교 에너지환경대학원 에너지환경공학과) ;
  • 신현상 (서울산업대학교 에너지환경대학원 에너지환경공학과) ;
  • 이동석 (강원대학교 지구환경공학부) ;
  • 이명호 (한국원자력연구원 원자력화학연구부) ;
  • 정의창 (한국원자력연구원 원자력화학연구부)
  • Published : 2009.08.31
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Abstract

The sorption of europium (Eu (III)) onto kaolinite and the influence of humic acids over a range of pH 3 ~ 11 has been studied by batch adsorption experiment (V/m = 250 : 1 mL/g, $C_{Eu(III)}\;=\;1\;{\times}\;10^{-5}\;mol/L$, $C_{HA}\;=\;5{\sim}50\;mg/L$, $P_{CO2}=10^{-3.5}\;atm$). The concentrations of HA and Eu(III) in aqueous phase were measured by UV absorbance at 254nm (e.g., $UV_{254}$) and ICP-MS after microwave digestion for HA removals, respectively. Results showed that the HA sorption onto kaolinite was decreased with increasing pH and their sorption isotherms fit well with the Langmuir adsorption model (except pH 3). Maximum amount ($q_{max}$) for the HA sorption at pH 4 to 11 was ranged from 4.73 to 0.47 mg/g. Europium adsorption onto the kaolinite in the absence of HA was typical, showing an increases with pH and a distinct adsorption edge at pH 3 to 5. However in the presence of HA, Eu adsorption to kaolinite was significantly affected. HA was shown to enhance Eu adsorption in the acidic pH range (pH 3 ~ 4) due to the formation of additional binding sites for Eu coming from HA adsorbed onto kaolinite surface, but reduce Eu adsorption in the intermediate and high pH above 6 due to the formation of aqueous Eu-HA complexes. The results on the ternary interaction of kaolinte-Eu-HA are compared with those on the binary system of kaolinite-HA and kaolinite-Eu and adsorption mechanism with pH was discussed.

본 연구에서는 pH(3 ~ 11)에 따른 카올리나이트(kaolinite)와 유로퓸(Eu(III)의 흡착에 있어서 휴믹산(HA)이 미치는 영향을 회분식 실험(V/m = 250 : 1 mL/g, $C_{Eu(III)}\;=\;1\;{\times}\;10^{-5}\;mol/L$, $C_{HA}\;=\;5{\sim}50\;mg/L$, $P_{CO2}=10^{-3.5}\;atm$)을 통해 조사하였다. 반응 상등액 중 HA 농도는 254 nm에서의 UV 흡광도(즉, $UV_{254}$) 분석을 통해 결정하였고, Eu(III) 농도는 마이크로웨이브(microwave)를 통한 전처리 후 ICP-MS를 이용하여 측정하였다. 실험결과, 카올리나이트에 대한 HA의 흡착은 전형적인 Langmuir 흡착 특성(pH 3 제외)을 보였으며, pH가 증가할수록 감소하였다. pH 4 ~ 11에서의 최대 흡착량($q_{max}$)은 4.73 ~ 0.47 mg/g의 범위이었다. 카올리나이트에 대한 Eu(III) 흡착은 pH 3 ~ 5에서 급격히 증가한 이 후 pH 6이상에서 흡착포화(adsorption edge)에 도달하는 전형적인 Eu-광물질 흡착곡선을 보였다. 그러나 HA가 존재하는 경우 pH에 따른 흡착특성에 변화를 보였다. 즉, pH가 낮은 산성영역(pH 3 ~ 4)에서는 카올리나이트에 흡착된 HA에 의한 Eu의 추가 흡착으로 인해 Eu의 흡착율이 상승하나, 중성 및 알칼리 영역(pH > 6)에서는 용존성 EuHA 착물 형성으로 인해 Eu 흡착율이 크게 감소하였다. 이러한 카올리나이트-Eu-HA 삼성분계에서의 흡착실험 결과는 카올리나이트-HA, 카올리나이트-Eu 등의 결과와 비교 해석하였고, pH에 따른 흡착 기작의 차이점을 고찰하였다.

Keywords

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