Journal of Korean Society of Environmental Engineers (대한환경공학회지)

Korean Society of Environmental Engineers (대한환경공학회)
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Effect of Phenolic Mediators and Humic Acid on the Removal of 1-Indanone Using Manganese Oxide

망간산화물(Birnessite)을 이용한 1- Indanone 제거 시 페놀계 반응매개체와 휴믹산(HA) 영향 평가

  • Choi, Chan-Kyu (Department of Energy and Environment, The Graduate School of Energy and Environment, Seoul National University of Science and Technology) ;
  • Eom, Won-Suk (Department of Environmental Engineering, Seoul National University of Science and Technology) ;
  • Shin, Hyun-Sang (Department of Environmental Engineering, Seoul National University of Science and Technology)
  • 최찬규 (서울과학기술대학교 에너지환경대학원 에너지환경공학과) ;
  • 엄원숙 (서울과학기술대학교 환경공학과) ;
  • 신현상 (서울과학기술대학교 환경공학과)
  • Received : 2012.07.05
  • Accepted : 2012.07.23
  • Published : 2012.07.30
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Abstract

An investigation for removal of 1-indanone (1-ID), which were commonly produced from the biological and/or chemical treatment and natural weathering of the PAHs-contaminated soils, via oxidative transformation mediated by birnessite in the presence of various phenolic mediators is described. This study also examines the potential effect of the natural occurring substance humic acid (HA) on the oxidative transformation. The experiment was carried out in aqueous phase as a batch test (10 mg/L 1-ID, 0.3 mM phenolic mediators, $1.0g/L\;{\delta}-MnO_2$, at pH 5). All of the 11 tested phenoilic mediators belong to the group of natural occurring phenols and are widely used as model constituents of humic substances. From the results of HPLC analysis, it is demonstrated that 1-ID was not reactive to birnessite itself, but it can be effectively removed in birnessite-mediated cross coupling reactions in the presence of the phenolic mediators. The percent removals of 1-ID after 2 day incubation were ranged from 9.2 to 71.2% depending on the phenolic mediators applied. The initial rate constant ($K_{int}$, $hr^{-1}$) values for the 1-ID removals obtained from the pseudo-first-order kinetic plots also widely ranged from 0.18 to 15.0. Results of the correlative analysis between the removal efficiencies and structural characteristics of phenolic mediators indicate that the transformation of the 1-ID was considerably enhanced by the addition of electron-donating substituents (e.g., -OH, $-OCH_3$) at the benzne ring, and much less enhanced by the addition of electron-withdrawing substituents (e.g., -COOH, -CHO). The presence of HA showed that removal efficiencies of 1-ID in the birnessite-phenolic mediator systems decreased with increasing HA concentrations. However at low concentration of HA (< 2 mg/L), it caused some enhancement in the removals of 1-ID as compared to the control.

본 연구에서는 PAHs 오염토양의 자연 풍화 및 화학적 생물학적 처리과정에서 반응부산물로 흔히 발견되는 PAH-케톤화합물인 1-indanon (1-ID)을 대상으로 페놀계 반응매개체 존재 하에서의 망간산화물에 의한 산화 변환 제거특성 및 용존 자연유기물인 휴믹산(HA)의 존재에 따른 영향을 조사하였다. 반응성 평가 실험은 수용액 상에서 회분식(10 mg/L 1-ID, 0.3 mM phenolic mediators, $1.0g/L\;{\delta}-MnO_2$, at pH 5)으로 수행 하였으며, 페놀계의 반응매개체(phenolic mediator)는 자연산 페놀화합물로서 휴믹물질의 모델 화합물로서도 널리 사용되고 있는 11종을 사용하였다. 실험결과 1-ID은 망간산화물 자체에 대하여는 비반응성을 띠었으나 페놀계 반응매개체 존재 하에서 교차-결합(cross-coupling)반응을 통해 제거됨을 HPLC 분석을 통해 확인하였으며, 1-ID의 제거율은 반응 2일 경과 후 9.2~71.2%범위에서 페놀계 반응매개체의 구조적 특성에 따라 다르게 나타났다. 각 반응매개체 존재 하에서의 1-ID의 교차결합 반응은 유사1차 반응 속도식을 따랐으며, 초기 반응속도 상수 값($K_{int}$, $hr^{-1}$)은 0.48~15.0의 넓은 범위에서 나타났다. 1-ID의 제거효율(제거율, 속도상수)은 -OH, $-OCH_3$ 등 전자주게(electron donating) 작용기를 포함하는 반응매개체에서 높았으며, -COOH, -CHO 등 전자받게(electron withdrowing) 작용기를 포함하는 반응매개체일수록 낮았다. 또한 동일 반응 조건에서 HA 존재에 따른 영향을 검토한 결과 낮은 HA 농도(< 2 mg/L) 조건에서는 1-ID 제거효율의 상승효과를 보였으나 전체적으로는 HA 주입 농도가 증가할수록 교차 결합 반응효율이 저하됨을 확인하였다.

Keywords

Acknowledgement

Supported by : 서울과학기술대학교

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