Journal of Soil and Groundwater Environment (한국지하수토양환경학회지:지하수토양환경)

Korean Society of Soil and Groundwater Environment (한국지하수토양환경학회)
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Polycyclic Aromatic Hydrocarbon (PAH) Binding to Dissolved Humic Substances (HS): Size Exclusion Effect

  • Hur, Jin (School of the Environment, Clemson University)
  • Published : 2004.09.01
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Abstract

Binding mechanisms of polycyclic aromatic hydrocarbons (PAHs) with a purified Aldrich humic acid (PAHA) and its ultrafiltration (UF) size fractions were investigated. Organic carbon normalized binding coefficient ($K_oc$) values were estimated by both a conventional Stern-Volmer fluorescence quenching technique and a modified fluorescence quenching method. Pyrene $K_oc$ values depended on PAHA concentration as well as freely dissolved pyrene concentration. Such nonlinear sorption-type behaviors suggested the existence of specific interactions. Smaller molecular size PAH (naphthalene) exhibited higher $K_oc$ value with medium-size PAHA UF fractions whereas larger size PAH (pyrene) had higher extent of binding with larger PAHA UF fractions. The inconsistent observation for naphthalene versus pyrene was well explained by size exclusion effect, one of the previously suggested specific mechanisms for PAH binding. In general, the extent of pyrene binding increased with lower pH likely due to the neutralization of acidic functional groups in HS and the subsequent increase in hydrophobic HS region. However, pyrene $K_oc$ results with a large UF fraction (>100K Da) corroborated the existence of the size exclusion effect as demonstrated by an increase in $K_oc$ values at a certain higher pH range. The size exclusion effect appears to be effective only for the specific conditions (HS size or pH) that render HS hole st겨ctures to fit a target PAH.

정제된 Aldrich 휴믹산(PAHA)과 한외 여과된 다양한 크기의 PAHA 성분들(PAHA UF fractions)을 이용하여 여러 고리 방향족 탄화수소(PAH)와의 결합 메커니즘을 조사하였다. 유기탄소 결합계수($K_oc$)는 전통적인 Stern-Volmer 형광 소광법과 변형 형광 소광법 두 가지를 이용하여 구하였다. 구해진 Pyrene $K_oc$ 값은 PAHA 농도와 자유 용존 pyrene 농도에 의존하였다. 이러한 비선형 흡착결합 양상은 두 물질간의 흡착성 고유상호작용이 존재한다는 것을 암시하였다. 상대적으로 분자크기가 작은 naphthalene은 중간 크기의 PAHA UF fractions과의 결합에서 높은 $KK_oc$ 값을 보여준 반면 분자 크기의 큰 PAH,즉 pyrene의 경우에는 PAHA UF fractions 크기가 크면 클수록 더 결합이 잘 되었다. 이러한 두 PAH 물질간의 불일치한 크기별 결합양상은 현재까지 제시된 고유 결합 메커니즘들 중의 하나 인 크기별 배제(size exclusion) 효과로 잘 설명되었다. 다양한 pH 조건하에서의 PAH $K_oc$ 실험에서는 일반적으로 pH가 낮아질수록 휴믹산의 산성작용기가 중화되고 그에 따라 휴믹산내의 소수성 영역이 커짐으로 인해 pyrene과 휴믹산과의 결합정도는 커졌다. 그러나 큰 사이즈의 PAHA UF fraction(>100K Da)을 사용한 실험에서는 낮은 pH가 아닌 특정 pH 범위에서 또 하나의 높은 pyrene $KK_oc$ 값을 보여줌으로서 크기별 배제 효과가 존재함을 뚜렷이 보여주었다. 이러한 크기별 배제 효과는 휴믹산의 홀(hole)구조가 PAH 크기에 적합하게 구성되어 있는 조건(휴믹성분 크기 혹은 pH)에서만 작용하는 것으로 보인다.

Keywords

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