• Journal of Korean Society of Environmental Engineers
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• v.30 no.9
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• pp.893-899
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• 2008

Changes in spectroscopic characteristics and pyrene binding coefficients of terrestrial dissolved organic matters(DOM) were investigated during microbial incubation. The incubation studies were conducted for 21 days using a leaf litter DOM and a soilderived DOM with an inoculum from a river. The dissolved organic carbon(DOC), the specific UV absorbance(SUVA), the synchronous fluorescence spectra, and the pyrene organic carbon-normalized binding coefficient(K$_{oc}$) of the DOM were measured at the incubation days of 0, 3, 7, 14 and 21. After the 21-day incubation, DOC were reduced to 61% and 51% of the original concentrations of the litter DOM and the soil-derived DOM, respectively. Comparison of the spectroscopic characteristics before and after the incubation revealed that the SUVA, the fulvic-like fluorescence(FLF), the humic-like fluorescence(HLF) of the different DOM were enhanced by the incubation whereas the protein-like fluorescence(PLF) was reduced. This indicates that more aromatic and humic-like compounds were enriched during the biodegradation process while biodegradable and weak carbon structures were depleted. Irrespective of the DOM sources, SUVA values showed a positive relationship with pyrene K$_{oc}$ with a correlation coefficient of 0.97. The FLF and HLF also exhibited good correlations with K$_{oc}$ values although different regression equations were obtained from the different DOM. Our results suggest that the selected spectroscopic characteristics could be good estimation indices for the changes of the binding reactivity of DOM for hydrophobic organic contaminants during biodegradation process.

• Journal of Soil and Groundwater Environment
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• v.9 no.3
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• pp.12-19
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• 2004

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.

• Journal of Soil and Groundwater Environment
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• v.10 no.5
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• pp.61-69
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• 2005

Changes in pyrene binding by dissolved and kaolinite-associated humic substances (HS) due to HS adsorptive fractionation processes were examined using purified Aldrich humic acid (PAHA) at different pH (4, 7 and 9). Irrespective of solution pH, molecular weight (MW) fractionation occurred upon adsorption of PAHA onto kaolinite, resulting in the deviation of residual PAHA MW from the original MW prior to sorption. Variation in $K_{OC}$ by bulk PAHA was observed at different pH due to relative contributions of partitioning and size exclusion effects (i.e., specific interactions). For all pH conditions investigated, carbon-normalized pyrene binding coefficients for nonadsorbed, residual fractions $(K_{OC}(res))$ were different from the original dissolved PAHA $K_{OC}$ value $(K_{OC}(orig))$ prior to contact with the kaolinite suspensions. Positive correlations between pyrene $(K_{OC}(res))$ and weight-average molecular weight $(MW_W)$ for residual PAHA fractions were observed for pH 7 and 9. However, such a positive correlation was not found at pH 4 due to the absence of the dramatic fractionation observed for high pH conditions (i.e., exclusive fractionation with respect to higher MW), suggesting that actual MW distribution pattern is more important for sorption-fractionated HS than the composite MW value. For adsorbed PAHA, conformational changes of PAHA upon adsorption seem to be important for the extent of pyrene binding. At relatively high pH (7 and 9), lower extent of pyrene binding was observed for adsorbed PAHA versus nonadsorbed PAHA. The conformation effects were more pronounced at higher pH.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.11
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• pp.1067-1074
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• 2008

In this study, the organic carbon normalized-sorption coefficients (Koc) for the binding affinity of phenanthrene (PHE) to 16 different soil humic and fulvic acids of various origins were determined by fluorescence quenching. The humic and fulvic acids used in this study were isolated from 6 different domestic soils including Mt. Hanla soil, IHSS standard soil and peat as well as Aldrich humic acid and characterized by elemental composition, ultraviolet absorption at 254 nm, composition of main structural fragments determined by CPMAS $^{13}$C NMR. The Koc values($\times$10$^4$, L/kg C) for each of HA and FA samples were in the range of 1.48$\sim$8.65 and higher in HA compared to that of FA(3.13$\sim$8.65 vs 1.48$\sim$2.48) in the experimental condition([PHE]/[HS] = 0.02$\sim$0.2(mg/L)/(mg-OC/L), pH 6). The correlation study between the structural descriptors of humic and fulvic acids and log Koc values of phenanthrene, show that the magnitude of Koc values positively correlated with the UV$_{254}$ absorptivity([ABS]$_{254}$) and two $^{13}$C NMR descriptors (C$_{Ar-H,C}$, $\sum$C$_{Ar}$/$\sum$C$_{Alk}$), while negatively correlated with the independent descriptors of the(N+O)/C atomic ratios and $^{13}$C NMR descriptors (I$_{C-O}$/I$_{C-H,C}$). These results confirmed that the binding affinity for the hydrophobic organic compound, phenanthrene are significantly influenced by the polarity and aromaticity of soil humc and fulvic acids.