Prediction of polarity-dependent environmental behaviors of humic substances (HS) using a HS hydrophobicity index based on hydrophilic interaction chromatography.

Tae Jun Park, Hyun-Sang Shin, Jin Hur

The Science of the total environment 2022 Oct 15

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A variety of analytical methods have been applied to describe the properties of aquatic humic substances (HS). However, there are only a few methods available to probe HS hydrophobicity because of the heterogeneous character of HS. In this study, hydrophilic interaction chromatography (HILIC) equipped with a UV detector was employed to describe the heterogeneous distribution of HS with respect to its hydrophobicity and to suggest a representative HS hydrophobicity index. To this end, various mobile phases were explored to achieve the optimal separation capability of HILIC. The highest resolution was obtained with a mobile phase comprising acetonitrile and water at a ratio of 70:30 (v:v). A calibration curve was successfully constructed using eight different HS precursor compounds, which allowed for the successful conversion of the retention time (RT) into the octanol-water partition coefficient (Kow) (log Kow = -2.83 × (RT) + 17.44, R2 = 0.950). Several possible HS hydrophobicity indices were derived from the HILIC chromatogram. Among those, the weight-average log KOW value exhibited the strongest negative correlation with the well-known polarity index, (O + N)/C ratios, of seven reference HS samples. This new HILIC-based index (i.e., average log KOW) also presented a good relationship with the HS binding coefficients with pyrene as well as the extent of HS adsorption onto kaolinite at a given solution chemistry (i.e., at a high ionic strength and a neutral pH), both of which are known to be largely governed by the hydrophobic nature of HS. This study demonstrated that the average KOW value based on HILIC is an intuitive and robust HS hydrophobicity index to fully represent the heterogeneous distribution of hydrophobicity within a bulk HS and could be applied to predict many environmental behaviors related to HS hydrophobicity or HS polarity. Copyright © 2022 Elsevier B.V. All rights reserved.

Citation

Tae Jun Park, Hyun-Sang Shin, Jin Hur. Prediction of polarity-dependent environmental behaviors of humic substances (HS) using a HS hydrophobicity index based on hydrophilic interaction chromatography. The Science of the total environment. 2022 Oct 15;843:156993