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Sorption of chlorophenols on microporous minerals: mechanism and influence of metal cations, solution pH, and humic acid

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Abstract

Sorption of 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) on a range of dealuminated zeolites were investigated to understand the mechanism of their sorption on microporous minerals, while the influence of common metal cations, solution pH, and humic acid was also studied. Sorption of chlorophenols was found to increase with the hydrophobicity of the sorbates and that of the microporous minerals, indicating the important role of hydrophobic interactions, while sorption was also stronger in the micropores of narrower sizes because of greater enhancement of the dispersion interactions. The presence of metal cations could enhance chlorophenol sorption due to the additional electrostatic attraction between metal cations exchanged into the mineral micropores and the chlorophenolates, and this effect was apparent on the mineral sorbent with a high density of surface cations (2.62 sites/nm2) in its micropores. Under circum-neutral or acidic conditions, neutral chlorophenol molecules adsorbed into the hydrophobic micropores through displacing the “loosely bound” water molecules, while their sorption was negligible under moderately alkaline conditions due to electrostatic repulsion between the negatively charged zeolite framework and anionic chlorophenolates. The influence of humic acid on sorption of chlorophenols on dealuminated Y zeolites suggests that its molecules did not block the micropores but created a secondary sorption sites by forming a “coating layer” on the external surface of the zeolites. These mechanistic insights could help better understand the interactions of ionizable chlorophenols and metal cations in mineral micropores and guide the selection and design of reusable microporous mineral sorbents for sorptive removal of chlorophenols from aqueous stream.

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Acknowledgments

The constructive comments of the anonymous reviewers on an earlier version of this manuscript are greatly appreciated. This work was supported in parts by the Natural Science Foundation of China (grant nos. 41472324 and 41322024), the National Water Pollution Control and Treatment Science and Technology Project (2015ZX07406005-001), and the National Program for Support of Top-notch Young Professionals.

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Authors and Affiliations

  1. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China

    Hui Yang

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Hui Yang

  3. School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing, 100083, China

    Yuanan Hu

  4. MOE Laboratory for Earth Surface Processes, College of Urban and Environmental Sciences, Peking University, Beijing, 100871, China

    Hefa Cheng

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  1. Hui Yang
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  2. Yuanan Hu
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  3. Hefa Cheng
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Correspondence to Hefa Cheng.

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Responsible editor: Philippe Garrigues

Submitted to: Environmental Science and Pollution Research

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Yang, H., Hu, Y. & Cheng, H. Sorption of chlorophenols on microporous minerals: mechanism and influence of metal cations, solution pH, and humic acid. Environ Sci Pollut Res 23, 19266–19280 (2016). https://doi.org/10.1007/s11356-016-7128-9

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