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Effect of carboxylic and thiol ligands (oxalate, cysteine) on the kinetics of desorption of Hg(II) from kaolinite

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Abstract

Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio-uptake of Hg in the environment. We studied the kinetics of the desorption of Hg(II) from kaolinite as affected by oxalate and cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, and 7), ligand concentration (0.25 and 1.0 mM), and temperature (15°C, 25°C, and 35°C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH dependent. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed at pH 3 within 2 h, compared to <10% at pH 7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80 min with the desorption less than 20%, but the inhibition of the desorption appeared to be less prominent afterwards. The effect of the ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the Hg(II) desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particle surfaces and in the solution phase probably can also affect the Hg(II) desorption.

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Acknowledgments

This work was supported in part by the US Department of Energy (DOE) Office of Biological and Environmental Research as part of the Science Focus Area at Oak Ridge National Laboratory (ORNL) and by the Environmental Sciences Ph.D. Program of the College of Arts and Sciences at Tennessee Tech University. ORNL is managed by UT-Battelle LLC for DOE under contract DE-AC05-00OR22725. The Research Assistantship provided for Wasana U Senevirathna by the Center for the Management, Utilization, and Protection of Water Resources of TTU is appreciated. We thank Dr. Jerry Lin for his advice on the dithizone method for spectrophotometric analysis of Hg(II). We thank all the reviewers for their suggestions and comments regarding the revision of the present article.

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Authors and Affiliations

  1. Department of Chemistry, Tennessee Tech University, Cookeville, TN, 38505, Box 5055, USA

    Wasana U Senevirathna & Hong Zhang

  2. Center for the Management, Utilization, and Protection of Water Resources, Tennessee Tech University, Cookeville, TN, 38505, Box 5055, USA

    Wasana U Senevirathna & Hong Zhang

  3. Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA

    Baohua Gu

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  1. Wasana U Senevirathna
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Correspondence to Hong Zhang.

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U Senevirathna, W., Zhang, H. & Gu, B. Effect of carboxylic and thiol ligands (oxalate, cysteine) on the kinetics of desorption of Hg(II) from kaolinite. Water Air Soil Pollut 215, 573–584 (2011). https://doi.org/10.1007/s11270-010-0500-3

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