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Adsorption of Soil-Derived Humic Acid by Seven Clay Minerals: A Systematic Study

Published online by Cambridge University Press:  01 January 2024

Rebecca A. Chotzen
Department of Soil and Water Sciences, Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot 7610001, Israel
Tamara Polubesova*
Department of Soil and Water Sciences, Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot 7610001, Israel
Benny Chefetz
Department of Soil and Water Sciences, Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot 7610001, Israel
Yael G. Mishael*
Department of Soil and Water Sciences, Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, P.O. Box 12, Rehovot 7610001, Israel
*E-mail address of corresponding author:,
*E-mail address of corresponding author:,


Humic acid (HA)-clay complexes are well known for their contribution to soil structure and environmental processes. Despite extensive research, the mechanisms governing HA adsorption are yet to be resolved. A systematic study was conducted to characterize the adsorption of a soil-derived HA to seven clay minerals. Clay surfaces affected HA adsorption directly due to structural differences and indirectly by altering solution pH. The following order of HA removal was obtained for the clay minerals at their natural pH: illite ≫ palygorskite > kaolinite > sepiolite > montmorillonite = hectorite ≫ talc. Removal of HA (precipitation and adsorption) by kaolinite and illite was attributed to the low pH they induce, resulting in protonation of the clay and HA surfaces. In spite of the low pH, the zeta potential for HA remained negative, which promoted HA adsorption to the protonated clay surfaces by ligand exchange. Ionic strength did not affect HA adsorption to clay minerals with low zeta potentials, indicating that charge screening is not a major mechanism of HA adsorption for these minerals, and supporting the suggestion that ligand exchange is the main adsorption mechanism to pH-dependent sites. The increase in ionic strength did, however, promote HA adsorption to clay minerals with high zeta potentials. At pH 8–9 the order of HA affinity for clay minerals was: palygorskite >>sepiolite > montmorillonite = hectorite > kaolinite > illite > talc, emphasizing strong HA interactions with the fibrous clays. This strong affinity was attributed to their large surface areas and to strong interactions with OH groups on these clay surfaces. Results indicated that HA did not enter the intracrystalline channels of the fibrous clays but suggested that their macro-fiber structure facilitates HA adsorption. The sorption of HA to kaolinite further increased in the presence of Cu2+, and the sorption of Cu2+ increased in the presence of HA, due to a number of synergistic effects. This study emphasizes the diverse effects of clay structure and solution chemistry on HA adsorption.

Copyright © Clay Minerals Society 2016

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This paper is published as part of a special section on the subject of ‘Clays in the Critical Zone,’ arising out of presentations made during the 2015 Clay Minerals Society-Euroclay Conference held in Edinburgh, UK.


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