Trace elements adsorption by natural and chemically modified humic acids

Humic substances with or without chemical modification can serve as environmentally benign and inexpensive adsorbents of potentially toxic trace elements (PTTEs) in the environment. The present study investigated the absorption of Pb, Zn, Cu and Ni by natural and potassium persulfate (K₂S₂O₈) modified humic acids (HAs) isolated from a lowland peat through batch experiments. The adsorption of the studied PTTEs on the natural HA was satisfactorily described by the Langmuir isotherm model with maximum monolayer adsorption capacities of 318.2, 286.5, 225.0 and 136.8 mmol/kg for Pb, Cu, Zn and Ni, respectively. A thorough characterization of the natural and modified HA using ¹³C nuclear magnetic resonance spectroscopy demonstrated that the chemical modification of natural HA with K₂S₂O₈ led to an increase in the content of carboxyl groups, and ketone and quinoid fragments in the HA structure. Consequently, the modified HA absorbed 16.3, 14.2, 10.6 and 6.9% more Pb, Ni, Zn and Cu, respectively, than the original natural HA. The isotherm data modeling together with adsorbent characterization suggested that the adsorption of PTTEs was controlled mainly by chemisorption mechanisms where inner-sphere complexations of metal ions with HA functional groups took place.