An Experimental and Modelling Study of Cu2+ Binding on Humic Acids at Various Solution Conditions. Application of the NICA-Donnan Model

Abstract

Humic substances are characterized by a strong binding capacity for both metals and organic pollutants, affecting their mobility and bioavailability. The understanding of the mechanisms of proton and metal binding to humic substances is of fundamental importance in geochemical modelling and prediction of cation speciation in the environment. This work reports results on copper binding on humic acids obtained through a thorough experimental and modelling approach. Two humic acids, a reference purified peat humic acid isolated by the International Humic Substances Society (IHSS) and a humic acid from a Greek soil, were experimentally studied at various pH values (4, 6 and 8), humic acid concentrations (ranging from 20 to 200 mg L−1) and ionic strength (0.1 and 0.01 M NaNO3). The binding of copper to humic acids was determined over wide ranges of copper ion concentrations using a copper ion selective electrode. The copper binding isotherms obtained at different conditions have shown that copper binding is dependent on the pH and ionic strength of the solution and on the concentration of both humic acids. Copper binding experimental data were fitted to non-ideal competitive adsorption NICA-Donnan model and the model parameter values were calculated. Both Cu2+ and CuOH+ species binding to humic acid with different binding affinities were considered. Two sets of the NICA-Donnan parameters have been calculated: one for humic acid concentrations of ≥100 mg L−1and one for humic acid concentration of 20 mg L−1. The meaning of the parameters values for each concentration level is also discussed.