Adsorption of Cu(II) on soil humin: batch and spectroscopy studies

Understanding the interactions of humic substances with metal ions is of great importance in forecasting the behaviors and fates of trace metals in the environment. Humin is the least understood humic substance fraction due to its close association with the mineral matrix in soil. In this study, humin was prepared from three zonal soils (i.e., dark brown soil, yellow brown soil, and latosol) in eastern China by demineralization using HF-HCl solution after removing alkaline-soluble humic substance fractions. The adsorption properties of Cu(II) onto both humin and humic acid were examined using batch and spectroscopy (SEM, EDS, FTIR, XPS, and XAS) techniques. With respect to humic acid, humin was more aliphatic and less polar. The adsorption kinetics of humin and humic acid were best fit with pseudo-second-order kinetics equation, and the adsorption isotherms were well depicted by the Langmuir model. However, the quantity of adsorbed Cu(II) on humin was inferior to that of Cu(II) adsorbed onto humic acid. After adsorption, the surface morphology of humin and humic acid changed. Carboxyl, hydroxyl, aromatic N, and primary amine N on the surfaces of the two humic substance fractions took part in Cu(II) adsorption, and Cu(II) was bound with O/N and C atoms via inner-sphere complexation. Our results suggested that humin and humic acid had different adsorption capacity but similar adsorption mechanisms toward Cu(II).