Sequestration of divalent heavy metal ions from aqueous environment by adsorption using biomass-bentonite composites as potential adsorbent: Equilibrium and kinetic studies

Abstract

Hybrid clay adsorbents have been investigated in recent studies as cheap and effective adsorbents for eliminating micropollutants, such as heavy metal ions from aqueous solution. Here, we modified bentonite (BEN) with palm kernel shell and groundnut shell by calcination to obtain palm kernel shell-modified bentonite (BPKS) and groundnut shell-modified bentonite (BGS). We studied the batch equilibrium adsorption of Pb²⁺, Cd²⁺ and Ni²⁺ ions under the influence of dosage, solution pH, contact time and concentration. Under these conditions, we found that the modified adsorbents (BGS and BPKS) had a higher equilibrium adsorption (q_e) for the metal ions than unmodified BEN. BEN exhibited Langmuir adsorption capacities (Q_o) of 32.47, 14.04 and 14.16 mg/g for Pb²⁺, Cd²⁺ and Ni²⁺, respectively. BGS and BPKS had Q_o values of 29.15, 14.27, 16.61 and 31.75, 17.67, 15.625 mg/g for Pb²⁺, Cd²⁺, Ni²⁺, respectively. Investigations revealed that the rate of adsorption on the three adsorbents is best described by a pseudo-second-order kinetic model, with R² values ≥ 0.9; the intra-particle diffusion model establishes a surface interaction mechanism involving the exchange of electrons between the surfaces of the adsorbents and the adsorbate. Scanning electron microscopy results suggest porous and heterogeneous adsorbent surfaces, indicating a physio-sorption phenomenon. The modifications increased the surface area of BEN from 78.435 to 194.850 and 140.650 m²/g in BGS and BPKS, respectively, using BET surface area analysis. However, the average pore width of BEN reduces from 3.8 to 3.3 nm in both BGS and BPKS. Also, the modification enhanced the cation exchange capacity in BPKS only. The findings from this study offered invaluable insights into how biomass can enhance the physicochemical properties of BEN, as needed for practical environmental application and/or optimization, during the removal of Pb²⁺, Cd²⁺ and Ni²⁺ ions from aqueous media.