Adsorption of As(V) at Humic Acid-Kaolinite-Bacteria Interfaces: Kinetics, Thermodynamics, and Mechanisms

The immobilization and transformation of arsenic at the mineral-organic interface in soil environments ultimately depend on the soil components and their interactions. Herein, the effect of humic acid (HA) and a typical bacterium (a Gram-positive Bacillus subtilis) coating on the adsorption of arsenate As(V) to kaolinite (Kao) mineral was investigated. The As(V) adsorption reaction kinetics, isotherms, thermodynamics, and mechanism on the clay mineral-organic composites of kaolinite-Bacillus subtilis (Kao-B.s) and humic acid-kaolinite-Bacillus subtilis (Kao-HA-B.s) were investigated. The As(V) adsorption on the composites was better fitted to pseudo-second-order kinetics and the Freundlich model. The adsorption capacity of As(V) followed the order of Kao-HA-B.s > Kao-B.s > B.s > Kao-HA > Kao. The positive ΔH (31.44, 5.87 kJ mol−1) and ΔG (0.10–0.96 kJ mol−1) values confirmed that the adsorption of As(V) by all composites was nonspontaneous and endothermic in character at room temperature. The FT-IR, XRD, and thermodynamic results revealed that the adsorption mechanism of As(V) on the kaolinite–organic interfaces could be attributed to the electrostatic forces between the terminal aluminum or silanol groups of kaolinite and As(V) and the complexation between HA, bacteria, and As(V), which formed an inner-sphere complex and surface complex, respectively. The experimental results showed that the adsorption of As(V) on the Kao-HA or Kao-bacteria system was accompanied by significant additive interactions, while the ternary Kao-HA-bacteria system had a significant inhibitory effect on As(V) binding at a higher HA content due to the shielding effect, with the promotion effect shown at a lower concentration for dispersion effect for HA on the kaolinite particles.