Cation-group interaction as the predominant force for adsorption of substituted dinitrobenzenes by smectite clays

Elucidation of the interaction between NACs and smectites is important to the understanding of the potential for transport of nitroaromatic compounds (NACs) in soils and to implementation of NAC-contaminated soil remediation. The adsorption of dinitrotoluene isomers (DNTs) and substituted dinitrobenzenes (SDNBs) by smectite was determined by batch equilibration and characterized by FTIR and XPS, along with molecular dynamics simulations. The adsorption of DNTs differed substantially among the isomers, attributed to the overall degree of nitro deflection relative to the aromatic ring plane. The substituents in SDNBs strengthened the electrostatic interaction between smectite K⁺ and nitro groups, facilitating SDNB adsorption to smectite. The competition between 2,4-DNT and 1,3-DNB, as well as the inclusion complexation of K⁺ by crown ether 18c6e, both reduced 2,4-DNT adsorption to smectite by weakening the K⁺-nitro interaction. All the results demonstrated that the electrostatic interaction between smectite K⁺ and nitro of NACs was the predominant force in mediating their adsorption. This was supported by FTIR spectra that the N-O bands shifted due to the weakening of N-O bonds and strengthening of C-N bonds via the electron transfer to cations. The XPS of smectite further manifested the cation-nitro interactions that the binding energies of K 2p 1/2, K 2p 3/2, and Si 2p shifted higher with 1,3-DNB adsorbed. Molecular dynamics simulations indicated the aromatic planes of 2,4-DNP and 2,4-DNAs were parallel to the basal plane of smectite and the oxygens of nitro groups in the molecules were directly coordinated with smectite K⁺.