Microscopic understanding about adsorption and transport of different Cr(VI) species at mineral interfaces

Highlights: • Cr(VI) adsorbs favorably at both surfaces of kaolinite while mechanisms are distinct; • pH variation alters Cr(VI) stabilities markedly and trends differ for two surfaces; • Electron transfers are pH-dependent and clay surfaces act as electron reservoirs; • Cr₂O₇^2- transformation to CrO₄^2- is blocked at pH ≈ PZC and preferred at pH < PZC; • Cr(VI) removal and reclamation should proceed at pH > 7 and pH < PZC, respectively. Cr(VI) ranks as one of the most toxic heavy metals and herein, microscopic mechanisms for adsorption and transport of different Cr(VI) oxyanions (Cr₂O₇^2- and CrO₄^2-) at kaolinite interfaces are addressed by dispersion-corrected periodic density functional theory calculations. Cr(VI) oxyanions adsorb favorably at both tetrahedral and octahedral surfaces, and K⁺ ions serve as bridge for Cr(VI) oxyanions and tetrahedral surfaces while Cr(VI) oxyanions serve as bridge for K⁺ ions and octahedral surfaces. Adsorption structures are altered significantly by pH variation, and stability trends at different pH ranges are deciphered by the dominant interaction force with clay surfaces: Electrostatic interaction with K⁺ ions at tetrahedral surfaces whereas combined action of electrostatic and H-bonding interactions with Cr(VI) oxyanions at octahedral surfaces. Electron transfers are strongly pH-dependent, and clay surfaces serve as electron reservoirs. CrO₄^2- rather than Cr₂O₇^2- is dominant at clay interfaces, and HCrO₄^- can co-exist under acidic conditions. Cr₂O₇^2- transformation to CrO₄^2- is kinetically blocked at pH ≈ PZC while preferred at pH < PZC. Cr(VI) removal and reclamation should proceed at pH > 7.0 and pH < PZC, respectively. Results greatly promote the understanding about Cr(VI) bioavailability and fate in surficial environments and are also useful for Cr(VI) removal and reclamation.