Recent Published Articles

Mechanistic insight into Cr(VI) retention by Si-containing ferrihydrite


Song Wang , Ying Hu , Qiang Xue , Honghan Chen , Huaming Guo , Kenneth C. Carroll

DOI:10.1016/j.jes.2023.05.040

Received April 02, 2023,Revised , Accepted May 28, 2023, Available online June 03, 2023

Volume 36,2024,Pages 217-225

Hexavalent chromium [Cr(VI)] causes serious harm to the environment due to its high toxicity, solubility, and mobility. Ferrihydrites (Fh) are the main adsorbent and trapping agent of Cr(VI) in soils and aquifers, and they usually coexist with silicate (Si), forming Si-containing ferrihydrite (Si-Fh) mixtures. However, the mechanism of Cr(VI) retention by Si-Fh mixtures is poorly understood. In this study, the behaviors and mechanisms of Cr(VI) adsorption onto Si-Fh with different Si/Fe molar ratios was investigated. Transmission electron microscope, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and other techniques were used to characterize Si-Fh and Cr(VI)-loading of Si-Fh. The results show that specific surface area of Si-Fh increases gradually with increasing Si/Fe ratios, but Cr(VI) adsorption on Si-Fh decreases with increasing Si/Fe ratios. This is because with an increase in Si/Fe molar ratio, the point of zero charge of Si-Fh gradually decreases and electrostatic repulsion between Si-Fh and Cr(VI) increases. However, the complexation of Cr(VI) is enhanced due to the increase in adsorbed hydroxyl (A-OH-) on Si-Fh with increasing Si/Fe molar ratio, which partly counteracts the effect of the electrostatic repulsion. Overall, the increase in the electrostatic repulsion has a greater impact on adsorption than the additional complexation with Si-Fh. Density functional theory calculation further supports this observation, showing the increases in electron variation of bonding atoms and reaction energies of inner spherical complexes with the increase in Si/Fe ratio.

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