Highly stable and efficient Cr(VI) immobilization from water by adsorption with the La-substituted ferrihydrite as a naturally-occurring geosorbent in soils

Ferrihydrite (Fh) is a vital geosorbent in the natural environment. Here, Fh materials with lanthanum (La) substituted in varied La/La + Fe ratios were synthesized, and these La-Fh materials were investigated in-depth via adsorption kinetic and isothermal experiments to explore their adsorption performance for chromate [Cr(VI)] in soils. Material properties of La-Fh were further characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). The results clearly indicate that La3+ can be integrated into the Fh lattice, but the increase in La amount substituted into Fh is slowed down when the La/La + Fe ratio reaches to a larger value. Those La3+ cations that fail to become integrated may either get adsorbed or form a phase of La(OH)3 on La-Fh surfaces. We also find that La substitution reduces the specific surface area (SSA) of La-Fh samples but raises their pHpzc, which hampers La-Fh conversion to hematite and thus increases the chemical stability. These changes are related to the La-Fh structure and surface aspects, but they do not negatively affect the Cr(VI) adsorption efficacy, which can be promoted over a wide pH range to an alkaline pH. For instance, the maximum adsorption amount of Cr(VI) by 20%La-Fh is 30.2 mg/g at a near-neutral pH. However, the entire chromate adsorption processes are affected by H2PO4− and humic acid due to their strong affinities for Cr(VI), but almost not influenced by NO3− and Cl−. All the Cr(VI)-Fh reactions are well described by the fitted adsorption Freundlich model and conform to the pseudo-second-order reaction kinetic equation. The mechanisms which enhance La-Fh's adsorption ability for Cr(VI) are governed by chemical interactions, because La substitution can increase the hydroxyl density on Fh surfaces and thus improve the reactivity of La-Fh towards Cr(VI), leading to an evidently enhanced Cr(VI) immobilization onto La-Fh.