Effect of kinetics, pH, aqueous speciation and presence of ferrihydrite on vanadium (V) uptake by allophanic and smectitic clays

Sorption of oxyanions, such as pentavalent vanadium (V(V)), by reactive, poorly crystallized clay minerals and Fe-(hydr)oxides surfaces significantly contributes to the nutrient and pollutant transport in soils. However, only a few studies yet exist, which evaluate and quantify the role of such common soil substituents on V sorption. In this contribution, the uptake of V(V) by allophane with molar Al/Si ratios of 1.5 (ALO-1) and 1.8 (ALO-2) and by montmorillonite-beidellite (MNT-BEI) clays was investigated using kinetic and equilibrium experiments. The effects of pH, V speciation, contact time and presence of 6-line ferrihydrite (FHY) were evaluated at 25 °C. The clayey substrates with(out) FHY were characterized using X-ray diffraction, X-ray fluorescence, high-resolution transmission electron microscopy with energy-dispersive X-ray spectroscopy and selected area electron diffraction and N₂-Brunauer-Emmett-Teller physisorption methods. Fast (≥ 15 min) adsorption of V(V) was followed by pseudo-first-order reaction kinetics and progressed through instantaneous diffusion processes at the exterior surface. Subsequently, V(V) transportation and adsorption within the interior substrate, as inferred from Weber-Morris intra-particle diffusion model plots, was observed. The presence of FHY had a positive effect on V(V) adsorption ([V]_T = 0.02 mmol/L), which followed in the order MNT-BEI-FHY and MNT-BEI (≥ 95% removal), ALO-1-FHY and ALO-2-FHY (≥ 90% removal), ALO-1 (≥ 70% removal) and ALO-2 (≥ 40% removal) in the pH range from ~6 to ~8. The results of this study demonstrate the high affinity of ferrihydrite as well as allophanic and smectitic clays for V(V) adsorption, suggesting that these components can limit the V mobility in soils over a wide pH range.