Removal and environmentally safe disposal of As(III) and As(V)-loaded ferrihydrite/biosilica composites.

Pure ferrihydrite and ferrihydrite-biosilica composite were synthesized and studied for the removal of As(III) and As(V). The synthesized materials have an adsorption capacity higher than some reported materials in the literature - 140 and 90 mg g-1 for As(III) and As(V), respectively. The pH of the solution was shown to impact greatly on As(V) adsorption, but not on As (III), which is stable as a protonated, uncharged oxyanion, at pH < 9.2. The adsorption products were subjected to thermal treatment (500 °C for 2 h), promoting ferric arsenate formation. The adsorbed As on ferrihydrite (Fh) was shown to inhibit the phase transformation of Fh to hematite. More so, thermal treatment was shown to oxidize As(III) to As (V). The changes in the adsorption residues after thermal treatment also had an impact on As mobility. The As (III) associated with the Fh phase increased from 42 to 95%, according to a sequential extraction protocol. Therefore, this work presents a process for As removal, followed by thermal treatment of arsenic-loaded ferrihydrites which enables environmentally safe disposal of As residues.

Defects induced by Al substitution enhance As(V) adsorption on ferrihydrites.

An original rationale is proposed to explain the controversial role of aluminum, a common substitutive element in ferrihydrite (Fh), on arsenic adsorption. The adsorption of arsenic on synthetic Al-for-Fe substituted Fh (AlFh) with up to 20 mol% Al was investigated at pH 5 and 8. The reduced interplanar spacings observed by selected area electron diffraction show that all AlFh samples are isomorphically substituted up to 20 mol% Al. A 15 mol% Al incorporation increases the arsenic uptake by 28%. In contrast, the Langmuir binding constants decrease, suggesting weaker bonds. Arsenic uptake reduces by 50% as pH rises from 5 to 8. The Al-for-Fe substitution in ferrihydrite causes structural defects, proton-compensated by OH groups, as indicated by the Vegard rule deviation. X-ray photoelectron spectroscopy demonstrates the increase in the relative amount of surface M-OH sites (45% to 77%) with Al concentration (AlFh-0 to AlFh-20), respectively. The enhanced As(V) uptake was ascribed to the insertion of hydroxyls on the Fh structural defects. Fourier-transformed-infrared spectroscopy showed that the sites modified by Al introduction are involved in As adsorption. These findings help to understand aluminum's role in arsenic adsorption, fixation, and fate in the environment.