Facet-dependent adsorption of aromatic organoarsenicals on hematite: The mechanism and environmental impact

Abstract

Aromatic organoarsenic feed additives have been extensively used in poultry and livestock farming; however, a risk of releasing toxic inorganic arsenic exists when they are exposed to the environment. An in-depth understanding of the adsorption -migration behavior of aromatic organoarsenicals on environmental media is limited. In this study, p-arsanilic acid (p-ASA) and roxarsone (ROX) were considered as examples to systematically study their adsorption behaviors on the surface of hematite, a representative iron oxide in soil. By comparing the adsorption abilities and adsorption kinetics of hematite exposed with different facets (hexagonal nanoplates, HNPs, mainly exposed with {001} facets and hexagonal nanocubes, HNCs, exposed with {012} facets), combined with in situ shell-isolated nanoparticle enhanced Raman spectroscopy characterization and density functional theory simulation, the facet-dependent adsorption performance was observed and the mechanism revealed. The results showed that p-ASA formed a bidentate binuclear complex on HNCs and HNPs, whereas ROX formed monodentate mononuclear and bidentate binuclear configurations on the {001} and {012} facets, respectively. These differences not only lead to facet-dependent adsorption capacities but also affect their stability, as verified by sequential extraction experiments, affecting the environmental behavior and fate of aromatic organoarsenicals. This study not only provides insights into the environmental behavior of aromatic organoarsenicals but also offers theoretical support for the development of functional adsorbents and remediation strategies.