Structural and mechanistic study of antimonite complexation with organic ligands at the goethite-water interface

Chemosphere. 2022 Aug:301:134682. doi: 10.1016/j.chemosphere.2022.134682. Epub 2022 Apr 23.

Abstract

Antimony is a re-emerging contaminant, and its complexation with natural organic matter is rising to ever-increasing levels due to global climate change, which has far-reaching impacts on its environmental fate and mobility. A molecular-level understanding of the interactions between Sb(III) and organic ligands at the solid-liquid interface is of paramount importance in deciphering the effect of these organic ligands. Herein, we identified and characterized Sb(III)-organic ligand complexes in solution and at the goethite-water interface using complementary techniques. The FT-ICR MS, XANES, and DFT calculations show that organic ligands bind Sb(III) through nucleophilic functional groups, such as -COO-, -OH and -HS. The formation of surface ternary Sb(III)-bridging complexes retarded the Sb(III) surface precipitation starting from 3.8 mg-Sb/L to a much higher level at 8.3-13.5 mg-Sb/L. The strong bond between Sb(III) and organic ligands is the key factor to inhibit Sb(III) adsorption, surface precipitation and oxidation under sunlight irradiation. Our results showed the chemical basis for the multifaceted functions of organic ligands in stabilizing trace metalloids such as Sb(III) in the environment.

Keywords: Adsorption; Antimonite; Complexation structure; Organic ligands; Surface precipitation.