Antimony(V) Incorporation into Schwertmannite: Critical Insights on Antimony Retention in Acidic Environments

Environ Sci Technol. 2022 Dec 20;56(24):17776-17784. doi: 10.1021/acs.est.2c07341. Epub 2022 Nov 29.

Abstract

This study examines incorporation of Sb(V) into schwertmannite─an Fe(III) oxyhydroxysulfate mineral that can be an important Sb host phase in acidic environments. Schwertmannite was synthesized from solutions containing a range of Sb(V)/Fe(III) ratios, and the resulting solids were investigated using geochemical analysis, powder X-ray diffraction (XRD), dissolution kinetic experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. Shell-fitting and wavelet transform analyses of Sb K-edge EXAFS data, together with congruent Sb and Fe release during schwertmannite dissolution, indicate that schwertmannite incorporates Sb(V) via heterovalent substitution for Fe(III). Elemental analysis combined with XRD and Fe K-edge EXAFS spectroscopy shows that schwertmannite can incorporate Sb(V) via this mechanism at up to about 8 mol % substitution when formed from solutions having Sb/Fe ratios ≤0.04 (higher ratios inhibit schwertmannite formation). Incorporation of Sb(V) into schwertmannite involves formation of edge and double-corner sharing linkages between SbVO6 and FeIII(O,OH)6 octahedra which strongly stabilize schwertmannite against dissolution. This implies that Sb(V)-coprecipitated schwertmannite may represent a potential long-term sink for Sb in acidic environments.

Keywords: EXAFS; Sb; antimonate; coprecipitation; shell fitting; wavelet transform.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adsorption
  • Antimony / chemistry
  • Ferric Compounds* / chemistry
  • Iron Compounds* / chemistry
  • Iron Compounds* / metabolism
  • Minerals / chemistry
  • Oxidation-Reduction

Substances

  • schwertmannite
  • Ferric Compounds
  • Antimony
  • Iron Compounds
  • Minerals