Effects of dimethylarsenate coprecipitation with ferrihydrite on Fe(II)-induced mineral transformation and the release of dimethylarsenate.

Organoarsenicals are toxic pollutants of global concern, and their environmental geochemical behavior might be greatly controlled by iron (Fe) (hydr)oxides through coprecipitation, which is rarely investigated. Here, the effects of the incorporation of dimethylarsenate (DMAs(V)), a typical organoarsenical, into the ferrihydrite (Fh) structure on the mineral physicochemical properties and Fe(II)-induced phase transformation of DMAs(V)-Fh coprecipitates with As/Fe molar ratios up to 0.0876 ± 0.0036 under anoxic conditions and the accompanying DMAs(V) release were investigated. The presence of DMAs(V) during Fh formation gradually decreases the mineral crystallinity. With increasing DMAs(V) content, the specific surface areas of the coprecipitates are decreased owing to particle aggregation, while the micropore sizes are negligible changed. Fourier transformed infrared (FTIR) and As K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy show that, part of DMAs(V) binds to Fh surfaces in the coprecipitates by forming bidentate binuclear inner-sphere complexes through As-O-Fe bonds. During the reaction of the coprecipitate with 1 mM Fe(II) for 336 h, DMAs(V) inhibits the Fh transformation to goethite. No goethite forms at pH 4; at pH 7 low content of DMAs(V) hinders the further conversion of lepidocrocite to goethite, while high content of DMAs(V) completely inhibits goethite formation. DMAs(V) in the coprecipitate is continuously released into the solution, with the released proportion being generally increased with the increase of DMAs(V) content, pH and Fe(II) addition, probably owing to the desorption of weak inner- and outer-sphere DMAs(V) complexes bound on the Fh surfaces upon the Fh aging and transformation to lepidocrocite and goethite. These results provide deep insights into the fate and mobility of organoarsenical pollutants mediated by Fe (hydr)oxides in natural environments, and help design effective and ecofriendly remediation strategies for As polluted soils and sediments.