Arsenic(III) sorption on organo-ferrihydrite coprecipitates: Insights from maize and rape straw-derived DOM

Abstract

The mobility of arsenic (As) specie in agricultural soils is significantly impacted by the interaction between ferrihydrite (Fh) and dissolved organic material (DOM) from returning crop straw. However, additional research is necessary to provide molecular evidence for the interaction of toxic and mobile As (As(III)) specie and crop straw-based organo- Fh coprecipitates (OFCs). This study investigated the As(III) sorption behaviours of OFCs synthesized with maize or rape derived-DOM under various environmental conditions and the primary molecular sorption mechanisms using As K-edge X-ray absorption near edge structure (XANES) spectroscopy. According to our findings, pure Fh adsorbed more As(III) relative to the other two OFCs, and the presence of natural organic matter in the OFCs induced more As(III) adsorption at pH 5.0. Findings from this study indicated a maximum As(III) sorption on Ma (53.71 mg g⁻1) and Ra OFC (52.46 mg g⁻1) at pH 5.0, with a sharp decrease as the pH increased from 5.0 to 8.0. Additionally, As K-edge XANES spectroscopy indicated that ∼30% of adsorbed As(III) on the OFCs undergoes transformation to As(V) at pH 7–8. Functional groups from the DOM, such as O–H, COOH, and CO, contributed to As(III) desorption and its oxidation to As(V), whereas ionic strength analysis revealed inner complexation as the dominant As(III) sorption mechanism on the OFCs. Overall, the results indicate that the interaction of natural organic matter (NOM) with As(III) at higher pH promotes As(III) mobility, which is crucial when evaluating As migration and bioavailability in alkaline agricultural soils.