Silicate impedes arsenic release and oxidation from ferrihydrite

Silicate fertilization is a common farming practice and an effective method to mitigate arsenic (As) pollution in paddy. Investigating the interaction between silicate and ferrihydrite on As retention is key to comprehensively understand the mechanism of As sequestration by silicate fertilization. Our results indicated that the transformation of ferrihydrite into goethite and hematite was inversely proportional to Si/Fe ratios. The added silicate impeded the decrease of solution pH from neutral to acidity, and imposed strong inhibitory effect on goethite formation. The aqueous As in silicate-free system was 3.43 times higher than that with Si/Fe ratio at 0.33, but similar results were not observed in those with high-level As pollution due to the inhibitory effect of As on ferrihydrite transformation. Solid characterization showed that silicate was monomerically adsorbed to ferrihydrite through Si-O-Fe bond, which impeded the reductive dissolution, Fe atom exchange, internal atomic rearrangement and dehydration of ferrihydrite. As(III) oxidation weakened in silicate-coprecipitated ferrihydrite due to the lack of Fe(II) catalysis stem from ferrihydrite dissolution. This work demonstrated that As release could be effectively impeded through the inhibitory effect of silicate on ferrihydrite transformation, thereby providing new insights into the understanding of As accumulation reduction in rice by silicate fertilization.