Alteration of ferrihydrite reductive dissolution and transformation by adsorbed As and structural Al: Implications for As retention

Reduction of As(V) and reductive dissolution and transformation of Fe (hydr)oxides are two dominant processes controlling As retention in soils and sediments. When developed within soils and sediments, Fe (hydr)oxides typically contain various impurities—Al being one of the most prominent—but little is known about how structural Al within Fe (hydr)oxides alters its biotransformation and subsequent As retention. Using a combination of batch and advective flow column studies with Fe(II) and Shewanella sp. ANA-3, we examined (1) the extent to which structural Al influences reductive dissolution and transformations of ferrihydrite, a highly reactive Fe hydroxide, and (2) the impact of adsorbed As on dissolution and transformation of (Al-substituted) ferrihydrite and subsequent As retention. Structural Al diminishes the extent of ferrihydrite reductive transformation; nearly three-orders of magnitude greater concentration of Fe(II) is required to induce Al-ferrihydrite transformation compared to pure two-line ferrihydrite. Structural Al decreases Fe(II) retention/incorporation on/into ferrihydrite and impedes Fe(II)-catalyzed transformation of ferrihydrite. Moreover, owing to cessation of Fe(II)-induced transformation to secondary products, Al-ferrihydrite dissolves (incongruently) to a greater extent compared to pure ferrihydrite during reaction with Shewanella sp. ANA-3. Additionally, adsorption of As(V) to Al-ferrihydrite completely arrests Fe(II)-catalyzed transformation of ferrihydrite, and it diminishes the difference in the rate and extent of ferrihydrite and Al-ferrihydrite reduction by Shewanella sp. ANA-3. Our study further shows that reductive dissolution of Al-ferrihydrite results in enrichment of Al sites, and As(V) reduction accelerates As release due to the low affinity of As(III) on these non-ferric sites.