Mechanism of Competitive Reduction of Fe(III) and As(V) Mediated by Electron Shuttles and Bacteria

Arsenic (As) contamination in groundwater represents a critical global environmental health issue. The reductive dissolution of arsenic-bearing iron oxides by dissimilatory metal-reducing bacteria (DMRB) is a key biogeochemical process driving arsenic mobilization and release in groundwater. However, the mechanism of exogenous electron shuttles in this process remains poorly understood. This study investigated the impact of the quinone-based electron shuttle anthraquinone-2,6-disulfonate (AQDS) on the reductive dissolution of arsenic-loaded goethite by the model DMRB Shewanella putrefaciens CN32 (S.P CN32). The mobilization and transformation behaviors of arsenic and iron were compared under different pH conditions and using different arsenic-loading methods (coprecipitation vs. adsorption). Results demonstrated that AQDS acted as an electron transfer mediator. It significantly enhanced the reductive dissolution of Fe(III). It also significantly enhanced the reduction of As(V). These actions collectively accelerated arsenic release and mobilization. The study also revealed a competitive preferential order in microbial reduction, where the thermodynamically more favorable Fe(III) reduction preceded As(V) reduction. Environmental pH co-regulated this process. Its influence worked through microbial activity and mineral surface properties. A neutral pH was most conducive to the AQDS-mediated bioreduction of arsenic and iron. This study elucidates the critical role of electron shuttles in the biogeochemical cycling of arsenic in contaminated sites, providing a scientific basis for a deeper understanding of the formation mechanisms and risk assessment of high-arsenic groundwater.