Biogenic Amorphous FeOOH Activated Additional Intracellular Electron Flow Pathways for Accelerating Reductive Dechlorination of Tetrachloroethylene

Dissimilatory iron-reducing bacteria (DIRB) with extracellular electron transfer (EET) capabilities have shown significant potential for bioremediating halogenated hydrocarbon contaminated sites rich in iron and humic substances. However, the role and microbial molecular mechanisms of iron-humic acid (Fe-HA) complexes in the reductive dehalogenation process of DIRB remains inadequately elucidated. In this study, we developed a sustainable carbon cycling approach using Fe-HA complexes to modulate the electron flux from sawdust (SD), enabling almost complete reductive dechlorination by most DIRB (e.g., Shewanella oneidensis MR-1) that lack complex iron-sulfur molybdo enzymes. The SD-Fe-HA/MR-1 system achieved a 96.52% removal efficiency of tetrachloroethylene (PCE) at concentrations up to 250 µmol/L within 60 days. Material characterization revealed that DIRB facilitated the hydrolysis of macromolecular carbon sources by inducing the formation of amorphous ferrihydrite (FeOOH) in Fe-HA complexes. More importantly, the bioavailable FeOOH activated additional intracellular electron flow pathways, increasing the activity of potential dehalogenases. Transcriptome further highlight the innovative role of biogenic amorphous FeOOH in integrating intracellular redox metabolism with extracellular charge exchange to facilitate reductive dechlorination in DIRB. These findings provide novel insights into accelerating reductive dechlorination in in-situ contaminated sites lacking obligate dehalogenating bacteria.