Engineering Biogenic Magnetite for Sustained Cr(VI) Remediation in Flow-through Systems

In this work, we report a route to enhance the reactivity and longevity of biogenic magnetite in Cr(VI) remediation under continuous-flow conditions by combining functionalization of the biomagnetite surface with a precious metal catalyst, nanoscale palladium, and exposure to formate. Column influent conditions were varied to simulate oxic, anoxic, and nitrate cocontaminated environments. The addition of sodium formate as an electron donor for Pd-fiinctionalized magnetite increased capacity and longevity allowing 80% removal of Cr(VI) after 300 h in anoxic conditions, whereas complete breakthrough occurred after 60 h in anoxic nonformate and nonfunctionalized systems. Removal of Cr(VI) was optimized under anoxic conditions, and the presence of oxidizing agents results in a modest loss in reductive capacity. Examination of reacted Pd-fiinctionalized magnetite reveals close association of Fe with Cr, suggesting that Pd-coupled oxidation of formate serves to regenerate the reactive surface. XMCD studies revealed that Cr(III) is partially substituted for Fe in the magnetite structure, which serves to immobilize Cr. No evidence for a mechanistic interference by nitrate cocontamination was observed, suggesting that this novel system could provide robust, effective and sustained reduction of contaminants, even in the presence of common oxidizing cocontaminants, outperforming the reductive capacity of nonfunctionalized biogenic magnetite.