Cu, Pb, And Zn Sorption To Biogenic Iron (Oxyhydr)Oxides Formed In Circumneutral Environments

The transportation and immobilization of potentially toxic metals in near-surface environments may be partially controlled by sorption processes at the solid-water interface. Myriad studies have shown that iron (oxyhydr)oxides have large sorption capacities and form strong surface complexes with metal ions. Biogenic iron (oxyhydr)oxides (BIOS) form at redox gradients where dissolved ferrous iron encounters oxygenated conditions, allowing bacteria to outcompete abiotic Fe oxidation. This process produces biominerals with distinct surface and structural properties (incorporation of cell-derived organic matter, poor crystallinity, and small particle sizes) that may alter their metal-binding affinity and sorption processes. To better understand metal binding by BIOS, Cu, Pb, and Zn, sorption rate and isotherm studies were conducted with synthetic two-line ferrihydrite and BIOS. Additionally, X-ray absorption spectroscopy and total scattering were used to elucidate the BIOS mineral structure and metal ion surface structures. On a mass normalization basis, BIOS sorbed approximately 8, 4, and 2 times more Cu, Pb, and Zn, respectively, than 2LFh over similar dissolved concentrations. Spectroscopic analyses revealed poorly crystalline structures and small coherent scattering domain sizes for BIOS. Additionally, extended X-ray absorption fine-structure spectroscopy revealed Cu, Pb, and Zn sorbed to BIOS via inner-sphere complexes, similar to 2LFh. These results suggest that, in metal contaminated environments, BIOS are more efficient in metal binding than their synthetic counterparts.