Fe(II) Interactions with Smectites: Temporal Changes in Redox Reactivity and the Formation of Green Rust

In this study, temporal changes in the redox properties of three 0.5 g/L smectite suspensions were investigateda montmorillonite (MAu-1) and two nontronites (NAu-1 and NAu-2) in the presence of 1 mM aqueous Fe(II) at pH 7.8. X-ray absorption spectroscopy revealed that the amount of Fe(II) added quantitatively transformed into chloride-green rust (Cl-GR) within 5 min and persisted over 18 days. Over the same time, the reduction potential of all three suspensions increased by 50 to 150 mV to equilibrate at approximately -100 mV vs SHE. The reduction of a model organic contaminant, 4-chloronitrobenzene (4-CINB), also became increasingly slower over time with virtually no 4-CINB reduction being observed after 18 days. There was a strong correlation between reduction potential and the quantity of 4-ClNB reduced by MAu-1, although other factors were likely involved in the decreased redox reactivity observed in the nontronites. It is hypothesized that the temporal increase in reduction potential results from clay mineral dissolution resulting in increased Fe(III) contents in the Cl-GR. These results demonstrate that long-term studies are recommended to accurately predict contaminant management strategies.