Reduction Pathway-Dependent Formation of Reactive Fe(II) Sites in Clay Minerals.

Structural Fe in clay minerals is an important, potentially renewable source of electron equivalents for contaminant reduction, yet our knowledge of how clay mineral Fe reduction pathways and Fe reduction extent affect clay mineral Fe(II) reactivity is limited. Here, we used a nitroaromatic compound (NAC) as a reactive probe molecule to assess the reactivity of chemically reduced (dithionite) and Fe(II)-reduced nontronite across a range of reduction extents. We observed biphasic transformation kinetics for all nontronite reduction extents of ≥5% Fe(II)/Fe(total) regardless of the reduction pathway, indicating that two Fe(II) sites of different reactivities form in nontronite at environmentally relevant reduction extents.