Interactions of ferrous iron with clay mineral surfaces during sorption and subsequent oxidation

In submerged soils and sediments, clay minerals are often exposed to anoxic waters containing ferrous iron (Fe2+). Here, we investigated the sorption of Fe2+ onto a synthetic montmorillonite (Syn-1) low in structural Fe (<0.05 mmol Fe per kg) under anoxic conditions and the effects of subsequent oxidation. Samples were prepared at two Fe-loadings (0.05 and 0.5 mol Fe added per kg clay) and equilibrated for 1 and 30 days under anoxic conditions (O2 < 0.1 ppm), followed by exposure to ambient air. Iron solid-phase speciation and mineral identity was analysed by 57Fe Mössbauer spectroscopy and synchrotron X-ray absorption spectroscopy (XAS). Mössbauer analyses showed that Fe(ii) was partially oxidized (14-100% of total added Fe2+) upon sorption to Syn-1 under anoxic conditions. XAS results revealed that the added Fe2+ mainly formed precipitates (layered Fe minerals, Fe(iii)-bearing clay minerals, ferrihydrite, and lepidocrocite) in different quantities depending on the Fe-loading. Exposing the suspensions to ambient air resulted in rapid and complete oxidation of sorbed Fe(ii) and the formation of Fe(iii)-phases (Fe(iii)-bearing clay minerals, ferrihydrite, and lepidocrocite), demonstrating that the clay minerals were unable to protect ferrous Fe from oxidation, even when equilibrated 30 days under anoxic conditions prior to oxidation. Our findings clarify the role of clay minerals in the formation and stability of Fe-bearing solid phases during redox cycles in periodically anoxic environments.