Iron(III)-Bearing Clay Minerals Enhance Bioreduction of Nitrobenzene by Shewanella putrefaciens CN32

Iron-bearing clay minerals are ubiquitous in the environment, and the clay-Fe(II)/Fe(III) redox couple plays important roles in abiotic reduction of several classes of environmental contaminants. We investigated the role of Fe-bearing clay minerals on the bioreduction of nitrobenzene. In experiments with Shewanella putrefaciens CN32 and excess electron donor, we found that the Fe-bearing clay minerals montmorillonite SWy-2 and nontronite NAu-2 enhanced nitrobenzene bioreduction. On short time scales (<50 h), nitrobenzene reduction was primarily biologically driven, but at later time points, nitrobenzene reduction by biologically formed structural Fe(II) in the clay minerals became increasingly important. We found that chemically reduced (dithionite) iron-bearing clay minerals reduced nitrobenzene more rapidly than biologically reduced iron-bearing clay minerals despite the minerals having similar structural Fe(II) concentrations. We also found that chemically reduced NAu-2 reduced nitrobenzene faster as compared to chemically reduced SWy-2. The different reactivity of SWy-2 versus NAu-2 toward nitrobenzene was caused by different forms of structural clay-Fe(II) in the clay minerals and different reduction potentials (Eh) of the clay minerals. Because most contaminated aquifers become reduced via biological activity, the reactivity of biogenic clay-Fe(II) toward reducible contaminants is particularly important.