The redox activity of Fe-bearing minerals is coupled
with the transformation
of organic matter (OM) in redox dynamic environments, but the underlying
mechanism remains unclear. In this work, a Fe redox cycling experiment
of nontronite (NAu-2), an Fe-rich smectite, was performed via combined
abiotic and biotic methods, and the accompanying transformation of
humic acid (HA) as a representative OM was investigated. Chemical
reduction and subsequent abiotic reoxidation of NAu-2 produced abundant
hydroxyl radicals (thereafter termed as ·OH) that effectively
transformed the chemical and molecular composition of HA. More importantly,
transformed HA served as a more premium electron donor/carbon source
to couple with subsequent biological reduction of Fe(III) in reoxidized
NAu-2 by Geobacter sulfurreducens, a model Fe-reducing
bacterium. Destruction of aromatic structures and formation of carboxylates
were mechanisms responsible for transforming HA into an energetically
more bioavailable substrate. Relative to unaltered HA, transformed
HA increased the extent of the bioreduction by 105%, and Fe(III) reduction
was coupled with oxidation and even mineralization of transformed
HA, resulting in bleached HA and formation of microbial products and
cell debris. ·OH transformation slightly decreased the electron
shuttling capacity of HA in bioreduction. Our results provide a mechanistic
explanation for rapid OM mineralization driven by Fe redox cycling
in redox-fluctuating environments.