Oxidation states of iron and manganese in lignocellulose altered by the brown rot fungus Gloeophyllum trabeum measured in-situ using X-ray absorption near edge spectroscopy (XANES)

Abstract

Brown rot fungi utilize iron as part of a chelator-mediated Fenton (CMF) reaction during wood biodegradation. Research suggests these fungi reduce Fe3+ to promote oxygen radical generation resulting in depolymerization of the wood cell wall. High levels of Mn are also found in wood decayed by brown rot fungi. However, little is known about the oxidation states of Fe and Mn during the decay process. X-ray absorption near edge spectroscopy (XANES) can be used to examine metal oxidation states and coordination chemistry. XANES experiments were conducted on wood decayed by Gloeophyllum trabeum over 2–8 weeks with results showing that Mn2+ and Fe3+ predominated for metal oxidation states. However, Fe2+ was present at sites of greater fungal growth In certain cases, the μXANES measurements showed that the fraction of Fe2+ in the wood samples was as high as 50%. Localized areas of reduced iron corresponded with areas of greater fungal hyphal mass which is in agreement with how brown rot fungi decay wood via the CMF reaction. The limited change in oxidation state of Mn observed in wood with active fungal activity suggests that the role of manganese in CMF biodegradation chemistry should be further explored.