Sixteenth Quarterly Report Regulation of Coal Polymer Degradation by Fungi

Three phenomena which concern coal solubilization and depolymerization were studied during this reporting period. Previous investigations have shown that lignin peroxidases mediate the oxidation of soluble coal macromolecule. Because it appears to be a substrate, soluble coal macromolecule is also an inhibitor of veratryl alcohol oxidation, a reaction that is mediated by these enzymes. The mechanism of inhibition is complex in that oxidation (as assayed by decolorization) of soluble coal macromolecule requires the presence of veratryl alcohol and veratryl alcohol oxidation occurs only after a substantial lag period during which the soluble coal macromolecule is oxidized. In a previous quarterly report we proposed a reaction mechanism by which this may occur. During the present reporting period we showed that our proposed reaction mechanism is consistent with classical enzyme kinetic theory describing enzyme activity in the presence of a potent inhibitor (i.e., an inhibitor with a very low KI ). The oxidative decolorization and depolymerization of soluble coal macromolecule was also studied. Because wood rotting fungi produce hydrogen peroxide via a variety of reactions, we studied the effect of hydrogen peroxide on soluble coal macromolecule decolorization and depolymerization. Results showed that substantial decolorization occurred only at hydrogen peroxide concentrations that are clearly non-physiological (i.e., 50 mM or greater). It was noted, however, that when grown on solid lignocellulosic substrates, wood rotting fungi, overtime, cumulatively could produce amounts of hydrogen peroxide that might cause significant oxidative degradation of soluble coal macromolecule. Thirdly, we have shown that during oxalate mediated solubilization of low rank coal, a pH increase is observed. During this reporting period we have shown that the pH of solutions containing only sodium oxalate also undergo an increase in pH, but to a lesser extent than that observed in mixtures containing sodium oxalate and low rank coal. It is our hypothesis that bicarbonate ion is formed during oxalate mediated solubilization of low rank coal and this is responsible for the increase in pH that is observed. A general reaction by which this occurs is proposed herein