The molecular composition of lignin in spruce decayed by white-rot fungi (Phanerochaete chrysosporium and Trametes versicolor) using pyrolysis-GC–MS and thermochemolysis with tetramethylammonium hydroxide

Pyrolysis-gas chromatography-mass spectrometry (Py-GC–MS) and off-line thermochemolysis with tetramethylammonium hydroxide followed by GC–MS were used in the molecular characterisation of lignin in spruce wood decayed by Phanerochaete chrysosporium and Trametes versicolor. Mono-methoxyphenols were the main pyrolysis products from the undegraded lignin. Py-GC–MS provided qualitative evidence that 2-methoxy-4-(prop-2-enal)phenol and trans-2-methoxy-4-(1-hydroxy-prop-2-enyl)phenol content decreased whereas 1,2-dihydroxybenzene increased in intensity relative to other products upon fungal decay. Comparison of methylated phenols from thermochemolysis revealed that ratio of methyl 3,4-dimethoxybenzoate to 3,4-dimethoxybenzaldehyde increased from 0.69 in control spruce to 2.3 after decay by P. chrysosporium and 3.7 following growth of T. versicolor. The results indicate that white-rot fungi cleave alkyl side chains of β-O-4 linked mono-methoxyphenylpropane structures between the α–β carbon atoms to give lignin residues enriched in carboxylic acids as well as demethylating methoxy groups attached to aromatic nuclei to give dihydroxybenzene products. Py-GC–MS and thermochemolysis are complementary methods for tracking demethylation of aromatic nuclei and oxidation of alkyl side chains caused by white-rot fungi.