Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European Arctic

Free radicals (FRs) are intermediate participants in the transformation process of soil organic matter, and free radical activity is a fundamental property of humic substances. The aim of this work was to conduct a comparative study of the paramagnetic properties of humic acids (HAs) isolated from Histosols by electron paramagnetic resonance (EPR) spectroscopy. The studied Histosols are found in permafrost peatlands in four natural geographic subzones of the European Arctic (from forest tundra to northern tundra). The results obtained showed that in anaerobic conditions on the peatlands in the tundra zone, the formation of semiquinone-type radicals occurs through the reduction of quinone fragments of HAs and leads to an increase in the concentration of paramagnetic centres within HAs. PCA analysis allowed us to reveal relationships between the properties of the initial raw peat samples, the molecular composition of the isolated HAs, and their paramagnetic parameters. It was found that FR localization occurs predominantly on aromatic fragments of lignin nature, which are confined to the low molecular weight fraction of HAs. The g-factor values of the EPR spectra of HAs indicate the presence of carbon- and oxygen-centred FRs in the HA structure, with a predominance of the latter.