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 H...

Full description

Bibliographic Details
Main Authors: Evgeny Lodygin, Roman Vasilevich, Evgeny Abakumov
Format: Article
Language:English
Published: MDPI AG 2023-12-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/29/1/104
_version_ 1797358398513086464
author Evgeny Lodygin
Roman Vasilevich
Evgeny Abakumov
author_facet Evgeny Lodygin
Roman Vasilevich
Evgeny Abakumov
author_sort Evgeny Lodygin
collection DOAJ
description 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.
first_indexed 2024-03-08T15:01:23Z
format Article
id doaj.art-778639651d2a4fa8bbea37bec786e944
institution Directory Open Access Journal
issn 1420-3049
language English
last_indexed 2024-03-08T15:01:23Z
publishDate 2023-12-01
publisher MDPI AG
record_format Article
series Molecules
spelling doaj.art-778639651d2a4fa8bbea37bec786e9442024-01-10T15:04:09ZengMDPI AGMolecules1420-30492023-12-0129110410.3390/molecules29010104Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European ArcticEvgeny Lodygin0Roman Vasilevich1Evgeny Abakumov2Institute of Biology, Komi Science Center, Ural Branch, Russian Academy of Sciences, 28, Kommunisticheskaya St., 167982 Syktyvkar, RussiaInstitute of Biology, Komi Science Center, Ural Branch, Russian Academy of Sciences, 28, Kommunisticheskaya St., 167982 Syktyvkar, RussiaDepartment of Applied Ecology, Faculty of Biology, St. Petersburg State University, 16th Liniya V.O., 29, 199178 St. Petersburg, RussiaFree 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.https://www.mdpi.com/1420-3049/29/1/104soil organic matterfree radicalsEPR spectroscopyHistosols
spellingShingle Evgeny Lodygin
Roman Vasilevich
Evgeny Abakumov
Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European Arctic
Molecules
soil organic matter
free radicals
EPR spectroscopy
Histosols
title Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European Arctic
title_full Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European Arctic
title_fullStr Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European Arctic
title_full_unstemmed Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European Arctic
title_short Relating Paramagnetic Properties to Molecular Parameters of Humic Acids Isolated from Permafrost Peatlands in the European Arctic
title_sort relating paramagnetic properties to molecular parameters of humic acids isolated from permafrost peatlands in the european arctic
topic soil organic matter
free radicals
EPR spectroscopy
Histosols
url https://www.mdpi.com/1420-3049/29/1/104
work_keys_str_mv AT evgenylodygin relatingparamagneticpropertiestomolecularparametersofhumicacidsisolatedfrompermafrostpeatlandsintheeuropeanarctic
AT romanvasilevich relatingparamagneticpropertiestomolecularparametersofhumicacidsisolatedfrompermafrostpeatlandsintheeuropeanarctic
AT evgenyabakumov relatingparamagneticpropertiestomolecularparametersofhumicacidsisolatedfrompermafrostpeatlandsintheeuropeanarctic