Electrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat

Exposure to oxygen and aerobic biological activity during drought periods alters the availability of terminal electron acceptors (TEA) in the peat catotelm layer. We investigated the changes in the electrochemical and chemical characteristics of humic acids (HA) induced by subjecting air-dried sphag...

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Autores principales: Carlo Bravo, Rosanna Toniolo, Marco Contin, Maria De Nobili
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Publicado: MDPI AG 2021
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spelling oai:doaj.org-article:f578664533e34c4cbc31b4e274e1e71f2021-11-25T18:09:33ZElectrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat10.3390/land101111892073-445Xhttps://doaj.org/article/f578664533e34c4cbc31b4e274e1e71f2021-11-01T00:00:00Zhttps://www.mdpi.com/2073-445X/10/11/1189https://doaj.org/toc/2073-445XExposure to oxygen and aerobic biological activity during drought periods alters the availability of terminal electron acceptors (TEA) in the peat catotelm layer. We investigated the changes in the electrochemical and chemical characteristics of humic acids (HA) induced by subjecting air-dried sphagnum peat to biological oxidation or reduction during a 90-day incubation experiment. Structural modifications of HAs from anaerobically (HA<sub>red</sub>) and aerobically (HA<sub>ox</sub>) incubated peat were investigated by ATR-FTIR, UV–vis, and EEM fluorescence spectroscopy. Number and strength of acid groups were characterized by titration, while changes in redox properties were characterized by cyclic voltammetry and quantified by coulometry with mediated electrochemical oxidation (MEO). Exposure to oxygen had small effects, but compared to anaerobic incubation, decreased by 20% the capacity of HA to reduce the radical ion of 2,2′-Azinobis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS<sup>●−</sup>), passing from 2.77 ± 0.13 mmol<sub>e-</sub> g<sub>HA</sub><sup>−1</sup> in HA<sub>red</sub> to 2.21 ± 0.10 mmol<sub>e-</sub> g<sub>HA</sub><sup>−1</sup> in HA<sub>ox</sub>. Pseudo-first-order electron transfer kinetic constants were 13.3 ± 1.2 s<sup>−1</sup> for HA<sub>ox</sub> and 16.7 ± 1.4 s<sup>−1</sup> for HA<sub>red</sub>. Alterations in the hydrological status of the catotelm have minor effects on the actual in situ availability of organic TEA, but if coupled to intensified biological activity they may result in significant variations of greenhouse gases emissions.Carlo BravoRosanna TonioloMarco ContinMaria De NobiliMDPI AGarticlehumic acidspeatredox changeselectron donating capacityelectron transfer kinetic constantsAgricultureSENLand, Vol 10, Iss 1189, p 1189 (2021)
institution DOAJ
collection DOAJ
language EN
topic humic acids
peat
redox changes
electron donating capacity
electron transfer kinetic constants
Agriculture
S
spellingShingle humic acids
peat
redox changes
electron donating capacity
electron transfer kinetic constants
Agriculture
S
Carlo Bravo
Rosanna Toniolo
Marco Contin
Maria De Nobili
Electrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat
description Exposure to oxygen and aerobic biological activity during drought periods alters the availability of terminal electron acceptors (TEA) in the peat catotelm layer. We investigated the changes in the electrochemical and chemical characteristics of humic acids (HA) induced by subjecting air-dried sphagnum peat to biological oxidation or reduction during a 90-day incubation experiment. Structural modifications of HAs from anaerobically (HA<sub>red</sub>) and aerobically (HA<sub>ox</sub>) incubated peat were investigated by ATR-FTIR, UV–vis, and EEM fluorescence spectroscopy. Number and strength of acid groups were characterized by titration, while changes in redox properties were characterized by cyclic voltammetry and quantified by coulometry with mediated electrochemical oxidation (MEO). Exposure to oxygen had small effects, but compared to anaerobic incubation, decreased by 20% the capacity of HA to reduce the radical ion of 2,2′-Azinobis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS<sup>●−</sup>), passing from 2.77 ± 0.13 mmol<sub>e-</sub> g<sub>HA</sub><sup>−1</sup> in HA<sub>red</sub> to 2.21 ± 0.10 mmol<sub>e-</sub> g<sub>HA</sub><sup>−1</sup> in HA<sub>ox</sub>. Pseudo-first-order electron transfer kinetic constants were 13.3 ± 1.2 s<sup>−1</sup> for HA<sub>ox</sub> and 16.7 ± 1.4 s<sup>−1</sup> for HA<sub>red</sub>. Alterations in the hydrological status of the catotelm have minor effects on the actual in situ availability of organic TEA, but if coupled to intensified biological activity they may result in significant variations of greenhouse gases emissions.
format article
author Carlo Bravo
Rosanna Toniolo
Marco Contin
Maria De Nobili
author_facet Carlo Bravo
Rosanna Toniolo
Marco Contin
Maria De Nobili
author_sort Carlo Bravo
title Electrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat
title_short Electrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat
title_full Electrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat
title_fullStr Electrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat
title_full_unstemmed Electrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat
title_sort electrochemical and structural modifications of humic acids in aerobically and anaerobically incubated peat
publisher MDPI AG
publishDate 2021
url https://doaj.org/article/f578664533e34c4cbc31b4e274e1e71f
work_keys_str_mv AT carlobravo electrochemicalandstructuralmodificationsofhumicacidsinaerobicallyandanaerobicallyincubatedpeat
AT rosannatoniolo electrochemicalandstructuralmodificationsofhumicacidsinaerobicallyandanaerobicallyincubatedpeat
AT marcocontin electrochemicalandstructuralmodificationsofhumicacidsinaerobicallyandanaerobicallyincubatedpeat
AT mariadenobili electrochemicalandstructuralmodificationsofhumicacidsinaerobicallyandanaerobicallyincubatedpeat
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