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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2021
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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) |
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humic acids peat redox changes electron donating capacity electron transfer kinetic constants Agriculture S |
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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 |
_version_ |
1718411596137496576 |