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

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  • Carlo Bravo

    (Department of Agricultural, Food, Environmental and Animal Sciences (DI4A), University of Udine, Via delle Scienze 206, 33100 Udine, Italy)

  • Rosanna Toniolo

    (Department of Agricultural, Food, Environmental and Animal Sciences (DI4A), University of Udine, Via delle Scienze 206, 33100 Udine, Italy)

  • Marco Contin

    (Department of Agricultural, Food, Environmental and Animal Sciences (DI4A), University of Udine, Via delle Scienze 206, 33100 Udine, Italy)

  • Maria De Nobili

    (Department of Agricultural, Food, Environmental and Animal Sciences (DI4A), University of Udine, Via delle Scienze 206, 33100 Udine, Italy)

Abstract

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 red ) and aerobically (HA ox ) 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 ●− ), passing from 2.77 ± 0.13 mmol e- g HA −1 in HA red to 2.21 ± 0.10 mmol e- g HA −1 in HA ox . Pseudo-first-order electron transfer kinetic constants were 13.3 ± 1.2 s −1 for HA ox and 16.7 ± 1.4 s −1 for HA red . 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.

Suggested Citation

  • Carlo Bravo & Rosanna Toniolo & Marco Contin & Maria De Nobili, 2021. "Electrochemical and Structural Modifications of Humic Acids in Aerobically and Anaerobically Incubated Peat," Land, MDPI, vol. 10(11), pages 1-13, November.
  • Handle: RePEc:gam:jlands:v:10:y:2021:i:11:p:1189-:d:672661
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    References listed on IDEAS

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    1. Paul J. Morris, 2021. "Wetter is better for peat carbon," Nature Climate Change, Nature, vol. 11(7), pages 561-562, July.
    2. Yuanyuan Huang & Phillipe Ciais & Yiqi Luo & Dan Zhu & Yingping Wang & Chunjing Qiu & Daniel S. Goll & Bertrand Guenet & David Makowski & Inge Graaf & Jens Leifeld & Min Jung Kwon & Jing Hu & Laiye Qu, 2021. "Tradeoff of CO2 and CH4 emissions from global peatlands under water-table drawdown," Nature Climate Change, Nature, vol. 11(7), pages 618-622, July.
    3. Eric A. Davidson & Ivan A. Janssens, 2006. "Temperature sensitivity of soil carbon decomposition and feedbacks to climate change," Nature, Nature, vol. 440(7081), pages 165-173, March.
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