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

Carlo Bravo, Rosanna Toniolo, Marco Contin and Maria De Nobili
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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

Land, 2021, vol. 10, issue 11, 1-13

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.

Keywords: humic acids; peat; redox changes; electron donating capacity; electron transfer kinetic constants (search for similar items in EconPapers)
JEL-codes: Q15 Q2 Q24 Q28 Q5 R14 R52 (search for similar items in EconPapers)
Date: 2021
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