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 sphagnum peat to biological oxidation or reduction during a 90-day incubation experiment. Structural modifications of HAs from anaerobically (HAred) and aerobically (HAox) 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 mmole- gHA−1 in HAred to 2.21 ± 0.10 mmole- gHA−1 in HAox. Pseudo-first-order electron transfer kinetic constants were 13.3 ± 1.2 s−1 for HAox and 16.7 ± 1.4 s−1 for HAred. 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.

Diatomic molecules

Double ionisation of most of the experimentally accessible diatomic molecules has been studied previously by several techniques, including Auger spectroscopy, double electron transfer, kinetic energy release, and high-level theory. New double photoionisation spectra of HBr, HI, N2, CO, NO, O2, Br2, ICl, and I2 are presented here with analysis to identify the electronic states of the doubly charged ions. A simple empirical model is introduced to estimate double ionisation energies on the basis of orbital energies. For CO, NO, and O2, an indirect double ionisation mechanism is found, involving dissociation of a singly charged molecular ion followed by atomic autoionisation of one fragment. Energies of the dication states are listed with distinction between adiabatic and vertical values.

Electron transfer rate analysis of a site-specifically wired copper oxidase

Electron transfer kinetic parameters of site-specifically wired copper oxidase were investigated.