The mechanism of oxygen reduction reaction (ORR) on transition metal-doped nitrogen codoped single-walled nanotubes, C₁₁₄H₂₄MN₄ (MN₄-CNT where M = Zn, Cu, or Ag; N = pyridinic nitrogen), has been studied with the density functional theory method at the ωB97XD/DGDZVP level of theory. The charge density analysis revealed two active sites of the catalyst toward ORR: the MN₄ site and the C═C bond of the N–C═C–N metal-chelating fragment (C₂ site). The structure of O-containing adsorbates (O₂^*, HOO*, O*, HO*, etc.) on the two sites and the corresponding adsorption energies were determined. The analysis of the free energy diagrams allows to conclude that the 4e^– mechanism of ORR is thermodynamically preferable for all the studied catalysts. The probability of the 2e^– mechanism of ORR with the formation of hydrogen peroxide decreases in the order Cu > Ag > Zn. The most and the least exergonic steps of the conventional 4e^– mechanism of ORR on each active site of model catalysts as well as the electrode potentials of deceleration and of maximum catalytic activity in both acidic and alkaline media are determined. The relative catalytic activity toward ORR increases in the order Zn < Ag ≪ Cu and is mainly attributed to the C₂ site rather than the MN₄ site, while combined catalytic activity of the two sites (AgN₄/C₂ sites) is predicted for the AgN₄-CNT catalyst.

An area of discolored water 50 m wide and 30 m long was found in September 2017 close to the dam of the Irkutsk hydroelectric power station. Water from this spot was sampled for investigation in the present study. Microscopic analysis revealed that the suspended matter in the sample was composed of clumps of filaments, vegetative cells, akinetes and heterocysts that formed short filaments and solitary cells. This matter was found to consist of partially degraded cells of the cyanobacterium Dolichospermum lemmermannii. Nucleotide sequencing of DNA isolated from the biomass revealed the presence of the sxtA gene which is involved in the synthesis of saxitoxin. Water from the polluted area contained 600 ± 100 μg L⁻¹ saxitoxin as measured by HPLC-MS with pre-column modification of the toxin with 2,4-dinitrophenylhydrazine. Immunoassay analysis (ELISA) showed a concentration of saxitoxins in the water of 2900 ± 900 μg L⁻¹. Hydrochemical and microbiological analyses suggested the contaminated area appeared as a result of a D. lemmermannii bloom, followed by its decay and release of saxitoxin and nutrients. The present paper describes the results of a case study. Better understanding of the phenomenon will depend on the possibility to perform implementation of a large-scale monitoring program.