Alexander Rodionov

Fe(III) mineral reduction followed by partial dissolution and reactive oxygen species generation during 2,4,6-trinitrotoluene transformation by the aerobic yeast Yarrowia lipolytica

Understanding the factors that influence pollutant transformation in the presence of ferric (oxyhydr)oxides is crucial to the efficient application of different remediation strategies. In this study we determined the effect of goethite, hematite, magnetite and ferrihydrite on the transformation of 2,4,6-trinitrotoluene (TNT) by Yarrowia lipolytica AN-L15. The presence of ferric (oxyhydr)oxides led to a small decrease in the rate of TNT removal. In all cases, a significant release of NO2− from TNT and further NO2− oxidation to NO3− was observed. A fraction of the released NO2− was abiotically decomposed to NO and NO2, and then NO was likely oxidized abiotically to NO2 by O2. ESR analysis revealed the generation of superoxide in the culture medium; its further protonation at low pH resulted in the formation of hydroperoxyl radical. Presumably, a fraction of NO released during TNT degradation reacted with superoxide and formed peroxynitrite, which was further rearranged to NO3− at the acidic pH values observed in this study. A transformation and reduction of ferric (oxyhydr)oxides followed by partial dissolution (in the range of 7–86% of the initial Fe(III)) were observed in the presence of cells and TNT. Mössbauer spectroscopy showed some minor changes for goethite, magnetite and ferrihydrite samples during their incubation with Y. lipolytica and TNT. This study shows that i) reactive oxygen and nitrogen species generated during TNT transformation by Y. lipolytica participate in the abiotic conversion of TNT and ii) the presence of iron(III) minerals leads to a minor decrease in TNT transformation.

Electron paramagnetic resonance of radiation-induced paramagnetic centers in an aerogel

Silicon oxide aerogel samples irradiated with x rays at room temperature have been analyzed using the electron paramagnetic resonance method. It has been found that three types of paramagnetic centers appear: paramagnetic centers with a g factor of 2.0035, centers associated with the presence of protons in SiO2 globules, and centers in the adsorbed film on the aerogel surface. The fast (Tfast = 30 h) and slow (Tslow = 70 d) processes have been revealed in the recombination of these centers.

EPR study of ordered Al2O3-based aerogel

Samples of oriented aerogel based on aluminum oxide are studied by the electron paramagnetic resonance (EPR) technique under steady-state and pulse conditions. At least two types of paramagnetic centers interacting with Al nuclei on the surface of aerogel are revealed. Their spectra are characterized by the presence or absence of superhyperfine structure in the EPR spectra, respectively. The X-ray irradiation at room temperature gives rise to the formation of additional long-lived paramagnetic centers of the second kind. Their characteristic decay times for the “fast” and “slow” processes are determined. The interaction of induced paramagnetic centers with protons located on the surface of aerogel is revealed.