Urban geochemical changes and pollution with potentially harmful elements in seven Russian cities

This paper presents results of an analysis of potentially harmful elements (PHEs, Pb, Zn and Cu) and conservative element (CE, Fe) concentrations in urban surface deposited sediment (USDS). The study was conducted in seven large Russian cities located in different geographic and climatic zones, and in territories with different geology and anthropogenic pressures: Chelyabinsk, Magnitogorsk, Nizhniy Novgorod, Nizhniy Tagil, Rostov-on-Don, Tyumen, and Ufa. The initial geochemical baseline relationships between PHEs and CE concentrations in the USDS were reconstructed for each city applying an approach based on linear weighted fitting of PHE as a function of CE with lower weights assigned to more polluted samples. The reconstructed average initial baseline Pb, Cu, and Zn concentrations varied between 17–52, 25–196, and 91–413 mg kg−1, respectively. Several new criteria for assessing the degree of geochemical transformation and pollution of the urban environment, such as the percentage of polluted samples, average pollutant concentration in polluted samples, and weighting degree index δ, were suggested and compared with common criteria, such as the PHE concentration and the geo-accumulation index. The environmental rank of a city significantly differed depending on whether the criterion for ranking was total PHE pollution or changes in comparison with the initial geochemical baseline. © 2020, The Author(s).Russian Science Foundation, RSF: 18-77-10024The study was supported by Russian Science Foundation (grant No. 18-77-10024)

Resonant photoemission at the absorption edge of Mn and Ti and electronic structure of 1T-Mn0.2_{0.2}TiSe2_2

Resonant valence-band X-ray photoelectron spectra (ResPES) excited near 2p$_{3/2}$ core level energies, 2p X-ray photoelectron spectra (XPS) and L$_{3,2}$ X-ray absorption spectra (XAS) of Ti and Mn in single crystal of 1T-Mn$_2$TiSe$_2$ were studied for the first time. The ionic-covalent character of bonds formed by Mn atoms with the neighboring Se atoms in the octahedral coordination is established. From the XPS and XAS measurements compared with results of atomic multiplet calculations of Ti and Mn L$_{3,2}$ XAS it is found that Ti atoms are in ionic state of 4+ and Mn atoms are in the state of 2+. In ResPES of Mn$_{0.2}$TiSe$_2$ excited near Ti 2p$_{3/2}$ and Mn 2p$_{3/2}$ absorption edges the Ti 3d and Mn 3d bands at binding energies just below the Fermi level are observed. According to band structure calculations E$(\textbf{k})$ the Ti 3d states are localized in the vicinity of $\mathsf{\Gamma}$ point and the Mn 3d states are localized along the direction K-$\mathsf{\Gamma}$-M in the Brillouin zone of the crystal.Comment: 18 pages (preprint), 9 figure

MxTiSe2 (M = Cr, Mn, Cu) electronic structure study by methods of resonant X-ray photoemission spectroscopy and X-Ray absorption spectroscopy

Electronic structure and chemical bonding in TiX2 (X=S, Se, Te), TMxTiSe2 (TM=Cr, Mn, Cu) and CrxTi1-xSe2 were studied by x-ray resonance photoemission and absorption spectroscopy. These methods are detected to be strong sensitive to chemical bonding. Charge transfer from the intercalated atoms to Ti 3d band is detected. Narrow Ti 3d and Cu 3d bands are observed under Fermi level in CuxTiSe2.Comment: 7 pages, 4 figeres, ISIC 16 conferenc

Localization of charge carriers in layered crystals MexTiSe 2 (Me = Cr, Mn, Cu) studied by the resonant photoemission

The probability of charge transfer in layered titanium diselenide between monolayers containing Cr, Mn, and Cu with different concentrations and host lattice TiSe2 is estimated according to the resonant photoemission data. For this purpose, the Raman-Auger contributions and narrow bands just below the Fermi energy were separated in the valence band spectra. These contributions provide the information about charge transfer. It is shown that the localization of the 3d electrons is typical for Cr and Cu atoms and strongly depends on theirs concentration. In MnxTiSe2, Mn 3d electrons are delocalized and the probability of the charge transfer is the greatest as compared with other compounds under investigation. © 2013 AIP Publishing LLC

Gross alpha and gross beta activity concentrations in the dust fractions of urban surface-deposited sediment in russian cities

Studies of gross alpha and gross beta activity in road-and surface-deposited sediments were conducted in three Russian cities in different geographical zones. To perform radiation measurements, new methods were applied which allow dealing with low mass and low volume dustsized (2–100 μm) samples obtained after the size fractionation procedure. The 2–10 μm fraction size had the highest gross beta activity concentration (GB)—1.32 Bq/g in Nizhny Novgorod and Rostov-On-Don, while the 50–100 μm fraction size was most prominent in Ekaterinburg. This can be attributed to the presence of radionuclides that are transferred through natural and anthropogenic processes. The highest gross alpha activity concentration (GA) in fraction sizes was found in Rostov-on-Don city within the 50–100 μm range—0.22 Bq/g. The fraction sizes 50–100 μm have a higher gross alpha activity concentration than 2–10 μm and 10–50 μm fraction sizes due to natural partitioning of the main minerals constituting the urban surface-deposited sediment (USDS). Observed dependencies reflect the geochemical processes which take place during the formation and transport of urban surface sediments. Developed experimental methods of radiation measurements formed the methodological base of urban geochemical studies. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.The study was supported by Russian Science Foundation (grant No. 18-77-10024). Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable