Potentially toxic elements in urban soils of the coastal city of the Sea of Azov: Levels, sources, pollution and risk assessment.

Coastal cities are major centers of economic activity, which at the same time has negative consequences for the environment. The present study aimed to determine the concentrations and sources of PTEs in the urban soils of Taganrog, as well as to assess the ecological and human health risks. A total of 47 urban and 5 background topsoils samples were analyzed by ICP-MS and ICP-AES. A significant excess of Cu, Zn, and Sb was noted in urban soils compared to the upper continental crust and average world-soil (1.7-2.9 times). Statistical analysis showed that the elements in soils were of geogenic, mixed and anthropogenic origin. According to the single pollution index (PI), the greatest danger of soil pollution was represented by anthropogenic elements, namely Cu, W, Pb, Zn, Cd, and Sn, the levels of which were increased in residential and industrial areas. The median contents of As, Mn, Cr, Sr, Mo, Sb, Cu, W, Pb, and Zn were 1.1-2.1 times higher, while Cd and Sn were 2.5 folds higher in the urban soils compared to the background ones. The total pollution index (ZC) showed that only 15% of the soils had high level of pollution, which is typical for the industrial areas. Overall ecological risks were negligible or low in 92% of soils, and were mainly due to elevated levels of Cu, Zn, As, and Pb. Non-carcinogenic risks to humans were mainly related to exposure to La and Pb. The hazard index (HI) values for all PTEs were less than ten, indicating that overall non-carcinogenic risk for adults and children was low-to-moderate and, moderate, respectively. The total carcinogenic risk (TCR) exceeded threshold and corresponded to low risk, with Pb, As, and Co being the most important contributors. Thus, the industrial activities of Taganrog is the main source of priority pollutants.

High-Pressure Synthesis of Cubic ZnO and Its Solid Solutions with MgO Doped with Li, Na, and K.

The possibility of doping ZnO in its metastable rock salt structure with Li, Na, and K intended to act as acceptor dopants was investigated. For the first time, MgxZn1-xO alloys and pure ZnO with a rock salt structure doped with Li, Na, and K metals was obtained by high-pressure synthesis from pure oxides with the addition of carbonates or acetates of the corresponding metals as dopant sources. Successful stabilization of the metastable rock salt structure and phase purity were confirmed by X-ray diffraction. Transmission electron microscopy was used to study the particle size of nanocrystalline precursors, while the presence of Li, Na, and K metals in rock salt ZnO was detected by electron energy-loss spectroscopy and X-ray photoelectron spectroscopy in MgxZn1-xO alloys. Electron paramagnetic resonance measurements revealed the acceptor behavior of Li, Na, and K dopants based on the influence of the latter on native defects and natural impurities in ZnO-MgO alloys. In addition, diffuse reflectance spectroscopy was used to derive band gaps of quenched rock salt ZnO and its alloys with MgO.

Topology of WC/Co Interfaces in Cemented Carbides.

WC-Co cemented carbides build one of the important classes of metal matrix composites. We show in this paper that the use of machine vision methods makes it possible to obtain sufficiently informative statistical data on the topology of the interfaces between tungsten carbide grains (WC) and a cobalt matrix (Co). For the first time, the outlines of the regions of the cobalt binder were chosen as a tool for describing the structure of cemented carbides. Numerical processing of micrographs of cross sections of three WC-Co alloys, which differ in the average grain size, was carried out. The distribution density of the angles in the contours of cobalt "lakes" is bimodal. The peaks close to 110° (so-called outcoming angles) correspond to the contacts between the cobalt binder and the WC/WC grain boundaries. The peaks close to 240° (or incoming angles) correspond to the WC "capes" contacting the cobalt "lakes" and are determined by the angles between facets of WC crystallites. The distribution density of the linear dimensions of the regions of the cobalt binder, approximated with ellipses, were also obtained. The distribution density exponentially decreases with the lengths of the semi-axes of the ellipsoid, approximating the area of the cobalt binder. The possible connection between the obtained data on the shape of cobalt areas and the crack trajectories in cemented carbides is discussed.

Effect of Manganese Distribution on Sensor Properties of SnO2/MnOx Nanocomposites.

Nanocomposites SnO2/MnOx with various manganese content (up to [Mn]/[Sn] = 10 mol. %) and different manganese distribution were prepared by wet chemical technique and characterized by X-ray diffraction, scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis and mapping, IR and Raman spectroscopy, total reflection X-ray fluorescence, mass-spectrometry with inductive-coupled plasma (ICP-MS), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR) spectroscopy. A different distribution of manganese between the volume and the surface of the SnO2 crystallites was revealed depending on the total Mn concentration. Furthermore, the identification of surface MnO2 segregation was performed via Raman spectroscopy. There is a strong dependence of the sensor signal toward CO and, especially, NO) on the presence of MnO2 surface segregation. However, manganese ions intruding the SnO2 crystal structure were shown to not almost effect on sensor properties of the material.

Assessment of soil development during rapid urbanization using the carbon and nitrogen stable isotope composition.

The proposed paper is devoted to the analysis of the urbanization effects on soil cover using physico-chemical parameters and stable isotopic signatures on the example of Tyumen. The study methods included analysis of C and N elemental and isotope (δ13C and δ15N) composition, analysis of soil physico-chemical properties and major oxides content. The results of the survey have shown that soil properties within the city limits vary significantly depending on both anthropogenic activities and geomorphological context. The urban soils of Tyumen differ from very strongly acidic with pH values down to 4.8 to strongly alkaline with pH values reaching 8.9, and from sandy loams to silty loams by texture. The study results have shown that δ13C values varied from - 33.86 to - 25.14‰ and δ15N values varied in range, especially, from - 1.66 to 13.38‰. The range of these signatures was smaller than those reported for urbanized areas in Europe and USA. The δ13C values in our case were more related to the geological and landscape parameters of the study area, rather than with urban disturbances and development of urban ecosystems. At the same time, the δ15N values probably indicate zones with increased atmospheric N deposition in the case of Tyumen. The application δ13C and δ15N is a promising tool for analysis of urban soil disturbances and functions, though the regional context should be taken into account.

Melamine Barbiturate as a Light-Induced Nanostructured Supramolecular Material for a Bioinspired Oxygen and Organic Radical Trap and Stabilization.

Use of coantioxidant systems is a prospective way to increase the effectiveness of antioxidant species in tissue repair and regeneration. In this paper, we introduce a novel scheme of a reactive oxygen species (ROS) trap and neutralization during self-assembly of supramolecular melamine barbiturate material. The performed reaction chain mimics the biological process of ROS generation in key stages and enables one to obtain stable hydroperoxyl and organic radicals in a melamine barbiturate structure. Melamine barbiturate also neutralizes hydroxyl radicals, and the effectiveness of the radical trap is controlled with ROS scavenger incorporation. The number of radicals dramatically increases during light-inducing and depends on pH. The proposed scheme of the ROS trap and neutralization opens a way to the use of supramolecular assemblies as a component of coantioxidant systems and a source of organic radicals.

Heavy metal contamination levels, source distribution, and risk assessment in fine sand of urban surface deposited sediments of Ekaterinburg, Russia.

Urban surface deposited sediments (USDS) are unique indicators of local pollution that pose a potential threat to the living environment and human health. Ekaterinburg is a highly populated metropolitan area in Russia with rapid urbanization and industrialization activities. In Ekaterinburg's residential areas, about 35, 12, and 16 samples are represented by green zones, roads, driveways, and sidewalks, respectively. The total concentrations of heavy metals was detected using a chemical analyzer inductively coupled plasma mass spectrometry (ICP-MS). Zn, Sn, Sb, and Pb have the highest concentrations in the green zone, while V, Fe, Co, and Cu represent the utmost values on roads. Moreover, Mn and Ni are the prevailing metals in the fine sand fraction of driveways along with sidewalks. Broadly, the high pollution in the studied zones is generated by anthropogenic activities and traffic emissions. The potential ecological risk (RI) was observed in high risk (IR > 600), even though the results of all heavy metals reveal no adverse health effects from the considered noncarcinogenic metal for adults and children by different exposure pathways except the children's exposure to Co in case of the dermal contact, where the HI values of Co for children in the studied zones are higher than the proposed level (> 1). In all urban zones, the total carcinogenic risk (TLCR) values are predicted as a high potential inhalation exposure.

Potentially toxic elements in surface soils of the Lower Don floodplain and the Taganrog Bay coast: sources, spatial distribution and pollution assessment.

The pollution of floodplain, deltaic and adjacent coastal soils in large fluvial systems, considered an urgent environmental problem, as well as potentially toxic elements in such environments, can negatively affect aquatic ecosystems, as well as pose significant risks to human health. This paper is devoted to the geochemistry of potentially toxic elements in soils of the Lower Don basin, which is one of the largest and most anthropogenically transformed water bodies in Southern Russia, as well as the adjacent areas of the Taganrog Bay coast. The median element concentrations in the soils of the study area were consistent with the world soil average and the contents of elements in background soils. Comparative assessment of the spatial distributions as well as the results of Pearson's correlations, cluster analysis and principal component analysis showed that Cr, Ni, Cu and Zn are predominantly of natural origin; Mn and As are of mixed sources; and Cd and Pb are predominantly of anthropogenic origin. The geochemical anomalies of elements were associated with the impact of local anthropogenic sources. Geochemical background values for Cr, Mn, Ni, Cu, Zn, As, Cd and Pb in the soils of the Lower Don and the Taganrog Bay coast determined using the 'median + 2 median absolute deviations' approach are presented. The highest values of the integrated pollution indices were observed in floodplain soils of small rivers.

Bioaccessible PAH influence on distribution of antibiotic resistance genes and soil toxicity of different types of land use.

For a better understanding of the dissemination of antibiotic resistance genes (ARGs) in natural microbial communities, it is necessary to study the factors influencing it. There are not enough studies showing the connection of some pollutants with the dissemination of ARGs and especially few works on the effect of polycyclic aromatic compounds (PAHs) on the spread of resistance in microbiocenosis. In this respect, the aim of the study was to determine the effect of bioaccessible PAHs on soil resistome. The toxicity and the content of bioaccessible PAHs and ARGs were studied in 64 samples of soils of different types of land use in the Rostov Region of Russia. In most soils, a close positive correlation was demonstrated between different ARGs and bioaccessible PAHs with different content of rings in the structure. Six of the seven studied ARGs correlated with the content of 2-, 3-, 4-, 5- or 6-ring PAHs. The greatest number of close correlations was found between the content of PAHs and ARGs in the soils of protected areas, for agricultural purposes, and in soils of hospitals. The diverse composition of microbial communities in these soils might greatly facilitate this process. A close correlation between various toxic effects identified with a battery of whole-cell bacterial biosensors and bioaccessible PAHs of various compositions was established. This correlation showed possible mechanisms of PAHs' influence on microorganisms (DNA damage, oxidative stress, etc.), which led to a significant increase in horizontal gene transfer and spread of some ARGs in soil microbial communities. All this information, taken together, suggests that bioaccessible PAHs can enhance the spread of antibiotic resistance genes.

Photoelectron Properties and Organic Molecules Photodegradation Activity of Titania Nanotubes with CuxO Nanoparticles Heat Treated in Air and Argon.

Titania is very famous photocatalyst for decomposition of organic pollutants. Its photocatalytic properties significantly depend on the morphology and chemical composition of the samples. Herein, the TiO2 nanotubes/CuxO nanoheterostructures have been synthesized and the effect of heat treatment performed in molecular atmospheres of air and argon on their photoelectrochemical and photocatalytic properties has been studied. The prepared samples have a higher reaction rate constant compared to TiO2 nanotubes in the decomposition reaction of methylene blue molecules. It is established that in argon treated nanoheterostructures, the copper oxide is present in two phases, CuO and Cu2O, while in air treated ones there is only CuO. In the TiO2 nanotubes/CuxO samples, Cu2+ ions and molecular O2- radicals were detected while in TiO2 nanotubes only carbon dangling bond defects are present. The dynamics of O2- radicals under illumination are discussed. It was shown that the TiO2 nanotubes do not exhibit photocatalytic activity under visible light. The mechanism of the photocatalytic reaction on the surface of the TiO2 nanotubes/CuxO samples was proposed. It is assumed that a photocatalytic decomposition of organic molecules under visible light at the surface of the nanoheterostructures under investigation is realized mainly by the reaction of these molecules with photogenerated O2- radicals. The results obtained are completely original and indicate the high promise of the prepared photocatalysts.

Non-corresponding contaminants in marine surface sediments as a factor of ARGs spread in the Sea of Azov.

The present study aims to analyze the level and total toxicity of the most common pollutants in surface sediments and assess their impact on the occurrence of antibiotic resistance genes (ARGs) in the Sea of Azov. Biotesting using the whole-cell bacterial lux-biosensors showed high integral toxicity of surface sediments and the presence of genotoxicants and substances that cause oxidative stress and protein damage. Using cluster analysis, it was shown that the distribution of pollutants in the Sea of Azov depends on the type of surface sediments. The relative abundance and distribution of 14 ARGs in surface sediments were shown. Principle component analyses results suggest that non-corresponding contaminants do not exert direct influence on the ARGs abundance in the surface sediments of the Sea of Azov. Thus, the need to investigate the significance of non-corresponding pollutants in the selection and distribution of ARGs in the aquatic environment remains a pressing problem.

Potentially harmful elements in urban surface deposited sediment of Ekaterinburg, Russia: Occurrence, source appointment and risk assessment.

In this study, the human health risks of potentially harmful elements (PHEs) in urban surface deposited sediments (USDS) were examined by collecting urban dust samples, measuring their PHE concentrations, and using index evaluation. About 35, 12 and 16 samples are represented a green zones, roads, driveways and sidewalks in residential areas of Ekaterinburg, respectively. The dust fraction (0.002-0.1 mm) was obtained by sieving, filtration, and decantation process. Total concentrations of 10 PHEs were measured using inductively coupled plasma mass spectrometry. The highest concentrations of Pb were found in USDS from green zones, while Fe, V, Mn, Co, Ni, Sn, and Sb on roads, Cu and Zn on driveways and sidewalks. The contamination levels in the investigated land-use areas were studied, where the highest contamination was contributed from Sb in the driveways and sidewalk. Moreover, the pollution in the studied zones was a high load, contributing to anthropogenic activities and traffic emissions. No non-cancerogenic risk was attributed from the PHEs based on the results of health indices (HI < 1) for both adult and children, except Co and Ni which has HI > 1 for children. The total carcinogenic risk (TLCR) in all urban landscape areas is defined as a high potential inhalation exposure and a low potential ingestion and dermal exposure.

Geochemical transformation of soil cover and vegetation in a drained floodplain lake affected by long-term discharge of effluents from rayon industry plants, lower Don River Basin, Southern Russia.

Lake Atamanskoye is one of the most polluted aquatic environments in the South of Russia. This water body was affected by long-term pollution by effluent from industrial rayon plants located in the city of Kamensk-Shakhtinsky. Accumulation of pollutants resulted in the degradation of Lake Atamanskoye, which is currently drained. This research focused on the geochemical transformation of soils and vegetation within the territory of the former water body and its surroundings. Methods of study included the evaluation of potentially toxic elements (PTEs) in soils and plants by X-ray fluorescence, as well as the contents of their forms by sequential extraction and statistical processing of the data. The results revealed that Spolic Technosols and Fluvisols represent the most widespread soils within Lake Atamanskoye. The concentration of metals found in the soils of the lakebed is several orders of magnitude higher than the regional geochemical background and world soil baseline values due to long-term industrial pollution. The natural and technogenic soils were subdivided into two groups according to pH. Alkaline soils in the presence of carbonates were characterised by high levels of PTEs, while acidic soils with higher proportions of exchangeable fractions and higher potential for metal accumulation in adjacent plants had lower levels of PTEs.

Pollution status and human health risk assessment of potentially toxic elements and polycyclic aromatic hydrocarbons in urban street dust of Tyumen city, Russia.

This study investigated levels and sources of pollution and potential health risks associated with potentially toxic elements (PTEs) and polycyclic aromatic hydrocarbons (PAHs) in urban street dust collected from Tyumen city, a large transport centre with one of the highest motorization rates in Russia. Twenty street dust samples were collected from four grades of roads in five different land use areas. Research methods included measurements of physical and chemical properties of street dust, concentrations of 18 PTEs using inductively coupled plasma mass spectrometry, 12 PAHs using high-performance liquid chromatography, and statistical analysis of the data. Concentrations of Ni, Cr, Sb, and Mo, as well as medium and high molecular weight PAHs in urban street dust, were notably higher than in soils within the city, which indicates that transport is the main source of these elements. Concentrations of Cu, Cd, Pb, Zn, Mn, and As in street dust of Tyumen were lower compared to many large cities, while Cr, Ni, and Co were higher. Concentrations of PAH were comparable to other large nonindustrial cities. Total contamination of street dust by both PTEs and PAHs showed more robust relationships with the number of roadway lanes rather than land use. The estimated carcinogenic risks were low in 70% of samples and medium in 30% of samples. Noncarcinogenic risks were attributed to exposure to Co, Ni, V, and As. The total noncarcinogenic risk for adults was found to be negligible, while the risk was found to be moderate for children.

Anodic TiO2nanotube arrays for photocatalytic CO2conversion: comparative photocatalysis and EPR study.

Titania (TiO2) is a widely used semiconductor for the photocatalytic decomposition of organic impurities in air, water and the conversion of CO2into hydrocarbon fuel precursors. TiO2in the form of nanotubes arrays is the most attractive for practical use because of the morphological advantages providing more favorable diffusion of photocatalytic reaction products and a low recombination rate of photogenerated electrons and holes. We have carried out a comparative study of the photocatalytic activity of gas-phase conversion of CO2to hydrocarbon products and the defect properties of multi-walled and single-walled arrays of TiO2nanotubes. Methanol and methane have been detected in the CO2photoreduction process. The photocatalytic evolution rate of multi-walled TiO2nanotubes is twice as fast for methane as for single-walled TiO2nanotubes after four hours of irradiation and four times faster for methanol. The type and features of the structural defects have been investigated by EPR spectroscopy. For the first time, it has been shown that Ti3+/oxygen vacancy centers are mainly located inside the outer layer of nanotubes, while carbon dangling bonds have been observed directly on the surface of the inner layer. Carbon defects have been found to be the centers of adsorption and accumulation of photoinduced charge carriers. The results are entirely new; they clarify the role of different types of defects in the photocatalytic conversion of CO2to hydrocarbon compounds and show good prospects for applying TiO2nanotube arrays.

Evaluating the effect of historical development on urban soils using microartifacts and geochemical indices.

The proposed research is devoted to the effects of the urbanization on the soil cover through the assessment of common organic and inorganic pollutants as well as anthropogenic microartifacts (MAs) over 20 sites characterizing different land use areas within the city of Tyumen, Russia. The analytical methods included measurements of physical-chemical properties of soils (total organic carbon content, pH, and texture), the total concentrations of potentially toxic elements (V, Cr, Co, Ni, Cu, Zn, As, Sr, and Pb) using X-ray fluorescence analysis, and the concentrations of 12 priority polycyclic aromatic hydrocarbons using high-performance liquid chromatography, and the evaluation of the composition of anthropogenic MAs assemblies by optical microscopy. The results of the study showed that the soils of all studied sites within the industrial areas were characterized by a high level of combined pollution with elements and compounds. For other sites, the duration of urbanization was the strongest factor that influenced the levels of pollution. The sites with the highest pollution levels were also characterized by the highest proportion and diversity of MAs. In contrast to the urban soils of the cities in North America and Western Europe, anthropogenic MAs associated with the use of coal (ash, slag, and silicon spheres) were present, but to a far lesser extent. Apparently, this is due to the fairly late development and intensive growth of Tyumen in the second half of the twentieth century, as well as the use of natural gas and fuel oil. At the same time, MAs associated with construction and domestic debris prevailed both in the soils of demolition sites and residential areas, which indirectly indicates the rapid and chaotic nature of urbanization, characteristic of Tyumen.

The Key Role of Active Sites in the Development of Selective Metal Oxide Sensor Materials.

Development of sensor materials based on metal oxide semiconductors (MOS) for selective gas sensors is challenging for the tasks of air quality monitoring, early fire detection, gas leaks search, breath analysis, etc. An extensive range of sensor materials has been elaborated, but no consistent guidelines can be found for choosing a material composition targeting the selective detection of specific gases. Fundamental relations between material composition and sensing behavior have not been unambiguously established. In the present review, we summarize our recent works on the research of active sites and gas sensing behavior of n-type semiconductor metal oxides with different composition (simple oxides ZnO, In2O3, SnO2, WO3; mixed-metal oxides BaSnO3, Bi2WO6), and functionalized by catalytic noble metals (Ru, Pd, Au). The materials were variously characterized. The composition, metal-oxygen bonding, microstructure, active sites, sensing behavior, and interaction routes with gases (CO, NH3, SO2, VOC, NO2) were examined. The key role of active sites in determining the selectivity of sensor materials is substantiated. It was shown that the metal-oxygen bond energy of the MOS correlates with the surface acidity and the concentration of surface oxygen species and oxygen vacancies, which control the adsorption and redox conversion of analyte gas molecules. The effects of cations in mixed-metal oxides on the sensitivity and selectivity of BaSnO3 and Bi2WO6 to SO2 and VOCs, respectively, are rationalized. The determining role of catalytic noble metals in oxidation of reducing analyte gases and the impact of acid sites of MOS to gas adsorption are demonstrated.

Environmental and human health risk assessment of potentially toxic elements in soils around the largest coal-fired power station in Southern Russia.

The combustion of solid fuel at power plants pollutes adjacent areas with potentially toxic elements (PTEs), which increases risks to public health in the vicinity of these facilities. The proposed paper presents the results of a geochemical study of PTEs (Cr, Mn, Ni, Cu, Zn, Cd, and Pb) contamination in the vicinity of Novocherkassk Power Plant (NPP) as it relates to environmental and human health risks. The impact zone of NPP is pronounced for a distance of approximately 7 km northwest of the enterprise-the second largest coal power plant in Southern Russia. Data from monitoring sites lead us to conclude that spatial patterns of soil pollution are strongly influenced by the peculiarities of local atmospheric circulation, while the characteristics of soils within the study area play a secondary role. The highest levels of PTEs and their exchangeable forms exceed both regional background and sanitary and hygienic standards within a radius of 3 km to the west of the plant, which corresponds to a zone of soils contaminated with Cr, Ni, Cu, Zn, Cd, and Pb. The carcinogenic risk to human health slightly exceeds the permissible standard of 1 × 10-6 for soils in close vicinity of the enterprise due to the potential human intake of Ni, Cd, and Pb. The results of the health risk assessment indicate no noncarcinogenic risks for adults, while for children, they are low.

Melamine-Barbiturate Supramolecular Assembly as a pH-Dependent Organic Radical Trap Material.

In the last two decades, a large number of self-assembled materials were synthesized and they have already found their way into large-scale industry and science. Hydrogen-bond-based supramolecular adducts are found to have unique properties and to be perfect host structures for trapping target molecules or ions. Such chemical systems are believed to resemble living matter and can substitute a living cell in a number of cases. Herein, a report on an organic material based on supramolecular assembly of barbituric acid and melamine is presented. Surprisingly, the structure is found to host and stabilize radicals under mild conditions allowing its use for biological applications. The number of free radicals is found to be easily tuned by changing the pH of the environment and it increases when exposed to light up to a saturation level. We describe a preparation method as well as stability properties of melamine-barbiturate self-assembly, potentiometric titration, and hydrogen ions adsorption data and EPR spectra concerning the composite.

Titania-based nanoheterostructured microspheres for prolonged visible-light-driven photocatalysis.

Titanium dioxide is a widely used photocatalytic material possessing such advantages as safety, low cost, and high reactivity under the ultraviolet light illumination. However, its applicability in sunlight is limited due to the wide band gap and, as a consequence, the low quantum yield. Doping of titanium dioxide with metal or non-metal atoms and creating heterojunctions based on it are some of the most efficient ways to overcome this drawback. Herein we propose a new facile way of synthesis of nitrogen-doped TiO2/MoO3 and TiO2/WO3 microsphere-shaped nanocomposite photocatalysts, combining the advantages of these two methods. It is revealed that such structures are not only photo-active when exposed to visible light, but can also accumulate a photoinduced charge, thus allowing the catalytic reaction to be prolonged for a long time after the illumination is switched off (up to 48 h). With the help of EPR spectroscopy, paramagnetic defects in the samples were determined. The obtained results show good application prospects of the visible-light-driven TiO2-based nanoheterostructured microspheres in the environmental purification.