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.

Biochar and metal-tolerant bacteria in alleviating ZnO nanoparticles toxicity in barley.

The constant use of zinc oxide nanoparticles (ZnO NPs) in agriculture could increase their concentration in soil, and cause a threat to sustainable crop production. The present study was designed to determine the role of spore-forming and metal-tolerant bacteria, and biochar in alleviating the toxic effects of a high dose of ZnO NPs (2000 mg kg-1) spiked to the soil (Haplic Chernozem) on barley (Hordeum sativum L). The mobile compounds of Zn in soil and their accumulation in H. sativum tissues were increased significantly. The addition of biochar (2.5% of total soil) and bacteria (1010 CFU kg-1) separately and in combination showed a favorable impact on H. sativum growth in ZnO NPs polluted soil. The application of bacteria (separately) to the contaminated soil reduced the mobility of Zn compounds by 7%, due to loosely bound Zn compounds, whereas only biochar inputs lowered Zn mobile compounds mobility by 33%, even the combined application of biochar and bacteria also suppressed the soil Zn mobile compounds. Individual application of biochar and bacteria reduced the Zn plant uptake, i.e., underground parts (roots) by 44% and 20%, and in the above-ground parts of H. sativum plants by 39% and 13%, respectively, compared to ZnO NPs polluted soil treatments. Biochar, both separately and in combination with bacteria improved the root length by 48 and 85%, and plant height by 53 and 40%, respectively, compared to the polluted control. The root length and plant height decreased by 52 and 40% in ZnO NPs spiked soil compared clean soil treatments. Anatomical results showed an improvement in the structural organization of cellular-sub-cellular tissues of root and leaf. The changes in ultrastructural organization of assimilation tissue cells were noted all treatments due to the toxic effects of ZnO NPs compared with control treatment. The results indicate that metal-tolerant bacteria and biochar could be effective as a soil amendment to reduce metal toxicity, enhance crop growth, and improve soil health.

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.

Nano-biochar: A novel solution for sustainable agriculture and environmental remediation.

Currently, the applications of biochar (BC) in agricultural practices and for environmental remediation purposes have demonstrated multifaceted advantages despite a few limitations. Nano-BC offers considerable opportunities especially for the remediation of hazardous contaminants as well as the improvement of crop productivity. Positive outcomes of nano-BC on soil physico-chemical and biological characteristics have indicated its suitability for agricultural applications. Nano-BC may effectively regulate the mobilization and sorption of important micro- and macro-nutrients, along with the hazardous contaminants including potentially toxic metals, pesticides, etc. Additionally, the sorption characteristics of nano-BC depends substantially on feedstock materials and pyrolysis temperatures. Nevertheless, the conducted investigations regarding nano-BC are in infant stages, requiring extensive field investigations. The nano-enhanced properties of BC on one hand dramatically improve its effectiveness and sustainability, on the other hand, there may be associated with toxicity development in diverse aquatic and/or terrestrial environments. Therefore, risk assessment on soil organisms and its indirect impact on human health is another area of concern linked with the field application of nano-BC. The present review delineates the potentiality of nano-BC as an emerging sorbent for sustainable agriculture and environmental applications.

Methods to determine the affinity of heavy metals for the chemically extracted carrier phases in soils.

A new index is proposed to determine the affinity of heavy metals (HM) to their carrier phases (AHM-fraction), which, in contrast to the traditional index CHM = 100 CHM-fraction/CHM-soil, considers the sum of all metals in the fraction as a share of the bulk content of all HM in the soil. The metal has affinity for the given phase if AHM-fraction > 1; vice versa, the affinity is absent if AHM-fraction < 1. Comparison of the affinity series of metals for a certain phase based on two indices revealed their discrepancy in most cases. The new index can take into consideration the discrepancy in affinity of the given metal for phases extracted by different strength reagents. The effect of the new indicator was tested on several contaminated soils: Haplic Chernozem, Stagnic Phaeozems, and Calcaric Fluvic Arenosol, as well as on two Spolic Technosols. Compared with the index CHM, the results of the new analysis of contaminated soils with the ATM fraction demonstrated that the Zn content in Calcaric Fluvic Arenosol is decreased considerably due to its low buffer capacity. Since the content of organic matter in Calcaric Fluvic Arenosol is insignificant, only organophile elements, such as Cu and Pb, can make up complexes with organic ligands, in contrast to the fixation of Ni and Mn by organic matter in Chernozems. Due to the low buffering capacity of Calcaric Fluvic Arenosol, the mobile forms of Cd and Zn increased, and these forms of Cr decreased. Therefore, the low buffering soil cannot fix Cd and Zn. Increase in contamination in Spolic Technosols (approximate permissible concentration, APC > 5) as compared to the index CHM, the value of the AHM-fraction of metals in the residue (except for cadmium) increased. In addition, the share of Pb and Cu increases in the organic matter. Thus, the use of a new indicator-the affinity of heavy metals to the carrier phases showed their advantage over the traditional index CHM.

Analysis and assessment of heavy metal contamination in the vicinity of Lake Atamanskoe (Rostov region, Russia) using multivariate statistical methods.

Assessment of spatial patterns of potentially toxic metals is one of the most urgent tasks in soil chemistry. In this study, descriptive statistics and three methods of multivariate statistical analysis, such as the hierarchical cluster analysis (HCA), correlation analysis, and conditional inference tree (CIT), were used to identify patterns and potential sources of heavy metals (Co, Ni, Cu, Cr, Pb, MnO, and Zn). The investigation was carried out on 81 sample points, using 20 testing parameters. A strong positive correlation found among Ni, Cu, Zn, and HCA results has confirmed the common origin of the elements from waste discharge. Hierarchical CA divided the 81 test sites into 5 classes based on the soil quality and HMs contamination similarity. Regression trees for Cr, Pb, Zn, and Cu were verified by the splitting factor including HMs content and soil chemistry factors. The CIT has revealed that the elements (Cr, Pb, Zn, and Cu) concentration values are split at the first level by some other metal, indicating common anthropogenic impact resulting from industrial waste discharges. The factors at the next hierarchical level of splitting, in addition to the HMs, include compounds belonging to soil chemistry variables (SiO2, Al2O3, and K2O). The CIT nonlinear regression model is in good agreement with the data: R2 values for log-transformed concentrations of Cr, Pb, Zn, and Cu are equal to 0.775; 0.774; 0.775; 0.804, respectively.

Spatial distribution of heavy metals in soils of the flood plain of the Seversky Donets River (Russia) based on geostatistical methods.

Soil contamination by heavy metals (HM) is a worldwide problem for human health. To reduce risk to human health from exposure to toxic chemicals associated with soil contamination, it is necessary to monitor and assess HM concentrations in the soil for places where the concentration exceeds the acceptable levels. Spatial patterning is a necessary tool for assessment of the exposure risk of HM contamination. Soil sampling (n = 65) was carried out in technogenically polluted soils located at Rostov oblast to study the content and spatial distribution of four HM (Cu, Zn, Pb, and Cr) in the surface layer (0-20 cm) of the impact zone of former Lake Atamanskoe (floodplain of the Seversky Donets River valley, Rostov region) with an area of 3.91 km2. Extremely high values of HM concentrations were found with the maximum values of 702 mg/kg, 72,886 mg/kg, 2300 mg/kg, 259 mg/kg for Cu, Zn, Pb, and Cr, respectively. Inverse distance-weighted (IDW) interpolation was used to prepare 3D monoelement images of HM. Lognormal kriging and indicator kriging techniques were applied to create elemental spatial distribution maps and HM probability maps. The results showed that the total content of Cu, Zn, Pb, and Cr was moderately spatially dependent (nugget-to-sill ratio ranged from 31 to 38%), whereas the contamination index Zc formed strong spatial dependence patterns (nugget-to-sill ratio ranged from 0 to 21.4%). The obtained results of this study could serve as a guide to the authorities in identifying those areas which need remediation. Moreover, this study provides a tool for assessing the hygienic situation in the vicinity of Kamensk-Shakhtinsky (Rostov region) for decision making that can help to minimize the environmental risk of technogenic soil contamination of HM.

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.

Sorption of benzo[a]pyrene by Chernozem and carbonaceous sorbents: comparison of kinetics and interaction mechanisms.

Benzo[a]pyrene (BaP) is a polycyclic aromatic hydrocarbon, highly persistent and toxic and a widespread environmental pollutant. Although various technologies have been developed to remove BaP from the environment, its sorption through solid matrixes has received increasing attention due to cost-effectiveness. The present research compares the adsorption capacity of Haplic Chernozem, granular activated carbon and biochar in relation to BaP from water solution. Laboratory experiments with different initial BaP concentrations in the liquid phase and different ratios of the solid and liquid phases show that Freundlich model describes well the adsorption isotherms of BaP by the soil and both sorbents. Moreover, the BaP isotherm sorption by the Haplic Chernozem is better illustrated by the Freundlich model than the Langmuir equation. The results reveal that the sorption capacity of the carbonaceous adsorbents at a ratio 1:20 (solid to liquid phases) is orders of magnitude higher (13 368 ng mL-1 of activated carbon and 3 578 ng mL-1 of biochar) compared to the soil (57.8 ng mL-1). At the ratio of 0.5:20, the adsorption capacity of the carbonaceous sorbents was 17-45 times higher than that of the soil. This is due to the higher pore volume and specific surface area of the carbonaceous sorbents than soil particles, assessed through scanning electron microscopy. The sorption kinetic of BaP by Chernozem was compared with the adsorption kinetics by the carbonaceous sorbents. Results indicate that the adsorption dynamic involves two steps. The first one is associated with a fast BaP adsorption on the large available surface and inside macro- and meso-pores of the sorbent particles of the granular activated carbon and biochar. Then, the adsorption is followed by a slower process of BaP penetration into the microporous space and/or redistribution into a hydrophobic fraction. The effectiveness of the sorption process depends on both the sorbent properties and the solvent competition. Overall, the granular activated carbon and biochar are highly effective adsorbents for BaP, whereas the Haplic Chernozem has a rather limited capacity to remove BaP from contaminated solutions.

Soil organic matter and biological activity under long-term contamination with copper.

Organic matter (OM) and enzymes activity can act as indicators of the time and level of soil contamination with heavy metal. The goal of this study is evaluation of the effect of chronic long-term soil contamination with Cu on OM and biological activity in Spolic Technosols. The monitoring plot is located in the zone of industrial wastewater storage and sludge reservoirs in the Seversky Donets River flood plain. The total amount of Cu in the investigated soils varied greatly from 52 to 437 mg/kg. The results of Cu sequential fractionation the contaminated soil have shown that the chemical fraction composition of metal changed when the soil contamination level increased. The amount of Cu compounds associated with OM and Fe and Mn oxides was also higher. Fractions of OM from the humic and fulvic acids groups were studied. Soil was subjected to extraction with cold and hot water, and the content of water-soluble OM (WSOM) was determined. An increased solubility of humic and fulvic acids as well as elevated content of cold and hot extraction WSOM was established. The cold-extracted amount of WSOM increased with an enhance in the Cu content. The long-term contamination of soil with Cu leads to an adaptation of microorganisms to this adverse environmental factor, and this adaptation is manifested in the WSOM content increase. The effect of Cu contamination on microbiological activity was assessed by plate-counting culturable microorganisms and determining urease and dehydrogenase enzymatic activity. A high level of soil contamination with Cu showed a noticeable negative effect on the number of soil bacteria; however, active and potentially active bacteria were observed even in the highly contaminated soils. The changes in soil OM and microbial communities caused by Cu pollution can lead to disruption of ecosystem functioning.

Biochar-assisted Fenton-like oxidation of benzo[a]pyrene-contaminated soil.

In the present study, the biochar derived from sunflower husks was used as a mediator in the heterogeneous Fenton process. The physical and chemical characteristics were studied in terms of specific surface area, elemental contents, surface morphology, surface functional groups, thermal stability, and X-ray crystallography. The main aim was to evaluate the effectiveness of biochar in a heterogeneous Fenton process catalyzed by hematite toward the degradation of benzo[a]pyrene (BaP) in Haplic Chernozem. The Fenton-like reaction was performed at a pH of 7.8 without pH adjustment in chernozem soil. The effects of operating parameters, such as hematite dosage and H2O2 concentrations, were investigated with respect to the removal efficiency of BaP. The overall degradation of 65% was observed at the optimized conditions where 2 mg g-1 hematite and 1.25 M H2O2 corresponded to the H2O2 to Fe ratio of 22:1. Moreover, the biochar amendment showed an increment in the removal efficiency and promotion in the growth of spring barley (Hordeum sativum distichum). The BaP removal was reached 75 and 95% after 2.5 and 5% w/w addition of biochar, respectively. The results suggested that the Fenton-like reaction's effectiveness would be greatly enhanced by the ability of biochar for activation of H2O2 and ejection of the electron to reduce Fe(III) to Fe(II). Finally, the presence of biochar could enhance the soil physicochemical properties, as evidenced by the better growth of Hordeum sativum distichum compared to the soil without biochar. These promising results open up new opportunities toward the application of a modified Fenton reaction with biochar for remediating BaP-polluted soils.

Application of XAFS and XRD methods for describing the copper and zinc adsorption characteristics in hydromorphic soils.

Modeling metal sorption in soils is of great importance to predict the fate of heavy metals and to assess the actual risk driven from pollution. The present study focuses on adsorption of HM ions on two types of hydromorphic soils, including calcaric fluvisols loamic and calcaric fluvic arenosols. The individual and competitive adsorption behaviors of Cu and Zn on soils and soil constituents are evaluated comprehensively. It is established that the sorption processes were best described with the Langmuir model. The results suggest that the calcaric fluvic arenosols are more vulnerable to heavy metal input compared to fluvisols loamic. In all cases, Cu had a higher range of values of the adsorption process parameters relative to Zn. The Zn is likely to be the most critical environmental factor in such soils since it exhibited a decreased sorption under competitive conditions. The retention mechanisms of HM in hydromorphic soils are considered. Based on theoretical calculations of ion activity in soil solutions using solubility diagrams of Cu and Zn compounds, the possibility of precipitation of Cu hydroxide and Zn carbonate in the studied soils is shown. Direct physical methods of nondestructive testing (XAFS and XRD) are applied to experimentally prove the formation of these HM compounds on the surface of montmorillonite, the dominant mineral in hydromorphic soils, and calcite. Thus, the combination of both physicochemical methods and direct physical methods can provide a large amount of real information about the mechanisms of HM retain with solid phases.

The influence of long-term Zn and Cu contamination in Spolic Technosols on water-soluble organic matter and soil biological activity.

Potentially toxic elements (PTE) pollution has a pronounced negative effect on the soil and its components. The characteristics of soil organic matter and the activity of soil enzymes can serve as sensitive indicators of the degree of changes occurring in the soil. This study aims to assess the effect of long-term severe soil contamination with Zn and Cu on water-soluble organic matter (WSOM) and the associated changes in the biochemical activity of microorganisms. The total content of Zn and Cu in the studied soils varies greatly: Zn from 118 to 65,311 mg/kg, Cu from 52 to 437 mg/kg. The content of WSOM was determined using cold and hot extraction. It was revealed that the WSOM, extracted with cold water is a sensitive indicator reflecting the nature of the interaction of Zn and Cu with it. With an increase in the Cu and Zn content, the amount of WSOM extracted with cold water increases due to rise in the complex-bound metal compounds associated with it. The content of complex-bound compounds Zn in Spolic Technosols reaches 50% of the total metal content. It is shown that one of the biogeochemical mechanisms of microorganisms' adaptation to metal contamination is clearly manifested by the increase in the content of WSOM. The precipitation of metal carbonates develops in the soil which reduces the mobility and toxicity of PTE. Due to this mechanism, a decrease in the activity of dehydrogenases and urease was not prominent in all studied soils, despite the very high level of pollution and the transformation of organic matter. The study of the relationship of PTE with the most easily transformed part of WSOM and the activity of soil enzymes is of great importance for an objective assessment of possible environmental risks.

Subcritical water extraction of organic acids from chicken manure.

BACKGROUND: Chicken manure waste has a wide range of organic substances and mineral elements. This enriched source has stimulated great scientific interest in finding cleaner and more environmentally benign nutrient recovery options. This study aimed to determine an effective and eco-friendly method (i.e. subcritical water extraction) for processing fresh poultry manure. RESULTS: The high content of total organic carbon, including humic acids carbon and fulvic acids carbon, in extract was found to release under subcritical conditions. The organic compounds obtained by extraction with subcritical water correspond to humic acid in composition because of the presence in the sample of all the functional groups: polymer bonded by molecular hydrogen bond (3400 cm-1 ), the presence of CH2 and CH3 groups (2870 cm-1 ), the presence of carboxyl groups (1720 cm-1 ) and quinones (1640-1680 cm-1 ). The solid phase left over was characterized by a high content of organic carbon, phosphorus, potassium, and microelements. The maximum extraction of humic acid and fulvic acid carbon was found between 210 and 250 °C at a pressure of 50-60 atm, and the content was a maximum of 3647.2 × 10-6 g kg-1 at an extraction temperature of 250 °C. CONCLUSION: Given the high content of humic acid found in the extracted medium, the proposed subcritical extraction opens up new opportunities for nutrients recovery in the poultry industry. © 2020 Society of Chemical Industry.

Nitrogen state of Haplic Chernozem of the European part of Southern Russia in the implementation of resource-saving technologies.

BACKGROUND: The prolonged use of traditional moldboard ploughing often results in soil degradation and, ultimately, has an impact on national food security. Therefore, the implementation of resource-saving technologies (minimal and No-till) is a promising approach in the development of agriculture, especially in drought regions. The present study reports the results of long-term research on the effect of various tillage methods (moldboard ploughing, minimal tillage and No-till technique) on the nitrogen content of Haplic Chernozem of the European part of Southern Russia. The revealed regularities can be used as a theoretical basis for the effective use of resource-saving technologies, including No-till, in the zone of insufficient moisture. RESULTS: Long-term (59 years) cultivation of winter wheat using traditional moldboard ploughing has decreased the soil organic material (SOM) by 35% and total nitrogen by 32% in the soil. Minimization of tillage, in contrast, recovers the nitrogen potential of the soil in winter wheat agrocenoses. There is a statistically confirmed dependence of the content of SOM and total nitrogen on the tillage method of the upper soil horizon, with no significant effect of the tillage methods on intensity ammonification and nitrification. However, the content of nitrate-nitrogen during resource-saving tillage methods (22.8-24.4 mg kg-1 ) was higher than that after ploughing (20.3 mg kg-1 ) during all the years of the study, indicating the higher content of easily mineralizable nitrogen-containing compounds in the soil after minimal tillage. CONCLUSION: The use of resource-saving tillage technologies under conditions of insufficient moisture stabilizes the nitrogen content in soil and can improve nitrogen nutrition of plants. © 2020 Society of Chemical Industry.

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.

Transformation of copper oxide and copper oxide nanoparticles in the soil and their accumulation by Hordeum sativum.

In recent years, the study of the influence of nanoparticles (NPs) on the environment has attracted much interest as nanotechnology is becoming the key technology of the future generation. The comparative studies on the effects of macro- and nanosized copper oxide (CuO) on plants rarely cover the state and behaviour of CuO in the soil-plant system. This work considers the transformation of CuO in Haplic Chernozem depending on the degree of dispersion and its toxic effects on spring barley (Hordeum sativum) growth. To investigate the transformation of the studied particles of metal oxide in the soil and plant, both chemical method of analysis and synchrotron radiation X-ray powder diffraction, X-ray absorption near-edge structure spectroscopy (XANES) and X-ray absorption fine-structure spectroscopy (EXAFS) were used. It was shown that CuO NPs underwent a stronger transformation due to the high reactivity of smaller particles. The Cu mobility was observed to increase within the soil profile as confirmed by the model pollution experiment. This is mainly due to the formation of complex forms of metal with organic matter. A dose of 300 mg/kg of macro- and nanosized CuO did not significantly affect the development and productivity of spring barley. The effect of high doses of macro- and nanosized CuO (2000 and 10,000 mg/kg) had a negative impact on the growth of spring barley. The application of nanosized CuO had a greater toxic effect than the macrosized CuO on the plants. The XANES and EXAFS data revealed that CuO NPs accumulated in the soil and plants. The linear combination fit shown that Cu atoms, incorporated into the plants, have environment typical of CuO. This indicates a high environmental risk when soil is contaminated with CuO NPs compared with its arrival as CuO.

Effects of benzo[a]pyrene toxicity on morphology and ultrastructure of Hordeum sativum.

Many studies have been devoted to investigation of toxic benzo(a)pyrene (BaP) compound, but studies involving changes at the cellular level are insufficient to understand the mechanisms of polycyclic aromatic hydrocarbons (PAHs) effect on plants. To study the toxicity of BaP, a model vegetation experiment was conducted on cultivation of spring barley (Hordeum sativum distichum) on artificially polluted BaP soil at different concentrations. The article discusses the intake of BaP from the soil into the plant and its effect on the organismic and cellular levels of plant organization. The BaP content in the organs of spring barley was determined by the method of saponification. With an increase in the concentration of BaP in the soil, its content in plants also rises, which leads to inhibition of growth processes. The BaP content in the green part of Hordeum sativum increased from 0.3 µg kg-1 in control soil up to 2.6 µg kg-1 and 16.8 µg kg-1 under 20 and 400 ng/g BaP applying in soil, as well as in roots: 0.9 µg kg-1, 7.7 µg kg-1, 42.8 µg kg-1, respectively. Using light and electron microscopy, changes in the tissues and cells of plants were found and it was established that accumulation of BaP in plant tissues caused varying degrees of ultrastructural damage depending on the concentration of pollutant. BaP had the greatest effect on the root, significant changes were found in it both at histological and cytological levels, while changes in the leaves were observed only at the cytological level. The results provide significant information about the mechanism of action of BaP on agricultural plants.

Speciation of Zn and Cu in Technosol and evaluation of a sequential extraction procedure using XAS, XRD and SEM-EDX analyses.

Metal speciation, linked directly to bioaccessibility and lability, is a key to be considered when assessing associated human and environmental health risks originated from anthropogenic activities. To identify the Zn and Cu speciation in the highly contaminated, technogenically transformed soils (Technosol) from the impact zone near the industrial sludge reservoirs of chemical plant (Siverskyi Donets River floodplain, southern Russia), the validity of the BCR sequential extraction procedure using the X-ray absorption fine-structure and X-ray powder diffraction (XRD) analyses was examined after each of the three stages. After the removal of exchange and carbonate-bonded Zn and Cu compounds from Technosol (first stage of extraction), the resulting residual soil showed enrichment in a great diversity of metal compounds, primarily with Me-S and Me-O bonds. The number of compounds with a higher solubility decreased at the subsequent stages of extraction. In the residual soil left over after extracting the first and second fractions, the dominant Zn-S bond appeared as würtzite (hexagonal ZnS) that made up more than 50%, while the Cu-S bond was almost completely represented only by chalcocite (Cu2S). The XRD analysis revealed the authigenic minerals of metals with S: sphalerite (cubic ZnS), würtzite (hexagonal ZnS), covellite (CuS) and bornite (Cu5FeS4). The scanning electron microscopy data confirmed that würtzite was the dominant form of Me with sulfur-containing and carbonate-containing minerals. The Zn-S bond was the main component (57%), whereas the Cu-O bond was dominant in the residual fraction (the fraction after the third-stage extraction). The results revealed that the composition of the residual fractions might include some of the most stable and hard-to-recover metal compounds of technogenic origin. Thus, the application of the novel instrumental methods, coupled with the chemical fractionation, revealed the incomplete selectivity of the extractants in the extraction of Zn and Cu in long-term highly contaminated soils.

The toxic effect of CuO of different dispersion degrees on the structure and ultrastructure of spring barley cells (Hordeum sativum distichum).

Nowadays, nanotechnology is one of the most dynamically developing and most promising technologies. However, the safety issues of using metal nanoparticles, their environmental impact on soil and plants are poorly understood. These studies are especially important in terms of copper-based nanomaterials because they are widely used in agriculture. Concerning that, it is important to study the mechanism behind the mode of CuO nanoparticles action at the ultrastructural intracellular level. It is established that the contamination with CuO has had a negative influence on the development of spring barley. A greater toxic effect has been exerted by the introduction of CuO nanoparticles as compared to the macrodispersed form. A comparative analysis of the toxic effects of copper oxides and nano-oxides on plants has shown changes in the tissue and intracellular levels in the barley roots. However, qualitative changes in plant leaves have not practically been observed. In general, conclusions can be made that copper oxide in nano-dispersed form penetrates better from the soil into the plant and can accumulate in large quantities in it.