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.

Speciation of macro- and nanoparticles of Cr2O3 in Hordeum vulgare L. and subsequent toxicity: A comparative study.

Chromium (Cr) is reported to be hazardous to environmental components and surrounding biota when levels exceed allowable thresholds. As Cr is extensively utilized in different industries, thereby comprehensively studied for its toxicity. Along with Cr, the applications of nano-Cr or chromium oxide nanoparticles (Cr2O3-NPs) are also expanding; however, the literature is scarce or limited on their phytotoxicity. Thereby, the current work investigated the morpho-physiological insights of macro- and nanoparticles of Cr in Hordeum vulgare L. plants. The increased accumulation and translocation of Cr under the exposure of both forms disturbed the cellular metabolism that might have inhibited germination and growth as well as interfered with the photosynthesis of plants. The overall extent of toxicity was noticeably higher under nanoparticles' exposure than macroparticles of Cr. The potential cue for such phytotoxic consequences mediated by Cr nanoparticles could be an increased bioavailability of Cr ions which was also supported by their total content, mobility, and factor toxicity index. Besides, to support further these findings, synchrotron X-ray technique was used to reliably identify Cr-containing compounds in the plant tissues. The X-ray spectra of the near spectral region and the far region of the spectrum of K-edge of Cr were obtained, and it was established that the dominant crystalline phase corresponds to Cr2O3 (eskolaite) from the recorded observations. Thus, the obtained results would allow revealing the mechanism of macro- and nanoparticles of Cr induced impacts on plant at the tissue, cellular- and sub-cellular levels.

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.

Phytoremediation of copper-contaminated soil by Artemisia absinthium: comparative effect of chelating agents.

Phytoremediation is a promising method for the removal of toxic trace elements, specifically of copper, from the contaminated soil in the mining regions of Armenia. Thereby, the objectives of our study were the assessment of copper accumulation capacity and phytoremediation suitability of wormwood (Artemisia absinthium L.), a potential metal hyperaccumulator, as well as the identification of the influence of some chelating agents and their combinations on copper phytoremediation effectiveness. The results of studies have shown that A. absinthium is a relatively well-adapted plant species with the ability to grow in copper-contaminated soils collected from the surroundings of Zangezur Copper and Molybdenum Combine (south-east of Armenia). The observed decrease in plant growth in contaminated soil was possible to restore by the use of ammonium nitrate. It was revealed that for the remediation of copper-contaminated soils by phytostabilisation method, A. absinthium could be grown without the application of chelating agents, as being a perennial herb, it is able to accumulate relatively high contents of copper in its root and do not transfer this metal to the above-ground part at the same time. As opposed to the phytostabilisation method, for the cleaning of copper-contaminated soils through phytoextraction method by A. absinthium, the application of chemical amendments is needed for the enhancement of copper bioavailability and for its intensive transportation to the above-ground part of the plant. Collating the effects of various chemical agents on the plant, we concluded that the growth scheme, when the application of NH4NO3, a promoter of plant growth, is combined with the joint use of citric and malic acids, can be applied as the most expedient approach for remediation of copper-contaminated soils by phytoextraction method.

Influence of soil pollution on the morphology of roots and leaves of Verbascum thapsus L.

The impact of inorganic pollutants in the zone of industrial wastewater settling tanks (South of Russia) was studied. The levels of Mn, Cr, Ni, Cu, Zn, Pb, Cd were determined for Verbascum thapsus L., which are part of the mesophilic succession of wild plants in the studied technogenically polluted territory. The bioavailability of heavy metals (HM) for plants from transformed soils has been established. Anatomical and morphological features in the tissues of the plants affected by HM were analyzed using light-optical and electron microscopic methods. Contamination of the soil cover with Mn, Cr, Ni, Cu, Zn, Pb and Cd has been established with maximum content of Zn. It was revealed that the HM content in the V. thapsus plants exceeded the maximum permissible levels (Russian state standard): Zn by 23, Pb by 2, Cr by 31 and Cd by 3 times. The lower level of HM content in the inflorescences of mullein plants in comparison with the root system, stems and leaves indicates the resistance of generative organs to technogenic pollution. In the root and leaves of the V. thapsus, the anatomical and ultrastructural observation were carried out using light-optical and transmission electron microscopy. Changes in the ultrastructure of plants under the influence of anthropogenic impact have been revealed. The most significant changes of the ultrastructure of the polluted plants were found in the cell organelles of leaves (mitochondria, plastids, peroxisomes, etc.) including spatial transformation of the thylakoid system of plastids during the metal accumulation by plants, which may determine the mechanism of plant adaptation to technogenic pollution.

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.

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.

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.

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.

Bioindication of soil pollution in the delta of the Don River and the coast of the Taganrog Bay with heavy metals based on anatomical, morphological and biogeochemical studies of macrophyte (Typha australis Schum. & Thonn).

The results of biogeochemical and bioindication studies on the resistance of natural populations of macrophyte plant-cattail (Typha australis Schum. & Thonn) on the coast of the Taganrog Bay of the Sea of Azov and the sea edge of the Don River delta with regard to local pollution zones are presented. Plant resistance has been assessed through manifestation of their protective functions in relation to heavy metals. An excess in the lithospheric Clarkes and MPC in Zn, Cd and Pb in Fluvisols has been found. The total index of soil pollution (Zc) has made it possible to identify areas with different categories of contamination within the study area exposed to human impact. High mobility of Zn, Cd, Pb, Cr and Ni in Fluvisols has been revealed, which is confirmed by the significant bioavailability of Zn, Cr and Cd that are accumulated in the macrophyte plant tissues. The absorption of heavy metals by cattail plants is allowed for both the soil and the water of the nearby reservoir, where aquatic systems are a kind of "biological filter" contributing to water purification from pollutants. The impact of the environmental stress factor has been found to be manifested not only in the features of heavy metal accumulation and distribution in plant tissues, but also at the morphological and anatomical level according to the type of prolification. Changes in the cell membranes as well as in main cytoplasmic organelles (mitochondria, plastids, pyroxis, etc.) of the root and leaf cells have been identified, the most significant changes in the ultrastructure being noted in the tissues of leaf chlorenchyma. It is assumed that the identified structural changes contribute to slowing down of the ontogenetic development of plants and reduction in their morphometric parameters when exposed to anthropogenic pollution. Therefore, cattails can be effectively used as biological indicators while determining environmental pressures.