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The soils of forest ecosystems are often affected by the industrial activity of mining and metallurgical enterprises, and insufficiently investigated for the content of pollutants due to enterprise emissions. Some pollutants, such as arsenic, are transported over long distances by these emissions. To analyze this connection, the present study was conducted on the eastern slope of Mount Yurma, the Southern Urals, Russia, to determine the content of arsenic in the soils of mountain forest areas in the impact zone of the copper smelter (Karabash). The physical and chemical parameters, total content of arsenic, mineralogical composition of silt, and concentration of arsenic in the silty fraction in soils located at different altitudes were determined using atomic absorption spectroscopy (AAS) and X-ray diffraction (XRD) techniques. The soils under study are physico-chemically and chemically acidic in the upper horizons with a pH of 3.26 to 4.05. The carbon of organic matter decreases with depth from 7.98 to 0.06%. Exchangeable Ca and Mg cations in the range of 2.6–8.6 mg-eq per 100 g of soil were determined. The mineralogical composition of the silty fraction consists mainly of quartz and aluminosilicates. Following an analysis of the arsenic content in the above-ground leaf litter, the bioconcentration factor (BCF) was calculated. Arsenic exceeding Clarke concentrations was recorded. In all upper soil horizons, concentrations of total arsenic exceeded background values by 3.7–5.2 times, with maximum values in the horizons A—25.3 mg/kg, in the horizons O—64.4 mg/kg. The obtained BCF > 1 data points to the biological arsenic accumulation by plants and, as a result, its input into the soil via industrial emissions from the smelter. It was found that the silty fraction plays a special role in the accumulation of arsenic in the studied soils. Accumulation of arsenic occurred mainly due to the secondary minerals of Ca and Mg. Differences in the accumulation of arsenic in the forest litter depending on the plant association were noted. The obtained results could serve as a guideline for monitoring the areas around the enterprise and enhancing the understanding of pollutants' distribution in the soils of remote areas and mountain landscapes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Purpose: To study the adaptive potential of the plant Typha laxmannii Lepech. to heavy metal (HM) stress on the basis of analysis of its morphological and anatomical features under the conditions of an anthropogenically transformed ecosystem of the Don River Delta. Methods: The soils on the monitored plots are of the Fluvisol type. The soil characteristics and total concentrations of Mn, Ni, Cd, Cu, Zn, Pb and Cr in soils and cattail plants were analysed. Anatomical-morphological and electron-microscopic examinations revealed the toxic effect of HMs on the roots and leaves of T. laxmannii plants. Results: The studied soils were found to contain high levels of the Zn, Cr, Pb and Cu. It was shown that the sources of Zn, Pb and Cu in the soils were anthropogenic in nature. The high Cr level in soils was due to the natural lithogenic factor. The contents of HM mobile forms in the soils exceeded the maximum permissible concentrations of Cd, Zn, Pb and Ni. An examination of communities of T. laxmannii grown in the impact zone revealed, proliferation anomalies. Ultrastructural studies of plants showed changes in cell membranes, as well as in the main cytoplasmic organelles. Conclusion: The revealed structural changes are assumed to contribute to a slowdown in the ontogenetic development of plants and a decrease in their morphometric parameters under anthropogenic pollution. No significant ultrastructure changes were observed in the roots compared with the leaves, which indicates their high adaptive potential. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Purpose: The effect of Cu, Zn, and Pb high rates on the physical properties and organic matter of Haplic Chernozem (Clayic) (A1 horizon 0-20 cm) under model experimental conditions was studied.Materials and methods: In a model experiment, soil samples of Haplic Chernozem (Clayic) were artificially contaminated with 2000 mg/kg of Cu, Zn, and Pb acetates added separately. The particle-size fraction, the microaggregates distribution, the structural status, the total content and fractional and group composition of organic matter, physico-mechanical properties were determined in soil without metals and soil contaminated with metals.Results and discussion: At the soil contamination with Cu, Zn, and Pb, the content of organo-mineral colloids increased, which results to the increasing of the clay fraction content by 4.5% compared to the control. The analysis of the microaggregate size composition of the studied soil shows that the content of coarser aggregates (1-0.25 mm) increases and the content of finer (0.05-0.001 mm) aggregates decreases after the addition of HMs and correspond to the HMs series: Cu → Zn → Pb. A significant decrease in the coefficient of water stability in the control from 3.0 to 1.4-1.5 in the contaminated treatments. The structural status (estimated from total agronomically valuable aggregates) changes from excellent to good. The addition of Cu, Zn, and Pb to the soil affects the quantitative composition of organic matter. The contents of free and sesquioxide-bound humic acids and free fulvic acids increased. The contamination with Zn and Pb causes the aliphatization of organic matter.Conclusions: Under conditions of model experiment, the contamination of Haplic Chernozem (Clayic) with high rates of Cu, Zn, and Pb leads to changes of the microaggregates distribution, the structural status, and the qualitative composition of organic matter. [ABSTRACT FROM AUTHOR]

Purpose: The aim was to study Cu (II), Zn (II), and Pb (II) forms in technogenically transformed soils adjacent to the Karabashmed copper smelter.Materials and methods: Studies were performed in the plume zone of the Karabash smelter and in the floodplains of Ryzhii Brook and Sak-Egla River. Geomorphological and geochemical migration processes prevail in technogenic landscapes. The differentiation of landscape-geochemical conditions plays the dominant role, which determines the localization of metals. The total Mn, Cr, Ni, Cu, Zn, Pb, Cd, and As contents and the macroelement compositions of soils were determined by X-ray fluorescence. The composition of Cu, Pb, and Zn compounds in soils was determined by the Tessier sequential fractionation. The determination of the geochemical fractions of heavy metals in soils is a key issue in the study of their mobility. The metals were fractionated into the following five fractions: exchangeable, bound to carbonates, bound to Fe and Mn oxides, bound to organic matter, and residual fractions.Results and discussion: It is shown that the total Zn and As contents in the 0- to 5-cm layer of soils on monitoring plots exceed their lithosphere clarks in hundreds of times, and the total Cu, Pb, and Cr contents exceed their lithosphere clarks in tens of times. Factors and processes controlling the distribution and transport of Cu, Pb, and Zn forms in soils were determined. According to landscape-geochemical differentiation, the eluvial (automorphic) catena (plot T4) takes the main technogenic load of dust fallouts from the Karabash copper smelter. The accumulation of material brought from above and the geochemical precipitation of discharges from tailings dumps occur in superaqual catenas (plots T1, T2, and T3). In the technogenically transformed soils, the basic stabilizers of the mobility of Cu is organic matter, for Pb it is Fe-Mn (hydro) oxides, and for Zn - it is clay minerals.Conclusions: The distributions of Cu, Zn, and Pb forms in the studied technogenically transformed soils are due to a number of factors: First, these are the composition of technogenic pollutants contaminating ecosystems and the time during which the contamination occurred, and second, this is the combination of physicochemical properties controlling the buffer properties of the polydisperse system of soils and parent materials. [ABSTRACT FROM AUTHOR]

Interaction of Cu (II) ions with the matrix of soil and mineral phases of layered silicates was assessed by the Miller method of selective sequential fractionation and a set of synchrotron X-ray methods, including X-ray powder diffraction (XRD) and X-ray absorption spectroscopy (XANES). It was shown that the input of Cu into Calcic Chernozem in the form of monoxide (CuO) and salt (Cu(NO3)2) affected the transformation of Cu compounds and their affinity for metal-bearing phases. It was found that the contamination of soil with a soluble Cu(II) salt increased the bioavailability of the metal and the role of organic matter and Fe oxides in the fixation and retention of Cu. During the incubation of soil with Cu monoxide, the content of the metal in the residual fractions increased, which was related to the possible entry of Cu in the form of isomorphic impurities into silicates, as well as to the incomplete dissolution of exogenic compounds at the high level of their input into the soil. A mechanism for the structural transformation of minerals was revealed, which showed that ion exchange processes result in the sorption of Cu (II) ions from the saturated solution by active sites on the internal surface of the lattice of dioctahedral aluminosilicates. Surface hydroxyls at the octahedral aluminum atom play the main role. X-ray diagnostics revealed that excess Cu(II) ions are removed from the system due to the formation and precipitation of coarsely crystalline Cu(NO3)(OH)3. [ABSTRACT FROM AUTHOR]