Sulfate-reducing bacteria unearthed: ecological functions of the diverse prokaryotic group in terrestrial environments.

Sulfate-reducing prokaryotes (SRPs) are essential microorganisms that play crucial roles in various ecological processes. Even though SRPs have been studied for over a century, there are still gaps in our understanding of their biology. In the past two decades, a significant amount of data on SRP ecology has been accumulated. This review aims to consolidate that information, focusing on SRPs in soils, their relation to the rare biosphere, uncultured sulfate reducers, and their interactions with other organisms in terrestrial ecosystems. SRPs in soils form part of the rare biosphere and contribute to various processes as a low-density population. The data reveal a diverse range of sulfate-reducing taxa intricately involved in terrestrial carbon and sulfur cycles. While some taxa like Desulfitobacterium and Desulfosporosinus are well studied, others are more enigmatic. For example, members of the Acidobacteriota phylum appear to hold significant importance for the terrestrial sulfur cycle. Many aspects of SRP ecology remain mysterious, including sulfate reduction in different bacterial phyla, interactions with bacteria and fungi in soils, and the existence of soil sulfate-reducing archaea. Utilizing metagenomic, metatranscriptomic, and culture-dependent approaches will help uncover the diversity, functional potential, and adaptations of SRPs in the global environment.

Synthesis and properties of nano-cadmium oxide and its size-dependent responses by barley plant.

Present study included technological methods that made it possible to synthesize CdO nanoparticles and carry out their qualitative and quantitative diagnostics, confirming the as-prepared CdO nanoparticles (NPs) were spherical and had a size of 25 nm. Then, under the conditions of the model experiment the effect of CdO in macro and nanosized particles on absorption, transformation, and structural and functional changes occurring in cells and tissues of Hordeum vulgare L. (spring barley) during its ontogenesis was analyzed. Different analytical techniques were used to detect the transformation of CdO forms: Fourier-transform infrared spectroscopy (FTIR), Dynamic light scattering (DLS), X-ray fluorescence analysis (XRF), Scanning electron microscopy (SEM-EDXMA and TEM), X-ray diffraction (XRD), and X-ray absorption fine structure, consists of XANES - X-ray absorption near edge structure, and EXAFS - Extended X-ray absorption fine structure. Quantitative differences in the elemental chemical composition of barley root and leaf samples were observed. The predominant root uptake of Cd was revealed. CdO-NPs were found to penetrate deeply into barley plant tissues, where they accumulated and formed new mineral phases such as Cd5(PO4)3Cl and CdSO4 according to XRD analysis. The molecular-structural state of the local Cd environment in plant samples corresponding to Cd-O and Cd-Cd. The toxicity of CdO-NPs was found to significantly affect the morphology of intracellular structures are the main organelles of photosynthesis therefore, destructive changes in them obviously reduce the level of metabolic processes ensuring the growth of plants. This study is an attempt to show results how it is possible to combine some instrumental techniques to characterize and behavior of NPs in complex matrices of living organisms.

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.

The effect of resource-saving tillage technologies on the mobility, distribution and migration of trace elements in soil.

The influence of agricultural tillage technologies on the accumulation and distribution of trace elements in the soil is poorly studied. At the same time, intensive agriculture requires large amounts of fertilizers, growth stimulators, pesticides, and other substances, which can effect the ecological safety of the plant products and soil. This paper represents studying the effect of various agricultural techniques (including resource-saving technologies) on the mobility and profile distribution of Pb, Zn, and Cu in Haplic Chernozem. No significant influence of resource-saving tillage technologies was found on the total Pb content. Contrary, the resource-saving tillage technologies was observed to promote the growth of the total Zn and Cu content depending on the cultivation method (by 26% Zn, 34% Cu at minimal tillage, and 28% for both elements using No-till in Ap horizon). Amongst different applied agrotechnologies, there was no influence found on the profile distribution of total elements content. Only two horizons showed the total Pb content accumulation: biogenic (Ap-A) and carbonate (BC-C) horizon. In contrast, the only biogenic accumulation for Zn was determined. Copper characterizes by even distribution over the soil profile. The use of resource-saving agricultural technologies increases exchangeable fraction of Zn, Pb and Cu in soil almost by 1.5-2.0 times in the Ap horizon compared to moldboard ploughing. Despite the increase in the exchangeable fraction of Zn and Cu, this amount of micronutrients is not enough for adequate plant nutrition. The use of various agricultural technologies at Haplic Chernozem led to changes in the distribution of studied elements' exchangeable fraction over the soil profile. The study results suggested a need to increase the amount of Cu and Zn fertilizers applied to the soil with resource-saving cultivation technologies.

Genotoxic and morpho-physiological responses of ZnO macro- and nano-forms in plants.

In the current study, two plants, viz., Pisum sativum L. and Hordeum vulgare L., were exposed to nano- and macro-dispersed ZnO at 1, 10, and 30 times of maximal permissible concentration (MPC). The main objective of the study is to depict and compare the genotoxicity in terms of chromosomal anomalies, cytotoxicity (i.e., mitotic index), and phytotoxicity (viz., germination, morphometry, maximal quantum yield, and chlorophyll fluorescence imaging) of macro- and nano-forms of ZnO along with their accumulation and translocation. In the case of genotoxic and cytotoxic responses, the maximal effect was observed at 30 MPC, regardless of the macro- or nano-forms of ZnO. The phytotoxic observations revealed that the treatment with macro- and nano-forms of ZnO significantly affected the germination rate, germination energy, and length of roots and shoots of H. vulgare in a dose-dependent manner. The factor toxicity index of treated soil demonstrated that toxicity soared as concentrations increased and that at 30 MPC, toxicity was average and high in macro- and nano-dispersed ZnO, respectively. Furthermore, the photosynthetic parameters were observed to be negatively affected in both treatments, but the maximal effect was observed in the case of nano-dispersed form. It was noted that the mobility of nano-dispersed ZnO in the soil was higher than macro-dispersed. The increased mobility of nano-dispersed ZnO might have boosted their accumulation and translocation that subsequently led to the oxidative stress due to the accelerated production of reactive oxygen species, thus strengthen toxicity implications in plants.

New approach to soil management focusing on soil health and air quality: one earth one life (critical review).

Soil plays a key role in ecosphere and air quality regulation. Obsolete environmental technologies lead to soil quality loss, air, water, and land systems pollution. Pedosphere and plants are intertwined with the air quality. Ionized O2 is capable to intensify atmosphere turbulence, providing particulate matter (PM2.5) coalescence and dry deposition. Addressing environmental quality, a Biogeosystem Technique (BGT*) heuristic transcendental (nonstandard and not direct imitation of nature) methodology has been developed. A BGT* main focus is an enrichment of Earth's biogeochemical cycles through land use and air cleaning. An intra-soil processing, which provides the soil multilevel architecture, is one of the BGT* ingredients. A next BGT* implementation is intra-soil pulse continuously discrete watering for optimal soil water regime and freshwater saving up to 10-20 times. The BGT* comprises intra-soil dispersed environmentally safe recycling of the PM sediments, heavy metals (HMs) and other pollutants, controlling biofilm-mediated microbial community interactions in the soil. This provides abundant biogeochemical cycle formation and better functioning of the humic substances, biological preparation, and microbial biofilms as a soil-biological starter, ensuring priority plants and trees nutrition, growth and resistance to phytopathogens. A higher underground and aboveground soil biological product increases a reversible C biological sequestration from the atmosphere. An additional light O2 ions photosynthetic production ensures a PM2.5 and PM0.1 coalescence and strengthens an intra-soil transformation of PM sediments into nutrients and improves atmosphere quality. The BGT* provides PM and HMs intra-soil passivation, increases soil biological productivity, stabilizes a climate system of the earth and promotes a green circular economy.

Cell free extract-mediated biogenic synthesis of ZnONPs and their application with kanamycin as a bactericidal combination.

Antimicrobial resistance (AMR) is a main public health issue and a challenge for the scientific community all over the globe. Hence, there is a burning need to build new bactericides that resist the AMR. The ZnONPs were produced by cell free extract of mint (Mentha piperita L.) leaves. Antibiotics that are ineffective against resistant bacteria like Escherichia coli and Staphylococcus aureus were treated. The antibiotics were first screened, and then antibacterial activity was checked by disk diffusion, and MIC of Mp-ZnONPs individually and using Kanamycin (KAN) were determined against these pathogens by broth microdilution method. The synergism between Mp-ZnONPs and KAN was confirmed by checkerboard assay. The MIC showed robust antibacterial activity against the tested pathogens. The combination of KAN and Mp-ZnONPs reduces the MIC of KAN as it efficiently inhibits E. coli's growth, and KAN significantly enhances the antibacterial activity of Mp-ZnONPs. Taken together, Mp-ZnONPs have strong antimicrobial activity, and KAN significantly improves it against the tested pathogens, which would offer an effective, novel, and benign therapeutic methodology to regulate the incidence. The combination of Mp-ZnONPs and KAN would lead to the development of novel bactericides, that could be used in the formulation of pharmaceutical products.

Biosynthesis and beneficial effects of microbial gibberellins on crops for sustainable agriculture.

Soil microbes promote plant growth through several mechanisms such as secretion of chemical compounds including plant growth hormones. Among the phytohormones, auxins, ethylene, cytokinins, abscisic acid and gibberellins are the best understood compounds. Gibberellins were first isolated in 1935 from the fungus Gibberella fujikuroi and are synthesized by several soil microbes. The effect of gibberellins on plant growth and development has been studied, as has the biosynthesis pathways, enzymes, genes and their regulation. This review revisits the history of gibberellin research highlighting microbial gibberellins and their effects on plant health with an emphasis on the early discoveries and current advances that can find vital applications in agricultural practices.

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.

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.

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.

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.

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.

Intra-soil waste recycling provides safety of environment.

Amelioration and remediation technology was developed for phosphogypsum utilization in Haplic Chernozem of South-European facies (Rostov Region). The technology comprises phosphogypsum dispersed application into the soil layer of 20-45 cm during intra-soil milling. In the model experiment, the phosphogypsum doses 0 (control), 10, 20, and 40 t ha-1 were studied. The Cd thermodynamic forms in soil solution were calculated via the developed mathematical chemical-thermodynamic model and program ION-3. The form of ion in soil solution (or water extract) was considered accounting the calcium-carbonate equilibrium (CCE) and association of ion pairs CaCO30; CaSO40, MgCO30, MgSO40, CaHCO3+, MgHCO3+, NaCO3-, NaSO4-, CaOH+, MgOH+. For calculation of the equilibrium of microelements concentration in soil solution ion including heavy metals (HMs), the coefficient of microelement association kas was proposed. According to calculations, Cd2+ ion in soil solution was mostly bounded to associates CdOH+, partly to associates CdCO30 and CdHCO3+. The calculated kas of Cd was 1.24 units in the control option of experiment and decreased to 0.95 units at phosphogypsum dose 40 t ha-1. The ratio of "active [Cd2+] to total Cd" reduced from 33.5% in control option to 28.0% in the option of phosphogypsum dose 40 t ha-1. The biogeochemical barrier for penetration of HMs from soil to plant roots was high after application of phosphogypsum. According to calculation by ION-3, the standard soil environmental limitations overestimate the toxicity of Cd in soil solution. New decision for intra-soil milling and simultaneous application of phosphogypsum was developed to provide the environmentally safe waste recycling.

Thermodynamic mathematical model of the Kastanozem complex and new principles of sustainable semiarid protective silviculture management.

The Kastanozem complex in the dry steppe of southern Russia underlies an artificially-constructed forest strips. Deep ploughing to a depth of 45 cm was used to process the soil prior to planting. Between 20 and 40 cm depth, soil density was high, 1.57 t m-3. Soil hardness was also high, 440 psi. Soil aggregates greater than 5 cm in size were impermeable to tree roots. The content of such aggregates was high, comprising 35%. The number of tree roots with diameters greater than 0.5 cm that cross the soil profile was as low as 0.15 to 0.3 pcs cm-2. The soil matric potential signifying water availability was low in the vegetation period -0.9 MPa to a depth of 1.0 m. According to modelling experiments, the main salt components in the soil solution drive the transfer of soil organic matter (SOM) and heavy metals (HM). The composition of the soil solution determined by the calcium carbonate equilibrium (CCE) and the association and complexation of ions. ION-3 software was used to calculate the ion equilibrium in the soil solution. Macro-ions Cа2+, Mg2+, SO42-, and CO32- partly bonded as ion pairs. Oversaturation of the soil solution with CaCO3 was calculated according to the analytical content of macro-ion, which was high up to 1000 units, and its value decreased in response to ionic strength, activity, association, complexation, and thermodynamic equilibrium of macro-ions in the soil solution. Oversaturation calculated for Salic Solonetz and Gleyic Solonetz soil solutions was small considering the SOM content. Calculations indicate the profile and lateral loss of C from the soil to the vadose zone. The content of Pb in the soil solution was calculated sirca 75%-80%. The calculated coefficient of Pb2+ association was as high as 52.0. The probability of Pb passivation by SOM in the Kastanozem complex was significant. The probability of uncontrolled transfer and accumulation of HM in the soil and vadose zone was high. Biogeosystem Technique (BGT*) transcendental methodology, an innovative methodology created for stable geomorphological system formation to achieve sustainable agriculture and silviculture, was applied. The BGT* elements were: intra-soil milling of the 30-60 cm soil layer for geophysical conditioning; intra-soil continuously-discrete pulse watering for plants and trees to improve the hydrologic regime. The BGT* methodology reduced HM mobility, controlled biodegradation, enriched nutrient biogeochemical cycling, increased C content, increased soil productivity, and reversible carbon sequester in biological form.

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.

The identification of phytoextraction potential of Melilotus officinalis and Amaranthus retroflexus growing on copper- and molybdenum-polluted soils.

The contamination of soils by heavy metals from the mining industry nowadays is one of the greatest threats to environment and human health. The cleaning of polluted soils using cost-effective and eco-friendly methods such as phytoextraction has wide public recognition. Considering the above-mentioned ones, the objectives of the present study were the identification of Cu and Mo accumulation capability and the phytoextraction potential of Melilotus officinalis and Amaranthus retroflexus as well as the determination of the influence of ammonium nitrate and EDTA on phytoextraction effectiveness. The contaminated soil samples for phytoremediation experiments under ex situ conditions were collected from the surroundings of the Zangezur Copper and Molybdenum Combine, Armenia. During the studies, it was found out that M. officinalis and A. retroflexus are capable of growing in polluted soils. M. officinalis grown in polluted soil had greater ability to accumulate heavy metals in roots, while the ability to transport the copper to aboveground parts was more pronounced in A. retroflexus. During the growing of these plant species for phytoextraction of soils contaminated by copper, it is necessary to use chelates, in particular the EDTA, for the enhancement of the effectiveness of phytoextraction process. EDTA due to chelating influence increased the availability of copper for plants and its mobility in them that lead to greater accumulation of this metal in shoots. The application of chelates did not have a significant impact on molybdenum accumulation intensity in plants; therefore, in case of this metal, it is unreasonable to use additional chelating compounds.

The influence of application of biochar and metal-tolerant bacteria in polluted soil on morpho-physiological and anatomical parameters of spring barley.

The paper presents the results of the model experiment on spring barley (Hordeum vulgare L.) grown in polluted soil. The influence of separate and combined application of wood biochar and heavy metal-tolerant bacteria on morpho-physiological, anatomical and ultrastructural parameters of H. vulgare L. has been studied. The joint application of biochar and bacteria increased the shoot length by 2.1-fold, root length by 1.7-fold, leaf length by 2.3-fold and dry weight by threefold compared to polluted variant, bringing the plant parameters to the control level. The maximal quantum yield of photosystem II decreased by 8.3% in H. vulgare L. grown in contaminated soil, whereas this decrease was less in biochar (7%), bacteria (6%) and in combined application of bacteria and biochar (5%). As for the transpiration rate, the H. vulgare L. grown in polluted soil has shown a decrease in transpiration rate by 26%. At the same time, the simultaneous application of biochar and bacteria has led to a significant improvement in the transpiration rate (14%). The H. vulgare L. also showed anatomical (integrity of epidermal, vascular bundles, parenchymal and chlorenchymal cells) and ultrastructural (chloroplasts, thylakoid system, plastoglobules, starch grains, mitochondria, peroxisomes, ribosomes, endoplasmic reticulum, vacuoles) changes, revealed by light-optical and transmission electron microscopy of leaf sections. The effects were most prominent in H. vulgare L., grown in polluted soil but gradually improved with application of biochar, bacteria and their combination. The use of biochar in combination with metal-tolerant bacteria is an efficient tool for remediation of soils, contaminated with heavy metals. The positive changes caused by the treatment can be consistently traced at all levels of plant organization.

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.

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.