Dina G. Nevidomskaya

New approaches to studying heavy metals in soils by X-ray absorption spectroscopy (XANES)) and extractive fractionation

A comprehensive approach to studying the nature of interaction between heavy-metal ions and the organic–mineral matrix of soils involves application of modern physical analytical techniques and chemical methods of extractive fractionation. XANES was used to obtain the first data on the near-edge fine structure of X-ray spectra for a number of heavy-metal species in ordinary chernozem. Data on the structure of soil samples saturated with Zn2+ and Cu2+ obtained by XANES (X-ray absorption near-edge structure) make it possible to elucidate the interaction mechanisms of the metals and the types of chemical bonds formed thereby. As contamination doze of with Cu and Zn is increased (from 2000 to 10 000 mg/kg soil), particularly if the metals are introduced in the form of readily solubility salts, bonding between the metals and soil components weakens. Data of extractive fractionation of metal compounds from samples saturated with Cu and Zn compounds testify that the Cu2+ ion is preferably retained in the organic matter of the soil, whereas the Zn2+ ion is bound mostly to silicates, carbonates, and Fe and Mn (hydro)oxides.

Erratum to: Forms of Cu (II), Zn (II), and Pb (II) compounds in technogenically transformed soils adjacent to the Karabashmed copper smelter

Purpose The aim was to study Cu (II), Zn (II), and Pb (II) forms in technogenically transformed soils adjacent to the Karabashmed copper smelter.

Morphological and anatomical changes of Phragmites australis Cav. due to the uptake and accumulation of heavy metals from polluted soils

The effect of strong chemical contamination of soils on the growth and structure of reed (Phragmites australis Cav.) roots and stems has been investigated. Soils and plants on monitoring plots in the zone of industrial sewage tanks and sludge reservoirs in the city of Kamensk-Shakhtinskii (southern Russia) were studied. Polyelement pollution of soils on the studied monitoring plots was revealed, with exceedances of Clarkes in hundreds of times for Zn and Cd, in tens of times for Pb, and in several times for Cu, Ni, Cr, and Mn. An ecological-geochemical estimation revealed an extremely hazardous level of soil contamination HMs in total. It is shown that the high level of soil contamination decelerates the ontogenetic development of plants and decreases their morphometric parameters. Electron-microscopic study of plants revealed changes in the ultrastructure of cell membranes, as well as the main cytoplasmic organelles of root and stem cells (mitochondria, plastids, etc.). It is suggested that the revealed structural changes in epidermis and mesoderm under the impact of metals hamper the radial migration of fluid in the root from the peripheral parts. These changes are one of the reasons for the decrease in the level of nutrient uptake and translocation from roots to shoots.

Determining the speciation of Zn in soils around the sediment ponds of chemical plants by XRD and XAFS spectroscopy and sequential extraction

For a correct assessment of risk of polluted soil, it is crucial to establish the speciation and mobility of the contaminants. The aim of this study was to investigate the speciation and transformation of Zn in strongly technogenically transformed contaminated Spolic Technosols for a long time in territory of sludge collectors by combining analytical techniques and synchrotron techniques. Sequential fractionation of Zn compounds in studied soils revealed increasing metal mobility. Phyllosilicates and Fe and Mn hydroxides were the main stabilizers of Zn mobility. A high degree of transformation was identified for the composition of the mineral phase in Spolic Technosols by X-ray powder diffraction. Technogenic phases (Zn-containing authigenic minerals) were revealed in Spolic Technosols samples through the analysis of their Zn K-edge EXAFS and XANES spectra. In one of the samples Zn local environment was formed by predominantly oxygen atoms, and in the other one mixed ZnS and ZnO bonding was found. Zn speciation in the studied technogenically transformed soils was due to the composition of pollutants contaminating the floodplain landscapes for a long time, and, second, this is the combination of physicochemical properties controlling the buffer properties of investigated soils. X-ray spectroscopic and X-ray powder diffraction analyses combined with sequential extraction assays is an effective tool to check the affinity of the soil components for heavy metal cations.

Time effect on the stabilization of technogenic copper compounds in solid phases of Haplic Chernozem

We studied the regularities of Cu stabilization in Haplic Chernozem contaminated with easily soluble (acetates, nitrates, sulfates, chlorides) and poorly soluble (acetates, nitrates, sulfates, chlorides) metal compounds in a five-year model experiment were studied. A low contents of Cu loosely bound compounds (LBC) (no >5% of total content) unchanging over time were revealed in the uncontaminated soil, which is indicative of the stability of soil processes. The Cu LBC content decreased over time in the soils contaminated with easily soluble compounds and increased in the soils contaminated with poorly soluble compounds. In both cases, the contents of Cu LBCs after 5 years of incubation remained higher than in the original uncontaminated soil. The effect of the attendant anions on the Cu LBC content was more apparent under the Cu application of 2000 mg kg-1 than at 300 mg kg-1. An inverse process characterized by an increase in the concentration of Cu LBCs over time was observed in the soil contaminated with Cu orthophosphate and oxide. Soil contaminated with different Cu compounds results in soil acidification. According to the effect on the decrease in soil pH, the attendant anions form the following series: SO42- ≈ Cl- > NO3- > Ac- > PO42- > O2-, which correlates with the Cu LBC content. Thus, the stabilization of Cu compounds in the soil is affected by the attendant anions and the interaction time of the metal with the soil solid phases.

Quantitative speciation of Zn in technosols using chemical fractionation and X-ray absorption spectroscopy

Human activity, such as mining, is often detrimental to the environment. For risk assessment of polluted soils, it is crucial to establish the speciation of the contaminants such as zinc. The aim of the work was to identify the Zn species in contaminated anthropogenically transformed soils known as ‘spolic technosols’. The Zn speciation in technosols was studied using a combined fractionation scheme and a set of X-ray synchrotron methods. Spolic technosols within the Karabashmed Company zone of the southern Urals have a very high level of Zn contamination. The role of soil components in metal fixation in both the loosely and firmly bound states were revealed. Iron oxides actively participate in the immobilization of Zn. The studу of the local structure of technosols by X-ray absorption spectroscopy showed that Zn is coordinated to six oxygen atoms forming a distorted octahedron with Zn–O bond lengths close to those in ZnSO4. The presence of short bonds, formed by Zn atoms, has been also revealed. Thus, the application of two independent methods can be helpful in defining Zn speciation in polluted soils.

Copper Adsorption by Chernozem Soils and Parent Rocks in Southern Russia

Laboratory data in Cu2+ adsorption by chernozems and parent rocks in Rostov region show that adsorption isotherms can be approximated by the Langmuir equation, whose parameters (Kl and C∞) were calculated for all of the samples. The values of C∞ show a strong negative correlation with the values of cationexchange capacity (CEC) (r =–0.88 at Р = 0.95), and Kl is correlated with the content of physical clay (particles <0.01 mm) (r = 0.78) and with clay (particles <0.001 mm) content in ordinary chernozem and southern chernozems of various particle size distribution (r = 0.80). Even stronger correlations were detected between these parameters in southern chernozems (r = 0.89 for the physical clay (PC) and r = 0.91 for the silt). However, none of the samples displays a significant correlation of C∞ and Kl with the contents of physical clay and silt. This led us to conclude that the composition of the samples, for example, their organic matter, can affect Cu2+ adsorption by the soils and parent rocks. Acidification mechanisms of the equilibrium solutions during the Cu2+ adsorption by soils are discussed, as also are the reasons for the absence of balance between Cu2+ adsorbed by soils and exchangeable cations transferred into solution. Analysis of the fine structures of the XANES and EXAFS spectra suggests that Cu2+ can form coordinated chelate complex compounds with humic acids (HA) of soils and can substitute Al3+ at octahedral sites when interacting with clay minerals in soils.

Erratum to: Chemical contamination in upper horizon of Haplic Chernozem as a transformation factor of its physicochemical properties

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.

Effect of Aerotechnogenic Emissions on the Content of Heavy Metals in Herbaceous Plants of the Lower Don Region

The effect of soil properties and distance from the source of technogenic emission on the input of Pb, Zn, Cd, Cu, Mn, Cr, and Ni into daisy family plants (Asteraceae) has been studied. It has been found that the high level of anthropogenic load related to the atmospheric emissions from the Novocherkassk power plant (NPP) favors the accumulation of heavy metals (HMs) in herbaceous plants. Contamination with Pb, Cd, Cr, and Ni is revealed in plants growing near the NPP. The main factors affecting the distribution of HMs in the above- and underground organs of plants include individual physiological features of plant species controlling the barrier functions of different plant organs. Ambrosia artemisiifolia L., Artemisia austriaca Pall. ex. Wild. Jack., and Tanacetum vulgare L. are accumulators of HMs. The resistance of herbaceous plants to pollution has been determined from the acropetal coefficient and actual biogeochemical mobility of HMs. Ambrosia artemisiifolia L. is most resistant to contamination with Mn; Achillea nobilis L. is most resistant to Pb, Ni, and Cd; Cichorium intybus L. is most resistant to Zn and Cu.

Heavy metals in soils and plants of the don river estuary and the Taganrog Bay coast

Natural and anthropogenic factors determining the distribution and accumulation features of Pb, Cu, Zn, Cr, Ni, Cd, Mn, and As in the soil–plant system of the Don River estuary and the northern and southern Russian coasts of Taganrog Bay estuary have been studied. High mobility of Cu, Zn, Pb, and Cd has been revealed in alluvial soils. This is confirmed by the significant bioavailability of Cu, Zn, and, to a lesser degree, Cd and the technophily of Pb, which are accumulated in tissues of macrophytic plants. Statistically significant positive correlations have been found between the mobile forms of Cu, Zn, Cd, and Mn in the soil and the accumulation of metals in plants. Impact zones with increased metal contents in aquatic ecosystems can be revealed by bioindication from the morphofunctional parameters of macrophytic plants (with Typha L. as an example).