Forms of heavy metal compounds in soils of the steppe zone

A parallel scheme of extractions was used for determining heavy metal compounds in uncontaminated and artificially contaminated soils of Rostov oblast. A method for calculating the contents of complex and specifically adsorbed metal compounds from the difference in their concentrations in different extracts was suggested. It was found that the portion of firmly fixed metal compounds decreases and the portion of potentially mobile (exchangeable, complex, and specifically adsorbed) metal compounds increases with an increase in the degree of contamination of chernozems and chestnut soils with lead, copper, and zinc over a one-to two-year-long observation period. This was due to the capacity of heavy metal ions to substitute for the exchangeable cations in the exchange complex of the studied soils, to form complexes with the soil organic matter, and to participate in the specific adsorption. Some differences in the behavior of different metals were found.     

Barrier functions of the soil-plant system

In a field experiment on ordinary chernozem, the content of weakly bound metal compounds increased by 11–14 times upon the contamination of the soil with Pb and Zn salts, which led to a low quality of barley grown on these soils; metal concentrations in the barley grain exceeded the maximum permissible concentrations. Various ameliorants were tested, and a mixture of chalk and manure proved to be the most efficient ameliorant. Characteristics of the barrier function of the soil-plant system in relation to the contaminating metals were 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.     

Dynamics of benzo[α]pyrene accumulation in soils under the influence of aerotechnogenic emissions

The regularities of benzo[α]pyrene (BaP) accumulation and distribution in chernozems (Haplic Chernozems), meadow-chernozemic soils (Haplic Chernozems (Stagnic)), and alluvial soils (Fluvisols) affected by the aerotechnogenic emissions from the Novocherkasskaya Electric Power Station (NEPS) were studied on the basis of long-term (2002–2011) monitoring data. A 5-km-wide zone stretching to the northwest from the electric power station and coinciding with the predominant wind direction was found to be most contaminated, with the maximum accumulation of BaP at about 1.6 km from the source. The coefficients of vertical BaP distribution between the layers of 0–5 and 5–20 cm closely correlated with the contents of physical clay, clay, and humus, and with the cation exchange capacity. The content of BaP in soils was shown to be indicative of the level of technogenic loads related to the combustion products of hydrocarbon fuels.     

Adsorption features of Cu(II), Pb(II), and Zn(II) by an ordinary chernozem from nitrate,chloride, acetate,and sulfate solutions

The effect of Cl^?,SO ₄ ^2? , CH₃COO^?, and NO ₃ ^? anions on the adsorption of copper, lead, and zinc by an ordinary chernozem has been studied. The effect of the anions on the adsorption of Cu²⁺, Pb²⁺, Zn²⁺ ions is significant but uncertain. It has been shown that the attendant anions affect the shape of the adsorption isotherms, which are described by the Langmuir, Freundlich, or Henri equations. The constants of the adsorption from a nitrate solution calculated from the Langmuir equation (K _L) decrease in the following order: Cu²⁺ > Pb²⁺ >> Zn²⁺. The values of the maximum adsorption (C _max) decrease in the following order: Cu²⁺ ≥ Zn²⁺ > Pb²⁺ for acetate solutions and in the series Pb²⁺ > Zn²⁺ ≥ Cu²⁺ for nitrate solutions. The values of the Henry constants (K _H) calculated for the adsorption of the same cations from chloride solutions decrease in the same order as the values of K _L. The CH₃COO^? anion has the highest effect on the constant values. The NO ₃ ^? and Cl^? anions “switch their places” depending on the attendant cation, but their effect is always lower than that of the acetate anion. The values of C _max for copper and zinc are most affected by the CH₃COO^? anion, and the adsorption of zinc is most affected by the Cl^? and NO ₃ ^? anions. The assessment of the mobility of the adsorbed cations from the extraction with ammonium acetate (pH 4.8) has shown that the content of the desorbed metals is always lower than the content of the adsorbed cations and varies from 0.025 to 83%. According to their mobility, the adsorbed metals form the following order: Zn²⁺ > Pb²⁺ > Cu²⁺. The effect of the attendant anions on the extractability of the adsorbed cations decreases in the following order: chlorides > sulfates > acetates > nitrates.     

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.

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.