Changes in the morphological properties of chernozems of Rostov oblast in the area of landfills

The transformation of soil morphology in the area of landfills is caused by the technogenic disturbance of the soil profile; artificial soil compaction; local soil waterlogging and the development of hydromorphism; the removal of heterogeneous deposits from the body of reclaimed landfills and their accumulation in the subordinate landscapes; and the gleyzation and production of biogases in primitive soils developed from the new substrate. Various combinations of these processes result in the formation of several different morphological types of the soil profile.     

Plant contamination by heavy metals in the impact zone of Novocherkassk Power Station in the south of Russia

Journal of Soils and Sediments - The aim of this study is the assessment of Ni, Mn, Cd, Cu, Pb, Cr and Zn accumulation by different herbaceous species and soils on the technogenic areas around...     

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

Journal of Soils and Sediments -     

Comprehensive study of Pb (II) speciation in soil by X-ray absorption spectroscopy (XANES and EXAFS) and sequential fractionation

Purpose

The study is aimed at the analysis of the spatial–structural organization of Pb(II) in Chernozem soils and the relationship between the metal ion and the soil components using X-ray absorption spectroscopy and chemical extractive fractionation.

Materials and methods

In a model experiment, soil samples were artificially contaminated with elevated rates of Pb(NO₃)₂ and PbO (2000 and 10,000 mg kg^?1). The samples of mineral phases (bentonite, gibbsite, kaolinite, calcite, and hydromuscovite) were saturated with Pb²⁺ ions. The sequential fractionation of Pb in the soil was conducted by the Tessier method. X-ray absorption near-edge fine structure (XANES) spectra at the Pb L_III-edge (13.040 keV) were obtained on a Rigaku R-XAS Looper spectrometer. Extended X-ray absorption fine structure (EXAFS) L_III-edge Pb was measured at the Structural Materials Science beamline of the Kurchatov Center for Synchrotron Radiation.

Results and discussion

The results of successive extraction showed that Pb is associated with strongly bound organic substances, Fe and Mn (hydr)oxides, and carbonates. An increase in the portion of exchangeable fraction is observed under extreme loads. At the addition of Pb in the form of oxide and nitrate to the soil, the fractional compositions were similar, which indicates the good transformation of PbO in Chernozem. The features of XANES spectra indicate different orbital transitions in the electron shells of Pb²⁺ ions for monoxide (PbO) and soluble salt (Pb(NO₃)₂), which affect the ion properties and determine the individual structure of the coordination sphere. The analysis of XANES revealed that sorption of Pb in the soil samples and in the samples of mineral phases does not change its bond valence.

Conclusions

The increased degree of soil contamination with Pb is accompanied by decreasing the stable connection between metal and soil components. Lead ions in bentonite, kaolinite, hydromuscovite, gibbsite, and calcite are incorporated in the positions of the inner-sphere complex replacing some aluminum ions in the octahedral sites. This results in changes the Pb–O distances in Pb-bearing octahedrons. We may suggest that Pb²⁺ is also sorbed by dimer (Pb–Pb) silicate and/or aluminum groups. The structure of adsorbent surface plays the key role in the sorption of Pb²⁺ by mineral phases.

     

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).     

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.

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.

     

Protective mechanism of the soil–plant system with respect to heavy metals

Purpose

The aim of this work was to select and assess the efficiency of different amendments applied to ordinary chernozems artificially contaminated with heavy metals (Zn and Pb).

Materials and methods

The effect of different amendments on ordinary chernozem contaminated with Zn and Pb acetate salts was studied in a long-term 3-year field experiment. Glauconite, chalk, manure, and their combinations were chosen as ameliorating agents. Spring barley (Hordeum sativum) was used as test culture for three successive years. The heavy metal concentration in all the soil samples decomposed by HF?+?HClO₄ was determined by atomic absorption spectrophotometry (AAS). One normal concentration of CH₃COONH₄ at pH 4.8 was used to estimate the actual mobility of metals. The compounds of heavy metals extracted by 1 N HCl are regarded as mobile compounds. The concentration of metals in the plants was determined using the dry combustion in a mixture of HNO₃ and HCl at 450 °C. The content of heavy metals in extracts from soil and plant samples was determined by AAS.

Results and discussion

The content of weakly bound metal compounds increased upon the contamination of the soil with Pb and Zn salts, which led to a low quality of barley grown in these soils. Metal concentrations in the barley grain exceeded the maximum permissible concentrations (MPCs). The content of Zn and Pb in grains was higher than the MPC for at least 3 years after the soil pollution. The application of amendments significantly decreased the mobility of metals, and the simultaneous application of chalk and manure was most significant. The share of weakly bound metal compounds in the contaminated soils decreased to the level typical for the clean soils or even below.

Conclusions

The combined application of chalk and manure to Zn- and Pb-contaminated ordinary chernozems decreased the content of weakly bound metal compounds in the soil and lowered their concentrations in barley plants. The polyfunctional properties of the soil components with respect to their capacity for metal fixation were established. The decrease in the intensity of Zn accumulation in grains of barley shows the presence of a barrier at the root–stalk and stalk–grain interfaces.

     

Heavy metals in the soil–plant system of the Don River estuarine region and the Taganrog Bay coast

Purpose

The aim of this work was to study the level and degree of mobility of heavy metals in the soil–plant system and to perform bioindication observations in the Don River estuarine region and the Russian sector of the Taganrog Bay coast.

Materials and methods

The objects of the study included samples of zonal soils (chernozem) and intrazonal soils (alluvial meadow and alluvial-stratified soils, Solonchak, sandy primitive soil) from monitoring stations of the Don river estuarine region and the Taganrog Bay coast, as well as their higher plants: Phragmites australis Cav., Typha angustifolia L., Carex riparia Curtis, Cichorium intybus L., Bolboschoenus maritimus L. Palla, and Rumex confertus Willd. The total concentrations of Mn, Ni, Cd, Cu, Zn, Pb, and Cr in the soils were determined by X-ray fluorescent scanning spectrometer. The concentration of heavy metal mobile forms exchangeable, complex compounds, and acid-soluble metal were extracted using the following reagents: 1 N NH₄Ac, pH 4.8; 1 % EDTA in NH₄Ac, pH 4.8; 1 N HCl, respectively. Heavy metals in plants were prepared for analysis by dry combustion at 450 °C. The heavy metal concentration in extracts from plants and soils was determined by AAS.

Results and discussion

The total contents of heavy metals in the soil may be described with a successively decreasing series: Mn?>?Cr?>?Zn?>?Ni?>?Cu?>?Pb?>?As?>?Cd. The total concentrations of As, Cd, and Zn in the soil exceed the maximum permissible concentrations levels. Contamination of alluvial soils in the estuarine zone with mobile Сu, Zn, Pb, and Cd has been revealed, which is confirmed by the high bioavailability of Cu and Zn and, to a lesser degree, Cd and Pb accumulating in the tissues of macrophytic plants. Data on the translocation of elements to plant organs have showed their predominant accumulation in the roots. Bioindication by the morphofunctional parameters of macrophytic plants (with a Typha L. species as an example) can be used for revealing the existence of impact zones with elevated contents of metals in aquatic ecosystems.

Conclusions

The results revealed that increased content of Zn, Pb, Cu, Ni, and As in soil have anthropogenic sources. The high content of Cr in the soils is related to the lithogenic factor and, hence, has a natural source.

     

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.