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 LIII-edge (13.040 keV) were obtained on a Rigaku R-XAS Looper spectrometer. Extended X-ray absorption fine structure (EXAFS) LIII-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.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 methodsIn 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 discussionAt 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.
ConclusionsUnder 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.
相似文献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.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 methodsThe 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 discussionThe 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.
ConclusionsThe 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.
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