Purpose

The present paper concerns the distribution and mobility of heavy metals (Cu, Pb, Zn and Fe) in the soils of some abandoned mine sites in Italy and their transfer to wild flora.

Materials and methods

Soils and plants were sampled from mixed sulphide mine dumps in different parts of Italy, and the concentrations of heavy metals were determined.

Results and discussion

The phytoremediation ability of Salix species (Salix eleagnos, Salix purpurea and Salix caprea), Taraxacum officinale and P?lantago major for heavy metals and, in particular, zinc was estimated. The results showed that soils affected by mining activities presented total Zn, Cu, Pb and Fe concentrations above the internationally recommended permissible limits. A highly significant correlation occurred between metal concentrations in soils.

Conclusions

The obtained results confirmed the environmental effects of mine waste; exploring wild flora ability to absorb metals, besides metal exploitation, proved a useful tool for planning possible remediation projects.

Purpose

In spite of equal lithology, the local climate can affect soils’ geochemical characteristics. We investigated the dependence of heavy metal content on climatic factors according to a hierarchical nested analysis of variance design (ANOVA).

Materials and methods

We examined the heavy metal content in soils developed on the Upper Triassic dolomite at six locations situated at increasing distances from the Adriatic Sea towards inland. We tested the influence of the locations’ position, i.e. climate, vegetation cover, small-scale variability and analytical error. Co, Cr, Cu, Ni, Pb and Zn contents were determined by emission spectrometry.

Results and discussion

An initial increase in annual precipitation towards inland is followed by a steady decrease. Very high small-scale variability prevented statistically significant differences from being established at the location level due to the high variance components exhibited. However, the simpler one-way and non-parametric varieties of ANOVA confirmed significant differences in Co, Cr and Ni among locations. The differences are more pronounced in grassland soils where the Cu and Pb contents also differ between locations. There is a positive correlation among annual precipitation, Co, Cr and Ni, and it seems that the prevailing winds can also influence their content in soils.

Conclusions

The Co, Cr, Cu and Ni values are readily the highest in those locations with the greatest precipitation, possibly due to their resistance to leaching. The soils could be additionally enriched by an eolian contribution from the SW located outcropping flysch rocks. The established variability could be due to somewhat different dolomite composition. The reasons for the observed geochemical variability are complex and only partly due to climate.

Purpose

Colloid-facilitated transport of metals is widely observed while manure is used for the improvement of contaminated soil. Details on the mechanism of colloid-associated metal transport are still lacking. This work investigated the nature of water-dispersible colloids (WDC) from different organic manures, differentiated the significance of clay and organic colloids in the metal transport, and finally provided direct and quantitative evidence for the importance of WDC in the colloid-facilitated transport of metals.

Materials and methods

Column experiments were conducted to assess the overall significance of WDC from effective microbial inoculated manure (EM) and leaf mulch (LM) for metal transport in alkali-contaminated soil. The properties of organic colloids such as hydrophilicity, aromaticity, and functional characteristics were analyzed by DAX-8 resin column, specific UV absorbance, and Fourier-transform infrared spectroscopy, respectively. Colloid identification and metal species determination were conducted using a combination of X-ray absorption near-edge structure, X-ray fluorescence spectroscopy, and transmission electron microscopy coupled with energy-dispersive X-ray analysis.

Results and discussion

Approximately 100 % of Pb, 69 % of Zn, and 38 % of Cu in the colloidal particles came from soil clay in the presence of EM colloids, while more than 80 % of Pb, Zn, and Cu in the LM colloids. Combined with the quantities of colloidal metals, it revealed that clay release was inhibited in the former and enhanced in the latter. The quantities of Cu and Zn associated with the EM colloids were much higher than that with the LM colloids. The contrary result was observed for Pb. LM colloids increased the quantities of organically associated Pb significantly.

Conclusions

Clay-associated metal transfer was influenced by the nature of WDC. Microbial manure colloids inhibited the clay-associated transfer of metals in the soils probably due to the presence of polysaccharide and microbially derived extracellular proteins. Leaf mulch colloids, with more hydrophobicity and aromaticity, enhanced the clay-facilitated transfer of metals in the soils.

Purpose

Soil metal pollution is a widespread problem around the world and remediation of these soils is difficult. The objective of this study was to investigate the effect of two different strategies on the chemical fractions of metals in a soil of a depleted copper mine: (1) amending with a mixture of a technosol made of wastes and biochar and (2) amending combined with planting vegetation (Brassica juncea).

Materials and methods

A 3-month greenhouse experiment was carried out to evaluate the effects of organic amendments and vegetation on the metal fractionation of Cu, Ni, Pb and Zn in a mine soil of the depleted copper mine at Touro (Spain). We compared the influence of organic amendments alone (technosol?+?biochar) and combined with mustard plants (Brassica juncea L.).

Results and discussion

The results showed that amending with a technosol made of wastes promoted plant growth (from 0.7 to 2.9 g of biomass produced) and reduced the CaCl₂-extractable metal concentration in soil, reduced the mobility factor of Cu from 18.3 to 1.6, Ni from 47.5 to 2.3 and Pb from 17.9 to 2.1, and also reduced the concentration of metals in the mobile soil fractions. It was not possible to grow up Brassica juncea plants in the untreated settling pond soil due to the extremely degraded conditions of that soil. However, the application of the used technosol increased the Pb and Zn pseudototal concentrations in the amended soils.

Conclusions

We conclude that the combination of amending with wastes and planting B. juncea provides little additional benefit for remediating a metal-polluted soil compared with incorporation of wastes alone.

Purpose

Riparian zone contamination is a growing problem for several European catchments due to high anthropogenic pressures. This study investigates As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in the Sava River riparian zone, characterized by wide agricultural areas, various geological substrates, and different types of industrial pollution. The accumulation and mobility of these elements were studied because they are listed as priority substances in the Water Framework Directive and environmental objectives for surface waters.

Materials and methods

Sampling was performed during the sampling campaign of the EU 7th FW-funded GLOBAQUA project in September 2015 during a low-water event. Soil samples were collected along the Sava River at 12 selected sampling sites, from a depth of 0–30 cm, at a distance of 10–15 m from the river bank. The extent of pollution was estimated by determining total and readily soluble element concentrations in the soils. Potential ecological risk and the source of the selected elements in the soils was determined using the enrichment factor (EF), potential ecological risk index (RI), and statistical methods such as the principal component analysis (PCA) and multiple linear regression analysis (MLRA).

Results and discussion

This study showed that concentrations of the selected elements increase along the Sava. In terms of origin, PCA and MLRA indicated that Cr and Ni in soils are predominantly lithogenic, while As, Cd, Pb, and Zn are both lithogenic and anthropogenic (ore deposits, industry, and agriculture). PCA singled out Cu since its origin in soil is most probably from specific point-source pollution. EF was generally minor to moderate for most of the examined elements, apart from Cu, for which the EF was significant at one sampling site. Overall ecological risk (RI) fell within the low-risk category for most sites, apart from Belgrade sampling site (BEO), where high total Cd content affected individual and overall ecological risk indicators, indicating Cd could represent a considerable ecological risk for the downstream riparian zone.

Conclusions

At downstream sites, there was a noticeable increase in PTE content, with Cd, Cr, Ni, and Zn exceeding the proposed threshold values for European soils, indicating rising contamination in riparian soils. In terms of the ecological risk, only Cd could pose a potential ecological threat for the downstream riparian zone.

Purpose

Soil washing with chelators is a viable treatment alternative for remediating multi-contaminated soils. The aim of this study was to investigate the removal efficiencies of Cd, Zn, Pb, and Cu in alkaline and acid multi-metal-contaminated soils by washing with the mixed chelators (MC).

Materials and methods

The batch experiments were carried out to evaluate the removal efficiencies of heavy metals in contaminated soils by the MC with different molar ratios of EDTA, GLDA, and citric acid, and evaluated the washing factors, including contact time, pH, MC concentration, and single and multiple washings at the same MC dose, on the removal efficiencies.

Results and discussion

Results showed that the removal efficiencies for Cd, Zn, Pb, and Cu by the MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) were as much as those of the only EDTA washing from both soil at the same application dose of total chelators; moreover, the application dose of EDTA decreased by 80%. For the alkaline-contaminated soil, the removal efficiencies of Cd, Zn, Pb, and Cu decreased with the increasing of the solution pH, which was opposite to acid-contaminated soil. This was attributed to that the metal-ligand complex could be obviously re-adsorbed on the soil surface sites, particularly in low pH values. The removal efficiencies of Cd, Zn, Pb, and Cu depended on MC concentration. A higher MC concentration led to a more effective removal of Cd, Zn, Pb, and Cu in alkaline-contaminated soil; however, their changes were slightly increased in acid-contaminated soil. At the same dose of MC, single washing with higher MC concentration might be favorable to remove heavy metals, moreover, with much less wastewater generation.

Conclusions

The MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) may be a useful, environmentally friendly, and cost-effective chelators to remediate heavily multi-metal-contaminated soil.

Purpose

Remediation of metal contaminated soil with biochar is attracting extensive interest in recent years. Understanding the significance of variable biochar properties and soil types helps elucidating the meticulous roles of biochar in immobilizing/mobilizing metals/metalloids in contaminated soils.

Materials and methods

Six biochars were produced from widely available agricultural wastes (i.e., soybean stover, peanut shells and pine needles) at two pyrolysis temperatures of 300 and 700 °C, respectively. The Pb-, Cu-, and Sb-contaminated shooting range soils and Pb-, Zn-, and As-contaminated agricultural soils were amended with the produced biochars. The mobility of metals/metalloids was assessed by the standard batch leaching test, principal component analysis and speciation modeling.

Results and discussion

The changes in soil properties were correlated to feedstock types and pyrolysis temperatures of biochars based on the principal component analysis. Biochars produced at 300 °C were more efficient in decreasing Pb and Cu mobility (>93 %) in alkaline shooting range soil via surface complexation with carboxyl groups and Fe-/Al-minerals of biochars as well as metal-phosphates precipitation. By contrast, biochars produced at 700 °C outperformed their counterparts in decreasing Pb and Zn mobility (100 %) in acidic agricultural soil by metal-hydroxides precipitation due to biochar-induced pH increase. However, Sb and As mobility in both soils was unfavorably increased by biochar amendment, possibly due to the enhanced electrostatic repulsion and competition with phosphate.

Conclusions

It is noteworthy that the application of biochars is not equally effective in immobilizing metals or mobilizing metalloids in different soils. We should apply biochar to multi-metal contaminated soil with great caution and tailor biochar production for achieving desired outcome and avoiding adverse impact on soil ecosystem.

Purpose

Understanding the spatial distribution and sources of soil heavy metals (HMs) in a large city helps prevent and control soil pollution. This study aimed to investigate the spatial patterns of soil HMs and identify their main sources in a regional scale.

Materials and methods

A total of 110 topsoil samples were collected from Tai’an City, China. Cd, Cr, Cu, Hg, Ni, Pb, and Zn concentrations in each soil sample were determined. Geostatistics, geographic information system (GIS), and positive matrix factorization (PMF) were used to explore the spatial distribution of seven soil HMs and to reveal the main sources of soil HMs in Tai’an City, respectively.

Results and discussion

Soil Cd, Cr, Pb, and Zn generally showed slight pollution levels in the study area. However, soil Hg and Cu contents reached moderate to heavy pollution levels in some areas. Soil Hg content increased from north to south across the city, and the highest Hg concentration was detected in Ningyang County. Soil Cd, Cu, and Zn distributions exhibited a similar pattern, and their contents increased from west to east; the highest Cd, Cu, and Zn concentrations were found in Xintai County. The highest soil Ni concentration was obtained in the northeast of Feicheng and Xintai counties. PMF analysis revealed the following four potential sources of agricultural soil HMs in Tai’an City: industrial and mining activities, agricultural activities, residential living activities, and business activities. Soil Hg mainly originated from residential living activities, which accounted for 75.3% of the total source. The main sources of soil Ni were residential living activities, agricultural activities, and industrial and mining activities, which account for 38.2, 27.50, and 25.1% of the total source, respectively. Soil Cu was mainly produced by agricultural activities (36.6%), followed by residential living activities (29.8%) and industrial and mining activities (25.8%).

Conclusions

PMF combined with GIS could be effectively applied to determine the main sources of HMs in agricultural soils in a regional scale.

Purpose

Phosphate (P) fertilizers are being widely used to increase crop yield, especially in P-deficient soils. However, repeated applications of P could influence trace element bioaccumulation in crops. The effects of 5-year P enrichment on trace element (Cu, Zn, Cd, Pb, As, and Hg) accumulation in Oryza sativa L. were thus examined.

Materials and methods

Two paddy soils with different initial P availabilities were amended with and without P fertilizer from 2009 to 2013. Trace elements and P levels in rice and soils were analyzed.

Results and discussion

In soil initially with limited P, P amendment enhanced grain Pb, As, and Hg concentrations by 1.8, 1.5, and 1.4-fold, respectively, but tended to decrease the grain Cd level by 0.73-fold, as compared to the control. However, in soil initially with sufficient P, P amendment tended to reduce accumulation of all examined elements in rice grain.

Conclusions

Phosphate amendment in initially P-limited and P-sufficient soils had different effects on trace element availability in soil (as reflected by extractable element) and plant physiology (growth and metal translocation), resulting in contrasting patterns of trace element accumulation in rice between the two types of soils. Our study emphasized the necessity to consider the promoting effects of P on Pb, As, and Hg accumulation in grain in initial P-deprived soil.

Purpose

Field portable X-ray fluorescence (FPXRF) technology can offer a rapid and cost-effective determination of the total elemental concentrations in soils. The aims of this study were (i) to test the capability of FPXRF to predict the element concentrations of a very large soil sample set and (ii) to assess the influence of soil moisture, known to strongly affect the quality of FPXRF analyses.

Materials and methods

A large set of 215 soil samples were analysed for Ba, Ca, Cr, Cu, Fe, Mn, Pb, Rb, Sn, Sr and Zn by inductively coupled plasma atomic emission spectroscopy (ICPAES) after aqua regia digestion and with a FPXRF analyser using a short acquisition time. Soil samples were then saturated with ultrapure water to test the influence of soil water content on FPXRF signal.

Results and discussion

For all of the elements, the total concentrations obtained with ICPAES and FPXRF showed a very high degree of linearity, indicating that FPXRF can effectively predict element concentrations in soils. A Lambert-Beer law was successfully used to describe the decrease in the FPXRF concentrations with increasing soil moisture. The attenuation coefficient obtained for each element allowed us to satisfactorily predict the FPXRF concentrations of samples for water contents as high as 136.8 %.

Conclusions

These results show that the effect of water on signal attenuation can be corrected and that FPXRF may gradually replace chemical methods for the analysis of environmental samples.

Purpose

Soils formed in metallic mines and serpentinite quarries, among other unfavourable features, have high levels of heavy metals. They can release into the environment causing surface and subsurface water contamination, uptake by plants, their accumulation in the food chain and adverse effects on living organisms. In this work, we studied the magnitude of the soils’ toxic effects not only on spontaneous plants but also on two species with phytoremediation potential.

Materials and methods

Several soils from two different exploitations were selected: a lead and zinc mine and a serpentinite quarry. Soils were characterized, and the pseudo-total and extractable contents of Co, Cr and Ni in soils from a serpentinite quarry were determined. The Cd, Pb and Zn pseudo-total and extractable contents were determined in soils developed in the Pb/Zn abandoned mine. Using a biotest, the chronic toxicity of the soil samples on higher plants was determined. Festuca ovina L., Cytisus scoparius (L.) Link., Sinapis alba L. and Brassica juncea L. were selected, the first two because they are spontaneous plants in the study areas and the last two because they have heavy metal phytoremediation potential.

Results and discussion

Pseudo-total contents of Co, Cr and Ni in the serpentinite quarry soils and of Zn, Pb and Cd in the Zn/Pb mine soils exceed generic reference levels. CaCl₂ is the reactant that extracts the highest proportion of Co, Cr and Ni in the quarry soils and EDTA the largest proportion of Pb Zn and Cd content in the mine soils. The germination index values based on seed germination and root elongation bioassays revealed increasing plant sensitivity to the mine soils in the following order: B. juncea?<?S. alba?<?F. ovina?<?C. scoparius. The wide range of GI values indicates that the response of test plants to soil heavy metals depended on their concentrations and soil characteristics, especially pH and organic matter content.

Conclusions

The pollution index indicates severe Cd, Pb and Zn contamination in the mine soils, as well as high Cr and Ni and moderate Co contamination in the serpentinite quarry soils. The performed biotests were suitable for identifying toxic soils and showed that the studied soils are toxic to the spontaneous plants, more to C. scoparius than to F. ovina. They also indicate that the mine soils are more toxic than the quarry soils for both species.

Purpose

The present study deals with the geochemical fractions of Pb, Cd, Zn, Cu and As present on profiles using chemical simple extraction process. This work was conducted on Portman Bay, located in the SE Spain and strongly affected by mining activities.

Materials and methods

Four simple extractions were applied to selected samples in order to evaluate the potential mobility of metals. X-ray diffraction (XRD) was applied to the characterisation of samples and the residues remaining after each extraction, providing additional information about the sediment phases carrying the elements studied.

Results and discussion

The results obtained after the extractions suggested that the highest potentially toxic element (PTE) content was obtained in the oxidising medium. The mineralogical composition is an important factor that should be taken into account in the evaluation of PTE mobility, firstly because the mineral phases react differently in the proposed situations depending on their chemical nature, and secondly, because the presence of a particular phase depends on the degree of weathering.

Conclusions

The evaluation of PTE mobility and mineralogical composition under different environmental conditions may be very important in the execution of restoration projects which could involve dredging and mobilisation of materials.

Purpose

Kutná Hora was a centre of medieval mining and remains an important contamination source in the present day. Surprisingly, very little attention has been paid to the associated contamination. Although some studies have been performed, the majority of information regarding contamination is only accessible in the archives and no overview has been published. The purpose of this study is to perform a meta-analysis of all accessible data and to shed light on this topic.

Materials and methods

The data mainly come from analyses of HNO₃ solutions of sediments. We used statistical analyses (exploratory data analysis, PCA). The results were visualised and evaluated in the GIS environment.

Results and discussion

The complex of heavy metals As, Be, Cd, Co, Cr, Cu, Hg, Pb, V, and Zn can be divided into three main groups of different interpretation: (1) uninfluenced by mining activities—Be, Co, Cr, Hg, and V; (2) smelting processes—Cu, Pb, and Zn; and (3) mining—As and Cd. These groups also show different spatial distribution patterns, absolute concentration values and binding with different environmental types—landscape features.

Conclusions

The contamination of Kutná Hora can be characterised by element grouping and also by spatial diversification. This could be used in future research as a bearer of proxy information. Surprisingly, it also seems that the spatial range of contamination of sediments could be shorter than is generally presumed.

Purpose

Heavy metal contamination is a priority issue affecting millions of hectares of soil throughout the world. One of the most promising, environmentally friendly, and cost-effective approaches to restore polluted soils could be applying organic amendments. We investigated the remediation potential of three types of humic products with regard to their effect on the bioavailability of Pb and Zn, content of nutrients, and the ability to mitigate acute phytotoxicity in contaminated soil.

Materials and methods

Spodosol samples were spiked with Pb (550 mg kg^?1) and Zn (880 mg kg^?1). Then, two different commercial humic products (from peat and lignosulfonate) and natural humic acids (from brown oxidized coal) were added in two doses to reach an equal content of carbon: a 10% increment and a 30% increment of the initial total organic carbon in the soil. After 30 days, the content of metals and nutrients (S, K, Na, Ca, Mn, P) was determined by the sequential extraction (i?H₂O, ii?NH₄COOH pH 4.8, iii–CH₃COOH). The effect of humic products on heavy metals bioavailability was evaluated using the calculated partition indexes. Seed germination and root elongation of Sinapis alba were also determined. Chemical and biochemical variables were aggregated by the principal component analysis.

Results and discussion

Humic products reduced the amount of bioavailable fractions of Pb and Zn in soils. The partition index, which quantitatively describes bioavailable fractions of the Zn and Pb in the soil, was 28–49% lower than in the spiked (Pb+Zn) control. The inhibition of root elongation and seed germination of mustard by Zn and Pb was significantly mitigated by humic products; in the soil test, the root length and seed germination were up to 36–87% higher than those of the Pb+Zn control and did not differ from those in the non-amended treatments. This effect may have been associated with the structural differences (H/C and O/C ratio) and content of nutrients (Na and K) in humic products.

Conclusions

Commercial humic products used in poor multi-contaminated soils can maintain plant growth by improving nutrient status due to heavy metals immobilization and can be a promising approach to remediate the soil contaminated with heavy metals at extremely high concentrations.

Purpose

A series of empirical and mechanistic geochemical models were developed to describe the solid-solution partitioning of copper (Cu) in typical fresh spiked Chinese soils.

Materials and methods

The influence of soil properties on Cu partitioning was assessed in a wide range of soils using multiple regression analysis. Geochemical models (WHAM VI and Visual MINTEQ) and simulation analyses in combination with experimental data (i.e., the bulk of soil properties and Cu contents) were performed in order to provide additional insight into the mechanisms controlling the Cu partitioning. Calculation of soluble Cu contents based on the two models was then simplified and optimized by adjusting input variables, and the calibrated outputs were used to produce reasonable predictions of soluble metal concentrations.

Results and discussion

The results of the multiple regression analyses presented in this paper show strong correlations between soluble Cu concentrations and soil Cu concentrations and properties, with adjusted coefficients of determination (R_adj²) ranging between 0.84 and 0.91. Soil organic carbon (OC) content was an insignificant factor in most cases, but the active fraction of dissolved organic matter was important in improving model estimates. The best fit of root mean square error (RMSE) varied between 0.42 and 0.77 for the WHAM VI model and between 0.28 and 0.57 for the Visual MINTEQ model across all pH categories.

Conclusions

The models presented in this paper are suitable for investigating and simulating Cu solid-solution partitioning in a wide range of Chinese soils.

Purpose

The aim of this work was to assess the concentrations of potentially toxic elements and to evaluate the soil quality of a typical Prosecco Denomination of Controlled and Guaranteed Origin vineyard of the Veneto region, NE Italy.

Materials and methods

Soil samples and leaves of Taraxacum officinale and Vitis vinifera were collected during spring–summer 2014. Element determination (Al, Cd, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, V, and Zn) were performed with ICP-OES after microwave digestion of samples. Soil quality was assessed via the biological soil quality (BSQ-ar) index. Lipid peroxidation test was performed to evaluate the vegetation oxidative stress, based on malondialdehyde (MDA) content via spectrophotometer.

Results and discussion

High concentrations of Al, Mg, and P were identified in soil, while high contents of Al, Cu, Fe, and Zn were found in V. vinifera leaves. The high concentrations in soil are probably due to agricultural activities, whereas those in leaves are probably due to atmospheric deposition and repeated use of foliar sprays in viticulture. The bioconcentration factor showed an effective transport of Cu, P, and Zn, from soil to leaf. The BSQ-ar values registered were similar to those obtained in preserved soils; hence, the biological class (VI) of these soils is high. The MDA content in T. officinale and V. vinifera leaves was below the reference value for T. officinale (2.9?±?0.2 μM), suggesting that the metal content did not stress the vegetation in the investigated site.

Conclusions

The MDA value for V. vinifera (1.1?±?0.7 μM) could be adopted as another control value for soil quality, which in our case is of “good quality.” Moreover, our results suggest that high concentrations of elements detected in the analyzed samples do not influence negatively the quality of soil, but a better agronomic management could improve soil quality in the studied area.

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.

Purpose

The aim of this study was to characterize the conditions of the lateral migration of potentially toxic elements (PTEs) and to identify the zones of their accumulation in soil catenas of ore-mining landscapes in the cities of Zakamensk (Buryat Republic, Russia) and Erdenet (Mongolia) which are situated in the basin of the Selenga River.

Materials and methods

Eight soil catenas across the river valley with 31 pits in Zakamensk area and five catenas with 15 pits in Erdenet area were studied. Soil samples were collected in four landscape–geochemical positions: autonomous, on tops of the hills; trans-eluvial, on slopes of river valleys; trans-accumulative, at the footslopes; and superaqual, on the river floodplains. The total contents of 16 PTEs in the 148 samples were determined by mass spectrometry and by atomic emission spectrometry with inductively coupled plasma.

Results and discussion

It is found that the chemical composition of undisturbed soils is greatly affected by the widespread distribution of volcanic rocks enriched with W, Mo, Cd, Bi, and Sr in Zakamensk and with V, Co, Sr, and As in Erdenet. The difference between geochemical positions is relatively small. Under the influence of technogenic loads in the cities, the concentrations of PTE change along soil catenas increases by an order of magnitude. For chalcophile elements—Mo, Bi, Pb, Sb, and Cu in Zakamensk and Cu, Zn, Mo, Cd, Sn, and W in Erdenet—the type of their lateral distribution in the soil catenas changes because of the intense migration from the tailings and facilities with water and air flows. The accumulation of PTEs takes place on the chemisorptive (V, Co, Ba, As, Cr, and Ni), gley (Mo and Sb), organomineral (Sn), and alkaline (Sr and W) lateral geochemical barriers (LGBs) confined to subordinate positions. The artificial technological LGBs are formed due to the increased content of sand derived from the tailings by water erosion in Zakamensk and the input of silt particles windblown from the technogenic sources in Erdenet. This causes the rise in the concentrations of major ore elements (Mo, W, and Cu) and the accompanying elements (Pb, Bi, As, Sr, Cr, and Ni).

Conclusions

The results of soil–geochemical studies using the catenary approach and concept of LGBs made it possible to understand the main features of migration and fixation of PTEs in soils of the mining centers. They indicate the formation of a system of LGBs with intensive accumulation of major ore elements and associated ones in the subordinate landscapes of Zakamensk and Erdenet.

Purpose

Small arm shooting ranges located in peatland areas are gathering increased attention due to severe metal and antimony (Sb) contamination and challenging conditions for remediation. The goal of the present study was to gain further understanding of the distribution, binding and transport of lead (Pb), copper (Cu) and Sb in peatland contaminated by small arm shooting range activities.

Materials and methods

A field experiment was carried out at a recently closed shooting range facility in Norway, including (i) peat soil sampling for various selective extractions (water, chemical extractions, extractions by diffusive gradients in thin films, DGT), (ii) establishing groundwater wells for groundwater sampling and monitoring of groundwater level and (iii) sampling of water and sediments in surface water. The results from groundwater monitoring were used to carry out hydrogeological numerical simulations using Seep/W and CTran/W. These models were used to evaluate the residence time of the contaminants in the peatland.

Results and discussion

Increased metal concentrations were observed in the top layer of the peatland, indicating low vertical transport. Groundwater revealed high concentrations of Pb (22 ± 5 μg/L), Cu (16 ± 6 μg/L) and Sb (11 ± 2 μg/L), the dominating contaminant source to the downstream surface water. Hydrogeological modelling indicated that transport mainly happened in the upper peat layer, as a result of a higher hydraulic conductivity close to the surface and a high groundwater table. Pb (6.9 ± 0.1 μg/L), Cu (24.0 ± 0.0 μg/L) and Sb (7.4 ± 0.1 μg/L) concentrations in the stream samples confirmed the spreading of contaminants at levels toxic to aquatic organisms. Pb and Cu were most likely associated with dissolved organic carbon (DOC), whereas Sb showed no correlation with DOC.

Conclusions

The elements contaminating the peatland may leak to the nearby water course over a long-term period. Copper showed the highest concentration in the stream water despite considerably higher levels of Pb in the peat soil. Strong complexation of Cu to dissolved organic matter might explain this observation. Only a little fraction of the contaminants is transported in a particulate form, and therefore are increased sedimentation measures not considered as viable remediation option.

Purpose

This study aimed at investigating the rhizosphere effects of Populus euramericana Dorskamp on the mobility of Zn, Pb and Cd in contaminated technosols from a former smelting site.

Materials and methods

A rhizobox experiment was conducted with poplars, where the plant stem cuttings were grown in contaminated technosols for 2 months under glasshouse conditions. After plant growth, rhizosphere and bulk soil pore water (SPW) were sampled together. SPW properties such as pH, dissolved organic carbon (DOC) and total dissolved concentrations of Zn, Pb and Cd were determined. The concentrations of Zn, Pb and Cd in plant organs were also determined.

Results and discussion

Rhizosphere SPW pH increased for all studied soils by 0.3 to 0.6 units compared to bulk soils. A significant increase was also observed for DOC concentrations regardless of the soil type or total metal concentrations, which might be attributed to the plant root activity. For all studied soils, the rhizosphere SPW metal concentrations decreased significantly after plant growth compared to bulk soils which might be attributed to the increase in pH and effects of root exudates. Zn, Pb and Cd accumulated in plant organs and the higher metal concentrations were found in plant roots compared to plant shoots.

Conclusions

The restricted transfer of the studied metals to the plant shoots confirms the potential role of this species in the immobilization of these metals. Thus, P. euramericana Dorskamp can be used for phytostabilization of technosols.