Application of sorbents in different soil types from small arms shooting ranges for immobilization of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb)

Journal of Soils and Sediments - Soil contamination of ammunition residues at shooting ranges for small arms may be followed by leaching of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb)....     

Phytostabilisation of a copper contaminated topsoil aided by basic slags: assessment of Cu mobility and phytoavailability

Purpose

Basic slags are alkaline by-products of the steel industry with potential properties to ameliorate nutrient supply and metal stabilisation in contaminated soils. This study aimed at investigating the potential of a P-spiked Link Donawitz slag and a conventional basic slag called Carmeuse for the aided phytostabilisation of a Cu-contaminated soil at a wood treatment site. The effects of basic slag addition on Cu fractionation, mobility and (phyto) availability were assessed.

Materials and methods

Both slags were incorporated at 1 % w/w into the Cu-contaminated soil phytostabilised with Cu-tolerant plants, using either outdoor lysimeters or a field plot. Untreated soil (UNT), amended soils with the P-spiked Link Donawitz slag (PLDS) and the conventional slag (CARM) respectively, and a control soil (CTRL) were sampled, potted and cultivated with dwarf bean. Physico-chemical analysis, determination of total soil elements and a Cu-sequential extraction scheme were carried out for all soils. Physico-chemical characteristics of soil pore water and Cu speciation (rhizon, ion selective electrode and diffusive gradient in thin film (DGT)) were determined. Shoot dry weight yield and leaf ionome (i.e. all inorganic ions present in the primary leaves) of dwarf beans were investigated.

Results and discussion

The slag incorporation at only 1 % w/w increased the soil pH from 1.5 to 2 U and electrical conductivity in soil pore water by three times. The residual Cu fraction increased for both slag amended soils compared to the UNT soil by six times in parallel to the decrease of the Cu oxidisable fraction (1.5 times) and to a less extent the reducible fraction. The incorporation of both slags did not reduce the total dissolved Cu concentration in the soil pore water but significantly reduced the real dissolved Cu concentration ca five times, the Cu labile pool as measured by DGT (at least two times) and the Cu phytoavailability. The dwarf bean total biomass was also improved with the slag addition especially for the P-spiked Linz–Donawitz slag.

Conclusions

The addition of both slags in the contaminated soil increased Cu concentration in the residual fraction and thus reduced its potential mobility. Though the total dissolved Cu soil pore water concentration remained identical, its speciation changed as the real dissolved fraction diminished and lowered the Cu bioavailability. The addition of small amount of P-spiked Linz–Donawitz and Carmeuse slags was beneficial for this Cu-contaminated soil in the context of aided phytostabilisation.

     

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.

     

Simultaneous determination of Cd(II), Cu(II), Pb(II), and Zn(II) in citrus essential oils by derivative potentiometric stripping analysis

Citrus essential oils are widely used in the food, cosmetics, and pharmaceutical industries, so the determination of heavy metals content is of great importance to guarantee their quality. The present work deals with the quantification of Cd(II), Cu(II), Pb(II), and Zn(II) in different varieties of citrus essential oils, using derivative potentiometric stripping analysis. Two different metals extraction procedures, involving concentrated hydrochloric acid treatment and acid-alcoholic dissolution, are tested on lemon, mandarin, sweet orange, and bergamot essential oils, and they give very similar results. Cd(II), Cu(II), Pb(II), and Zn(II) recovery tests spanned from 95 to 100.50%, providing evidence that metals quantification remained unaffected by the cleanup steps of the two procedures. The repeatability of the hydrochloric acid extraction method, applied on different varieties of essential oils, is >95.00% for Cd(II), Cu(II), Pb(II), and Zn(II), whereas the repeatability of the acid-alcoholic dissolution method is >93.00% for Cu and Cd only in lemon oil. Detection limits obtained for the four analytes, using both procedures, ranged from 0.10 to 0.98 ng g(-)(1) in lemon, mandarin, sweet orange, and bergamot essential oils.     

Speciation of cadmium,copper, lead,and zinc in contaminated soils

Abstract

To investigate the activity of free cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (Cd_T, Cu_T, Pb_T, and Zn_T, respectively), 0.43 MHNO₃‐extractable Cd, Cu, Pb, and Zn (Cd_N, Cu_N, Pb_N, and Zn_N, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca²⁺]. The activity of free Pb²⁺, Cd²⁺, Cu²⁺, and Zn²⁺ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L^‐1, Cu from 3.43 to 7.42 μg L^‐1, Pb from 1.23 to 5.8 μg L^‐1, and Zn from 24.5 to 34.3 μg L^‐. In saturation soil extracts, the activity of free Cd²⁺ ions constituted 42 to 82% of the dissolved fraction, for Cu²⁺the range was 0.1 to 7.8%, for Pb²⁺ 0.1 to 5.1% and for Zn²⁺2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd²⁺, Cu^2t, Pb²⁺, and Zn²⁺ ions.     

Competition from Cu(II), Zn(II) and Cd(II) in Pb(II) Binding to Suwannee River Fulvic Acid

This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration as Pb(II). However, Cd(II) and Zn(II) did not seem to compete with Pb(II) for strong binding sites of SRFA. These two metals did compete with Pb(II) for the weaker binding sites of SRFA. Heterogeneity of SRFA was found to play a crucial role in metal–SRFA interactions. The environmental significance of this research for freshwater is that even at relatively low Pb(II) loadings, the metals associated with lead in minerals, e.g. Cu(II), may successfully compete with Pb(II) for the same binding sites of the naturally occurring organic complexants, with the result that some of the Pb(II) may exist as free Pb²⁺ ions, which has been reported to be one of the toxic forms of Pb in aquatic environment.     

A Study of Diffusive Gradients in Thin Films for the Chemical Speciation of Zn(II), Cd(II), Pb(II), and Cu(II): The Role of Kinetics

The lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes were studied using diffusive gradients in thin films (DGT). A unique feature of this research was (1) the use of DGTs with diffusive layer thicknesses ranging from 0.4 to 2.0 mm to study lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes, combined with (2) the application of a competing ligand exchange (CLE) method using Chelex 100, the same chelating resin that is used in DGT, to study the kinetic speciation. The CLE experiments were run immediately after the completion of the DGT experiments, thereby allowing effects of the competing ligand to be separated from the effects introduced by the use of the polyacrylamide gel that is used in DGT. The results indicate that Zn(II) and Cd(II) tend to form more labile and more mobile complexes with humic acid than Pb(II) or Cu(II). The dissociation rate constants of Zn(II), Cd(II), and Pb(II) were found to increase with the ionic potential of the metal, suggesting that the binding between some trace metals and humic acid has a significant covalent component. Furthermore, the results suggest that the Eigen mechanism may not be strictly obeyed for metals such as Cu(II) which have high rate constants of water exchange, k _w. Consequently, the markedly slow kinetics of Cu(II)-HA species suggests that the usual equilibrium assumption may not be valid in freshwaters.     

Retention and mobility of cations in a small peatland: trends and mechanisms

Inputs and net storage or release of cations can have a large impact on the acid-base balance of any ecosystem. Because of the absence of mineral soils, ion exchange and accretion in biomass are the major internal processes governing cation accumulation in peatlands. It is widely believed that peatlands have a large capacity to store cations, and thus to affect the acidity of surface waters. A long-term record of hydrologic and chemical inputs and outputs to the S-2 peatland in the Marcell Experimental Forest was used to construct annual and monthly mass balances for the four major cations. Bulk deposition and throughfall measurements suggest that deposition of Na, Ca and Mg has increased over the period 1971–1984; wet-only and dry bucket measurements do not show such a change. Seasonal and annual variations in cation inputs are not visible in the cation export from the peatland because the large cation reservoir on exchange sites in peat buffers the surface waters and prevents them from responding rapidly to changing inputs. Nevertheless, ion exchange represents a relatively minor source of acidity to this peatland, and accumulation of cations in woody biomass accounts for the majority of the cation retention. The major mechanism of retention in the peatland is different for each cation; accumulation in woody biomass is most important for Ca, storage on ion exchange sites in peat is most important for Mg, green plant tissues are the dominant site of K storage, and Na is bound by unknown mechanisms in the peat. Retention efficiencies show large annual variations but average 50% for Ca, 22% for Mg, 29–44% for Na, and 21% for K.     

Element (Ag, Cd, Cu, Pb, Sb, Tl and Zn), element ratio and lead isotope profiles in a sediment affected by a mining operation episode during the late 19th century

Mining operations at Mårsätter in 1877–81 resulted in increased metal loading to a small lake, notably as sulphidic tailings. The event is taken as an opportunity to study the present environmental impact of a historical single major metal release. Lake water and four sediment cores were sampled and analysed for principal and trace elements in solid and aqueous phases as well as general hydrochemical conditions. Chronologies were determined from ²⁰⁶Pb/²⁰⁷Pb ratios and historical records. Ordinary sedimentation after the event has lead to that the tailings are found as a distinct layer at a depth of 18–22 cm in the sediment. The layer is characterized by elevated metal concentrations in the solid and pore water phases, respectively, circum neutral pH and sulphate concentrations below detection. Geochemical modelling indicated a preference for carbonate equilibrium in the waste while sulphides prevailed above it. It is concluded that the growth of the ordinary sediment on top of the waste has lead to a physicochemical barrier that seals of the waste from the overlying sediment. Chemical or physical rupture of the barrier will release the metals to downstream regions. According to the chronologies at least three sources have contributed to the present elevated levels of metals, in additions to the release of tailings. Copper from a historical blast furnace prior to the event at Mårsätter, transport from mineralized parts of the watershed and release of contaminated water from present mining operations maintain elevated levels of notably zinc, silver, cadmium and lead. At present less than 10% of the lead content at the sediment/water interface comes from atmospheric deposition. Increased levels of antimony and thallium were not observed prior to ca 1950.     

Preparation of Titanate Whiskers Starting from Metatitanic Acid and Their Adsorption Performances for Cu(II), Pb(II), and Cr(III) Ions

The accumulation of metals and nutrients in biosolid-amended soils and the risk of their excess uptake by plants is a topic of great concern. This study examines the elemental uptake and accumulation in five vegetable plants grown on biosolid-applied soils and the use of spectral reflectance to monitor the resulting plant stress. Soil, shoot, root, and fruit samples were collected and analyzed for several elemental concentrations. The chemical concentrations in soils and all the plant parts increased with increase in applied biosolid concentrations. The Cu and Zn concentrations in the plant shoots increased in the order of collard?<?radish?<?lettuce?<?tomato?<?pepper. The Cu and Zn concentrations accumulated significantly in the fruits of the tomato plants compared to other plants. Among all the plants, the shoot concentration factor (SCF) of Zn was significantly higher for pepper plants, indicating increase in uptake of Zn. The shoot relative uptake index (SRUI) of Cu and Zn increased in the order of collard?<?radish?<?lettuce?<?tomato?<?pepper. The shoot dry weight and spectral reflectance of the radish plants in the near-infrared (NIR) region (800–1,300 nm) decreased significantly with increase in biosolid concentration compared to other plants. Increase in plant stress with increase in biosolid dose was evident in radish plants through significant reduction in Normalized Difference Vegetative Index (NDVI). This study indicates the potential use of spectral reflectance as a tool for the screening and monitoring of stress-sensitive plant species and their physiology and as a result, indirectly assesses the chemical concentrations in soils and plants.     

Communities of microscopic fungi in contaminated and reference Al-Fe-humus podzols and their influence on copper mobility

The transformation of microscopic fungi communities under the impact of contamination, the influence of environmental conditions (soil temperature and moisture) on the development of fungal communities in the course of model successions and on the copper mobility in soil, and the most favorable conditions for copper mobilization were studied in Al-Fe-humus podzols of the Kola peninsula contaminated with heavy metals (Cu and Ni). The long-term aerotechnogenic contamination affects the structure of the microbial communities; the species diversity of the communities can somewhat increase at the expense of the increasing diversity of rare, atypical, and “weed” species and decreasing numbers of dominants. The dynamics of fungal communities are less expressed in the contaminated soils as compared with the reference soils. The conditions of rather low temperature (5°C) and an increased moisture content (120% of the field water capacity) are the most favorable for mycelium growth and copper mobilization. Such conditions are typical of the soils in the studied region. Hence, there is a possibility for the soil self-purification due to gradual mobilization of the copper and its subsequent leaching.     

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.     

Toxicity of Sb and Cu in Sewage Sludge to Terrestrial Plants (Lettuce,Oat, Radish), and of Sludge Elutriate to Aquatic Organisms (Daphnia and Lemna) and its Interaction

Antimony (Sb) and Copper (Cu) are two metals of major concern in sewage sludge. Antimony because its use in society is increasing and this might lead to increased Sb concentrations in sludge. Copper because its total volume in use in society is large and because of corrosion from water pipes it is most difficult to reduce the Cu concentrations in sludge. Fresh digested sewage sludge was spiked with Cu or Sb and the sludge was cultivated with oat (Avena sativa), lettuce (Lactuca sativa) or radish (Raphanus sativus). Elutriates from the cultivated sludge were tested for toxicity with Lemna minor (7-d growth) and Daphnia magna (48 h immobility). Before cultivation the elutriates were toxic to Lemna and Daphnia due to high concentrations of ammonia (NH₃) and nitrite (NO₂ ^-). Cultivation decreased the concentrations of both NH₃ and NO₂ ^-, thereby reducing the impact of these compounds in the toxicity tests. Cultivation also decreased the metal concentrations and pH. Daphnia magna was the most sensitive test organism in this study with a 48 h EC₅₀ of 1130 mg Cu kg^-1 dry wt and 5 mg Sb kg^-1 dry wt in elutriates from sludge cultivated with oat. In sludge cultivated with radish the 48 h EC₅₀ was 1700 mg Cu kg^-1 dry wt and 22 mg Sb kg^-1 dry wt. The effect of Cu could be predicted by pH and Cu concentrationin the elutriate, but the effect of Sb could not solely be explained by its concentration in the elutriate.     

Separation and preconcentration of Cd(II), Cu(II), Ni(II), and Pb(II) in water and food samples using Amberlite XAD-2 functionalized with 3-(2-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione and determination by inductively coupled plasma-atomic emission spectrometry

A separation and preconcentration procedure was developed for the determination of trace amounts of Cd(II), Cu(II), Ni(II), and Pb(II) in water and food samples using Amberlite XAD-2 fuctionalized with a new chelating ligand, 3-(2-nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione (Amberlite XAD-2-NPTT). The chelating resin was characterized by Fourier transform infrared spectroscopy (FT-IR) and used as a solid sorbent for enrichment of analytes from samples. The sorbed elements were subsequently eluted with 10 mL of 1.0 M HNO(3), and the eluates were analyzed by inductively coupled plasma-atomic emission spectrometry. The influences of the analytical parameters including pH, amount of adsorbent, eluent type and volume, flow rate of the sample solution, volume of the sample solution, and effect of matrix on the preconcentration of metal ions have been studied. The optimum pH for the sorption of four metal ions was about 6.0. The limits of detection were found to be 0.22, 0.18, 0.20, and 0.16 μg L(-1) for Cd(II), Cu(II), Ni(II), and Pb(II), respectively, with a preconcentration factor 60. The proposed method was applied successfully for the determination of metal ions in water and food samples.     

Uptake of SigmaDDT, arsenic, cadmium, copper, and lead by lettuce and radish grown in contaminated horticultural soils

Horticultural soils can contain elevated concentrations of selected trace elements and organochlorine pesticides as a result of long-term use of agrichemicals and soil amendments. A glasshouse study was undertaken to assess the uptake of weathered SigmaDDT {sum of the p, p'- and o, p-isomers of DDT [1,1,1-trichloro-2,2- bis( p-chlorophenyl)ethane], DDE [1,1-dichloro-2,2- bis( p-chlorophenyl)ethylene] and DDD[1,1-dichloro-2,2- bis( p-chlorophenyl)ethane]}, arsenic (As), cadmium (Cd), copper (Cu), and lead (Pb) residues by lettuce ( Lactuca sativa) and radish ( Raphanus sativus) from field-aged New Zealand horticultural soils. Concentrations of SigmaDDT, DDT, DDE, Cd, Cu, and Pb in lettuce increased with increasing soil concentrations. In radish, similar relationships were observed for SigmaDDT, DDE, and Cu. The bioaccumulation factors were less than 1 with the exception of Cd and decreased with increasing soil concentrations. Lettuce Cd concentrations for plants grown on four out of 10 assayed soils were equivalent to or exceeded the New Zealand food standard for leafy vegetables of 0.1 mg kg (-1) fresh weight. Concentrations of As, Pb, and SigmaDDT did not exceed available food standards. Overall, these results demonstrate that aged residues of SigmaDDT, As, Cd, Cu, and Pb in horticultural soils have remained phytoavailable. To be protective of human health, site-specific risk assessments and soil guideline derivations for residential settings with vegetable gardens need to consider the produce consumption pathway.     

Evaluation of Physicochemical Methods for Treatment of Cu, Pb, Sb, and Zn in Canadian Small Arm Firing Ranges Backstop Soils

This paper presents the results of physicochemical treatment on Pb-, Cu-, Sb-, and Zn-contaminated Canadian small arm firing range (SAFR) backstop soils in order to evaluate the potential of such methods for remediation of SAFR backstop soils. Remediation target for the treatment assays was to attain the Québec Department of Environment commercial C criterion or more realistically, to reach the soil burial D criterion. Two treatment lines (TL) were evaluated. TL-1, consisting of jig and Wilfley table (WT) treatments on the 0.5–3 mm and 53–500 μm soil size fractions (SF), respectively, and chemical leaching on the <53 μm SF and TL-2, consisting of jig on the 1–4 mm SF, spiral, and WT treatments on 250 μm–1 mm SF, and Kelsey jig assays on the <250 μm SF. For both TL, the untreated SF (>3 mm for TL-1; >4 mm for TL-2), and the gravimetric separation concentrates could be sent for recycling in smelter facilities. Results showed that the finer SF (<53 μm SF for TL-1; <250 μm SF for TL-2) were very difficult to treat. Even with metal removed mass proportions up to 78% for Pb, concentrations were still very high after chemical leaching; and the Kelsey jig showed deceiving metal removed mass proportions (up to 47% for Pb). In both TL, the jig and the WT showed Pb removed mass proportions up to 98% and treated mass proportions up to 77% in their respective SF. Whole process efficiencies in the cleaned soils showed that TL-1 led to the remediation of up to 65% of the initial total soil, and TL-2, 36%. TL-1 and TL-2 results showed that the WT effectively treated soils of 53 μm–1 mm SF, and the jig, soils of the 1–4 mm SF. Our study shows that gravimetric concentration techniques are very promising for the treatment of SAFR backstop soils, and further research has to be done in order to treat the SF lower than 53 μm.     

Determination of Thallium and Other Elements (As,Cd, Cu,Mn, Pb,Se, Sb,and Zn) in Water and Sediment Samples from the Vicinity of the Zinc-Lead Smelter in Poland (3 pp)

Background, Goal and Scope   The aim of this study was to check the concentration of some elements in water samples collected near Pb-Zn mining and smelting works and comparison of the obtained data with results achieved for sediment samples originated from the same reservoirs. Objective   Here, 8 water samples and 3 bottom sediments collected from water reservoirs in the vicinity of 3 big Polish Pb-Zn smelters were analysed.Methods   Water analysis was performed after filtration through a 0.45 &#181;m filter and pH adjustment to 2. For decomposition of dried sediment samples, microwave assisted digestion with total dissolution of silicate matrix was applied. The elements studied were determined using ICP-MS and ICP-OES methods. Results and Discussion   The concentrations of most studied elements in water samples were on the 0.X &#181;g/L level, while only the contents of Tl, As, Mn, Cd, Pb and Sb in two water reservoirs were above the limits established for drinking water. The content of studied metals in sediments was in a wide range from X mg/kg (Se and Sb) to X000 mg/kg (Pb and Zn).Conclusions  and Recommendation. The study indicates that the impact of Tl, As, Cd, Cu, Mn, Pb, Zn, Se and Sb on bottom sediments is much more extensive than on the water in ponds located in the vicinity of a post-flotation waste heap. Monitoring of surface and underground waters, if limited only to the dissolved elements, can lead to faulty conclusions about environmental pollution. The bottom sediments mainly contain easily mobilised phases, and water-sediment equilibrium could be changed easily.     

Nitrogen fixation by white clover (Trifolium repens) in grasslands on soils contaminated with cadmium, lead and zinc

The nitrogenase activity (potential nitrogen fixation) of a mixed white clover-grass sward growing on a range of soils containing up to 216 μg g^?1 Cd, 30 000μg g^?1 Pb and 20 000 μg g^?1 Zn was determined using the acetylene-reduction assay. The plants were incubated in situ using an intact soil-core technique. Little change in the rate of C₂H₂ reduction was observed during the daylight hours although a marked seasonal fluctuation was found, the maximum activity during the spring and declining to 20% of this by the autumn. Some reductions of nodule and plant size, and in nitrogenase activity, was observed in the most heavily contaminated sites. These effects were small; the plants and nodules otherwise appeared healthy. The potential for nitrogen fixation was equally high in all the sites at up to 80 g N ha^?1 h^?1 in the spring.