Abstract: The efficiency of poplar (Populus nigra L. � Populus maximowiczii Henry.) was assessed during a two-year chemically enhanced phytoextraction of metals from contaminated soils. The tested metal mobilizing agents were EDTA (ethylenediaminetetraacetic acid) and NH4Cl. EDTA was more efficient than chlorides in solubilizing metals (especially Pb) from the soil matrix. The application of chlorides only increased the solubility of Cd and Zn. However, the increased uptake of metals after the application of higher concentrations of mobilizing agents was associated with low biomass yields of the poplar plants and the extraction efficiencies after the two vegetation periods were thus comparable to the untreated plants. Additionally, the application of mobilizing agents led to phytotoxicity effects and increased mobility of metals. Higher phytoextraction efficiencies were observed for Cd and Zn compared to Pb and Cu. Poplars are therefore not suitable for chemically enhanced phytoextraction of metals from severely contaminated agricultural soils.

Abstract: Several single-step extraction procedures have been proposed for the evaluation of metal availability in soils. Among many, the 0.05 M EDTA (ethylenediaminetetraacetic acid) extraction is widely used. Despite it has been often criticised, this protocol remains an effective and simple approach for a fast determination of the potential availability of several metals (e.g., Pb, Cd, Cu, Zn etc.). However, other metals present in soils at high concentrations (Fe, Ca) can possibly influence the results. This is even more emphasised in the case of Fe as EDTA partly dissolves Fe-(hydr)oxides. The results of this study showed that especially the concentration and crystallinity of Fe play a very important role during the extraction and this fact should be taken into account during result interpretation.

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Abstract: The content of Pb, Cd, Mn, K, Ca, Mg and Pb-206/Pb-207 isotope ratios in spruce tree rings (Picea abies) and peat cores from the Brdy Hills area (10 km W of the Pb smelter) were compared with those in spruce tree rings in the vicinity of the Pb smelter. Maximum Pb content in tree rings (up to 60 mg kg(-1) Pb) corresponds to a peak of metallurgical production in the mid 1970s and highest smelter emissions in the early 1970s. The Pb concentration curves obtained from peat deposit profiles closely correlate with the Pb concentrations in tree rings at both sampling sites. The small differences between the individual tree cores, with the identical general trend, may be attributed to the difference in distance from the smelter and the altitude of each sampling site. Similar behaviour to Pb can be observed for Cd and Ca. Lead isotope composition in tree rings (Pb-206/Pb-207 similar to 1.143-1.174) is controlled mainly by the smelter emissions (Pb-206/Pb-207 similar to 1.16-1.17), with the exception of the youngest segments from the more distant locality from the smelter, which yield isotopic signatures corresponding to car-emission Pb (Pb-206/Pb-207 similar to 1.143-1.150). Higher content of Mn, Mg and Ca in tree rings corresponding to the 1970s and 1980s may be related to soil chemistry changes caused by acid deposition. In addition, an increase in K, Mg (and in some cases also Mn) in the youngest part of wood cores corresponds to the physiological processes in sapwood, and may be influenced by a decrease in Pb in organic soil horizons, which limited the cycling of basic inorganic nutrients.

Abstract: Eight trace elements were determined using ICP-MS in 78 fruiting body samples of 22 edible mushroom species. The mushrooms were collected from four sites in a rural area, unpolluted by human activity. Median values (dry matter) were as follows: Arsenic (As) 1.45 mg kg(-1), barium (Ba) 1.41 mg kg(-1), cobalt (Co) 0.28 mg kg(-1), copper (Cu) 47.0 mg kg(-1), rubidium (Rb) 130 mg kg(-1), silver (Ag) 2.95 mg kg(-1), thallium (Tl) 0.02 mg kg(-1) and vanadium (V) 0.25 mg kg(-1). Higher trace element accumulation was observed in samples of Macrolepiota procera, Macrolepiota rhacodes, Lycoperdon perlatum, Lycoperdon gigantea and Xerocomus chrysenteron for As and Cu, and in samples of Cantharellus cibarius and of genera Boletus and Suillus for Rb.

Abstract: In several cases ethylenediaminetetraacetic acid (EDTA) proved to be an efficient mobilising amendment during chemically enhanced phytoextraction of heavy metals. The presence of Fe-(hydr)oxides and their dissolution after the addition of EDTA can limit the phytoextraction of the targeted heavy metals due to the high stability of the formed Fe(III)EDTA complexes. This study has focused on the influence of Fe- and Mn-oxides and hydroxides dissolution on heavy metal uptake by Zea mays in a two-year EDTA-enhanced phytoextraction process. Incubation experiments and speciation modelling proved the increased concentrations of Mn and Fe through the dissolution of Mn-and Fe-(hydr)oxides. Furthermore, increased Fe and Mn accumulation was observed in maize plants after the second year of the phytoextraction process. Therefore, the presence of Mn- and especially Fe-(hydr)oxides proved to be a limiting factor during EDTA-enhanced phytoextraction of heavy metals from contaminated soils.

Abstract: Constructed wetlands with horizontal subsurface flow (HF CWs) designed for treatment of municipal sewage have been monitored extensively with respect to removal of organics, suspended solids, nitrogen, phosphorus and bacteria. However, the information on the removal of various metals and metalloids in these systems is very limited. During the period 2002�2004 aboveground and belowground biomass of Phragmites australis (common reed) and Phalaris arundinacea (reed canarygrass) were sampled in three HF CWs in the Czech Republic. Concentrations of monitored elements in both aboveground and belowground plant tissues were similar to those found in plants growing in natural stands. The concentrations were much lower as compared to those found in plants growing in wetlands receiving acid mine drainage waters, waters from smelters or highway runoff. Concentrations decrease in the order of roots > rhizomes > leaves > stems. The leaf:stem concentration ratios were quite similar for all monitored elements ranging between 1.0 and 1.9. The root:leaf concentration ratio varied widely between 1.5 (Cu) and 54 (Cr) with a mean value of 20.0. Belowground/aboveground plant tissue concentration ratios varied from 2.2 (Cu) to 32 (Cr) with the average value of 9.9.

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Abstract: Chelant-enhanced phytoextraction of heavy metals is an emerging technological approach for a non-destructive remediation of contaminated soils. The main objectives of this study were (i) to assess the extraction efficiency of two different synthetic chelating agents (ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS)) for desorbing Pb from two contaminated agricultural soils originating from a mining and smelting district and (ii) to assess the phytoextraction efficiency of maize (Zea mays) and poplar (Populus sp.) after EDTA application. EDTA was more efficient than EDDS in desorbing and complexing Pb from both soils, removing as much as 60% of Pb. Maize exhibited better results than poplar when extracting Pb from the more acidic (pH 4) and more contaminated (up to 1360 mg Pb kg�1) agricultural soil originating from the smelting area. On the other hand, poplars proved to be more efficient when grown on the near-neutral (pH 6) and less contaminated (up to 200 mg Pb kg�1) agricultural soil originating from the mining area. Furthermore, the addition of EDTA led to a significant increase of Pb content especially in poplar leaves, proving a strong translocation rate within the poplar plants.

Abstract: High metal contents in edible mushrooms growing in severely contaminated industrial areas pose an important toxicological risk. In the presented study, trace element (Pb, Cd, Zn, Cu, Ag, As, Se) contents were determined in caps and stipes of three different edible mushroom species (Boletus edulis Bull. Fr., Xerocomus badius Fr. Gilb., Xerocomus chrysenteron Bull. Quél.). Additionally, information about the chemical fractionation of metals in separate soil horizons and Pb isotopic data from soils and fruiting bodies allowed a more detailed insight on the uptake mechanisms of metals by the studied mushroom species. Total metal and metalloid concentrations in the organic soil horizons reached 36 234 mg Pb kg� 1; 11.9 mg Cd kg� 1; 519 mg Zn kg� 1; 488 mg Cu kg� 1; 25.1 mg Ag kg� 1; 120 mg As kg� 1 and 5.88 Se mg kg� 1. In order to evaluate the accumulation capacity of the studied species, bioconcentration factors (BCF) were calculated for separate trace elements. For selected metals (Pb, Cd, Zn, Cu), a modified BCF calculation (using EDTA-extractable concentrations of metals in soil) was proposed. High contents of Pb (up to 165 mg kg� 1) and Cd (up to 55 mg kg� 1) exceeded all the regulatory limits in all the studied species. This was also the case for Se (up to 57 mg kg� 1) in B. edulis. Intensive consumption of this species grown in such polluted areas can therefore pose toxicological risks for human health. A novel finding was that X. badius can act as an Ag accumulating species when grown at polluted sites due to the high concentrations of Ag (up to 190 mg kg� 1) in caps. Pb isotopic data showed that Pb originating from the recent air pollution control residues is present mainly in the exchangeable/acid-extractable fraction of the organic horizons and is taken up by fruiting bodies; especially in the case of B. edulis, where fast Pb accumulation occurs. Due to the high species-dependent variations of metal contents, the studied mushrooms are not suitable as bioindicators of environmental pollution.

Abstract: In several cases ethylenediaminetetraacetic acid (EDTA) proved to be an efficient mobilising amendment during chemically enhanced phytoextraction of heavy metals. The presence of Fe-(hydr)oxides and their dissolution after the addition of EDTA can limit the phytoextraction of the targeted heavy metals due to the high stability of the formed Fe(III)EDTA complexes. This study has focused on the influence of Fe- and Mn-oxides and hydroxides dissolution on heavy metal uptake by Zea mays in a two-year EDTA-enhanced phytoextraction process. Incubation experiments and speciation modelling proved the increased concentrations of Mn and Fe through the dissolution of Mn-and Fe-(hydr)oxides. Furthermore, increased Fe and Mn accumulation was observed in maize plants after the second year of the phytoextraction process. Therefore, the presence of Mn- and especially Fe-(hydr)oxides proved to be a limiting factor during EDTA-enhanced phytoextraction of heavy metals from contaminated soils.

Abstract: Efficiencies of He/NH3 and He/H2 collision gases were compared in a conventional type of hexapole cell of an inductively coupled plasma mass spectrometer (ICP-MS). The optimum conditions [hexapole and quadrupole bias voltage (VH and VQ) and collision/reaction gas flow rates] were tested for vanadium determination (51V) in chloride matrices. When the He/H2 mixture was used, the optimum values of VH and VQ were �10.0 and �8.0 V, respectively. This set-up corresponds to the kinetic energy discrimination effect. When the He/NH3 mixture was used, the optimum values of VH and VQ were +10.0 and �7.0 V, respectively. Positive VH values correspond to the ion kinetic energy effect, which allows the reactivity of the ions entering the collision/reaction cell with the reaction gas to be controlled. The obtained results showed that the He/H2 mixture is not optimal for V determination in samples containing chlorides due to the insufficient suppression of the polyatomic interference of 35Cl16O+. Data obtained from vanadium determination using the He/NH3 mixture were consistent for all selected Cl� concentrations, and the results were acceptable. The detection limit was comparable with detection limits obtained from ICP-MS equipped with a dynamic reaction cell. Analyses of elements forming interfering molecules, e.g., iron (56Fe), arsenic (75As) and selenium (80Se), were in good agreement with the certified values for both studied collision/reaction gas mixtures.

Abstract: Lead isotopic studies in soils provide an efficient tool for tracing the sources of lead pollution. Five different extraction/digestion techniques (0.05 M EDTA, 0.5 M HNO3, 2 M HNO3, aqua regia, total digestion) were used for lead isotopic composition (206Pb/207Pb) determination in three forest soil profiles with different kinds of prevailing Pb contamination (unpolluted area, smelting area and vicinity of a motorway). The results obtained showed that all extraction/digestion methods used for the determination of 206Pb/207Pb ratios in surface horizons containing high organic matter contents gave statistically identical values (according to the Tukey test). In mineral soil horizons, differences between the individual extraction/digestion methods could be observed (the lowest 206Pb/207Pb ratios were obtained from EDTA extracts, corresponding to weakly bound anthropogenic lead, and the highest 206Pb/207Pb ratios were obtained from total digestion). The combination of total digestion and EDTA extraction (labile lead fraction) seems to be the optimal combination for 206Pb/207Pb ratio determination and optimal result interpretation.

Abstract: The Pb contents and 206Pb/207Pb and 208Pb/206Pb isotopic ratios were studied in the soils and wines (2004 harvest) of three vineyard areas of the Czech Republic. The areas differ in their geological basements and anthropogenic loading. The isotopic compositions of wine in areas with intensive industry (Most, North Bohemia 206Pb/207Pbwine = 1.178 ± 0.004) and the agricultural areas of Central Bohemia (Roudnice nad Labem 206Pb/207Pbwine = 1.176 ± 0.007) are similar to the Pb isotopic composition of airborne particulate material typical of polluted and industrial environments (206Pb/207Pb = 1.17�1.19). The isotopic composition of wine from Prague (206Pb/207Pbwine = 1.174 ± 0.003) is different from that of the soil, which was severely contaminated in the past by vehicular Pb (206Pb/207Pbsoil = 1.147�1.168). This fact shows that interception of airborne Pb by plants is greater than its uptake by the root system.

Abstract: �ímov water reservoir on the river Malše is the main source of drinking water for the town of �eské Bud�jovice and for the majority of inhabitants in the South Bohemian region, Czech Republic. Changes in cadmium and lead contents in bottom sediments before and after an extensive flood on the river Malše in August, 2002 were therefore determined. A five-step sequential extraction procedure was used in order to obtain more detailed information about the influence of the flood on heavy metal retention. In order to determine the mobility of lead and cadmium, the mobility factor (MF) for these heavy metals was calculated. The mobility factor of cadmium showed a significant decrease in the upper parts of the sediment profiles after the flood (e.g., from 59.4% to 49.1%) caused by a release of cadmium especially from the exchangeable fraction. There were no significant changes in the lead mobility factor after the flood, but a decrease of lead concentration in the exchangeable fraction was observed. Presented results show that the flood led to a leaching of the heavy metals present in bottom sediments into the environment.

Abstract: In August 2002 extreme floods affected Bohemia a part of the Czech Republic, along Vltava and Labe rivers. After the flood had culminated, soil samples of arable and meadow soil (flooded and control-non-flooded) have been collected in the surroundings of the cities of �eské Bud�jovice (CB, South Bohemia, the Vltava river, the upper flood stream) and �stí nad Labem (UL, the Labe river, the lower flood stream). Different parameters of arable soils have been affected more significantly than those of meadow soils. Soil texture e.g. has been shifted from sandy loam to loam (CB) and clay loam (UL). Organic carbon, total phosphorus and nitrogen contents have been increased as well as the content of some hazardous elements such as arsenic. A shift of soil pH from 6.1 to 4.8 has been noticed in CB and an opposite one from 5.1 to 7.1 was measured in UL. Available phosphorus decreased in CB by 56% while a four-fold increase was measured in UL. Chlorinated organic pesticides level was significantly reduced, but that of polycyclic aromatic hydrocarbons (PAH) increased up to the maximum values of legal limits. The UL arable soil also became heavily contaminated by PAH. The CB arable soil demonstrated high microbial activity, while UL arable soil suffered under stress conditions in this respect. The flooded meadow soils became covered with a layer of drifted soil sediment, which retained enhanced content of the PAH's different hazardous elements, and, in addition, the soil aeration was reduced.

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