EDTA enhanced heavy metal phytoextraction: metal accumulation,leaching and toxicity

Synthetic chelates such as ethylene diamine tetraacetic acid (EDTA) have been shown to enhance phytoextraction of some heavy metals from contaminated soil. In a soil column study, we examined the effect of EDTA on the uptake of Pb, Zn and Cd by Chinese cabbage (Brassica rapa), mobilization and leaching of heavy metals and the toxicity effects of EDTA additions on plants. The most effective was a single dose of 10 mmol EDTA kg^–1 soil where we detected Pb, Zn and Cd concentrations that were 104.6, 3.2 and 2.3-times higher in the aboveground plant biomass compared to the control treatments. The same EDTA addition decreased the concentration of Pb, Zn and Cd in roots of tested plants by 41, 71 and 69%, respectively compared to concentrations in the roots of control plants. In columns treated with 10 mmol kg^–1 EDTA, up to 37.9, 10.4 and 56.3% of initial total Pb, Zn and Cd in soil were leached down the soil profile, suggesting high solubility of heavy metals-EDTA complexes. EDTA treatment had a strong phytotoxic effect on the red clover (Trifolium pratense) in bioassay experiment. Moreover, the high dose EDTA additions inhibited the development of arbuscular mycorrhiza. The results of phospholipid fatty acid analyses indicated toxic effects of EDTA on soil fungi and increased environmental stress of soil microfauna.     

Metal accumulation and response of antioxidant enzymes in seedlings and adult sunflower mutants with improved metal removal traits on a metal-contaminated soil

Sunflower mutant lines with an enhanced tolerance and metal accumulation capacity obtained by mutation breeding have been proposed for Zn, Cd and Cu removal from metal-contaminated soils in previous studies. However, soils contaminated with trace elements induce various biochemical alterations in plants leading to oxidative stress. There is a lack of knowledge concerning the metal accumulation and antioxidant responses during the growth and development of sunflowers. This study, therefore, aimed to characterise metal accumulation and possible metal detoxification mechanisms in young seedlings and adult sunflowers. Beside the inbred line, two mutant lines with an improved growth and enhanced metal uptake capacity on a metal contaminated soil were investigated in more detail.Sunflowers cultivated on a metal-contaminated soil in the greenhouse showed a decrease in shoot biomass and chlorophyll concentration in two different developmental stages. Adult sunflowers showed a lower sensitivity to metal toxicity than young seedlings, whereas mutant lines were more tolerant to metal stress than the control. Mutant lines also produced a higher amount of carotenoids on a metal-contaminated soil than on the control soil, indicating a possible protective mechanism of sunflower mutants against oxidative stress caused by Cd and excess Zn.Heavy metals primarily increased the activity of antioxidant enzymes involved in the ascorbate–glutathione cycle in sunflower leaves. Activity of dehydroascorbate reductase (DHAR), monodehydroascorbate reductase (MDHAR) and glutathione reductase (GR) was strongly increased in young seedlings exposed to heavy metals. The enzyme activities were even more pronounced in mutant lines. A significantly increased ascorbate peroxidase (APOX) activity in adult sunflowers exposed to heavy metals indicated an elevated use of ascorbate after a longer exposure to metal stress.An increased antioxidant level corresponded to a high Cd and Zn accumulation in young and adult sunflowers. Metal distribution, zinc translocation in particular, from the root into the shoot tissue obviously increased during sunflower growth and ripening. Altogether, these results suggest that sunflower plants, primarily the mutant lines, possess an efficient defence mechanism against oxidative stress caused by metal toxicity. A good tolerance of sunflowers toward heavy metals coupled with an increased metal accumulation capacity might contribute to an efficient removal of heavy metals from a polluted area.     

Plant uptake and the leaching of metals during the hot EDDS-enhanced phytoextraction process

Using pot experiments, the effect of the application of the biodegradable chelating agent S,S-ethylenediaminedisuccinic acid (EDDS) in hot solutions at 90 degrees C on the uptake of Cu, Pb, Zn, and Cd by corn (Zea mays L. cv. Nongda No. 108) and beans (P vulgaris L. white bean), and the potential leaching of metals from soil, were studied. When EDDS was applied as a hot solution at the rate of 1 mmol kg(-1), the concentrations and total phytoextraction of metals in plant shoots exceeded or approximated those in the shoots of plants treated with normal EDDS at the rate of 5 mmol kg(-1). On the other hand, the leaching of Cu, Pb, Zn, and Cd after the application of the hot EDDS solution at the rate of 1 mmol kg(-1) was reduced by 46%, 21%, 57%, and 35% in comparison with that from the application of normal EDDS at 5 mmol kg(-1), respectively. For treatment with 1 mmol kg(-1) of EDDS, the leached metals decreased to the levels of the control group (that without EDDS amendment) 14 d after the application of EDDS. The soil amendment with biodegradable EDDS in hot solutions may provide a good alternative to chelate-enhanced phytoextraction in enhancing metal uptake by plants and limiting metals from leaching out of the soil.     

Effects of different sewage sludge applications on heavy metal accumulation,growth and yield of spinach (Spinacia oleracea L.)

In this study, we present the response of spinach to different amendment rates of sewage sludge (0, 10, 20, 30, 40 and 50 g kg^?1) in a greenhouse pot experiment, where plant growth, biomass and heavy metal uptake were measured. The results showed that sewage sludge application increased soil electric conductivity (EC), organic matter, chromium and zinc concentrations and decreased soil pH. All heavy metal concentrations of the sewage sludge were below the permissible limits for land application of sewage sludge recommended by the Council of the European Communities. Biomass and all growth parameters (except the shoot/root ratio) of spinach showed a positive response to sewage sludge applications up to 40 g kg^?1 compared to the control soil. Increasing the sewage sludge amendment rate caused an increase in all heavy metal concentrations (except lead) in spinach root and shoot. However, all heavy metal concentrations (except chromium and iron) were in the normal range and did not reach the phytotoxic levels. The spinach was characterized by a bioaccumulation factor <1.0 for all heavy metals. The translocation factor (TF) varied among the heavy metals as well as among the sewage sludge amendment rates. Spinach translocation mechanisms clearly restricted heavy metal transport to the edible parts (shoot) because the TFs for all heavy metals (except zinc) were <1.0. In conclusion, sewage sludge used in the present study can be considered for use as a fertilizer in spinach production systems in Saudi Arabia, and the results can serve as a management method for sewage sludge.     

The Application of Soil Amendments to the Retardance of Rainwater-Leached Metals from CCA-Treated Wood Ash in Soil

The burning of wood treated with chromated copper arsenate (CCA) produces an ash that contains high concentrations of copper, chromium, and arsenic. The subsequent leaching of these metals from burn sites can produce soil and water contamination. Soils have varying natural abilities to reduce leaching and impact metals speciation and toxicity by sorption, conversion, and sedimentation-related mechanisms. Recent regulations have resulted in increased quantities of CCA-treated lumber entering the waste stream, making the study of metals leaching from ash, and the amendment of soils to more effectively immobilize metals, important areas of investigation.

The performance of various soil amendments to immobilize or retard Cu, Cr, and As species in soil/CCA-ash mixtures was studied. The amendments evaluated were agricultural lime (CaCO₃/MgCO₃), soil softener (CaSO₄ · 2H₂O), and iron sulfate (FeSO₄). Results of this investigation show that native soil alone retards the mobility of As and Cr, amendments applied alone or in combinations further retard metal mobility compared to the control soil/CCA-ash mixture. The CaSO₄ soil amendment is most effective in reducing the rainwater leaching of Cr and As from CCA-ash in soil reducing the mobility by 72.4% and 77.3%, respectively, compared to the control soil-ash mixture. Cu mobility is increased in the presence of the native soil and by all amendments.     

In-Situ Remediation of Lead–Zinc Polymetallic Mine Contaminated Soils by MnFe2O4 Microparticles

In-situ remediation is a practical approach to remediate soils contaminated with heavy metals. The MnFe₂O₄ microparticles (MM) were prepared for the in-situ remediation of contaminated soils from a lead–zinc polymetallic mine in Inner Mongolia province, China. The effects of MM dosage, pH on remediation efficiency, were determined with static vibration leaching experiment, and the release risk of heavy metals of treated soil was studied by column leaching experiment. The results showed that the leached Cu, Pb, Zn, and As concentration decreased drastically with increasing MM dosage, when the dosage was lower than 10 g/kg. Moreover, the decrease of pH caused increase of leached concentration of Cu, Pb, Zn, but slight decrease of leached As concentration. For the amended soil, concentrations of leached heavy metals were lower than Grade III limit of Chinese Environmental Quality Standards for Ground and Surface water (GB3838-2002) under simulated acid rain leaching condition. In comparison with non-amended soils, the total amount of Cu, Pb, Zn, and As release from amended soils was reduced by 93.6%, 69.2%, 57.0%, and 99.7%, respectively. The MM is a kind of promising amendment for heavy metals contaminated soil.     

Effects of Municipal Sewage Sludge Doses on the Chlorophyll Contents and Heavy Metal Concentration of Sugar Beet (Beta vulgaris var. saccharifera)

The present study was conducted to assess the suitability of sewage sludge amendment (SSA) in soil for Beta vulgaris var. saccharifera (sugar beet) by evaluating the heavy metal accumulation and physiological responses of plants grown at a 10%, 25%, and 50% sewage sludge amendment rate. The sewage sludge amendment was modified by the physicochemical properties of soil, thus increasing the availability of heavy metals in the soil and consequently increasing accumulation in plant parts. Cd, Pb, Ni, and Cu concentrations in roots were significantly higher in plants grown at 25% as compared to 50% SSA; however, Cr and Zn concentration was higher at 50% than 25% SSA. The concentrations of heavy metal showed a trend of Zn > Ni > Cu > Cr > Pb > Cd in roots and Zn > Cu > Ni > Cr > Pb > Cd in leaves. The only instance in which the chlorophyll content did not increase after the sewage sludge treatments was 50%. There were approximately 1.12-fold differences between the control and 50% sewage sludge application for chlorophyll content. The sewage sludge amendment led to a significant increase in Pb, Cr, Cd, Cu, Zn, and Ni concentrations of the soil. The heavy metal accumulation in the soil after the treatments did not exceed the limits for the land application of sewage sludge recommended by the US Environmental Protection Agency (US EPA). The increased concentration of heavy metals in the soil due to the sewage sludge amendment led to increases in heavy metal uptake and the leaf and root concentrations of Ni, Zn, Cd, Cu, Cr, Pb, and Zn in plants as compared to those grown on unamended soil. More accumulation occurred in roots and leaves than in shoots for most of the heavy metals. The concentrations of Cd, Cr, and Pb were more than the permissible limits of national standards in the edible portion of sugar beet grown on different sewage sludge amendment ratios. The study concludes that the sewage sludge amendment in the soil for growing sugar beet may not be a good option due to risk of contamination of Cr, Pb, and Cd.     

Enhanced phytoextraction: II. Effect of EDTA and citric acid on heavy metal uptake by Helianthus annuus from a calcareous soil

High biomass producing plant species, such as Helianthus annuus, have potential for removing large amounts of trace metals by harvesting the aboveground biomass if sufficient metal concentrations in their biomass can be achieved However, the low bioavailability of heavy metals in soils and the limited translocation of heavy metals to the shoots by most high biomass producing plant species limit the efficiency of the phytoextraction process. Amendment of a contaminated soil with ethylene diamine tetraacetic acid (EDTA) or citric acid increases soluble heavy metal concentrations, potentially rendering them more available for plant uptake. This article discusses the effects of EDTA and citric acid on the uptake of heavy metals and translocation to aboveground harvestable plant parts in Helianthus annuus. EDTA was included in the research for comparison purposes in our quest for less persistent alternatives, suitable for enhanced phytoextraction. Plants were grown in a calcareous soil moderately contaminated with Cu, Pb, Zn, and Cd and treated with increasing concentrations of EDTA (0.1, 1, 3, 5, 7, and 10 mmol kg(-1) soil) or citric acid (0.01, 0.05, 0.25, 0.442, and 0.5 mol kg(-1) soil). Heavy metal concentrations in harvested shoots increased with EDTA concentration but the actual amount of phytoextracted heavy metals decreased at high EDTA concentrations, due to severe growth depression. Helianthus annuus suffered heavy metal stress due to the significantly increased bioavailable metal fraction in the soil. The rapid mineralization of citric acid and the high buffering capacity of the soil made citric acid inefficient in increasing the phytoextracted amounts of heavy metals. Treatments that did not exceed the buffering capacity of the soil (< 0.442 mol kg(-1) soil) did not result in any significant increase in shoot heavy metal concentrations. Treatments with high concentrations resulted in a dissolution of the carbonates and compaction of the soil. These physicochemical changes caused growth depression of Helianthus annuus. EDTA and citric acid added before sowing of Helianthus annuus did not appear to be efficient amendments when phytoextraction of heavy metals from calcareous soils is considered.     

Enhanced phytoextraction: I. Effect of EDTA and citric acid on heavy metal mobility in a calcareous soil

Phytoextraction, the use of plants to extract heavy metals from contaminated soils, could be an interesting alternative to conventional remediation technologies. However, calcareous soils with relatively high total metal contents are difficult to phytoremediate due to low soluble metal concentrations. Soil amendments such as ethylene diaminetetraacetate (EDTA) have been suggested to increase heavy metal bioavailability and uptake in aboveground plant parts. Strong persistence of EDTA and risks of leaching of potentially toxic metals and essential nutrients have led to research on easily biodegradable soil amendments such as citric acid. In our research, EDTA is regarded as a scientific benchmark with which degradable alternatives are compared for enhanced phytoextraction purposes. The effects of increasing doses of EDTA (0.1,1,10 mmol kg(-1) dry soil) and citric acid (0.01, 0.05, 0.25, 0.442, 0.5 mol kg(-1) dry soil) on bioavailable fractions of Cu, Zn, Cd, and Pb were assessed in one part of our study and results are presented in this article. The evolution of labile soil fractions of heavy metals over time was evaluated using water paste saturation extraction (approximately soluble fraction), extraction with 1 M NH4OAc at pH 7 (approximately exchangeable fraction), and extraction with 0.5 M NH4OAc + 05 M HOAc + 0.02 M EDTA at pH 4.65 (approximately potentially bioavailable fraction). Both citric acid and EDTA produced a rapid initial increase in labile heavy metal fractions. Metal mobilization remained constant in time for soils treated with EDTA, but a strong exponential decrease of labile metal fractions was noted for soils treated with citric acid. The half life of heavy metal mobilization by citric acid varied between 1.5 and 5.7 d. In the following article, the effect of heavy metal mobilization on uptake by Helianthus annuus will be presented.     

Impact of Pyrolysis Treatment on Heavy Metals in Sediment

This paper describes a laboratory study that examined the effect of pyrolysis treatment on the behavior of Hg, Cr, Zn, Pb, Cu and Cd in a stream sediment. The influences of pyrolysis on the evaporation, sequential extraction and leaching behavior of these metals were investigated. Cr, Zn, Pb and Cu were retained quantitively in the solid residue at temperatures up to 800°C while mercury and cadmium were completely or partially evaporated. The metal form distribution in the sludge samples was determined by the sequential extraction procedure. The procedure revealed that as a consequence of pyrolysis, the metals were more strongly fixed in the treated sediment, as could be seen by the decrease with temperature of the first two sequential-extracted fractions and increase of the residue fraction. The leaching results showed that the quantities of the studied metals leached in the two pyrolysis samples were lower than those in the untreated sediment. The amounts of metals leached from the pyrolysis residues correlated significantly with the first extracted fraction (exchangeable fraction).     

Heavy metal removal from contaminated scallop waste for feed and fertilizer application

The present work elucidates environmental friendly removal process of heavy metals by using biomass waste and natural product. The process consists of the following three steps: (1) leaching of all metals including heavy metals by dilute sulfuric acid, (2) removal of turbid organic materials from the leach liquor by means of coagulation using astringent persimmon extract enriched with persimmon tannin leaving all heavy metal ions in the leach liquor and (3) adsorptive removal of heavy metals by means of adsorption onto the gel prepared from apple waste. The operational conditions at these three steps were discussed in detail, among which the pH adjustment is the key factor; i.e. the lower the pHs the higher the efficiency of the leaching, while reverse was the case for the adsorption.     

The effect of soil type and degree of metal contamination upon uptake of Cd,Pb and Cu in bush beans (Phaseolus vulgaris L.)

Summary Five soils of increasing specific surface area (SSA) were loaded to five levels of contamination with Cd, Pb and Cu, and bean plants (Phaseolus vulgaris L.) were grown on the soils for 30 days. A linear correlation was found between the concentration of Cd in the soil solutions and the amount absorbed by the plant per gram root material for four out of the five soils, and, in the case of Cu, for all five soils. Quantitatively, there was insufficient Cd or Cu in the soil solution to account for plant uptake of these metals. The amount of Cd absorbed by plants could also be related to the adsorption density (concentration/SSA soil) of the metal in four of the five soils, whereas the Cu content of plants could be related to the adsorption density of all five soils. It is thought that the metals were removed from the soil solution by root absorption and replenished by metal cations adsorbed onto surface sites in the soil. Consideration of the adsorption density of these metals in the soil may be a useful means to determine the permissible limits for heavy metal application for a wide range of soils. Lead uptake was significantly correlated to total Pb in soils, but not to the adsorption density or soil solution concentrations. The possible interpretation of the results are discussed.     

Removal of trace metals by Sorghum bicolor and Helianthus annuus in a site polluted by industrial wastes: a field experience.

Using the perspective of full scale application of phytoremediation techniques, research is focusing on the optimization of agronomic practices. Two annual high biomass yield crops, Sorghum bicolor and Helianthus annuus, were grown in a polymetallic soil. The experimental site, polluted by pyrite cinders, is located in an industrial site that has been listed in the clean-up national priority list since 2001. Specific aims of this work were to observe the concentration of metals in plants during the crop cycle and to establish the amount of metal removed by the crops. The field trial, arranged in a randomized block design, started in 2005. The concentrations of heavy metals in the soil were: As 309, Cd 4.29, Co 50.9, Cu 1527 and Zn 980mg kg(-1). The crops grown on the polluted soil received mineral fertilization (Fert) and organic amendment (Org), while plants in control soil (Ctrl) did not receive anything. The plots were watered during the crop cycle during two drought periods, using a sprinkler irrigation system. The phytoextraction potential of crops was estimated during the whole growth cycle and the plant biomass that was collected in each sampling date was ICP-analyzed. Plant-biomass growth curves were obtained. The concentrations of the metals in the shoots and in the total plant biomass were recorded. Finally, the metal removal was calculated for the harvestable parts of the crops. The amelioration of the nutritive status of the substrate that resulted, was highly effective for the biomass yield. However, fertilization and soil amendment did not heighten the concentration of metals in the harvestable tissue of the plants during the crop cycle. In some cases, organic matter appeared to bind the elements making them less available for the plants. The evaluation of the potential of phytoremediation of our plants compared to other crops in terms of metal removal was positive. Our results of metal removal are consistent with the results from other in situ experiments. The Zn removal by S. bicolor and H. annuus reached about 2000g ha(-1) and 1000g ha(-1), respectively.     

Leaching Behavior of Heavy Metals and Transformation of Their Speciation in Polluted Soil Receiving Simulated Acid Rain

Heavy metals that leach from contaminated soils under acid rain are of increasing concern. In this study, simulated acid rain (SAR) was pumped through columns of artificially contaminated purple soil. Column leaching tests and sequential extraction were conducted for the heavy metals Cu, Pb, Cd, and Zn to determine the extent of their leaching as well as to examine the transformation of their speciation in the artificially contaminated soil columns. Results showed that the maximum leachate concentrations of Cu, Pb, Cd, and Zn were less than those specified in the Chinese Quality Standards for Groundwater (Grade IV), thereby suggesting that the heavy metals that leached from the polluted purple soil receiving acid rain may not pose as risks to water quality. Most of the Pb and Cd leachate concentrations were below their detection limits. By contrast, higher Cu and Zn leachate concentrations were found because they were released by the soil in larger amounts as compared with those of Pb and Cd. The differences in the Cu and Zn leachate concentrations between the controls (SAR at pH 5.6) and the treatments (SAR at pH 3.0 and 4.5) were significant. Similar trends were observed in the total leached amounts of Cu and Zn. The proportions of Cu, Pb, Cd, and Zn in the EXC and OX fractions were generally increased after the leaching experiment at three pH levels, whereas those of the RES, OM, and CAR fractions were slightly decreased. Acid rain favors the leaching of heavy metals from the contaminated purple soil and makes the heavy metal fractions become more labile. Moreover, a pH decrease from 5.6 to 3.0 significantly enhanced such effects.     

Remobilization of toxic heavy metals adsorbed to bacterial wall-clay composites.

Significant quantities of Ag(I), Cu(II), and Cr(III) were bound to isolated Bacillus subtilis 168 walls, Escherichia coli K-12 envelopes, kaolinite and smectite clays, and the corresponding organic material-clay aggregates (1:1, wt/wt). These sorbed metals were leached with HNO3, Ca(NO3)2, EDTA, fulvic acid, and lysozyme at several concentrations over 48 h at room temperature. The remobilization of the sorbed metals depended on the physical properties of the organic and clay surfaces and on the character and concentration of the leaching agents. In general, the order of remobilization of metals was Cr much less than Ag less than Cu. Cr was very stable in the wall, clay, and composite systems; pH 3.0, 500 microM EDTA, 120-ppm [mg liter-1] fulvic acid, and 160-ppm Ca remobilized less than 32% (wt/wt) of sorbed Cr. Ag (45 to 87%) and Cu (up to 100%) were readily removed by these agents. Although each leaching agent was effective at mobilizing certain metals, elevated Ca or acidic pH produced the greatest overall mobility. The organic chelators were less effective. Lysozyme digestion of Bacillus walls remobilized Cu from walls and Cu-wall-kaolinite composites, but Ag, Cr, and smectite partially inhibited enzyme activity, and the metals remained insoluble. The extent of metal remobilization was not always dependent on increasing concentrations of leaching agents; for example, Ag mobility decreased with some clays and some composites treated with high fulvic acid, EDTA, and lysozyme concentrations. Sometimes the organic material-clay composites reacted in a manner distinctly different from that of their individual counterparts; e.g., 25% less Cu was remobilized from wall- and envelope-smectite composites than from walls, envelopes, or smectite individually in 500 microM EDTA. Alternatively, treatment with 160-ppm Ca removed 1.5 to 10 times more Ag from envelope-kaolinite composites than from the individual components. The particle size of the deposited metal may account for some of the stability changes; those metals that formed large, compact aggregates (Cr and Ag) as seen by transmission electron microscopy were less likely to be remobilized. In summary, it is apparent that remobilization of toxic heavy metals in sediments, soils, and the vadose zone is a complicated issue. Predictions based on single inorganic or organic component systems are too simplistic.     

Remobilization of toxic heavy metals adsorbed to bacterial wall-clay composites

Significant quantities of Ag(I), Cu(II), and Cr(III) were bound to isolated Bacillus subtilis 168 walls, Escherichia coli K-12 envelopes, kaolinite and smectite clays, and the corresponding organic material-clay aggregates (1:1, wt/wt). These sorbed metals were leached with HNO3, Ca(NO3)2, EDTA, fulvic acid, and lysozyme at several concentrations over 48 h at room temperature. The remobilization of the sorbed metals depended on the physical properties of the organic and clay surfaces and on the character and concentration of the leaching agents. In general, the order of remobilization of metals was Cr much less than Ag less than Cu. Cr was very stable in the wall, clay, and composite systems; pH 3.0, 500 microM EDTA, 120-ppm [mg liter-1] fulvic acid, and 160-ppm Ca remobilized less than 32% (wt/wt) of sorbed Cr. Ag (45 to 87%) and Cu (up to 100%) were readily removed by these agents. Although each leaching agent was effective at mobilizing certain metals, elevated Ca or acidic pH produced the greatest overall mobility. The organic chelators were less effective. Lysozyme digestion of Bacillus walls remobilized Cu from walls and Cu-wall-kaolinite composites, but Ag, Cr, and smectite partially inhibited enzyme activity, and the metals remained insoluble. The extent of metal remobilization was not always dependent on increasing concentrations of leaching agents; for example, Ag mobility decreased with some clays and some composites treated with high fulvic acid, EDTA, and lysozyme concentrations. Sometimes the organic material-clay composites reacted in a manner distinctly different from that of their individual counterparts; e.g., 25% less Cu was remobilized from wall- and envelope-smectite composites than from walls, envelopes, or smectite individually in 500 microM EDTA. Alternatively, treatment with 160-ppm Ca removed 1.5 to 10 times more Ag from envelope-kaolinite composites than from the individual components. The particle size of the deposited metal may account for some of the stability changes; those metals that formed large, compact aggregates (Cr and Ag) as seen by transmission electron microscopy were less likely to be remobilized. In summary, it is apparent that remobilization of toxic heavy metals in sediments, soils, and the vadose zone is a complicated issue. Predictions based on single inorganic or organic component systems are too simplistic.     

A novel strategy using biodegradable EDDS for the chemically enhanced phytoextraction of soils contaminated with heavy metals

For the sake of cost and potential environmental risk, it is necessary to minimize the amount of chelants used in chemically enhanced phytoextraction. In the present study, a biodegradable chelating agent, EDDS was added in a hot solution at 90°C to the soil in which garland chrysanthemum (Chrysanthemum coronarium L.) and beans (Phaseolus vulgaris L., white bean) were growing. The application of hot chelant solutions was much more efficient than the application of normal chelant solutions (25°C) in improving the uptake of heavy metals by plants. When 1 mmol kg⁻¹ of EDDS as a hot solution was applied to soil, the concentrations of Cu, Zn and Cd and the total phytoextraction by the shoots of the two plant species exceeded or approximated those in the shoots of plants treated with 5 mmol kg⁻¹ of normal EDTA solution. The concentrations of metals in the shoots of beans were significantly correlated with the relative electrolyte leakage rate of root cells, indicating that the root damage resulting from the hot solution might play an important role in the process of chelant-enhanced metal uptake. The soil leaching study demonstrated that decreasing the dosage of chelant resulted in decreased concentrations of soluble metals in soils. On the 28th day following the application of chelant, the concentrations of soluble metals in the EDDS treated soil were not significantly different from the concentrations in the control soil to which chelants had not been applied. The application of biodegradable EDDS in hot solutions to soil may be an efficient alternative in chemically-enhanced phytoextraction to increase metal removal and to reduce possible leaching.Section Editor: J. Barcelo     

Effects of tannery waste on growth dynamics and metal uptake in Salix alba L

Abstract

This paper aims at providing a preliminary study of the effects of different doses of tannery waste containing high amounts of organic substances, mineral elements and heavy metals on growth dynamics and metal accumulation in willow plants. Scions of Salix alba L., clone S61-02, were grown in the open near Pisa (Italy), in pots filled with a natural soil. Willows were pruned for a unique shoot and cultivated with three different treatments: non-amended soil, soil amended with 150 or 300 g of tannery waste. Non-destructive measures of plant height and leaf area were performed during one growth season. Determination of biomass, and chemical analyses of the minerals were performed at the end of the experiment. The waste-treated plants increased all growth parameters significantly more than the non-treated ones. The concentration of the analysed elements (N, P, K, Ca, Mg, S, B, Fe, Mn, Cu, Zn, Cr) changed significantly between treatments and organs. The results can be useful for developing phytostabilization and/or phytoextraction strategies of tannery waste using S. alba.     

Comparison of Extractants for Removing Heavy Metals from Contaminated Clayey Soils

This article describes the removal of heavy metals from contaminated clayey soils by soil washing using various extractants. Two clayey soils, kaolin, a low buffering soil with pH of 5, and glacial till, a high buffering soil with pH of 8, were used to represent various soil conditions. These soils were spiked with chromium (Cr), nickel (Ni), and cadmium (Cd) to simulate improper disposal of typical electroplating waste constituents. The following extracting solutions were investigated for the removal of heavy metals from the soils: deionized water, distilled water, and tap water; acetic acid and phosphoric acid; chelating agents ethylenediaminetetraacetic acid (EDTA) and citric acid; and the oxidizing agents potassium permanganate and hydrogen peroxide. The effect of extractant concentration on removal of heavy metals was also investigated. Complete removal of Cr was achieved using 0.1?M potassium permanganate for kaolin, while a maximum of 54% was removed from glacial till. A maximum Ni removal of 80% was achieved using tapwater for kaolin, while a maximum removal of 48 to 52% was achieved using either 1?M acetic acid or 0.1?M citric acid for glacial till. A maximum Cd removal of 50% was achieved using any of the extractants for kaolin, while a maximum removal of 45 to 48% was obtained using either acids or chelating agents for glacial till. Overall, this study showed that complete removal of Cr, Ni, and Cd from clayey soils is difficult to achieve using the soil-washing process, and also the use of one extractant may not be effective in removing all metals. A sequential extraction using different extractants may be needed for the removal of multiple metal contaminants from clayey soils.     

Heavy metal accumulation in wheat and barley: The effects of soil presence and liquid manure amendment

An experiment was undertaken to evaluate the effect of liquid manure amendment on heavy metal accumulation in wheat and barley. For this purpose, both kinds of seedlings were grown simultaneously in a Petri dish, while wheat seedlings were also grown in pots containing unpolluted agricultural soil. All of the seedlings were irrigated with one of the three prepared solutions: artificial rainwater solution, heavy metal solution and liquid manure solution containing NH₄NO₃, H₃PO₄ and KOH along with equal amounts of heavy metals as in the second solution. Twenty days later, 1 g of plant tissue was digested with the mixture of HNO₃ and H₂O₂ for ICP-OES/HG-ICP-OES analysis. The results showed that the uptake of arsenic and mercury was highest for both plants grown in a Petri dish. Furthermore, the wheat grown in a Petri dish also had a high content of nickel, cadmium and copper, while the pot-grown wheat contained high amounts of iron and manganese, probably due to the adsorption of nickel, cadmium, copper and mercury on soil phases. The lower uptake of all heavy metals was observed after the amendment of liquid manure, with the exception of manganese in wheat and mercury in all plants.