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.     

Enhanced phytoextraction: in search of EDTA alternatives

Enhanced phytoextraction proposes the use of soil amendments to increase the heavy-metal content of above-ground harvestable plant tissues. This study compares the effect of synthetic aminopolycarboxylic acids [ethylenediamine tetraacetatic acid (EDTA), nitriloacetic acid (NTA), and diethylenetriamine pentaacetic acid (DTPA)] with a number of biodegradable, low-molecular weight, organic acids (citric acid, ascorbic acid, oxalic acid, salicylic acid, and NH4 acetate) as potential soil amendments for enhancing phytoextraction of heavy metals (Cu, Zn, Cd, Pb, and Ni) by Zea mays. The treatments in this study were applied at a dose of 2 mmol/kg(-1) 1 d before sowing. To compare possible effects between presow and postgermination treatments, a second smaller experiment was conducted in which EDTA, citric acid, and NH4 acetate were added 10 d after germination as opposed to 1 d before sowing. The soil used in this screening was a moderately contaminated topsoil derived from a dredged sediment disposal site. This site has been in an oxidized state for more than 8 years before being used in this research. The high carbonate, high organic matter, and high clay content characteristic to this type of sediment are thought to suppress heavy-metal phytoavailability. Both EDTA and DTPA resulted in increased levels of heavy metals in the above-ground biomass. However, the observed increases in uptake were not as large as reported in the literature. Neither the NTA nor organic acid treatments had any significant effect on uptake when applied prior to sowing. This was attributed to the rapid mineralization of these substances and the relatively low doses applied. The generally low extraction observed in this experiment restricts the use of phytoextraction as an effective remediation alternative under the current conditions, with regard to amendments used, applied dose (2 mmol/kg(-1) soil), application time (presow), plant species (Zea mays), and sediment (calcareous clayey soil) under study.     

Soil amendment application frequency contributes to phytoextraction of lead by sunflower at different nutrient levels

Phytoextraction has been proposed as an alternative remediation technology for soils polluted with heavy metals, but is generally perceived to be too slow. Enhancing accumulation of trace pollutants in harvestable plant tissues is a prerequisite for such technology to be practical. The main aims of this paper were to investigate whether a combination of nutrients and ethylenediaminetetraacetic acid (EDTA) enhanced Pb uptake of sunflower (Helianthus annuus) plants, and if timing of EDTA application altered Pb uptake and environmental persistence. Plants were grown in greenhouse pot experiments. Pb distributions and uptake of the whole plant were studied using chemical and flame atomic absorption spectrometry analyses. Pb mobilization by EDTA appeared to be dose dependent, with more mobilization for the high than the low dose. There were distinct differences in mobilization patterns of various nutrient amendments. EDTA mobilized Pb more in the medium than the highest and lowest nutrient levels. Heterogeneous soil humus components exerted mobilizing and stabilizing effects, so the medium nutrition was most effective for phytoextraction. At low nutrient levels, Pb concentration in the shoot with one low EDTA application was less than two applications to the same total EDTA dosage. So in the poor soil, two applications of EDTA was more effective than once. The half-life of two low EDTA treatment applications was longer than for one application, to the same total dosage. In general, sunflower was suited to phytoremediation of moderately Pb-contaminated soil by phytoextraction.     

Phytoextraction of Pb and Cu contaminated soil with maize and microencapsulated EDTA

Chelate-assisted phytoextraction using agricultural crops has been widely investigated as a remediation technique for soils contaminated with low mobility potentially toxic elements. Here, we report the use of a controlled-release microencapsulated EDTA (Cap-EDTA) by emulsion solvent evaporation to phytoremediate soil contaminated with Pb and Cu. Incubation experiments were carried out to assess the effect of Cap- and non-microencapsulated EDTA (Ncap-EDTA) on the mobility of soil metals. Results showed EDTA effectively increased the mobility of Pb and Cu in the soil solution and Cap-EDTA application provided lower and more constant water-soluble concentrations of Pb and Cu in comparison with. Phytotoxicity may be alleviated and plant uptake of Pb and Cu may be increased after the incorporation of Cap-EDTA. In addition phytoextraction efficiencies of maize after Cap- and Ncap-EDTA application were tested in a pot experiment. Maize shoot concentrations of Pb and Cu were lower with Cap-EDTA application than with Ncap-EDTA. However, shoot dry weight was significantly higher with Cap-EDTA application. Consequently, the Pb and Cu phytoextraction potential of maize significantly increased with Cap-EDTA application compared with the control and Ncap-EDTA application.     

The EDTA Amendment in Phytoextraction of 134Cs From Soil by Indian Mustard (Brassica juncea)

Soil contamination with radiocaesium is a significant problem at any countries when a nuclear accident occurred. Recently, phytoextraction technique is developed to remediate the contaminated environment. However, the application is limited by the availability of the contaminant for root uptake. Therefore, a green house trial experiment of soil amendment with ethylene diamine tetraacetic acid (EDTA) has been conducted to examine ¹³⁴Cs availability for root uptake. Two groups of Indian mustard (Brassica juncea) were cultivated in ¹³⁴Cs contaminated soil. The soil in the first group was treated with EDTA amendment, while the other was not. Plant growth was observed gravimetrically and the ¹³⁴Cs concentration in soil as well as plants were determined using gamma spectrometry. The plant uptake capacity was determined as transfer factor (F_v), and the F_v values of 0.22 ± 0.0786 and 0.12 ± 0.039 were obtained for the soil treated with and without EDTA amendment, respectively. The phytoextraction efficiency of the plant cultivated in ¹³⁴Cs contaminated soil both with and without EDTA amendment was low. The EDTA amendment to the soil seems to enhance the ¹³⁴Cs availability for root uptake of Indian mustard and can still be considered to assist the field phytoremediation of contaminated soil.     

Transient Phytoextraction Agents: Establishing Criteria for the Use of Chelants in Phytoextraction of Recalcitrant Metals

The phytoremediation of recalcitrant metals such as lead and uranium rely on soil amendments to enhance metal availability within the rhizosphere. Because these amendments may persist in soils, agents that not only biodegrade rapidly but also are effective in triggering metal uptake in plants are needed for metals phytoextraction to be considered as an accepted practice. In this study, several biodegradable organic acids and chelating agents were assessed to determine if these amendments can be used in an effective manner, and if their activity and use is consistent with a proposed class of soil amendments for phytoextraction, here termed transient phytoextraction agents (TPAs). A TPA is proposed as an agent that would exhibit both effectiveness in triggering plant accumulation of the targeted metal while minimizing the risk of migration through rapid degradation or inactivation of the soluble complex. Eleven candidate TPAs (acetic acid, ascorbic acid, citric acid, malic acid, oxalic acid, succinic acid, ethylenediaminedisuccinic acid, dicarboxymethylglutamic acid, nitrilotriacetic acid, BayPure® CX 100, and the siderophore desferrioxamine B) were tested in batch studies to evaluate their complexation behavior using contaminated soils, with uranium and lead as the target metals. A growth chamber study was then conducted with Brassica juncea (Indian mustard), Helianthus annuus (sunflower), and Festuca arundinacea (tall fescue) grown in a lead-contaminated soil that was treated with the candidate TPAs to assess phytoextraction effectiveness. For the soils tested, citric acid, oxalic acid, and succinic acid were found to be effective complexing agents for uranium phytoextraction, whereas Baypure® CX 100 and citric acid exhibited effectiveness for lead phytoextraction.     

Potential of S-containing and P-containing complexones in improving phytoextraction of mercury by Trifolium repens L.

Mercury is a global pollutant in the modern world. There is a large number of areas in the world where mercury is present in soils in significant quantities. Remediation methods which have traditionally been proposed may pose a risk of secondary mercury contamination and/or adverse health effects for cleaners. Phytoextraction of heavy metals from the soil environment is currently considered one of the promising non-invasive methods of remediation. But this approach has limited effectiveness. Chemically induced phytoextraction can increase the efficiency of this process both by converting less bioavailable mercury compounds to bioavailable fractions in the soil and by increasing the rate of transfer of metals in plants. This paper presents the results of a screening study of various chemical amendments to enhance the phytoextraction of mercury by Trifolium repens L. The results showed good potential for the induction of phytoextraction of phosphorus(P) and sulfur (S)-containing chelates. With this study, for the first time for the phytoextraction of mercury, the monoethanolamine salt of 2,2′-(ethylenedithio) diacetic acid was used as the S-containing chelate, and the disubstituted potassium salt of 1-hydroxy ethylidene-1,1-diphosphonic acid was used as the P-containing chelate. Further attention is given to study the effect that exogenous application of phytohormones and plant growth regulators has on the efficiency of mercury absorption and physiological status of plants, which performed well in combination with a P-containing chelate.     

EDTA-Enhanced Phytoremediation of Heavy Metals: A Review

The increase in heavy metal terrestrial ecosystems’ contamination through anthropogenic activities is a widespread and serious global problem due to their various environmental and human implications. For these reasons, several techniques, including phytoremediation of heavy metals, have been extensively studied. In spite of significant recent advancement, ethylene diamine tetraacetic acid (EDTA)-enhanced heavy metal phytoextraction as well as related ecological risks are still topical and remain an important area of research. In fact, EDTA favors the solubilization of metals and metalloids in soils, and was therefore extensively studied during the last two decades in order to improve phytoextraction efficiency and reduce treatment duration. This review highlights the recent findings (2010–2012) and mechanisms behind EDTA-enhanced (1) solubilization of heavy metals in soil, (2) mobilization/transport of soluble metals towards plant root zone, and (3) metal absorption by plant roots and translocation towards aerial parts. The review also presents potential risks associated with EDTA-enhanced phytoextraction: (1) environmental persistence of EDTA and/or metal-EDTA complex; (2) potential toxicity of EDTA and/or metal-EDTA complex to plants; and (3) leaching and contamination of groundwater. Moreover, field-scale cost of EDTA-enhanced remediation and the role of EDTA in time required for heavy metal remediation is discussed.     

The Effect of EDTA Addition on the Phytoremediation Efficiency of Pb and Cr by Echinochloa crus galii (L.) Beave and Associated Potential Leaching Risk

Metal-contaminated soils constitute a serious environmental problem with adverse consequences for human health. This study was conducted to determine phytoextraction efficiency of Echinochloa crus galii for Pb and Cr and the EDTA-assisted (0. 2.5, 5, 10 mmol kg^?1) phytoextraction and the potential for leaching of the metals during the phytoextraction process. The results revealed that the bioconcentration factors of roots of the plant were relatively higher than the bioconcentration factors of the shoot. Thus, the plant species of E. crus galii would be applicable for Pb and Cr phytostabilization. Addition of EDTA had virtually a significant effect on uptake of the metals by the plant and elevated Pb and Cr concentrations in plant organs as compared with the control. Optimum phytoextraction was observed when 5 mmol kg^?1 EDTA was added in a single dosage 60 days after the plant cultivation and consequently soil Pb and Cr concentration decreased with the passage of time.     

Chemically enhanced phytoextraction of risk elements from a contaminated agricultural soil using Zea mays and Triticum aestivum: performance and metal mobilization over a three year period

Enhanced phytoextraction using EDTA for the remediation of an agricultural soil contaminated with less mobile risk elements Cd and Pb originating from smelting activities in Príbram (Czech Republic) was assessed on the laboratory and the field scale. EDTA was applied to the first years crop Zea mays. Metal mobilization and metal uptake by the plants in the soil were monitored for two additional years when Triticum aestivum was planted. The application ofEDTA effectively increased water-soluble Cd and Pb concentrations in the soil. These concentrations decreased over time. Anyhow, increased concentrations could be still observed in the third experimental year indicating a low possibility of groundwater pollution after the addition of EDTA during and also after the enhanced phytoextraction process under prevailing climatic conditions. EDTA-applications caused phytotoxicity and thereby decreased biomass production and increased Cd and Pb uptake by the plants. Phytoextraction efficiency and phytoextraction potential were too low for Cd and Pb phytoextraction in the field in a reasonable time frame (as less than one-tenth of a percent of total Cd and Pb could be removed). This strongly indicates that EDTA-enhanced phytoextraction as implemented in this study is not a suitable remediation technique for risk metal contaminated soils.     

Chelate-Enhanced Phytoremediation of Soils Polluted with Heavy Metals

In general, hyperaccumulators are low biomass, slow-growing plants. High biomass non-hyperaccumulator plants by themselves are not a valid alternative for phytoextraction as they also have many limitations, such as small root uptake and little root-to-shoot translocation. In this context, chemically-induced phytoextraction (based on the fact that the application of certain chemicals, mostly chelating agents, to the soil significantly enhances metal accumulation by plants) has been proposed as an alternative for the cleaning up of metal polluted soils. But chelate-induced phytoextraction increases the risk of adverse environmental effects due to metal mobilization during extended periods of time. In order to minimize the phytotoxicity and environmental problems associated with the use of chelating agents, nowadays, research is being carried out on the gradual application of small doses of the chelating agent during the growth period. However, EDTA utilization in the future will most likely be limited to ex situconditions where control of the leachates can be achieved. There are other mobilizing agents which are much less harmful to the environment such as citric acid, NTA, and particularly EDDS. Research should also be aimed towards more innovative agronomic practices. Environmentally safe methods of chelate-induced phytoextraction must be developed before steps towards further development and commercialization of this remediation technology are taken. Most importantly, more applied projects in this field are needed to clarify the real potential and risks of this technology.     

几种有机添加剂对遏蓝菜和东南景天吸收提取Zn的效应

通过盆栽试验,比较研究乙二胺四乙酸二钠盐(EDTA)、味精废液、柠檬酸、乙酸、草酸和混合试剂(柠檬酸∶味精废液∶EDTA∶KC l=10∶1∶2∶3)对Zn超累积植物遏蓝菜(T h lasp i caeru lescens)和东南景天(S edum a lf red ii)吸收提取Zn的影响。结果表明:各种添加剂均提高土壤中的水提取态和NH4NO3提取态Zn的含量,其顺序为EDTA混合试剂>味精废液>有机酸。除乙酸和味精废液外,其余添加剂都显著促进遏蓝菜的生长,以混合试剂的增产效果最好;但只有EDTA和混合试剂在浓度为10mm o l/kg土时提高了东南景天的生物量。混合试剂在浓度为6~10 mm o l/kg土时促进遏蓝菜对Zn的吸收和向地上部转移;EDTA和浓度为10mm o l/kg的混合试剂能显著促进东南景天对Zn的吸收和向地上部的转移。因此东南景天配合环境风险较小、用量为10mm o l/kg土的混合试剂较适合我国南方的Zn污染土壤。     

Effect of high boron application on boron content and growth of melons

Synthetic chelates, such as ethylene diamine tetraacetic acid (EDTA), have been shown to enhance phytoextraction of Pb from contaminated soil but also cause leaching of heavy metal-chelate complexes, posing a groundwater contamination threat. In a soil column study, we examined the effect of EDTA and a biodegradable chelate [S,S] isomere of ethylene diamine disuccinate ([S,S]-EDDS), newly introduced in phytoextraction research, on the uptake of Pb by the Chinese cabbage (Brassica rapa) and Pb leaching through the soil profile. Soil water sorption characteristics were modified by acrylamide hydrogel. The addition of 0.1 and 0.2% (w/w) of hydrogel amendments increased soil field water capacity from initial 24.6% to 28.5% and 31.3%, respectively. The additions of 2.5, 5 and 10 mmol EDTA kg^–1 soil were more effective in enhancing Pb plant uptake than comparable [S,S]-EDDS treatments, but caused (as also 10 mmol kg^–1 [S,S]-EDDS additions) unacceptably high Pb leaching in treatments with any soil water sorption conditions tested. The most efficient level of EDTA (10 mmol kg^–1) enhanced plant Pb uptake by 97 times compared to the control. Shoots Pb concentrations reached 500 mg kg^–1 of dry biomass. However, in this treatment 36.2% of total initial Pb was leached from the soil during the first four weeks after chelate addition. Hydrogel soil amendments were more effective in treatments with [S,S]-EDDS than with EDTA. In treatments with 10 mmol kg^–1[S,S]-EDDS hydrogel amended soils, plant Pb uptake was significantly reduced and Pb leach was as high as 44.2% of total initial soil Pb. At lower [S,S]-EDDS concentrations, the effect of hydrogel soil amendment on Pb leaching was the opposite. The addition of 5 mmol kg^–1 [S,S]-EDDS soil to the soil amended with 0.2% hydrogel increased Pb uptake by 18 times while only 0.2% of total initial Pb was leached. In all treatments, the concentrations of Pb in dry plant biomass were far from concentrations required for efficient soil remediation within a reasonable time span.     

Effects of soil amendments and EDTA on lead uptake by Chromolaena odorata: greenhouse and field trial experiments

Greenhouse and field trial experiments were performed to evaluate the use of Chromolaena odorata with various soil amendments for phytoextraction of Pb contaminated soil Pb mine soils contain low amount of nutrients, so the additions of organic (cow manure) and inorganic (Osmocote and NH4NO3 and KCl) fertilizers with EDTA were used to enhance plant growth and Pb accumulation. Greenhouse study showed that cow manure decreased available Pb concentrations and resulted in the highest Pb concentration in roots (4660 mg kg(-1)) and shoots (389.2 mg kg(-1)). EDTA increased Pb accumulation in shoots (17-fold) and roots (11-fold) in plants grown in soil with Osmocote with Pb uptake up to 203.5 mg plant(-1). Application of all fertilizers had no significant effects on relative growth rates of C. odorata. Field trial study showed that C. odorata grown in soil with 99545 mg kg(-1) total Pb accumulated up to 3730.2 and 6698.2 mg kg(-1) in shoots and roots, respectively, with the highest phytoextraction coefficient (1.25) and translocation factor (1.18). These results indicated that C. odorata could be used for phytoextraction of Pb contaminated soil. In addition, more effective Pb accumulation could be enhanced by Osmocote fertilizer. However, the use of EDTA in the field should be concerned with their leaching problems.     

Enhanced Phytoremediation Capacity of Chenopodium album L. Grown on Pb-Contaminated Soils Using EDTA and Reduction of Leaching Risk

Leaching of metals due to enhanced mobility during ethylenediaminetetraacetic acid (EDTA)-assisted phytoextraction has been demonstrated as one of the potential hazards associated with this technology. This study was conducted to determine phytoextraction efficiency of Chenopodium album L. for Pb and EDTA-assisted (1.5, 3, and 9 mmol kg^?1) phytoextraction and potential for leaching of Pb. The results demonstrated that BCF_shoot (bioconcentration factor) was relatively higher than the BCF_root. Translocation factor in the shoot was higher than the roots. Thus, plant species would be applicable for Pb phytoextraction. EDTA enhanced translocation of Pb from roots to shoots. Lead content in the plant parts was maximum in the shoot and root of 9EDTA and 3EDTA, respectively. However, there was no significant difference between 3EDTA and 9EDTA. Lead concentration in the plant parts increased significantly from vegetative stage into flowering stage. Lead content taken up by the plant was lowest when EDTA was applied in a single dose. Therefore, application of EDTA in several increments rather than a single split reduced the leaching risk. Totally, optimum phytoextraction was observed when 3 mmol kg^?1 EDTA was added in triple dosage 60 days after the plant cultivation under triple application mode. The results indicated the plant has the potential for Pb phytoextraction, but it should not be used unless the biomass containing such accumulated metal is removed for disposal. Significant improvement over current ETDA-assisted phytoextraction of Pb may be possible but should be implemented cautiously because of environmental risk.     

Negative Effects of Chelants on Soil Qualities of Five Soil Series

Due to the low phytoavailability of some heavy metals (HMs), a prolonged period is required when phytoextraction is used to remove these HMs from contaminated soils. The use of chelants and other chemical compounds are often used to increase the phytoavailability of the HMs for plant uptake. Negative effects of chemical agents on the soil and groundwater have rarely been reported during chemical-enhanced phytoextraction. This research applied chelants to various soil series with different characteristics to assess their impacts on soil quality. The experimental results showed that the application of 5 mmol kg^?1 of all chelants had a negative effect on the soil quality. This was especially true for electrical conductivity (EC) when diethylene trinitrilo pentaacetic acid (DTPA) was used as the chemical extracting agent.     

Effects of EDTA and EDDS on Heavy Metal Activation and Accumulation of Metals by Soybean in Alkaline Soil

The application of chelating agents for phytoextraction has demonstrated that it is an efficient method to activate heavy metals in polluted soil. We conducted pot experiments using soybean, which has been considered an indicator plant, to study the effects of EDTA and EDDS on heavy metals’ activation, and on the soybean. The study results indicated that EDDS decreased the chlorophyll content of the leaves and increased the malondialdehyde (MDA) content of the soybean. EDTA also decreased the chlorophyll content of the leaves. EDDS had a strong influence on activating Cu (2583-8900-fold) and Zn. The addition of 5 mmol kg^?1 of EDDS markedly increased the uptake of metals. Compared with the control, EDDS increased the Cu uptake (100-205-fold). EDTA greatly increased the activation of heavy metals; it also increased Cu uptake in a concentration-dependent manner. EDTA also increased the biological concentration factor (BCF) and the transfer factor (TF) in a concentration-dependent manner. The BCF and the TF reached maximum levels when 5 mmol kg^?1 EDDS was applied to the pots.     

A Laboratory Assessment of Potentials and Limitations of Using EDTA,Rhamnolipids, and Compost-derived Humic Substances (HS) in Enhanced Phytoextraction of Copper and Zinc Polluted Calcareous Soils

Phytoextraction is an economically and environmentally attractive in-situ method for cleaning heavy metal polluted soil. Phytoextraction is a rather slow process, but it can be enhanced by the application of chelating agents such as the synthetic ethylenediaminetetraacetic acid (EDTA). However, EDTA is persistent, toxic, and can promote heavy metal leaching. Replacement of EDTA by natural, non-toxic compounds such as humic substances (HS) or rhamnolipids (bacterial-produced biosurfactants) might be environmentally attractive but before recommending such alternatives, their suitability must be assessed. Therefore, compost-derived HS and rhamnolipids were compared with EDTA as natural non-toxic alternatives in a multi-step batch extraction test. The test included 10 steps carried out on two Cu and Zn polluted calcareous soils using a solution:soil ratio of 10 (L/kg). In each step, soil was extracted with an extractant containing EDTA, HS, or rhamnolipids corresponding to 250 mmol DOC/kg of soil (3 g C/kg). By HS extraction, each step resulted in the release of ～0.29 mg Cu/L and ～0.19 mg Zn/L, which is considered to enhance plant uptake without leading to unacceptable leaching and toxification of the plants (and the environment), suggesting HS can enhance phytoextraction. In contrast, the EDTA and the rhamnolipid treatments were found to be unsuitable because the EDTA released Cu and Zn in concentrations that may be toxic to plants and can lead to leaching, whereas the rhamnolipids showed insufficient capacity to mobilize Cu (and Zn). However, future investigations in the field are needed to confirm these laboratory results.     

The use of dialdehyde starch derivatives in the phytoremediation of soils contaminated with heavy metals

Products of the reaction between dialdehyde starch and Y-NH₂ compounds (e.g. semicarbazide or hydrazine) are effective ligands for metal ions. The usefulness of these derivatives was tested in the experiment, both in terms of the immobilization of heavy metal ions in soil and the potential application in phytoextraction processes. The experimental model comprised maize and the ions of such metals as: Zn(II), Pb(II), Cu(II), Cd(II), and Ni(II). The amount of maize yield, as well as heavy metal content and uptake by the aboveground parts and roots of maize, were studied during a three-year pot experiment. The results of the study indicate the significant impact of heavy metals on reduced yield and increased heavy metal content in maize. Soil-applied dialdehyde starch derivatives resulted in lower yields, particularly disemicarbazone (DASS), but in heavy metal-contaminated soils they largely limited the negative impact of these metals both on yielding and heavy metal content in plants, particularly dihydrazone (DASH). It was demonstrated that the application of dihydrazone (DASH) to a soil polluted with heavy metals boosted the uptake of Zn, Pb, Cu, and Cd from the soil, hence there is a possibility to use this compound in the phytoextraction of these metals from the soil. Decreased Ni uptake was also determined, hence the possibility of using this compound in the immobilization of this metal. The study showed that dialdehyde starch disemicarbazone was ineffective in the discussed processes.