Feasibility of phytoextraction to remediate cadmium and zinc contaminated soils

A Cd and Zn contaminated soil was mixed and equilibrated with an uncontaminated, but otherwise similar soil to establish a gradient in soil contamination levels. Growth of Thlaspi caerulescens (Ganges ecotype) significantly decreased the metal concentrations in soil solution. Plant uptake of Cd and Zn exceeded the decrease of the soluble metal concentrations by several orders of magnitude. Hence, desorption of metals must have occurred to maintain the soil solution concentrations. A coupled regression model was developed to describe the transfer of metals from soil to solution and plant shoots. This model was applied to estimate the phytoextraction duration required to decrease the soil Cd concentration from 10 to 0.5 mg kg⁻¹. A biomass production of 1 and 5 t dm ha⁻¹ yr⁻¹ yields a duration of 42 and 11 yr, respectively. Successful phytoextraction operations based on T. caerulescens require an increased biomass production.     

Leaching variations of heavy metals in chelator-assisted phytoextraction by Zea mays L. exposed to acid rainfall

Chelant-enhanced phytoextraction method has been put forward as an effective soil remediation method, whereas the heavy metal leaching could not be ignored. In this study, a cropping-leaching experiment, using soil columns, was applied to study the metal leaching variations during assisted phytoextraction of Cd- and Pb-polluted soils, using seedlings of Zea mays, applying three different chelators (EDTA, EDDS, and rhamnolipid), and artificial rainfall (acid rainfall or normal rainfall). It showed that artificial rainfall, especially artificial acid rain, after chelator application led to the increase of heavy metals in the leaching solution. EDTA increased both Cd and Pb concentrations in the leaching solution, obviously, whereas EDDS and rhamnolipid increased Cd concentration but not Pb. The amount of Cd and Pb decreased as the leaching solution increased, the patterns as well matched LRMs (linear regression models), with R-square (R ²) higher than 90 and 82% for Cd and Pb, respectively. The maximum cumulative Cd and Pb in the leaching solutions were 18.44 and 16.68%, respectively, which was amended by EDTA and acid rainwater (pH 4.5), and followed by EDDS (pH 4.5), EDDS (pH 6.5), rhamnolipid (0.5 g kg⁻¹ soil, pH 4.5), and rhamnolipid (pH 6.5).

     

Arbuscular mycorrhizal fungi enhance both absorption and stabilization of Cd by Alfred stonecrop (Sedum alfredii Hance) and perennial ryegrass (Lolium perenne L.) in a Cd-contaminated acidic soil

A greenhouse pot experiment was conducted to compare the phytoextraction efficiencies of Cd by hyper-accumulating Alfred stonecrop (Sedum alfredii Hance) and fast-growing perennial ryegrass (Lolium perenne L.) from a Cd-contaminated (1.6 mg kg⁻¹) acidic soil, and their responses to the inoculations of two arbuscular mycorrhizal (AM) fungal strains, Glomus caledonium 90036 (Gc) and Glomus mosseae M47V (Gm). Ryegrass and stonecrop were harvested after growing for 9 and 27 wk, respectively. Without AM fungal inoculation, the weekly Cd extraction by stonecrop (8.0 μg pot⁻¹) was 4.3 times higher than that by ryegrass (1.5 μg pot⁻¹). Both Gc and Gm significantly increased (P < 0.05) root mycorrhizal colonization rates, soil acid phosphatase activities, and available P concentrations, and thereby plant P absorptions (except for Gm-inoculated ryegrass), shoot biomasses, and Cd absorptions (except for Gm-inoculated stonecrop), while only Gc-inoculated stonecrop significantly accelerated (P < 0.05) the phytoextraction efficiency of Cd by 78%. In addition, both Gc and Gm significantly decreased (P < 0.05) phytoavailable Cd concentrations by 21–38% via elevating soil pH. The results suggested the potential application of hyper-accumulating Alfred stonecrop associated with AM fungi (notably Gc) for both extraction and stabilization of Cd in the in situ treatment of Cd-contaminated acidic soil.     

Eisenia fetida avoidance behavior as a tool for assessing the efficiency of remediation of Pb, Zn and Cd polluted soil

Remediation by means of soil leaching with ethylenediaminetetraacetic acid (EDTA) is capable of extracting the most labile soil fractions, leaving the residual metals in biologically non-available forms. We evaluated the feasibility of the standardized earthworm (Eisenia fetida) avoidance test for assessing the efficiency of soil remediation of Pb, Zn and Cd polluted soil. Chemical extraction tests (six-step sequential extraction, toxicity characteristic leaching procedure, physiologically based extraction test, diethylenediaminepentaacetic acid extraction) indicated that the mobility, oral bioaccessibility and phytoavailability of Pb, Zn and Cd were consistently reduced. However, the avoidance test showed no significant avoidance of polluted soil in favor of that which had been remediated. Pb, Zn and Cd accumulation in E. fetida mirrored the decreasing pattern of metal potential bioavailability gained by leaching the soil with increasing EDTA concentrations. The calculated bioaccumulation factors indicated the possibility of underestimating the metal bioavailability in soil using chemical extraction tests.     

The use of poplar during a two-year induced phytoextraction of metals from contaminated agricultural soils

The efficiency of poplar (Populus nigra L.xPopulus 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.     

Recycling of EDTA solution after soil washing of Pb, Zn, Cd and As contaminated soil

Soil washing with EDTA is known to be an effective means of removing toxic metals from contaminated soil. A practical way of recycling of used soil washing solution remains, however, an unsolved technical problem. We demonstrate here, in a laboratory scale experiment, the feasibility of using acid precipitation to recover up to 50% of EDTA from used soil washing solution obtained after extraction of Pb (5330 mg kg⁻¹), Zn (3400 mg kg⁻¹), Cd (35 mg kg⁻¹) and As (279 mg kg⁻¹) contaminated soil. Up to 100% of EDTA residual in the washing solution and 100%, 97%, 98% and 100% of initial Pb, Zn, Cd and As concentration in the solution, respectively, were removed in an electrolytic cell using a graphite anode. We employed the recovered EDTA and treated washing solution to prepare recycled soil washing solution with the same potential for extracting toxic metals from soil as the original. The efficiency of soil washing depends on the EDTA concentration. Using twice recycled 30 mmol EDTA kg⁻¹ soil, we removed 44%, 20%, 53% and 61% of Pb, Zn, Cd and As, respectively, from contaminated soil.     

Phytoextraction of heavy metal polluted soils using Sedum plumbizincicola inoculated with metal mobilizing Phyllobacterium myrsinacearum RC6b

The aim of this study was to investigate the effects of metal mobilizing plant-growth beneficial bacterium Phyllobacterium myrsinacearum RC6b on plant growth and Cd, Zn and Pb uptake by Sedum plumbizincicola under laboratory conditions. Among a collection of metal-resistant bacteria, P. myrsinacearum RC6b was specifically chosen as a most favorable metal mobilizer based on its capability of mobilizing high concentrations of Cd, Zn and Pb in soils. P. myrsinacearum RC6b exhibited a high degree of resistance to Cd (350 mg L⁻¹), Zn (1000 mg L⁻¹) and Pb (1200 mg L⁻¹). Furthermore, P. myrsinacearum RC6b showed multiple plant growth beneficial features including the production of 1-aminocyclopropane-1-carboxylic acid deaminase, indole-3-acetic acid, siderophore and solubilization of insoluble phosphate. Inoculation of P. myrsinacearum RC6b significantly increased S. plumbizincicola growth and organ metal concentrations except Pb, which concentration was lower in root and stem of inoculated plants. The results suggest that the metal mobilizing P. myrsinacearum RC6b could be used as an effective inoculant for the improvement of phytoremediation in multi-metal polluted soils.     

Hyperaccumulation of zinc by Corydalis davidii in Zn-polluted soils

A field survey was conducted to identify potential Zn accumulators from an artisanal Zn smelting area in southwest China’s Guizhou Province. Hydroponic and soil culture experiments were performed to investigate the accumulation ability of Zn in Corydalis davidii. Zn concentrations in roots, stems and leaves of C. davidii in the smelting site were 1.1-3.5, 1.2-11.2, and 3.3-14 mg g⁻¹, respectively, whereas Zn concentrations in roots, stems and leaves of C. davidii in the contaminated site impacted by the Zn smelting were 1.0-2.4, 1.9-6.5, and 3.0-1.1 mg g⁻¹, respectively. Zn concentrations in leaves and stems of C. davidii were observed at above 10 mg g⁻¹ that refers to the threshold of Zn hyperaccumulator. The concentration distribution of Zn in C. davidii was leaf > stem > root, and the Zn bioaccumulation factors of C. davidii were above 1. It is concluded that C. davidii has high tolerance to concentrate Zn stress, and that C. davidii is a newly discovered Zn-hyperaccumulator with high biomass in the aboveground parts. Based on the cultivation experiments, C. davidii could reduce Zn concentration by 26.6, 21.2, and 10.2 mg kg⁻¹yr⁻¹ by phytoextraction from the smelting slag, Zn-contaminated soil, and background soil, respectively.     

Leaching of heavy metals from contaminated soils using EDTA

Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.     

The exposition of a calcareous Mediterranean soil to toxic concentrations of Cr, Cd and Pb produces changes in the microbiota mainly related to differential metal bioavailability

The involvement of the bacterial community of an agricultural Mediterranean calcareous soil in relation to several heavy metals has been studied in microcosms under controlled laboratory conditions. Soil samples were artificially polluted with Cr(VI), Cd(II) and Pb(II) at concentrations ranging from 0.1 to 5000 mg kg⁻¹ and incubated along 28 d. The lowest concentrations with significant effects in soil respirometry were 10 mg kg⁻¹ Cr and 1000 mg kg⁻¹ Cd and Pb. However, only treatments showing more than 40% inhibition of respirometric activity led to significant changes in bacterial composition, as indicated by PCR-DGGE analyses. Presumable Cr- and Cd-resistant bacteria were detected in polluted microcosms, but development of the microbiota was severely impaired at the highest amendments of both metals. Results also showed that bioavailability is an important factor determining the impact of the heavy metals assayed, and even an inverted potential toxicity ranking could be achieved if their soluble fraction is considered instead of the total concentration. Moreover, multiresistant bacteria were isolated from Cr-polluted soil microcosms, some of them showing the capacity to reduce Cr(VI) concentrations between 26% and 84% of the initial value. Potentially useful strains for bioremediation were related to Arthrobacter crystallopoietes, Stenotrophomonas maltophilia and several species of Bacillus.     

Effects of iron(III)chelates on the solubility of heavy metals in calcareous soils

In this study I evaluated the effects of complexing agents on the solubility of heavy metals in an incubation experiment up to 56 days when complexing agents were applied as Fe-chelates (Fe-EDDS(S,S), Fe-EDDS(mix), Fe-EDTA and Fe-EDDHA) on calcareous soils at a level sufficient to correct Fe chlorosis (0.1 mmol kg⁻¹). Of these ligands, EDDHA was the most efficient in keeping Fe in water-soluble form, and EDDS increased the solubility of Cu and Zn most, and only EDTA increased the solubility of Cd and Pb. EDTA increased the solubility of Ni steadily during the incubation period, equalling about 5-8% of the added EDTA concentration. [S,S]-EDDS was biodegraded within 56 days, whereas EDDS(mix) was less biodegradable. Ni-chelates were the most recalcitrant against biodegradation. The study shows that even a moderate input of chelates to soil increases the solubility of toxic heavy metals and their risk of leaching.     

The potential of willow for remediation of heavy metal polluted calcareous urban soils

Growth performance and heavy metal uptake by willow (Salix viminalis) from strongly and moderately polluted calcareous soils were investigated in field and growth chamber trials to assess the suitability of willow for phytoremediation. Field uptakes were 2-10 times higher than growth chamber uptakes. Despite high concentrations of cadmium (≥80 mg/kg) and zinc (≥3000 mg/kg) in leaves of willow grown on strongly polluted soil with up to 18 mg Cd/kg, 1400 mg Cu/kg, 500 mg Pb/kg and 3300 mg Zn/kg, it is unsuited on strongly polluted soils because of poor growth. However, willow proved promising on moderately polluted soils (2.5 mg Cd/kg and 400 mg Zn/kg), where it extracted 0.13% of total Cd and 0.29% of the total Zn per year probably representing the most mobile fraction. Cu and Pb are strongly fixed in calcareous soils.     

Non-enhanced phytoextraction of cadmium,zinc, and lead by high-yielding crops

Heavy metal soil contamination from mining and smelting has been reported in several regions around the world, and phytoextraction, using plants to accumulate risk elements in aboveground harvestable organs, is a useful method of substantially reducing this contamination. In our 3-year experiment, we tested the hypothesis that phytoextraction can be successful in local soil conditions without external fertilizer input. The phytoextraction efficiency of 15 high-yielding crop species was assessed in a field experiment performed at the Litavka River alluvium in the P?íbram region of Czechia. This area is heavily polluted by Cd, Zn, and Pb from smelter installations which also polluted the river water and flood sediments. Heavy metal concentrations were analyzed in the herbaceous plants’ aboveground and belowground biomass and in woody plants’ leaves and branches. The highest Cd and Zn mean concentrations in the aboveground biomass were recorded in Salix x fragilis L. (10.14 and 343 mg kg^?1 in twigs and 16.74 and 1188 mg kg^?1 in leaves, respectively). The heavy metal content in woody plants was significantly higher in leaves than in twigs. In addition, Malva verticillata L. had the highest Cd, Pb, and Zn concentrations in herbaceous species (6.26, 12.44, and 207 mg kg^?1, respectively). The calculated heavy metal removal capacities in this study proved high phytoextraction efficiency in woody species; especially for Salix × fragilis L. In other tested plants, Sorghum bicolor L., Helianthus tuberosus L., Miscanthus sinensis Andersson, and Phalaris arundinacea L. species are also recommended for phytoextraction.     

Salinity increases mobility of heavy metals in soils

The effect of salinity induced by CaCl₂, MgCl₂, NaCl and Na₂SO₄ on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl₂ and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl₂ was applied, Cd and Cu were mobilized the most. Finally, an increase of Na₂SO₄ also promoted the strongest mobilization of Cd and Cu.As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl₂ and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions.The main mechanism regulating Pb and Cd mobility was competition with Ca²⁺ for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg²⁺. The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca²⁺ for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.     

Effects of phytoextraction on heavy metal concentrations and pH of pore-water of biosolids determined using an in situ sampling technique

Heavy metal concentrations and pH of pore-water in contaminated substrates are important factors in controlling metal uptake by plants. We investigated the effects of phytoextraction on these properties in the solution phase of biosolids and diluted biosolids in a 12-month phytoextraction column experiment. Phytoextraction using Salix and Populus spp. temporarily decreased pore-water pH of the substrates over the experimental period followed by a return to initial pH conditions. Salix × reichardtii and Populus balsamifera effectively extracted Ni, Zn and Cd and actively mobilized these metals from the solid to the solution phase. S. × reichardtii had the stronger effect on mobilization of metals due to its larger root system. Phytoextraction did not affect Cu in the solution phase of the biosolids. Heavy metals were leached down to lower depths of the columns during the phytoextraction process.     

Chelate-induced phytoextraction of metal polluted soils with Brachiaria decumbens

Chelate-induced phytoextraction with high biomass plant species has been proposed for the clean-up of heavy metal polluted soils. In the current work, the effect of the application of two different chelating agents, i.e. EDTA and EDDS, on the metal phytoextraction capacity of Brachiaria decumbens was studied. Although EDTA was, in general, more effective in soil metal solubilization, EDDS, a chelate less harmful to the environment, was more efficient inducing metal accumulation in B. decumbens shoots than EDTA. Indeed, in a moderately heavy metal polluted soil, EDDS caused a 2.54, 2.74 and 4.30-fold increase in Cd, Zn, and Pb shoot metal concentration, respectively, as compared to control plants. In this same soil, EDTA caused a 1.77, 1.11 and 1.87-fold increase in Cd, Zn, and Pb shoot metal concentration, respectively, as compared to control plants. EDDS was also more effective than EDTA in stimulating the translocation of metals from roots to shoots. B. decumbens plants were able to grow in the metal polluted soils showing no visible symptoms of phytotoxicity, which suggests their metal tolerance. Finally, B. decumbens, a fast-growing, high biomass, aluminum tolerant plant species, that has a well-established agronomic system, fulfills most of the requirements for chemically-induced phytoextraction.     

Bioaccumulation in Porcellio scaber (Crustacea, Isopoda) as a measure of the EDTA remediation efficiency of metal-polluted soil

Leaching using EDTA applied to a Pb, Zn and Cd polluted soil significantly reduced soil metal concentrations and the pool of metals in labile soil fractions. Metal mobility (Toxicity Characteristic Leaching Procedure), phytoavailability (diethylenetriaminepentaacetic acid extraction) and human oral-bioavailability (Physiologically Based Extraction Test) were reduced by 85-92%, 68-91% and 88-95%, respectively. The metal accumulation capacity of the terrestrial isopod Porcellio scaber (Crustacea) was used as in vivo assay of metal bioavailability, before and after soil remediation. After feeding on metal contaminated soil for two weeks, P. scaber accumulated Pb, Zn and Cd in a concentration dependent manner. The amounts of accumulated metals were, however, higher than expected on the basis of extraction (in vitro) tests. The combined results of chemical extractions and the in vivo test with P. scaber provide a more relevant picture of the availability stripping of metals after soil remediation.     

Effects of sewage sludge biochar on plant metal availability after application to a Mediterranean soil

Pyrolytic conversion of sewage sludge into biochar could be a sustainable management option for Mediterranean agricultural soils. The aim of this work is to evaluate the effects of biochar from sewage sludge pyrolysis on soil properties; heavy metals solubility and bioavailability in a Mediterranean agricultural soil and compared with those of raw sewage sludge. Biochar (B) was prepared by pyrolysis of selected sewage sludge (SL) at 500 °C. The pyrolysis process decreased the plant-available of Cu, Ni, Zn and Pb, the mobile forms of Cu, Ni, Zn, Cd and Pb and also the risk of leaching of Cu, Ni, Zn and Cd. A selected Mediterranean soil was amended with SL and B at two different rates in mass: 4% and 8%. The incubation experiment (200 d) was conducted in order to study carbon mineralization and trace metal solubility and bioavailability of these treatments. Both types of amendments increased soil respiration with respect to the control soil. The increase was lower in the case of B than when SL was directly added. Metals mobility was studied in soil after the incubation and it can be established that the risk of leaching of Cu, Ni and Zn were lower in the soil treated with biochar that in sewage sludge treatment. Biochar amended samples also reduced plant availability of Ni, Zn, Cd and Pb when compared to sewage sludge amended samples.     

Moderate phosphorus application enhances Zn mobility and uptake in hyperaccumulator Sedum alfredii

While phytoextraction tools are increasingly applied to remediation of contaminated soils, strategies are needed to optimize plant uptake by improving soil conditions. Mineral nutrition affects plant growth and metal absorption and subsequently the accumulation of heavy metal through hyper-accumulator plants. Microcosm experiments were conducted in greenhouse to examine the effect of different phosphorus (P) sources on zinc (Zn) phytoextraction by Sedum alfredii in aged Zn-contaminated paddy soil. The Zn accumulation, soil pH, microbial biomass and enzyme activity, available Zn changes. and Zn phytoremediation efficiency in soil after plant harvest were determined. Upon addition of P, Zn uptake of S. alfredii significantly increased. Mehlich-3 extractable or the fractions of exchangeable and carbonate-bound soil Zn were significantly increased at higher P applications. Soil pH significantly decreased with increasing P application rates. Soil microbial biomass in the P-treated soils was significantly higher (P?<?0.05) than those in the control. Shoot Zn concentration was positively correlated with Mehlich-3 extractable P (P?<?0.0001) or exchangeable/carbonate-bound Zn (P?<?0.001), but negatively related to soil pH (P?<?0.0001). These results indicate that application of P fertilizers has the potential to enhance Zn mobility and uptake by hyperaccumulating plant S. alfredii, thus increasing phytoremediation efficiency of Zn-contaminated soils.     

Kinetic characterizing of soil trace metal availability using Soil/EDTA/Chelex mixture

The kinetic aspects are not usually tackled when mimicking the soil trace metal mobilization. In this work, a simple procedure is developed for measuring the kinetics of Pb, Cu and Cd transfer from the soil solid phase towards a resin sink. A ternary system of Soil/EDTA/Chelex was employed for mimicking the metal transfer from two agricultural soil samples into the Chelex. Two different kinetic regimes (P₁ and P₂) were observed. The kinetic profile of Pb was distinctly different from those of Cd and Cu. Basing on kinetic principles, two kinetic models were proposed for estimating the apparent rate constants of leaching and removal processes in, respectively, two binary mixtures of soil/EDTA and EDTA extracts/Chelex. Contrary to Pb, solid phase pools of Cd and Cu exchanged with the solution on short time scales. The kinetic rate of desorption occurred in following order: Pb < Cu ? Cd. Comparing the kinetics of binary systems, the desorption process was hypothesized to control the metal transfer. The parameters related to the desorption process were extended to the kinetic regimes of Soil/EDTA/Chelex and revealed that the soil to Chelex transfer of Pb is under kinetics control whereas the bulk concentration (affected by the size of particulate reservoir) is likely to control the Cd transfer. Cu presents an intermediate case.