Chelator induced phytoextraction and in situ soil washing of Cu

In a soil column experiment, we investigated the effect of 5 mmol kg(-1) soil addition of citric acid, ethylenediamine tetraacetate (EDTA), diethylenetriamine-pentaacetate (DTPA) and [S,S]-stereoisomer of ethylenediamine-disuccinate (EDDS) on phytoextraction of Cu from a vineyard soil with 162.6 mg kg(-1) Cu, into the test plant Brassica rapa var. pekinensis. We also examined the use of a horizontal permeable barrier, composed of layers of nutrient enriched sawdust and apatite, for reduction of chelator induced Cu leaching. The addition of all chelators, except citric acid, enhanced Cu mobility and caused leaching of 19.5-23% of initial total Cu from the soil column. However, Cu plant uptake did not increase accordingly; the most effective was the EDDS treatment, in which plant Cu concentration reached 37.8 +/-1.3 mg kg(-1) Cu and increased by 3.3-times over the control treatment. The addition of none of the chelators in the concentration range from 5 to 15 mmol kg(-1) exerted any toxic effect on respiratory soil microorganisms. When EDDS was applied into the columns with horizontal permeable barriers, only 0.53 +/- 0.32% of the initial total Cu was leached. Cu (36.7%) was washed from the 18 cm soil layer above the barrier and accumulated in the barrier. Our results indicate that rather than for a reduction of Cu leaching during rather ineffective chelate induced Cu phytoextraction, horizontal permeable barriers could be more effective in a new remediation technique of controlled in situ soil washing of Cu with biodegradable chelates.     

Heap leaching of Pb and Zn contaminated soil using ozone/UV treatment of EDTA extractants

The feasibility of a novel EDTA-based soil heap leaching method with treatment and reuse of extractants in a closed process loop was evaluated on a laboratory scale. Ozone and UV irradiation were used for oxidative decomposition of EDTA-metal complexes in extractants from Pb (1243 mg kg(-1)) and Zn (1190 mg kg(-1)) contaminated soil. Released metals were absorbed in a commercial metal absorbent Slovakite. Six-consecutive additions of 2.5 mmol kg(-1) EDTA (total 15 mmol kg(-1) EDTA) removed 49.6 +/- 0.6% and 19.7 +/- 1.7% of initial total Pb and Zn from soil (4.6 kg) packed in 22 cm high columns. The efficiency of extraction was similar to small-scale simulations of heap leaching (15 0 g of soil), where EDTA used in the same manner removed 49.7 +/- 1.0% and 13.7 +/- 0.4% of Pb and Zn. The new heap leaching method produced discharge extractant with fairly low final concentrations of Pb, Zn and EDTA (1.98 +/- 2.17 mg l(-1), 4.55 +/- 2.36 mg l(-1), and 0.05 +/- 0.04 mM, respectively), which could presumably be reduced even further with continuation of treatment. The results of our study indicate that for soils contaminated primarily with Pb, treating the EDTA extractants with ozone/UV and reuse of extractants enables efficient soil heap leaching with very little or no wastewater generation, easy control over emissions, and lowers the requirements for process water.     

Environmental risk assessment for trisodium [S,S]-ethylene diamine disuccinate, a biodegradable chelator used in detergent applications

Environmental safety data are presented for [S,S]-Ethylene Diamine Disuccinate ([S,S]EDDS), a new, biodegradable, strong transition metal chelator. An environmental risk assessment for its use in detergent applications, which takes into account the chelating properties of [S,S]-EDDS, is proposed.

A property of [S,S]-EDDS that distinguishes it from other strong transition metal chelators is its, “ready” and transparent (no recalcitrant metabolites) biodegradation profile. Because its sorption to activated sludge solids is low ( Kp of 40 1/kg), removal of [S,S]EDDS during sewage treatment, which is greater than 96% as determined by the Continuous Activated Sludge test , is mainly ascribed to biodegradation. At projected use volumes in detergent applications [S,S] - EDDS predicted steady-state concentration in rivers leaving the mixing zone will be below 5 pg/I due to rapid biodegradation. [S,S]-EDDS exhibits low toxicity to fish and Daphnia ( both EC₅₀s> 1000 mg/l). By contrast, due to limitation of the algal test for chelators apparent toxicity was observed (EC₅₀ = 0.290 mg/l, NOEC - No observable Effect Concentration = 0.125 mg/l). Schowanek et al. [1] demonstrated that this is not toxicity sensu stricto but a chelation effect of trace metals in the test medium and of resulting essential nutrients limitation. This requires specific attention when the results of algal toxicity are to be extrapolated to a field situation to perform realistic risk assessment. Metal speciation calculations, using MINEQL+, show that at the predicted environmental concentrations of [S,S] - EDDS (1–5 μg/l), such a chelation effect would be insignificant. These calculations allow to estimate the NOEC for chelation effects in the field to be in the range of 0.250-0.500 mg/l, depending on the background water chemistry. These values are well above the laboratory NOEC.

An environmental risk assessment was performed using the EUSES (1.0) program. EUSES is currently the EU recommended tool for conducting risk assessments (TGD 1995). It was applied to estimate the river water and soil concentrations from production, formulation and private use life stages. The estimated PEC/PNEC ratio in all relevant environmental compartments is smaller than 1, indicating “no immediate concern” at the anticipated usage level.     

Leaching and uptake of heavy metals by ten different species of plants during an EDTA-assisted phytoextraction process

In a pot experiment, the potential use of 10 plant species, including six dicotyledon species and four monocotyledon species, was investigated for the EDTA-enhanced phytoextraction of Pb from contaminated soil. Mung bean and buckwheat had a higher sensitivity to the EDTA treatment in soils. In the 2.5 and 5.0 mmol kg(-1) EDTA treatments, the Pb concentrations in the shoots of the six dicotyledon species ranged from 1,000 to 3,000 mg kg(-1) of dry matter, which were higher than those of the monocotyledon species. The highest amount of phytoextracted Pb (2.9 mg Pb pot(-1)) was achieved in sunflowers, due to the high concentration of Pb in their shoots and large biomass, followed by corns (1.8 mg Pb pot(-1)) and peas (1.1 mg Pb pot(-1)). The leaching behavior of heavy metals as a result of applying EDTA to the surface of the soil was also investigated using short soil-leaching columns (9.0-cm diameter, 20-cm height) by the percolation of artificial rainfall. About 3.5%, 15.8%, 13.7% and 20.6% of soil Pb, Cu, Zn and Cd, respectively, were leached from the soil columns after the application of 5.0 mmol kg(-1) of EDTA. The growth of sunflowers in the soil columns had little effect on the amount of metals that were leached out. This was probably due to the shallowness of the layer of soil, the short time-span of the uptake of metals by the plant and the plant's simple root systems.     

The two-phase leaching of Pb, Zn and Cd contaminated soil using EDTA and electrochemical treatment of the washing solution

The feasibility of a novel two-phase method for remediation of Pb (1374 mg kg(-1)), Zn (1007 mg kg(-1)), and Cd (9.1 mg kg(-1)) contaminated soil was evaluated. In the first phase we used EDTA for leaching heavy metals from the soil. In the second phase we used an electrochemical advanced oxidation process (EAOP) for the treatment and reuse of washing solution for soil rinsing (removal of the soil-retained, chelant-mobilized metallic species). In EAOP, a boron-doped diamond anode was used for the generation of hydroxyl radicals and oxidative decomposition of EDTA-metal complexes at a constant current density (15 mA cm(-2)). The released metals were removed from the solution by filtration as insoluble participate and by electro-deposition on the cathode. Four consecutive additions of 5.0 mm ol kg(-1) EDTA (total 20 mmol kg(-1)) removed 44% Pb, 14% Zn and 35% Cd from the soil. The mobility of the Pb, Zn and Cd (Toxicity Characteristic Leaching Procedure) left in the soil after remediation was reduced by 1.6, 3.4 and 1.5 times, respectively. The Pb oral availability (Physiologically Based Extraction Test) in the simulated stomach phase was reduced by 2.4 and in the intestinal phase by 1.7 times. The discharge solution was clear, almost colorless, with pH 7.73 and 0.47 mg L(-1) Pb, 1.03 mg L(-1) Zn, bellow the limits of quantification of Cd and 0.023 mM EDTA. The novel method enables soil leaching with small water requirements and no wastewater generation or other emissions into the environment.     

氯化铁和硫酸铁对酸性土壤中有效态镉和铅污染的修复作用

采用浸泡实验法研究了氯化铁和硫酸铁对酸性土壤中有效态镉和铅污染的修复效果,结果表明,氯化铁和硫酸铁均能有效去除土壤有效态镉和铅污染,Fe(Ⅲ)用量为50~100 mmol/kg时,有效态Cd和Pb的去除效果可达70%~96%。氯化铁和硫酸铁能去除土壤中的水溶态、碳酸盐结合态、腐殖酸结合态、铁锰氧化物结合态和强有机结合态Cd和Pb及交换态Cd。氯化铁和硫酸铁对Cd均既有洗脱修复作用又有固定修复作用,且洗脱修复作用的贡献稍大;氯化铁用量较小时(50 mmol/kg)对Pb既有固定修复又有洗脱修复作用,固定修复作用稍大;用量较大时(100 mmol /kg),对Pb只有洗脱修复作用。硫酸铁对Pb的修复作用则以固定修复作用为主,洗脱修复作用很小。     

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.     

Electrochemical EDTA recycling with sacrificial Al anode for remediation of Pb contaminated soil

Recycling chelant is a precondition for cost-effective EDTA-based soil remediation. Extraction with EDTA removed 67.5% of Pb from the contaminated soil and yielded washing solution with 1535 mg L⁻¹ Pb and 33.4 mM EDTA. Electrochemical treatment of the washing solution using Al anode, current density 96 mA cm⁻² and pH 10 removed 90% of Pb from the solution (by electrodeposition on the stainless steel cathode) while the concentration of EDTA in the treated solution remained the same. The obtained data indicate that the Pb in the EDTA complex was replaced by electro-corroded Al after electro-reduction of the EDTA and subsequently removed from the solution. Additional soil extraction with the treated washing solution resulted in total removal of 87% of Pb from the contaminated soil. The recycled EDTA retained the Pb extraction potential through several steps of soil extraction and washing solution treatment, although part of the EDTA was lost by soil absorption.     

Effect of multiple washing operations on the removal of potentially toxic metals from an alkaline farmland soil and the strategy for agricultural reuse

Few studies have carried out soil washing experiments using pot experiments to simulate in situ soil washing operations, particularly for alkaline soils. This study explored the effects of multiple washing operations using pot experiments on the removal efficiencies of potentially toxic metals (PTM) from alkaline farmland soil and the reuse strategy of washed soil for safe agricultural production. The results showed that the removal efficiencies of Cd, Pb, Cu, and Zn after seven washings with a mixed chelator (EDTA, GLDA, and citric acid) were 41.1%, 47.1%, 14.7%, and 26.5%, respectively, which was close to the results of the EDTA treatment. For the alkaline soil studied, the second washing with the mixed chelators most effectively removed PTM owing to the activation of them after the first washing operation. The mixed chelator more effectively increased the proportion of stable fraction of PTM and maintained soil nutrients (e.g., nitrogen content) than EDTA, indicating little disturbance of alkaline soil quality after washing with the mixed chelator. After the amendment of the washed soil, there was no visible difference in the biomass weight of crops from the soils washed with different agents, indicating that the inhibitory effect of both washing agents on plant growth was effectively alleviated. The Cd and Pb contents in Z. mays were below the threshold of Hygienical Standard for Feeds of China (GB 13078–2017) (1 and 30 mg·kg^?1). Moreover, after three cropping operations, the available concentrations of PTM in the soil washed with the mixed chelator were lower than those in the soil washed with EDTA, indicating the value and potential of agricultural reuse of alkaline farmland soil washed with the mixed chelator.

Graphical abstract

     

Scaling up a treatment to simultaneously remove persistent organic pollutants and heavy metals from contaminated soils

Soil washing is a treatment process that can be used to remediate both organic and inorganic pollutants from contaminated soils, sludges, and sediments. A soil washing procedure was evaluated utilizing about 100 g samples of soil that had been field-contaminated with arsenic, chromium, copper, pentachlorophenol (PCP), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). The highest level of mobilization/detoxification was achieved in three soil washes with a mixture of 0.1M [S,S]-ethyelnediaminedisuccinate ([S,S]-EDDS) and 2% Brij 98 at pH 9 with 20 min of ultrasonication treatment at room temperature. This combination mobilized 70% of arsenic, 75% of chromium, 80% of copper, 90% of PCP, and 79% of PCDDs and PCDFs, so that the decontaminated soil met the maximum acceptable concentrations of the generic C-level criteria regulated by the Ministère du Développement Durable, de l’Environnement et des Parcs for the Province of Québec, Canada.The organic pollutants were back-extracted from the aqueous suspension with hexane. Heavy metals were virtually completely precipitated from the aqueous washing suspension with Mg⁰ particles at room temperature. The PCP was detoxified by catalytic hydrodechlorination with a stream of 5% (v/v) H₂-supercritical CO₂ that transported the organosoluble fraction through a reaction chamber containing 2% Pd/γ-Al₂O₃.In toto, this soil washing procedure demonstrates that persistent organic pollutants and selected heavy metals can be co-extracted efficiently from a field-contaminated soil with three successive washes with the same soil washing solution containing [S,S]-EDDS and a non-ionic surfactant (Brij 98) in admixture. An industrial-scale ex situ soil washing procedure with a combination of a non-ionic surfactant and a complexing reagent seems to be a plausible remediation technique for this former wooden utility pole storage facility.     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Effects of lead and chelators on growth, photosynthetic activity and Pb uptake in Sesbania drummondii grown in soil

Effects of lead (Pb) and chelators, such as EDTA, HEDTA, DTPA, NTA and citric acid, were studied to evaluate the growth potential of Sesbania drummondii in soils contaminated with high concentrations of Pb. S. drummondii seedlings were grown in soil containing 7.5 g Pb(NO(3))(2) and 0-10 mmol chelators/kg soil for a period of 2 and 4 weeks and assessed for growth profile (length of root and shoot), chlorophyll a fluorescence kinetics (F(v)/F(m) and F(v)/F(o)) and Pb accumulations in root and shoot. Growth of plants in the presence of Pb+chelators was significantly higher (P<0.05) than the controls grown in the presence of Pb alone. F(v)/F(m) and F(v)/F(o) values of treated seedlings remained unaffected, indicating normal photosynthetic efficiency and strength of plants in the presence of chelators. On application of chelators, while root uptake of Pb increased four-five folds, shoot accumulations increased up to 40-folds as compared to controls (Pb only) depending on the type of chelator used. Shoot accumulations of Pb varied from 0.1 to 0.42% (dry weight) depending on the concentration of chelators used.     

Use of vegetable oil in a pilot-scale denitrifying barrier

Nitrate in drinking water is a hazard to both humans and animals. Contaminated water can cause methemoglobinemia and may pose a cancer risk. Permeable barriers containing innocuous oils, which stimulate denitrification, can remove nitrate from flowing groundwater. For this study, a sand tank (1.1 x 2.0 x 0.085 m in size) containing sand was used as a one-dimensional open-top scale model of an aquifer. A meter-long area near the center of the tank contained sand coated with soybean oil. This region served as a permeable denitrifying barrier. Water containing 20 mg l(-1) nitrate-N was pumped through the barrier at a high flow rate, 1112 l week(-1), for 30 weeks. During the 30-week study, the barrier removed 39% of the total nitrate-N present in the water. The barrier was most efficient during the first 10 weeks of the study when almost all of the nitrate and nitrogen was removed. Efficiency declined with time so that by week 30 almost no nitrate was removed by the system. Nitrite levels in the effluent water remained low throughout the study. Barriers could be used to protect groundwater from nitrate contamination or for the in situ treatment of contaminated water. At the low flow rates that exist in most aquifers, such barriers should be effective at removing nitrate from groundwater for a much longer period of time.     

Influence of ozonation on extractability of Pb and Zn from contaminated soils

The effect of soil ozonation on Pb and Zn extraction with EDTA, bioavailability (Ruby's Physiologically Based Extraction Test, PBET) and mobility (Toxicity Characteristic Leaching Procedure, TCLP) of Pb was studied on contaminated soils taken from 7 different locations in the Mezica Valley, Slovenia. EDTA extraction (40 mmol kg(-1)) removed from 27.4+/-1.5% to 64.8+/-1.5% of Pb, and from 1.9+/-0.2% to 22.4+/-2.0% of Zn from tested soils, and significantly reduced soil Pb bioavailability (PBET) and mobility (TCLP). Pretreatment of tested soils with ozone before EDTA extraction enhanced EDTA extractability of Pb for 11.0 to 28.9%, but had no effect on the extractability of Zn. In most of the soils, ozonation had no statistically significant effect on bioavailability and mobility of Pb, residual after EDTA extraction. Using linear regression analysis we found a significant increase (p<0.01) in EDTA extractability of Pb after soil ozonation in soils with a higher initial Pb content. EDTA extractability of Pb after soil ozonation was also significantly higher for soils with a lower Pb extractability when treated with EDTA alone. We found no correlation between soil organic matter content and the percentage of the Pb fraction bound to soil organic matter (where from 25.6+/-1.3% to 73.2+/-0.6% of Pb reside in tested soils) and Pb extractability with EDTA after soil ozonation.     

Remediation of toxic metal contaminated soil by washing with biodegradable aminopolycarboxylate chelants

Ex situ soil washing with synthetic extractants such as, aminopolycarboxylate chelants (APCs) is a viable treatment alternative for metal-contaminated site remediation. EDTA and its homologs are widely used among the APCs in the ex situ soil washing processes. These APCs are merely biodegradable and highly persistent in the aquatic environments leading to the post-use toxic effects. Therefore, an increasing interest is focused on the development and use of the eco-friendly APCs having better biodegradability and less environmental toxicity. The paper deals with the results from the lab-scale washing treatments of a real sample of metal-contaminated soil for the removal of the ecotoxic metal ions (Cd, Cu, Ni, Pb, and Zn) using five biodegradable APCs, namely [S,S]-ethylenediaminedisuccinic acid, imminodisuccinic acid, methylglycinediacetic acid, DL-2-(2-carboxymethyl) nitrilotriacetic acid (GLDA), and 3-hydroxy-2,2′-iminodisuccinic acid. The performance of those biodegradable APCs was evaluated for their interaction with the soil mineral constituents in terms of the solution pH and metal-chelant stability constants, and compared with that of EDTA. Speciation calculations were performed to identify the optimal conditions for the washing process in terms of the metal-chelant interactions as well as to understand the selectivity in the separation ability of the biodegradable chelants towards the metal ions. A linear relationship between the metal extraction capacity of the individual chelants towards each of the metal ions from the soil matrix and metal-chelant conditional stability constants for a solution pH greater than 6 was observed. Additional considerations were derived from the behavior of the major potentially interfering cations (Al, Ca, Fe, Mg, and Mn), and it was hypothesized that use of an excess of chelant may minimize the possible competition effects during the single-step washing treatments. Sequential extraction procedure was used to determine the metal distribution in the soil before and after the extractive decontamination using biodegradable APCs, and the capability of the APCs in removing the metal ions even from the theoretically immobilized fraction of the contaminated soil was observed. GLDA appeared to possess the greatest potential to decontaminate the soil through ex situ washing treatment compared to the other biodegradable chelants used in the study.     

Optimizing the molarity of a EDTA washing solution for saturated-soil remediation of trace metal contaminated soils

Three experiments were conducted to optimize the use of ethylenediaminetetraacetic acid (EDTA) for reclaiming urban soils contaminated with trace metals. As compared to Na(2)EDTA, (NH(4))(2)EDTA extracted 60% more Zn and equivalent amounts of Cd, Cu and Pb from a sandy loam. When successively saturating and draining loamy sand columns during a washing cycle, which submerged it once with a (NH(4))(2)EDTA wash and four times with deionised water, the post-wash rinses largely contributed to the total cumulative extraction of Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn. Both the washing solution and the deionised water rinses were added in a 2:5 liquid to soil (L:S) weight ratio. For equal amounts of EDTA, concentrating the washing solution and applying it and the ensuing rinses in a smaller 1:5 L:S weight ratio, instead of a 2:5 L:S weight ratio, increased the extraction of targeted Cr, Cu, Ni, Pb and Zn.     

Evaluation of surrogate measures of cadmium, lead, and zinc bioavailability to Eisenia fetida

We evaluated weak-electrolyte (0.1 M Ca(NO3)2) soil extractions and ion-exchange membranes coated with a metal chelator as measures of Cd, Pb, and Zn bioavailability in spiked artificial soil by comparing their metal availability estimates to acute lethal toxicity in the earthworm Eisenia fetida. Ca(NO3)2 extractions were precisely related to toxicity in all toxicity tests, and enabled the development of time-independent LC50S (incipient lethal-levels, ILLs) calculated using exposure levels based on extraction data. ILLs with 95% CIs for the Cd, Pb, and Zn toxicity tests were 9.8 (9.4-10.3), 1.16 (1.11-1.22), and 6.33 (6.18-6.49) Ca(NO3)2-extractable mmol metal/kg soil, respectively. Mixture toxicity of Cd, Pb, and Zn, assessed using the toxic unit (TU) approach, was 1.35 TU, suggesting additivity. Chelating ion-exchange membrane uptake was variable, and not well related to toxicity. Weak-electrolyte extractions show promise as precise, inexpensive surrogate measures of Cd, Pb, and Zn bioavailability in soil.     

Evaluation of chemical immobilization treatments for reducing heavy metal transport in a smelter-contaminated soil

Three chemical immobilization materials, agricultural limestone (AL), mineral rock phosphate (RP), and diammonium phosphate (DAP), were evaluated using solute transport experiments to determine their ability to reduce subsurface heavy metal transport in a smelter contaminated soil. Percent reductions in metals transported were based on comparison with cumulative totals of metal species eluted through 60 pore volumes from an untreated soil. Reductions of metal eluted from the AL treatment were 55% for Cd, 45.2% for Pb, and 21.9% for Zn. Rock phosphate mixed with soil at 60 and 180 g kg(-1) was generally ineffective for reducing Cd, Pb, and Zn elution with <27% reduction for Cd, Pb, and Zn. Rock phosphate placed under contaminated soil as a reactive barrier (i.e. layered RP) at 180 g kg(-1) reduced Cd 53% and Zn 24%, and was the most efficient treatment for reducing Pb (99.9%) transport. DAP treatments were superior to all other materials for reducing Cd and Zn elution with reduction >77% for Zn and >91% for Cd from the 90 g DAP kg(-1) treatment. Increasing DAP from 10 to 90 g kg(-1) increased total arsenic released from 0.13 to 29.5 mg kg(-1) and total P eluted from 2.31 to 335 mg. DAP at 10 g kg(-1) was the most effective treatment for immobilizing the combination of Cd, Pb, and Zn, with reductions of 94.6, 98.9, and 95.8%, respectively.     

EDTA在铅污染土壤治理中的优化处理方法

为了探究EDTA在土壤重金属污染治理中的优化处理方法,采用湿筛和水中重力沉降的方法,从人工Pb污染土壤（原土）中分离提取砂土、粉土和粘土,分析讨论了EDTA对土壤中Pb的去除效果,并从EDTA清洗前后土壤中Pb的BCR形态分布出发,分析了EDTA对不同粒径土壤中各形态Pb的去除效果。研究发现,实验用土壤中砂土、粉土和粘土含量分别为11.2%、75.6%和13.2%,EDTA浓度越高,土壤中Pb去除效果越好,且砂土中Pb最易被去除（~100%）,粉土与原土其次（88.66%~96.50%）,粘土最难被去除（64.78%~79.60%）,但随着EDTA浓度增加,粒径对去除Pb的影响减弱。在土壤修复实践中,可通过利用不同浓度EDTA处理不同粒径土壤的方法达到优化效果。BCR形态分布说明外源性Pb进入土壤后主要以弱酸提取态和可还原态存在,EDTA清洗主要去除弱酸提取态和可还原态,粘土中的各形态去除率均最小。     

The EDTA effect on phytoextraction of single and combined metals-contaminated soils using rainbow pink (Dianthus chinensis)

Rainbow pink (Dianthus chinensis), a potential phytoextraction plant, can accumulate high concentrations of Cd from metal-contaminated soils. The soils used in this study were artificially added with different metals including (1) CK: original soil, (2) Cd-treated soil: 10 mg Cd kg(-1), (3) Zn-treated soil: 100 mg Zn kg(-1), (4) Pb-treated soil: 1000 mg Pb kg(-1), (5) Cd-Zn-treated soil: 10 mg Cd kg(-1) and 100 mg Zn kg(-1), (6) Cd-Pb-treated soil: 10 mg Cd kg(-1) and 1000 mg Pb kg(-1), (7) Zn-Pb-treated soil: 100 mg Zn kg(-1) and 1000 mg Pb kg(-1), and (8) Cd-Zn-Pb-treated soil: 10 mg Cd kg(-1), 100 mg Zn kg(-1), and 1000 mg Pb kg(-1). Three concentrations of 2Na-EDTA solutions (0 (control), 2, and 5 mmol kg(-1) soil) were added to the different metals-treated soils to study the influence of applied EDTA on single and combined metals-contaminated soils phytoextraction using rainbow pink. The results showed that the Cd, Zn, Pb, Fe, or Mn concentrations in different metals-treated soil solutions significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). The metal concentrations in different metals-treated soils extracted by deionized water also significantly increased after applying 5 mmol EDTA kg(-1) (p<0.05). Because of the high extraction capacity of both 0.005 M DTPA (pH 5.3) and 0.05 M EDTA (pH 7.0), applying EDTA did not significantly increase the Cd, Zn, or Pb concentration in both extracts for most of the treatments. Applying EDTA solutions can significantly increase the Cd and Pb concentrations in the shoots of rainbow pink (p<0.05). However, this was not statistically significant for Zn because of the low Zn concentration added into the contaminated soils. The results from this study indicate that applying 5 mmol EDTA kg(-1) can significantly increase the Cd, Zn, or Pb concentrations both in the soil solution or extracted using deionized water in single or combined metals-contaminated soils, thus increasing the accumulated metals concentrations in rainbow pink shoots. The proposed method worked especially well for Pb (p<0.05). The application of 2 mmol EDTA kg(-1) might too low to enhance the phytoextraction effect when used in silty clay soils.