Removal of Heavy Metals from Calcareous Contaminated Soils by EDTA Leaching

The performance of EDTA for the treatment of calcareous soils contaminated with heavy metals from mining and smelting activities was evaluated in this study. Soil samples containing variable levels of contamination, from 500 to 35 000 mg kg^-1 Pb and 700 to 20 000 mg kg^-1 Zn, were subjected to EDTA treatment and the extraction of heavy metals was found to vary, ranging between 50 and 98% for Pb and 50 to 100% for Zn. Total residual concentrations were above the limits set by regulatory authorities; leachable metals, however, were efficiently removed and treated soils were all acceptable in terms of toxicity. The effect of EDTA concentration and pulp density was studied on a soil sample containing 12 000 mg kg^-1 Pb and 10 000 mg kg^-1 Zn. Heavy metals removal was improved at low pulp densities and when EDTA concentration was increased from 0.025 to 0.25 M. The tetrasodium salt Na₄-EDTA was found to be less effective for metals removal compared to the disodium salt Na₂-EDTA, though applied at higher concentrations. This experimental work has also demonstrated the great importance of soil matrix for the overall evaluation of the EDTA leaching as a cost effective remedial option. The simultaneous dissolution of calcite was found to consume approximately 90% of the available EDTA. It was thus concluded that for the treatment of calcareous soils the design criteria and cost estimations should be based on the calcite content of the soil.     

Remediation of Lead Contaminated Soils by Stabilization/Solidification

Most available remediation technologies for treatment of heavymetal contaminated soils are very expensive and result in residues requiring further treatment. Stabilization/solidification (immobilization) techniques however, which aredesigned to decrease leaching potential of heavy metals from soil by addition of chemical additives, provide very cost-effective solutions for heavy metal contaminated soils. Thisstudy investigates the most efficient additive for immobilization of lead. To achieve this goal, several leachingexperiments were conducted for mixtures of different additives(lime, activated carbon, clay, zeolite, sand and cement) withartificially Pb contaminated (spiked) soil samples in accordancewith the Toxicity Characterization Leaching Procedure (TCLP) developed by U.S. EPA. Results showed that among the additivestried, activated carbon, clay, zeolite and sand are not very efficient for Pb immobilization. On the other hand, lime andcement are significantly effective in Pb immobilization with 88% efficiency at 1:21 lime:soil ratio and 99% efficiency at1:15 cement:soil ratio, respectively.     

Removal of Anthracene from Recently Contaminated and Aged Soils

Water, Air, &; Soil Pollution - Suspended microplastic and black carbon (BC) particles were determined in surface waters of the Jade system, southern North Sea, including freshwater sources. On...     

Removal of Metals from Contaminated Soils by Mineral Processing Techniques Followed by Chemical Leaching

A contaminated soil was exhaustively sampled at various depthson a rectangular sampling grid of 12 by 15 m (107 samples).Four metal contaminated soil samples were submitted to physicaltreatment methods followed by chemical leaching. The treatmentflowsheet consisted of crushing the 2–10 mm contaminatedfraction, various sieving and use of a wet magnetic separatorprocess for the >63 μm size fraction (SF). Subsequently theWilfley shaking table was applied to the 63-850 μm SF while ajig gravimetric separator was used on the SF >850 μm. Themagnetic separator had a small removal efficiency. Out of fourSF, one was successfully decontaminated by the Wilfley table andtwo other SF were successfully decontaminated by the jig; bothtreatments removed a significant part of metals from all soils.Chemical leaching using hydrochloric and acetic acids at atemperature of 37 °C was performed on 9 SF out of 12. After completion of the treatment, soils were recombined and tested with the Toxicity characteristics leaching procedure (TCLP) of the United States Environmental Protection Agency anda gastric juice simulation test (GJST). Untreated small size particles leach more metals with the GJST than coarse particles.Decreases in Pb concentrations varied from 33.9 to 82.5%, thehighest values corresponding to the most heavily contaminated soils. Decreases in Pb TCLP between 54.1 and 99.5% were observedand the maximal value for a treated soil was 1.53 mg Pb L^-1.The GJST decrease varied from 48.5 and 92.5% (highest leachingpotential before treatment). No problematic levels of leachingoccurred, as leaching of Pb, Cu, Zn and Sn after treatment wasrelatively low. The amount of soil to be treated was estimated from a micro and macro characterization. For an heterogeneous soil like the one studied here, the estimated cost for a 100 000 metric tons project on a 2 year span is relatively low at nearly 60 $CDN/mt.     

Fungal Generation of Organic Acids for Removal of Lead from Contaminated Soil

The use of solid-state fermentation (SFF) of low cost substrates by fungal species to generate organic acid solutions for washing of lead from a contaminated soil was evaluated in this study. SFF filtrates were generated by fermentation of four substrates (corn cobs, apple pomace, rice and hay) with three fungal species (Aspergillus niger NRRL 2001 (A. niger 1), Aspergillus niger ATCC 64065 (A. niger 2), Aspergillus foetidus NRRL 337) at three fermentation times. The concentration and speciation of organic acids of the filtrates was found to be a function of the substrate type, the fungal species and the fermentation time. Fermentation of rice resulted in the highest concentrations of citric acid while fermentation of corn cobs, apple pomace and hay tended to generate oxalic acid with an increasing fraction of this acid as the fermentation progressed. Batch extraction tests that employed the SSF filtrates revealed that soluble lead concentrations as high as 35 mg/l could be achieved. Filtrates containing elevated concentrations of citric acid resulted in the greatest lead extraction while oxalic acid inhibited solubilization. Due to the buffering of pH that was provided by the soil in the batch tests this factor did not appear to influence lead extraction. Lead extraction was observed over an extended period of time in a column test. Lead extraction was strongly influenced by the pH of the soil column and less strongly influenced by the organic acid content of the SSF filtrate. The speciation of organic acids was substantially modified from primarily citric acid in the SSF filtrate to gluconic acid in the soil column discharge.     

有机酸和磷对两种污染土壤铅的释放作用研究

用土壤培养和化学浸提法研究了不同低分子量有机酸和磷对污染土壤中铅释放的影响。结果表明,随有机酸浓度增加,铅污染红壤、棕壤中可溶出铅量均增加。当供试有机酸浓度≥1mmol·L-1时,相同浓度有机酸溶出铅量为柠檬酸〉乙酸〉草酸;当有机酸浓度≤0.5mmol·L-1时,溶出铅量为草酸〉柠檬酸〉乙酸。将2g·kg-1磷及50mmol·kg-1有机酸与铅污染红壤以不同方式混合后,柠檬酸处理的溶出铅比率（在污染土壤中加入P、有机酸后溶出铅含量与单加有机酸溶出铅含量之比）为66%（先加有机酸再加磷）、58%（有机酸与磷同时加入）、70%（先加磷再加有机酸）,草酸处理（方式同上）的溶出铅比率为90%、89%、94%,乙酸处理（方式同上）的为10%、8%、10%。铅污染棕壤上,以上处理的溶出铅比率分别为106.46%、104.43%、105.19%（柠檬酸）;43%、48%、58%（草酸）;38%、42%、55%（乙酸）。供试条件下,红壤最低溶出铅比率低于棕壤。     

Accumulation of Lead and Arsenic by Carrots Grown on Lead-Arsenate Contaminated Orchard Soils

Concerns have been raised of possible human food chain transfer of lead and arsenic from crops grown on orchard soils with histories of lead arsenate use. The objective of this study was to determine arsenic and lead uptake by three cultivars of carrots grown on four orchard soils with histories of lead arsenate use. Total concentrations of arsenic and lead in these soils ranged from 93 to 291 and from 350 to 961 mg kg^?1 for arsenic and lead, respectively. Arsenic in peeled carrot ranged from 0.38 to 1.64 mg kg^?1, while lead ranged from 2.67 to 7.3 mg kg^?1 dry weight. This study demonstrated that carrots will accumulate arsenic and lead in the root, which may become a human health risk when consumed. However, further studies are needed to determine what fraction of arsenic and lead in these carrots are bioavailable to humans when consumed.     

In-Situ Immobilization of Cadmium and Lead by Different Amendments in Two Contaminated Soils

Different soil amendments, including 1% zeolite, 1% bentonite,5% Penghu soil (PHS), 5% Penghu soil + 1% manganese oxide (PHS + MO), 1% MO, and 1.5% silicate slag (SS), were used to immobilize Cd and Pb in two contaminated soils evaluated by single and sequential extractions and by uptake of Chinese cabbage (Brassica Chinensis L.). Results indicated that the PHS and MO significantly (p < 0.05) reduced the 0.1 M HCl extractable Cd and Pb in the two contaminated soils. Allamendment treatments did not change the organic and residual amounts of Cd and Pb in soils A and B, but the PHS andPHS + MOtreatments significantly reduced the exchangeable amounts of Cdand Pb in the two soils as measured by sequential extraction. Thecombination of PHS and MO amendments was associated with ahigh pH value and negative soil surface charge showed the best immobilizing efficiency of Cd and Pb in this study. All soil amendments investigated did not increase the dry matter weight of the plant, and most of them decreased the uptake of Cd and Pb, especially for the PHS and MO. The PHS and MO treatments reduced the extractability of Cd and Pb in two soils and theiruptake by the plant, but only the Pb content in Chinese cabbagefrom the amended soils was less than the background levels of heavy metals in leaf vegetables of Taiwan.     

Selective Removal of Lead from Calcareous Polluted Soils using the Ca-EDTA Salt

EDTA is a powerful chelating reagentwhich has been often proposed for the decontaminationof lead polluted soils. Despite the pronouncedselectivity of this reagent for Pb, a low degree ofutilisation is observed when treating calcareoussoils, due to the co-dissolution of calcite. Thisstudy demonstrates that it is possible to suppresscalcite dissolution and optimise the degree of EDTAutilisation, using the calcium salt of EDTA, insteadof the common sodium salts. Initial experiments, whichwere carried out mixing pure cerrusite (PbCO₃)with a Na₂CaEDTA solution, have shown that Pb isquantitatively solubilised, while calcium precipitatesin the form of aragonite. The performance of thisreagent in the decontamination of soils has beentested on a soil sample from Lavrion (Greece)containing 7.3–8.8% of Ca and heavily polluted withPb at levels up to 3.5%. The parameters which weretested include the reaction time, the stoichiometricexcess of Na₂CaEDTA with respect to Pb and theeffect of successive treatment stages with freshNa₂CaEDTA solutions. The experimental resultshave shown that long reaction times, exceeding 24 hr, are required in order to obtain sufficient Pbremoval and preserve the calcium content of the soil.Lead extraction increases from 27 to 40% prolongingthe reaction time from 1 to 24 hr atNa₂CaEDTA/Pb = 1 mol/mol. Increasing theNa₂CaEDTA/Pb molar ratio from 1 to 3.5 mol/mol,enhances the dissolution of Pb from 40 to 53%, whichis not proportional to the stoichiometric excesssupplied. The efficiency of Pb removal is maximized,up to 75%, applying three successive leaching stages.The major benefit of Na₂CaEDTA in comparison withthe disodium EDTA salt is the preservation of soilcalcite. The initial calcium content of the soil wasfound to increase by 4% using the Ca salt; on thecontrary, the treatment with Na₂H₂EDTA undersimilar experimental conditions has resulted indissolving 27% of soil Ca.     

茶皂素对污染土壤中重金属的修复作用

采用振荡离心的方法研究了生物表面活性剂茶皂素在不同浓度、pH值和离子强度下对污染土壤中重金属去除效果的影响;并采用BCR法研究了茶皂素处理前后土样中各形态的重金属含量变化。试验结果表明:随着茶皂素浓度的增加,重金属的去除率随之增加,在茶皂素浓度为7%时,对供试土样中重金属的去除率达到最大值,去除率分别为Cd 96.36%,Zn 71.73%,Pb 43.71%,Cu 20.56%;随着土壤环境pH值的增加,重金属的去除率随之减少,适宜的pH范围在5.0左右;离子强度对Pb,Cu的去除效率影响不大,Zn,Cd的去除率随着离子强度的增加而减少。比较茶皂素处理前后土样中重金属各形态含量的变化,发现酸溶态的重金属更易被茶皂素去除,其次为可还原态、可氧化态和残渣态的重金属很难被去除。     

Surfactant-Enhanced Soil Washing for Removal of Petroleum Hydrocarbons from Contaminated Soils: A Review

An increase in energy demand leads to further exploration, transportation, and utilization of petroleum, which creates severe soil contamination because of recurrent accidents and oil spills. Remediation of these contaminated soils is challenging. Among many treatment methods practiced for remediation of petroleum-contaminated soils, surfactant-enhanced soil washing has been widely practiced as a preferred treatment option, as it is a fast and environmentally accepted method. In this paper, we review research undertaken on various anionic, nonionic, cationic, biological, and mixed surfactants for the remediation of petroleum hydrocarbon-contaminated soils. Upcoming surfactants like gemini and switchable surfactants are summarized. We assess the challenges and opportunities of in-situ and ex-situ soil washing, the mechanisms of surfactant-enhanced soil washing, and the criteria to follow for surfactant selection. Furthermore, we briefly discuss the operational and environmental factors affecting soil washing efficiency and soil and surfactant properties affecting surfactant adsorption. We also describe the advantages of coupling soil washing with effluent treatment and surfactant reuse challenges and opportunities. Moreover, challenges and possible new directions for future research on surfactant-enhanced soil washing are proposed.     

Plant Availability and Uptake of Lead, Zinc, and Cadmium in Soils Contaminated with Anti-corrosion Paint from Pylons in Comparison to Heavy Metal Contaminated Urban Soils

Red lead (Pb₃O₄) has been used extensively in the past as an anti-corrosion paint for the protection of steel constructions. Prominent examples being some of the 200,000 high-voltage pylons in Germany which have been treated with red lead anti-corrosion paints until about 1970. Through weathering and maintenance work, paint compounds and particles are deposited on the soils beneath these constructions. In the present study, six such “pylon soils” were investigated in order to characterize the plant availability and plant uptake of Pb, Cd, and Zn. For comparison, three urban soils with similar levels of heavy metal contamination were included. One phase extractions with 1 M NH₄NO₃, sequential extractions (seven steps), and extractions at different soil pH were used to evaluate the heavy metal binding forms in the soil and availability to plants. Greenhouse experiments were conducted to determine heavy metal uptake by Lolium multiflorum and Lactuca sativa var. crispa in untreated and limed red lead paint contaminated soils. Concentrations of Pb and Zn in the pylon soils were elevated with maximum values of 783 mg Pb kg⁻¹ and 635 Zn mg kg⁻¹ while the soil Cd content was similar to nearby reference soils. The pylon soils were characterized by exceptionally high proportions of NH₄NO₃-extractable Pb reaching up to 17% of total Pb. Even if the relatively low pH of the soils is considered (pH 4.3–4.9), this appears to be a specific feature of the red lead contamination since similarly contaminated urban soils have to be acidified to pH 2.5 to achieve a similarly high Pb extractability. The Pb content in L. multiflorum shoots reached maximum values of 73 mg kg⁻¹ after a cultivation time of 4 weeks in pylon soil. Lime amendment reduced the plant uptake of Pb and Zn significantly by up to 91%. But L. sativa var. crispa cultivated on soils limed to neutral pH still contained critical Pb concentrations (up to 0.6 mg kg⁻¹ fresh weight). Possible mechanisms for the exceptionally high plant availability of soil Pb derived from red lead paint are discussed.     

Availability and Toxic Level of Cadmium,Lead and Nickel in Contaminated Soils

ABSTRACT

The entry of Cd, Pb and Ni into the environment is a cause of concern due to potential toxicity of these metals to plants, animals, and humans. The present study evaluated the availability of Cd, Pb, and Ni to plants through soils. We examined three soil types (Typic Quartzipsamment (TQ), Xantic Hapludox (XH) and Rhodic Hapludox (RH)) with addition four rates of heavy metals: Cd (0, 2, 4 and 12 mg), Pb (0, 45, 90 and 270 mg) and Ni (0, 20, 40, 120 mg) per kg soil with reference to the corresponding rates defined in soil investigation values of the Brazilian environmental legislation. The availability of Cd, Pb and Ni was higher in the TQ than in XH and RH, and the roots and shoots of corn plants grown in TQ yielded the highest concentrations of toxic metals. Soil extraction with diethylene-triaminepentaacetic acid (DTPA) effectively assessed the bioavailability of Cd and Pb, while soil extractions with Mehlich-1 and aqua regia effectivety evaluated the bioavailability of Ni. The levels at which Cd, Pb, and Ni became toxic for plants were determined via extractioned by Mehlich-1, DTPA, Mehlich-3, and aqua regia. Plant growth was shown to influence heavy metal toxicity, with higher growth rates lowering the toxic effect of the metal. Cd, Ni, and Pb exhibited higher availiability in soils with low clay concentrations and were more easily absorbed by plants in those soils.     

东方香蒲（Typha orientalis Presl）对重度污染土壤中As、Cd、Pb的耐性与累积特征

通过温室盆栽试验研究东方香蒲对重度污染土壤中As、Cd、Pb的耐受性能与累积特征。研究结果表明,与未污染土壤处理相比,当土壤中As、Cd、Pb含量分别达到48.4、16.9mg·kg-1和316mg·kg-1时,东方香蒲生物量、叶绿素含量和过氧化氢酶活性等均无显著降低,东方香蒲对土壤中As、Cd、Pb表现了较强的耐受性能;当土壤中As、Cd、Pb含量分别达到285、42.1、1008mg·kg-1时,东方香蒲生物量、叶绿素含量和过氧化氢酶活性等均明显下降（P〈0.05）,表现出植株矮小、叶片枯黄等中毒症状。东方香蒲对土壤中As、Cd、Pb的累积主要在根部,其含量分别可达31.69、35.12mg·kg-1和87.12mg·kg-1,而在茎叶中仅为2.06、2.83mg·kg-1和20.18mg·kg-1,根部向地上部转移系数小。研究结果表明,东方香蒲可作为As、Cd、Pb重度污染土壤植物稳定修复的潜在目标植物之一。     

Arsenic Uptake by Two Hyperaccumulator Ferns from Four Arsenic Contaminated Soils

A greenhouse study was conducted to evaluate and compare arsenic accumulation from four arsenic contaminated soils by two arsenic hyperaccumulators, Pteris vittata and Pteris cretica. After growing in soils for six weeks, the plants were harvested and separated into above- and below-ground biomass. Total As, P, Ca, K, glutathione and biomass were measured for the plants, and total As, Mehlich-3 P and As, exchangeable K and Ca, and arsenic fractionation were performed for the soils. Pteris vittata had significantly higher total biomass (14 g/plant) and As accumulation than P. cretica. Arsenic accumulation in both ferns followed the arsenic concentrations in the soil. The P/As molar ratio in the fronds, growing in arsenic contaminated soils, ranged from 80 to 939 in P. vittata and 130 to 421 in P. cretica. Plant arsenic concentrations were significantly positively correlated with Mehlich-3 arsenic in the soils. Soil pH was also significantly correlated with Mehlich-3 arsenic before and after plant uptake. Plant As uptake was significantly correlated with exchangeable potassium in the soil before plant uptake. Glutathione availability was not implicated as a major detoxification mechanism in these ferns. Though both plants were effective in taking up arsenic from various arsenic contaminated soils, P. vittata was overall a better candidate for phytoremediation of arsenic contaminated soils.     

Ultrasonic Enhanced Desorption of DDT from Contaminated Soils

In this study, using high-power low-frequency ultrasound, heated slurries with anionic surfactant sodium dodecyl sulfate (SDS) were treated to enhance desorption of DDT from soils with high clay, silt, and organic matter content and different pH (5.6?C8.4). The results were compared with DDT extracted using a strong solvent combination as reference. Slurry ranges from 5 to 20 wt.% were studied. For a soil slurry (10 wt.%) at pH 6.9 with 0.1% v/v SDS surfactant heated to 40°C for 30 min, desorption was above 80% in 30 s using 20 kHz, 932 W/L ultrasonic intensity without solvent extraction. Other soils gave lower desorption efficiency in the range 40?C60% after 30 s ultrasonic treatment. The percentage of organic matter, dissolved organic carbon, soil surface area, clay and silt percentage, and soil pH level were the key parameters influencing variations in desorption of DDT in the three soils in similar experimental conditions. DDT dissolution in SDS and soil organic matter removal employing the ultrasonic-enhanced organic matter roll-up mechanism emerged as the two best possible methods of DDT desorption. The method offers a practical, potentially low-cost alternative to high volume, costly, hazardous solvent extraction of DDT.     

A Model for Evaluating the Feasibility of an Extraction Procedure for Heavy Metal Removal from Contaminated Soils

A model was developed that allowed for the evaluation of a soil metal cleaning technique in a rapid and cost effective manner. Metal flow (Pb, Cu, Zn, and Cd) during a counter-current soil-acid extraction procedure, consisting of a decarbonation, solubilisation, and washing step, was determined. Required input data are total soil metal content and metal equilibrium distribution coefficients, derived from batch equilibration experiments. The model was calibrated and validated against experimentally obtained results. Model predictions adequately described metal behaviour and removal in each of the extraction steps. Based on the results, optimum operating conditions for the steps involved in the extraction procedure were determined and the feasibility of the counter-current extraction procedure for heavy metal removal from a contaminated soil evaluated.     

Effect of Extraction Variables on the Biodegradable Chelant-Assisted Removal of Toxic Metals from Artificially Contaminated European Reference Soils

Development of aminopolycarboxylate chelants (APCs) having enhanced biodegradability is gaining increasing focus to replace the EDTA and its homologs with those used widely for the ex situ treatment of contaminated soils and are potential eco-threats. The paper reports the chelant-assisted extraction of the toxic metals (Cd, Cu, Pb, and Zn) from the metal-spiked European reference soils (Eurosoil 1 and Eurosoil 4) using biodegradable APCs, namely EDDS, GLDA, and HIDS. The effects of chelant-to-metal molar ratio, solution pH, and metal/chelant stability constants were evaluated, and compared with that of EDTA. The selectivity aptitude of the biodegradable chelants towards the toxic metals was assumed from the speciation calculations, and a proportionate correlation was observed at neutral pH. Pre- and post-extractive solid phase distributions of the target metals were defined using the sequential extraction procedure and dissolution of metals from the theoretically immobilized fraction was witnessed. The effect of competing species (Al, Ca, Fe, Mg, and Mn) concentrations was proven to be minimized with an excess of chelant in solution. The highlight of the outcomes is the superior decontamination ability of GLDA, a biodegradable APC, at minimum chelant concentration in solution and applicability at a wide range of pH environments.     

Stimulatory effect on pea of Typha Angustifolia L. extracts and their chemical composition

In this study, the influence of aqueous and organic extracts of different plant parts (flowers, leaves, and stems) of Typha angustifolia on the germination and early seedling growth of field pea (Pisum sativum L.) was evaluated. Chemical composition of extracts of different plant parts of Typha was also determined. Aqueous (20, 40, 60, 80, and 100 g L^?1) and organic extracts (at 0.5, 1, and 2 mg mL^?1) were applied to the seeds of two pea cultivars, Douce de Provence and Lincoln, placed in Petri dishes. Application of extracts had a beneficial effect on germination and early seedling growth of both pea cultivars. However, aqueous extract of leaves showed the most beneficial effect at 60 and 40 g L^?1 for the cultivars Douce de Provence and Lincoln, respectively. The effect could be attributed to the allelochemicals present in the aqueous extracts. Petroleum ether and chloroform extracts of leaves had the most stimulating effect on the germination and early seedling growth of pea. Analysis of Typha extracts indicated the presence of vitamin E in leaves, which could be responsible forthis stimulation. Moreover, Typha leaves also had substantial amount of flavonoids. In conclusion, the allelopathic activity of of Typha was dependent on the plant part, the solvent nature, the concentration of the extracts tested, and on the pea cultivar. Application of leaf extract was the most effective in improving the germination rate and early seedling growth of pea.