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.     

有机酸土柱淋洗法修复重金属污染土壤

通过室内模拟实验,采用土柱淋洗方法,研究草酸、柠檬酸、乙酸和酒石酸溶液对某电镀厂附近土壤中重金属的去除效果。探讨了淋洗剂浓度、淋洗次数和淋洗时间等对淋洗效果的影响,研究草酸淋洗前后土壤中重金属形态的变化。结果表明,淋洗过程中铬的去除效果明显滞后于铜、锌和镍3种重金属离子。1 mol/L的草酸在土水比为1∶1,淋洗5h,淋洗4次的条件下可以达到最佳淋洗效果,Cu、Zn、Ni和Cr的去除率分别是99.6%、66.98%、88.7%和18.23%。     

Ecotoxicological assessment of metal-polluted urban soils using bioassays with three soil invertebrates

This study aimed at assessing the quality of urban soils by integrating chemical and ecotoxicological approaches. Soils from five sites in downtown Naples, Italy, were sampled and characterized for physical-chemical properties and total and water-extractable metal concentrations. Bioassays with Eisenia andrei, Enchytraeus crypticus and Folsomia candida were performed to assess toxicity of the soils, using survival, reproduction and growth as the endpoints. Metal bioaccumulation in the animals was also measured. The properties and metal concentrations of the soils strongly differed. Metal bioaccumulation was related with total metal concentrations in soil and was highest in E. crypticus, which was more sensitive than E. andrei and F. candida. Responses of the three species to the investigated soils seemed due to both metal contamination and soil properties.     

Effects of metals on life cycle parameters of the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils

Two control and eight field-contaminated, metal-polluted soils were inoculated with Eisenia fetida (Savigny, 1826). Three, 7, 14, 21, 28 and 42 days after inoculation, earthworm survival, body weight, cocoon production and hatching rate were measured. Seventeen metals were analysed in E. fetida tissue, bulk soil and soil solution. Soil organic carbon content, texture, pH and cation exchange capacity were also measured. Cocoon production and hatching rate were more sensitive to adverse conditions than survival or weight change. Soil properties other than metal concentration impacted toxicity. The most toxic soils were organic-poor (1-10 g C kg(-1)), sandy soils (c. 74% sand), with intermediate metal concentrations (e.g. 7150-13,100 mg Pb kg(-1), 2970-53,400 mg Zn kg(-1)). Significant relationships between soil properties and the life cycle parameters were determined. The best coefficients of correlation were generally found for texture, pH, Ag, Cd, Mg, Pb, Tl, and Zn both singularly and in multivariate regressions. Studies that use metal-amended artificial soils are not useful to predict toxicity of field multi-contaminated soils.     

Modeling EDTA enhanced electrokinetic remediation of lead contaminated soils

Electrokinetic extraction has been tested for lead removal from Algerian contaminated soils. For this purpose, a chelating reagent (EDTA, 0.1M) has been injected into the catholyte. This procedure is expected to enhance the process by desorption of the contaminant and formation of new mobile species negatively charged. A mathematical model based on Nernst-Planck theory has also been developed to predict the evolution of lead distribution across the soil as a function of time. The results of several experiments carried out on various duration (10, 20 and 40 days) have shown the importance on treatment efficiency of pollution age and contaminant speciation as determined by sequential chemical extraction.     

Factors affecting EDTA extraction of lead from lead-contaminated soils

The effects of solution:soil ratio, major cations present in soils, and the ethylenediaminetetraacetic acid (EDTA):lead stoichiometric ratio on the extraction of lead using EDTA were studied for three different Superfund site soils, one rifle range soil, and one artificially lead-contaminated soil. Extraction of lead from the lead-contaminated soils was not affected by a solution:soil ratio as low as 3:1 but instead was dependent on the quantity of EDTA present. Results of the experiments showed that the extraction efficiencies were different for each soil. If sufficiently large amount of EDTA was applied (EDTA-Pb stoichiometric ratio greater than 10), most of the lead were extracted for all soils tested except for a Superfund site soil from a lead mining area. The differences in extraction efficiencies may be due to the major cations present in soils which may compete with lead for active sites on EDTA. For example, iron ions most probably competed strongly with lead for EDTA ligand sites for pH less than 6. In addition, copper and zinc may potentially compete with lead for EDTA ligand sites. Experimental results showed that addition of EDTA to the soil resulted in a very large increase in metals solubility. The total molar concentrations of major cations extracted were as much as 20 times the added molar concentration of EDTA. For some of the soils tested, lead may have been occluded in the iron oxides present in the soil which may affect lead extraction. While major cations present in the soil may be one of the factors affecting lead extraction efficiency, the type of lead species present also play a role.     

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.     

Multi-step leaching of Pb and Zn contaminated soils with EDTA

The efficiency of multi-step leaching of heavy metal contaminated soils was evaluated in a laboratory scale study. Four different soils contaminated with Pb (1136+/-16-4424+/-313mgkg(-1)) and Zn (288+/-5-5489+/-471mgkg(-1)) were obtained from industrial sites in the Mezica Valley, Slovenia and Príbram district, Czech Republic. Different dosages (2.5-40mmolkg(-1)) of ethylenediamine tetraacetate (EDTA) were used to treat soils in 1-10 leaching steps. Higher EDTA dosages did not result in a proportional gain in Pb and Zn removal. EDTA extracted Pb more efficiently than Zn from three of four tested soils. The percentage of removed Zn did not exceed 75% regardless of the soil, EDTA dosage and leaching steps. Significantly more Pb (in three of four soils) and Zn were removed from soils when the same amount of EDTA was applied in several leaching steps. The interference of major soil cations Fe and Ca with EDTA complexation as a possible factor affecting Pb and Zn removal efficiency with multi-step heap leaching was examined and is discussed. The results of our study indicate that, for some soils, using multi-step leaching instead of the more traditionally used single dose EDTA treatment could improve heavy metal removal efficiency and thus the economics of soil remediation.     

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.     

Feasibility of using metals to remediate water containing TCE

The feasibility of treating underground water contaminated by a chlorinated organic compound with bimetallics Fe/Ni, Zn/Ni and Zn single metal was studied. Column tests to simulate a reactive permeable wall in a funnel-and-gate system were used. Research results indicated that bimetallic Fe⁰/Ni⁰ and Zn⁰/Ni⁰ all had a very strong degraded power to trichloroethylene (TCE ) at concentration up to 25 mg/l under different flow rates (27 cm/day–20 m/day). Furthermore, the concentrations of TCE and various ions in the treated effluent were nearly lower than the values specified in related standards for drinking water in Taiwan. These results showed that this technique could be effectively and safely used as an underground water remediation process.     

Low-grade MgO used to stabilize heavy metals in highly contaminated soils

Low-grade MgO may be an economically feasible alternative in the stabilization of heavy metals from heavily contaminated soils. The use of MgO is described acting as a buffering agent within the pH 9-11 range, minimizing heavy metals solubility and avoiding the redissolution that occurs when lime is used. The effectiveness of LG-MgO has been studied as stabilizer agent of heavily polluted soils mainly contaminated by the flue-dust of the pyrite roasting. The use of LG-MgO as a reactive medium ensures that significant rates of metal fixation, greater than 80%, are achieved. The heavy metals leachate from the stabilized soil samples show a concentration lower than the limit set to classify the waste as non-special residue. Regardless of the quantity of stabilizer employed (greater than 10%), LG-MgO provides an alkali reservoir that allows guaranteeing long-term stabilization without varying the pH conditions.     

EDTA及其回收溶液治理重金属污染土壤的研究

试验结果表明,EDTA能够有效地萃取土壤重金属,由于其价格较贵和不易被降解等特点,限制了它的广泛运用.在运用MINTEQA2模型对萃取液中重金属离子形态分析的基础上,选用Na2S沉淀法将重金属从EDTA萃取液中有效分离.同时将回收的EDTA连续进行萃取土壤重金属,由于回收EDTA浓度下降的原因,其效果比新鲜EDTA的要稍微差一点,但从经济和效率上来说,仍旧可以用来治理重金属污染的土壤.     

Metal concentrations in used engine oils: Relevance to site assessments of soils

Used engine oils contain metals, which upon entering soils may pose risks to human health or the environment. In this study, previously published concentrations of 23 metals in 213 used engine oil samples from the early 1970s to the mid-1990s are statistically evaluated. Neat (100%) used engine oils were found to contain relatively high concentrations of lead, calcium, and zinc, attributable to piston blow-by of leaded gasoline, calcium salt detergent additives, and zinc-bearing anti-corrosion/anti-oxidation additives, respectively. Wear metal concentrations were lower. The lead concentration in used engine oils in the U.S. declined between the 1970s and early 1990s, potentially providing a basis to constrain the “age” of used engine oil(s) in soils. The concentrations of 23 metals in used engine oils were compared to soil risk benchmarks in 15 representative jurisdictions in the U.S., Canada, Australia, and Europe. The maximum concentrations in neat (100%) used engine oil of eight metals – Be, Co, Fe, Mn, Ni, Se, Ag, and Ti – were lower than their collective minimum benchmarks in soils for the jurisdictions surveyed, indicating their concentrations in soils could not be reasonably expected to exceed any soil benchmarks. Nine metals (As, Ba, Cd, Cr, Cu, Pb, Sn, V and Zn), but particularly arsenic, cadmium, lead, tin, and zinc, were identified as potential contaminants of concern (PCOC) for soils from locations impacted with used engine oils, owing to their higher median concentrations (i.e., 2.5, 1.4, 1038, 5.0, and 922 mg/kg in oil, respectively) relative to most soil benchmarks. Site-specific benchmarks and metal concentrations at reasonable oil in soil concentrations require consideration when developing the suite of PCOC metal analytes for conducting site assessments of soils impacted by used engine oil.     

植物-固体菌剂联合修复石油污染土壤的基础研究

以高效石油降解菌N2、KB为目的菌种,玉米粉、麸皮和锯末为载体制备固体菌剂,并测定了这3种载体的饱和持水量、pH值和吸菌量。以吸菌量为评价指标,结合经济性综合选择最优载体,同时还考察了温度、pH值和料水比对最优载体吸菌量的影响。通过测定微生物数量和石油降解率的变化,考察了植物微生物联合修复效果。结果表明,与玉米粉和麸皮相比,锯末饱和持水量更大、吸菌量较大。锯末是木材厂的下脚料,可以实现高价值资源化利用。在温度30℃,pH为7,料水比1：1.5的最适培养条件下,固体菌剂中N2和KB两种细菌的活菌数量分别高达1.00×109CFU·g-1和1.58×109 CFU·g-1。采用生物菌剂和柳枝稷对石油污染土壤进行植物-微生物联合修复实验,100 d后石油降解率可达到50.5%。     

Copper activity in soil solutions of calcareous soils

Copper partitioning was studied in seven calcareous soils at moisture content corresponding to 1.2 times the field moisture content (soil water potential 7.84 J kg(-1)). Copper retention was accompanied by the release in soil solution of Ca(2+), Mg(2+), Na(+), and H(+), and the total amount of these cations released was 0.8 to 1.09 times the amount of Cu sorbed (mol(c):mol(c)). The relationships between Cu activity and pH, and the balance of cations in soils correspond with the surface precipitation of CuCO(3) as the main mechanism of Cu retention. The values of ion activity product of surface precipitate were close for all studied soils with the average log(IAP(CuCO(3)))=-15.51. The relationship between copper activity in soil solutions and soil properties is well fit by a regression relating pCu (-log copper ion activity) with soil pH, total Cu, and carbonate content.     

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.     

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.     

Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

Study on the possibility of hydrogen peroxide pretreatment and plant system to remediate soil pollution

Hydrogen peroxide was widely selected as the chemical oxidant in chemical remediation or as the donor of oxygen in in situ aerobic bioremediation of organic pollutants. In this paper, hydrogen peroxide pretreatment and plant system was done to examine its possibility to remediate the heavy metal contaminated soil or heavy metal-organic combined contaminated soil. Heavy metal contaminated soil was collected from the heavily industrialized area, in Fuyang county, Zhejiang province, China. And heavy metal-organic combined contaminated soil was prepared from the same contaminated soil by spiking 100 microg g(-1) 2,4-dichlorophenol (2,4-DCP). Results showed that H2O2 could improve the dissipation of 2,4-DCP and enhance the availability of Cu and Zn in soil. The greatly increased DOC (dissolved organic carbon) in the oxidation process was probably the main reason for the greatly increased water soluble Cu in higher pH condition. Water soluble Zn, however, easily rebound to soil components with the time being and had no positive relation with dissolved organic carbon. Planting with ryegrass influenced the behavior of pollutants in soil. It was observed that the dissipation of 2,4-DCP could be enhanced by the presence of plant roots and the availability of Cu and Zn in the planted soil was changed due to the mobilization and rebound mechanisms in the rhizosphere. Co-contamination of 2,4-DCP caused the greater availability of Cu and Zn in H2O2 pretreatment. But with the ryegrass planting, it was easier to rebound to the less available phase in the rhizosphere. Both Cu and Zn concentration in shoots increased with the H2O2 treatment. Therefore our results suggested that H2O2 pretreatment was probably a promising way for promoting the dissipation of persistent organic pollutants and enhancing the solubility of Cu and Zn in soil. A combination of H2O2 pretreatment and suitable plant might be an efficient alternative for remedying heavy metal or heavy metal-organic contaminated soil.     

Potential of the microbial community present in an unimpacted beach sediment to remediate petroleum hydrocarbons

The potential of the microbial communities present in the intertidal zone of an unimpacted beach (a beach that did not suffer any significant oil spill) to degrade hydrocarbons was investigated. For that, laboratory-based microcosms (50-ml flasks) were set up with sandy beach sediment spiked with crude oil and incubated with local seawater for 15 days in the dark. Three bioremediation treatments were tested (biostimulation (BS), autochthonous bioaugmentation (AB), and combined treatment of biostimulation + bioaugmentation (BS + AB)) and the results were compared with natural attenuation (NA). Visual inspection showed clearly an oil solubility increase (confirmed by a higher hydrocarbons concentration in supernatant solutions) for all tested treatments when compared to NA. Significant degradation of the oil, shown by different profiles of petroleum hydrocarbons, was also observed for the different treatments particularly for BS + AB. Therefore, the microbial community of this unimpacted beach sediment could respond to an oil spill, degrading hydrocarbons. But to increase the natural attenuation pace, obtained results indicated that BS + AB is an appropriate approach for the bioremediation of beaches recently impacted by an oil spill. The autochthonous microbial cultures can be obtained “before” or “after” the contamination of the target site, being inoculated into the site right after it contamination.