Evaluation of Electrokinetic Removal of Heavy Metals from Tailing Soils

Electrokinetic remediation was studied for the removal of toxic heavy metals from tailing soils. The study emphasized the dependency of removal efficiencies upon their speciations, as demonstrated by the different extraction methods used, which included sequential extraction, total digestion, and 0.1 N HCl extraction. The tailing soils examined showed different physicochemical characteristics, such as initial pH, particle size distribution, and major mineral constituents, and they contained high concentrations of target metal contaminants in various forms. The electrokinetic removal efficiencies of heavy metals were significantly influenced by their partitioning prior to treatment, and the pHs of the tailing soils. The mobile and weakly bound fractions of heavy metals, such as the exchangeable fraction, were easily removed by electrokinetic treatment (more than 90% removal efficiency), but immobile and strongly bound fractions, such as the organically bound species and residual fractions, were not significantly removed (less than 20% removal efficiencies).     

Complicating Factors of Using Ethylenediamine Tetraacetic Acid to Enhance Electrokinetic Remediation of Multiple Heavy Metals in Clayey Soils

Batch and electrokinetic experiments were conducted to investigate the removal of three different heavy metals, chromium(VI), nickel(II), and cadmium(II), from a clayey soil by using ethylenediamine tetraacetic acid (EDTA) as a complexing agent. The batch experiments revealed that high removal of these heavy metals (62–100%) was possible by using either a 0.1?M or 0.2?M EDTA concentration over a wide range of pH conditions (2–10). However, the results of the electrokinetic experiments using EDTA at the cathode showed low heavy metal removal efficiency. Using EDTA at the cathode along with the pH control at the anode with NaOH increased the pH throughout the soil and achieved high (95%) Cr(VI) removal, but the removal of Ni(II) and Cd(II) was limited due to the precipitation of these metals near the cathode. Apparently, the low mobility of EDTA and its migration direction, which opposed electroosmotic flow, prevented EDTA complexation from occurring. Overall, this study found that many complicating factors affect EDTA-enhanced electrokinetic remediation, and further research is necessary to optimize this process to achieve high contaminant removal efficiency.     

Lead Extraction from Contaminated Soil Using Water-Soluble Polymers

The applicability of water-soluble polymers as extractants for the remediation of heavy metal-contaminated soils has been explored using a lead-contaminated Superfund soil as a sample system. Polyethylenimine (PEI) was functionalized with bromo- or chloroacetic acid to give an aminocarboxylate chelating group, which effectively binds lead. The resulting polymer, PEIC, has extraction properties similar to the molecular chelator ethylenediaminetetraacetic acid. A series of studies was done to probe optimum conditions for lead extraction from soils obtained from the Cal-West Superfund site in New Mexico that contained approximately 10,000 ppm of Pb. In batch extraction experiments using polymer functionalized at two different levels, the polymers removed greater than 97% of the lead from the soils. Subsequent experiments demonstrated that the selective extraction of lead could be controlled by varying polymer functionalization levels. Concentration and regeneration of the polymers using ultrafiltration was also demonstrated. Release of lead from the polymer was accomplished by acidification to pH 1 with HCl. Subsequent ultrafiltration allowed recovery of the extractant polymer for reuse.     

Experimental Studies on Heavy Metal Extraction from Contaminated Soil Using Ammonium Citrate as Alkaline Chelate during the Electrokinetic Process

Researchers have performed experimental studies using ammonium citrate (AC) during the electrokinetic (EK) remediation process for the extraction of cadmium (Cd) and copper (Cu) from the contaminated soil. They evaluated the efficiency of ammonium citrate by considering it as a washing solution and a purging solution at the anode electrode compartment. The efficiency of electrokinetic extraction was observed to be significantly influenced by the pH and buffering nature of the soil medium. The experimental studies indicate that the removal of cadmium and copper was 48.9% and 30.0%, respectively, when ammonium citrate was used both washing and purging solution. The solubility of both cadmium (Cd++) and copper (Cu++) in EK-treated soils has also been estimated by sequential extraction studies with deionized (DI) water. The analytical techniques, X-ray diffraction (XRD), X-ray fluorescence (XRF), and scanning electron microscope (SEM) provide the evidence of migration of cations during treatment of contaminated soil by process of electroosmosis (EO). The SEM images of both cadmium- and copper-contaminated soils show that these soils have a fluffier and more porous structure. This might be caused by the change in surface charges of the clay particles as a result of introduction of heavy metals. The mineralogical compositions of soil are not altered significantly by electrokinetic process.     

Enhanced Electrokinetic Remediation of Heavy Metals in Glacial Till Soils Using Different Electrolyte Solutions

Previous electrokinetic remediation studies involving the geochemical characterization of heavy metals in high acid buffering soils, such as glacial till soil, revealed significant hexavalent chromium migration towards the anode. The migration of cationic contaminants, such as nickel and cadmium, towards the cathode was insignificant due to their precipitation under the high pH conditions that result when the soil has a high acid buffering capacity. Therefore the present laboratory study was undertaken to investigate the performance of different electrolyte (or purging) solutions, which were introduced to either dissolve the metal precipitates and/or form soluble metal complexes. Tests were conducted on a glacial till soil that was spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1,000, 500, and 250 mg/kg, respectively, under the application of a 1.0 VDC/cm voltage gradient. The electrolyte solutions tested were 0.1M EDTA (ethylenediaminetetraacetic acid), 1.0M acetic acid, 1.0M citric acid, 0.1M NaCl/0.1M EDTA, and 0.05M sulfuric acid/0.5M sulfuric acid. The results showed that 46–82% of the Cr(VI) was removed from the soil, depending on the purging solution used. The highest removal of Ni(II) and Cd(II) was 48 and 26%, respectively, and this removal was achieved using 1.0M acetic acid. Although cationic contaminant removal was low, the use of 0.1M NaCl as an anode purging solution and 0.1M EDTA as a cathode purging solution resulted in significant contaminant migration towards the soil regions adjacent to the electrodes. Compared to low buffering capacity soils, such as kaolin, the removal of heavy metals from the glacial till soil was low, and this was attributed to the more complex composition of glacial till. Overall, this study showed that the selection of the purging solutions for the enhanced removal of heavy metals from soils should be primarily based upon the contaminant characteristics and the soil composition.     

Screening Level Risk Assessment of Heavy Metal Contamination in Cleveland Area Commons

Commons are public lands that are often used for recreational activities and are generally assumed to be free of soil contamination. However, in old industrial cities, urban commons may have accumulated heavy metal burdens from airborne contamination. This paper examines the heavy metal burdens and risk analysis results for 50 commons in the greater Cleveland, Ohio area. The U.S. Environmental Protection Agency Method 3050B and 1N HCl soil extraction results are presented for Cd, Cr, Cu, Ni, Pb, and Zn mass burdens, and are interpreted relative to Ohio residential soil guidance and “typical” values from the remediation guidance of 30 states. Results demonstrate that most of these soils have heavy metal burdens that are well above naturally occurring levels, and several (at least 8 of the 50 sites tested) have heavy metal burdens that exceed Ohio’s residential soil contamination guidance. Lead and cadmium were found to be the most significant contributors to site hazard index values.     

Enhanced Soil Flushing for Simultaneous Removal of PAHs and Heavy Metals from Industrial Contaminated Soil

Polycyclic aromatic hydrocarbons (PAHs) and heavy metals are environmental concerns and must be removed to acceptable levels. This paper evaluates different flushing agents to enhance the remediation of soil contaminated with PAHs and heavy metals at a former manufactured gas plant site. Four flushing column tests at a constant hydraulic gradient of 1.2 were conducted using four different flushing agents, which included deionized water, chelant (0.2?M EDTA), surfactant (5% Igepal CA-720), and cyclodextrin (10% hydroxypropyl-β-cyclodextrin or HPCD). Additional column tests using Igepal and HPCD at a lower hydraulic gradient of 0.2 were conducted to investigate the effects of rate-limited desorption or solubilization of PAHs. The results showed that the EDTA produced the maximum metal removal from the soil compared with deionized water, Igepal, and HPCD under different hydraulic gradient conditions. The 0.2?M EDTA flushing solution removed approximately 25–75% of the toxic heavy metals found in the soil. None of the PAHs were removed from the soil when deionized water and EDTA were the flushing solutions. The PAHs removal efficiencies in the Igepal and HPCD systems decreased as the hydraulic gradient decreased. However, the surfactant-enhanced systems were more efficient in removing PAHs from the soil than the HPCD systems under high- and low-hydraulic gradients. The results also demonstrated that the removal of PAHs in surfactant-enhanced systems depended upon the micelles formation, whereas in the HPCD-enhanced systems, it depended upon the sterioselective diffusion of the PAHs to the nonpolar cavity of the HPCD. Overall, this study showed that the contaminant removal in soil flushing systems depends on the flushing solution affinity and selectivity toward the target contaminant and the existing hydraulic gradient condition.     

Prediction of Heavy Metals Mobility and Bioavailability in Contaminated Soil Using Sequential Extraction and Biosensors

Several chemical and biological methods have been developed in the last decade to evaluate heavy metals mobility and bioavailability in contaminated soils. In this study, two methods, Biomet sensors and chemical sequential extraction [potentially bioavailable assessment sequential extraction (PBASE) method], were used to predict heavy metals bioavailability in the surface and heavy metals mobility in the subsurface of smelter-contaminated soils, respectively. The heavy metals considered (arsenic, copper, iron, lead, and zinc) were those detected in a previous sampling campaign performed in the contaminated area. Biomet biosensor results indicated that 15–25% of Cu and Zn were bioavailable for plants and animals uptake in the soil surface, whereas higher values were obtained for As and Pb (>60%). In the soil subsurface, iron was identified as the less mobile element, followed by As and Pb, since they were mainly present in the nonsoluble fractions of PBASE method. In contrast, Cu and Zn showed similar distribution between the soluble and nonsoluble fractions. Therefore, PBASE and Biomet are useful and complementary methods which supply different information about heavy metals occurrence in contaminated soils: the first method indicates their potential mobility, whereas the second one shows their potential bioavailability for biota.     

Advanced Oxidation for Treatment of Aqueous Extracts from EDTA Extraction of Pb and Zn Contaminated Soil

The feasibility of using advanced oxidation processes (AOPs): ozone, ozone/sonification, and ozone/ultraviolet (UV) irradiation in treatment to remove heavy metals and ethylenediamine tetraacetate (EDTA) from aqueous extracts, obtained after soil extraction with EDTA, was examined. Extraction of soil contaminated with 1,243?mg?kg?1 Pb and 1,190?mg?kg?1 Zn with 40?mmol?kg?1 EDTA removed 41.8±0.9 and 7.2±.0.2% of Pb and Zn. Of the AOPs tested, only the use of ozone/UV enabled the decomposition of EDTA–heavy metals complexes in aqueous soil extracts, and recovery of released Pb and Zn by sorption on a commercial sorbent Slovakite. After treatment, the concentration of Pb, Zn, and EDTA in the extracts was fairly low (2.87±1.15?mg?L?1, 7.58±2.12?mg?L?1, and 0.012±0.002?mmol?L?1, respectively), and could presumably be reduced even further with a continuation of treatment. The treated extract was used for subsequent soil rinsing, which removed an additional 12.7±1.6 and 2.7±0.1% of soil Pb and Zn. The results of our study indicate that the use of ozone/UV is a feasible option for treatment of aqueous soil extracts from EDTA extraction. Treated extracts could be safely discharged or reused to lower requirements for process water.     

Modeling Elution Histories of Copper and Lead from Contaminated Soil Treated by Poly(amidoamine) Dendrimers

A dynamic “two-site” model was formulated and tested for simulating the elution histories of copper (Cu2+) and lead (Pb2+) from a contaminated soil treated by poly(amidoamine) dendrimers. In the model, the metal sorption sites of the soil were divided into two compartments: one with a fast desorption rate and the other with a slow desorption rate. The model was tested for simulating and predicting Cu2+ and Pb2+ elution histories obtained from column experiments. Compared to the classical “one-site” model and the modified “gamma distribution” model, the “two-site” model not only provides much improved power for simulating the observed metal elution data, but also can more accurately predict the metal elution histories under various experimental conditions including initial metal concentration in soil, dendrimer concentration, and pH.     

Estimation of Operation Time for Soil Vapor Extraction Systems

Soil vapor extraction (SVE) has become an acceptable method of removing volatile organic compounds from soil. However, determining the length of time these systems should operate has been historically difficult. This paper presents a procedure for determining this length of operation. The procedure incorporates principles of uncertainty analysis, contaminant transport, and decision theory. An example is provided to illustrate the use of the procedure. Additional analysis of the results shows that a simple calculation can be made that will determine if a SVE system that has been operating for a period of time and is in the later stages of contaminant removal should continue to operate. This calculation consists of dividing the cost of treating the remaining contaminated soil with an alternative method (e.g., ex situ biological treatment) by the annual operation and maintenance cost and comparing this ratio to the inverse of the interest rate. If this ratio is less than the inverse of the interest rate the system should be shut off.     

Study on Pb and PAHs Emission Levels of Heavy Metals- and PAHs-Contaminated Soil during Thermal Treatment Process

The objective of this study was to use thermal treatment to treat soil contaminated with heavy metals and polycyclic aromatic hydrocarbons (PAHs). The emissions of lead (Pb) and PAHs during the thermal treatment process were evaluated. The parameters included pretreatment, temperature, and speed of the rotary kiln. Cadmium (Cd) had a higher mobility in thermally treated contaminated soil slag than other heavy metals because the primary fraction of Cd was the exchangeable fraction (90%). Of the temperatures tested in this study, the highest emission concentration of Pb occurred at 700°C. The Pb emission concentrations in the gas phase and solid phase were 44?μg/N?m3 and 138.35?μg/N?m3, respectively. In PAHs emissions, naphthalene, acenaphthene (Acp), and fluorene were the main species in the gas phase, at different operating temperatures. The concentrations of these species ranged from 615.5 to 2,002.3?μg/N?m3. Acp and chrysene were the main species in the solid phase at different temperatures, and the concentrations of these species ranged from 25.5 to 113?μg/N?m3.     

重金属污染土壤治理技术应用现状与展望

本文概述了土壤重金属污染的特点及污染的来源，主要从工程措施、农业措施和生物修复措施三方面对国内外各种治理技术进行分析与评论，指出其优缺点。并在此基础上提出了自己的一些见解和看法，为今后这方面的研究提供一些参考。     

Evaluation of Chemical Treatments for a Mixed Contaminant Soil

Treatability tests were conducted on soil from the reservoir No. 2 burning ground at the former Plum Brook Ordnance Works in Sandusky, Ohio. This soil is contaminated with explosives 2,4,6-trinitrotolune (TNT) and 2,4/2,6-dinitrotoluene (DNT), polychlorinated biphenyls (PCB, Aroclor 1260), as well as lead. Lime treatment (alkaline hydrolysis) and persulfate oxidation were tested individually and in combination to treat explosives and PCBs. Lime treatment removed 98% of TNT, 75% of DNT, and 80% of PCBs. Similar removal levels were found for persulfate treatment as well as lime followed by persulfate. The percentage of contaminant removal was found to be independent of initial contaminant concentrations. Treatments of the most contaminated soil did not meet the preliminary remediation goals for explosives or PCBs but would allow for disposal in a nonhazardous waste landfill. Treatment of soil with lower initial concentrations easily met the residential (most stringent) preliminary remediation goals of 16, 61, and 0.22?mg?kg?1 for TNT, 2,6-DNT, and PCB (Aroclor 1260), respectively. Neither alkaline hydrolysis nor persulfate oxidation transferred more than 0.02% of the lead from the soil into the reaction waters. Lead was successfully stabilized via phosphate addition.     

基于体外模拟法评价南京某污灌区土壤及蔬菜重金属污染现状

为探究南京市郊某污灌区环境治理效果、小白菜中重金属健康风险及其根际土壤重金属超标情况,采用靶标危害系数及体外模拟法对研究区小白菜重金属健康风险进行评估,利用农用地土壤污染风险管控标准(试行)(GB 15618—2018)对比小白菜根际土壤重金属超标情况。结果显示,Cd在小白菜根际土壤中最小值达到0.95mg/kg,最大值达到了1.14mg/kg,平均1.05mg/kg,超过农用地土壤污染风险管控标准。对于成人和儿童,其THQ的最大值从大到小排序为Cu>Pb>Cr>Cd>Zn,小白菜对成人及儿童的HI值分别为6.75×10^-3和5.76×10^-3,两者均小于1,表明使用该模型评估得出小白菜中重金属对暴露人体造成的健康影响不明显。成人通过食用研究区小白菜日均摄入Pb、Zn、Cu和Cd的含量范围依次为337~430、3 294~3 025、359~540及288~483mg。儿童通过食用研究区小白菜日均摄入Pb、Zn、Cu和Cd的含量范围分别为221~282、1 985~2 162、235~354及189~317mg。综上所述,重金属生物可给量均未超过每周可耐受摄入量值,证明食用污灌区小白菜不存在重金属健康风险。与前次研究相比(采样时间相隔七年),相关部门对该区域环境治理取得了很好的效果,但还应注意Cd在土壤及小白菜中的迁移及富集。