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.     

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).     

Enhancement of Electrokinetic Extraction from Lead-Spiked Soils

An innovative system was developed to enhance electrokinetic extraction of heavy metals from contaminated soils. The system consists of a layer that was continuously flushed with nitric acid at pH 3 near the cathodic region and two reservoirs with 0.4 M NaOAc at pH 3.8 and acetic acid at pH 4 flushing the anode and cathode, respectively. Both pure kaolinite and carbonate-rich illitic soils were tested. With traditional electrokinetic systems, approximately 60% of lead was transported to the cathode for kaolinite, whereas there was little removal for carbonate-rich illitic soil. This result indicates that clay minerals have an important effect on the desorption process. The integrated electrokinetic system maximized contaminant extraction and minimized precipitation in the cathodic region. Over 80% of the lead was removed from carbonate-rich illitic soil, with 5,000-mg∕kg initial lead contaminated concentration, and leached out through the flushing layer. The system operated successfully in laboratory bench tests with carbonate-rich illitic soil.     

Sequential Electrokinetic Remediation of Mixed Contaminants in Low Permeability Soils

The coexistence of heavy metals and polycyclic aromatic hydrocarbons (PAHs) at many of the contaminated sites poses a severe threat to public health and the environment. Very few technologies, such as soil washing/flushing and stabilization/solidification, are available to remediate such sites; however, these technologies are ineffective and expensive to treat contaminants in low permeability clayey soils. Previous studies have shown that electrokinetic remediation has potential to remove heavy metals and organic compounds when they exist individually in clayey soils. In the present study, the feasibility of using surfactants and organic acids sequentially and vice versa during electrokinetic remediation was evaluated for the removal of both heavy metals and PAHs from clayey soils. Kaolin was selected as a model clayey soil and it was spiked with phenanthrene and nickel at concentrations of 500 mg/kg dry each to simulate typical field mixed contamination. Bench-scale electrokinetic experiments were performed with the sequential anode conditioning with: (1) 1 M citric acid followed by 5% Igepal CA-720; (2) 1 M citric acid followed by 5% Tween 80; and (3) 5% Igepal CA-720 followed by 1 M citric acid. A periodic voltage gradient of 2 V/cm (with 5 days on and 2 days off cycles) was applied in all the tests. A removal of about 96% of phenanthrene was observed in the test with 5% Igepal CA-720 followed by 1 M citric acid sequence. Most of the nickel (>90%) migrated from anode to cathode in this test; however, it precipitated in the section very close to the cathode due to the high pH conditions. Conversely, the removal efficiency of nickel was about 96 and 88% in the tests with 1 M citric acid followed by 5% Igepal CA-720 sequence and 1?M citric acid followed by 5% Tween 80 sequence, respectively. However, the migration and removal efficiency of phenanthrene in both of these tests were very low. Overall, it can be concluded that the sequential use of 5% Igepal CA-720 followed by 1 M citric acid may be an effective remedial strategy to remove coexisting heavy metals and PAHs from clayey soils.     

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.     

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.     

Sequentially Enhanced Electrokinetic Remediation of Heavy Metals in Low Buffering Clayey Soils

This paper presents the results of an experimental investigation undertaken to evaluate different purging solutions to enhance the removal of multiple heavy metals, particularly chromium, nickel, and cadmium, from a low buffering clay, specifically kaolin, during electrokinetic remediation. Experiments were conducted on kaolin spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1,000, 500, and 250 mg/kg, respectively, which simulate typical electroplating waste contamination. A total of five different tests were performed to investigate the effect of different electrode purging solutions on the electrokinetic remedial efficiency. A constant DC voltage gradient of 1 V/cm was applied for all the tests. The removal of heavy metals from the soil using tap water as the purging solution was very low. When 1 M acetic acid was used as the purging solution in the cathode, the removal of chromium, nickel, and cadmium was increased to 20, 19, and 13%, respectively. Using 0.1 M ethylene diamine tetraacetic acid as the purging solution in the cathode, 83% of the initial Cr was removed; however, the nickel and cadmium removal was very low. A sequentially enhanced electrokinetic remediation approach involving the use of water as a purging solution at both the anode and cathode initially, followed by the use of acetic acid as the cathode purging solution and a NaOH alkaline solution as the anode purging solution was tested. This sequential approach resulted in a maximum removal of chromium, nickel, and cadmium of 68–71, 71–73, and 87–94%, respectively. This study shows that the sequential use of appropriate electrode purging solutions, rather than a single electrode purging solution, is necessary to remediate multiple heavy metals in soils using electrokinetics.     

Electrokinetic Remediation Modeling Incorporating Geochemical Effects

Electrokinetic remediation technology is one of the developing technologies that offers great promise for the cleanup of soils contaminated with heavy metals. However, the performance of an electrokinetic remediation system depends on the interaction of a complex set of interrelated system variables and parameters. Many of these interactions were addressed in this study by incorporating geochemical reactions into electrokinetic remediation modeling. A one-dimensional transport model was developed to predict the transport and speciation of heavy metals (chromium, nickel, and cadmium) in soil during electrokinetic remediation as a function of time and space. The model incorporates: (1) pH-dependent adsorption of contaminants to the soil surface; (2) sensitivity of soil surface potential and electroosmotic flow to the pore water properties; and (3) synergistic effects of multiple chemical species on electrokinetic remediation. The model considers that: (1) Electrical potential in the soil is constant with time; (2) surface complexation reactions are applicable in the highly concentrated clay suspensions; (3) the effect of temperature is negligible; and (4) dissolution of soil constituents is negligible. The predicted pH profiles, electroosmotic flow, and transport of chromium, nickel, and cadmium in kaolin soil during electrokinetic remediation were found to reasonably agree with the bench-scale electrokinetic experimental results. The predicted contaminant speciation and distribution (aqueous, adsorbed, and precipitated) allow for an understanding of the transport processes and chemical reactions that control electrokinetic remediation.     

Electrokinetic Remediation of Cadmium-Contaminated Clay

Electrokinetic extraction has been demonstrated to be very effective in removing heavy metals from Georgia kaolinite. The relatively high removal efficiency depends on the extremely acidic soil environment generated by the electrokinetic process. However, the efficiency observed in Georgia kaolinite cannot be achieved in soils of high acid/base buffer capacity without enhancement. In this study, the effect of ethylenediaminetetraacetic acid (EDTA) to enhance electrokinetic extraction of cadmium from Milwhite kaolinite was examined. The influence of electro-osmotic flow direction on the migration of cadmium, EDTA, and their complexes were also investigated. It was observed that injection of EDTA from the cathode reservoir by a reverse electro-osmotic flow could mobilize the cadmium in the specimen effectively. A less significant mobilization of cadmium was observed when the electro-osmotic flow was directed toward the cathode. However, accumulation of cadmium near the anode was observed regardless of the electro-osmotic flow direction.     

北京地区农用地土壤重金属污染与健康风险评价

为系统了解北京地区农用地土壤重金属污染状况,通过检索收集2000年以来北京地区农用地土壤重金属污染相关研究文献数据,并结合空间分析、地累积指数法和人体健康风险评价等方法对其分布规律、污染状况和健康风险进行研究。结果表明,北京地区农用地土壤中8种重金属（As、Cd、Cr、Cu、Hg、Ni、Pb和Zn）平均含量均低于筛选值,但大部点位的重金属含量已超背景值且存在明显的空间变异。地累积指数污染评价显示区域土壤Hg和Cr地累积风险最大,其污染点位占比分别达82%和67%,其余重金属累积污染风险较低。不同暴露途径下,各单一重金属或复合作用导致的非致癌和致癌风险均为可接受水平。但相较于其他重金属而言,土壤As的潜在致癌和非致癌风险最大,建议相关部门加强区域土壤As的监测与管控治理,以期实现区域农业活动可持续绿色安全生产。     

Magnitude and Variability of Biogenic Interference in Cold Regions Soils

In organic soils commonly found in cold regions, many compounds with similar characteristics are found in petroleum contamination and natural organic material (NOM). These similarities make it difficult to distinguish between natural compounds and true contamination using standard test methods. “Biogenic interference” is the term used to describe the NOM quantified as “petroleum” during a standard test for soil contamination. The inability to differentiate between biogenic interference and soil contamination is of concern because it can cause cleanup standards to be set at lower limits than the actual contamination warrants. This paper presents the results from over 200 uncontaminated soil samples that were analyzed to determine the magnitude and variability of biogenic interference in soils from cold regions. Studies were conducted to evaluate the correlation between fundamental physical∕chemical properties of soil and extractable NOM levels. Samples were also collected and analyzed to evaluate spatial (vertical and horizontal) variations in background extractable NOM at one site. A final set of samples was analyzed to determine the range of background extractable NOM levels at uncontaminated sites throughout Alaska. The results show that uncontaminated soil from across Alaska can contain several hundred to several thousand mg∕kg of extractable naturally occurring diesel and residual range organics. A high degree of variability was observed in the amount of extractable NOM at different sites across Alaska and within a single site.     

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.     

赣州市土壤重金属形态分布特征及污染评价

以赣州市6大功能区土壤重金属为研究对象,采取表层0~20cm土壤共50个样品,测定土壤中重金属Pb、Zn、Cu、Cd和Cr含量并分析其来源,采用改进BCR连续提取法进行形态分析,结合次生相与原生相分布比值法、单因子指数法进行污染评价。结果表明研究区土壤中Pb和Cu元素变异系数较大,重金属Zn, Cu和Pb之间相关性显著。通过单因子指数法评价结果可以看出,赣州市6大功能区都受到重金属Cd的重度污染,居民区和工业区受到重金属Cr的轻度污染,交通区受到重金属Pb和Zn的轻度污染。研究区土壤重金属Cd、Cr、Cu、Pb、Zn形态都以残渣态为主,次生相与原生相比值都是小于1的属于无污染。      

冷水江锑矿废弃地乡土树种重金属富集能力研究

采集并分析了冷水江锑矿区废弃地乡土树种及其根际土壤重金属含量,研究了树种对重金属的富集和转运特征。结果表明:矿区废弃地土壤中Cd含量超出国家土壤污染风险筛选值(GB 15618—2018),Sb含量是全国土壤背景值的104~226倍,以Cd、Sb重污染为主,伴有As、Hg、Pb复合污染。采集的8种乡土树种均对重金属元素表现出一定的耐受性,柏木、楸树对Hg、Cd和Sb的富集与运转能力较强;构树对Pb、Hg、Cd和Sb的富集与运转能力较强;南酸枣对Hg、Cd和Sb富集能力强,Cd、Sb运转能力较弱;七里香、梓树、棕榈和大叶女贞对Hg、Cd富集与运转能力强。根据废弃地重金属污染情况与树种对重金属的富集系数、运转系数,得出柏木、楸树、南酸枣和构树适合作为锑矿区废弃地植物修复的优选树种。     

Respiratory symptoms and pulmonary function in coal miners: looking into the effects of simple pneumoconiosis

Most soil quality guidelines do not distinguish among the various forms of metals in soils; insoluble, nonreactive, and nonbioavailable forms are deemed as hazardous as highly soluble, reactive, and toxic forms. The objective of this study was to better understand the long-term effects of copper on microorganisms in relation to its chemical speciation in the soil environment. Carbon mineralization processes and the global structure of different microbial communities (fungi, eubacteria, actinomycetes) are still affected after more than 50 years of copper contamination in 20 soils sampled from two different agricultural sites. The microbial respiration lag period (LP) preceding the beginning of mineralization process increases with the level of soil copper contamination and is not significantly affected by other environmental factors such as soil pH and soil organic matter (SOM) content. The total copper concentration showed the best correlation with the LP when each site is considered separately. However, when considering the whole set of data, soil solution free Cu2+ activity (pCu2+) is the best predictor of Cu toxicity determined by LP (quite likely because pCu2+ integrates the soil physicochemical variability). The maximum mineralization rate (MMR), even if well correlated with the pCu2+, appears not to be a good biomonitor of copper contamination in soils since it is highly sensitive to soil characteristics such as SOM content. This study emphasizes the importance of the physicochemical properties of the environment on soil heavy metal toxicity and on soil toxicological measurements. These properties must be characterized in soil toxicological studies with respect to (1) their interactions with heavy metals, and (2) their direct impact on the selected biological test. The measurement of pCu2+ to characterize the level of soil contamination and of lag period as a bioindicator of metal effects in the soil are recognized as useful tools for the evaluation of the biological quality of soils.     

Pyrolysis-GC∕FID Test for Biogenic Interference in Contaminated Soil

“Biogenic interference” is that portion of natural organic matter in soil that cannot be distinguished from petroleum in a standard test for contamination. Biogenic interference is normally a small fraction of total natural organic matter. In organic soils, however, biogenic interference alone can exceed “petroleum” limits set by regulatory agencies. A test using a pyrolysis-gas chromatograph∕flame ionization detector (GC∕FID) was developed to quantify biogenic interference in soil samples from northern Alaska. The samples had no known history of contamination, so all measured “petroleum” was derived from biogenic interference. The pyrolysis test was found to predict biogenic interference in soil samples more accurately than any combination of standard soil tests, including C:N ratio, pH, percent organic carbon, extractable carbon, humic acids, fulvic acids, low molecular weight acids, hydrophobic neutrals, and hydrophilic neutrals. Analysis of samples contaminated in the laboratory confirmed that the pyrolysis test could quantify biogenic interference in soils recently contaminated by petroleum.     

双桥河流域农田土壤重金属分析与评价

金矿石的开采及选冶生产会将矿石中的重金属释放到环境中,对环境造成污染。为了研究金矿石开采及选冶生产对土壤环境质量的影响,在研究区域采集不同地貌单元的土壤样品,分析测定其重金属含量;通过与国家土壤环境质量标准比较,以及与邻区土壤样品分析测定结果对照,结果表明,不同地貌单元农田土壤中汞污染最严重,超标倍数平均值为1.29,是各地貌单元的主要污染物;山前冲洪积斜塬区、河流冲洪积阶地区及黄土沟壑台塬区土壤重金属综合污染指数分别为1.98,1.53,1.59,达到轻度污染;土壤综合累积污染指数分别为23.57,18.66,19.56,达到极严重累计污染。研究结果说明,人类矿业活动对土壤环境质量的影响值得重视,土壤中重金属污染与矿业活动频繁息息相关。     

电动联合可渗透反应墙强化修复重金属污染土壤研究进展

已有大量研究证明电动（EK）-可渗透反应墙（PRB）联合技术能用于重金属污染土壤的修复,但其修复效率低且能耗高,还可能导致聚焦效应等问题,因此深入EK-PRB在强化修复方面的研究是十分必要的。简述了EK-PRB技术的原理,介绍了EK-PRB技术的主要影响因素,归纳了EK-PRB强化修复方法的优缺点和修复效果,介绍了EK-PRB技术的研究进展,并对该技术强化修复重金属进行了展望,指出深入探究的方向,以便为EK-PRB修复多种重金属污染土壤的实际应用打下基础。     

Do microglial cells have a neuroprotective function?

Generally, soil heavy metal contamination consists of a mixture of heavy metals. Soil chemical properties and interaction with other pollutants in soil affect the external heavy metal bioavailability. Moreover, interaction with other pollutants accumulated in organisms may change the toxicity of each pollutant. Therefore, the hypotheses was tested that addition of Cd or Pb to Cu-contaminated soil would lead to an increase in tissue Cu accumulation in the earthworm, Dendrobaena veneta, caused by (i) induction of metallothionein by Cd, or (ii) an increase in Cu concentration in soil solution due to the exchange of adsorbed Cu for Pb. Tissue heavy metal concentrations were determined after exposure in contaminated soils for 3 or 21 days. Considerable amounts of Cu, Cd, and Pb were accumulated, indicating that these heavy metals were available for uptake by D. veneta. Both Cd and Pb, however, did not significantly affect tissue Cu accumulation.     

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.