Characterization of Heavy Metal Fractions in Agricultural Soils by Sequential Extraction Procedure: The Relationship Between Soil Properties and Heavy Metal Fractions

The present research was conducted to determine heavy metals in agricultural soils from Çanakkale, Turkey, using a sequential extraction procedure (acid soluble, reducible, oxidizable, and residual) as proposed by the Community Bureau of Reference (BCR) of the European Commission. Soil samples were taken from 12 different cultivated sites and analyzed for Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn concentrations. The results revealed an order of Mn > Cd > Pb > Co > Ni > Cu > Zn > Cr for the heavy metals based on the sum of the first three fractions (acid soluble + reducible + oxidizable). The relationships between soil properties and each metal fraction were identified through Pearsons's correlation analysis. Hierarchical cluster analysis was performed to determine the behaviors and similarities of metals in each fraction. While Mn, Pb, and Zn exhibited subjective behaviors in the acid-soluble fraction, Cd, Co, Cu, Cr, and Ni exhibited similar behaviors with each other.     

Heavy Metal Contamination in Roadside Soil and Their Mobility in Relations to pH and Organic Carbon

Concentrations of Pb, Zn, Cd, Ni, Cu, Cr, and Mn were determined to assess the impact of automobiles on heavy metal contamination of roadside soil. Soil samples at four polluted sites and a control site were collected at a depth of 0, 2, 5, 10, 15, 20, 30?cm. A comparison of elemental levels between polluted and control sites exhibited exceptionally higher concentrations at the former sites. The Pb levels in polluted sites varied from 70 to 280.5?µgg^?1and it rapidly decreased with depth. Similarly, mean concentrations of Zn, Cd, Ni, Cu, Cr, and Mn were significantly higher at polluted sites and followed a decreasing trend with the increase in depth. Correlation coefficients between heavy metals and traffic density were positively significant except for nickel. Profile samples showed that Pb, Zn, Cd, Cu, and Mn were largely concentrated in the top 5?cm confirming airborne contamination. The vertical movement and partitioning of metals, except Ni and Cr, exhibited predominant association with soil pH and organic carbon. The results have been presented using Heavy Metal Index.     

福建漳州菜园土壤重金属污染评价及防治

调查福建省漳州市菜园土壤重金属Cd、Pb、Hg、Cr及非金属有害元素As含量,并采用单项污染指数法和综合污染指数法进行评价。结果表明,以福建土壤背景值为评价标准,漳州市部分菜园土壤受到重金属污染,单项污染指数的顺序为Cd(2.39) >Hg(2.00) >Pb(1.40) >Cr(0.63) >As(0.57),污染元素主要为Cd、Pb、Hg,其中Cd、Hg为中度污染;综合污染指数为1.75,属轻度污染。而以土壤环境质量二级标准为评价标准,其综合污染指数为0.14,污染等级为未受污染。     

A Practical Examination of the Use of Geostatistics in the Remediation of a Site with a Complex Metal Contamination History

Targeted remediation strategies offer the potential to treat only those areas where contamination exceeds predefined threshold levels. We used geostatistical techniques to characterize spatial distribution of heavy metals across a contaminated site, with the aim of delineating the contaminants, which is essential for successful implementation of targeted remediation strategies. Samples collected from three depths, 0–20 cm, 20–40 cm and 40–60 cm at 50 sample locations, were analyzed for As, Sb, Hg, Pb, Cd and Cu contents. The geostatistical analysis of this data enabled the identification of a number of contamination hotspots and trends. The visual interpretation of the data was supported by the statistical analysis in the form of Spearman's rank correlation coefficient. Additionally, classical statistics, based on the central limit theorem, showed that, in terms of obtaining the true mean for each of the contaminants within acceptable limits of precision, the site has been more than adequately sampled.It has been demonstrated that kriging can offer the potential to map the spatial distribution of contaminants. However, the possibility of an undetected hotspot remains, even when probabilistic modelling and a secondary phase of validatory sampling are employed. This together with the large number of samples required may preclude the commercial use of geostatistics in the remediation of contaminated land.     

重金属污染土壤修复技术中有关淋洗剂的研究进展

淋洗法是修复污染土壤的一种很有效的方法 ,是对污染土壤生物修复的一种补充 ,使污染土壤修复的系统化成为可能。淋洗法就是使用淋洗剂来清洗土壤 ,使土壤中污染物随淋洗液流出 ,然后对淋洗液及土壤进行后续处理 ,从而达到修复污染土壤的目的。而淋洗剂的选择是影响这一技术效率高低的主要因素之一。本文对目前淋洗剂的应用情况 ,作用机制进行了总结和评价。探讨了天然有机酸、生物表面活性剂等对环境影响小的淋洗液的应用前景。并根据“以废治污”的指导思想提出并分析了以柠檬酸废水和味精废水作为淋洗剂修复重金属污染土壤的可行性。     

Study of Heavy Metal Distribution in Soils Impacted with Crude Oil in Southern Nigeria

The study presents the levels and enrichment factors of heavy metals in soils of southern Nigeria that have received significant impact of crude oil spillage. The results revealed that the concentrations of heavy metals in the examined soils fitted into levels found in agricultural soils except for cadmium. Heavily impacted sites showed elevated levels of heavy metals compared to less impacted sites and background levels. The mean enrichment factors for Cd, Cu, Cr, Pb, Mn, Ni, and Zn were 37.3, 2.8, 14.4, 14.0, 0.77, 5.4, and 1.27 for topsoil and 37.5, 1.30, 7.81, 1.59, 4.12, and 1.28 for subsoil, respectively. This clearly indicates that there is gradual build-up of heavy metals in these soils as a result of the oil spillage and related anthropogenic activities in this area.     

Complexation of a Ligand with a Surfactant Micelle for Soil Heavy Metal Desorption

The ligands iodide (I^?) and thiocyanate (SCN^?), alone or in admixture, in combination with a non-ionic surfactant, Triton X-100, were evaluated as washing agents for heavy metal desorption from a contaminated soil. After seven successive washings, selective sequential extraction (SSE) was performed to determine the heavy metal content that remained associated with each geo-chemical fraction of the soil. The surfactant with 0.336 mol L^?1 of ligand I^? removed 75% Cd and 23% Cu, whereas the mobilization of Zn and Pb were not significant after 7 washings. At a concentration of 0.286 mol L^?1, the ligand SCN^? in the presence of surfactant removed 36% Cd, 44% Cu and 77% Zn. Among the washing agents, the combination of I^? and SCN^? produced the highest desorption efficiencies 95% Cd, 48% Cu, and 3.1% Pb, but not for Zn. The SCN^? ligand extracted the most Zn (77%). The SSE procedure indicated that the I^? removed metals from the exchangeable, carbonate and oxide fractions whereas SCN^? removed metals only from the exchangeable fraction. Both ligands, in the presence of surfactant, removed Cu from all fractions except the exchangeable sites, whereas only SCN^? plus surfactant removed Zn from all fractions. The ligand mixture plus surfactant mobilized only limited quantities of Pb from the oxide and residual fractions.     

Traffic-Related Heavy Metal Accumulation in Soils and Plants in Northwest China

Pollution caused by traffic activities is increasingly becoming a great threat to urban environmental quality and human health in many municipalities in Northwest China. The Sophora japonica L., a native tree species occurring widely in many regions of Northwest China, was used as a case study to assess the potential effects of traffic pollution on heavy metal accumulation in leaves of S. japonica trees and associated soils. Fifty-four leaf samples and 41 relevant soil samples (0–10 cm) were collected systematically along main trunk roads and at parks distant from main trunk roads in the city of Lanzhou, Northwest China, respectively. Traffic pollution has resulted in significant accumulation of heavy metals in both the roadside leaves and soils, but the pattern and level of accumulation varied remarkably between elements. The nine elements examined can be classified into three groups relating to their responses to traffic pollution. The first group, including Zn, Cd, Hg, Pb and Cr, showed greater accumulation in both roadside soils and leaves. The second group, including Co, Ni and As, indicated greater accumulation in the roadside leaves only. The third group included only Cu and demonstrated a greater accumulation in the roadside soils only. Overall, Zn, Cd, Hg, Pb, Cu and Cr concentrations in the roadside soils were higher (8–72%) than those in the park soils, as well as much higher (32–300%) than the background values of the respective elements set for local soils (Lanzhou). Zn, Cd, As, Hg, Pb, Cr, Ni and Co concentrations in the roadside leaves were higher (27–111%) than those in the park leaves. The differences found among elements in the levels of accumulation suggest that the relative importance of the individual elements contributing to urban environmental deterioration will vary considerably.     

黑土中几种重金属的化学形态

在自然界中,重金属元素的总浓度不能正确反映出它们对生物的效应和地球化学的过程。重金属的毒性在很大程度上取决于它们存在的化学形态。重金属进入土壤这个有机、无机复合体后,通过溶解、沉淀、凝聚、络合、吸附等各种反应,形成重金属的不同化学形态,并表现出不同的活性。东北地区的黑土,其主要特征是富含有机质,为了探索土壤有机质含量与土壤重金属的亲合力及其在土壤中存在的各种形态,我们用A.Tesser等提出的连续浸提法,作了重金属元素在黑土中存在形态的研究,这对进一步研究土壤净化功能与土壤环境容量具有一定意义。     

Organic Contamination in Soils Associated with Cemeteries

This study examined the organic contaminants in soils from an older cemetery in Ohio. Thirty soil samples at various depths and distances from graves were obtained and analyzed using organic solvent extraction, concentration, and gas chromatography with mass selective detector. The signatures of methylene chloride-extracted organic compounds show interesting trends vertically within the cemetery, with less apparent horizontal trends. Alkanes in the 18 to 34 carbon number range dominated most core samples. However, the abundance of the lighter C₁₈ to C₂₆ alkanes is unique to the deep samples onsite. Statistically, depth is relatively unimportant in predicting the abundances of the heavier compounds, whereas distance from the nearest grave is significant to predicting the area of light and heavy alkanes. These signatures are very similar to those obtained through maturation and release of organic matter in the subsurface. Evidence indicates release of organic compounds into the surrounding vicinity of the cemetery, but not necessarily off-site.     

Phytostabilization of Acidic Soils with Heavy Metal Contamination Using Three Forage Grasses in Combination with Organic and Inorganic Amendments

Two experiments were conducted to investigate the effects of organic and inorganic amendments on metal stabilization and the potential of three forage grasses, i.e., Pennisetum americanum × Pennisetum, Euchlaena mexicana, and Sorghum dochna, for phytostabilization of acidic heavy metal-contaminated soils. The three grasses died 5 days after transplanting into the contaminated soils. Organic fertilizer (pig slurry and plant ash) only or combined with lime, NPK fertilizer, and sewage sludge resulted in adequate grass growth in the contaminated soils through a significant increase in the soil pH, N, P, K, and organic matter contents, and a decrease in the metal concentrations. The shoot biomass of P. americanum×P. purpureum and S. dochna was 1.92 and 2.00 times higher than that of E. Mexicana. The solubility of Cd, Pb, and Zn strongly depends on organic matter, while the solubility of Cu strongly depends on both soil organic matter and pH. The concentrations of Cd, Pb, and Zn in plant shoots growing in soil with a mixed amendment were significantly lower than plants growing in soil amended with an organic fertilizer only, whereas the Cu concentrations in plant shoots exhibited the opposite trend. The results indicated that 5% organic fertilizer only or combined with 5% sewage sludge were appropriate amendments and S. dochna and P. americanum × Pennisetum are suitable plants for phytostabilization of acidic heavy metal-polluted soils.     

Chemical Extraction of Arsenic and Heavy Metals from Contaminated Soils Under High Temperature and Pressure Conditions in Abandoned Mines in South Korea

The chemical extraction of As and heavy metals from contaminated soils, sampled from the Geopoong and Keumpoong mines in South Korea, was investigated under subcritical conditions. Soil samples from the abandoned mines were heavily contaminated with As, Cd, Cu, Pb, and Zn. The extent of metal removed from the contaminated soils by extractants varied according to the chemical forms of the metals in the soils. When temperature increased, the extraction of As increased accordingly, showing 92-100% removal with 100 mM of NaOH at 300°C. In contrast, the extraction of cationic metals by citric acid and ethylenediaminetetraacetic acid (EDTA) decreased markedly at 200–300°C because their chelating ability was decreased via decarboxylation and dehydration at high temperatures. Furthermore, the extraction of cationic metals was significantly affected by solution pH. Our results suggest that chemical extraction of cationic metals under subcritical conditions may be affected by several factors, including character of metal, type of extracting reagent, existing forms of metal in the soil, temperature, and soil pH.     

Instances of Soil and Crop Heavy Metal Contamination in China

Both general and specific investigations of soil and crop heavy metal contamination were carried out across China. The former was focused mainly on Cd, Hg, As, Pb, and Cr in soils and vegetables in suburbs of four large cities; the latter investigated Cd levels in both soils and rice or wheat in contaminated areas throughout 15 provinces of the country. The results indicated that levels of Cd, Hg, and Pb in soils and some in crops were greater than the Governmental Standards (Chinese government limits for soil and crop heavy metal contents). Soil Cd ranged from 0.46 to 1.04?mg kg^?1, on average, in the four cities and was as high as 145?mg kg^?1 in soil and 7?mg kg^?1 in rice in the wide area of the country. Among different species, tuberous vegetables seemed to accumulate a larger portion of heavy metals than leafy and fruit vegetables, except celery. For both rice and wheat, two staple food crops, the latter seemed to have much higher concentrations of Cd and Pb than the former grown in the same area. Furthermore, the endosperm of both wheat and rice crops had the highest portion of Cd and Cr. Rice endosperm and wheat chaff accumulated the highest Pb, although the concentrations of all three metals were variable in different parts of the grains. For example, 8.3, 6.9, 1.4, and 0.6?mg kg^?1 of Pb were found in chaff, cortex, embryo, and endosperm of wheat compared with 0.11, 0.65, 0.71, and 0.19?mg kg^?1 in the same parts of rice, respectively. Untreated sewage water irrigation was the major cause of increasing soil and crop metals. Short periods of the sewage water irrigation increased individual metals in soils by 2 to 80% and increased metals in crops by 14 to 209%. Atmospheric deposition, industrial or municipal wastes, sewage sludge improperly used as fertilizers, and metal-containing phosphate fertilizers played an important role as well in some specific areas.     

Heavy Metal Balances, Part I

The control of heavy metals in such a way that soil functioning and product quality are not impeded is a prerequisie to sustainable agricutture. The current status of heavy metal accumulation in agricultural soils differs widely by region, by metal, and by agricultural system; levels of concern have already been reached in several regions (for instance, in the Netherlands and Australia). An analysis of the input and output fluxes of cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) in agriculture and of their resulting accumulation in agricultural soils is necessary to define strategies that ensure sustainable management of these metals in agricultural systems. In this article, general aspects of heavy-metal balance studies are described for the agricultural sector within the broader context of substance flow analysis and industrial ecology. The approach chosen in this study is both precautionary and related to actual problem areas.     

Mycorrhizal and Endophytic Fungal Colonization in Arrhenatherum elatius L. Roots According to the Soil Contamination in Heavy Metals

The aim of this work was to jointly study non-mycorrhizal (dark septate fungi) and mycorrhizal (arbuscular mycorrhizae) colonization along a large range of heavy metal pollution in soil in order to determine the effective contribution of each type of endophytes in relation to heavy metal uptake and tolerance. Hence, eight sites were chosen in the mining area of northern France with respect both to a large range of heavy metal contamination (Cd, Pb, Zn) and monospecific colonization by Arrhenatherum elatius. Root colonization with both arbuscular mycorrhizae (AM) and dark septate fungi (DSF) as well as spore density in rhizospheric soil were estimated in relation to soil characteristics. Mycorrhizal infestation (hyphae, arbuscules and vesicles) was adversely affected by soil pollution almost to exclusion. The intensity of colonization with DSF was very low in presence of AM in non-contaminated soils but higher in polluted soils. The effect of the fungal colonization on the heavy metal tolerance of Arrhenatherum elatius is discussed.     

我国土壤重金属污染植物吸取修复研究进展

我国从上世纪90年代中后期开始土壤重金属（含类金属砷）污染的植物吸取修复研究及技术探索,先后发现了一批具有较高研究价值和应用前景的铜、砷、镉、锰等重金属的积累或超积累植物,并从重金属耐性和超积累生理机制、植物吸取修复的根际过程与机制、吸取修复强化措施和修复植物处置与资源化利用等方面进行了研究,同时开展了植物吸取修复技术的示范与应用,已有一些较成功的植物修复工程应用案例,使我国重金属污染土壤植物修复技术,尤其是植物吸取修复技术在国际上产生了较强的影响力。本文就近年来我国土壤重金属污染植物吸取修复研究进展进行了综述,并对今后的发展趋势进行了展望。     

武汉市蔬菜重金属污染现状的调查与评价

通过对武汉市6种蔬菜的供食部位及所对应的土壤中重金属Hg(汞)、Cu(铜)、Pb(铅)、Cd(镉)、Cr(铬)、Zn(锌)、As(砷)含量及分布特征进行了检测,结果表明:Pb、Cr是武汉市蔬菜中主要的污染元素;Hg、Cd只在个别叶菜类上超标;Zn、Cu、As无超标样。在所时应的土样中,普遍存在污染的是Cd,其它6种重金属元素均未超标。     

Physicochemical and Mineralogical Characterization of Uranium-Contaminated Soils

Physicochemical and mineralogical properties of the contaminants should be taken into account to decide a remediation strategy for a given radionuclide because development and optimization of soil remedial technologies are based on physicochemical and mineralogical separation techniques. The objectives of this study are to (1) demonstrate how a priori physicochemical and mineralogical characterization of soil contaminants can direct the development of remediation strategies and their performance evaluation for soil treatments and (2) understand the nature of uranium contamination and its association with the soil matrix by chemical extractions. This study examined two U-contaminated sites (K311 and K1300) at the DOE K-25 site, presently located at East Tennessee Technology Park, Oak Ridge, Tennessee. Uranium concentrations of the soils ranged from 1499 to 216,413 Bq kg^?1 at both sites. Scanning electron microscopy with backscattered electron spectroscopy and X-ray diffraction analysis showed that the dominant U phases are U oxides (schoepite), U-Ca-silicate (uranophane) and U silicate (coffinite) from the K311 site soils, whereas U-Ca-oxide and U-Ca-phosphate dominate in the K1300 site soils. Sodium carbonate/bicarbonate leaching was effective on the K1300 site soils, whereas citric acid leaching is effective on the K311 site soils. Sequential leaching showed that the majority of the uranium in the contaminated soils was contained in carbonate minerals (45%) and iron oxides (40%). Conventional leaching showed that citric acid treatment was most effective on the K311 site soils, whereas the sodium carbonate/ bicarbonate treatment was most effective on the K1300 site soils.     

Heavy Metal Contamination in Urban Surface Soil of Klang District (Malaysia)

This study aimed to determine bioavailability of heavy metal concentrations (Al, Fe, Zn, Cu, Co, Cd, Pb and Cr) in 76 urban surface soil samples of Klang district (Malaysia). This study also aimed to determine health risks posed by bioavailability of heavy metals in urban soil on adults and children. For bioavailability of heavy metal concentrations, a physiologically bioavailability extraction test in vitro digestion model was used. Mean values of bioavailability heavy metal concentrations for this study were found to be the highest in Al (25.44 mg/kg) and lowest in Cr (0.10 mg/kg). Results of Spearman correlation coefficient (r) values showed significant correlations were observed for Al-Fe (r = 0.681), Cd-Co (r = 0.495), Cu-Zn (r = 0.232), Fe-Pb (r = 0.260), Fe-Zn (r = 0.239). For cluster analysis, output showed that these heavy metals could be classified into four clusters: Cluster 1 consisted of Cd, Cr, Co, and Pb; Cluster 2 consisted of Zn and Cu; Cluster 3 consisted of Fe; and Cluster 4 consisted of Al. For Clusters 1 and 2, anthropogenic sources were believed to be the sources, while for Clusters 3 and 4 the heavy metals originated from natural sources. Health risks were determined in adults and children through health risk assessment. For adults, Hazard Quotient (HQ) value was <1, indicating no non-carcinogenic risk, while for children, the HQ value was >1, indicating a non-carcinogenic risk. Meanwhile, for carcinogenic risk, heavy metal contamination in the Klang district might not pose a carcinogenic risk to adults while it may pose a carcinogenic risk to children because TR values in this study were >1.0E-04 for children. Output has identified the general health risk in the Klang district. Moreover, this study's findings will contribute to fill in the gap of knowledge on heavy metals' impacts on human health and urban development in the Klang District.     

Contamination Levels Remaining in Aznalcóllar Spill-Affected Soils (Spain) Following Pyritic Sludge Removal

Potentially toxic elements (PTE) in aqua regia extracts were analyzed by ICP in order to determine the remaining degree of contamination of the selected points along Agrio and Guadiamar rivers. The studied area was affected in 1998 by the accidental spillage from a flotation plant for complex sulfides located at Aznalcóllar (Spain), it was covered by acidic waters and pyritic sludge. Emergency response for the remediation of the contaminated soils, for avoiding greater ecological impact, and waiting for possible ulterior remedial actions, was the removal of the superficial sludge. Sampling was done after the sludge removal operations 1 year after the spill, at different depths down to 300?cm. The results show that the soils affected are still contaminated by several PTE at different degrees and depths depending on their particular conditions. In general, superficial soil samples became highly contaminated. The contamination of soils is due, in general, to processes of sludge infiltration and PTE leaching. The sludge infiltration is due, in part, to the heavy machinery used to remove the sludge. A moderate degree of contamination remains in some soils down to 120 or 300?cm.