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.     

Removal of Heavy Metals from Contaminated Soil and Sediments Using the Biosurfactant Surfactin

The feasibility of using a biodegradable surfactant, surfactin from Bacillus subtilis, for the removal of heavy metals from a contaminated soil (890?mg/kg zinc, 420?mg/kg copper, 12.6% oil and grease) and sediments (110?mg/kg copper, 3300?mg/kg zinc) was evaluated. Results showed that after one and five batch washings of the soil, 25 and 70% of the copper, 6 and 25% of the zinc, and 5 and 15% of the cadmium could be removed by 0.1% surfactin with 1% NaOH, respectively. From the sediment, 15% of the copper and 6% of the zinc could be removed after a single washing with 0.25% surfactin/1% NaOH. The geochemical speciation of the heavy metals among the exchangeable, oxide, carbonate, organic, and residual fractions was determined by selective sequential extraction procedure. For both matrices, the exchangeable fractions were minimal, while the carbonate and the oxide fractions accounted for over 90% of the zinc present and the organic fraction constituted over 70% of the copper. Results after washing indicated that surfactin with NaOH could remove copper from the organic fraction, zinc from the oxide, and cadmium from the carbonate fractions. The residual fraction remained untouched. These experiments indicate that the sequential extraction studies could be useful in designing soil-washing procedures.     

Heavy Metal Contamination in the Brownfield Soils of Cleveland

The results esults of a survey of heavy metal contamination at Cleveland area brownfields and public spaces are presented. Soils were analyzed using a 24?h, 1N HCl extraction procedure. The study was conducted to seek brownfield soils that manifest properties of “old” sequestered contamination and to develop a better understanding of the nature and extent of heavy metal burdens at brownfield sites in the Greater Cleveland area. The results indicated that Cleveland brownfields commonly yield soil burdens well above remediation triggers for residential soils and often yield values above industrial remediation triggers. It was also discovered that public areas in the vicinity of brownfields commonly have heavy metal contamination significantly above background levels and occasionally above residential remediation triggers. These results indicate that brownfields redevelopment initiatives should proceed with caution. The appropriate remediation goals or restrictions must be imposed to control urban exposure to heavy metal contamination.     

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.     

福建漳州市香蕉园土壤重金属污染调查分析

调查福建省漳州市香蕉园土壤重金属Cd、Pb、Hg、Cr、Cu及非重金属有害元素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,漳州市部分香蕉园土壤受到重金属污染,单项污染指数的顺序为Hg(1.60)> Pb(1.26)> Cd(1.07)> Cu(0.76)> As(0.50)> Cr(0.38),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1.16,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0.34,表明未受污染。对不同取样点土壤重金属污染情况比较分析,说明道路交通、生活垃圾及生活污水均会造成香蕉园土壤不同程度的重金属污染,主要表现为Cd、Pb、Hg的污染。     

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。     

Removal of Heavy Metals from Sewage Sludge Used as Soil Fertilizer

This work has examined sewage sludge of the following heavy metal concentrations (mg/kg): Cd-3.43; Co-5.25; Cu-131; Fe-51300; Mn-177; Ni-37.5; Pb-104; Zn-3300. Metals speciation by sequential extraction according to Tessier et al. (1979), and Rudd et al. (1988), and a procedure recommended by European Community Bureau of Reference (BCR) (Ure et al., 1993; Quevauiller et al., 1996; Davidson et al., 1999), as well as analysis of chemical forms of metals, have been carried out. It has been found that only Zn concentration is higher than the value permissible for agricultural sewage sludge application (2500 mg/kg). The results obtained by Tessier et al. (1979) Tessier, A., Campbell, P. C. and Bisson, M. 1979. Sequential extraction procedure for the speciation of particulate trace metals.. Anal. Chem., 51: 844–851. [Crossref], [Web of Science ®] [Google Scholar], and BCR procedures (Ure et al., 1993; Quevauiller et al., 1996; Davidson et al., 1999) appeared to be consistent. A comparison of the sequential analysis and the analysis of chemical forms of metals indicates that the sum of metal concentrations for the exchangeable, carbonate and bound to Fe/Mn oxyhydroxides forms (found by Tessier et al., 1979, and BCR analyses (Ure et al., 1993; Quevauiller et al., 1996; Davidson, et al., 1999)) corresponds to the sum of sulfate, oxide, metallic and siliceous forms. The concentrations of the forms bound to organic matter or sulfides correspond to the sulfide form while the residue corresponds to the ferrate form. Preparative extraction of metals from the sewage sludge using sodium salt of ethylenediaminetetraacetic acid (EDTA-Na), sodium pyrophosphate (V) and ammonia water has also been investigated. As far as the examined leaching agents are concerned, EDTA-Na appeared to be the best. Single leaching with this agent results in the following metal concentrations remaining in the sludge (mg/kg): Cd-1.1; Co-2.1; Cu-105; Fe-17700; Mn-28.3; Ni-12.8; Pb-44; Zn-1200. They meet the requirements of Polish regulations concerning the use of sewage sludge as a soil fertilizer.     

Advances in Cotton Tolerance to Heavy Metal Stress and Applications to Remediate Heavy Metal-Contaminated Farmland Soil

Heavy metal-contaminated soil is one of the major environmental pollution problems of agricultural production and human health in the world. Remediation of heavy metals in soil is one of the most popular research subjects. Different remediation strategies have been reported to remove heavy metals from contaminated soil, among which phytoremediation is the most important one. Compared with other major crops, cotton shows the strongest and most widespread resistance to abiotic stresses, such as heavy metals. Although heavy metal stress adversely affects the growth and development of cotton, cotton possesses a set of sophisticated stress-resistance strategies. As the main product of cotton is nonedible fibers, which have a large biomass and strong heavy metal absorption and enrichment capacities, cotton is an ideal crop to restore heavy metal-contaminated soils and has unique advantages in terms of both ecological and economic benefits, with great application prospects. In this review, based on domestic and foreign research results in recent years, the effects of heavy metals on cotton growth and product quality were analyzed, the heavy metal absorption, accumulation, translocation and enrichment characteristics of cotton plants were summarized, and the adaptation and tolerance mechanisms of cotton to heavy metals were explored. Furthermore, the view that cotton is an effective crop to remediate heavy metal pollution in farmland soil has been proposed, and popularization and application suggestions for planting cotton to repair heavy metal pollution have been put forward to provide a reference for the comprehensive evaluation of the economic feasibility of cotton to repair heavy metal pollution in farmland soil.     

利用能源植物治理土壤重金属污染

随着工农业的发展,土壤重金属污染日益加剧,严重威胁着粮食生产和人类健康。植物修复因其成本低、环境友好以及可大规模原位修复等优点备受关注,成为近年来迅速发展的重金属污染土壤治理技术。在介绍国内外植物修复技术发展与应用现状的基础上,提倡大力发展能源植物修复重金属污染土地,并结合湖南重金属污染田间试验结果,重点对甜高粱(Sorghum bicolor(Linn.)Moench)用于重金属污染土壤修复的优势、可行性及提高修复效率的措施进行了深入分析与探讨。利用甜高粱治理土壤重金属污染,能将土壤修复与生物能源生产有机结合,使重金属从粮食链转入能源链,同时兼顾了生态和经济效益,具有广阔的应用前景。     

Ecofriendly Heavy Metal Stabilization: Microbial Induced Mineral Precipitation (MIMP) and Biomineralization for Heavy Metals within the Contaminated Soil by Indigenous Bacteria

Heavy metals (HMs) pollution is a serious problem, worldwide. The present study focuses on HMs removal (HMs mobility restricted within soil) by microbial induced mineral precipitation (MIMP) using indigenous isolates. Indigenous isolates were identified as Bacillus subtilis C(225)(MK334652), Oceanobacillus indicireducens 5(225)(MK334653), and Bacillus pumilus 7(225)(MK334654) by 16S-rRNA from HMs polluted industrial-soil (soil-225) that is used for bioremediation. The studied soil contained high level (mg/kg) of Cr(307.41?±?1.02), Cu(576.35?±?1.02), and Zn(708.81?±?1.50) as per Taiwan permissible limit (TPL) and/or Canadian Soil Quality Guidelines (CSQG). Minimum inhibitory concentration (MIC) of Bacillus species were higher compare to Oceanobacillus. Bioavailable-fraction (F₁) of HMs (Cr/Cu/Zn) in untreated 225-soil was noticed to be higher compared to F₂–F₅ fraction. Bacillus subtilis C(225) are more efficient for HMs-mineralization, compared to other isolates where Cr/Cu/Zn immobilized within soil, transforming from bioavailable-fraction (F₁) (high-mobility) (60–90% reduction) to residual-fraction F₅ (low-mobility) (50–80% increment). Organic-bound-fraction (F₄) (medium-mobility) of Cr increased (42.66?±?2.1%), compared to Cu/Zn, by Bacillus subtilis C(225). Urease (40.8%) and dehydrogenase (8.3%) activity increased in bio-remediated soil, compared to control. MIMP of HMs by ingenious bacteria reflects the transformation-pathway from F₁ to F₅ of HMs to fix strongly within soils with inadequate mobility. Thus, MIMP by indigenous microbe can be applicable for HMs stabilization/removal in contaminated soil for ecofriendly environmental cleanup.     

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。     

广州市花都城区绿地土壤肥力与重金属污染分析

在对广州市花都城区绿地土壤取样调查的基础上,采用全国第二次土壤普查养分分级标准和内梅罗污染指数法等对其土壤肥力和重金属污染情况进行分析评价,揭示花都城区绿地土壤存在的问题。结果表明,花都城区绿地土壤容重变幅在1.25～1.75 g·cm^–3之间,孔隙度变幅在30.81%～47.42%之间,pH在6.16～7.68之间,有机质含量在四级及以下标准,严重缺乏氮素和磷素。不同绿地类型中,厂区路旁绿地土壤重金属污染最严重,其次为主干道两侧绿地;研究区As污染最严重,Pb次之,未受Zn污染,存在不同程度的Cu、Cd、Cr、Ni、Hg污染。相关性分析表明,土壤pH与全钾、碱解氮含量极显著相关,有机质与全氮极显著相关,全氮、全磷分别与碱解氮、有效磷显著正相关,全钾与碱解氮显著负相关;重金属元素中,Cu与Zn、Cr、Ni极显著相关,Zn与Cu、Pb、Cd、Cr、Ni极显著相关,Pb与Zn、Cd极显著相关,Cr与Cu、Zn、Ni极显著相关,As和Hg与其他重金属元素均无显著相关性。     

植物对重金属的耐性机理

植物对重金属的耐性机理杨居荣,黄翌（北京师范大学环境科学研究所,１００８７５）ＭｅｃｈａｎｉｓｍｏｆＨｅａｖｙＭｅｔａｌＴｏｌｅｒａｎｃｅｏｆＰｌａｎｔｓ．￥ＹａｎｇＪｕｒｏｎｇ;ＨｕａｎｇＹｉ（ＩｎｓｔｉｔｕｔｅｏｆＥｎｖｉｒｏｎ－ｍｅｎｔａｌＳｃ...     

Sludge-Derived Cu and Zn in a Humic-Gley Soil: Effect of Dissolved Metal-Organic Matter Complexes on Sorption and Partitioning

A sequential extraction scheme was combined with sorption isotherm analysis in order to investigate sorption of sewage sludge-derived Cu and Zn to the A-horizon of a humic-gley soil as a whole, and to the operationally defined exchangeable (1?M MgCl₂), carbonate (1?M NaOAc), Fe/Mn oxide (0.04?M NH₂OH.HCl), and organic (0.02?M HNO₃+30% H₂O₂) soil fractions. Sorption parameters were compared for a sample of sludge leachate (with 97.4% of Cu and 63.2% of Zn present as dissolved metal-organic matter complexes, as calculated by geochemical modeling involving MINTEQA2 and verified using an ion exchange resin method) with that of a reference solution exhibiting the same chemical characteristics as the leachate, except for the presence of dissolved organic material. Dissolved metal-organic matter complexes were found to significantly (P<0.05) depress sorption to the bulk soil and each fraction. The greatest depression of Cu and Zn sorption was observed for the exchangeable, carbonate, and Fe/Mn oxide fractions, while the organic fraction of the soil was the least affected. This reflects a greater affinity for the exchangeable, carbonate, and Fe/Mn oxide fractions by the free divalent metal (Cu²⁺, Zn²⁺), with sorption by these fractions attributed to cation exchange, chemisorption, and co-precipitation processes. The sorption characteristics of the organic fraction indicated that Cu and Zn sorption by soil organic matter mostly involved dissolved metal-organic matter complexes. This may be attributed to hydrophobic interactions between nonpolar regions of the dissolved metal-organic matter complexes and solid-phase soil organic matter.     

用转基因植物修复重金属污染的土壤

将新的性状转入高生物量植物中,以此开发高效的转基因植物修复系统,用于重金属污染的土壤修复是一项具有广阔应用前景的技术.大量实验表明,将细菌、真菌、动物、人类及植物本身与重金属脱毒相关的基因转入高生物量植物,异源表达产物可介导转基因植物耐受和高积累重金属及类似物.综述了这方面的研究进展.     

重金属残留的快速检测

环境及农畜产品中的重金属残留已对人类安全构成严重威胁,急需快速、高效的重金属残留检测方法。该文总结了国内外有关采用生物、化学传感器、免疫学方法等快速检测环境及农畜产品中重金属残留的研究进展,并对其发展前景及市场化作了预测及展望。     

Effect of Namomaterials on Heavy Metal Transport in Alkaline Soil

A high level of heavy metals in soil would negatively impact human health if these metals are consumed by humans through the food chain. The effect of nanomaterials, including SiO₂-Al₂O₃-Fe₂O₃, on heavy metals in alkaline soil was studied through simulating leaching in the soil column. Nanomaterials that weighed 4%, 6%, and 10% of the soil mass were added to a soil column in which garlic was planted. Leaching tests were conducted. Heavy metals in the soil leachate of different soil depths and different parts of the plant planted in the soil column were determined using a high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS). The results indicated that the migration of heavy metals through alkaline soil was inhibited. In the test with nanomaterials of 4% soil mass, 63% Cu, 79% Cd, 68% Pb, 89% Zn, and 76% Ni were decreased compared to the control. When the addition of nanomaterials was up to 6% of soil mass, 82% Cu, 92% Cd, 76% Pb, 91% Zn, and 88% Ni were reduced, respectively. No additional apparent results were observed with more nanomaterials added to the soil column. The nanomaterials effectively prevented heavy metal migration, especially inhibiting heavy metal migration downward. Nanomaterials will be promising in subsequent studies.     

Experimental Assessment of Using Soluble Humic Substances for Remediation of Heavy Metal Polluted Soils

Since heavy metals are nondegradable and strongly bonded in soils, remediation of heavy metal polluted soils by extraction is difficult and current extraction techniques require harsh chemicals such as ethylenediaminetetraacetic acid (EDTA). However, use of EDTA is environmentally problematic because of costs, persistence, toxicity and deterioration of soil structure. Therefore, the potential of soluble natural humic substances (HS) to extract heavy metals from contaminated soils is tested as an environmentally friendly substitute for EDTA. A strongly polluted, calcareous urban soil (CRC soil) and a moderately polluted agricultural soil (CUP soil) were extracted at neutral pH in batch mode by three HS solutions from beech and Norway spruce litter (Beech-HS and Spruce-HS) and processed cow slurry (Bio-HS), all containing 25 mM dissolved organic carbon (DOC). After 10 extractions with a solution to soil ratio of 5:1 (L/kg), 8% to 39% of the total Cd, Cu, Ni and Pb soil contents, lowest for Ni and highest for Cu/Pb, were extracted. Natural and processed HS samples had comparable capacities to extract the heavy metals. A comparison of 100 mM DOC of Bio-HS and EDTA as extractants for Cu from the CRC soil showed extraction of 67% by EDTA and 41% by Bio-HS, indicating somewhat higher efficiency of EDTA than of HS. Sequential extraction of the CRC soil after Bio-HS and EDTA extraction showed removal of exchangeable, carbonate- and metal oxide-bound Cu but also of some residual Cu. It is therefore concluded that HS appears to be an attractive and promising alternative to EDTA as remediation agent for heavy metal polluted soils provided cheap HS of good quality is easily available.     

Heavy Metal Partitioning in Bottom Sediments of the Matanza-Riachuelo River and Main Tributary Streams

This study provides geochemical partitioning, potential bioavailability, and enrichment of Cd, Cu, Pb, and Zn in bottom sediments collected from the Matanza-Riachuelo River and its main tributary streams. A modified Tessier sequential extraction procedure, complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, was applied to determine the partitioning of metals into four fractions (metals bound to amorphous sulfide, carbonate, and exchangeable), bound to Fe/Mn oxides (reducible), bound to organic matter/sulfide (oxidizable) and residual. Spatial and vertical distributions of metals were studied. The core sediments show a decreasing concentration of metals with depth. In top sediments, non-residual Cu was mainly associated with oxidizable phase, whereas Pb, Cd, and Zn were mainly associated with amorphous sulfide. Pb exhibited the highest enrichment in all sites. The ratio AVS/SEM was greater than one at sediment sections close to the water column, indicating that metals extracted with hydrochloric acid were mainly associated with the amorphous sulfide. The strong influence of amorphous sulfide in the retention of Cd, Pb, and Zn in anoxic sediments of Matanza-Riachuelo river system suggests that dredging and aeration could lead to the remobilization of metals from sediments to the water column, hence making the metals more available to the biota.     

Soil Heavy Metal Pollution Assessment Near the Largest Landfill of China

To assess the extent and potential hazards of heavy metal pollution at Shanghai Laogang Landfill, the largest landfill in China, surface soil samples were collected near the landfill and concentrations of Cu, Zn, Cd, Pb, and Cr were determined. The results revealed that the concentrations of heavy metals, except Pb, were higher in the surface soil near the landfill than in the background soil. Principal component analysis and hierarchical cluster analysis suggested that the enrichment of Cu in soil was probably related to agricultural activities and Cd and Pb to landfill leachates, whereas Zn and Cr concentrations were probably controlled by soil matrix characteristics. The pollution indices (PIs) of the metals were: Cd > Cu > Cr > Zn > Pb. Among the five measured metals, Cd showed the largest toxic response and might cause higher ecological hazards than other metals. The integrated potential eco-risk index (RI) of the five metals ranged from 26.0 to 104.9, suggesting a low-level eco-risk potential. This study indicated the accumulations of Cu, Zn, Cd, Pb, and Cr did not reach high pollution levels, and therefore posed a low eco-risk potential in surface soil near the landfill.