Distribution of Heavy Metals in Calcareous and Non-Calcareous Soils in Spain

The distribution of chemical forms of Cd, Ni, Cr, Co, Ag, Pb, Cu, Mn and Zn in eight contaminated soils from Spain was studied using a sequential extraction procedure that fractionates the metal into soluble-exchangeable, specifically sorbed-carbonate bound, oxidizable, reducible and residual forms. SEM and EDXA analysis was used to analyse the soil matrix to determine the distribution of heavy metals. The residual, reducible and carbonate-sorbed forms were dominant. Metals were generally dispersed throughout the soil matrix and could not be located by SEM-EDXA.     

Distribution of Cd, Ni, Cr, and Pb in Amended Soils from Alicante Province (SE, Spain)

Heavy metals can be transferred from soils to other ecosystem parts and affect ecosystems and human health through the food chain. Today the use of biosolids to improve the nutrient contents of a soil is a common practice. Contamination of soils by potentially toxic elements (e.g., Cd, Ni, Cr, Pb) from amendments of biosolids is subject to strict controls within the European Community in relation to total permissible metal concentrations, soil properties and intended use. In this context, heavy metal concentrations were studied in agricultural soils devoted to vegetable crops in the province of Alicante (SE Spain), where an intensive agriculture takes place. This study is aimed at ascertaining the chemical partitioning of Cd, Ni, Cr, and Pb in agricultural soils repeatedly amended with sludge. Selected soil properties relevant to control the mobility and bioavaibility of heavy metals were analyzed for the general characterisation of these agricultural soils. The distribution of chemical forms of Cd, Ni, Cr, and Pb in five biosolids-amended soils was studied using a sequential extraction procedure that fractionates the metal into soluble-exchangeable, specifically sorbed-carbonate bound, oxidizable, reducible, and residual forms. The biosolids incorporation has modified the soil composition, leading to the increment of heavy metals. The residual, reducible, and carbonate-sorbed forms were dominant. Detailed knowledge of the soil at the application site, especially pH, CEC, buffering capacity, organic matter, clay minerals, and clay content, is essential.     

杭州市城市土壤中重金属、磷和其它元素的特征

Health implications of inhaling and/or ingesting dust particles with high concentrations of heavy metals from urban soils are a subject of intense concern. Understanding the geochemistry of these metals is key to their effective management. Total concentrations of heavy metals, phosphorus (P) and 8 other elements from topsoil samples collected at 82 locations in Hangzhou City were measured to: a) assess their distribution in urban environments; and b) understand their differentiation as related to land use. Metal mobility was also studied using a three-step sequential chemical fractionation procedure. About 8.5%, 1.2%, 3.6%, 11.0% and 30.3% of the soil samples had Cd, Cr, Cu, Pb, and Zn concentrations, respectively, above their allowable limits for public and private green areas and residential use. However, in commercial and industrial areas, most samples had metal concentrations below their allowable limits. Statistical analyses revealed that the 16 measured elements in urban soils could be divided into four groups based on natural or anthropic sources using a hierarchical cluster analysis. Additionally, Cu, Pb, and P showed similar spatial distributions with significant pollution in commercial zones, suggesting vehicle traffic or commercial activities as dominant pollutant sources. Also, Cd, Co, Cr, Ni, Zn, Mn and Fe had the highest concentrations in industrial locations, signifying that industrial activities were the main sources of these seven metals. Moreover, the data highlighted land-use as a major influence on heavy metal concentrations and forms found in topsoils with large proportions of soil Cd, Co, Cr, and Ni found in residual fractions and soil Cu, Pb and Zn mainly as extractable fractions.     

Heavy Metals, Phosphorus and Some Other Elements in UrbanSoils of Hangzhou City, China

Health implications of inhaling and/or ingesting dust particles with high concentrations of heavy metals from urbansoils are a subject of intense concern. Understanding the geochemistry of these metals is key to their effective management. Total concentrations of heavy metals, phosphorus (P) and 8 other elements from topsoil samples collected at 82locations in Hangzhou City were measured to:a) assess their distribution in urban environments;and b) understand theirdifferentiation as related to land use. Metal mobility was also studied using a three-step sequential chemical fractionationprocedure. About 8.5%, 1.2%, 3.6%, 11.0% and 30.3% of the soil samples had Cd, Cr, Cu, Pb, and Zn concentrations,respectively, above their allowable limits for public and private green areas and residential use. However, in commercialand industrial areas, most samples had metal concentrations below their allowable limits. Statistical analyses revealedthat the 16 measured elements in urban soils could be divided into four groups based on natural or anthropic sourcesusing a hierarchical cluster analysis. Additionally, Cu, Pb, and P showed similar spatial distributions with significantpollution in commercial zones, suggesting vehicle traffic or commercial activities as dominant pollutant sources. Also, Cd,Co, Cr, Ni, Zn, Mn and Fe had the highest concentrations in industrial locations, signifying that industrial activities werethe main sources of these seven metals. Moreover, the data highlighted land-use as a major influence on heavy metalconcentrations and forms found in topsoils with large proportions of soil Cd, Co, Cr, and Ni found in residual fractionsand soil Cu, Pb and Zn mainly as extractable fractions.     

Distribution of Trace Elements in Soils from the Sudbury Smelting Area (Ontario,Canada)

The sequential extraction procedure proposed by the European Commission Measurement and Testing Programme, combined with Scanning Electron Microscopy and Energy Dispersive X-ray Analysis(SEM/EDS), was applied to identify and quantify the chemical andmineralogical forms of Cu, Ni, Fe, Mn, Zn, Pb, Cr and Cd presentin the topsoil from a mining and smelting area near Sudbury (Ontario, Canada). The possible mobility of the chemical forms was also assessed. The metal fractions: (1) soluble and exchangeable, (2) occluded in manganese oxides and in easily reducible iron oxides, (3) organically bound and in form of sulphides, (4) residual mainly present in the mineral lattice structures were separated. Cu and Ni were the major metallic contaminants, occurring in soils in broad ranges of concentrations: Cu 11–1890 and Ni 23–2150 mg kg^-1. Cu was uniformly distributed among allthe extracted fractions. Ni was found associated mainly withthe residual forms, accounting for 17–92%, with an averageof 64%, of the total Ni present in the soils. Fe, Mn, Zn,Pb, Cr and Cd, while occurring in most analysed samples innormal soil concentrations, were primarily held in theresidual mineral fraction (on average >50%). The solubleand exchangeable forms made a small contribution (≤8.1%)to the total content of metals extracted. At least 14% ofthe total Cd, Mn and Pb was mobilised from the reducibleforms. The oxidizable fraction assumed mean values higher than10% only for Pb and Zn. Statistical treatment of the experimental data showed significant correlations between totalmetal content of the soils, some soil properties such as pH value, clay and organic matter content, and metal concentrationsin the various fractions. SEM/EDS analysis showed Fe in form ofoxides and sulphides in soils and Cu, Ni, Mn, Zn and Cr in association with iron oxides. Numerous black carbonaceous particles and precipitates of aluminium fluoride salts, observedin the solid residue left after `total’ digestion, were found tocontain Fe, Ni and Cr.     

新乡市环宇大道工业区周边土壤重金属的污染特征和评价

通过实地采样及室内化学分析的方法,研究了新乡市环宇大道工业区周边土壤Pb、Cd、Ni、Zn、Cu和Cr 6种重金属污染特征和风险评价,并应用Tessier五步连续萃取的方法对土壤中超标的Cd,Ni和Zn进行形态分析。结果表明:(1)土壤中Pb、Cd、Ni、Zn、Cu和Cr的平均含量分别是63.08 mg kg-1、176.85 mg kg-1、307.2 mg kg-1、485.6 mg kg-1,38.7 mg kg-1和47.9 mg kg-1,Pb、Cu、Cr平均含量达标,Cd、Ni、Zn平均含量均超标,分别是国家土壤环境质量二级标准的176.85、5.12、1.62倍。(2)Ni和Zn主要以铁锰氧化物结合态和残渣态存在,Cd主要以铁锰氧化物结合态存在,其次为碳酸盐结合态,3种重金属的迁移能力依次为:Cd>Zn>Ni。(3)每种重金属都存在不同程度的潜在生态风险,Cd的潜在生态风险最大并构成了很强的危害。     

Assessment of Metal Availability in a Contaminated Soil by Sequential Extraction

A contaminated soil from Pieve Vergonte (Piedmont, Italy) has been investigated in order to point out the availability and extractability of a series of metal ions and consequently their potential release into other environmental compartments. A sequential extraction procedure has been adopted in order to subdivide total concentrations into five operational fractions with different potential toxicity. A chemometric analysis has been used for the characterization of similarities or differences of behaviour. High concentrations of the main pollutants, namely Cu, Pb and Zn, were extracted into the exchangeable, carbonate-bound/specifically adsorbed and Fe-Mn oxide bound fractions, showing the risk of release of these metals into the environment. A remobilization of Cr, Mn and Ni could also take place, but to a lesser extent. The other investigated metals (Al, Fe, La, Sc, V, Ti and Y) were mainly bound to the residual and, in some samples, to the Fe-Mn oxide bound fractions. The high availability of several potentially toxic metals shows that the soil needs remediation.     

污染水稻土中重金属的形态分布及其影响因素

通过BCR3步提取法研究了江西省贵溪铜冶炼厂污染区水稻土中重金属的形态分布。研究表明,废渣场渗滤液污染区域(渣场区)的污染较污水灌溉污染区(污灌区)严重,渣场区土壤中Cu、Pb、Cd的含量高于污灌区,而污灌区土壤Ni含量较高。在表层(0～20cm)水稻土中,Cu以可氧化态为主,Pb以可还原态和可氧化态为主,Cd以酸溶态为主,Ni以残渣态为主,不同重金属元素的有效态所占总量百分比大小顺序是Cd>Cu>Pb>Ni。土壤重金属不同形态之间也呈现一定的相关性,说明Cu与Pb、Cd、Ni之间具有同源性。土壤pH主要影响了污灌区中Cu的形态分布,以及渣场区土壤酸溶态Ni的分布。土壤有机质含量对各重金属形态分布的影响不明显。     

Source Identification and Speciation of Metals in the Topsoil of the Khli Ti Watershed, Thailand

The enrichment factor, multivariate analysis and metal speciation studies were used to identify degree, source and dispersal of metal contamination in Khli Ti watershed, Thailand. Topsoil samples were collected throughout the watershed, analyzed for total metal concentration. Sequential extraction was also carried out to determine geochemical phases of metals which were identified as exchangeable and bound to carbonates, Fe–Mn oxides, organic matter and residuals. Soil characteristics including pH, total organic carbon, redox potential, cation exchange capacity and texture were also analyzed. Principal component analysis yielded three metal groups which explained 83% of the variance. The concentrations of metals which were derived from lithogenic origin, such as Co, Cr, Fe, Ni and V were in natural background levels and were mostly bound to the residual phase. The remaining elements (i.e. Ba, Cd, Cu, Pb, Sb and Zn) were associated with the contamination from previous activities of the Pb-ore concentrator and Zn–Pb mining. Anthropogenic contamination mainly increased Pb and Zn bound to Fe–Mn oxides at the expense of residual fraction. Even though low exchangeable Pb contents in Khli Ti soils indicated low availability to plants, Pb bound to Fe–Mn oxides fraction might increase its mobility under reducing conditions.     

渤海湾各形态重金属的地球化学特征及其环境意义

根据2008年对渤海湾的调查,重点研究了渤海湾湾内和湾口柱状沉积物重金属的生物地球化学特征,通过剖析不同形态重金属的特征,结合渤海湾生态环境信息的综合分析,系统探讨了渤海湾沉积物重金属的演变趋势、影响控制因素以及潜在生态风险。结果表明,湾内海河口附近沉积柱重金属含量有几次突变,20～22cm段极小值可对应1939年海河北系的洪水,10～12cm段极小值可对应1963年海河南系的洪水,1963年至今重金属含量有逐渐增加的趋势。不同形态重金属百分含量从大到小为：残渣态〉铁锰氧化物结合态〉碳酸盐结合态〉有机结合态〉可交换态,且重金属在海河口附近都表现出较高的可浸取态百分含量。风险评价结果表明,重金属总量富集因子由大到小为：Pb〉Cd〉Zn〉Cr〉V〉Co〉Cu〉Ni,其中Pb、Cd和Zn的富集因子均大于1,说明其有污染,但渤海湾沉积物总体质量良好,潜在生态风险较低。从重金属形态角度评价,V和Cr无污染,Zn、Co、Cu、Ni和Pb在湾内及湾外均有不同程度的污染,而Pb的污染最为严重。     

杭州市城市土壤重金属的潜在可淋洗性研究

研究了杭州市城市土壤 8个重金属元素 (Cd、Co、Cr、Cu、Ni、Pb、Zn、Mn)的含量、形态和潜在可淋洗性。结果表明 ,该城市土壤中Cd、Cr、Cu、Ni、Pb、Zn和Mn均有明显的积累 ,其中Cd、Co、Cr和Ni主要以稳定的残余态为主 ,而Cu、Pb、Zn和Mn则以可提取态为主 ,因此在强还原、强酸性或有利于有机质分解条件下Cu、Pb、Zn、Mn的释放潜力较高。用荷兰能源研究中心的淋洗方法 (pH4 0 )测试表明 ,该市城市土壤的重金属可淋洗性较低 ,在一般条件下该城市土壤重金属不会有较大的释放 ,这与该城市土壤中酸可提取态重金属比例较低并含有较高的有机质及粘粒含量有关     

Effect of solid-phase speciation on metal mobility and phytoavailability in sludge-amended soil

Sequential extraction was utilized for partitioning Cd, Cr, Ni, and Zn, in soil and sludge samples into five operationally-defined fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. The highest amounts of Cd, Ni, and Zn, expressed as per cent of the total, were found in the Fe-Mn oxide fraction of the sewage sludge. Chromium was significantly associated with the organic fraction of the sludge. The residue was the most abundant fraction for all metals studied in the untreated soil, and for Cd and Ni in the sludge-treated soil. The concentration of exchangeable Cd and Cr was relatively low in the untreated soil and did not change much after sludge application, whereas the concentrations of exchangeable Zn increased about 50 times and the concentrations of exchangeable Ni doubled in the sludge-treated soil. The lysimetric experiment revealed an increase in Zn and Ni uptake by ryegrass and in the percentage of metals leached from the soil profile after massive sludge application. In contrast only negligible changes were observed for Cd and Cr. The assumption that mobility and biological availability are related to metal speciation was confirmed by the agreement between the distribution pattern of Cd, Cr, Ni and Zn in the soils, the uptake of the metals by plants and their capacity for leaching out from the soils.     

Roadside Accumulation of Heavy Metals in Soils in Franklin County,Massachusetts, and Surrounding Towns

Abstract

Metals cycle through the environment, and although many metals are required by biota, several have no known biological function and can be toxic. Metal concentrations [cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), palladium (Pd), vanadium (V), and zinc (Zn)] are surveyed with an eye toward soil chemistry, environmental and anthropogenic conditions, and potential remediation in 15 locations in and adjacent to Franklin County, MA. Road‐condition information was gathered, soil pH determined, and soils analyzed for soil metal content via a five‐phase sequential extraction and ICP‐AES analyses. Results indicate the majority of similarities are linked to soil pH and soil geochemistry, with only a few metals (Cr, Pb, and Zn) showing clear anthropogenic trends.     

四川省紫色土天然和添加的镍不同形态的分布及转化

The distribution and transformation of added and native Ni in purple soils were investigated with both sequential extraction procedure and isotopic tracer technique.The distribution of added and native Ni was greatly dependent on soil properties.Low soil pH was favorable for soluble plus exchangeable(EX) Fraction,while Fe/Mn oxides and clay for Fe/Mn oxide bound(OX) and residual(RES) fractions.The added Ni,however,has not yet reached the distribution equilibrium up to the 150th day after incubation.This was reflected in the fact that the proportion of EX fraction from added Ni was 150%-600% as much as that of native Ni,while that of RES fraction was only about 80%,Once entering soil,the applied soluble Ni was rapidly transformed into other fractions,but the organic complexe (OM) fraction of added Ni was relatively stable during incubation.The carbonate bound(CAB)fraction showed a progressive increase and attained a peak value after 0-14d of incubation and thereafter decreased gradually.The occurrence time of this peak advanced as initial soil pH increased.but the peak would disappear when initial soil pH was higher than 7.5(or containing free CaCO3).The transformation processes of the EX,OX and RES fractions could be described by Elovich and two-constant rate equations,and the rate were positively correlated with soil pH,CEC and clay.These finding could explain why there are differences in ecological and environmental effects of Ni in different soils and at various intervals.     

铜锌镍锰赋存形态的土体变化特征研究

本文用逐步连续分级法研究了砂姜黑土中铜锌镍锰的化学形态在土壤剖面中的变化特征以及耕作措施等对其的影响力。结果表明，砂姜黑土中代换态、有机态和无定形铁结合态铜锌镍锰的相对含量随剖面深度增加而降低；氧化锰态和残留态则随剖面加深而提高；碳酸盐结合态因元素种类和耕种方式而异，抑或增加抑或降低；晶形氧化铁态可以分成两类，铜镍变化不很明显，锌锰随剖面深度增加而增加。早耕熟化尤其是水旱轮作后，土壤中铜锌镍锰由植物无效的残留态或者有效性较低的晶形铁态（锌和锰）向有效性较高的代换态、有机态和无定形铁态转化，从而提高了土壤中铜锌镍锰的可移动性和有效性.     

Zinc Transformation in a Calcareous Soil as Affected by Applied Zinc Sulfate,Vermicompost, and Incubation Time

An experiment was conducted to evaluate the effect of zinc (Zn) rates and vermicompost levels on distribution of Zn forms of a calcareous soil. After incubation periods, soil samples were air dried, and a sequential extraction scheme was used to fractionate Zn into soluble and exchangeable, bound to carbonate, organically bound, bound to manganese (Mn) oxide, bound to amorphous iron (Fe) oxide, bound to crystalline Fe oxide, and residual forms. In untreated soil, Zn was mainly in the residual fraction. Increasing rates of applied Zn significantly increased all forms of Zn. Carbonate and residual forms showed the greatest increase. Application of vermicompost significantly increased all fractions except Mn-oxide form. This increase was more pronounced for organically bound, soluble, and exchangeable forms, indicating an increase in bioavailability of soil Zn. Incubation time significantly decreased soluble, exchangeable, and organically bound forms but increased other forms of Zn, meaning a significant reduction in Zn phytoavailability in soil with time.     

PARTITIONING OF HEAVY METALS IN PODZOL SOILS CONTAMINATED BY MINE DRAINAGE WATERS,DALARNA, SWEDEN

The discharge of acidic mine drainage waters onto a hillslope in Dalarna, central Sweden, has lead to the contamination of the podzol soils with Cu, Fe, Ni, Pb, Zn and sulfate. Samples from contaminated and reference soils have been collected for chemical and mineralogical analyses. Jarosite is identified by x-ray diffraction analysis as a precipitate in the upper horizons (A, E, B) of the contaminated soils, where the soil acidity (pH_KCl～2.6) promotes jarosite stability. The sequential chemical extraction of soil samples indicates that, in the reference A horizon, Cu, Pb, Ni and Zn are bound primarily to cation exchange sites and organic matter. In the A horizon of the contaminated soils closest to the rock dump, metal partitioning is dominated by the Fe oxide fractions, despite the high organic matter content; Pb is almost completely bound to crystalline Fe oxides, possibly adsorbed to Fe oxides or occuring in a jarosite solid solution. In the reference B and C horizons, Cu, Ni and Zn are primarily adsorbed/coprecipitated in the Fe oxide fractions, while Pb remains with a large fraction bound to organic matter. In the Fe-rich B horizon of the contaminated soils, the partitioning of the metals in cation exchange sites and to organic matter has greatly increased relative to the reference soils, resulting from the mobilization of organo-metal complexes down the profile.     

泉州走马埭典型土壤重金属的赋存形态分析

采用改进的Tessier连续萃取方法研究了泉州走马埭国家农田示范保护区典型土壤中重金属(Cr、Ni、Cu、Zn、Cd、Pb)的化学形态分布,通过土壤重金属的赋存形态分析比较了6种重金属的生物可利用性。研究结果表明,土壤中不同重金属元素化学形态分布具有不同的特点:Cr和Ni主要以残渣态存在,其余形态所占的比例很小;Cu以残渣态含量最高,碳酸盐结合态含量最低;Zn以残渣态为主,可交换态含量最低;Cd以可交换态和碳酸盐结合态为主,水溶态含量最低;Pb以残渣态和铁锰氧化物结合态为主,水溶态含量最低。土壤中除Cd外,Zn、Cu、Cr、Pb、Ni在正常自然条件下相对比较稳定。     

Long‐term transformations of cadmium,cobalt, copper,nickel, zinc,vanadium, manganese,and iron in arid‐zone soils under saturated condition

Abstract

The bioavailability and toxicity of metals in soils to plants, hence to animals and human beings through the food chain, and their mobility in the ecosystems highly depends upon their forms, pathways and kinetic rates of transformation in soil. Long‐term transformation pathways, kinetics and lability of cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), zinc (Zn), manganese (Mn), and iron (Fe) in two arid‐zone soils were studied under saturated water regime (simulating the moisture regime in the soil during the raining season and shortly after irrigation) by using operationally selective sequential dissolution techniques. Iron, Mn, Co, vanadium (V), Ni, Zn, and Cu were transformed from the non‐available form (reducible oxide fraction) and potential available form (easily reducible oxide fraction) into the available and readily available form (exchangeable and carbonate fractions), thereby increasing their mobility, availability or toxicity. However, Cd was transformed from the readily available form into the potentially available form, thus decreasing its lability. The fast transformations of all metals occurred in the first month, followed by a much slower process.     

新乡市寺庄顶污灌区土壤中重金属的形态分布及生物有效性研究

对长期电池废水灌溉的新乡市寺庄顶污灌区和对照区土壤重金属进行取样分析,结果表明,对照区土壤中Cd,Ni,Zn,Cu和Cr含量都能达标,污灌区土壤中Cr含量能达标,Cd,Ni,Zn和Cu的含量超标,其平均含量分别为65.31,1 196.64,2 799.25,145.78 mg/kg,是国家土壤环境质量二级标准的108.85,19.94,9.33和1.46倍。形态分析结果表明,污灌区污染最严重的Cd主要以铁-锰氧化物结合态存在,所占比例平均为56.84%;Ni主要以铁-锰氧化物结合态和残余态存在,所占比例平均为37.44%和39.55%;Zn主要以残余态存在,所占比例平均为78.24%;Cu主要以有机结合态存在,所占比例平均为57.70%;Cr主要以有机结合态和残余态存在,所占比例平均为45.55%和34.18%。与对照相比,污灌降低了Cd,Ni,Zn,Cu和Cr残余态所占比例,提高了重金属迁移能力和生物有效性。在4种超标重金属中Cd可交换态所占比例最高,平均为24.54%,由于其生物有效性最高,Cd迁移能力和植物毒性最值得关注。