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     

Use of Sequential Extraction in the Study of Heavy Metal Retention by Silty Soils

This study focused on the capability of two silty soils (tills) having low clay contents and CEC to retain and release two heavy metals, Pb and Cu. Samples of two non contaminated till deposits from the Eastern Townships region of Quebec, Canada, were artificially contaminated with concentrated solutions of these heavy metals. The latter were later extracted from the various geochemical phases of the soils by using the sequential extraction procedure. The results show that silty soils may have a relatively high heavy metal retention capacity due to the presence of carbonate and that this retention capacity can be comparable in magnitude to the retention capacity of certain clayey soils. This is particularly positive in the context of municipal waste disposal (landfills) in Quebec, where some old sanitary landfill sites are underlain by till deposits. A high buffering capacity is not as desirable in the case a deposit needs to undergo remediation.     

Distribution and fractionation of heavy metals in pairs of arable and afforested soils in Denmark

Afforestation of sandy arable soils in northern Europe is likely to lead to an increase in the soil's acidity and changes in the behaviour of the organic matter, and this might affect the ability of the soil to retain heavy metals. It is important to assess the impact of such a change in the land use on the solubility of the heavy metals and to assess the risk of leaching to surface‐ and groundwater and the possible entrapment of heavy metals in the tree canopy. The impact of afforestation was assessed by excavating soil profiles in adjacent 34‐year‐old Norway spruce stands and arable plots at four different sites. We found that after 34 years the pH had decreased and cations were depleted in the topsoil under forest. The aqua regia‐extractable heavy metals were determined, and the heavy metal binding within the soil was assessed using a modified version of the BCR (Community Bureau of Reference) sequential extraction procedure. Higher contents of heavy metal were found in the arable plots in the loamy sand soils. Cadmium was found only in the most mobile fractions. The content of Pb in the subsoil was strongly correlated with the clay content, but not in the topsoil, which suggested that Pb had been added to the topsoil. We found strong correlations between the clay content and the Cu, Ni and Zn in the residual fraction, leading us to conclude that much of the Cu, Ni and Zn is of geological origin. No significant differences in the heavy metal fractionation between forest and arable soil were found, presumably because 34 years of different land use is not long enough to produce such differences.     

The role of earthworms (<Emphasis Type="Italic">Eisenia fetida</Emphasis>) in influencing bioavailability of heavy metals in soils

The effects of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), microbial populations, fraction distribution and bioavailability of heavy metals (Zn, Cu, Cr, Cd, Co, Ni, and Pb) in five Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community Bureau of Reference (BCR; now Standards, Measurements and Testing Programme of the European Community) was used to fractionate the metals in soils into water soluble, exchangeable and carbonate bound (B1), Fe-oxides and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). After the soils were treated with earthworms, the soil pH, water-soluble metal fraction and DOC increased. A significant correlation was obtained between the increased DOC and the increased metals in the water-soluble fraction. The heavy metals in fraction B1 increased after earthworm treatments, while those in fraction B3 decreased. No significant differences were observed for heavy metals in fraction B2. The microbial populations in soil were enumerated with the dilution plate method using several media in the presence of earthworms. The microbial populations increased due to earthworm activity. The biomass of wheat shoots and roots, and the heavy metal concentrations in wheat roots and shoots, were also increased due to the earthworm activity. The present results demonstrated that earthworm activity increases the mobility and bioavailability of heavy metals in soils.     

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。     

Lead Speciation in the Dusts Emitted from Non-Ferrous Metallurgy Processes

The paper presents results for the speciation analysis of lead in dusts derived from dedusting of technological gasses from metallurgical processes of non-ferrous metals with different elementary content, made in accordance with two equal sequential extractions. Analytical procedure A provided possibilities for determination of fraction of Pb(2+), metallic lead and fraction containing mainly lead sulfides. The second procedure (procedure B) was sequential extraction in accordance with Tessier. The results obtained in accordance with procedure A indicate that, regardless of the dust origin, the dominant group of Pb compounds is composed of lead salts which are soluble under alkaline conditions or lead compounds that form plumbites in the reaction with NaOH.     

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。     

Influences of lignin from paper mill sludge on soil properties and metal accumulation in wheat

The influences of lignin application on soil properties of three different soils, Jiangxi soil (Ultisol, Hapludult), Heilongjiang soil (Alfisol, Entioboralf) and Beijing soil (Alfisol, Haplustalf), and metal accumulation in wheat (Triticum aestivum L.) were studied in a pot experiment. By lignin amendment, soil pH, organic matter (OM) and cation exchange capacity (CEC) increased, except for CEC in the Beijing soil. Analysis showed that available P and K in lignin-amended soils were also elevated, except for P in the Jiangxi soil. A three-step sequential extraction procedure proposed by the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission was used to investigate the fraction redistribution of heavy metals in soils with lignin application. The fractions were specified as B1: water soluble, exchangeable and carbonate bound, and weakly adsorbed; B2: Fe-Mn oxide bound; and B3: organic matter and sulfide bound. Generally, the heavy metal content of the B2 fraction decreased whereas that of the B3 fraction increased. Lignin application to arable soils can not only improve plant growth in vitro, but also reduce the accumulation of the heavy metals Cu, Zn, Cd, Pb, Cr and Ni in wheat plants.     

香港土壤研究Ⅶ.BCR提取法研究重金属的形态及其潜在环境风险

基于类型土壤的重金属元素形态分析研究相对较少,本研究以香港地区7个亚纲的土壤剖面为例,利用欧共体参比司(BCR)制定的三步连续提取法研究了类型土壤中重金属Cd、Cu、Pb和Zn的化学形态及其潜在环境风险。结果表明,Pb、Cd和Zn元素除残留态外,HOAc溶解态的比例也相对较高,但不同类型的土壤有所差别,而Cu元素则以残留态和可氧化态为主。在这7种类型土壤中,正常潜育土和湿润淋溶土中的重金属潜在环境风险相对较高,而在这4种重金属元素中,又以Pb元素的潜在环境风险最大。     

尾矿库尾砂及周边农田土壤重金属形态分布及其生物有效性

采用BCR（community bureau of reference）连续提取法对大宝山矿山槽对坑尾矿库尾砂和周边农田土壤重金属Cd、Pb、Cu和Zn的形态分布及其生物有效性进行了分析。结果表明,尾砂中Cd、Pb、Cu和Zn残渣态占绝对优势,占其总量的百分数均在85%以上。农田土壤中Cd、Cu和Zn都以残渣态为主,分别占其总量的60%、60%和90%以上,Pb以残渣态和可还原态为主,占其总量的93.44%。农田土壤重金属有效性较尾砂大,尾砂和农田土壤重金属生物有效性均以Pb为最高。     

Forms and distribution of heavy metals in soils of the Axios delta of northern Greece

Abstract

Distribution and availability of heavy metals to plants is important when assessing the environmental quality of an area. The objectives of this study, conducted in 1992–1993, were: a) to determine the levels of the heavy metals, cadmium (Cd), chromium (Cr), copper(Cu), lead (Pb), manganese (Mn), nickel (Ni), and zinc (Zn), in the soils of the Axios Delta (a Ramsar wetland site in Northern Greece) so that the degree of pollution could be ascertained, b) to identify the various heavy metal forms present in soils using a fractionation scheme based on sequential extraction, and c) to find possible dependence on soil physicochemical properties. Total heavy metal content of the soils studied was generally higher than the levels reported in the literature for similar soils, suggesting some degree of pollution with heavy metals. The exchangeable forms of the heavy metals, however, were very low indicating that under present conditions, the availability of the heavy metals to plants is at a minimum. Most of the heavy metals occurred in forms that are considered immobile constituents of inorganic minerals or carbonate compounds. Only Cu and Zn were present in appreciable quantities as organically‐based forms that can become potentially available under certain conditions. Spatial distribution of Zn and Cu was related to the organic matter distribution, and there were indications suggesting that the immobile fraction of the heavy metals was adsorbed on to Mn‐oxides.     

Evaluation of Different Extraction Methods for the Assessment of Heavy Metal Bioavailability in Various Soils

The main objective of this study was to compare the effectiveness of different methods (heavy metals in pore water (PW), diffusive gradients in thin films (DGT), diethylene triamine pentaacetic acid (DTPA) extraction, and total heavy metals (THM) in soil) for the assessment of heavy metal bioavailability from soils having various properties and heavy metal contents. The effect of soil heavy metal pollution on shoot yield and sulfatase enzyme activity was also studied. Wheat (Triticum aestivum) was grown in different soils from Spain (n?=?10) and New Zealand (n?=?20) in a constant environment room for 25 days. The bioavailabilities of Cd, Cr, Cu, Ni, Pb, and Zn were assessed by comparing the metal contents extracted by the different methods with those found in the roots. The most widely applicable method was DGT, as satisfactory Cu, Ni, Pb, and Zn root concentrations were obtained, and it was able to distinguish between low and high Cr values. The analysis of the metal concentrations in PW was effective for the determination of Cr, Ni, and Zn content in root. Copper and Pb root concentrations were satisfactorily assessed by DTPA extraction, but the method was less successful with determining the Ni and Cr contents and suitable just to distinguish between high and low concentrations of Zn. The THM in soil method satisfactorily predicted Cu and Pb root concentrations but could only be used to distinguish between low and high Cr and Zn values. The Cd root concentration was not successfully predicted for any of the used methods. Neither shoot yield nor sulfatase enzyme activity was affected by the metal concentrations.     

干旱区绿洲土壤Cd／Pb复合污染下重金属形态转化与生物有效性

采用盆栽试验及连续浸提形态分级方法,研究了Cd和Pb在土壤中的形态分布规律及其对油菜的生物有效性的影响。结果表明,当土壤受外源Cd/Pb污染后,重金属的形态分布特征发生了变化,以可交换态（EXC）响应最大,Cd、Pb的赋存形态分别以碳酸盐结合态（CAB）、铁锰氧化态（FMO）和碳酸盐结合态（CAB）为主;一定浓度范围内的Cd/Pb复合胁迫能促进油菜的生长,油菜根系和茎叶的Cd、Pb含量均随着Cd/Pb复合胁迫水平的升高而持续增加。茎叶中的Cd含量远远高于根系,Pb含量反之。油菜可将更多的Cd从根系转移至茎叶,而将更多的Pb滞留在根系中;对油菜根系吸收Cd最重要的形态为可交换态（EXC）和碳酸盐结合态（CAB）,而对茎叶吸收Cd以及油菜吸收Pb贡献最大的则为碳酸盐结合态（CAB）。     

The Relationship between Bulk and Mobile Forms of Heavy Metals in Soils of Kursk

The contamination of Kursk urboecotopes by heavy metals (Pb, Cd, Zn, Cu, Ni) is considered. The relationships between the contents of bulk and mobile forms of heavy metal ions have been examined. The results of monitoring studies attest to a tendency for the accumulation of both bulk and mobile forms of heavy metals in the humus-accumulative horizon, except for bulk cadmium and mobile nickel. Linear and nonlinear regression models of the bulk contents of Pb, Cd, Zn, and Ni as dependent on the contents of their mobile forms have been developed. These models allow us to calculate the bulk content of heavy metal ions in the soils of urboecotopes using simpler methods of the extraction and laboratory determination of their mobile forms.     

秦岭神安沟矿区沟道地表水和沉积物中重金属分布形态研究

为了探讨重金属在矿山水体环境中的富集规律,以秦岭神安沟矿区沟道地表水、沉积物中的重金属为研究对象,测试了各类重金属含量,并利用Tessier五步连续萃取法分析了沉积物中重金属的5种形态,旨在为该矿区环境恢复治理提供参考。结果显示,未受采矿活动影响的对照区地表水与沉积物均未检出Zn、Pb、Cd,对照区未受污染。受开采活动影响的上、中、下游地表水、沉积物受到Pb、Cd不同程度的污染,下游地表水Pb、Cd分别超标5.3倍、43.3倍,不符合农田灌溉用水水质要求;上、中、下游沉积物中重金属污染负荷指数均达Ⅲ级,沟道沉积物已受到严重污染。沉积物中重金属形态分布特征为：Zn、Cd以有机结合态所占比例最高,Pb以铁锰氧化物结合态所占比例最高,Zn、Pb的生物有效性高。由此得出下游地表水不适于灌溉。由于矿方目前已终止尾矿库淋滤水向沟道排放,沉积物中各类重金属含量已趋于稳定,矿区神安沟地表水、沉积物重金属污染严重,亟需治理恢复。     

The influence of compost addition on heavy metal distribution between operationally defined geochemical fractions and on metal accumulation in plant

Purpose

Metal distribution patterns among geochemical fractions are informative for metal phytoavailability. Compost added to polluted soils may adsorb metals on the less phytoavailable fractions. A bioassay experiment was conducted to establish possible correlations between metal concentrations in different soil fractions and metal contents in edible plant parts and to investigate the influence of different compost loads on heavy metal availability to plants.

Materials and methods

Chinese cabbage plants were grown in pots with sandy and clayey soils and soils mixed with different doses of biosolid compost spiked with soluble heavy metal salts (Cd, Cu, and Pb). The metals’ distribution pattern in the soil and mixed samples was determined by sequential extraction procedure (modified BCR protocol). The studied fractions, from most to least bioavailable, were water-extractable (WE), exchangeable-adsorbed (EXC), associated with carbonates and acetic acid-soluble forms (CARB), occluded by reducible (hydro)oxides of Fe and Mn (RO), and associated with organic matter (OM) and a residual fraction (RES). Metal concentrations in soil extracts and in the digested plant tissue were measured by ICP-AES.

Results and discussion

The highest compost doses (72 and 115 Mg ha^?1) enhanced cabbage yield significantly. No excessive phytoaccumulation of metals was observed in plants grown in the clayey soil or its mixtures with compost. The compost dose of 72 Mg ha^?1 was optimal in decreasing Cu accumulation by plants grown in sandy soil, and 28.8 Mg ha^?1 was found to be effective in reducing Cd and Pb uptake. Metals were accumulated in plants primarily from the WE, EXC, and CARB fractions, whereas other fractions decreased phytoaccumulation. Compost addition suppressed heavy metal mobility, but different fractions were active in pollutant sorption, depending on soil type and metal.

Conclusions

Compost addition increased metal proportions in the RO and OM fractions, reducing metal phytoavailability. This is especially important for sandy soils with low adsorption ability and higher vulnerability to metal pollution than clayey soils. A compost dose of 20% v/v (or 28.8 Mg ha^?1) effectively reduced plant accumulation of Cd and Pb. We propose using the first three steps of the modified BCR protocol as a three-step sequential-extraction procedure for the most phytoavailable fractions of heavy metal: WE, EXC, and CARB.     

茶皂素对污染土壤中重金属的修复作用

采用振荡离心的方法研究了生物表面活性剂茶皂素在不同浓度、pH值和离子强度下对污染土壤中重金属去除效果的影响;并采用BCR法研究了茶皂素处理前后土样中各形态的重金属含量变化。试验结果表明:随着茶皂素浓度的增加,重金属的去除率随之增加,在茶皂素浓度为7%时,对供试土样中重金属的去除率达到最大值,去除率分别为Cd 96.36%,Zn 71.73%,Pb 43.71%,Cu 20.56%;随着土壤环境pH值的增加,重金属的去除率随之减少,适宜的pH范围在5.0左右;离子强度对Pb,Cu的去除效率影响不大,Zn,Cd的去除率随着离子强度的增加而减少。比较茶皂素处理前后土样中重金属各形态含量的变化,发现酸溶态的重金属更易被茶皂素去除,其次为可还原态、可氧化态和残渣态的重金属很难被去除。     

Einflußgrößen der Schwermetallöslichkeit und -bindung in Böden

Solubility and retention of heavy metals in soils Model experiments were carried out under oxidizing conditions with soil samples from surface and subsurface horizons of different composition in order to investigate the solubility and retention of Cu, Zn, Cd, and Pb in soils. The solubility of heavy metals is mainly determined by ad- and desorption processes and complexation reactions of organic and inorganic ligands. Precipitation and dissolution of definite heavy metal compounds do not seem to govern the solution concentration in soils. An exception may probably be the formation of lead phosphate and zinc silicate under specific reaction conditions. The main factors which determine solubility and retention of heavy metals are total amount (except the proportion incorporated in the silicate structure) of the different metals, soil reaction, content of mobilizing and immobilizing organic substances, content of pedogenic oxides and clay minerals, and kind and concentration of salts and inorganic ligands. The results of the model experiments are used together with the results of other authors and general physico-chemical data to give an interpretation of the solubility behaviour of heavy metals in soils. The relations between heavy metal solubility, availability and mobility and possible procedures for melioration of soils contaminated with heavy metals are discussed.     

Biogeochemistry of heavy metals in contaminated excessively moistened soils (Analytical review)

The biogeochemical behavior of heavy metals in contaminated excessively moistened soils depends on the development of reducing conditions (either moderate or strong). Upon the moderate biogenic reduction, Cr as the metal with variable valence forms low-soluble compounds, which decreases its availability to plants and prevents its penetration into surface- and groundwater. Creation of artificial barriers for Cr fixation on contaminated sites is based on the stimulation of natural metal-reducing bacteria. Arsenic, being a metalloid with a variable valence, is mobilized upon the moderate biogenic reduction. The mobility of siderophilic heavy metals with a constant valence grows under the moderate reducing conditions at the expense of dissolution of iron (hydr)oxides as carriers of these metals. Zinc, which can enter the newly formed goethite lattice, is an exception. Strong reduction processes in organic excessively moist and flooded soils (usually enriched in S) lead to the formation of low-soluble sulfides of heavy elements with both variable (As) and constant (Cu, Ni, Zn, and Pb) valence. On changing aquatic regime in overmoistened soils and their drying, sulfides of heavy metals are oxidized, and previously fixed metals are mobilized.