连续提取法区分土壤重金属元素形态的研究及其应用

用连续提取法研究土壤中重金属的存在形态在土壤化学、植物营养和环境科学领域均具有重大意义，许多研究者对之进行了广泛深入的研究，近年来这方面的工作进展较快，本文对近年来国内外就土壤中重金属元素的形态区分方法及其应用作一简要综述。     

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。     

北京市得田沟金矿和崎峰茶金矿周边土壤重金属形态分析和潜在风险评价

对密云水库上游已关闭的得田沟金矿和崎峰茶金矿周边土壤中重金属的总量和形态分布进行分析,并通过富集因子法和风险评价编码法（RAC）对其污染状况进行了评价。结果表明,除As和Pb外的重金属平均含量都高于北京市土壤背景值,重金属的空间分布具有一定的差异性。土壤中Pb的铁锰氧化物结合态占总量的50%,其次为残渣态占33%;Cu的残渣态为72%,其次有机结合态为21%;Zn和Mn均以铁锰氧化物结合态和残渣态为主,分别占总量的93%和87%,其他重金属元素则以残渣态为主要形态。大多数重金属含量和可提取态含量的最大值都出现在堆积过尾矿石处（Z8、Z9和Z10）,污染程度较重。基于总量的富集因子结果表明,研究区内Cr有显著污染,Hg、Cu、Cd和Ni为中度污染,其他元素轻微污染或无污染;基于形态的RAC表明该地区重金属元素具有较低的风险水平。     

土壤酸度对重金属形态分配的影响

在通常条件下,重金属在土壤中的溶解度主要取决于土壤对它们的吸附性能。不同重金属在同种土壤中的吸附顺序为:铅>铜>锌>镍>钴>镉。交换态重金属含量随pH的升高有最大值出现。出现最大值时pH的高低与重金属的专性吸附能力有关。土壤有机质和氧化物胶体对重金属有很大的吸附容量。且随pH升高而显著增大。升高pH,充分发挥土壤有机质和氧北物胶体对重金属的净化作用,可能是控制酸性土壤重金属污染的一个可行措施。对土壤中重金属元素的形态研究,无论在土壤科学还是环境科学中,均具有重要的意义。本项工作系应用逐级提取法把土壤中的重金属Cu,Zn,Cd,Pb,Co,Ni分为水溶态,交换态,有机结合态和闭蓄态四种不同的化学形态,研究土壤酸度对它们在各种形态中分配规律的影响。此外,对土壤重金属污染的控制途径也提出了一些尝试性建议。     

北京市五环内绿地土壤4种重金属的形态特征及其生物有效性

[目的]了解北京市五环内绿地表层(0—20cm)土壤重金属(Cu,Cd,Pb和Zn)的形态特征及其生物有效性,为北京市绿地土壤重金属污染防治提供比较可靠的参考依据。[方法]在建成时间为2~400a的绿化区内共采集表层土壤样品151个,运用改进BCR提取法分析样品中重金属的赋存形态,而后通过风险评价编码法(RAC)和次生相与原生相分布比值法(RSP)对重金属生物有效性进行评估。[结果]样品中重金属Cu,Cd,Pb和Zn的含量分别为31.42,0.29,29.89,76.78 mg/kg,Cu,Zn在中部和东北部含量较高,Pb在中部地区含量较高,Cd在西北部、东北部和南部存在少量高值区。Cu,Cd,Pb和Zn形态分布的总体规律均为:残渣态可氧化态弱酸溶态可还原态,稳定态含量均远高于有效态,有效态含量比例表明重金属生物有效性大小顺序为:CdZnCuPb风险评价编码法(RAC)表明,Cd和Zn环境风险程度为低风险,Cu和Pb无环境风险。次生相与原生相分布比值法(RSP)显示,Cu,Cd,Pb和Zn元素RSP值分别为0.06,0.49,0.18,0.13,土壤整体上未受到重金属污染,但是有少部分地区存在被污染现象。[结论]北京市五环内绿地土壤总体上不存在重金属Cu,Cd,Pb和Zn污染,环境风险较低,但应对重金属赋存形态保持关注。     

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。     

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。     

皖南茶园土壤重金属化学形态及其生物有效性

以皖南茶园为研究对象,通过Tessier连续提取分级法对茶园土壤重金属(Zn,Cu,Pb,Ni)全量及其化学形态进行了分析,利用活性态重金属占全量之比来评价其生物有效性。结果表明,皖南茶园土壤中Zn,Cu,Pb,Ni含量均未超过国家标准;除Zn外,其他元素均高出背景值,存在较明显的富集现象;土壤中4种重金属在5种形态上表现出不同的分布规律,Zn,Cu,Ni以残渣态为主,分别占总量的72.55%,90.00%和81.79%,而Pb以铁锰氧化物结合态为主,占总量的70.09%;Zn,Cu,Pb,Ni的活性态部分占全量比例分别为5.04%,1.51%,0.97%和0.23%,土壤重金属活性态部分与茶叶中重金属含量之间呈现正相关关系,且皖南茶区的茶叶重金属含量在限量值的安全范围内。     

伊通河(长春市区段)沉积物重金属元素化学形态分布特征

对伊通河(长春市区段)沉积物中重金属元素的含量和形态的分布特征进行了研究。结果表明,重金属元素的总量呈现出沿河变化的趋势,且各重金属元素沿河变化程度有很大区别;沉积物中铁主要以残渣态存在,Mn、Pb、Cu、Zn元素残渣态含量很低,而有效态含量却很大(70％),即伊通河沉积物中存在着潜在的重金属污染。沉积物中重金属在各形态的叠加也有所区别,Pb和Cu主要叠加在有机物态和残渣态中,而Zn则主要叠加在铁锰氧化物态中。     

BCR法在污染农田黑土重金属形态分布研究中的应用

通过对东北地区污染农田黑土剖面的取样调查分析，对重金属Cd、Ph、Cu、Zn在农田黑土中的污染状况及其迁移特征进行了对比研究，并就BCR（the Community Bureau of Reference）连续提取法在农田土壤重金属污染评估中的应用进行了探讨。结果表明，重金属的迁移率大小依次为：Cd〉Cu〉Pb〉Zn，Cd的酸可溶态占全量的比率高于其它重金属。Pb的酸可提取态浓度随土壤深度增加而增大，公路附近土壤中PL、Cu及城市郊区土壤中Cd、Pb和Zn的氧化物结合态含量均随土壤深度的增加而升高，已存在向下迁移的趋势。4种重金属有机结合态在采样区土壤中基本都表现为耕层高于非耕层。研究表明，应用BCR连续提取法有助于确定土壤重金属污染以及重金属向下迁移状况，借助该法可以有效、可靠地对土壤重金属污染进行评估。     

稳定同位素示踪土壤中重金属环境行为的研究进展

随随着以多接收器电感耦合等离子体质谱仪（MC-ICP-MS）为代表的高精度质谱分析技术的革命性突破,稳定同位素的研究取得了跨越式发展。重金属稳定同位素成为了示踪土壤环境介质中重金属地球化学循环的有效工具,在识别污染来源、解析关键过程、跟踪环境行为等方面展现出极大的应用潜力。从同位素基本概念出发,系统介绍了利用重金属稳定同位素示踪土壤环境重金属污染的来源与归趋、土壤-植物体系重金属元素的迁移转化以及金属纳米颗粒的环境过程等方面的研究进展,并进一步总结了氧化还原、沉淀溶解、吸附解吸、络合反应、生物作用等影响重金属稳定同位素分馏的相关机制,最后针对当前应用和研究现状,提出了拓展稳定同位素示踪重金属环境行为的潜在研究方向和研究内容,对土壤重金属污染防治及修复具有重要的指导意义。     

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     

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.     

Methods of sequential extraction of heavy metals from soils: New approaches and the mineralogical control (a review)

The analysis of published data shows that the sequential extraction of heavy metals from soils according to the schemes suggested by Tessier and by the European Community Bureau of Reference (BCR) does not ensure the selectivity of the extraction of heavy metal compounds from certain carriers and can result in the artificial redistribution of heavy metals by fractions. A new approach is based on the assessment of the kinetics of metal extraction from certain carriers. A wide range of heavy metal compounds in soils have been identified using the method of synchrotron X-ray radiation. It is argued that the schemes of Tessier and the BCR are applicable for the determination of the contents of Pb humates, Pb and Zn carbonates, and heavy metals bound with hydroxides of Fe and Al. However, these methods are not suitable for the determination of phosphates and silicates of heavy metals.     

Changes in Chemical Species of Copper Added to Brown Forest Soil in Japan

Heavy metals are present as various chemical species in soil environments. Chemical species of heavy metals determinate their behavior in soil, so they must be more important concern than total contents in treating problems about heavy metal polluted soil. Microbial activity is thought to be one of the factors that affect chemical speciation of heavy metals. Although some possible microbial mechanisms have been suggested, their effects on heavy metals have not previously been thoroughly studied. In this study, we investigated whether microorganisms contribute to the fractionation of Cu in a forest soil. Copper-enriched, sterilized forest soil samples were buried at their places of origin, and subsamples were collected for analysis 3, 10, 17, 30, 60, and 90 days after burial. Tessier’s sequential extraction was employed to analyse Cu fractionation. Until two months after burial, the added Cu remained nearly unchanged. But a dramatic change was found in soil subsamples after three months. In both the A and B horizons, the carbonate fraction of Cu increased and the residual fraction decreased. We also found that clay minerals and persistent organic matter are important binding substances of Cu in the residual fraction. The change from residual to carbonate fraction could be caused by microbial activity.     

土壤重金属形态对径流中重金属流失的影响

土壤重金属的积累可促进地表径流中重金属的流失,流失量与土壤中重金属的形态有关。田间观测和室内模拟淋洗试验的结果都表明,径流或淋出液中重金属主要来源于土壤的交换态(包括水可溶态)重金属;土壤重金属总量与径流中重金属浓度相关不明显;用稀盐(0.01mol/LCaCl2)和1mol/LNH4OAc提取的土壤重金属量与径流和淋出液中重金属浓度都呈显著的相关,可较好地表征土壤中重金属流失潜力。     

Fractionation and Distribution of Metals in Guadiamar River Sediments (SW Spain)

Traditionally, the Guadiamar River (Seville, Southwest Spain) has received pollution from two different sources, in its upper section, from a pyrite exploitation (Los Frailes mine) and, in its lower section, from untreated urban and industrial wastes and from intensive agricultural activities. In 1998, the accidental spillage of about 6 million m³ of acid water and sludge from mine tailings to Guadiamar River worsened the pollution of an already contaminated area. The main polluting agents of the spillage were heavy metals. The total concentration of a metal provides scarce information about the effects on environmental processes or about the toxicity of the sediment samples. A more sophisticated fractionation of the sediment samples based on a species distribution can help to understand the behaviour and fate of the metals. This article describes a distribution study of the metals Al, Cd, Cu, Fe, Mn, Pb and Zn by fractionation analysis of sediments from eleven sample sites alongside the Guadiamar Riverbed. The samples were collected in summer 2002, four years after the spillage and after the area had been cleaned. Sequential extraction analysis resulted in the definition of four fraction categories: exchangeable metal (the most available fraction), reducible metal (bound to hydrous oxides of Fe and Mn), oxidizable metal (bound to organic matter and sulphides) and a residual fraction (bound to minerals). Significant increases in the available fraction of several potentially toxic metal ions like Cd, Mn and Zn were found. The distribution pattern was variable along the River. At the site closest to the mineworks, the soluble forms of Cd, Mn and Zn were significantly more abundant that those downstream. Cu and Pb were present in the reducible fraction while Fe was present associated in the residual fraction.     

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.     

Heavy metals in Egyptian spices and medicinal plants and the effect of processing on their levels

To determine the contamination of Egyptian spices and medicinal plants with heavy metals, a total of 303 samples, which represent 20 different types of spices and medicinal plants that were collected from areas of exportation in Egypt, were analyzed for heavy metals. Some of them have different growing seasons, and each has its own agricultural practices and several shipments. The results revealed that heavy metal contents in spice and medicinal plants depend on the plant species. The maximum levels of heavy metals in the analyzed samples were 14.4, 2.44, 33.75, 2.85, 0.10, 68.80, 343.0, 11.40, and 1046.25 microg/g for Pb, Cd, Cr, Ni, Sn, Zn, Mn, Cu, and Fe, respectively. Cobalt was not detected in any of the various samples under investigation. The levels of heavy metals determined in the analyzed samples were found to exceed the maximum allowable levels of Zentrale Erfassungs und Bewertungsstelle für Umweltchemikalien. The investigated medicinal plants were also processed by two different methods to determine the behavior of their metal contents during processing. It has been found that boiling the plant in water leads to the extraction of higher amounts of the metal from the plant than immersing it in the hot water. The achieved results were tabulated.     

Effect of composting on extractability and relative availability of heavy metals present in Calcutta municipal solid waste

How composting affects heavy metal content is largely unknown. Accordingly, we investigate the total content of six heavy metals, Cd/Zn ratio and the Zn-equiv, the relative availability and fractionation study to assess the suitability of compost derived out of those for environmental concerns. During composting, total metal content increased but their RA decreased. As a result of composting bioavailable form of metals also decreased. High significant correlations between different forms of heavy metals content and degree of humification were found for all the elements. Composting increases humic acid content than fulvic acid. This transformation is mainly responsible to serve as binding agent for metal thereby moderating the rapid metal mobilization.