Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities

Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO₃), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.     

茶园土壤不同形态镍的含量及其影响因素

通过自然茶园土壤采样和室内实验分析,探讨浙江、江苏和安徽13个茶园土壤镍的污染状况、形态分布规律以及不同形态镍的含量与土壤镍总量和土壤理化性质的关系。结果表明：部分茶园土壤受到不同程度的镍污染;茶园土壤镍的形态分布有一定差异,按镍的含量多少排序,一般为残渣态＞交换态＞铁锰氧化物结合态＞有机结合态＞碳酸盐结合态;除了交换态以外的所有其他形态的镍含量均随土壤镍含量的增加而显著增加;碳酸盐结合态、铁锰氧化物结合态和残渣态镍含量随土壤pH的升高呈显著增加趋势,而交换态镍则呈减少趋势,但不显著;随土壤有机质含量的增加,铁锰氧化物结合态镍显著减少,而其他形态增加或减少的趋势均不显著;碳酸盐结合态、有机结合态和残渣态的镍含量均随阳离子交换量的增加显著增加;随粘粒含量的增加所有形态中的镍呈增加趋势,但除了残渣态外增加趋势均不显著。     

Speciation and potential remobilization of heavy metals in sediments of the Taihu Lake, China

The species of Cu, Pb, Zn, Cd and Cr in sediments of the Taihu Lake, China, have been analyzed using the sequential chemical extraction method. Variations in the chemical fractions of these metals and their geographic distributions have also been studied. For all five metals, the residual fraction is highest but the exchangeable fraction is lowest among all the fractions. Compared to other metals, Cd has the highest percentage in the exchangeable fraction, and Cr is associated mainly with the residual fraction. Cu in the organic fraction and Pb in the Fe-Mn fraction are the important species, whereas the lowest percentages are found for Cd in the organic fraction, Cu in the Fe-Mn oxide fraction and Pb in the carbonate fraction. With respect to spatial differences, the total contents in the non-residual fractions of the metals in bay sediments are found to be higher than those in other sediments. The fractions of Cd, Cu and Cr showed significant variations in different regions. The fractions of Pb and Zn, however, did not show significant variations in spatial distribution, suggesting different amounts and different paths of anthropogenic input for the metals. Comparisons of the metal speciation indicated that Cd might be the most bioavailable metal, followed by Pb.     

深港西部通道填海区淤泥重金属化学形态分析

以深港西部通道填海区淤泥为研究对象,研究了重金属的化学形态特征,分析了填海工程活动带来的填海区地下水物理化学条件变化对重金属各个形态的影响。结果表明:除残留态外,填海区重金属存在形态主要为铁锰结合态、碳酸盐结合态和硫化物及有机结合态,其中,Pb和Ni以铁锰氧化物结合态和碳酸盐结合态为主,Cu以碳酸盐结合态和有机结合态为主,Zn以有机结合态和铁锰氧化物结合态为主,而Cd则以碳酸盐结合态为主。各金属在深港西部通道填海区淤泥的潜在迁移能力序列如下:Pb(39.68%)>Cu(31.59%)>Zn(20.49%)>Cd(12.80%)>Ni(10.98%)。     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

Chemical Fractionation of Aluminium in the Sediments of El-Burullus Lagoon of Nile Delta,Egypt

A five step sequential extraction technique, following Tessier’s protocol has been applied to determine the chemical association of aluminium with major sedimentary phases (exchangeable, carbonate, manganese and iron oxides, organic and residual fraction) in four short sediment cores collected from El-Burullus lagoon of the Nile delta, Egypt. This study is a first approach of chemical fractionation of aluminium in one of the protective areas of the Mediterranean Sea of Egypt. The total metal content was also determined. The results of the fractionation study indicated that aluminium was mainly associated with the residual fraction (>95%). The organic and Fe–Mn oxide fractions were the next important phases. The exchangeable and carbonate fractions were less than 1%, limiting its potential toxicity as a pollutant. The geochemical analysis of aluminium forms reflected the lithogenic origin of this metal in the study area.     

Speciation of trace metals in sediments of a tropical estuary

Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.     

Study on effective species of heavy metals in lacustrine sediment core from Xijiu Lake,Taihu Lake catchment,China

The BCR sequential extraction procedure is applied to probe into the speciation distribution of heavy metals (Cd, Cr, Zn, Cu and Pb) in lake sediments of Core XJ2 in Xijiu Lake, Taihu Lake catchment, China. The results showed that the effective species concentration of this five heavy metal elements increased obviously during the past century, the proportions of organic/sulphide fractions of Zn, Cu and Pb decreased while the Fe–Mn oxide fractions increased, and the proportion of Fe–Mn oxide fractions of Cd decreased while the exchangeable and carbonate fractions increased. The concentrations of exchangeable and carbonate fractions of these five elements were increased in the past century, especially the proportions of these fractions of Cd, Zn, Cu and Pb increased prominently. These changes could be attributed to the anthropogenic pollution. Since the changes of the heavy metal concentrations were corresponding to the history of human activities, especially the industry development, within the catchment.     

Accumulation and partitioning of heavy metals in mangrove rhizosphere sediments

A field study was conducted to clarify the effect of rhizosphere processes on the accumulation and partitioning of heavy metals (Pb, Zn, Cu, Cr, Cd and Ni) in mangrove sediments. Metals were fractionated by a sequential extraction procedure into three chemically distinct fractions: water soluble, exchangeable and carbonate bound (B1), Fe–Mn oxide bound (B2), and organic and sulfide bound (B3). Results indicate that rhizosphere processes tend to increase the metal concentrations in the rhizosphere sediments. However, plant uptake may result in the decrease of the metal concentrations in the rhizosphere sediments when the metal concentrations are relatively low in the bulk sediments. Compared with the bulk sediments, the rhizosphere sediments have low concentrations of heavy metals in the B1 and B2 fractions and high concentrations in the B3 fraction. Either an increase or decrease in the residual fraction of heavy metals in the rhizosphere sediments may appear, depending on whether the formation of the refractory metal-organic compounds or the activation of the residual fractions dominates. Results also indicate that mangrove plants absorb and store non-essential metals in the perennial tissues, thus reducing the export of non-essential metals via leaf litter transport. Mangrove plants are excellent candidates for phytostabilization of heavy metals in intertidal substrates.     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

金川镍矿尾矿砂中Ni和Cu赋存状态研究

金川镍矿浮选尾矿数量巨大,含有相当可观的有价金属,其中有价金属的回收受到越来越多的关注。金川老尾矿库尾矿砂中Ni和Cu赋存状态复杂,水溶性矿物态、可交换离子态、碳酸盐态、结晶度较差的Fe氧化物态、结晶度较好的Fe氧化物态、硫化物态和残渣态中都含有数量不等的有价金属Ni和Cu;尾矿砂风化作用释放的金属阳离子大多数在发生氧化的硫化物位置原位发生水解沉淀形成次生矿物,有价金属Ni和Cu在尾矿库中没有发生明显的富集。金川镍矿尾矿砂中Ni和Cu适于用化学酸溶浸出的方法进行二次回收。     

Speciation and mobility of heavy metals in mud in coastal reclamation areas in Shenzhen,China

Coastal reclamation has been carried out along the coastal areas near Shenzhen, China in a large scale since 1980s by dumping fill materials over the marine mud at the sea bottom. Usually the area to be reclaimed is drained first and some of the mud is air-dried for a few weeks before it is buried by fill. After reclamation, the terrestrial groundwater, which is relatively acidic and with high dissolved oxygen, gradually displaces the seawater, which is alkaline with high salinity. The changes in the burial conditions of mud and the properties of the pore water in the mud may induce the release of some heavy metals into the mud. Field survey confirms that the pH and salinity of the groundwater in the reclamation site are much lower than the seawater. Chemical analyses of mud and groundwater samples collected from the reclamation sites reclaimed in different years indicate that most of the heavy metals in the mud decrease gradually with time, but the heavy metals in the groundwater are increased. The release of heavy metals into pore water due to reactivation of heavy metals in the mud is of environmental concern. To understand why some of the heavy metals can be released from the mud more easily than others, a sequential extraction method was used to study the operationally determined chemical forms of five heavy metals (Cu, Ni, Pb, Zn, and Cd) in the mud samples. Heavy metals can be presented in five chemical forms: exchangeable, carbonate, Fe–Mn oxide, organic, and residual. Ni and Pb were mainly associated with the Fe–Mn oxide fraction and carbonate fraction; Zn was mainly associated with organic fraction and Fe–Mn oxide fraction, while Cu and Cd were associated with organic fraction and carbonate fraction, respectively. If the residual fraction can be considered as an inert phase of the metal that cannot be mobilized, it is the other four forms of heavy metal that cause the noticeable changes in the concentration of heavy metals in the mud. On the basis of the speciation of heavy metals, the mobility of metals have the following order: Pb (36.63%) > Cu (31.11%) > Zn (20.49%) > Ni (18.37%) > Cd (13.46%). The measured metal mobility fits reasonably well with the degree of concentration reduction of the metals with time of burial observed in the reclamation site.     

内蒙古拜仁达坝铅锌矿矿集区土壤中成矿元素分布及其赋存形态研究

对拜仁达坝铅锌矿矿集区3个多金属矿区的3个土壤粒级样品中Zn、Pb、Cu、Ag 4种主要成矿元素的7种赋存形式(水溶态、离子交换态、碳酸盐结合态、有机质结合态、铁锰氧化物结合态、硫化物结合态和残渣态)进行了测定。研究结果表明:1银都矿区土壤中Zn、Pb和Ag浓度最高,而道伦达坝矿区土壤中Cu的浓度最高;2拜仁达坝矿集区土壤中Zn、Pb和Cu主要以残渣态形式赋存,而Ag主要以铁锰氧化物结合态和硫化物结合态形式赋存;3拜仁达坝矿集区Zn、Pb和Cu元素在3个土壤粒级中的各个赋存形式所占的比例略有差别,但总体上大致相同,而Ag元素的赋存状态在3个土壤粒级的差异较大;4 3个矿区土壤中水溶态、离子交换态、碳酸盐结合态和有机质结合态的Zn和Pb差别不大;铁锰氧化物结合态、硫化物结合态和残渣态的Zn和Pb,以及Cu和Ag的7个赋存状态在3个矿区的差别较大。     

Geochemistry of metals in sediments from the mainstem of the Yellow River, China

Sediment samples at 10 locations in the mainstem of the Yellow River were taken in 1994. Five forms (exchangeable, carbonate, organic, Fe/Mn oxide and residual) of metals were extracted by the Tessier method. The total contents and contents of the five forms of 16 metal elements (Li, Na, K, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Al) were determined by ICP-AES. In sediments of the Yellow River, except for Na, mobile elements (such as K, Ca) do not show a negative correlation with the immobile elements. Alkaline metals (Li, Na, and K), Ti, and Al exist mainly in the residual form. The exchangeable forms of alkaline-earth elements (Ca, Sr, and Ba) are the highest, and their residual forms go up with the increase of the period in the periodic table of elements. Half of Mn exists in the residual form, and its non-residual forms exist mainly in carbonate and oxide forms. Except Mn, the iron group elements (Fe, Co, Ni, V, Cr) mainly exist in the residual and oxide forms. High carbonate content of Ca does not cause high contents of other elements in carbonate form, showing that chemical weathering is not strong in the area.     

Heavy metal mobility assessment in sediments from the Odiel River (Iberian Pyritic Belt) using sequential extraction

The Tessier sequential extraction scheme (SES) was applied to sediments from the Odiel river catchment (Iberian Pyritic Belt, SW of Spain), one of the most acid rivers on Earth, to assess the chemical association (exchangeable, carbonatic, bound to manganese and iron oxides, bound to organic matter and residual mineral) of heavy metals (Zn, Cd, Pb, Cu, Cr, Mn, Ni, Fe, and Hg). Sediments are very heterogeneous in their textural characteristics, showing different grain size. Twenty-seven samples were studied from from areas along the Odiel River, from the source to the mouth, with special interest in the Odiel Marshes Natural Park due to its ecological significance. Samples were classified as sandy (especially at the river mouth with low iron oxide and organic matter content) and clay-silty (in the middle of the river catchment with high iron oxide content). The numerous sandy samples with low pH values explain the low levels of metals upstream, although potential metals contributions arise from mining and ore. However, the presence of sulfate in the mining area and carbonate at the mouth may explain the high presence of lead and iron in these sandy zones. Some percentage of mobile Ni, Cu, and Zn were detected in the mining area, but the elevated relative percentage of exchangeable Cd in the estuary is even more remarkable. The percentage of Zn bound to carbonate is considerable in the catchment but especially in the estuary. However, Cu is only detected in the carbonate phase downstream, in spite of the low concentration of carbonate, which represents a drawback in the application of the Tessier SES to these types of samples. Finally, relatively high percentages of residual, non-mobile, Hg and Pb were observed, in the estuarine and mining areas, respectively. Sand, lime, and clay fractions of representative samples from Areas I, II, and III were used in a metal speciation study. Mainly, the elements analyzed had accumulated in the non-residual fractions. In the mining area of the Pyrite Belt, the elements analyzed are mainly bound to Fe–Mn oxides (Fe + Mn + Cu + Cr + Pb + Mn ± Zn) and the organic matter/sulfide fraction (Ni + Zn + Hg ± Cd), independent of sediment grain size. In conclusion, we show that the results of the study of chemical speciation in sediments from acid rivers are independent of the sediment grain size considered.     

太湖MS岩芯重金属元素地球化学形态研究

采用BCR三步提取法对太湖MS岩芯沉积物中Cu、Fe、Mn、Ni、Pb和Zn等6种重金属元素的化学形态进行了研究.结果表明,有效结合态的Cu、Ni和Pb主要以有机物及硫化物结合态、Fe-Mn氧化物结合态存在,Fe和Zn主要以Fe-Mn氧化物结合态存在,Mn主要以可交换态及碳酸盐结合态存在;Fe-Mn氧化物结合态的Ni、Pb和Zn与可还原态的Mn有较好的正相关关系,有机物及硫化物结合态的Cu、Mn、Ni、Pb和Zn与有机碳含量有较好的正相关关系;重金属形态分布体现了重金属元素地球化学性质的差异,以及重金属形态含量与沉积物理化性质的关系.沉积岩芯重金属元素形态垂向变化规律及次生相富集系数表明,Cu、Mn、Ni、Pb和Zn在沉积岩芯13～4 cm有效结合态含量较稳定,为自然沉积;4～0 cm有效结合态含量明显升高,存在一定程度的人为污染.根据137Cs测年结果判断,沉积岩芯Cu、Mn、Ni、Pb和Zn等重金属污染开始于20世纪70年代末期,主要污染元素及污染历史与太湖流域污染工业类型及经济发展阶段相吻合.     

Partitioning of heavy metals into mineral and organic fractions in a sediment core from Tokyo Bay

Sediment core was collected from Tokyo Bay. The surface enrichment of heavy metals due to human activities is recognized in the sediment. Partitioning of Cu, Zn, Fe and Mn into sulfide, carbonate, organic and silicate fractions has been determined with selective chemical leaching techniques for ²¹⁰Pb-dated sediment core samples. The heavy metal contents of silicate fractions without exchangeable sites are almost constant against depth in sediment core. However, the Cu, Zn and Mn contents of sulfide, carbonate and organic fractions vary with depth. Most Cu and Zn in the polluted sediment layer are associated with the iron sulfide fraction.     

Distribution and enrichment of heavy metals in a sediment core from the Pearl River Estuary

A sediment core collected from coastal zone near the Qiao Island in the Pearl River Estuary was analyzed for total metal concentrations, chemical partitioning, and physico-chemical properties. Three vertical distribution patterns of the heavy metals in the sediment core were identified, respectively. The dominant binding phases for Cu, Pb, Cr, and Zn were the residual and Fe/Mn oxides fractions. Cd in all sediments was mainly associated with exchangeable fraction. Influences of total organic carbon content and cation exchange capacity on the total concentrations and fractions of almost all the metals were not evident, whereas sand content might play an important role in the distributions of residual phases of Cr, Cu, Pb, and Zn. In addition, sediment pH had also an important influence on the Fe/Mn oxides, organic/sulfide and residual fractions of Cr, Cu, and Zn. Contamination assessment on the heavy metals in the sediment core adopting Index of Geoaccumulation showed that Cr, V, Be, Se, Sn, and Tl were unpolluted, while Cu, Ni, Pb, Zn, Cd, and Co were polluted in different degrees throughout the core. It was remarkable that the various pollution levels of the metals from moderate (for Cu, Pb, and Zn) to strong (for Cd) were observed in the top 45 cm of the profiles. The relative decrease of the residual fraction in the upper 45 cm of the core is striking, especially for Zn and Cu, and, also for Pb, and Cr. The change in fraction distribution in the upper 45 cm, which is very much contrasting to the one at larger depths, confirms that the residual fraction is related to the natural origin of these metals, whereas in the upper part, the non-residual fractions (mainly the Fe/Mn oxides fraction) are increased due to pollution in the last decade. The possible sources for Cu, Pb, Zn, and Cd contaminations were attributed to the increasing municipal and industrial wastewater discharges, agricultural runoff, atmospheric inputs, and runoff from upstream mining or smelting activities, which may be associated with an accelerating growth of economy in the Pearl River Delta region in the past decade.     

Grain size and geochemical partitioning of heavy metals in sediments of the Damodar River – a tributary of the lower Ganga, India

 The distribution of Si, Al, Fe, Mn, Cu, Zn, Ni and Cr in different grain-size fractions and geochemical association of Fe, Mn, Cu and Zn with <63-μm size fraction of bed sediments of Damodar River has been studied. In general, concentrations of heavy metals tend to increase as the size fractions get finer. However at two sites, near mining areas, the coarser particles show similar or even higher heavy metal concentrations than finer ones. The higher residence time and/or presence of coarser particles from mining wastes are possibly responsible for higher metal content in the coarser size fractions. The chemical fractionation study shows that lithogenic is the major chemical phase for heavy metals. Fe and Mn are the major elements of the lithogenic lattice, constituting 34–63% and 22–59%, respectively, of total concentrations. Fe-Mn oxide and organic bound fractions are significant phases in the non-lithogenic fraction. The carbonate fraction is less significant for heavy metal scavenging in the present environment and shows the following order of abundance Zn>Cu>Mn>Fe. The exchangeable fraction of the Damodar sediments contains very low amounts of heavy metals suggesting poor bioavailability of metals. Received: 18 August 1998 · Accepted: 1 December 1998     

恬矿库周围土壤中重金属存在形态特征研究

通过对大冶铜绿山铜铁矿尾矿库周围土壤中重金属形态分析实验,研究了重金属各种形态在土壤中的分布特征。由对比实验可知,尾矿库周围土壤中Ｃｕ、Ｐｂ、Ｚｎ、Ｃｄ等重金属含量都显著地高于对照样品,书经受到重金属的严重污染。土壤中重金属形态分布征为：ｗ（Ｃｒ、Ｚｎ、Ｆｅ）;可变换态〈碳酸盐态〈有机态〈铁锰氧化态〈残渣态;ｗ（Ｃｕ、Ｐｂ）：可变换态〈碳酸盐态〈有机态〈残渣态〈铁锰氧化态;ｗ（Ｃｄ）：残渣态,有机