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.     

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。     

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.     

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     

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.     

Application of chemometric methods to analyze the distribution and chemical fraction patterns of metals in sediment from a metropolitan river

Rivers in metropolitan areas are often highly polluted with materials that pose a threat to a large number of residents. Human influences lead to contaminants in metropolitan rivers having more complex sources than those in rural rivers. This complexity results in contamination that is unstable and rapidly changing. Here, the contents and chemical fractionation patterns of eleven toxic elements (As, Cd, Co, Cu, Cr, Mn, Ni, Pb, Zn, Y, and Hg) were evaluated in 13 samples collected from along the Beiyunhe River in Beijing, China. The results revealed that the metal contents were unevenly distributed along the river, with higher levels being observed in the downriver sites and the rendezvous sites. Additionally, more than 80% of the metals were found to be in the residual phase. The organic and sulfide phases were the most important extractable phases of most metals, with Ni, Co, Cu, and Cr primarily being associated with these phases and As, Cd, and Zn having a strong association with the iron/manganese oxide and hydroxide phases. Additionally, Mn was associated with the exchangeable and carbonate phases, with the lowest concentrations being observed in the organic and sulfide phases. Conversely, the metal exchangeable and carbonate phases were uniformly distributed throughout the river. Analysis of the metal sources revealed that particles input from the atmosphere comprised a considerable amount of the metals in the Beiyunhe River. However, these metals likely do not enter the sediment via atmospheric deposition directly, but rather through rainwater runoff into the river. The methods used in the present study will be useful in other studies that require analysis of complex data.     

Spring and conduit sediments as storage reservoirs for heavy metals in karst aquifers

Sediment samples were collected from six springs draining the karst aquifer at Fort Campbell, Kentucky/Tennessee. These were analyzed by ICP-MS following an extraction procedure that separates the metals into exchangeable, carbonate, oxide, organic and residual fractions. Aluminum and iron are primarily present in the residual fraction while manganese may be dominantly in either the oxide or carbonate fraction. The redox-sensitive metals (Fe and Mn) have the greatest fractional distribution in the spring with the thickest sediments. Trace metals detected include Cr, Cd, Ni, Pb, and Zn in the range of a few to 200 mg/kg. In Beaver Spring, nickel is distributed between the exchangeable, carbonate and organic fractions, while in Gordon Spring, nickel is largely residual. Chromium is almost entirely associated with the organic fraction in Beaver Spring while it is largely residual in Gordon Spring.     

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.     

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%)。     

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.     

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.     

Fractional Determination of Gold in Twenty Six Geological Reference Materials by Sequential Extraction with Graphite Furnace Atomic Absorption Spectrometry

A method is described to estimate the chemical form of gold (Au) in a variety of geological reference samples, combining a sequential extraction scheme with graphite furnace atomic absorption spectrometry, after extraction of Au as iodide or chloride with methyl isobutyl ketone. The fractions dissolved by sequential extraction are empirically defined as the exchangeable, amorphous, metallic, aqua regia-soluble and residual fractions. The amounts of Au in the amorphous fraction have been derived mainly from oxide or amorphous phases, and the chemical forms of Au are considered to be mostly amorphous and partly metallic. The metallic fraction of Au is likely to exist as submicroscopic grains of native metal which are relatively free from the rock-forming minerals, whereas the aqua regia-soluble or residual fraction of Au may be bound more intimately perhaps as inclusions or solid solutions of either native metal or electrum in most cases. Satisfactory agreement was observed between the sum of the Au values from exchangeable to residual fractions and the reported total Au values, except for a few samples which contained a large amount of reducing materials. Analytical results of Au for twenty six geological reference materials are tabulated, and geochemical and mineralogical features are discussed.     

Geochemical fractionation of heavy metals in Chilka Lake (east coast of India)—a tropical coastal lagoon

Chilka lake, the largest coastal lagoon of Asia is one of the most dynamic ecosystems along the Indian coast. Historically the lagoon has undergone a considerable reduction in surface area due, in part, to input from natural processes but mostly due to human activities. The purpose of this investigation is to document the heavy metals' affinity for specific geochemical phases in the recently deposited sediments in the lagoon. Thirty-three samples were collected and analyzed for different geochemical phases of Fe, Mn, Cu, Cr, Ni, Pb, and Zn utilizing a sequential extraction scheme. In the nonlithogenous fraction, the exchangeable fraction was not geochemically significant, having <2% of the total metal concentration for all the elements. However, the carbonate fraction contained the following percentages of the total concentration: <1% Fe, 13% Mn, 6% Cu, 4% Cr, 8% Ni, 13% Pb, and 12% Zn, suggesting the detrital origin of the sediments. Reducible and organic matter-bound fractions were the significant phases in the nonlithogenous fraction, containing 9% Fe, 16% Mn, 15% Cu, 16% Cr, 16% Ni, 14% Pb, and 14% Zn in the former and 4% Fe, 3% Mn, 17% Cu, 3% Cr, 14% Ni, 15% Pb, and 14% Zn in the latter. The phenomenon has been attributed to the scavenging affinity of Fe-Mn oxides and affinity for sorption into organic matter of the lagoon sediments. The lithogenous, residual fraction generally considered as a guide for natural background values was determined to contain 87% Fe, 67% Mn, 61% Cu, 77% Cr, 61.3% Ni, 56% Pb, and 60% Zn of the total concentrations.     

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.     

Chemical fractionation of metals in freshly deposited marine estuarine sediments of sundarban ecosystem,India

Sediment metal profiles were carefully examined for their distribution, chemical fractions, and mobility in three major marine-estuarine transects in the world’s largest mangrove (Sundarban) ecosystem because anthropogenic influences had been very often noticed. The level of pollutants was determined by CF and PLI. Metal contents in the freshly deposited sediment of Hugli transect were relatively high (Pb, Fe, Zn, Mn, Ni, and Co) in comparison to Matla and Saptamukhi due to lithogenic contribution from large catchments area (8 × 10⁵ km²). Principal component analysis and correlation coefficient revealed that the concentrations of metals were mainly governed by the variability of the sediment properties. Sediment was subjected to sequential chemical extractions to delineate metal fractions, namely exchangeable, carbonate, Fe–Mn oxide, organic, and residual. This indicated a valuable insight into the geochemical mode of the metal retention and their environmental behavior. Single extraction did not help significantly to explain the metal profiling.     

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.     

农用地土壤中汞元素形态特征浅析

以第四纪沉积物厚覆盖区农用地表层土壤汞元素为研究对象,分析了汞的水溶态、离子交换态、碳酸盐态、铁锰氧化态、腐殖酸态、强有机结合态、残渣态等7种形态存在特征,研究表明残渣态的含量比例与全量呈正相关关系,其他6种类型形态含量比例则与全量呈负相关关系,农用地土壤中汞的增量主要为残渣态的汞.     

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.     

The distribution and elevated solubility of lead,arsenic and cesium in contaminated paddy soil enhanced with the electrokinetic field

The objectives of this study were to investigate fractionation, solubility and potential bioavailability of Pb, As and Cs in Mississippi River Delta paddy soil under an electrokinetic field (EKF). Effects of EKF on soil pH changes and solid-phase distributions of metal(loid)s were examined. Results showed that fractionation of Pb, As and Cs was largely determined by the nature of elements, loading levels and EKF treatment. Native Pb in the soil was mostly in the amorphous iron oxide, organic matter and residual fractions, native As in the amorphous iron oxide, easily reducible oxide and residue fractions while native Cs in the residue fraction. Added Pb, As and Cs showed distinguished solid-phase distributions: Pb dominantly in the organic matter fraction; As in the amorphous iron oxide fraction, and Cs in the residue with a significant water-soluble plus exchangeable fraction. EKF treatment is effective on lowering soil pH to 1.5 near the anode due to water electrolysis releasing proton which is beneficial for dissolution of metal(loid)s, increasing their overall solubility. The acidification in the anode soil efficiently increased the water-soluble Pb and the exchangeable Cs, implying enhanced solubility and elevated their overall potential bioavailability in the anode region while lower solubility in the cathode area. The building up of water-soluble As in the anode region may be from electromigration of As anion from the cathode. This study shows significant enhancement of redistribution, elevated solubility and overall bioavailability of Pb, As and Cs in Mississippi Delta paddy soil under the EKF.     

德安锑矿区土壤中锑的形态分析及生物可给性初探

按Tessier连续浸提法对德安锑矿区土壤样品进行了分析,得出锑的存在状态主要以残渣态为主,其次是Fe/Mn结合态,有机/硫化物结合态和碳酸盐结合态,可交换态和水溶态占的比率最小。矿区土壤中锑生物可利用态锑占0.52%~3.51%,其浓度一般在1.78~17.48μg/g,中等可利用态占1.04%~5.56%,生物难利用态锑的浓度占92.1%~98.4%。