Trace Metal Fractionation by the Sequential Extraction Method in Sediments from the Lis River (Portugal)

The extractable contents of Zn, Pb, Cu, Cr, Mn, Ni, Fe and Al were evaluated in sediments from the Lis River (Portugal) using the three-step sequential extraction procedure described by Community Bureau of Reference (BCR, now the Standards, Measurement and Testing Programme) of the European Union. The distribution of trace metals among the exchangeable, water and acid soluble, reducible, oxidizable and residual fractions was determined. The highest metal concentrations were observed in samples collected at the most polluted river sites (animal husbandry, domestic, industrial and agricultural wastes). Pb, Cu, Cr, Ni, Fe and Al were found mainly associated with the residual and organic fractions. High concentrations of Zn and Mn were found in the exchangeable/acid soluble fraction.     

Transfection of siRNA into <Emphasis Type="Italic">Brachionus plicatilis</Emphasis> (Rotifera)

Lake Taihu is one of the most contaminated lakes in China. Surface sediment data show that the northern area of the Lake has the worst heavy metals pollution, and high heavy metal concentrations were attributed to discharge of untreated and partially treated industrial waste water from cities to the north of the lake. To study geochemical features and pollution history of heavy metals, total content and chemical fractionations of Cu, Fe, Mn, Ni, Pb, and Zn were analyzed for core sediments from western Lake Taihu using the speciation extraction procedure, proposed by the Commission of the European Communities Bureau of Reference (BCR), together with grain size and organic carbon measurements. Results show that sediments are composed of organic-poor clayey-fine silts for Cores MS and DLS, and have similar geochemical features shown by heavy metals. Cu, Fe, Ni, and Zn mainly are associated with the residue fraction, Mn is concentrated in the exchangeable-carbonate and residue fractions, and Pb is concentrated in the Fe–Mn oxide fraction and organic-sulfide fraction. The fractions of Ni, Pb, and Zn bound to Fe–Mn oxide show significant correlations with Mn from the Fe–Mn oxide fraction, and the organic-sulfide fractions of Cu, Mn, Ni, Pb, and Zn are correlated with TOC. The increase of Cu, Mn, Ni, Pb and Zn content and percentage of extractable fractions in the upper layers of the sediments are correlated with anthropogenic input of heavy metals due to rapid industrial development. This coincides with rapid economic development in the Taihu basin since late 1970s. Heavy metals in the surface sediments have certain potential biological toxicity as shown by the higher SEM/AVS ratio.     

Preliminary study on heavy metals contamination of soil using solid phase speciation and the influence on groundwater in Bozanta–Baia Mare Area,Romania

Abstract

A preliminary study on soil contamination with heavy metals and As based on solid phase speciation according to the Tessier scheme and the influence on groundwater in an area under anthropogenic influence (Bozanta-Baia Mare, Romania) was conducted. The partitioning of Al, As, Cd, Cu, Fe, Mn, Pb and Zn in five fractions is discussed in relation to soil characteristics, pH, organic matter content, mineralogical composition and distribution of the same elements in airborne particulate matter. The airborne particulate matter contains high quantities of As, Cd, Cu, Pb and Zn as exchangeable fraction. The sequential extraction carried out on soil samples revealed the main role of Fe-Mn oxides surface in the immobilization of metals. Organic matter has a specific role in complexation of Cu, Pb, As and Al, since high contents of these metals were recovered in the oxidizable fraction. Cadmium has a high selectivity for carbonate minerals. The amendment of soil with natural fertilizer increases the exchangeable fraction of metals with the highest toxicity. The available fraction for plants (exchangeable + carbonate-bound species) exceeded the alert values in soil, therefore the continuous monitoring of the area is necessary. The soil is unsuitable for agricultural use due to high contamination on surface with toxic elements resulted from anthropogenic activities. Groundwater is contaminated with very toxic elements (As, Cd and Pb) but also with Cu, Mn and Zn and is unsuitable as supply for drinking water.     

Total and speciation analyses of heavy metals in the sand fraction of Nigerian oil sands for human and ecological risk assessment

Total metal analysis and metal speciation of sand fraction of Nigerian oil sands were done to extract and partition heavy metals into six operationally defined fractions in order to assess environmental and health implications of the oil sand development. Soxhlet extraction of bitumen from the oil sand was done using toluene. Traces of water and extracting solvent were removed at 70°C from the sand fraction using oven. Elemental analysis was performed by Atomic Absorption Spectrophotometry. The heavy metals except Cu have low Pollution index values. Negative geo-accumulation index was obtained for the metals except Cu, indicating that the oil sands were uncontaminated with the metals. Strong and significant positive correlations existed between Fe/Pb, Zn/Cu, Cd/Pb, Ni/Cd, Ni/Pb, Cd/Fe, Ni/Fe and Cr/Zn, while strong and significant negative correlations existed between Mn/Pb and As/Mn, indicating common sources or chemical similarities and vice versa. T-test results indicated significant differences between the concentrations of the metals. Cross-plot analysis showed strong positive correlation between the sand fraction and Nigerian bitumen. Speciation analysis indicated highest and lowest indices of metal mobility for Zn and Pb, respectively. This study concluded that the sand fraction may not pose any environmental risks from elemental point of view.     

Characterization of Heavy Metal Fractions in Agricultural Soils by Sequential Extraction Procedure: The Relationship Between Soil Properties and Heavy Metal Fractions

The present research was conducted to determine heavy metals in agricultural soils from Çanakkale, Turkey, using a sequential extraction procedure (acid soluble, reducible, oxidizable, and residual) as proposed by the Community Bureau of Reference (BCR) of the European Commission. Soil samples were taken from 12 different cultivated sites and analyzed for Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn concentrations. The results revealed an order of Mn > Cd > Pb > Co > Ni > Cu > Zn > Cr for the heavy metals based on the sum of the first three fractions (acid soluble + reducible + oxidizable). The relationships between soil properties and each metal fraction were identified through Pearsons's correlation analysis. Hierarchical cluster analysis was performed to determine the behaviors and similarities of metals in each fraction. While Mn, Pb, and Zn exhibited subjective behaviors in the acid-soluble fraction, Cd, Co, Cu, Cr, and Ni exhibited similar behaviors with each other.     

Heavy Metal Partitioning in Bottom Sediments of the Matanza-Riachuelo River and Main Tributary Streams

This study provides geochemical partitioning, potential bioavailability, and enrichment of Cd, Cu, Pb, and Zn in bottom sediments collected from the Matanza-Riachuelo River and its main tributary streams. A modified Tessier sequential extraction procedure, complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, was applied to determine the partitioning of metals into four fractions (metals bound to amorphous sulfide, carbonate, and exchangeable), bound to Fe/Mn oxides (reducible), bound to organic matter/sulfide (oxidizable) and residual. Spatial and vertical distributions of metals were studied. The core sediments show a decreasing concentration of metals with depth. In top sediments, non-residual Cu was mainly associated with oxidizable phase, whereas Pb, Cd, and Zn were mainly associated with amorphous sulfide. Pb exhibited the highest enrichment in all sites. The ratio AVS/SEM was greater than one at sediment sections close to the water column, indicating that metals extracted with hydrochloric acid were mainly associated with the amorphous sulfide. The strong influence of amorphous sulfide in the retention of Cd, Pb, and Zn in anoxic sediments of Matanza-Riachuelo river system suggests that dredging and aeration could lead to the remobilization of metals from sediments to the water column, hence making the metals more available to the biota.     

Adsorption of Cu and Zn onto Mn/Fe Oxides and Organic Materials in the Extractable Fractions of River Surficial Sediments

The roles of the extractable components (Mn oxides, Fe oxides, and organic materials) of surficial sediments in controlling metals adsorption were investigated. Cu and Zn adsorptions were conducted before and after the surficial sediments extracted with hydroxylamine hydrochloride, an oxalate solution, and H ₂ O ₂ , respectively. The extraction removed target components with extraction efficiencies from 63 to 98%. Nonlinear regression analyses of Cu and Zn adsorptions based on the assumption of additive Langmuir adsorption isotherm were employed to estimate the relative contributions of sediment components to Cu and Zn adsorptions. The results indicate that the greatest contribution to total Cu and Zn adsorption to the surficial sediments on a molar basis was from Mn oxides in the extractable fractions. Both Cu and Zn adsorption capacities of Mn oxides exceeded those of Fe oxides by approximately one order of magnitude, fewer roles were attributed to the adsorption of organic material (OM), and the estimated contribution of the residual fraction to total Cu and Zn adsorption was insignificant. These information implied that the roles of metal oxides (Fe and Mn oxides) in the extractable form of the surficial sediments, especially Mn oxides, was the most important component in controlling heavy metal transportation in aquatic environments.     

Cumulative Title Index

Abstract

Metal fractionation is a powerful tool for studying the mobility, bioavailability and toxicity of metals in sediments and soils. A seven-step sequential extraction technique was used to determine the potential mobility of selected heavy metals (Fe, Mn, Zn, Cu, Pb, Cd and Ni) in the sediments of Lake Naivasha. Results indicate that residual fraction was the most important phase for the elements Fe, Mn, Cu and Zn. However, Pb and Cd are highly enriched in the non-residual phases. Nickel on the other hand was distributed evenly between the non-residual and the residual fractions.

The total concentrations of the heavy metals suggested a decreasing order of iron ?> manganese ? zinc > nickel > copper ? lead > cadmium. However, the detailed sequential extraction data indicated an order of release or mobility of cadmium > lead ? nickel ? zinc > manganese > copper > iron. The high percentage of Cd and Pb in the mobile fractions suggests high bioavailability of these two elements in the study area and maybe a pointer to anthropogenic input of the two elements in the study area.     

Bioavailability and mobility of heavy metals in soil in vicinity of a coal mine from Huaibei,China

This study investigated the concentrations of Co, Cr, Cu, Mn, Ni, Pb and Zn in surface soil and corn cob samples collected from agricultural fields near a coal mine from Huaibei, China. Meanwhile, the mobility and availability of heavy metals in soil samples were evaluated by a modified three-step The European Community Bureau of Reference (BCR) sequential extraction procedure. The total concentrations of metals in soil pose no ecological threats to the local plants. Transfer factors of essential metals, Cu and Zn, as well as those of non-essential metal Pb, were higher than those of the remained metals. The results of BCR fractionation analysis revealed that the acid soluble, reducible and oxidizable fractions of the Mn, Pb and Zn were higher than those of the residual fraction, suggesting that these elements may be more bioavailable. The pH and organic matter contents of soil were significant parameters affecting speciation of metals in soil samples. Hierarchical cluster analysis indicated significant correlations between metal levels in corn grains and more available (acid soluble and reducible) fractions in soil, indicating that heavy metals in the first two fractions were more available for corn crops. The elevated mobility and bioavailability of Pb in soil are of great concern in the study area.     

南京城市土壤重金属含量及其影响因素

研究了南京城市土壤重金属含量、来源及其与土壤性质的关系。结果表明,南京城市土壤中,Fe、Ni、Co、V污染不明显,但受到了不同程度的Mn、Cr、Cu、Zn、Pb污染,其中：Pb污染非常严重;重金属在土壤剖面分布没有规律性;Fe、Ni、Co、V元素主要来源于原土壤物质,Cu、Zn、Pb、Cr元素主要来源于人为输入,Mn可能在不同的土壤中来源不同;Fe、Cr、Ni、Co、V元素含量之间均呈极显著正相关,Cu、Zn、Pb、Cr元素含量之间均呈极显著正相关。Fe、Co、V、Ni含量与粘粒含量、CEC呈极显著正相关;Cu、Zn、Pb含量与粘粒含量呈极显著负相关;Cu、Zn、Pb、Cr含量与有机碳呈极显著正相关,Pb含量与pH呈极显著正相关。     

Metal contents and fractionation in contaminated soil after column leaching using [S,S]-EDDS

Abstract

Column leaching using [S, S]-ethylene diamine disuccinate ([S, S]-EDDS) on copper tailing soils was carried out to investigate metal content and fractionation after leaching. The soil column was divided into four layers after leaching. Fractionation of Cu, Pb, Zn, and Mn in soil was analyzed using a modified BCR sequential extraction method. Metal contents (Cu, Pb, Ca, Mn) in soil layers increased with the depth of the soil column after leaching in the [S, S]-EDDS treatment. The cumulative extraction efficiency was approximately 43.1% for Cu, 26.8% for Zn, 19.5% for Pb, 10.5% for Ca, 2.07% for Mg, 58.5% for Mn, and 7.92% for Fe. The removal of the reducible fractions of Cu and Mn and the exchangeable fraction of Zn was the most significant in the treatment with [S, S]-EDDS. The exchangeable fraction of Pb was the main fraction that was affected by leaching using [S, S]-EDDS. Distribution of Cu and Mn were severely modified by leaching with [S, S]-EDDS. Percentages of residual fractions of the tested heavy metals in the treatment with [S, S]-EDDS after leaching were much higher than that in the control. Although column leaching using [S, S]-EDDS could remove target metals effectively and impaired their availability, it also dissolved large amounts of major elements and modified the distribution of Mn appreciably.     

Fingernails as biological indices of metal exposure

Metal determination in human tissues is the most common application of biological monitoring for screening, diagnosis and assessment of metal exposures and their risks. Various biopsy-materials may be used. This paper deals with the quantitative determination of Cd, Pb, Cr, Mn, Fe, Ni, Cu, and Zn concentrations in nails of male subjects exposed to these metals alongwith their respective controls, while working in locomotive, carriage and roadways workshops, and lead battery factories. The levels of Cd, Pb, Cr, Mn, Fe, Ni, Cu and Zn in fingernails, assayed by atomic absorption spectrophotometry, were compared with their respective controls by student ‘t’ test. All the obtained values were correlated to the personal and medical history of the subjects under study. Significantly high levels of Cd, Pb, Cr, Fe, Ni, Cu and Zn were present in smokers, compared to nonsmokers. The concentrations of Cd, Pb, Cr, Mn and Fe were not significantly high in vegetarian subjects. It was also observed that there is no contribution of liquor towards nail-metal concentration. Significant correlations were observed between skin disease and Cr, Mn, Fe, Cu; hypertension and Cd, Mn, Cu; mental stress and Cd, Pb, Mn, Ni, Cu, Zn; diabetes and Cr, Mn, Ni; chest pain and Pb; respiratory trouble and Cr, Mn, Fe, Ni, Zn; tuberculosis and Zn; acidity and Cd; and ophthalmic problems and Mn, Fe, Ni, and Zn     

浙江油茶产地土壤和果实金属元素含量特征

为探讨油茶(Camellia oleifera)产地土壤和油茶果实中金属元素分布和富集特征,在油茶果实成熟期,对浙江5个油茶产地土壤及油茶果实中金属元素进行污染分析和富集能力评价.结果表明,浙江油茶产地土壤中Pb、Cr、Cd、As、Hg、Ni、Cu和Zn含量低于农用地土壤污染风险筛选值,综合污染等级为安全.个别产区常山...     

Distribution of heavy metals in the geochemical phases of sediments from the Tietê River,Brazil

Abstract

The fractionation of heavy metals in riverbed sediments along the Tietê River basin, a highly polluted river in southeast region of Brazil, was investigated using a four-step sequential extraction procedure, in order to determine the concentration and distribution of Cu, Co, Cr, Cd, Zn, Ni and Pb, in the river bottom sediments, related to the potential mobility of geochemical phases. Around the metropolitan area of the City of São Paulo, which has 25 million people, the pollution is associated with municipal wastes and industrial effluents. Potentials of high mobility were observed for Cu and Zn along the entire river basin, associated mainly to the organic fraction, while at the Pirapora and Anhembi stations (upper and middle parts of the basin, respectively) the reactive forms of Ni and Pb were more associated to the Fe and Mn oxides. Near the mouth of the Tietê River, no significant contaminations caused by Cr and Ni in riverbed sediments was verified confirming the presence of these metals in the residual or lithogenous phase.     

Phytoextraction capacity of the Chenopodium album L. grown on soil amended with tannery sludge

The metal accumulation potential of Chenopodium album L. grown on various amendments of tannery sludge (TS) was studied after 60 days of sapling planted. The analysis of the results showed that the levels of pH, cation exchange capacity, organic carbon, organic matter and DTPA extractable metals (except Mn) of amendments increased by the addition of tannery sludge ratio. Shoot length of the plant increased by the addition of sludge, whereas, no marked change was observed in root length, fresh and dry weight of the plant. Accumulation of the metals in the plants was found in the order; Fe > Mn > Zn > Cr > Cu > Pb > Ni > Cd. Translocation of toxic metals (Cr, Pb, Cd) in different parts of the tested plant was found in the order; leaves > stems > roots. An increase in the photosynthetic pigments, carotenoid and leaf protein contents of the plants were found to increase with increase in sludge amendments. Correlation analysis between metal accumulation in the plants with DTPA extractable metals emphasized that Mn, Ni, Cr, Pb and Cd showed positive correlation (p < 0.05), whereas, Fe, Zn and Cu showed negative correlation. Transfer factor analysis emphasized that 10% TS amendments were suitable for phytoextraction of Cr. Overall analysis of the data exhibited that the plants may be used for phytoextraction of Cr from tannery waste contaminated soil as most of the metal was accumulated in harvestable part which is a matter of serious concern, whenever used for edible purposes.     

Contrasting two methods for determining trace metal partitioning in oxidized lake sediments

A simultaneous (SIM) sediment extraction procedure for low carbonate sediments, which partitions sediment-bound trace metals (Fe, Mn, Zn, Cu, and Cd) into easily reducible (associated with Mn oxides), reducible (associated with Fe oxides) and alkaline extracted (bound to organic) metal is presented. The SIM method was compared to the sequential (SEQ) extraction procedure of Tessier et al. (1979). Both methods showed good agreement for the partitioning of Zn and Cd among the easily reducible, reducible and organic components of sediment. Both methods also showed the same general distribution of Mn, Fe and Cu among the three sediment components, however concentrations of metals recovered by the two methods differed; less Mn and Fe and more Cu was recovered from sediments by the SEQ vs. the SIM procedure. Less recovery of Mn is in part attributed to the loss of this metal in the `in between' reagent rinses required in the SEQ procedure. Greater recovery of Cu by the SEQ vs. the SIM method may be due to the pretreatment of sediment with strong reducing agents prior to the step used for liberating organically bound metals. Advantages of a SIM over the SEQ include rapid sample processing time (i.e. the treatment of 40 samples per day vs. 40 samples in three days), plus minimal sample manipulation. Hence, for partitioning metals into easily reducible, reducible and organic sediment components in sediments low in carbonate, we recommend the use of a SIM extraction over that of a SEQ procedure.     

湘西河流表层沉积物重金属污染特征及其潜在生态毒性风险

花垣河和峒河是湘西地区受到锰矿和铅锌矿生产影响严重的两条河流。通过表层沉积物采样分析了Cd、Pb、Cu、Ni、Cr、Zn和Mn的总量,根据BCR连续提取程序分析沉积物样品中重金属的地球化学赋存形态,采用内梅罗指数法和地积累指数法评价了沉积物重金属污染特征,根据重金属的富集程度探讨了重金属污染来源,采用淡水生态系统沉积物质量基准(SQGs,TEL/PEL)和毒性单位评价了花垣河和峒河沉积物中重金属元素的生态毒性风险。结果表明,花垣河和峒河绝大多数位点的表层沉积物中Cd、Pb、Cu、Ni、Cr、Zn和Mn的总量高于参照点,形成严重的复合污染,花垣河沉积物中重金属的污染水平明显高于峒河,但沿程变化规律不明显,而峒河沉积物中重金属的沿程变化较有规律,即上游含量低,中下游含量较高。两条河流表层沉积物中富集程度居前列的均为Cd、Pb、Zn和Mn。花垣河和峒河沉积物重金属污染主要来源于矿业生产所产生废渣和废水的点排放。在花垣河和峒河的大多数位点,Cd、Pb和Mn的形态具有共同特征,其生物可利用态均较大程度地超过生物不可利用态,而且Mn和Cd的生物可直接利用态所占比例远高于其它重金属,而Cu和Cr的生物可直接利用态所占比例很低。花垣河沉积物中Cd、Pb和Zn在所有位点极大地超过PEL,在峒河中下游,Cd、Pb、Ni和Zn超过PEL,具有较大的潜在生物毒性。除上游S1位点外,花垣河的其余各位点都具有明显的急性毒性,峒河中下游各位点具有明显的急性毒性,这些河段需要重点治理。     

The Concentration and Partitioning of Heavy Metals in Surface Sediments of the Maharlu Lake,SW Iran

In this study, an assessment is made of the environmental impacts of heavy metal concentration and fractionation in bed sediments of the saline Maharlu Lake, SW Iran. Total elemental analysis indicated that sediments were highly enriched in Pb and Cd. Sequential extraction analysis revealed that salt of the lake is probably highly contaminated with Cd, Pb, and Co. Due to the oxidizing conditions of the lake, the organic matter fraction of the elements was not significant. In all sediments, Cd, Pb, Co, Mn, and Zn were strongly associated with exchangeable plus carbonate fractions, with mean percentage of 76.4%, 65.3%, 56%, 40.9%, and 34.3%, respectively. On average, the percentage of Ni associated with the sum of the exchangeable and carbonate fractions was 19.8%. Cr, Fe, and Cu fractionation indicated that these metals are environmentally inert and immobile. Statistical relationships among metal fractions and sediment properties showed that Cd, Pb, Zn, Ni, Co, and Mn were mainly from recent anthropogenic sources, while such sources were less important for Cr, Cu, and Fe. The latter metals represented natural geochemical levels.     

Seasonal and spatial variations of heavy metals in surface sediments collected from the Baoxiang River in the Dianchi Watershed,China

To explore potential ecological hazards due to heavy metals in the Dianchi Lake Watershed, a three-stage European Community Bureau of Reference (BCR) sequential extraction procedure was applied to examine the spatial distributions and relative speciation ratios of Zn, Cu, Ni, Pb, and Cr in Baoxiang River sediments during wet and dry seasons. The metal species have similar spatial variations during different seasons. In the upstream reaches of the Baoxiang River, heavy metals reside primarily in the non-extractable residual fraction (72–90%). In the midstream, the residual fraction (35–89%) remains dominant, but the extractable fraction increases, featuring especially notable increases in the reducible fraction (5–40%). Downstream, the Cu, Ni, Pb, and Cr residual fractions remain high (46–80%) and the extractable fractions increase rapidly; the Zn extractable fraction is quite high (65.5%). Anthropogenic sources drive changes in heavy metal speciation. Changes in the river environment, such as pH and oxidation-reduction potential, also affect speciation. The reducible fraction of heavy metals in Baoxiang River sediments is most sensitive to pH. Potential ecological risk assessments for these five elements indicate that risks from Zn and Pb are mild to moderate in the middle and lower reaches of the river.     

Fractionation of heavy metals in contaminated soils surrounding non-ferrous metals smelting area in the North China Plain

Abstract

The accumulation of heavy metals in soil is a serious environmental problem. The risk of metals in soil is associated critically with their species. Operationally determined speciation analysis of Cr, Mn, Ni, Cu, Zn, Sb, Cd and Pb was carried out in the area of non-ferrous metals-smelting in the North China Plain, using inductively coupled plasma-mass spectroscopy after sequential chemical extraction. The average potential mobility fraction was calculated. The average potential mobility of the metals had the following order: Cd(44.7%) > Pb(29.6%) > Mn(14.8%) > Zn(12.5%) > Cu(5.9%) > Sb(5.0%) > Ni(2.1%) > Cr(0.8%). It is concluded that there is a distinct spatial heterogeneity in the concentration of heavy metals in the studied area. The results indicate that the polluting heavy metals, in particular Cd and Pb, have high potential mobility.