Chemical fractionation of heavy metals in urban soils of Guangzhou, China

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominately located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron–Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.     

北方某水库表层沉积物重金属的赋存形态及其环境影响因子分析

为了解北方某水库重金属污染状况,采用BCR连续提取法对该水库表层沉积物中Cu、Pb、Zn、Cd的赋存形态进行了分析,对其含量及空间分布进行了研究,结合重金属总量讨论了各元素的潜在环境风险。结果表明,该水库表层沉积物中Cu、Pb、Zn、Cd的平均质量比分别为65.20 mg/kg、36.69 mg/kg、137.5 mg/kg、2.38 mg/kg,与该地区土壤元素背景值、该地区水系沉积物平均值及全国水系沉积物平均值相比,4种重金属元素均有一定程度的累积,其中Cd累积最为严重。形态分析结果表明,Cd主要以醋酸可提取态及可还原态存在,具有很高的环境风险;Pb主要以极高比例的可还原态存在,潜在风险较高;Zn和Cu存在较大比例的酸可提取态及可还原态,也具有一定程度的潜在风险。各元素生物有效性即可提取态含量排序为:Cd>Cu>Pb>Zn。     

Comparison of three sequential extraction protocols for the fractionation of potentially toxic metals in coastal sediments

In the determination of the best sequential extraction procedures (SEP) for the speciation of metals in sediment samples from the Lagos lagoon system, three sequential extraction procedures were compared for the fractionation of Cd, Cr, Cu, Pb, and Zn. The SEP compared included a modified Tessier??s procedure carried out in five steps, while the two other procedures were the three-step original Community Bureau of Reference (BCR) and the modified BCR techniques (four steps). Quantification of the metal concentration was achieved with a flame atomic absorption spectrophotometer. The results obtained by the three methods were compared, and the modified BCR and Tessier SEP were found to extract more Cu, Cr, Pb, and Zn in the reducible phase and therefore a decrease in the oxidizable phase than the original BCR SEP. The most mobile elements were found to be Cd, Pb, and Zn. These are of environmental concern, as these potentially toxic metals could be easily released into the aquatic environment with consequent ingestion by aquatic organisms, thereby entering the food chain. The mass balance (percent recovery) was found to be between 85% and 115% in most cases. Prior to the comparison, the analytical performance of the laboratory was tested using a secondary reference material, GLAURM, using the three-step modified BCR procedure. The results showed high reliability of the analytical performance of the laboratory for all the metals considered.     

Fractionation of eleven elements by chemical bonding from airborne particulate matter collected in an industrial city in Argentina

A four-step chemical sequential extraction procedure was used to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in airborne particulate matter collected on glass fibre filters using a high-volume sampler. Two sets of samples were collected in 2001 (winter and summer campaigns) in representative zones of an industrial city of Argentina. The leaching scheme was applied to PM-10 particles and consisted in extracting the elements in four fractions, namely soluble and exchangeable elements; carbonates, oxides and reducible elements; bound to organic matter and sulfidic metals; and residual elements. Metals and metalloids at microg g(-1) level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). Analyte concentration varied from 14 microg g(-1) (equivalent to 1.0 ng m(-3)) for As to 11.8 mg g(-1) (equivalent to 2,089 ng m(-3)) for Al. Seven elements, namely Al, Cr, Fe, Mn, Pb, Ti and Zn showed similar distributions in both seasons while As was distributed in a significantly different manner in each season. The results exhibited low As contents in the first and second fractions that could be associated with routine coal combustion and a high content in the third and fourth fractions of the summer samples that could be linked to the use of pesticides. Aluminium, As, Cu, Mn, Ni, Ti, V and Zn were found in different percentages in the more bioavailable aqueous fraction with As, Mn, V and Zn exhibiting solubilities greater than 1% while Cr and Pb being insoluble. The content of Al, Cr, Cu, Fe, Ni, Pb, and Zn in the residual fraction was, in average, higher than 50%. A comparative assessment of the use of the underlying information available from fractionation studies compared to that obtained from total element content was done for Fe and Mn. It showed that the results obtained using chemical sequential extraction procedures allowed further discrimination of the potential air pollution sources.     

Trace metals in the shells of blue mussels (Mytilus edulis) from the Poland coast of Baltic sea

The Odiel salt marshes (Marismas del Odiel) are an important nature area declared a Biosphere Reserve, but they are greatly affected by pollution from the Odiel River. Surface sediments from this area were analysed using the latest version of the BCR sequential extraction procedure to determine the fractionation of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn among four geochemical phases (acid-soluble, reducible, oxidisable and residual). The total content of each of the metals and As was also determined. The results showed high concentrations of As, Cd, Cu, Pb and Zn, with maximums of 791 mg kg⁻¹ of As, 8.5 mg kg⁻¹ of Cd, 2,740 mg kg⁻¹ of Cu, 1,580 mg kg⁻¹ of Pb and 3,920 mg kg⁻¹ of Zn. The concentrations of Cr, Mn and Ni were low since there are no sources of pollution by them in the area. A comparison of the metal and As levels with the sediment quality guidelines showed that the pollution is sufficient to produce noxious effects in aquatic organisms in most of the Odiel salt marshes. Based on the chemical distribution of the elements, it was found that Cd and Zn were the most mobile (i.e., elements that can pass easily into the water under changing environmental conditions). However, Cr, Fe, Ni and As were present in the greatest percentages in the residual fraction, which implies that these elements are strongly linked to the sediments.     

Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

Fractionation and ecological risk of metals in urban river sediments in Zhongshan City, Pearl River Delta

Surface sediments collected from nine urban rivers located in Zhongshan City, Pearl River Delta, were analyzed for total concentration of metals with digestion and chemical fractionation adopting the modified European Community Bureau of Reference (BCR) sequential extraction procedure. The results showed that concentration and fractionation of metals varied significantly among the rivers. The total concentration of eight metals in most rivers did not exceed the China Environmental Quality Standard for Soil, Grade III. The potential ecological risk of metals to rivers were related to the land use patterns, in the order of manufacturing areas > residential areas > agriculture areas. The concentration of Pb in the reducible fraction was relatively high (60.0-84.3%). The dominant proportions of Cd, Zn and Cu were primary in the non-residual fraction (67.0%, 71.8% and 81.4% on average respectively), while the percentages of the residual fractions of Cr and Ni varied over a wide range (43-85% and 24-71% respectively). The approaches of the H?kanson ecological risk index and Secondary Phase Enrichment Factor were applied for ecological risk assessment and metal enrichment calculation. The results indicated Hg and Cd had posed high potential ecological risk to urban rivers in this region. Meanwhile, there was widespread pollution and high enrichment of Cu in river sediments in this region. Multiple regression analysis showed that five water quality parameters (pH, DO, COD(Mn), NH(4)(+)-N, TP) had little influence on the distribution of metal fractionation. This result revealed that the ecological risk of metals was not eliminated along with the improvement in water quality. Correlation studies showed that among the metals, Group A (Cd, As, Pb, Zn Hg, r = 0.730-0.924) and Group B (Cr, Cu, Ni, r = 0.815-0.948) were obtained, and the metal contaminations were from industrial activities rather than residential.     

Determination and speciation of heavy metals in sediments of the Juru River,Penang, Malaysia

The Juru River flows through largely urbanized areas and is grossly polluted by domestic wastes and discharges from pig farms. Other than carrying highly polluting organic materials, these wastes are also contaminated with heavy metals. To ascertain the extent of heavy metal pollution in the river, total and non-residual concentrations of Cu, Pb, Zn, Mn and Fe in sediment samples collected along the river were determined. The results indicate that both the total and non-residual metal concentrations in sediments can successfully be used to identify heavy metal pollution sources. The speciation of Zn, Mn and Fe in the sediment samples were investigated using a sequential leaching technique which identifies the elements among six operationally defined host fractions: (1) exchangeable, (2) carbonate and surface-associated, (3) easily reducible, (4) moderately reducible, (5) bound to organic matter and sulphides and (6) residual. The results indicate that Zn is mainly associated with the reducible fractions. Zn and Fe found in the moderately reducible fraction are significantly correlated, indicating that iron oxides is the preferred host phase by Zn.     

Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon

Determination of only total element in sediments does not give an accurate estimate of the likely environmental impacts. Speciation study of metals in sediment provides information on the potential availability of metals (toxic) to biota under various environmental conditions. In water, the toxic metal specie is the free hydrated metal ion. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on Qaraaoun Reservoir, Lebanon. Earlier studies focused only on total metal concentrations in sediment and water. The objective of this study was to determine metal speciation (Fe, Cr, Ni, Zn, Cu, Pb, Cd) in the (operationally defined) sediment chemical fractions and metal speciation in reservoir water. This would reflect on metal bioavailability and toxicity. Water samples and bed sediments were collected from nine sites during the dry season and a sequential chemical fraction scheme was applied to the <75-??m sieve sediment fraction. Metal content in each fraction was determined by the FAAS technique. The data showed that the highest percentages of total metal content in sediment fractions were for: Fe in residual followed by reducible, Cr and Ni in residual and in reducible, Cu in organic followed by exchangeable, Zn in residual and in organic, Pb in organic and carbonate, Cd was mainly in carbonate. Total metal content in water was determined by ICP-MS technique and aqueous metal speciation was predicted using AQUACHEM software interfaced to PHREEQC geochemical computer model. The water speciation data predicted that a high percentage of Pb and Ni were present as carbonate complex species and low percentages as free hydrated ions, highest percentage of Zn as carbonate complex species followed by free hydrated ion, highest percentage of Cd as free hydrated ion followed by carbonate complex species. The sensitivity attempt of free hydrated ion of Ni, Zn, Pb, and Cd in reservoir water revealed dependence of Zn and Cd on pH and alkalinity, while Ni and Pb were only dependent on pH.     

SEC-ICP-MS studies for elements binding to different molecular weight fractions of humic substances in compost extract obtained from urban solid waste

In this work, the speciation of elements in compost was studied with emphasis on their binding to humic substances. In order to assess the distribution of As, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, U, Th and Zn among molecular weight fractions of humic substances, the compost extract (extracted by 0.1 mol l(-1) sodium pyrophosphate) was analyzed by size exclusion chromatography coupled on-line with UV-Vis spectrophotometric and ICP-MS detection. Similar chromatograms were obtained for standard humic acid (Fluka) and for compost extract (254 nm, 400 nm) and three size fractions were operationally defined that corresponded to the apparent molecular weight ranges > 15 kDa, 1-15 kDa and < 1 kDa. The percentage of total element content in compost that was leached to the extract ranged from 30% up to 100% for different elements. The elution profiles of Co, Cr, Cu, Ni and Pb (ICP-MS) followed that of humic substances, while for other elements the bulk elution peak matched the retention time observed for the element in the absence of compost extract. Spiking experiments were carried out to confirm elements' binding and to estimate the affinity of individual elements for humic substances derived from compost. The results obtained indicated the following order of decreasing affinity: Cu > Ni > Co > Pb > Cd > (Cr, U, Th) > (As, Mn, Mo, Zn). After standard addition, further binding of Cu, Ni and Co with the two molecular weight fractions of humic substances was observed, indicating that humic substances derived from compost were not saturated with these elements.     

Fractionation and ecotoxicological implication of potentially toxic metals in sediments of three urban rivers and the Lagos Lagoon,Nigeria, West Africa

The potential environmental impact of sediment-bound Cd, Cr, Cu, Pb and Zn in three trans-urban rivers in Lagos state and in the Lagos Lagoon was assessed by use of the modified Community Bureau of Reference (BCR) sequential extraction. The quality of the data was checked using BCR CRM 143R and BCR CRM 701. Good agreement was obtained between found and certified/indicative values. Of the rivers, the Odo-Iyaalaro, was generally the most contaminated and the Ibeshe the least. Higher concentrations of metals were generally found in the dry season compared to the wet season. Cadmium and Zn were released mostly in the acid exchangeable step of the sequential extraction, indicating that they have the greatest potential mobility and bioavailability of the analytes studied. Chromium and Cu were associated mainly with the reducible and oxidisable fractions, and Pb predominantly with the reducible and residual fractions. Sediments with the highest pseudototal analyte concentrations also released higher proportions of analytes earlier in the sequential extraction procedure. The study suggests that, during the dry season, potentially toxic metals (PTM) may accumulate in sediments in relatively labile forms that are released and can potentially be transported or bioaccumulate in the rainy season. Application of risk assessment codes and Hankanson potential risk indices indicated that Cd was the element of greatest concern in the Lagos Lagoon system. The study indicated that there is a need to strengthen environmental management and pollution control measures to reduce risk from PTM, but that even relatively simple strategies, such as seasonal restrictions on dredging and fishing, could be beneficial.     

Distribution and fractionation of cadmium, copper, lead, nickel, and zinc in a calcareous sandy soil receiving municipal solid waste

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.     

Comparison of unmodified and modified BCR sequential extraction schemes for the fractionation of heavy metals in shrimp aquaculture sludge from Selangor, Malaysia

A study was carried out to investigate the fractionation of Cd, Cr, Cu, Fe, Mn, Pb, and Zn in shrimp aquaculture sludge from Selangor, Malaysia, using original (unmodified) and modified four-steps BCR (European Community Bureau of Reference, now known as the Standards Measurements and Testing Program) sequential extraction scheme. Step 2 of the unmodified BCR procedure (subsequently called Method A) involves treatment with 0.1 M hydroxylammonium chloride at pH 2, whereas 0.5 M hydroxylammonium chloride at pH 1.5 was used in the modified BCR procedure (subsequently called Method B). Metal analyses were carried out by flame atomic absorption spectrometry. A pseudo-total aqua-regia digest of BCR CRM 701 has also been undertaken for quality assurance purposes. The recovery of Method A for all metals studied ranges from 96.14% to 105.26%, while the recovery for Method B ranges from 95.94% to 122.40%. Our results reveal that Method A underestimated the proportion of metals bound to the easily reducible fraction except for copper. Therefore, the potential mobility of these elements is higher than others. Thus, to use this sludge as a fertilizer we have to first find a remediation for reduction of heavy metal contamination.     

Heavy Metal Availability in Soil Amended with Composted Urban Solid Wastes

A study was performed to evaluate the pH and the availability of Zn, Cu, Mn, Pb, and Ni in soil amended with increasing doses of composted solid wastes, collected in Rio de Janeiro, Rio de Janeiro State and in Coimbra, Minas Gerais State, Brazil. The influence of the time elapsed between compost application to the soil and the sampling of the plant growth substrate (soil + compost) for pH and metal availability analyses was also examined. The availability of heavy metals in the soil, in the compost and in the substrate was evaluated using DTPA solution for metal extraction. The increase of the compost doses added to the soil resulted in the increase of the pH in the substrate. The addition of the compost from the bigger city, Rio de Janeiro, resulted in higher increase in soil pH and available Zn, Cu, Pb, and Ni levels as compared to the addition of the compost from the smaller city, Coimbra. Increasing the time elapsed between the compost application to the soil and the sampling of the mixture resulted in higher available Zn, Cu, Mn, and Pb levels. The addition of the compost from Rio de Janeiro resulted in substrate metal concentrations in the order Zn > Pb > Ni > Cu > Mn and for the Coimbra compost the metal concentrations in the substrate was Zn > Pb > Cu > Ni > Mn. The higher values of pH and available metals obtained for the bigger city were attributed to the greatest metal contamination of its compost.     

Spatial, temporal, and speciation variations of heavy metals in sediments of Nan'ao Island, a representative mariculture base in Guangdong coast, China

Heavy metals in sediments from Baisha Bay, Nan'ao Island, one of Guangdong Province's largest mariculture bases in Southern China, were investigated. The results display that the concentrations of 6 heavy metals from surface sediments were 0.040-0.220 (Cd), 24.22-39.61 (Pb), 25.30-42.66 (Cr), 10.83-19.54 (Ni), 15.06-39.24 (Cu) and 55.12-141.73 mg kg(-1) (Zn), respectively. The highest concentrations and the greatest increasing rates of heavy metals were found in a sediment core in a fish cage culture area due to receiving sewage discharge, uneaten fish bait, and boat gasoline combustion. Cd was preferentially associated with the acid-soluble fraction and Pb mainly with the reducible fraction in surface sediments. Meanwhile, Cd and Pb displayed greatest labile fractions, indicating anthropogenic origin. A principal component analysis (PCA) revealed three groupings (Cd; Cr, Ni and Cu; Pb and Zn) that mainly result from different distributions of the metals in the various fractions. The ecological risk of the polluted sediments stemmed mainly from Cd, and from Pb and Cu to a lesser degree. It is suggested that the density of fish-stocking be controlled, periodic movement of rafts (cages) be introduced, and the total numbers of net-cages and human activities in the mariculture zones be restricted. in order to facilitate the recovery of the polluted sediment.     

Comparison of three sequential extraction procedures for partitioning of heavy metals in car park dusts

The aim of this study was to elucidate the amount of metal released at each step by using different extractants in three sequential extraction schemes for the partitioning of metal contents of car park deposited dust samples. For this purpose, three different sequential extraction procedures (SEP) were employed for the metal fractionation in car park dust samples collected from the campus of Erciyes University, Kayseri, Turkey. While two of the sequential extraction procedures contain five steps the other, namely the BCR sequential extraction scheme, has three steps. The first two methods fractionate metals to be exchangeable, bound to carbonates, bound to Mn oxides, bound to Fe oxides and bound to organic matter, and the BCR protocol fractionates the metals as acid soluble and exchangeable, reducible, and oxidisable. Determination of the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was performed by flame atomic absorption spectrometry (FAAS). The results obtained by the three methods were compared and showed that the amount of metal released at each step of the leaching procedure depended both on the type of reagents used and the sequence in which they were applied. The most mobile elements were Cd, Pb and Zn which are metals potentially toxic to the environment and are also known to originate from traffic. The calculated enrichment factors for Cd and Pb were substantially high (73.5-187 and 18.4-27.5, respectively) and somewhat lower for Zn (5.1-6.8). These results confirm that they are important metal pollutants for car parks. Detection limits and recoveries were found in the range of 0.01-1.39 microg ml(-1) and 68-126%, respectively, for the metals studied and the three sequential extraction procedures.     

Heavy metal speciation in solid-phase materials from a bacterial sulfate reducing bioreactor using sequential extraction procedure combined with acid volatile sulfide analysis

Heavy metal mobility, bioavailability and toxicity depends largely on the chemical form of metals and ultimately determines potential for environmental pollution. For this reason, determining the chemical form of heavy metals and metalloids, immobilized in sludges by biological mediated sulfate reduction, is important to evaluate their mobility and bioavailability. A modified Tessier sequential extraction procedure (SEP), complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, were applied to determine the partitioning of five heavy metals (defined as Fe, Ni, Zn and Cu, and the metalloid As) in anoxic solid-phase material (ASM) from an anaerobic, sulfate reducing bioreactor into six operationally defined fractions. These fractions were water soluble, exchangeable, bound to carbonates (acid soluble), bound to Fe-Mn oxides (reducible), bound to organic matter and sulfides (oxidizable) and residual. It was found that the distribution of Fe, Ni, Zn, Cu and As in ASM was strongly influenced by its association with the above solid fractions. The fraction corresponding to organic matter and sulfides appeared to be the most important scavenging phases of As, Fe, Ni, Zn and Cu in ASM (59.8-86.7%). This result was supported by AVS and SEM (Sigma Zn, Ni and Cu) measurements, which indicated that the heavy metals existed overwhelmingly as sulfides in the organic matter and sulfide fraction. A substantial amount of Fe and Ni at 16.4 and 20.1%, respectively, were also present in the carbonate fraction, while an appreciable portion of As (18.3%) and Zn (19.4%) was bound to Fe-Mn oxides. A significant amount of heavy metals was also associated with the residual fraction, ranging from 2.1% for Zn to 18.8% for As. Based on the average total extractable heavy metal (TEHM) values, the concentration of heavy metals in the ASM was in the order of Cu > Ni > Zn > Fe > As. If the mobility and bioavailability of heavy metals are assumed to be related to their solubility and chemical forms, and that they decrease with each successive extraction step, then the apparent mobility and bioavailability of these five heavy metals in ASM increase in the order of Cu < As < Ni < Fe < Zn. The SEM/AVS ratio was less than one in eight replicate ASM samples, indicating that the ASM was non-toxic with regards to having a low probability of bioavailable metals in the pore water.     

Speciation of Trace Metals in Coastal Sediments of El-Mex Bay South Mediterranean Sea–West of Alexandria (Egypt)

Sediments of El-Mex Bay estuary on the southern Mediterranean Sea have been analyzed for trace metals after sediment fractionation by sequential leaching. A sequential extraction procedure was applied to identify forms of Mn, Cu, Cd, Cr, Zn and Fe. The five steps of the sequential extraction procedure partitioned metals into: CH₃COONH₄ extractable (F1); NaOAC carbonate extractable (F2); NH₂OH.HCl/CH₃COOH reducible extractable (F3); H₂O₂–HNO₃ organic extractable (F4) and NHO₃/HClO₄/HF acid soluble residue (F5). Extracted concentrations of trace metals analyzed after all five steps, were found to be (μg/g) for Mn: 1930.2, Cu: 165.3, Cd: 60.9, Cr: 386.3, Zn: 2351.3 and Fe: 10895. Most of elements were found in reducible fraction except Fe found in acid soluble residue, characterizing stable compounds in sediments. Labile (non-residual) fractions of trace elements (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis was used to understand and visualize the associations between the labile fractions of trace metals and certain forms, since Fe-and Mn-oxides play an important role in trace metals sorption within aquatic systems, especially within El-Mex Bay sediments that characterized by varying metal bioavailability.     

微波消解法测定铅锌冶炼厂废旧除尘布袋及其飞灰中重金属的应用研究

以广东某铅锌冶炼厂的废旧除尘布袋及其布袋上的飞灰为实验材料,以HNO3-H2O2-HF对布袋及飞灰进行微波全量消解,采用BCR三步浸提法提取飞灰中Cu、Zn、Pb、Cr、Ni、Cd 6种重金属,并利用火焰原子吸收仪器检测布袋及飞灰中6种重金属的含量及飞灰中各形态含量。结果表明,铅锌冶炼厂废旧布袋和飞灰中重金属含量较高,远大于《国家土壤环境质量标准》(GB 15168—1995)三级标准值。不同重金属在飞灰中的形态分布差异较大,Ni主要以残渣态和酸可交换态为主,Cu和Pb以残渣态为主,Zn的4种形态分布都较均匀,Cd、Zn潜在的迁移性最强。     

Fractionation and elemental association of Zn, Cd and Pb in soils contaminated by Zn minings using a continuous-flow sequential extraction

Fractionation and elemental association of Zn, Cd, and Pb in soils near Zn mining areas were studied using a continuous-flow sequential extraction approach. The recently developed sequential extraction procedure not only gave fractional distribution data for evaluation of the mobility or potential environmental impact of the metals, but also the extraction profiles (extractograms) which were used for study of elemental association. In addition, the elemental atomic ratio plot extractogram can be used to demonstrate the degree of anthropogenic contamination. Seventy-nine soil samples were collected in the vicinity of a Zn mine and were fractionated into 4 phases i.e. exchangeable (F1), acid soluble (F2), reducible (F3) and oxidizable (F4) phases. Most samples were contaminated with Zn, Cd and Pb. The reducible phase is the most abundant fraction for Zn and Pb (>50%) while Cd is concentrated in the first 3 extraction steps. The distribution patterns of Cd were obviously affected by soil pH. 55% of Cd appears predominantly in the F1 fraction for acidic soils while in neutral and alkaline soils, it was mostly (70%) found in the F2 + F3 fractions. The extractograms obtained from the continuous-flow extraction system revealed close association between Zn, Cd, Pb and Fe in the acid soluble phase, Cd-Pb and Zn-Fe in the reducible phase for contaminated soils. A correlation study of the 3 metals using a correlation coefficient was also performed to compare the results with the elemental association revealed by the extractograms. Atomic ratio plot extractograms of Zn/Fe, Cd/Fe and Pb/Fe in the reducible phase, where contaminated metals are predominant, can be used to evaluate the degree of anthropogenic contamination. From the elemental atomic ratio plot, it is obvious that the contaminants Cd and Pb are mostly adsorbed on the surface of Fe oxides. Zn, which is present in an approximately 1 ratio 1 ratio with Fe in contaminated soils, does not show a similar trend to that found for Cd and Pb.