Distribution and speciation of selected metals in surface sediments, from the tropical Zuari estuary, central west coast of India

Estuarine sediments are major reservoirs for the metals. Distribution and mobility of metals within estuaries depends strongly on their specific chemical form. In the present study, surface sediments from Zuari estuary, Goa were analysed by a sequential procedure for Fe, Mn, Cu, Zn, Cr and Co to determine their distribution in five geochemical phases (Exchangeable, carbonate, Fe-Mn oxide (reducible) organic bound (oxidisable) and residual). The total metal content, sand, silt, clay and organic carbon were also determined of the surface sediments. The total metal contents were found to be greater than the background concentrations of average shale values as well as to that of earlier studies indicating enrichment probably due to the anthropogenic origin of metals. The results obtained from sequential procedure showed that among the studied elements, Mn and Co are potentially available in the bioavailable fractions (exchangeable, carbonate and Fe-Mn oxide bound fractions) indicating their importance in toxicity whereas rest of the metals viz. Fe, Cu, Zn and to some extent Cr are largely available in residual phase although they are available in other fractions. The main source of metals to the estuary is mining and its associated activities in the study area. Chemical speciation by sequential extraction procedure has helped in assessing the mobility, bioavailability, diagenesis and toxicity of metals and hence giving a better insight into the ultimate fate of pollutants, which are introduced into the estuarine environment. To understand the risk of the metals to the sediment dwelling organisms the data were compared with the Sediment Quality Values (SQV) using SQUIRT. Also, correlation and Factor analysis were carried out to understand the associations of metals in the different fractions with sand, silt, clay, organic carbon and with other metals.     

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.     

Trace metal fractionation in the Pichavaram mangrove–estuarine sediments in southeast India after the tsunami of 2004

The geochemistry of coastal sediments of southern India was altered after the tsunami in 2004. A five-step sequential extraction procedure was applied to assess the effects of tsunami on mobility and redistribution of selected elements (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn). Ten surface sediments and three cores were analyzed for different metal fractions (exchangeable, carbonate, reduced, oxidized, and residual). Total metal concentrations increased in mangrove sediments after the tsunami, but their spatial distribution did not show significant variation (except Mn). The sediments were mixed by the tsunami, and there was lack of variation in metal concentrations in different fractions with depth (except Pb and Mn). High concentrations of Pb and Zn occurred in the oxide fractions, whereas Cu, Cr, Cd, and Ni were high in the organic and sulfide-rich fractions. Metals in the residual fraction (lattice bound) had the highest concentration suggesting their non-availability and limited biological uptake in the system. Most of the metals (except Mn) do not constitute a risk based on the different geochemical indices.     

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.     

Interseasonal distribution and partitioning of heavy metals in subtidal sediment of Qua Iboe Estuary and associated Creeks, Niger Delta (Nigeria)

An analysis of the distribution and chemical forms of selected metals: cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and lead (Pb) in subtidal sediments of Qua Iboe Estuary and adjourning creeks, collected between June 2000 and January 2001, were studied using a sequential chemical extraction method. The concentration of metals in each extracted fraction was determined using inductively coupled plasma spectrometer (ICP-AES). Pb, Cd and Cu appear to be the most abundant metal in the sediments of the systems, and are predominantly associated with the residual, organic and oxidisable phases. Results indicate that there are also insignificant components that are bound to both the exchangeable and carbonates fractions. Ni is largely associated with bioavailable phases with insignificant bound to organic matter and residual fractions. In general, an insignificant component of Cd and Pb are bound to organic matter phase. Moreover, speciation results indicate that metal contamination in the ecosystems investigated primarily comes from human-mediated sources. Thus, based on index of geoaccumulation calculated, sediments of these ecosystems have been classified as uncontaminated by Cr, Cu and Ni, strongly contaminated by Pb and extremely contaminated by Cd.     

Total concentrations and speciation of heavy metals in soils of the Shenyang Zhangshi Irrigation Area, China

The Shenyang Zhangshi Irrigation Area (SZIA) was used for the spreading of municipal and industrial waste water, which is an economic way of irrigating crops, recycling nutrients and water treatment. Long-term irrigation resulted in a severe metal contamination of soils. To identify the soil phases implicated in retaining the metals, sequential extractions were performed. The most predominant metal was cadmium which was mainly associated with mobile, easily soluble and easily reducible fractions. Copper was mainly associated with the residual, EDTA extractable and moderately reducible fractions. Lead was bound to organic matter and poorly crystalline Fe-oxides. Nickel and zinc were mainly associated with the residual and strongly reducible fractions. Although copper, lead, nickel and zinc concentrations were of minor importance mobile metal concentrations of these metals as well as of cadmium exceeded German trigger values for plant production and plant growth.     

Total concentrations, fractionation and mobility of heavy metals in soils of urban area of Guwahati, India

This work describes the results of assessment of the heavy metals, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn in urban soil of Guwahati City, India from 31 sites of five different land use types covering residential, commercial, industrial, public utilities, and roadside. Sequential extraction procedure was used to evaluate the relative distribution of the eight metals in exchangeable, carbonate, reducible (Fe?CMn oxide), organic and sulfide, and residual fractions. Of the eight metals, Cd and Co occur in lower concentrations (Cd <?< Co) in all types of land, and concentration variation from one type of land use to another is not much significant for both the metals. Ni presence is more than Co, and the concentrations show some variation depending on land use status. Average Cr and Cu concentrations are ??100?mg/kg, but Cr has a significantly higher presence in industrial land use. The results are similar in case of Pb. The two metals, Mn and Zn have domination over the other metals, and the values are ??300?mg/kg. Industrial and roadside soil contains much more Mn, while commercial soil is most enriched with Zn. Of the metals, Ni has the largest proportion (~42%) bound to the exchangeable fraction and Co, Cr, and Pb also have appreciable proportion bound to the same fraction. A significant amount of Co is associated with carbonates. The reducible fraction has bound considerable quantity of Mn and Zn, while most of Cu is associated with the organic and sulfide fraction. Both Cd and Pb are dominantly associated with the residual fraction. Computation of the mobility factor of the metals indicates Mn to be the most mobile metal present in the soil samples.     

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.     

Metal Leachability and Anthropogenic Signal in Roadside Soils Estimated from Sequential Extraction and Stable Lead Isotopes

Several roadside soil samples were collected at two field sites in Sweden. They were analysed for total elemental content (using both ICP-MS and XRF) and stable lead isotopes. Extraction with deicing salt solution and sequential extraction were performed in order to elucidate the potential mobility due to the use of deicing agents. The total concentrations of elements, especially lead, have decreased and lead is presently almost at background concentrations (15-51 ppm for surface samples). However, the isotopic signature indicates that old gasoline lead still is left at the site constructed prior to 1975. The field site constructed in 1992 showed, however, no 206Pb/207Pb ratio below 1.14. Only minor amounts were leached using deicing salt solutions; for lead only 0.29%, on average, was extracted indicating that the mobile fraction already was released. Sequential extraction indicated that lead mainly was associated with reducible (34.4%) and oxidisable (35.4%) fractions. Exchangable and acid soluble fractions contained 20.3% while 10.0% was found in the residual fraction. The salt extraction released, however, very low concentrations indicating that most in fraction 1 is acid soluble (e.g. carbonates). Tungsten was also found at high concentrations indicating a possible impact from studded tires. For tungsten the following composition was obtained: residual (48.0%) > oxidisable (47.6%) > reducible (3.3%) > exchangeable/acid soluble (1.1%). From the isotopic studies it was also suggested that the order for incorporating anthropogenic lead into soils is exchangeable/carbonates > (hydr)oxides > organic matter > residual. The multivariate technique principal component analysis (PCA) seems promising for evaluating large sequential extraction datasets.     

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.     

Enrichment and fractionation of heavy metals in bed sediments of River Narmada, India

A metal fractionation study on bed sediments of River Narmada in Central India has been carried out to examine the enrichment and partitioning of different metal species between five geochemical phases (exchangeable fraction, carbonate fraction, Fe/Mn oxide fraction, organic fraction and residual fraction). The river receives toxic substances through a large number of tributaries and drains flowing in the catchment of the river. The toxic substances of particular interest are heavy metals derived from urban runoff as well as municipal sewage and industrial effluents. Heavy metals entering the river get adsorbed onto the suspended sediments, which in due course of time settle down in the bottom of the river. In this study fractionation of metal ions has been carried out with the objective to determine the eco-toxic potential of metal ions. Although, in most cases (except iron) the average trace/heavy metal concentrations in sediments were higher than the standard shale values, the risk assessment code as applied to the present study reveals that only about 1–3% of manganese, <1% of copper, 16–19% of nickel, 4–20% of chromium, 1–4% of lead, 8–13% of cadmium and 1–3% of zinc exist in exchangeable fraction and therefore falls under low to medium risk category. According to the Geo-accumulation Index (GAI), cadmium shows high accumulation in the river sediments, rest of other metals are under unpolluted to moderately polluted class.     

Metal Fractionation Studies in Surfacial and Core Sediments in the Achankovil River Basin in India

The Fractionation of Fe, Zn, Cu, Pb, Mn and Cd in the sediments of the Achankovil River, Western Ghats, India using a sequential extraction method was carried out to understand the metal availability in the basin for biotic and abiotic activities. Spatial distribution of heavy metals has been studied. Sediment grain size has significant control over the heavy metal distribution. The fluctuations in their concentration partly depend upon the lithology of the river basin and partly the anthropogenic activities. The sediments are dominated by sand and are moderately to strongly positively skewed and are very leptokurtotic in nature. The quartzite and feldspars are abundant minerals along with significant amount of mica with low clay content. The core sediments show increasing trend of heavy metal concentration with depth due to the recent addition of anthropogenic sources and post-diagenic activities. Significant amount of Cd (18%) was found in carbonate fraction, which may pose environmental problems due to its toxic nature. Small concentrations of metals, except Cd and Cu, are in exchangeable fraction, which indicate low bio-availability. Enrichment Factor (EF) for individual metals shows the contribution from terrregious and in part from anthropogenic sources. Selective Sequential Extraction (SSE) study shows the variation in specific metal distribution pattern, their distribution in different phases and their bio-availability. Maximum amount of the metals were bound to the non-residual fractions (mainly Fe-oxides). Overall, bio-availability of these micronutrients from sediments seems to be very less. Non-residual phase is the most important phase for majority of heavy metals studied. Among the non-residual fraction, maximum amount of the heavy metals bound to Fe-oxides. The study high lights the need for in-depth study of heavy metals distribution and fractionation in the smaller river basins to get precise information on the behavior and transport of heavy metals in the fluvial environment and their contribution to the world ocean.     

Speciation of selected heavy metals geochemistry in surface sediments from Tirumalairajan river estuary, east coast of India

Surface sediment samples from the Tirumalairajan river estuary were studied for grain size pattern, organic matter, and heavy metals (Fe, Mn, Zn, and Pb) using the sequential and bulk metal extraction methods to evaluate metal behavior. Ten surface sediment samples were collected during the monsoon and summer seasons of the year 2009. The observed orders of concentrations of heavy metals in the sediments were as follows: Fe?>?Mn?>?Zn?>?Pb. The results obtained from sequential extraction showed that, among the metals studied, a larger portion of the metals were associated with the residual phase, although they are available in other fractions. The low concentration of metals available in bioavailable phases indicated that the sediments of Tirumalairajan river estuary were relatively unpolluted. Correlation analysis was also carried out to understand the associations of metals in different phases with sand, silt, clay, and organic matter. To understand the risk of heavy metals to sediment-dwelling organisms, the data were compared with risk assessment code and sediment quality values using the screening quick reference table. The main source of metals to the estuary is from the irrigation field and its associated activities in the study area.     

Study of Geochemical Association of Some Trace Metals in the Sediments of Chilika Lake: A Multivariate Statistical Approach

In order to establish the natural processes and geochemical factors responsible for enrichment of trace metal ions (Cu, Co, Ni, Zn and Cr) with respect to textural parameters (sand, silt and clay weight percentages) along with depth, multivariate statistical approach has been carried out for sediments in different water zones of Chilika lake, the largest brackish water lagoon in Asia. The rotated varimax factor results reveal that Cobalt enrichment is controlled by both textural parameters as well as adsorption mechanism. In fresh and saline water region, textural parameters and in mixed water, adsorption phenomenon predominates. Zn in fresh water is related to clay, whereas it is in adsorbed state in mixed water. Cu in fresh water sediments is in absorbed state and in mixed water it is related to depth and Co concentration. Cr does not show any specific association in fresh water, but in both mixed and saline water it is associated with clay minerals. Although both textural parameters and adsorption mechanism play an important role for the enrichment of trace metal ions in these lagoonal sediments, their relative importance varies with specific metal ions as well as the water quality. Sequential extraction technique was used to characterize the various forms of metals in the < 63μ size sediments of Chilika lake. The concentrations determined indicated selective accumulation of the various metals in the different phases with spatial variability in different water zones. Slightly higher availability of Co and Zn near Balugaon township in exchangeable phase may be related to anthropogenic activities. Among the non-lithogenous (NL) phases, reducible phase associated with higher concentration of Ni, Cu and Cr. Organic bound Zn and Co contributed highest percentages among NL fractions. Residual fraction contributed more than 50% in most of the cases, reflected the predominance of physical weathering, high erosion rate along the drainage basin.     

Groundwater environmental capacity and its evaluation index

At present, anthropogenic contribution of heavy metals far exceeds natural input in some aquatic sediment, but the proportions are difficult to differentiate due to the changes in sediment characters. In this paper, the metal (Al, Fe, K, Mg, Ca, Cr, Cu, Ni, and Zn) concentrations, grain size, and total organic carbon (TOC) content in the surface and core sediments of Nansihu Lake Catchment (the open lake and six inflow rivers) were determined. The chemical speciations of the metals (Al, Fe, Cr, Cu, Ni, and Zn) in the surface sediments were also analyzed. Approaches of factor analysis, normalized enrichment factor (EF) and the new non-residual fractions enrichment factor (K_NRF) were used to differentiate the sources of the metals in the sediments, from detrital clastic debris or anthropogenic input, and to quantify the anthropogenic contamination. The results indicate that natural processes were more dominant in concentrating the metals in the surface and core sediments of the open lake. High concentration of Ca and deficiency of other metals in the upper layers of the sediment core were attributed to the input of carbonate minerals in the catchment with increasing human activities since 1980s. High TOC content magnified the deficiency of the metals. Nevertheless, the EF and K_NRF both reveal moderate to significant anthropogenic contamination of Cr, Cu, Ni, and Zn in the surface sediments of Laoyun River and the estuary and Cr in the surface sediments of Baima River. The proportion of non-residual fractions (acid soluble, reducible, and oxidizable fractions) of Cr, Cu, Ni, and Zn in the contaminated sediments increased to 37–99% from the background levels less than 30%.     

Pollution in the urban soils of Lianyungang,China, evaluated using a pollution index,mobility of heavy metals,and enzymatic activities

Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had significant negative correlations with total Cu, Pb, Cr, Zn, Cd, and heavy metal fractions. This showed that alkaline phosphatase activity was sensitive to heavy metals in heavily contaminated regions, whereas urease and invertase were less affected. The combination of the various methods may offer a powerful analytical technique in the study of heavy metal pollution in street soil.     

Speciative distribution and bioavailability of metals in agricultural soils receiving industrial wastewater

In order to assess the metal pollution status of agricultural lands of Mandi Bahauuddin receiving industrial wastewater, 35 top soil samples were investigated for the determination of selected metal levels, i.e., Fe, Cu, Cd, Cr, Ca, Ni, and Pb by flame atomic absorption spectroscopy under optimum analytical conditions. The distribution of these metals in different operationally defined chemical fractions was also determined by using the sequential extraction technique. The highest mean total concentration was found for Fe while the least one was observed for Pb. All the studied metals were found to be present at levels much enhanced than national and international standards. Moreover, most of the metals were distributed principally in residual fraction with the exception of Ni which was found to be associated mainly with oxidizable fraction. The significant correlations were observed between Fe-Mn oxide-bound and residual fractions and exchangeable and oxidizable fractions for most of the metals. The highest mobility was exhibited by Ni that evidenced its enhanced bioavailability in the soil. The multivariate statistical analyses in terms of principal component analysis (PCA) and cluster analysis (CA) revealed multiple sources for various geochemical fractions of different metals. CA also revealed that the nonresidual fractions of most of the metals were very closely associated while PCA presented a distinctive behavior of Ca in the soil. It was therefore suggested that in order to avoid the metal contamination arising from industrial wastewater, appropriate remediation strategies must be adopted.     

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.     

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.     

PM2.5中重金属形态分布及其在模拟酸雨中的释放

对西安市夏季PM_2.5中6种重金属元素的化学形态进行分析,并研究了模拟酸雨淋溶条件下PM_2.5中6种元素的释放过程。结果表明,近80%的Cr和Fe分布在有机质、氧化物、硫化物结合态和残渣态中,Cd在大气环境中的化学性质很活泼,具有很强的毒害性,Pb、As、和Hg 3种元素主要以碳酸盐态、可氧化态与可还原态存在于环境中;PM_2.5中6种元素均有不同程度的释放,Cd释放率高于其他元素,Fe释放率最低,pH降低有利于颗粒物中重金属元素的释放。