An assessment of heavy metal contamination in soils of fresh water aquifer system and evaluation of eco-toxicity by lithogenic implications

The chemistry of heavy metals in sediments with respect to bio-availability and chemical reactivity is regulated by pH, texture, and organic matter contents of the sediments and specific binding form and coupled reactivity of the metals within. To focus on the metal distribution (Fe, Mn, Pb, Cd, Zn, Co, Cu, and Cr) and behavior in a fresh water aquifer system along with the ecological toxicity parameters, a four-step sequential extraction method was applied on 18 Eastern Ghats’ type sediments from fluorosis-hit Nayagarh district, India. Geo-accumulation index of metals in the sediments indicates that they are practically uncontaminated and/or less contaminated with and Fe, Mn, and Cu; contaminated to moderately contaminated with Pb, Zn, and Cr; and strongly contaminated with Cd. Rather, more than 80 % recovered Cd metal concentration in sediments constitute the labile fractions. Temporal clustering of metal fractions indicates transition metal fraction distribution claiming the sediment pH regulation. Similarly, base metal distribution accounts for organic carbon and soil conductivity due to their greater availability in exchangeable and sulfide fractions. Correlation analysis and factor analysis scores demonstrate lack of inter-relationship between transition group and base metal fractions. High fluoride concentration in ground water is associated with high sodium-bicarbonate-iron affinity with elevated pH values (i.e., >7.0) and high positive factor score with the total iron concentration in ground water.     

Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments

Several leaching tests were applied and compared to study metal remobilisation on various unpolluted and contaminated soils and on several contaminated sediments. The trace elements considered were Cd, Cr, Cu, Ni, Pb and Zn, and leaching tests consisted of the application of reagents with contrasting characteristics and strengths in order to assess the information provided. An extraction with aqua regia permitted the estimation of the pseudo-total metal content in the sample. Mild extractants such as H2O, CaCl2 and NaNO3 showed low and similar leaching capacities. Acid (CH3COOH) and complexing (EDTA) agents were more effective in remobilising trace metals from soils and sediments. Cd and Zn showed similar extraction characteristics under both extractant solutions, whereas Cu and Pb were more sensitive to complexation, and Ni and Cr to acidification processes. Sequential chemical extractions provided additional information on the association of the trace elements with the different soil and sediment phases. Cd and Zn showed the highest mobility, Pb was associated to reducible solid phases, Cu and Ni to oxidisable phases, and Cr remained mostly in the residual fraction. The results obtained in this paper provided valuable information for choosing a leaching test, which is an instrument of environmental analysis for the estimation of trace metal mobility.     

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.     

Trace metal speciation and contamination in an intertidal estuary

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Tees estuary was carried out using a sequential extraction technique and Differential Stripping Voltammetry. The sediments of the estuary are mainly organic rich clay silts and metal concentrations exceed those in the water column. Speciation results show that contamination of the estuary is mainly from anthropogenic sources. Pb and Zn are associated with the reducible, residual and oxidisable fractions. The speciation pattern of Cd was similar to those of lead and zinc. However there were also some exchangeable and bound to carbonate fractions although these were less significant. Cu is largely associated with the oxidisable and residual fractions, with insignificant bound to carbonate, exchangeable and reducible fractions. The most bioavailable forms of the metals are the free inorganic ions. Total metal concentrations in the estuary display a downward trend since the 1970s.     

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.     

长江南京段近岸沉积物和土壤中重金属分布特征分析

通过测定沉积物和土壤中Cd、Pb、Cr、Zn、Cu、Ni 6种重金属元素的平均含量,计算其富集因子,分析长江南京段近岸沉积物和土壤中重金属的空间分布特征,结果表明,几种重金属在沉积物中的富集次序为:CdPbCr1NiCuZn,在土壤中为:CdZnCu1CrPbNi,除Zn和Cu外,其他几种金属在沉积物中的富集程度高于土壤,同时Cd的含量超过土壤环境质量三级标准。以Cd和Pb为例分析了重金属含量与沉积物粒级之间的关系,回归分析显示,Cd、Pb的含量与颗粒物的粒级呈显著的相关性,与细颗粒物的含量有密切关系,细颗粒携带的重金属,在长江水力分选作用下到达下游,成为沉积物中重金属的主要来源。     

Determination of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) by ICP-OES and their speciation in Algerian Mediterranean Sea sediments after a five-stage sequential extraction procedure

Surface sediment samples (n = 18) were collected from the Algerian Mediterranean coasts and analyzed for seven metals using inductively coupled plasma-optical emission spectrometry in order to asses the distribution and bioavailability of metals and to study the anthropogenic factors affecting their concentrations. Sediment samples were size-fractionated into three sizes: 1,080–500 (coarse), 500–250 (medium), and <250 mm (fine). Bulk sediments were subjected to both sequential extraction and total digestion to evaluate the reliability of the sequential extraction procedure (SEP), while the fractions have been only sequentially extracted for metals speciation. The metals were sequentially extracted into five phases namely exchangeable (P1), carbonates (P2), Fe–Mn oxides (P3), organic (P4) and residual (P5). Metal recoveries in sequential extractions were ±20% of the independently measured total metal concentrations; the high recovery rates indicate the good reliability of the SEP used in this study. Correlation coefficients indicated that the grain size has an effect on the distribution of metals in the investigated samples. The order of metal levels in the fractions was medium > fine > coarse for all the metals. The average total extractable metal concentrations for Cd, Cr, Cu, Fe, Ni, Pb, and Zn were 1.1, 8.8, 4.7, 1,291.3, 13.9, 5.7 and 20.4 μg/g, respectively. The northeastern shelf had the lowest metal levels while the highest were in northwestern part mainly due to the significant tourism activities in the northwestern part. Comparison of our results to Earth’s crust values and to previous studies points out that our samples were relatively unpolluted with respect to the heavy metals investigated; most of the metals are not from anthropogenic sources. Enrichment factors as the criteria for examining the impact of the anthropogenic sources of heavy metals were calculated, and it was observed that the investigated samples were not contaminated with Cr, Cu, and Fe, moderately contaminated with Ni, Pb, and Cd, and contaminated with Cd in some sites. The P5 phase had the highest percents of Cr, Cu, Fe, Ni, and Zn. Cadmium and lead were predominant in the P4 phase, while Cu, Fe and Zn were distributed in the order P5 > P3 > P4 > P2 > P1. The following order of bioavailability was found with the heavy metals Pb > Cr > Cd > Ni > Zn > Cu > Fe.     

Distribution and chemical partitioning of heavy metals in marine near-shore sediment cores: a case study from the Xugou, Lianyungang, China

The concentrations and chemical partitioning of heavy metals (Co, Cr, Ni, Zn, Cu, and Pb) in the marine near-shore sediment cores were investigated. Typically, the mean concentrations from Core B sediment samples were 98.6, 21.1, 47.0, 46.4, 107.6, and 31.9 mg kg^???1 for Cr, Co, Ni, Cu, Zn, and Pb, respectively. The heavy metal concentrations were normalized to commonly used reference elements Al, Li, Sc, and total organic carbon. Based on Pearson coefficients, Li was found to be a good normalizer for Co (r?= 0.974), Cr (r?= 0.967), Ni (r?= 0.898), and Zn (r?= 0.929) in 80 sediment samples from three sampling sites. However, the correlation coefficients between Li and Cu, and Li and Pb were relatively low. Multivariate statistic approaches (Principal Component Analysis and Cluster Analysis) were adopted for data treatment, allowing the identification of two main factors controlling the heavy metal variability in the sediments. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. The results showed that the residual, Fe/Mn oxides and Organic/sulfide fractions were dominant geochemical phases in the enriched sections, indicating low bioavailability of heavy metals in sediments.     

Factors affecting metal concentrations in the upper sediment layer of intertidal reedbeds along the river Scheldt

Factors that play a role in determining metal accumulation in sediments of 26 intertidal marshes which are mainly vegetated by reed plants (Phragmites australis) were assessed along the Scheldt estuary (Belgium and The Netherlands). In the upper 20 cm sediment layer, several physico-chemical properties (clay, silt and sand content, organic matter, carbonate and chloride content, pH and conductivity) and aqua regia extractable metals (Cd, Cr, Cu, Ni, Pb, Zn) were determined. The sediments were significantly contaminated with trace metals. The Cd concentrations often exceeded the Flemish soil remediation thresholds for nature areas, whereas Cr, Cu and Zn levels indicated moderate contamination. Pb concentrations occasionally were high, whereas Ni concentrations leaned towards background values. Organic matter was the single most important predictor variable for total metal contents in regression models, except for Cr. Additional significant predictor variables were clay or chloride content, depending on the metal. Observed metal concentrations at sites within a range of a few km from specific point-sources of metals (e.g. shipyards, industrial areas with metallurgic activities, affluents, major motorways) were somewhat higher than predicted by the models, whereas they were lower than predicted at sites which are regularly subjected to flooding by water of high salinity. The ratio between observed and predicted concentrations seems to be a valuable tool for the identification of areas which are specifically impacted by point sources.     

Mobility and ecological risk assessment of trace metals in polluted estuarine sediments using a sequential extraction scheme

The three-stage sequential extraction procedure for the fractionation of Cd, Cr, Cu, Ni, Pb, and Zn, proposed by the Commission of the European Communities Bureau of Reference, was applied to sediment five samples collected from the Sal estuary, Sergipe State, northeast Brazil, in September 2009. The method showed satisfactory recoveries, detection limits, and standard deviations for determinations of trace metals in the sediments. Cd and Pb were the metals most prevalent in the bioavailable fractions (carbonates, Fe and Mn oxides, organic matter, and sulfides), while Ni, Zn, Cu, and Cr showed higher percentages in the inert fraction. The order of mobility of the metals was Cd (66 %) > Pb (65 %) > Zn (59 %) > Ni (57 %) = Cr (57 %) > Cu (56 %). Possible toxicity related to these metals was examined using the risk assessment code, and by comparing the chemical data with sediment quality guideline ERL-ERM values. Results obtained using the two methods were in agreement, and showed low to medium risk for all metals, indicating that adverse effects on aquatic biota should rarely occur.     

The potential of the Phytotoxkit microbiotest for hazard evaluation of sediments in eutrophic freshwater ecosystems

The applicability of the Phytotoxkit microbiotest for toxicity assessment of sediments in eutrophic freshwater ecosystems was evaluated. Sediments were collected from Turawa dam reservoir (southwestern Poland) which, for years, has been subjected to a marked nutrient enrichment and heavy metal contamination. The test plant species were exposed to whole sediments, solid phases of sediments, and pore waters. Phytotoxicity was estimated on the basis of seed germination and root elongation measurements, combined into an overall germination index (GI). For pore waters, the majority of GI values were not statistically different from the controls, which was consistent with chemical data. For solid phases and whole sediments, GI values showed diversified effects ranging from growth stimulation to growth inhibition. The results obtained vary depending on the plant species and the type of sediment samples. Generally, tests with solid phases of sediments showed phytostimulation, suggesting that higher amount of nutrients adsorbed on organic matter-rich sediments might conceal the inhibitory impact of heavy metals (Cd, Cr, Cu, Mn, Ni, Pb, and Zn). However, this beneficial impact is indicative of a significant nutrient load and, with respect to aquatic ecosystems, its potential resuspention that might accelerate the reservoir eutrophication. Under appropriate conditions heavy metals exerted stronger negative impact on plants. Tests with whole sediments had a higher acidity (pH?5.85) and showed adverse effects, though plant responses vary from inhibition (Lepidium sativum) to stimulation (Sorghum saccharatum). The study demonstrated variability in toxicity of contaminated nutrient-rich sediments as well as effectiveness and usefulness of the Phytotoxkit microbiotest as a practical and reliable tool for evaluation of the hazard of eutrophic ecosystems to higher plants.     

Speciation and assessment of heavy metals in surface sediments of Jinjiang River tidal reach, southeast of China

The concentration and speciation of heavy metals (Cr, Ni, Cu, Zn, Cd, Pb) in surface sediments (??≤ 63 μm) of Jinjiang River tidal reach are determined to evaluate the metal behavior. A modified BCR three-step sequential extraction procedure is carried out, and the residual fraction is undertaken by microwave-assisted acid digestion. The index of geo-accumulation indicates that Cd appeared highest among all these heavy metals in surface sediments, Cr, Cu, Zn lower, and Ni, Pb the least. The percentage of Zn, Cd is comparatively higher in the acid soluble fraction, Pb and Cu higher in the reductive fraction, indicating larger potential danger to the environment. So it is essential for developing the future remediation plans and pollution control strategies.     

Source identification and assessment of sediment contamination of trace metals in Kogarah Bay,NSW, Australia

The distribution of trace metals (spatial and temporal) and sedimentary fractions were investigated to identify the concentrations and sources of trace metals within Kogarah Bay, NSW, Australia. A total of 59 surface sediments and six subsurface samples from core of the sediment were collected. The contamination factor and pollution load index indices used to evaluate environmental effects of trace metals. The study area was found to be uncontaminated with Cr and Ni, moderately contaminated with As and considerably contaminated with Cu, Zn and Pb. The concentrations of Cr and Ni were below both effect range low and effect range median, while As, Cu, Zn and Pb were slightly above effect range low. The highest concentrations of these trace metals such as Cu, Zn and Pb were found in the north, northwest and southeast of the bay, close to discharge points, stormwater outlets and around boatyards and watercrafts. The spatial distributions of metals were strongly related to muddy particles and organic matter. The temporal sediments of metals declined with increased sediment depth, which reflects accumulation of trace metals since European settlement in this area. Furthermore, the source of the trace metals was found to be stormwater outlets, gasoline fumes, boatyards and other human activities.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Assessment of heavy metals in sediments from a typical catchment of the Yangtze River, China

An intensive investigation was conducted to study the accumulation, speciation, and distribution of various heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) in sediments from the Yangtze River catchment of Wuhan, China. The potential ecological risks posed by these heavy metals also were estimated. The median concentrations of most heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) were higher than the background values of soils in Wuhan and were beyond the threshold effect level (TEL), implying heavy metal contamination of the sediments. Carbonate-bound Cd and exchangeable Cd, both of which had high bioavailability, were 40.2% and 30.5% of the total for Cd, respectively, demonstrating that Cd poses a high ecological risk in the sediments. The coefficients of the relationship among Pb, Hg, and Cu were greater than 0.797 using correlation analysis, indicating the highly positive correlation among these three elements. Besides, total organic carbon content played an important role in determining the behaviors of heavy metals in sediments. Principal component analysis was used to study the distribution and potential origin of heavy metals. The result suggested three principal components controlling their variability in sediments, which accounted for 36.72% (factor 1: Hg, Cu, and Pb), 28.69% (factor 2: Cr, Zn, and Ni), and 19.45% (factor 3: As and Cd) of the total variance. Overall, 75% of the studied sediment samples afforded relatively low potential ecological risk despite the fact that generally higher concentrations of heavy metals relative to TEL were detected in the sediments.     

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.     

Heavy metal binding fractions in the sediments of the Godavari estuary,East Coast of India

Sequential chemical extraction was used to study the operationally determined chemical forms of five heavy metals (Pb, Cu, Zn, Co and Ni) and their spatial distribution in the sediments. The binding behaviour of heavy metals associating with Fe–Mn oxides showed a good correlation towards Cu, Zn and Co, but moderate linear dependence with Ni and Pb. Among the five metals, correlation between Fe–Mn oxide bound Cu and Fe–Mn oxides (r = 0.95) is highest. The coefficient of determination (r ²) in organically bound heavy metals versus organic matter (OM) ranges from 0.772 to 0.952, which indicates a good linear dependence. The OM fraction in the sediments is more accessible to heavy metals and is the major ligand available for complexation. In particular, Zn and Cu are preferentially bound to OM. In general, Zn co-precipitation with carbonates is the dominant chemical form when Fe–Mn oxide and OM are less abundant. In this study, however, carbonates were less abundant, hence Zn bound to carbonates was less pronounced. Based on the results, even if the excessive binding sites are contained in the sediments, competition of various complexation reactions between sediment phases and heavy metals could dominate metal association.     

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.     

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.