Evaluation of the Chemcatcher and DGT passive samplers for monitoring metals with highly fluctuating water concentrations

Passive sampling devices accumulate chemicals continuously from water and can provide time weighted average (TWA) concentrations of pollutants over the exposure period. Hence, they offer a number of advantages over other conventional monitoring techniques such as spot or grab sampling. The diffusive gradient in thin film (DGT) and the Chemcatcher passive samplers can be used to provide TWA concentrations of labile metals, but the approaches to their calibration differ. DGT uses diffusion coefficients of metals in the hydrogel layer, whereas Chemcatcher uses metal specific uptake rates, with both sets of values obtained under controlled laboratory conditions with constant aqueous metal concentrations. However, little is known of how such samplers respond to fluctuating concentrations. We evaluated the responsiveness of these two passive sampling devices to rapidly changing concentrations of Cd, Cu, Ni, Pb and Zn in natural freshwater, over a relatively short deployment time. Maximum metal concentrations in water were varied between 70 and 140 microg L(-1). Experiments were carried out in a tank with a rotating carousel system and filled with Meuse river water, allowing a degree of control over experimental conditions while using natural river water. Fluctuating concentrations were obtained by stepwise addition of standard solutions of the metals. The reliability and accuracy of the TWA concentrations measured by the samplers were assessed by comparison with concentrations of the metals in spot samples of water taken regularly over the deployment period. The spot samples of water were either unfiltered (total), filtered (0.45 microm) or ultrafiltered (5 kDa). Predictive speciation modelling using the visual MINTEQ programme was also undertaken. There was reasonable agreement between the TWA concentrations of Cd and Ni obtained with Chemcatcher and DGT and the total Cd and Ni concentrations measured in repeated unfiltered spot samples. For elements (i.e. Cu, Pb, Zn) that associate to a significant degree with suspended solids, colloids or dissolved organic carbon, or form complexes with large organic ligands, optimum agreement was with the filtered or ultrafiltered fractions and with the predicted inorganic and inorganic-fulvic acid associated fractions. While Chemcatcher-based TWA concentration ranges for Cu and Zn were in best agreement with the total filtered fraction, there was lack of agreement for Pb. The combined use of DGT devices with open pore (OP) and restricted pore (RP) gels allowed the labile fraction of metal associated with large organic ligands or DOC to be differentiated and quantified, since this is available to DGT OP but unable to diffuse into the DGT RP. This evaluation of the two sampling devices clearly demonstrated their ability to react reliably to transient peaks in concentration of metal pollutants in water and indicated where future efforts are needed to improve calibration data. Such samplers may prove valuable in responding to the monitoring requirements of the European Union's Water Framework Directive.     

Trace metal speciation during dry and wet weather flows in the Tama River, Japan, by using diffusive gradients in thin films (DGT)

The labile species of Ni, Cu, Zn, Cd, and Pb in the Tama River, an urban river in Tokyo, Japan, were measured using diffusive gradients in thin films (DGT) method under dry and wet weather conditions, and the results were compared with total dissolved concentrations in hourly samples collected in parallel. A total of 10 DGT deployments were made and 251 hourly samples were collected during 2 rounds of sampling, conducted between August and October, 2006. Two types of diffusive gradients in thin films (DGT) devices-DGT-RG for labile inorganic and DGT-APA for total (inorganic and organic) labile species-were applied throughout the samplings. The proportions of metals measured by DGT, compared with the dissolved metal concentrations (filtered using a membrane of 0.5 microm pore size), were 38 +/- 5% (RG) and 45 +/- 8% (APA) for Ni and 45 +/- 22% (RG) and 53 +/- 23% (APA) for Zn. No labile Cu was detected throughout the sampling; Cu was assumed to be in stable complexed forms. Labile Pb was detected in 3 out of 10 deployments only; the rest were lower than the detection limit. Dissolved and labile Cd concentrations were below the detection limits. Three rain events encountered during the sampling periods were evaluated. Rains brought considerably higher loads of metals in dissolved form, and DGT measurements indicated that labile metal loads also increased. Selected DGT measurements were compared with the WHAM 6 speciation model and found to be similar to the model-computed results.     

Monitoring of labile metals in turbid coastal seawater using diffusive gradients in thin-films

Diffusive gradients in thin-films (DGT) have been investigated for in situ monitoring of labile metals in north Australian coastal seawater. Field and experimental data showed that DGT devices provided adequate detection limits, accuracy and precision for monitoring of near-pristine levels of labile Mn, Co, Cu, Cd and Pb when deployed for periods of 3 days. However, Zn could not be adequately determined due to high blank levels. The ratio of DGT-labile to 0.45 microm-filtered metal levels in natural seawater ranged from 0.44-0.63 for Cu but was close to unity for Co and Cd. Elevated levels of suspended particulate matter up to 57.3 mg l(-1) did not have an adverse effect on the performance of DGT.     

Chemical speciation and partitioning of trace metals (Cd, Co, Cu, Ni, Pb) in the lower Athabasca river and its tributaries (Alberta, Canada)

Concentrations of Cd, Co, Cu, Ni and Pb were measured in particulate and dissolved phases at 11 sites located upstream and near Athabasca oil sands development. The in situ discrimination between non-labile and labile dissolved metals was done using diffusive gradients in thin-films (DGT) devices. The DGT-labile fraction of Co and Ni was 30% lower near development sites whereas Cu, Cd and Pb showed minor changes spatially. It was found that an 8-fold increase in dissolved organic matter (DOM) near development induced a rapid decrease in DGT-labile metals. Dissolved metal concentrations were used along with DOM, major ions, nutrients, pH and conductivity to calculate the distribution of dissolved metal species using the speciation model WHAM. Labile-DGT metal concentrations agreed well with WHAM-predicted concentrations. It was also found that a significant amount of metals were associated with the non-DGT labile fraction (i.e. colloidal DOM) and colloid abundance was more important than suspended particulate matter abundance in influencing metal mobility near Athabasca oil soils development. Since changes in colloidal DOM levels are likely to be the result of surface mining activities, this confirms the serious effects of oil sands activities on metal biogeochemical cycles in the lower Athabasca River.     

Assessment of the labile fractions of copper and zinc in marinas and port areas in Southern Brazil

The dissolved labile and labile particulate fractions (LPF) of Cu and Zn were analyzed during different seasons and salinity conditions in estuarine waters of marina, port, and shipyard areas in the southern region of the Patos Lagoon (RS, Brazil). The dissolved labile concentration was determined using the diffusive gradients in thin films technique (DGT). DGT devices were deployed in seven locations of the estuary for 72 h and the physicochemical parameters were also measured. The LPF of Cu and Zn was determined by daily filtering of water samples. Seasonal variation of DGT–Cu concentrations was only significant (p?<?0.05) at one shipyard area, while DGT–Zn was significant (p?<?0.05) in every locations. The LPF of Cu and Zn concentrations demonstrated seasonal and spatial variability in all locations, mainly at shipyard areas during high salinity conditions. In general, except the control location, the sampling locations showed mean variations of 0.11–0.45 μg?L^?1 for DGT–Cu, 0.89–9.96 μg?L^?1 for DGT–Zn, 0.65–3.69 μg?g^?1 for LPF–Cu, and 1.35–10.87 μg?g^?1 for LPF–Zn. Shipyard areas demonstrated the most expressive values of labile Cu and Zn in both fractions. Strong relationship between DGT–Zn and LPF–Zn was found suggesting that the DGT–Zn fraction originates from the suspended particulate matter. Water salinity and suspended particulate matter content indicated their importance for the control of the labile concentrations of Cu and Zn in the water column. These parameters must be taken into consideration for comparison among labile metals in estuaries.     

Evaluation of diffusive gradients in thin films technique (DGT) for measuring Al, Cd, Co, Cu, Mn, Ni, and Zn in Amazonian rivers

Studies concerning the lability and bioavailability of trace metals have played a prominent role in the search for contamination of water resources. This work describes the first application yet of the diffusive gradients in thin films technique (DGT) to the determination of the fraction of free plus labile metals in waters from the Amazon Basin. Due to the complexity of the use of DGT for samples with low ionic strength and high organic matter content (characteristic of Amazonian rivers), a new analytical procedure was developed. The method is based on the determinations of apparent diffusion coefficients (D_ap) in the laboratory, by performing deployments in samples collected in the corresponding sites of study. The D_ap thereby determined is then used for in situ measurements. The suitability of the proposed approach for determination of labile Al, Cd, Co, Cu, Mn, Ni, and Zn in the Amazon River and Rio Negro (English: Black River) was evaluated. Except for Co, Mn (in a deployment at Rio Negro), Ni and Zn (in a deployment at Amazon River), labile in situ measurements were lower or similar to dissolved concentrations, indicating suitability of the proposed approach.     

Bioavailability of copper,cadmium, zinc,and lead in tropical savanna soils assessed by diffusive gradient in thin films (DGT) and ion exchange resin membranes

The technique of diffusion gradient in thin films (DGT) for assessing bioavailable metals has not been tested under field conditions. We assessed the relationships of DGT- and cation exchange resin-membrane-measured concentrations of Cd, Cu, Pb, and Zn with plant uptake of the metals under greenhouse and field conditions. In the greenhouse, the effective concentrations of Cu, Pb, and Zn by DGT correlated significantly with uptake by sorghum (Sorghum bicolor), but cation exchange resin-membrane-measured concentrations of Cd, Pb, and Zn did not correlate with sorghum uptake. In the field, the DGT-measured concentrations of Cd, Pb, and Zn were not linearly related to uptake Cd, Pb, and Zn by lettuce (Lactuca sativa) except for Cu uptake (r = 0.87, p < 0.05). Similarly, it was only the resin-membrane-extractable Pb that correlated with Pb uptake by lettuce (r = 0.77; p < 0.05). However, fitting non-linear regression models improved the plant metal uptake predictions by DGT-measured bioavailable Cd, Cu, Pb, and Zn under field conditions. In conclusion, the DGT technique was fairly predictive of bioavailability in the greenhouse, but not in the field.     

Monitoring of total and bioavailable heavy metals concentration in agricultural soils

The aim of this paper is to evaluate total and bioavailable concentration of heavy metals in agricultural soils in order to estimate their distribution, to identify the possible correlations among toxic elements and the pollution sources, to distinguish the samples in relation to sampling site or to sampling depth, and to evaluate the available fraction providing information about the risky for plants. In particular, we reinvestigated total concentrations of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V, and Zn and available concentrations of As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, and Zn in soil from Apulia (Southern Italy). Analytical results showed that total concentrations, for all soils, are in the range permitted by regulations in force in Italy, but some soils evidence slight enrichment of Cd, Cr, Cu, Pb, and Zn. All the heavy metals in the available fraction were below the detection limits of the analytical techniques used except Cu, Ni, Pb, and Zn.     

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water. This study includes analysis of tracers use for the indication of water pollution events and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal), and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e., diffusive gradient in the thin film and polar organic chemical integrated samplers) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac, and ketoprofen). Samples were analyzed using inductively coupled plasma mass spectrometry (MS; trace metals) and liquid chromatography–tandem MS electrospray ionization+/? (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: “stable” (Cd and Cr) and “time varying” (Cu, Zn, Ni, and Pb). The relationship Cd???Cu?>?Ag?>?Cr?≥?Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb–Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (runoff, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile, and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance modeling, medicaments were described as relevant socio-economic indicators, which can give a picture of main social aspects of the region.     

Geochemical fractionation of trace elements in sediments of Hugli River (Ganges) and Sundarban wetland (West Bengal, India)

A sequential extraction procedure was carried out to determinate the concentrations of 11 elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in different geochemical phases of sediments collected along the Hugli (Ganges) River Estuary and in the Sundarban mangrove wetland, eastern coastal part of India. The chemical speciation of elements was determined using the three-step sequential extraction procedure described by the European Community Bureau of Reference. Total metal concentration was determined using a microwave-assisted acid digestion procedure. Metal concentrations were near the background level except for As for which a moderate pollution can be hypothesized. The mobility order of the metals was: Cd?>?Mn?>?Cu?>?Zn?>?As?>?Co?>?Pb?>?Ni?>?Fe?>?Cr?>?Al. The highest percentage of Cd (>60%) was found in the most labile phase. Residual fraction was prevailing for Fe, Cr and Al, while Pb was mainly associated with the reducible fraction. Data were compared with Sediment Quality Guidelines to estimate the relationship between element concentrations and adverse biological effects on benthic community, finding the possibility of some toxic effects due to the presence of As in the entire studied area and Cd, only in Calcutta.     

Assessment of heavy metal concentration in the Khoshk River water and sediment, Shiraz, Southwest Iran

Heavy metal contents and contamination characteristics of the water and sediment of the Khoshk River, Shiraz, Southwest Iran were investigated. The abundance of heavy metals decreases as Zn > Mn > Cr > Ni >Pb > Cu > Cd in water samples and Mn > Cr > Pb > Ni > Zn > Cu > Cd in sediments, respectively. Based on the enrichment factor and geoaccumulation index values, sediments were loaded with Cr, Zn, Pb, Cu, and Cd. Pearson correlation matrix as well as cluster and principal components analyses and analysis of variance were implemented on data from sampling sites. Based on the locations of sampling sites in clusters and variable concentrations at these stations, it was concluded that municipal, industrial, and domestic discharges in the Shiraz urban area strongly affected heavy metals concentrations in the Khoshk River water and sediment. Results obtained from principal components analysis of sediment samples showed that the high concentration of Ni was mainly from natural origin, related to the composition of parent rocks, while the elevated values of Cr, Zn, Pb, Cd, and Cu were due to anthropogenic activities.     

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.     

Monitoring of (bio)available labile metal fraction in a drinking water treatment plant by diffusive gradients in thin films

A performance study of diffusive gradients in thin films (DGT) and inductively coupled plasma optical emission spectrometry (ICP-OES) was applied for the monitoring of the labile fraction of metals Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, in Sant Joan Despí Drinking Water Treatment Plant located in the South of Barcelona’s Metropolitan Area (Spain). The DWTP monitoring protocol was optimized by working for 1 day of deployment (24 h) with the DGT device in contact with both treated and river water matrixes. Additionally, it was demonstrated that an increase in the deployment time of 1 week did not decrease the evaluated concentrations of the studied metals. The quality parameters of the DGT device and ICP-OES determination, such as limit of quantification, accuracy expressed as relative error (%) and reproducibility expressed as relative standard deviation, were evaluated. Good results were obtained for all the metals in ultrapure water; limits of quantification ranged from 1.5 μg L^− 1 for cadmium to 28 μg L^− 1 for zinc when deployment time of 24 h was used and from 0.2 μg L^− 1 for cadmium to 4 μg L^− 1 for zinc when this time was increased by 1 week. Accuracy and precisions lower than or equal to 10% were obtained at a parametric concentration value of the metals regulated in the European Drinking Water Guidelines (98/83/EC). DGT deployment was tested in river and treated water, and good results were obtained for Cd, Ni, Co and Zn, whereas for the other metals, a continuous control of their metallic labile fractions was monitored. Therefore, DGT device allows the continuous monitoring of the labile metal species in a drinking water treatment plant.     

Study of trace elements in wet atmospheric precipitation in Tehran,Iran

In this study, measurements of the trace metals Zn, Cd, Cr, Ni, Pb, Cu, Fe and Al were performed on 53 wet atmospheric precipitation samples (snow and rainwater) collected at a central site of Tehran. Samples were collected using a bulk sampler equipped with a high-density polyethylene funnel from November to May in 2011 and 2012 on the roof of a building in the city centre. Trace metals in the filtered samples were measured with ICP-MS. Statistical analysis of the results revealed that Al, which is principally a crustal-derived element, was the highest mean measured concentration. The pH ranged from 4.2 to 7.1 with a mean value of 5.1. Crustal enrichment factors (EF_c) related to the relative abundance of elements in crustal material was calculated using Al as reference crustal. EF_c calculations indicated that samples were not enriched with Fe and Cr but were, fairly to extremely, enriched with Zn, Cd, Ni, Pb and Cu. Factor component analysis with varimax-normalized rotation was conducted to find the probable sources of the measured species. This resulted in two factors with eigenvalues greater than unity. Factor 1 showed an anthropogenic source, mostly industrial combustion and local traffic emissions, for Zn, Cd, Ni, Pb, and Cu while factor 2 showed a crustal contribution for Al, Fe and Cr.     

Application of DET (diffusive equilibrium in thin films) and DGT (diffusive gradients in thin films) techniques in the study of the mobility of sediment-bound metals in the outer section of Songkhla Lake, Southern Thailand

The techniques of diffusive equilibrium in thin films (DET) and diffusive gradients in thin films (DGT) were used in the outer section of Songkhla Lake, Thailand in order to obtain high-resolution profiles of total dissolved and labile trace metals in the sediment pore water and investigate benthic fluxes. Six DET probes and six DGT probes were deployed at the mouths of the Phawong, Samrong and U-Taphao canals. A close correspondence could be observed between the high-resolution profiles of Fe and As, revealing a close link between the reductive remobilization of Fe oxides and the reduction of As(V). Co and Ni DGT profiles showed a close correspondence with Mn, but a narrow mobilization zone. Reductive mobilization of Mn oxides and associated metals and sulfide precipitation control the behaviour of these metals. The DGT profiles of Cu, Zn, Cd and Pb show surface maximum, probably linked to organic matter degradation. Important benthic fluxes, especially for As, were found at the mouths of the U-Taphao and Phawong canals.     

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.     

渭河陕西段表层沉积物重金属污染特征及潜在风险

为了解渭河陕西段表层沉积物重金属的污染特征,采用ICP-MS分析了13个采样断面表层沉积物中As、Cd、Cr、Cu、Mn、Ni、Pb和Zn 8种重金属的含量,并对其来源和生态风险进行了评价。结果表明：渭河陕西段8种重金属的平均含量顺序依次为Mn > Zn > Cr > Cu > Ni > Pb > As > Cd;除Ni外的其余7种重金属的平均含量均超过陕西省A层土壤背景值。各断面表层沉积物重金属的潜在生态风险指数（RI）介于111.4~7 043.7,其中23.1%的断面有极强生态风险,46.2%的断面为中等生态风险,其余为轻微生态风险。Cd污染最为严重,对各断面的潜在生态风险介于较强生态风险与极强生态风险之间,对RI的贡献平均为85.2%;其余7种重金属在所有断面均属于轻微生态危害。渭河陕西段表层沉积物As、Cd、Cu和Zn主要为工业与农业来源;Cr和Ni主要为自然来源;Pb和Mn与城市污水和交通污染来源有关。     

Heavy Metal Levels in Biota and Sediments in the Northern Coast of the Marmara Sea

Concentration of Cd, Co, Cr, Ni, Zn, Fe, Mn, Pb and Cu were determinedin biota and sediment samples collected from the Marmara Sea in Turkey. The levels of Zn, Fe, Mn, Pb and Cu in the macroalgae are higher than previous studies in the Marmara Sea. Moreover, Cu and Zn concentrations at the present study are significantly high than Bosphorus and Black Sea algae. The order heavy metal concentrations in the mussel samples was: Fe > Zn > Ni > Mn > Cu > Pb > Cr > Cd > Co. The metal concentrations are generally lower when compared with the Black Sea mussels except Pb. At the same time, concentrations of Pb, Cu and Zn in the mussel species are lower when compared with the results in the Aegean Sea. The ranges of Mn and Cu in the tested fish samples are higher than Black Sea fish. On the other hand, Cd, Co, Cr, Zn and Pb concentrations are lower. The northern coast of the Marmara Sea having the highest metal concentrations in sediments as follows: Co, Cr, Ni, Fe at ?arköy ; Pb, Cu at M. Ere?li; Cd, Zn, Mn at Menek?e. The heavy metal levels in the sediment samples are lower than other areas in the Marmara Sea.     

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.     

Seasonal Variability of Heavy Metals in Surface Sediment of Lake Sapanca, Turkey

Lake Sapanca is exposed to heavy urbanization and industrialization because of its natural beauty and its proximity to the metropolitan İstanbul, Turkey. In this study, it was aimed to investigate seasonal changes of some heavy metals (Pb, Cr, Cu, Mn, Ni, Zn and Cd) concentration of surface sediment. Nine different stations were chosen as sampling points. Samples were taken every three months and the seasonal and annual average concentration of the elements were determined. Seasonal highest values of heavy metals were observed as follows; Cr, Cu, Mn, Ni and Zn in Summer, Cd in Autumn. There was no seasonal difference for Pb, Cr and Cd. It seems that Lake Sapanca has not been polluted yet. However, it was found that Cu and Ni concentrations in surface sediment exceed lowest effect level.