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.     

Chemcatcher and DGT passive sampling devices for regulatory monitoring of trace metals in surface water

This work aimed to evaluate whether the performance of passive sampling devices in measuring time-weighted average (TWA) concentrations supports their application in regulatory monitoring of trace metals in surface waters, such as for the European Union's Water Framework Directive (WFD). The ability of the Chemcatcher and the diffusive gradient in thin film (DGT) device sampler to provide comparable TWA concentrations of Cd, Cu, Ni, Pb and Zn was tested through consecutive and overlapping deployments (7-28 days) in the River Meuse (The Netherlands). In order to evaluate the consistency of these TWA labile metal concentrations, these were assessed against total and filtered concentrations measured at relatively high frequencies by two teams using standard monitoring procedures, and metal species predicted by equilibrium speciation modeling using Visual MINTEQ. For Cd and Zn, the concentrations obtained with filtered water samples and the passive sampling devices were generally similar. The samplers consistently underestimated filtered concentrations of Cu and Ni, in agreement with their respective predicted speciation. For Pb, a small labile fraction was mainly responsible for low sampler accumulation and hence high measurement uncertainty. While only the high frequency of spot sampling procedures enabled the observation of higher Cd concentrations during the first 14 days, consecutive DGT deployments were able to detect it and provide a reasonable estimate of ambient concentrations. The range of concentrations measured by spot and passive sampling, for exposures up to 28 days, demonstrated that both modes of monitoring were equally reliable. Passive sampling provides information that cannot be obtained by a realistic spot sampling frequency and this may impact on the ability to detect trends and assess monitoring data against environmental quality standards when concentrations fluctuate.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

The use of marine sponge, Haliclona tenuiramosa as bioindicator to monitor heavy metal pollution in the coasts of Gulf of Mannar, India

The results of the present research study indicate that the heavy metal accumulation in the marine sponges provide evidence as an excellent bioindicators for monitoring heavy metal pollution between near and offshore environments of Mandapam coast of "Gulf of Mannar (GoM), India". The heavy metal concentrations in sea water and accumulation in the tissues of Haliclona tenuiramosa were analyzed by ICP-MS (inductively coupled plasma-mass spectrometry). The concentrations of metals in the coastal waters of nearshore (< 0.5 km from shore) were always higher than those in the offshore waters (2-5 km away from shore). Likewise, sponges living in the nearshore accumulated greater concentrations of heavy metals (As, Cd, Co, Cu, Fe, Mn and Ni) ranging from 2 to 17 times higher concentration than the sponges located away from the shore. A positive correlation between concentration levels in water and bioaccumulation in tissues was observed. The bioaccumulation of heavy metals in sponge tissue were in order of Fe > Mn > Ni > Cu > As > Co > Cd in both the near and offshore stations. The present results justified that a more comprehensive monitoring of presence of heavy metals in H. tenuiramosa of surrounding GoM, is necessary to help a better mitigation of the problem.     

Biomonitoring study of heavy metals in biota and sediments in the South Eastern coast of Mediterranean sea, Egypt

Concentrations of Cd, Cu, Co, Zn, Mn and Fe were determined in biota and sediment samples collected from the Eastern Harbour and El-Mex Bay in the Mediterranean Sea, Egypt. The levels of Cu, Co, Zn, Mn and Fe in the macroalgae, Ulva lactuca, Enteromorpha compressa (green algae) and Jania rubens (red algae), recorded high concentrations except for Cd. Moreover, Fe was the most predominant metal in the seaweed. The two species of bivalves, Donax trunculus and Paphia textile, showed different amounts of metals in their tissue. The abundance of heavy metal concentrations in the mussel samples was found in the order Fe> Zn> Mn> Cu> Co> Cd and Fe> Zn> Mn> Cu> Cd> Co, respectively for the two species. The metals concentrations were generally higher compared with the previous studies in mussels from the same area. The levels of metals accumulated in the investigated fish samples, Saurida undosquamis, Siganus rivulatus, Lithognathus mormyrus and Sphyraena sphyraena, were higher than those of Marmara Sea (Turkey), for Co and Cd and lower for Cu, Zn, Mn and Fe. El-Mex Bay having the highest metals concentration in sediments as their order of abundance were Fe> Zn> Mn> Cu> Cd> Co. Nevertheless, a high variability in the metal levels occurs among the studied algae and biota and also between the investigated Harbour. A significant correlations (p < 0.05) were found for each of Zn and Fe in P. textile and of Co in D. trunculus relative to their concentrations in surficial sediments.     

Distribution and Statistical Analysis of Leachable and Total Heavy Metals in the Sediments of the Suez Gulf

The concentrations of nine heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pd and Zn) in the labile and total fractions of muddy and sandy sediment samples collected from twelve sites in Suez Gulf during April 1999 were studied to evaluate the pollution status of the Suez Gulf. The enrichment factors (EF) for each element were calculated. There are extremely high concentrations of Cd, Ni, Pb and slightly concentration of Cr and Cu in both muddy and sandy sediments. The concentration of Zn was moderately high and can be considered as seriously contaminate Metal pollution index (MPI) shows high values ranged between 46 to 156 and 40 to 232 for both sandy and muddy sediments, respectively. Concentrations of heavy metals were normalized against iron for total fraction in both of sandy and muddy sediments. Principal component analysis (PCA) was studied on the data matrix obtained and represented three-factor model explaining 92.22% for labile and 88.82% for total fractions of muddy sediment. The main source of contamination is the offshore oil fields and industrial wastes. This is largely a result of ineffective and inefficient operation equipment, illegal discharge of dirty ballast water from tankers and lack of supervision and prosecution of offenders.     

Macroalgae and DGT as indicators of available trace metals in marine coastal waters near a lead–zinc smelter

The levels of Cd, Cu, Pb, and Zn were determined in the commonest species of green, red, and brown algae collected from five coastal sites in south-western Sardinia (Italy), an area with a long history of mining and smelting. The usefulness of employing Enteromorpha sp. and Padina pavonica (L.) Thivy to monitor metal pollution was evaluated, while diffusive gradients in thin films (DGT) devices were used to measure dissolved metals in seawater. Levels of Cd and Pb were high enough to be of environmental concern in the whole study area. A significant relationship was found between the content of Pb in P. pavonica and DGT-labile Pb in seawater, suggesting that gross elemental concentrations of nonessential metals such as Pb in algal tissues are apparently controlled by the abundance of dissolved metal species in the ambient seawater. The results pointed out the usefulness of using both DGT and algal methods for a better understanding of trace metal availability in coastal waters.     

Bioavailability assessment of phosphorus and metals in soils and sediments: a review of diffusive gradients in thin films (DGT)

This paper provides an overview of the principle and latest development of the diffusive gradients in thin films (DGT) technology and its applications in environmental studies with a focus on bioavailability assessment of phosphorus and metals in sediments and soils. Compared with conventional methods, DGT, as a passive sampling method, has significant advantages: in situ measurement, time averaged concentrations and high spatial resolution. The in situ measurement avoids artificial influences including contamination of samples and sample treatment which may change the forms of chemicals. The time averaged concentration reflects representative measurement over a period of time. The high-resolution information captures the biogeochemical heterogeneity of elements of interest distributed in microenvironments, such as in the rhizosphere and the vicinity of the sediment-water interface. Moreover, DGT is a dynamic technique which simultaneously considers the diffusion of solutes and their kinetic resupply from the solid phases. All the advantages of DGT significantly promote the collection of “true” information of the bioavailable or labile forms of chemicals in the environment. DGT provides potential for applications in agriculture, environmental monitoring and the mining industry. However, the applications are still at the early testing stage. Further studies are needed to properly interpret the DGT-measured results under complex environmental conditions, and standard procedures and guideline values based on DGT are required to pave the way for its routine applications in environmental monitoring.     

The comparison of heavy metal accumulation ratios of some fish species in Enne Dame Lake (Kütahya/Turkey)

The metal accumulation levels for muscle, skin, gill, liver and intestine tissues of some Cyprinidae species (Carassius carassius, Condrostoma nasus, Leuciscus cephalus and Alburnus alburnus) in Enne Dame Lake (Kütahya/Turkey), which is mostly fed by hot spring waters, were investigated. Analyses were performed for copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), cobalt (Co), magnesium (Mg), nickel (Ni), chrome (Cr) and boron (B) using inductively coupled plasma-optic emission spectroscopy (ICP-OES), and cadmium (Cd) using atomic absorption spectrophotometer (AAS) utilizing microwave digestion techniques. The concentrations of the heavy metals found in the fish varied in the follow ing ranges: Cu: < DL-7.04, Zn: 6.96-357.25, Mn: < DL-20.70, Ni: < DL-6.21, Fe: 9.62-2500.33, Cr: < DL-1.74, Co: < DL-0.54, Cd: 0.01-0.27 and Mg: 197.44-904.90 mg/kg wet weight. While B had the second highest concentration in the water of the lake, it was not encountered in any tissue of the investigated species. In all tissues and the species, While the bioaccumulation factors (BAFs) of Mn, Zn, Fe and Cu were remarkably high, the BAFs of Mg, Cr, Co, and B were also fairly low or none. Although the heavy metal accumulation levels for the muscle were generally lower than other tissues, there were some exceptions. Cd level in the muscle of C. carassius was higher than the permissible limit stated by Turkish legislation, FAO and WHO. The mean metal amounts for all the investigated tissues and species are statistically compared and discussed in this study.     

Trace metal levels in fruit juices and carbonated beverages in Nigeria

Trace metal levels in selected fruit juices and carbonated beverages purchased in Lagos, Nigeria were determined using atomic absorption spectrophotometer (Unicam model 969) equipped with SOLAAR 32 windows software. Fruit juices analysed were grape, pineapple, apple, orange, lemon juices and their brand names were used. Some carbonated drinks were also evaluated for metal levels. Trace metals investigated were Cr, Cu, Pb, Mn, Ni, Zn, Sn, Fe, Cd and Co. Trace metal contents of fruit juices were found to be more than the metallic contents of carbonated beverages. Pb level in the fruit juices ranged from 0.08 to 0.57 mg/l but was not detected in the carbonated drinks. Concentrations of Pb in lemon juice and Mn in pineapple juice were relatively high. Cd and Co were not detected in the selected juices and beverages. Additionally, Pb, Cu, Cr and Fe were not detected in canned beverages but were present in bottled beverages. However, the metal levels of selected fruit juices and carbonated beverages were within permissible levels except for Mn in pineapple juice and Pb in lemon juice.     

Spatial distribution and metal contamination in the coastal sediments of Al-Khafji area,Arabian Gulf,Saudi Arabia

To document the spatial distribution and metal contamination in the coastal sediments of the Al-Khafji area in the northern part of the Saudi Arabian Gulf, 27 samples were collected for Al, V, Cr, Mn, Cu, Zn, Cd, Pb, Hg, Sr, As, Fe, Co, and Ni analysis using inductively coupled plasma-mass spectrometer (ICP-MS). The results revealed the following descending order of the metal concentrations: Sr > Fe > Al > As > Mn > Ni > V > Zn > Cr > Cu > Pb > Co > Hg > Cd. Average levels of enrichment factor of Sr, As, Hg, Cd, Ni, V, Cu, Co, and Pb were higher than 2 (218.10, 128.50, 80.94, 41.50, 12.31, 5.66, 2.95, 2.90, and 2.85, respectively) and that means the anthropogenic sources of these metals, while Al, Zn, Cr and Mn have enrichment factor less than 2, which implies natural sources. Average values of Sr, Hg, Cd, Cr, Ni, and As in the coastal sediments of Al-Khafji area were mostly higher than the values recorded from the background shale and earth crust and from those results along coasts of the Caspian Sea and the Mediterranean Sea. The highest levels of Cu in the northern part of the studied coastline might be due to Al-Khafji desalination plant, while levels of Al, Ni, Cr, Fe, Mn, Pb, and Zn in the central part may be a result of landfilling and industrial sewage. The highest levels of As, Cd, Co, Cu, Hg, and V in the southern part seem to be due to oil pollutants from Khafji Joint Operations (KJO). The higher values of Sr in the studied sediments in general and particularly in locality 7 could relate to the hypersalinity and aragonitic composition of the scleractinian corals abundant in that area.     

Historical trace metal fluxes in the Mexico City Metropolitan Zone as evidenced by a sedimentary record from the Espejo de los Lirios lake

The accumulation of selected trace metals (Ag, Cd, Co, Cr, Cu, Hg, Ni, Pb, V and Zn) was studied in a sediment core collected at Espejo de los Lirios lake, a precipitation-dominated seepage lake in Northern Mexico City Metropolitan Zone (MCMZ). A (210)Pb-derived chronology, obtained from the same core, was used to reconstruct the historical metal fluxes at the site, allowing evaluation of the impact of environmental changes promoted by the development of the City during the last approximately 125 years. The highest levels of metal enrichment above natural concentration levels (NCL) in the sediments from Espejo de los Lirios lake were found for Ag and Pb (approximately 250%) as well as a slight enrichment for Cd (55%), Cr (84%), Co (20%), Cu (60%), Hg (47%), Ni (45%), V (59%) and Zn (66%). Fluxes of trace metals appeared to have noticeably increased from the last 45 years showing the maximum increments for Cd, Co, Cr, Ni, V and Zn during the 1980's (9 to 13 fold natural fluxes), for Ag and Cu (17 and 12 fold, respectively) during the 1990's and for Hg and Pb (2 and 13 fold) during the middle 1970's. Low levels of metal enrichment observed have evidenced that the most conspicuous consequences of the expansive growth of this area of the MCMZ, are mostly related to deforestation and erosion of the surrounding areas, rather than to trace metal pollution. Based on PCA, it can be assumed that atmospheric deposition, weathering of bedrock and soil within the watershed and authigenic production, are the most important processes that explain the trace metal distribution in the site.     

Spatial and temporal variation of metal concentrations in adult honeybees (Apis mellifera L.)

Honeybees (Apis mellifera L.) have great potential for detecting and monitoring environmental pollution, given their wide-ranging foraging behaviour. Previous studies have demonstrated that concentrations of metals in adult honeybees were significantly higher at polluted than at control locations. These studies focused at a limited range of heavy metals and highly contrasting locations, and sampling was rarely repeated over a prolonged period. In our study, the potential of honeybees to detect and monitor metal pollution was further explored by measuring the concentration in adult honeybees of a wide range of trace metals, nine of which were not studied before, at three locations in the Netherlands over a 3-month period. The specific objective of the study was to assess the spatial and temporal variation in concentration in adult honeybees of Al, As, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ti, V and Zn. In the period of July-September 2006, replicated samples were taken at 2-week intervals from commercial-type bee hives. The metal concentration in micrograms per gram honeybee was determined by inductive coupled plasma-atomic emission spectrometry. Significant differences in concentration between sampling dates per location were found for Al, Cd, Co, Cr, Cu, Mn Sr, Ti and V, and significant differences in average concentration between locations were found for Co, Sr and V. The results indicate that honeybees can serve to detect temporal and spatial patterns in environmental metal concentrations, even at relatively low levels of pollution.     

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.