The Contribution of Ecdysis to the Fate of Copper, Zinc and Cadmium in Grass Shrimp, Palaemonetes pugio Holthius

Depuration through ecdysis by grass shrimp, Palaemonetes pugio, was examined by exposure to a sublethal mixture of copper, zinc and cadmium for 72 h, followed by placement in uncontaminated water to molt. Percent eliminated with the exuviae varied for each metal; of the total intermolt body burden, 11% Cu, 18% Zn and 26% Cd was associated with the exuviae. Cu concentrations of intermolt exoskeletons were significantly higher than of the exuviae of post-ecdysis shrimp suggesting that Cu contained in the exoskeleton was reabsorbed before molting. Exuvial Cd concentration was not significantly different than the concentration of the intermolt exoskeleton, suggesting that most Cd in the exoskeleton was depurated with the exuviae. Although Zn whole-body burdens were lower after a molt, Zn losses were most likely due to excretion because exuvial concentrations were significantly lower than in the intermolt exoskeleton. Cu, Cd and Zn concentrations in exuviae shed in metal-enriched water were significantly higher due to adsorption than exuviae produced in uncontaminated water.     

Copper,zinc, cadmium,nickel, iron and manganese in the Southern Bight of the North Sea

Ni, Cd, Cu, Zn, and Fe were determined in water and suspended matter samples and Mn in suspended matter samples from the Southern Bight region of the North Sea. Four distinct areas, comprising the Rhine estuary, the Dutch coastal waters, the centre of the Bight, and the English coastal water can be distinguished on the basis of the distribution of the trace metals. The total concentrations of all metals were high in the Rhine estuary, decreased in a seaward direction to reach very low values, comparable to continental shelf water, in the centre of the Bight, and increased again towards the English coast. Elevated concentrations of dissolved Cu, Ni, Cd and Zn near the English coast are not only due to river inputs. Over the entire region, the fraction of Cd, Ni and Zn in solution was consistently more important than the fraction in the suspended particulate phase. In contast, the fraction of Fe and Mn in the solid phase was consistently greater than the fraction in solution. Total concentrations of Fe, Mn and Cu are more dictated by the suspended particulate matter concentration than Cd, Ni and Zn.     

Bioaccumulation of trace metals in the submarine hydrothermal vent crab Xenograpsus testudinatus off Kueishan Island,Taiwan

The concentrations of ten trace metals were determined in the gills, muscles, hepatopancreas, and exoskeleton tissues of Xenograpsus testudinatus that lives around shallow and acidic hydrothermal vents off Kueishan Island, northeastern Taiwan. The analytical results demonstrate that the metal concentrations vary significantly with the type of crab tissue. The concentrations of Al, Cd, Co, Cu, Fe, Ni, and Zn are highest in the gills, whereas the concentration of Mn is highest in the exoskeleton. Cr and Pb concentrations are similar across the different tissues. The enhanced accumulation of most metals in the gills suggests the metal accumulation via the respiration pathway rather than the uptake of food. The results also reveal that the distribution patterns of metals in tissues are similar in the hepatopancreas and muscles, but very different in both the gills and the exoskeleton, perhaps because of the different pathways of metal utilization in the different crab tissues.     

Bioaccumulation of trace metals in the submarine hydrothermal vent crab Xenograpsus testudinatus off Kueishan Island, Taiwan

The concentrations of ten trace metals were determined in the gills, muscles, hepatopancreas, and exoskeleton tissues of Xenograpsus testudinatus that lives around shallow and acidic hydrothermal vents off Kueishan Island, northeastern Taiwan. The analytical results demonstrate that the metal concentrations vary significantly with the type of crab tissue. The concentrations of Al, Cd, Co, Cu, Fe, Ni, and Zn are highest in the gills, whereas the concentration of Mn is highest in the exoskeleton. Cr and Pb concentrations are similar across the different tissues. The enhanced accumulation of most metals in the gills suggests the metal accumulation via the respiration pathway rather than the uptake of food. The results also reveal that the distribution patterns of metals in tissues are similar in the hepatopancreas and muscles, but very different in both the gills and the exoskeleton, perhaps because of the different pathways of metal utilization in the different crab tissues.     

The speciation of dissolved copper,cadmium and zinc in Manila Bay,Philippines

At present, there is a very limited information on the levels and distribution of dissolved metals in Manila Bay. In this study, the horizontal and vertical distribution of operationally defined species (labile, bound and total) of dissolved copper (Cu), cadmium (Cd) and zinc (Zn) were determined using differential pulse anodic and cathodic stripping voltammetry in water samples obtained from 18 stations in November 1998. In addition, the 24-h variability in the concentrations of these species at different depths in the water column was determined. These measurements were complemented by the determination of temperature, salinity, dissolved oxygen, chlorophyll a, particulate organic carbon and nutrients. Results showed that more than 50% of total dissolved copper and cadmium were labile while 50% of total dissolved zinc was organically bound. Vertical profiles showed that Cu, Cd and Zn concentrations were generally high at the surface. Zinc and cadmium were characterised by the presence of a mid-depth minimum while copper did not show any clear vertical trend.

Dissolved Cu concentrations during the spatial and diurnal samplings ranged from 0.32 to 6.95 nM and 1.52 to 45.65 nM, respectively. For Cd, the concentrations in 18 stations ranged from 0.05 to 2.92 nM, and from 0.03 to 2.42 nM over a 24-h period. Zn concentrations ranged from 2.48 to 147.43 nM and 2.87 to 88.27 nM during the spatial and diurnal samplings, respectively. The large variation in the concentration of Cu, Cd and Zn in the bay was observed to be associated with the presence of a large vertical density gradient in the water column, which appeared to limit the exchange of materials between the surface and bottom waters. Elevated levels of these metals near point sources suggest anthropogenic inputs in the bay.     

In situ trace metal speciation in a eutrophic lake using the technique of diffusion gradients in thin films (DGT)

We evaluated the application of DGT (diffusion gradients in thin films) as a tool to determine Cu, Zn, Ni, Cd, Pb and Mn concentrations and speciation in a hardwater eutrophic lake. This technique was used in situ during six sampling periods over one year in Lake Greifen. The DGT-labile species of Cu and Ni amounted to 15-25% of the total dissolved concentrations. Speciation by ligand-exchange/DPCSV indicated that Cu and Ni were predominantly organically complexed (>99%). Thus, the DGT-labile species for Cu and Ni were much more abundant than the free ionic and inorganic species determined by ligand-exchange/DPCSV. The results can be explained by incomplete metal exchange of very strong complexes with the chelating resin in the DGT devices, metal exchange of less abundant weaker complexes, and by slow diffusion of exchangeable organic complexes. For Zn (36 to >90% DGT-labile) and Mn (50 to 100% DGT-labile), the results indicated that these metals are less strongly organically complexed. A larger fraction of Zn occurred in DGT-labile species in the hypolimnion than it did in the surface water, probably due to a larger concentration of strong ligands in the productive surface water. DGT-labile Cd- (0.01-0.02 nM) and Pb-species (0.03-0.06 nM) were detected at very low levels. The combination of measurements of dissolved and DGT-labile species showed a decrease of Cu, Zn, Cd and Mn concentration at 2.5 m from June to August, which was probably linked to intensive sedimentation of organic matter during summer stagnation. Mixing and oxygenation of the lake in winter-spring led to an increase in dissolved and DGT-labile Ni, Zn and Cd, whereas Mn decreased in the hypolimnion.     

Metals contamination along the watershed and estuarine areas of southern Bohai Sea,China

Distributions and magnitude of metals in water, sediment and soil collected from the watershed and estuarine areas of southern Bohai Sea, were investigated. The largest dissolved concentrations of As, Cu and Zn in water were 347.70, 2755.00, 2076.00 μg/L, respectively, much higher than corresponding drinking water guidelines. The greatest concentrations of Cu, Zn, Cr, Ni, Pb, As and Cd in sediments were 1462.2, 1602.17, 196.43, 67.15, 63.54, 73.86 and 1.41 mg/kg, dw, respectively. The mean concentrations of Cu, Ni, Cd, Zn, Cr, Pb and As in soils were 24.67, 24.73, 0.14, 64.75, 56.52, 25.12 and 9.34 mg/kg, dw, respectively. Land use was confirmed to be an important factor of influence on soil metal concentrations. Metal contents along the watershed of Jie River were significantly greater than in other locations. The detection of metals in relatively high concentrations from different environmental matrices in this region indicates the necessity of further studies.     

Distribution and migration of metals in trophic chains of the Yenisei ecosystem near Krasnoyarsk City

Methods of atomic absorption, flame photometry, and emission spectral analysis were used to study the concentrations of metals in water and major ecosystem components of the Yenisei River upstream of Krasnoyarsk City (conventionally background area). The mean bulk concentrations of Al and Cu in water exceeded the MAC for water bodies used for fishery. Cu concentration in freshwater shrimp was found to be reliably higher than that in the link of primary producers (periphyton), and Cd concentration in caddis fly larvae was found to exceed that in water moss. The maximal concentrations of metals among the examined aquatic organisms were recorded in periphyton. Cr concentration in the muscles of Arctic grayling was found to exceed some international standards.     

Sediment pollution and its effect on fish through food chain in the Yangtze River

Suspended sediment adsorbs pollutants from flowing water in rivers and deposits onto the bed. However, the pollutants accumulated in the river bed sediment may affect the bio-community through food chain for a long period of time. To study the problem the concentration of heavy metals （Cr, Cd, Hg, Cu, Fe, Zn, Pb and As） in water, sediment, and fish/invertebrate were investigated in the middle and lower reaches of the Yangtze River during 2006-2007. The concentrations of heavy metals were 100-10,000 times higher in the sediment than in the water. Benthic invertebrates had relatively high concentrations of heavy metals in their tissues due to their proximity to contaminated sediments. Benthic invertivore fish had moderately high concentrations of heavy metals whereas phytoplanktivore fish, such as the silver carp, accumulated the lowest concentration of heavy metals. The concentrations of Cu, Zn, and Fe were higher than Hg, Pb, Cd, Cr, and As in the tissue samples. The concentration of heavy metals was lower in the river sediments than in the lake sediments. Conversely, the concentration of heavy metals was higher in river water than in lake water. While a pollution event into a water body is often transitory, the effects of the pollutants may be long-lived due to their tendency to be absorbed in the sediments and then released into the food chain. The heavy metals were concentrated in the following order： bottom material 〉 demersal fish and benthic fauna 〉 middle-lower layer fish 〉 upper-middle layer fish 〉 water.     

Assessment of Urban Source Metal Levels in Influent,Effluent, and Sludge of Two Municipal Biological Nutrient Removal Wastewater Treatment Plants of Bursa,an Industrial City in Turkey

Removal of Al, As, Cd, total Cr (Tot. Cr), Cu, Total Fe (Tot. Fe), Mn, Ni, Pb, Sb, Sn, and Zn from urban effluent by wastewater treatment plants (WWTPs) operated under five‐stage Bardenpho® process were investigated and water soluble metals in the dewatered sludge were quantified. Samples were collected from two WWTPs on a weekly basis over an approximately 2.5‐year time span. Tot. Fe and Al were the most abundant, As, Pb, Ni, Cu, and Cd were the least abundant metals in the influents of both WWTPs. Removal efficiencies above 75% were achieved for Tot. Cr, Tot. Fe, Al, and Cu, whereas, no significant removal was observed for As, Cd, Pb, Sb, and Sn. Removal of Tot. Cr, Cu, Tot. Fe, Zn, Al, Mn, and Ni were influenced by influent suspended solids concentrations, and of Tot. Cr, Zn, and Cd were influenced by their initial content in the influent. Zn removal efficiency of biological nutrient removal (BNR) system in this study was higher and Cd removal efficiency was lower than that of conventional activated sludge reported in the literature. No remarkable difference for metals such as Cu, Mn, Ni, and Pb was observed between the removal efficiencies of conventional system and BNR system.     

Zum Einfluß des pH-Wertes und des Calciumgehaltes auf Metall-Fulvinsäure-Bindungen — Inversvoltammetrische und chemometrische Untersuchungen

The Influence of pH and Calcium Concentration on Metal-Fulvic Acid Bonds – Stripping Voltammetric and Chemometric Investigations. Electrochemically available metal concentrations of Cd, Cu and Zn were analyzed in dependence of different concentrations of calcium, fulvic acids and pH by Differential Pulse Anodic Stripping Voltammetry (DPASV). A statistical experimental design was the base to minimize the number of experiments and to include the multifarious interactions between the independent variables (Ca concentration, concentration of fulvic acids and the pH value) and otherwise the electrochemically available metal concentrations of Cd, Cu and Zn. At first analysis of experimental data was carried out by multiple linear regression. The main influence on available metal concentrations is the pH value especially for Cu. The Ca ion influence has not competitive effect and is only significant for Cd and Cu. It has an effect on the metal-fulvic acid-bonds. Two factor interactions exist for pH/fulvic acids and for Ca/fulvic acids too. The partial least squares regression (PLS) model was used to include the interactions between the metals Cd, Cu and Zn. For proving these two models the three parameters pH, Ca and fulvic acid were varied within the calibration range of the models and predicted values were compared with the experimental values. The approach with the PLS model is better than the approach with the multiple linear regression (normally used mathematical method of analysis of a factorial plan) with a relative error of 9.7% for modelling of Cd, 6.0% for Zn and 58% for Cu in relation to multiple linear regression with errors of 12% for Cd, 8.6% for Zn and 65% for Cu. The PLS modelling is a suited tool for modelling chemical interactions also in simulated natural matrices.     

Bioaccumulation from food and water of cadmium, selenium and zinc in an estuarine fish, Ambassis jacksoniensis

The glassfish, Ambassis jacksoniensis, is a key, mid-level species in an estuarine food web on the east coast of Australia. Estuaries are subject to contamination from urban and industrial activities. The biokinetics of Cd, Se and Zn accumulation by glassfish from water and food were assessed using radioisotopes. Metal uptake from water was not regulated over the range of water metal concentrations examined. Metal uptake from food was assessed using brine shrimp (Artemia sp.) fed radio-labelled algae. The assimilation efficiency from food was 9.5 ± 2.5%, 23 ± 2.2% and 4.6 ± 0.6% for Cd, Se and Zn, respectively. The potential for biomagnification was low for all metals. Food is the main metal uptake pathway for glassfish, with 97%, 99% and 98% of the uptake of Cd, Se and Zn, respectively, estimated to be from food.     

Effects of heavy metals on the survival and feeding behaviour of the sandy shore scavenging gastropod Nassarius festivus (Powys)

The effects of Cu, Cd, Zn and Cr on the survival and feeding behaviour of the sandy shore scavenging gastropod Nassarius festivus were compared. The 96-h LC₅₀ for Cu, Cd, Zn and Cr were 0.36, 1.52, 1.76 and 36.9 mg l⁻¹, respectively. Four sublethal concentrations of each metal plus a control were prepared and the snails were exposed to experimental solutions for 96 h. Feeding behaviour was studied after the snails were starved for five days. As compared with the control, the number of individuals feeding was significantly reduced by exposure to 0.05 mg l⁻¹ Cu, 0.2 mg l⁻¹ Zn, 0.5 mg l⁻¹ Cd and 5 mg l⁻¹ Cr. The time spent feeding was greater for individuals exposed to greater concentrations of Zn and Cd but no effect was found for Cu and Cr. Chemoreception of food was studied by placing the snails at a fixed distance of 15 cm from the bait. The success rate of reaching the bait was less for individuals exposed to Cr but no effect was found for Zn, Cu or Cd. The time required for an individual to reach the bait decreased as the concentration of Zn increased. In contrast, a longer time was required for individuals exposed to Cr whereas the effect of Cd and Cu was insignificant. The potential of using feeding behaviour and chemoreception in contaminant evaluations is discussed.     

Concentration of 7 Heavy Metals in Sediments and Mangrove Root Samples from Mai Po, Hong Kong

Concentration of 7 heavy metals, Zn, Fe, Cu, Cr, Cd, Pb and Ni in mudflat sediments, mangrove root sediments and root tissues of Acanthus ilicifolius, Aegicerus corniculatum and Kandelia candel from the Mai Po Nature Reserve, Northwest Hong Kong, were measured. Metal concentrations in the upper 0–10 cm of the sediment cores from the mudflat were 4–25% higher than those found in the bottom 21–30 cm. Relative Topsoil Enrichment Index approximated 1.0 for all the metals. Mudflat sediment concentrations of Fe, Ni, Cr, Cd and Cu were greater than those found in the mangrove sediments. Except for Fe, concentrations of the other 6 heavy metals were more elevated in the mangrove root sediments than in the corresponding root samples. Higher concentration factors for Zn, Fe and Cu may indicate bioaccumulation. Mean metal concentrations in both mudflat and mangrove sediments decreased in the order Fe > Zn > Pb > Ni > Cu > Cr > Cd. Mangrove root tissues also showed the same pattern except that Pb > Cu > Ni     

Regional variations in trace element concentrations in tissues of black tiger shrimp Penaeus monodon (Decapoda: Penaeidae) from South Vietnam

The goal of the present study was to examine the specific bioaccumulation of 22 trace elements in muscle, exoskeleton and hepatopancreas of black tiger shrimp Penaeus monodon from the Mekong River Delta (MRD), and the South Key Economic Zone (SKEZ), South Vietnam. The general tendency in most trace element concentrations among different tissues were hepatopancreas>exoskeleton>muscle. Comparisons of trace element levels in tissues between the two regions showed that concentrations of Se in muscle and As in all three tissues were higher in SKEZ; whereas in MRD, the higher concentrations of most elements such as Mn, Cu, Cd, Ba, Hg, were observed in tissues. These geographical variations in trace element levels may reflect the differences in human activities between the two regions of South Vietnam. The target hazard quotient (THQ) values for trace elements (<1) indicate that local residents are not exposed to potential health risks via the consumption of shrimp.     

Self-organizing map for the detection of seasonal variations in Sidi Chahed Dam sediments (Northern Morocco)

ABSTRACT

A database of 88 superficial sediment samples, distributed in space and time, was collected from the Sidi Chahed Dam (northeast of Meknes city, Morocco) and from four other reference stations (in the same region) located in supposedly uncontaminated environments. Analyses were focused on the physico-chemical characteristics and concentrations of heavy metals (Fe, Mn, As, Cu, Zn, Pb, Cr, Cd). The database was processed by advanced statistical analysis techniques. The method of classification by self-organizing maps (SOM) was used, permitting understanding and visualization of the spatial and temporal distribution of samples. Principal component analysis (PCA) and SOM hierarchical classification (SOM-HC) were used to validate the classification and detect seasonal variations in heavy metal concentrations. Dependencies between different metal tracers were considered and their spatio-temporal distribution is shown, together with the ranking of clusters, according to their pollution levels. Thus, autumn samples were the only ones with high concentrations of As, compared to the four reference stations. This is due to leaching of bare soil by the first stormy rains of autumn. In winter and spring samples, the concentrations of tracers Mn, Zn, Cu, Pb, Cd and Cr were relatively high compared to those of the reference stations. Summer sample concentrations were most comparable with the reference stations, probably due to the scarcity of rainfall and runoff in this season.

Editor Z.W. Kundzewicz Associate editor E. Gargouri     

Dissolved trace metal distributions in Port Jackson estuary (Sydney Harbour), Australia

Concentrations of dissolved metals (Cd, Cu, Ni, Mn and Zn) were determined for summer and winter, under low-flow conditions in Port Jackson, a microtidal, well-mixed estuary in south-east Australia. Mean concentrations of Cd (0.04+/-0.02 microg/l), Ni (0.86+/-0.40 microg/l), Mn (20.0+/-25 microg/l) and Zn (6.47+/-2.0 microg/l) were below water quality guidelines. Concentrations of Cu (1.68+/-0.37 microg/l), however, slightly exceeded recommended values. Dissolved Ni and Mn behaved mostly conservatively, whereas Cd, Cu and Zn showed mid-estuarine maxima. Peaks in Cd, Cu and Zn concentrations were located in the upper estuary, independent of the salinity and suspended particulate matter loading, and were consistent with anthropogenic inputs of metals in the estuary. Concentrations of dissolved Cu were highest in summer, whereas concentrations of Cd, Ni and Mn were significantly lower in summer than winter (P< or =0.05). The increase in temperature and biological activity during summer explained the seasonal variation. The sequence of log K(d) values (20-30 salinity) was Mn>Zn>Cu>Ni. These results give unique information concerning the contemporaneous distribution of dissolved trace metals in the Port Jackson estuary and they provide a data set against which the long-term contamination may be assessed.     

Water characterization in three industrialized harbours (Vigo, Bilbao and Pasajes) in north coast of Spain

Total dissolved Cu, Zn, Pb and Cd concentrations, speciation, fluorescence of organic matter and toxicity for sea urchin development have been studied during three years in water samples of three of the most industrialized harbours in North Coast of Spain: Vigo, Bilbao and Pasajes. Total metal concentrations were below 0.4 nM for Cd and generally below 2 nM for Pb. Zn and Cu levels were higher (2.8-9 nM Cu and 15-234 nM Zn) and denoted an anthropogenic enrichment. Ligand concentrations were usually between 50 and 200 nM for Cu and between 6 and 80 for Pb and Zn. Organic matter and speciation analysis yielded complementary information to characterize the samples, but no correlation was present between the parameters calculated by both methods. Samples were tested for toxicity with sea urchin embryo bioassay and three samples were toxic but the toxicity could not be explained with the metal levels here measured.     

The effects of depuration,size and sex on trace metal levels in bay mussels

The effects of depuration, size and sex on the concentrations of Mn, Ni, Cu, Zn and Cd were determined for gonadal and somatic tissues of Mytilus edulis from Yaquina Bay, Oregon. After depuration, Mn levels decreased significantly in both tissues while Cu and Ni concentrations increased in somatic tissues. The latter finding may have been associated with a stress response manifested by the appearance of new byssal threads and attachment to the vessel. Larger, and presumably older, mussels contained higher concentrations of Ni, Cu and Cd in their somatic tissues while smaller animals had greater somatic levels of Mn. There were no significant differences in gonad concentrations between the two size groups. Manganese and Zn levels were greater in the gonads of female mussels and Cd was more concentrated in the somatic tissues of females.     

Trace element accumulation in fishes collected from coastal waters of the Caspian Sea

Concentrations of 13 trace elements (V, Mn, Cr, Co, Cu, Zn, Se, Mo, Ag, Cd, Hg, Tl and Pb) were determined in muscle of bony fishes collected from coastal areas of the Caspian Sea (Kazakhstan, Azerbaijan, Turkmenistan and Iran). In all the fishes, Zn concentration was highest, followed by Cu, Se, Mn and Co, while levels of toxic elements (Ag, Cd, Cd, Tl and Pb) were relatively low. Concentrations of several elements were significantly varied between the species in each sampling area. For most of the trace elements examined, the concentrations decreased significantly with body weight of fishes. In contrast, a positive correlation with body weight was found for Co, Se and Pb concentrations in one fish species, and Hg in 2 fish species. Geographical difference in the concentrations of trace elements was examined using the Caspian roach collected from five stations of Iranian coastal waters. The concentrations of Co, Mo, Ag, Cd and Tl were higher in fishes from western stations than those from eastern stations, whereas the opposite trend was observed for Hg, indicating that local sources of trace metal pollution may be present in the Iranian coastal areas of the Caspian Sea. Levels of trace elements in Caspian fishes were relatively low in comparison to those of other regions, but Zn and Hg levels in some specimens exceeded the guideline values for food.