Measurement of environmental trace-metal levels in Mediterranean coastal areas with transplanted mussels and DGT techniques

Mussels (Mytilus galloprovincialis) and diffusive gradients in thin films (DGT) devices were deployed together for three one-month periods in coastal waters of Sardinia (Italy), in order to assess the levels of Cd, Cu, Ni, and Pb in areas differently affected by anthropogenic activities. DGT devices were more sensitive than mussels in detecting differences in metal concentrations between sites, while interpretation of the biomonitoring data revealed difficulties related to the biotic and abiotic factors that can influence the measurements. Regression analysis showed a significant correlation between Cd and Pb concentrations measured in the mussel tissues and bioavailable metal levels in seawater. Moreover transplanted mussels did not accumulate Cu and Ni following pre-exposure, although DGT showed significant concentrations of bioavailable forms of these metals in seawater. The results provided an estimate of the water quality with respect to dissolved metals and pointed out the usefulness of a combination of biomonitoring and DGT techniques for a better understanding of trace metal availability in coastal waters.     

Measurement of environmental trace-metal levels in Mediterranean coastal areas with transplanted mussels and DGT techniques

Mussels (Mytilus galloprovincialis) and diffusive gradients in thin films (DGT) devices were deployed together for three one-month periods in coastal waters of Sardinia (Italy), in order to assess the levels of Cd, Cu, Ni, and Pb in areas differently affected by anthropogenic activities. DGT devices were more sensitive than mussels in detecting differences in metal concentrations between sites, while interpretation of the biomonitoring data revealed difficulties related to the biotic and abiotic factors that can influence the measurements. Regression analysis showed a significant correlation between Cd and Pb concentrations measured in the mussel tissues and bioavailable metal levels in seawater. Moreover transplanted mussels did not accumulate Cu and Ni following pre-exposure, although DGT showed significant concentrations of bioavailable forms of these metals in seawater. The results provided an estimate of the water quality with respect to dissolved metals and pointed out the usefulness of a combination of biomonitoring and DGT techniques for a better understanding of trace metal availability in coastal waters.     

The distributions of particulate heavy metals and its indication to the transfer of sediments in the Changjiang Estuary and Hangzhou Bay,China

Particulate heavy metals (Cu, Pb, Cd) were measured following intensive sampling in June and October 1994 at 70 stations in the Changjiang Estuary and Hangzhou Bay, China. In the study area, particulate Cu and Pb have a similar level that is higher than the concentration of particulate Cd. Cu, Pb and Cd concentrations in suspended sediments are higher than those in bed load. In the middle of Hangzhou Bay, heavy metal concentrations in suspended sediments and bed load are similar. This may be the result of the frequent exchange between them, which is due to the strong dynamic condition. A negative relationship was observed between concentrations of heavy metals in bed load and bulk density. Fine-grained sediments were the main carriers of heavy metals. Sedimentary dynamics dominate the fate of heavy metals in these sites. The distributions of metals (especially Cu) in suspended sediments can indicate the transfer of sediments in this area.     

Evaluation of diffusive gradients in thin-films (DGTs) as a monitoring tool for the assessment of the chemical status of transitional waters within the Water Framework Directive

In this contribution, the potential use of diffusive gradients in thin-films (DGTs) for the chemical evaluation of transitional water bodies within the Water Framework Directive (WFD) has been studied. The water metal concentration has been evaluated in 13 estuaries in the southeastern Bay of Biscay. The DGTs were deployed in triplicate at two stations in each estuary, delimiting the tidal influence. The DGT results were in the ranges of 2-1570 ng L(-1) for cadmium, 66-515 ng L(-1) for copper, 30-3650 ng L(-1) for nickel and 0.8-95.5 μg L(-1) for zinc. The DGTs provided reliable average labile metal concentrations in highly dynamic systems that were comparable with DGT measurements in coastal and estuarine waters worldwide. In addition, it was possible to discriminate those estuaries more susceptible to environmental impacts, being consistent with the historical contamination of each estuary. Based on the obtained results, a sampling strategy for the monitoring of transitional water bodies using DGTs is proposed.     

Metal exposure and biological responses in resident and transplanted blue mussels (Mytilus edulis) from the Scheldt estuary

The Western Scheldt river and estuary is known to be highly polluted as it receives industrial, agricultural and domestic effluents from one of the most populated and industrialised zones in Europe. Aquatic organisms are exposed to pollutants, specifically metals that are present in different environmental phases, e.g. dissolved, suspended material or sediment phases. The objective of this study was to study the relationship that exists between environmental metal levels, the degree of metal uptake by aquatic organisms with the concomitant biological responses. For this purpose the bivalve mollusk, Mytilus edulis, was selected as bioaccumulation indicator organism. Environmental (water and sediment) and mussel samples were collected during the late winter (March 2000) from sampling sites in the Scheldt estuary. Sites were selected to represent a salinity gradient from the mouth of the estuary to the furthest distribution area of mussels upstream in the system. Together with standard water quality parameters (e.g. salinity, dissolved oxygen, dissolved organic carbon, etc.) concentrations of twelve metals were analysed in the water (dissolved and suspended matter) and sediments. Levels of these metals were also measured in the soft tissue of M. edulis, together with concomitant biomarker responses in resident mussel populations at each site. The biomarkers that were included in this study were condition index, scope for growth, survival in air, cell membrane stability, DNA damage, and metallothioneins. Data were subjected to multivariate statistical analysis. The physico-chemical parameters and metals in the environmental samples clustered the sites to reflect the distribution based on the salinity gradient. Bioaccumulation results revealed increased metal uptake along a pollution gradient with the highest metal bioaccumulation occurring at the upstream most sites and therefore closest to the in the industrial activities. However, the biomarker responses clustered the sites in a manner that reflected the influence of combination of internal exposure (bioaccumulation) and external exposure (physico-chemical conditions). These differences in biomarker responses clearly demonstrated were attributed to abiotic factors other than metal pollution alone e.g. localized short-term increases in increased suspended sediment concentrations and decreased dissolved oxygen concentrations.     

Metal exposure and biological responses in resident and transplanted blue mussels (Mytilus edulis) from the Scheldt estuary

The Western Scheldt river and estuary is known to be highly polluted as it receives industrial, agricultural and domestic effluents from one of the most populated and industrialised zones in Europe. Aquatic organisms are exposed to pollutants, specifically metals that are present in different environmental phases, e.g. dissolved, suspended material or sediment phases. The objective of this study was to study the relationship that exists between environmental metal levels, the degree of metal uptake by aquatic organisms with the concomitant biological responses. For this purpose the bivalve mollusk, Mytilus edulis, was selected as bioaccumulation indicator organism. Environmental (water and sediment) and mussel samples were collected during the late winter (March 2000) from sampling sites in the Scheldt estuary. Sites were selected to represent a salinity gradient from the mouth of the estuary to the furthest distribution area of mussels upstream in the system. Together with standard water quality parameters (e.g. salinity, dissolved oxygen, dissolved organic carbon, etc.) concentrations of twelve metals were analysed in the water (dissolved and suspended matter) and sediments. Levels of these metals were also measured in the soft tissue of M. edulis, together with concomitant biomarker responses in resident mussel populations at each site. The biomarkers that were included in this study were condition index, scope for growth, survival in air, cell membrane stability, DNA damage, and metallothioneins. Data were subjected to multivariate statistical analysis. The physico-chemical parameters and metals in the environmental samples clustered the sites to reflect the distribution based on the salinity gradient. Bioaccumulation results revealed increased metal uptake along a pollution gradient with the highest metal bioaccumulation occurring at the upstream most sites and therefore closest to the in the industrial activities. However, the biomarker responses clustered the sites in a manner that reflected the influence of combination of internal exposure (bioaccumulation) and external exposure (physico-chemical conditions). These differences in biomarker responses clearly demonstrated were attributed to abiotic factors other than metal pollution alone e.g. localized short-term increases in increased suspended sediment concentrations and decreased dissolved oxygen concentrations.     

Metal exposure and biological responses in resident and transplanted blue mussels (Mytilus edulis) from the Scheldt estuary

The Western Scheldt river and estuary is known to be highly polluted as it receives industrial, agricultural and domestic effluents from one of the most populated and industrialised zones in Europe. Aquatic organisms are exposed to pollutants, specifically metals that are present in different environmental phases, e.g. dissolved, suspended material or sediment phases. The objective of this study was to study the relationship that exists between environmental metal levels, the degree of metal uptake by aquatic organisms with the concomitant biological responses. For this purpose the bivalve mollusk, Mytilus edulis, was selected as bioaccumulation indicator organism. Environmental (water and sediment) and mussel samples were collected during the late winter (March 2000) from sampling sites in the Scheldt estuary. Sites were selected to represent a salinity gradient from the mouth of the estuary to the furthest distribution area of mussels upstream in the system. Together with standard water quality parameters (e.g. salinity, dissolved oxygen, dissolved organic carbon, etc.) concentrations of twelve metals were analysed in the water (dissolved and suspended matter) and sediments. Levels of these metals were also measured in the soft tissue of M. edulis, together with concomitant biomarker responses in resident mussel populations at each site. The biomarkers that were included in this study were condition index, scope for growth, survival in air, cell membrane stability, DNA damage, and metallothioneins. Data were subjected to multivariate statistical analysis. The physico-chemical parameters and metals in the environmental samples clustered the sites to reflect the distribution based on the salinity gradient. Bioaccumulation results revealed increased metal uptake along a pollution gradient with the highest metal bioaccumulation occurring at the upstream most sites and therefore closest to the in the industrial activities. However, the biomarker responses clustered the sites in a manner that reflected the influence of combination of internal exposure (bioaccumulation) and external exposure (physico-chemical conditions). These differences in biomarker responses clearly demonstrated were attributed to abiotic factors other than metal pollution alone e.g. localized short-term increases in increased suspended sediment concentrations and decreased dissolved oxygen concentrations.     

Baseline metal concentrations in Paramoera walkeri from East Antarctica

Remediation of the Thala Valley waste disposal site near Casey Station, East Antarctica was conducted in the austral summer of 2003/2004. Biomonitoring of the adjacent marine environment was undertaken using the gammaridean amphipod Paramoera walkeri as a sentinel species [Stark, J.S., Johnstone, G.J., Palmer, A.S., Snape, I., Larner, B.L., Riddle, M.J., in press, . Monitoring the remediation of a near shore waste disposal site in Antarctica using the amphipod Paramoera walkeri and diffusive gradients in thin films (DGTs). Marine Pollution Bulletin and references therein]. Determination of uptake of metals and hypothesis testing for differences that could be attributed to contamination required the establishment of baseline metal concentrations in P. walkeri. Baseline metal concentrations from two reference locations in the Windmill Islands are presented here. P. walkeri was a found to be a sensitive bioaccumulating organism that recorded spatial and temporal variability at the reference sites. Measurement of metals in P. walkeri required the development of a simple digestion procedure that used concentrated nitric acid. For the first time, rare earth metals were determined with additional clean procedures required to measure ultra low concentrations using magnetic sector ICP-MS. Certified and in-house reference materials were employed to ensure method reliability.     

Measuring bioavailable metals using diffusive gradients in thin films (DGT) and transplanted seaweed (Fucus vesiculosus), blue mussels (Mytilus edulis) and sea snails (Littorina saxatilis) suspended from monitoring buoys near a former lead–zinc mine in West Greenland

Measuring loads of bioavailable metals is important for environmental assessment near mines and other industrial sources. In this study, a setup of monitoring buoys was tested to assess loads of bioavailable metals near a former Pb–Zn mine in West Greenland using transplanted seaweed, mussels and sea snails. In addition, passive DGT samplers were installed. After a 9-day deployment period, concentrations of especially Pb, Zn and Fe in the species were all markedly elevated at the monitoring sites closest to the mine. Lead concentrations in all three species and the DGT-Pb results showed a significant linear correlation. Zinc and Fe concentrations were less correlated indicating that the mechanisms for Zn and Fe accumulation in the three species are more complex. The results show that there is still a significant load of metals from the mine and that such buoys can be an adequate method to assess present loads of bioavailable metals.     

Trace element studies in Laucala Bay, Suva, Fiji.

The trace metal distribution in the sediments of Laucala Bay, a coastal lagoon with a barrier reef and significant freshwater input, adjacent to Suva, the capital of Fiji (150,000 people), was studied from the point of view of assessing the significance of anthropogenic sources relative to natural ones. Surface sediments from 25 sites in the Bay were analysed for particle size distribution, organic carbon and major (Si, Al, Fe, Ca, Mg) and trace metal (Mn, Zn, Cu, Pb, Cd, Hg) contents. Suspended sediments from one site and shellfish samples from five sites were also analysed. The sediments were found to be mostly of terrigenous origin. Particle size distribution, organic carbon and major elemental composition of the sediments were generally related to location within the Bay. A significant natural source of trace metals in the sediments is the suspended solids transported into the Bay by rivers. The spatial distribution of trace metals could not be fully explained by the particle size distribution and mineral composition of the sediments. Contributions from anthropogenic sources were also suspected, but the degree of enrichment from such sources is not great at the present time.     

Sediment profile characterisation at contaminated and reference locations in the Windmill Islands, East Antarctica

Sediment profiles for pH, Eh, 28 elements, water and organic content are presented here for human impacted and reference locations in the Windmill Islands, East Antarctica. Variations in element concentrations are observed with increasing depth, especially at Brown Bay where the impact of past human activities is most pronounced in the top 10 cm. Spatial differences were observed between sediment profiles at reference and impacted locations and were largely explained by Pb variability in the top 5 cm. Median element concentrations from surface, middle and bottom regions of the sediment profile were compared to composite sample medians (no depth stratigraphy) for 11 elements at O’Brien Bay (reference) and Brown Bay (impacted). Pronounced differences were observed for Brown Bay, particularly surface and middle sections, implying that composite samples dilute the near surface anthropogenic signal by mixing with deeper uncontaminated sediment.     

Measurement of environmental trace-metal levels with transplanted mussels and diffusive gradients in thin films (DGT): a comparison of techniques

Transplanted mussels and diffusive gradients in thin films (DGT) were used to assess levels of cadmium, copper, lead and zinc at four sites situated inside and outside of two enclosed marinas, near Melbourne, Australia. Mussels accumulated all metals except cadmium. Over one year, there were large temporal differences in tissue metal levels in mussels, but differences between sites were only apparent for copper and lead. DGT showed temporal differences of the same kind as those seen in the mussels, but appeared to have more power to discriminate between sites. DGT found higher copper levels inside marinas than outside, and high levels of zinc were found inside one marina. Levels of copper and zinc were high enough to be of environmental concern for one site. The effect of fouling on DGT measurements will have to be quantified, or avoided by the use of multiple short-term exposures, if the technique is to become a widespread in situ monitoring tool.     

The usefulness of transplantation studies in monitoring of metals in the marine environment: South African experience

Due to their close proximity to the point sources of pollution, estuaries and harbours are exposed to metals. Mussels are used worldwide to monitor marine pollution due to their ability to take up contaminants and the ease of transplantation. Mussels were collected from two reference sites and transplanted in Richards Bay Harbour (2006 and 2010) and in three harbours. Transplanted and resident mussels were removed after 6 weeks exposure and metal concentrations were analysed using ICP-MS techniques. Transplanted mussels had higher metal concentrations than the resident mussels. This was attributed to regulation of metals by the resident mussels. Metal regulation was greater in mussels that are continuously submerged as opposed to those that undergo tidal influences. For monitoring it is essential that the reference population for transplantation is considered carefully as upwelling events in the pristine reference location results in significant increases in metal bioaccumulation.     

基于梯度扩散薄膜技术(DGT)的氨基生物炭覆盖沉积物水界面铜、铅释放研究

湖泊沉积物的重金属污染防治一直是环境领域的热点问题.本研究采用氨基生物炭作为覆盖材料,利用梯度扩散薄膜技术(DGT),研究了上覆水不同pH及水流扰动条件下Cu(Ⅱ)、Pb(Ⅱ)在沉积物水界面间的原位释放特征,以及氨基生物炭对湖泊沉积物重金属污染的原位修复效果.研究结果表明,在0 r/min或100 r/min水动力条件下,可移动态重金属离子有不断由沉积物向其他介质扩散的趋势,1.81 kg/m 2的氨基生物炭覆盖强度可降低Cu(Ⅱ)、Pb(Ⅱ)释放通量达89%以上,有效减小了水环境中重金属的潜在生态风险.在pH=5的酸性及pH=9的碱性水环境中原位修复效果较差,水体中大量的H+或络合物均会削弱氨基生物炭对重金属离子的吸附,当上覆水在pH=7的中性条件时原位修复效果最佳.100 r/min水流扰动下的上覆水Cu(Ⅱ)、Pb(Ⅱ)含量在释放平衡时较0 r/min条件下高出0.036~0.096μg/mL,说明高强度的水流扰动易造成覆盖材料的扬起和浮动,导致覆盖材料与重金属发生解吸.     

Association of metals with plastic production pellets in the marine environment

Plastic production pellets sampled from four beaches along a stretch of coastline (south Devon, SW England) and accompanying, loosely adhered and entrapped material removed ultrasonically have been analysed for major metals (Al, Fe, Mn) and trace metals (Cu, Zn, Pb, Ag, Cd, Co, Cr, Mo, Sb, Sn, U) following acid digestion. In most cases, metal concentrations in composite pellet samples from each site were less than but within an order of magnitude of corresponding concentrations in the pooled extraneous materials. However, normalisation of data with respect to Al revealed enrichment of Cd and Pb in plastic pellets at two sites. These observations are not wholly due to the association of pellets with fine material that is resistant to ultrasonication since new polyethylene pellets suspended in a harbour for 8 weeks accumulated metals from sea water through adsorption and precipitation. The environmental implications and potential applications of these findings are discussed.     

Anthropogenic influences on heavy metals across marine habitats in the western coast of Venezuela

Concentrations of ten metals were measured in waters and sediments at 14 sites during four sampling periods (1996–1997). These sites include various marine ecosystems that are highly influenced by industry, tourism and river discharges, nine of which are within the Morrocoy National Park. Spatially, metal concentrations in water were homogenous, whereas in sediments their distributions were related to grain size. Maximum concentrations of cadmium (Cd) and mean concentrations of copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) in water were above the guideline values proposed by NOAA, indicating the potential of these metals for producing chronic effects in marine biota. Sheltered sites showed the highest metal concentrations in sediments; with Cd and Zn above these guidelines. Enrichment factors and geo-accumulation indexes suggested that metals in sediments were largely of natural origin except for Pb, Cd and vanadium (V), which were apparently associated with industrial effluents. A disruption of the spatial distribution of metals after heavy rainfall, when exposed sites reached concentrations as high as those in sheltered sites, showed the influence of nearby rivers. The potential increase of such climatic events could represent additional stress for natural protected areas in the Caribbean.     

Legacy contaminant bioaccumulation in rock crabs in Sydney Harbour during remediation of the Sydney Tar Ponds,Nova Scotia,Canada

Concentrations of PAHs, PCBs, metals and lipids in hepatopancreas of rock crabs (Cancer irroratus) were measured in Sydney Harbour (SH) for one year prior to remediation and three years of remediation of the Sydney Tar Ponds (STP), Nova Scotia. Low level concentrations of PCBs and metals were measured, although PAHs were mostly undetected. Metal concentrations showed little spatio-temporal variability, although highest concentrations of As, Cd and Cu were measured at reference stations furthest from the STP remediation site. Mercury concentrations were at least an order of magnitude lower than Canadian guidelines. Moderately elevated PCB concentrations were detected in crabs near Muggah Creek, but these were generally not higher than those measured during baseline. Despite remediation activities, current contaminant burdens measured in crabs were much lower than previously reported in other studies of crabs and lobster in industrial harbours in eastern Canada, due in part to natural recovery of SH sediments.     

Integrated use of biomarkers (superoxide dismutase, catalase and lipid peroxidation) in mussels Mytilus galloprovincialis for assessing heavy metals' pollution in coastal areas from the Saronikos Gulf of Greece

Mussels are used as sentinel organisms and bioindicators to evaluate the toxic effects of chemical pollutants in marine organisms, especially heavy metals, representing an important tool for biomonitoring environmental pollution in coastal areas. Antioxidant defence enzymes play an important role in cellular antioxidant defence systems and protect from oxidative damage by reactive oxygen species (ROS). Indigenous mussels Mytilus galloprovincialis of the Saronikos Gulf of Greece were used for monitoring heavy metal pollution in three polluted sites in the area and in one unpolluted site. Seasonal variations of the activity of antioxidant defence enzymes, superoxide dismutase (SOD) and catalase (CAT), as well as lipid peroxidation (LP) were measured as biomarkers in a period of three years in relation to concentrations of trace metals in their gills and mantle and compared to mussels from an unpolluted sampling site. SOD activity increased at least 2 fold at the polluted sites when compared to the control site (the high activity was recorded in the spring time). CAT activity was increased 2-3 times at the polluted sites, with high activity in the winter and spring time, compared to the control site. LP concentration was twice higher at the polluted sites, following the same seasonal pattern. Trace metals contents in mussels collected at polluted sites were 3-4 fold higher compared to the control site and showed moderate variations along the months, with a winter maximum followed by a summer pre-spawning minimum matching the seasonal trends of temperature and salinity. Our results showed that metal pollution in the Elefsis Bay (the most polluted coastal area) causes relatively medium levels of oxidative stress in tissues of mussels due to cellular oxy-radical generation. This study, which is the first in the area, showed that seasonal variations of the activity of antioxidant defence enzymes and LP concentrations in mussels can be used as potential biomarkers of toxicity for long-term monitoring in marine coastal ecosystems.     

Impact of Turbidity on TCE and Degradation Products in Ground Water

Elevated particulate concentrations in ground water samples can bias contaminant concentration data. This has been particularly problematic for metal analyses where artificially increased turbidity levels can affect metals concentrations and confound interpretation of the data. However, few studies have been conducted to determine the impact of particulates on trichloroethylene (TCE), cis-dichloroethylene (c-DCE), and vinyl chloride concentrations.
Laboratory batch studies and field investigations were conducted to evaluate the effects of suspended solids on VOC concentrations in ground water samples analyzed by purge-and-trap gas chromatography. Three different solids were used to assess the effects of suspended particulates. The solids were aquifer material from a field site in North Carolina and two reference clay minerals (kaolinite and Namontimorillonite). During the laboratory portion of this study, the solids were used to determine effects on TCE concentrations under controlled laboratory conditions.
The same solids were used in a field study to compare the laboratory results with field results. Solids were added to the sample vials prior it) sample collection to intentionally increase turbidity levels in the water samples. Results of the study indicate essentially no decrease in TCE, c-DCH, or vinyl chloride concentrations due to increased turbidity levels.     

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.