Is PCBs concentration variability between and within freshwater fish species explained by their contamination pathways?

Many chemical, physiological, and trophic factors are known to affect bioaccumulation of polychlorinated biphenyls (PCBs) in biota. Understanding the primary factors affecting fish contamination is critical for predicting and assessing risks to upper-trophic level consumers, including humans. Here we identify PCB contamination pathways that could explain within- and between-species variability in fish concentration levels. Three freshwater river fish species (barbel, chub and bream) were sampled at three sites along the Rhone River (France) where fish consumption is partially prohibited because of PCB levels exceeding the European health-based benchmark. The trophic position was assessed using an innovative approach based on stable isotope analyses and Bayesian inference, which takes into account both isotope data variability and parameter uncertainty. The effect of foraging habitat on fish contamination was addressed using stable isotope mixing models. The fish trophic position and PCB concentrations were found to be unrelated while the exploitation of sediment detrital carbon as a food source appeared to be a critical factor affecting fish contamination. Fish length, PCB concentration of the sediment, and individual fish foraging habitat (exploitation of detrital versus planktonic carbon sources) explained 80% of within- and between-species variability observed in PCB concentrations. These results, obtained for species that have overlapping TPs and exploit different carbon sources, reveal that the important factor in fish PCB contamination is not only what fish consume, but also and essentially the feeding location.     

Pesticides and PCBs in sediments and fish from the Salton Sea, California, USA

The Salton Sea, the largest manmade lake in California, is officially designated by the State of California as an agricultural drainage reservoir. The purpose of this study was to determine organochlorine and organophosphorous pesticides, as well as polychlorinated biphenyl (PCB) concentrations in sediments and fish tissues in the Salton Sea and evaluate the relative ecological risk of these compounds. Sediment samples were taken during 2000-2001 and fish tissues (Tilapia mossambique, Cynoscion xanthulu) were collected in May 2001. All samples were analyzed for 12 chlorinated pesticides, 6 organophosphorus pesticides, and 55 polychlorinated biphenyl (PCB) congeners. SigmaDichlorodiphenyltrichloroethane (SigmaDDT) and total PCB concentrations observed in sediments ranged from 10 to 40 and 116 to 304 ng/g dry wt, respectively. DDT/DDD ratios in sediments and fish tissues of the northern Sea in 2001 indicated recent DDT exposure. Lindane, dieldrin, dichlorodiphenylethane (DDE) and total PCB concentrations detected in sediments exceeded probable effect levels established for freshwater ecosystems, and pp-DDE and total PCB concentrations were higher than effect range-median values developed for marine and estuarine sediments. In fish liver, concentrations of endrin and SigmaDDT exceeded threshold effect level established for invertebrates. SigmaDDT concentrations detected in fish tissues were higher than threshold concentrations for the protection of wildlife consumers of aquatic biota. DDE concentrations in fish muscles tissues were above the 50 ng/g concentration threshold for the protection of predatory birds. Dimethoate, diazinon, malathion, chlorpyrifos, disulfoton varied from < or = 0.15 to 9.5 ng/g dry wt in sediments and from < or = 0.1 to 80.3 ng/g wet wt in fish tissues. Disulfoton was found in relatively high concentrations (up to 80.3 ng/g) in all organs from Tilapia and Corvina. These results demonstrate continued contamination of specific organochlorine compounds in sediments and resident fish species of the Salton Sea.     

Distribution characteristics of polychlorinated biphenyls in crucian carp (Carassius auratus) from major rivers in Korea

Polychlorinated biphenyls (PCBs) levels in crucian carp were determined at 20 locations along four major river systems, several small-scale rivers and a wetland in Korea. Twenty-eight congeners, ranging from tri- to hepta-CBs were detected. A gas chromatograph with a mass selective detector was used to quantify the individual PCB congeners. The objectives of this study were to investigate the levels of contamination of PCBs in freshwater fish and to observe the pattern of their distribution. The sampling locations were chosen among 31 sampling sites that are currently used as environmental residue checkpoints by the Korean Ministry of Environment. Concentrations of individual congeners ranged from not detectable (n.d.) to 0.75 ng g(-1) on a wet weight basis. The total concentrations of PCBs at each site ranged from n.d. to 5.41 ng g(-1) of wet weight. The most heavily contaminated site was the Nakdong estuary located near the Shinpyung-Janglim factory district. The PCB 153 and 138 were the principal congeners and penta- and hexa-chlorinated biphenyls comprised the main congener groups.     

Prediction of PCB content in sportfish using semipermeable membrane devices (SPMDs)

Triolein-filled semipermeable membrane devices (SPMDs) were immersed at three locations along the St. Joseph River in northern Indiana for 30 days to see if the PCB content of fish from the same location could be predicted with this model device. Triolein from the SPMD's was analyzed for PCB using enzyme-linked immunosorbent assay (ELISA) and compared to residues detected in fish collected from the same locations. There was a significant difference (p < 0.05) in total PCB concentrations between SPMD samples. However, due to variability in PCB residues between species and low PCB residues in SPMDs, a direct correlation between PCBs in sportfish and SPMDs could not be determined.     

Immunohistochemical detection of polychlorinated biphenyls in field collected damselfish (Abudefduf sordidus; Pomacentridae) embryos and larvae

Antibodies against polychlorinated biphenyls (PCBs) were used to determine if immunohistochemical methods could detect PCBs in embryos and larvae of a territorial coral reef fish (Abudefduf sordidus; Pomacentridae) collected from Johnston Atoll, Central Pacific Ocean. Sites with differing levels of contamination were sampled, one with relatively high sediment PCB concentrations of up to 389.0 ng/g and another with low PCB concentrations of only 0.5 ng/g. Immunostaining suggested that PCB concentrations were higher in fish larvae from the PCB contaminated site and that PCB concentrations within abnormal embryos were higher than normal embryos from the same nest. This technique will be useful for detecting exposed populations in the field and assessing correlations with adverse effects, particularly in potential indicator organisms such as Abudefduf sordidus.     

Halogenated persistent organic pollutants in deep water fish from waters to the west of Scotland

Halogenated persistent organic pollutants [polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)] along with total lipid, were measured in the liver and muscle of three species of deep water fish (black scabbard, black dogfish (liver only) and roundnose grenadier) collected from the Rockall fishing area, to the west of Scotland, between 2006 and 2008. Both contaminant groups were detected in the muscle and liver, with concentrations of PCBs being higher than PBDEs. There were no significant differences in the PCB or PBDE concentrations between the three species, or different sampling locations in the Rockall fishing area. PCB concentrations (ΣICES (International Council for the Exploration of the Sea)7 PCBs) greater than 500 μg kg⁻¹ lipid weight were found in 26 of the 106 liver samples. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria. Estimated Toxic Equivalent (TEQ) concentrations, calculated using published models, in the fish muscle and liver indicated that consumption of deep water fish is unlikely to represent a risk to human health. The high squalene content in some of the black dogfish liver necessitated an additional clean-up step, involving gel permeation chromatography, when analyzing for PBDEs. Concentrations of PBDEs were low with many congeners being below detection limits, particularly in the muscle. There are currently no assessment criteria available for PBDEs. Furthermore, there is only very limited data on PBDEs in deep water fish. However, the concentrations observed in this study were similar to the concentrations recently reported in Mediterranean deep water fish.     

Polychlorinated biphenyl spatial patterns in San Francisco Bay forage fish

Industrialized waterways frequently contain nearshore hotspots of legacy polychlorinated biphenyl (PCB) contamination, with uncertain contribution to aquatic food web contamination. We evaluated the utility of estuarine forage fish as biosentinel indicators of local PCB contamination across multiple nearshore sites in San Francisco Bay. Topsmelt (Atherinops affinis) or Mississippi silverside (Menidia audens) contamination was compared between 12 targeted sites near historically polluted locations and 17 probabilistically chosen sites representative of ambient conditions. The average sum of 209 PCB congeners in fish from targeted stations (441 ± 432 ng g^?1 wet weight, mean ± SD) was significantly higher than probabilistic stations (138 ± 94 ng g^?1). Concentrations in both species were comparable to those of high lipid sport fish in the Bay, strongly correlated with spatial patterns in sediment contamination, and above selected literature thresholds for potential hazard to fish and wildlife. The highest concentrations were from targeted Central Bay locations, including Hunter’s Point Naval Shipyard (1347 ng g^?1; topsmelt) and Stege Marsh (1337 ng g^?1; silverside). Targeted sites exhibited increased abundance of lower chlorinated congeners, suggesting local source contributions, including Aroclor 1248. These findings indicate that current spatial patterns in PCB bioaccumulation correlate with historical sediment contamination due to industrial activity. They also demonstrate the utility of naturally occurring forage fish as biosentinels of localized PCB exposure.     

Polychlorinated biphenyl contamination trends in Lake Hartwell, South Carolina (USA): sediment recovery profiles spanning two decades

To assess the ca. 20-year polychlorinated biphenyl (PCB) contamination trends in Lake Hartwell, SC, sediment cores from the Twelve Mile Creek arm were collected in July 2004 at two sites (G30 and G33) first sampled in the mid-1980s. Congener-specific PCB data as a function of depth from the sediment-water interface for the 2004 sediment samples were compared to data obtained from 1987 and 1998 samples taken from the same locations. Despite modest decreases in total PCB levels near the G30 sediment-water interface, historical increases in average degrees of chlorination may elevate the overall toxic risk at this site. Unlike G30, the more rapid recovery in the near-surface sediment of G33 suggests that the effectiveness of the U.S. EPA natural attenuation record of decision is site-specific and is unlikely to result in uniform surface sediment recovery throughout the most contaminated regions of Lake Hartwell.     

Polychlorinated biphenyl, polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran residues in sediments and fish of the River Nile in the Cairo region

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.     

Factors influencing liver PCB concentrations in sparrowhawks (Accipiter nisus), kestrels (Falco tinnunculus) and herons (Ardea cinerea) in Britain

Large scale temporal and spatial changes in the exposure of terrestrial vertebrates to PCBs have been monitored in the UK by measuring liver residues in sparrowhawks (Accipiter nisus), kestrels (Falco tinnunculus) and grey herons (Ardea cinerea) from throughout the country. Residues in the three species are typically characterised by large intra- and inter-specific variation. Data for 306 sparrowhawks, 186 kestrels and 47 herons collected between 1992 and 1997 as part of a national Predatory Bird Monitoring Scheme were examined to determine how much of this variation was explained by body condition, age and sex, rather than other factors. In all three species, body condition was the single most important factor and accounted for up to 49% of the variation in PCB liver residues; starved birds had the highest liver concentrations. Age and sex were also significant but of lesser importance. Adult sparrowhawks and kestrels had liver PCB residues that were 2 to 10-fold higher than in first-year birds. Sex did not affect residue magnitude in a consistent manner. PCB concentrations in the liver were higher in males than females in both first-year and adult kestrels and in first-year sparrowhawks, but adult female sparrowhawks had similar PCB residues to adult males. Liver residues also varied seasonally. PCB concentrations in first-year sparrowhawks increased during the first year following fledging and a similar pattern was detected in adult female sparrowhawks following egg laying. When these physiological factors were taken into account, it was evident that while kestrels with high fat scores had significantly lower PCB concentrations than either sparrowhawks or herons, liver residues were similar in all three species when birds were in a starved condition. Overall during 1992-1997, the combined influence of body condition, age and sex explained more of the variation in liver PCB concentrations than species differences or other factors, such as geographical variation in exposure.     

Assessment of water quality in the Alqueva Reservoir (Portugal) using bioassays

Background, aim, and scope  

Alqueva Reservoir is the biggest artificial freshwater reservoir in Europe and is an important water supply for human and agricultural consumption in the Alentejo region (Portugal). Pollution can impair environmental and human health status, and to assure water quality and ecological balance, it is crucial to frequently monitor water supplies. In this study, we used an ecotoxicological test battery to identify the potential toxicity of water from this reservoir.     

Mercury levels and trends (1993-2009) in bream (Abramis brama L.) and zebra mussels (Dreissena polymorpha) from German surface waters

Mercury concentrations have been analysed in bream (Abramis brama L.) and zebra mussels (Dreissena polymorpha) collected at 17 freshwater sites in Germany from 1993-2009 and 1994-2009, respectively, within the German Environmental Specimen programme. Mercury concentrations in bream ranged from 21 to 881 ng g⁻¹ wet weight with lowest concentrations found at the reference site Lake Belau and highest in fish from the river Elbe and its tributaries. Statistical analysis revealed site-specific differences and significant decreasing temporal trends in mercury concentrations at most of the sampling sites. The decrease in mercury levels in bream was most pronounced in fish from the river Elbe and its tributary Mulde, while in fish from the river Saale mercury levels increased. Temporal trends seem to level off in recent years. Mercury concentrations in zebra mussels were much lower than those in bream according to their lower trophic position and varied by one order of magnitude from 4.1 to 42 ng g⁻¹ wet weight (33-336 ng g⁻¹ dry weight). For zebra mussels, trend analyses were performed for seven sampling sites at the rivers Saar and Elbe of which three showed significant downward trends. There was a significant correlation of the geometric mean concentrations in bream and zebra mussel over the entire study period at each sampling site (Pearson’s correlation coefficient = 0.892, p = 0.00002). A comparison of the concentrations in bream with the environmental quality standard (EQS) of 20 ng g⁻¹ wet weight set for mercury in biota by the EU showed that not a single result was in compliance with this limit value, not even those from the reference site. Current mercury levels in bream from German rivers exceed the EQS by a factor 4.5-20. Thus, piscivorous top predators are still at risk of secondary poisoning by mercury exposure via the food chain. It was suggested focusing monitoring of mercury in forage fish (trophic level 3 or 4) for compliance checking with the EQS for biota and considering the age dependency of mercury concentrations in fish in the monitoring strategy.     

Seasonal fluctuations of DDTs and PCBs in zooplankton and fish of Lake Maggiore (Northern Italy)

Concentrations of DDTs and PCBs were determined in the zooplankton and in three different fish species (shad, whitefish and roach) collected seasonally during 2009 and 2010 in three sites in Lake Maggiore, a south-alpine lake that has been contaminated by DDT since 1996. As previously observed in 2008, even during 2009 DDTs concentrations were higher in zooplankton than in fish, probably due to the very unstable situation of the lake still influenced by local inputs. The situation changed in 2010, when all DDT compounds increased in fish to levels much higher than those measured in zooplankton. Biomagnification was statistically demonstrated for pp′DDE in all the three fish species, indicating a probable signal of recovery of the lake.Although with respect to total PCBs we observed that the contamination levels varied across time periods and across fish species, biomagnification was evident from zooplankton to fish both in 2009 and in 2010. As concern individual PCBs, biomagnification from zooplankton to all three fish species was significant for PCB 153 and PCB 138.     

Longitudinal increases in PCDD/F and dl-PCB concentrations in human milk in northern China

There is a dearth of information on the temporal changes in polychlorinated dibenzodioxin/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) contamination, in both environmental and biological specimens, in China. We compared the concentrations of PCDD/Fs and dl-PCBs in human milk collected in Shijiazhuang, Hebei Province, in northern China in 2002 (n=30) and 2007 (n=20). The level of PCDD/Fs and dl-PCBs showed an increasing trend. The mean concentrations of PCDD/Fs plus dl-PCBs were 4.47 TEQ pg g(-1) fat and 6.24 TEQ pg g(-1) fat in human milk from Shijiazhuang in 2002 and in 2007, respectively. Based on statistical analysis of questionnaire data collected by in-person interviews with mothers, we found positive correlations between consumption of sea fish and PCDFs. The PCDDs, PCDFs, PCDD/Fs, and PCDD/Fs plus dl-PCBs levels in individuals consuming greater amounts of sea fish were higher than those consuming less sea fish, both with and without adjustments for potential confounding factors. Among 17 congeners of PCDD/Fs, the 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF congener concentrations in 2007 increased 134%, 55%, 53%, 57%, 65% and 130% when compared to 2002 levels, respectively. The 2007 dl-PCB congener levels were greater than those of the 2002 samples, with the exception of PCB81 and PCB77. Specifically, PCB105, PCB114, PCB118, PCB123 and PCB156 had increased greater than twofold from 2002 to 2007. Continuous surveillance of PCDD/F and dl-PCB levels in human milk is needed to accurately evaluate both environmental contamination and the human health risk to neonates in China.     

Polychlorinated biphenyls (PCBs) in fish from the Sana River (Bosnia and Herzegovina): A preliminary study on the health risk in sport fishermen

Fish is the main single source of polychlorinated biphenyls (PCBs) exposure in men. Anecdotal reports suggest high wild fish consumption rates among sport fishermen in Sanski Most area, Bosnia and Herzegovina (BiH). Presence of PCBs in the environment in BiH was previously documented. The main objective of this work was to estimate the magnitude of PCBs exposure and assess the potential health risk in sport fishermen in Sanski Most. The fishing pattern and magnitude of fish consumption were estimated in the questionnaire survey conducted during April 2012 among members (n = 60) of the local sport fishermen association in Sanski Most. Calculated median and high-end (90th percentile) fish consumption rates were 31 g d^?1 and 126 g d^?1, respectively. The PCB concentrations (as Aroclor 1254 equivalents), determined by ELISA immunoassay in 28 fish fillets ranged from undetectable to 208 μg kg^?1. Two different exposure scenarios were used: (a) median exposure, calculated from the median fish consumption rate and median PCB concentrations, and (b) “worst case” scenario, calculated from the high-end fish consumption rate and mean PCB concentrations. The results suggest negligible lifelong cancer and non-cancer risks in case of low to moderate fish consumption rate, but possibly unacceptable risk levels in high-end consumers.     

Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River,Romania

Background, aim and scope

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.

Results and discussion

Sediment texture was uniform in the cores from both reservoirs. Laminated sediment structure, without any obvious discontinuities, was observed. Hg concentrations in the sediment core from the Valcea Reservoir were low and constant (0.01–0.08 mg/kg). In Babeni Reservoir sediments, Hg concentrations were very high in the deeper core section (up to 45 mg/kg in the longest core) and decreased to lower concentrations toward the top of the cores (1.3–2.4 mg/kg). This decrease probably reflects technological progress in control of emissions from the Hg-cell-based chlor-alkali industry. Two strong peaks could be distinguished in older sediments. The mean rate of sedimentation (5.9 cm/year) was calculated from the depth of the ¹³⁷Cs Chernobyl peak. This was in good agreement with the sedimentation rate estimated at this site from a bathymetric study. Assuming a constant sedimentation rate, the two Hg peaks would reflect two contamination events in 1987 and 1991, respectively. However, it is also possible that the two peaks belong to the same contamination event in 1987 but were separated by a sediment layer richer in sand and silt. This layer had a low Hg concentration, which can be interpreted as a mass deposition event related to a major flood bringing Hg-free sediments.

Conclusions

Whilst the chlor-alkali plant partly switched to a cleaner technology in 1999, no obvious decrease of Hg concentrations was observed in recent decade. Results from the sediment core reflected the historical trend of Hg release from the chlor-alkali plant, revealed important contamination episodes and confirmed a legacy of contamination of Hg in recent sediments even if the concentrations of Hg decreased toward the surface due to a more efficient emission control.

Recommendations and perspectives

Although the Hg concentrations in Babeni Reservoir sediments were extremely high in the late eighties and they remain one order of magnitude higher in the surface sediments than in sediments from the upstream reservoir, little is known about the transfer of Hg to the biota and human population. Our initial measurements indicate the presence of monomethyl-Hg (MMHg) in pore water, but further studies are necessary to evaluate fluxes of MMHg at the sediment–water interface. Samples of fish and hair from various groups of the local population were recently collected to evaluate the potential hazard of Hg contamination to human health in the Rm Valcea region.

     

Environmental contamination with polychlorinated biphenyls in the area of their former manufacture in Slovakia

Evidently increased environmental pollution as a consequence of the 25-year manufacture of polychlorinated biphenyls (PCBs) in eastern Slovakia was observed. PCB levels determined in ambient air, soil, surface water, bottom sediment, wildlife (fish and game) samples collected in a potentially contaminated area of about 250 km2 (a part of the Michalovce district) were compared with those determined in a control area (Stropkov district). Up to 1700 ng/m3 were found in ambient air in a village close to a manufacturer's dumping site and a highly contaminated manufacturer's effluent canal whereas PCB concentrations in ambient air samples taken in villages in the control area were about 80 ng/m3 only. While soil samples taken from the agricultural fields of the polluted area contained PCBs at levels comparable with soil samples from the control area (about 0.008 mg/kg) much higher values (from 0.4 to 53,000 mg/kg) were determined in soil taken in the vicinity of manufacturer's landfill and storage sites and especially plants preparing asphalted gravel using formerly PCBs in their heat-exchanging systems. The contamination of the Laborec river and large Zemplinska Sirava reservoir is caused by the manufacturer's effluent canal since PCB levels in the canal sediment are still to be found about 3000 mg/kg. While PCB levels in sediment samples from Michalovce watercourses ranged between 1.7 and 6 mg/kg, sediment samples from the control Stropkov district ranged between 0.007 and 0.052 mg/kg only. Fish living in contaminated Michalovce waters contained about hundred times higher PCB levels than those caught in Stropkov ones. Similarly, game animals shot in Michalovce forests contained several times higher levels than those shot in Stropkov ones.     

Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River,Romania

Background, aim and scope

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.

Results and discussion

Sediment texture was uniform in the cores from both reservoirs. Laminated sediment structure, without any obvious discontinuities, was observed. Hg concentrations in the sediment core from the Valcea Reservoir were low and constant (0.01–0.08 mg/kg). In Babeni Reservoir sediments, Hg concentrations were very high in the deeper core section (up to 45 mg/kg in the longest core) and decreased to lower concentrations toward the top of the cores (1.3–2.4 mg/kg). This decrease probably reflects technological progress in control of emissions from the Hg-cell-based chlor-alkali industry. Two strong peaks could be distinguished in older sediments. The mean rate of sedimentation (5.9 cm/year) was calculated from the depth of the ¹³⁷Cs Chernobyl peak. This was in good agreement with the sedimentation rate estimated at this site from a bathymetric study. Assuming a constant sedimentation rate, the two Hg peaks would reflect two contamination events in 1987 and 1991, respectively. However, it is also possible that the two peaks belong to the same contamination event in 1987 but were separated by a sediment layer richer in sand and silt. This layer had a low Hg concentration, which can be interpreted as a mass deposition event related to a major flood bringing Hg-free sediments.

Conclusions

Whilst the chlor-alkali plant partly switched to a cleaner technology in 1999, no obvious decrease of Hg concentrations was observed in recent decade. Results from the sediment core reflected the historical trend of Hg release from the chlor-alkali plant, revealed important contamination episodes and confirmed a legacy of contamination of Hg in recent sediments even if the concentrations of Hg decreased toward the surface due to a more efficient emission control.

Recommendations and perspectives

Although the Hg concentrations in Babeni Reservoir sediments were extremely high in the late eighties and they remain one order of magnitude higher in the surface sediments than in sediments from the upstream reservoir, little is known about the transfer of Hg to the biota and human population. Our initial measurements indicate the presence of monomethyl-Hg (MMHg) in pore water, but further studies are necessary to evaluate fluxes of MMHg at the sediment–water interface. Samples of fish and hair from various groups of the local population were recently collected to evaluate the potential hazard of Hg contamination to human health in the Rm Valcea region.

     

Low hepatic 7-ethoxyresorufin-O-deethylase (EROD) activity and minor alterations in retinoid and thyroid hormone levels in flounder (Platichthys flesus) exposed to the polychlorinated biphenyl (PCB) mixture, Clophen A50

The effect of the polychlorinated biphenyl (PCB) mixture Clophen A50 on hepatic cytochrome P4501A1 dependent EROD (7-ethoxyresorufin-O-deethylase) activity, plasma thyroid hormone levels and plasma, kidney and liver retinoid concentrations of the euryhaline flatfish flounder (Platichthys flesus) was determined 2 and 10 days after i.p. (intraperitoneal) injection with 20, 100 and 500 mg Clophen A50/kg body weight. No effect of Clophen A50 on total cytochrome P450 content in flounder liver was observed at both time points. A six-fold, dose-dependent, significant increase in EROD activity was found at exposure day 10 in flounder receiving 100 or 500 mg Clophen A50/kg body weight. Plasma retinol concentrations were not altered at both time points after Clophen A50 administration, whereas renal retinol levels showed a minor dose-related increase at day 2 and day 10 of exposure. Significant alterations in hepatic retinoid concentrations were observed, which were not dependent on the dose of PCB administered. In addition Clophen A50 administration did not result in a dose-related alteration of total T4 concentrations in plasma. Total T3 concentrations in plasma were only significantly increased at day 2 after exposure, whereas free T4 concentrations were increased at both time points after Clophen A50 administration. These data indicate that with regard to the parameters investigated and in contrast to other fish species studied, the flounder is not a sensitive species to PCB exposure.     

Persistent organic pollutants (POPs) in antarctic fish: levels,patterns, changes

Organochlorine compounds were analysed in three fish species of different feeding types from the area of Elephant Island in the Antarctic. In 1996, hexachlorobenzene (HCB) (means: 15-20 ng/g lipid), p,p'-DDE (5-13 ng/g lipid) and mirex (1-7 ng/g lipid) predominated, while PCBs were minor components (PCB 153: 0.4-2 ng/g lipid). Concentration patterns were species-dependent: PCB 180, PCB 153, mirex, nonachlor III, trans-nonachlor and the toxaphene compound B8-1413 were highest in the bottom invertebrate feeder Gobionotothen gibberifrons and lowest in the krill feeder Champsocephalus gunnari. Levels of p,p'-DDE, PCB 138 and heptachloro-1'-methyl-1,2'-bipyrrole (Q1), a natural bioaccumulative product, were highest in the fish feeder Chaenocephalus aceratus, whereas HCB was present in about equal concentrations in all species. Most compounds were taken up preferentially via the benthic food chain, the chlorinated bipyrrole via the pelagic food chain and HCB from the water. In antarctic fish, biomagnification was generally more important than bioconcentration. Between 1987 and 1996, most persistent organic pollutant (POP) levels showed significant increases in the benthos feeder and the fish feeder, while they remained nearly constant or increased less in the krill feeder. Hence, the former species represent indicator species for changing POP levels in Antarctica. Ratios (1996/1987) of average concentrations in G. gibberifrons were: PCB 138 0.7, HCB 0.8, B8-1413 1.5, PCB 180 1.7, PCB 153 1.8, p,p'-DDE 2.0, nonachlor III 2.9, trans-nonachlor 3.3, mirex 6.7. By comparison with trends in the northern hemisphere it is concluded that global distribution of HCB is close to equilibrium. Changing levels of other POPs reflect global redistribution and increasing transfer to antarctic waters probably due to recent usage in the southern hemisphere and climate changes.