Polychlorinated biphenyls in freshwater salmonids from the Kerguelen Islands in the Southern Ocean

The Subantarctic Kerguelen Islands (49°S, 70°E) contain freshwater ecosystems among the most isolated in the world. Concentrations of polychlorinated biphenyls (PCBs) were assessed in the muscle of 48 brook trout and 38 brown trout caught during summer and spring 2006 in the rivers, lakes and ponds of Kerguelen. The sum of 29 PCBs averaged 404 and 358 ng g⁻¹ lipid, and dioxin-like PCB was 19 and 69 ng g⁻¹ lipid, in brook and brown trout, respectively. The values showed a high variability and some fish accumulated PCBs at levels similar to those of fish from impacted areas. While inter-sex differences were limited, the season and the morphotype appeared to have the most influence. Fish captured in summer had muscle PCB concentrations about three times higher than those caught in spring and the ‘river’ morphotype of brook trout showed the highest PCB levels.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls, naphthalenes and polybrominated diphenyl ethers in the edible fish caught from the Baltic Sea and lakes in Finland

A total of 156 fish composite samples were collected from five areas of the Baltic Sea and from three lakes and analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polybrominated diphenyl ethers (PBDEs). The European Union's maximum permissible level for PCDD/Fs, 4 pg WHO-TEQ/g fresh weight (fw), was exceeded in salmon, river lamprey and Baltic herring. In other species from the Baltic Sea, the 90th percentile was 3.42 pg WHO(PCDD/F)-TEQ/g fw. In the lake fish, the concentrations of PCDD/Fs, PCBs and PCNs were only 29-46% of those in the same species caught from the Baltic Sea, whereas the concentrations of PBDEs in the lake fish were as high as in the Baltic Sea fish. Dioxin-like PCBs contributed to the total dioxin-like toxicity of PCBs and PCDD/Fs by 49+/-12% in all the analysed samples.     

Organochlorine contaminants in different tissues from Platichthys flesus (Pisces,Pleuronectidea)

Polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) are organic contaminants that tend to accumulate in fish. Estuaries are exposed to high anthropogenic activities, therefore tending to accumulate more contaminants than the adjacent coastal waters. Platichthys flesus, a fish with high economic value, was analysed for PCBs and HCB along its different age groups, in liver, gills, gonads and muscle. Younger fishes were caught in the estuary, whereas older fishes were caught in the adjacent coastal waters and acquired at Figueira da Foz Regional Office of Docapesca-Portos e Lotas, SA. Both contaminants concentrations follow the pattern: liver > gills > muscle. Hepatosomatic index had the lowest values in younger fishes and the highest values in older fishes. Condition factor values remain stable with age. Younger fishes had higher PCBs concentrations than the older fishes. In opposition HCB was only detected in fish from 3+ to 5+ and its concentration tended to increase with age. Overall P. flesus is considered safe for human intake.     

Levels and distribution of organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in sediments and biota from the Danube Delta, Romania

Concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), such as dichlorodiphenyltrichloroethane (DDT) and analogues, hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB), were measured in sediments and biota (invertebrates, 11 fish species and cormorant tissues) collected in 2001 from the Danube Delta, the biggest European wetland. DDTs were the predominant pollutants in all samples. A high variability in the concentrations of pollutants within the same species was observed and this was related to sampling location, age, length and sex. DDTs were also the main organohalogenated contaminants in cormorant muscle and liver, followed by PCBs, HCHs, HCB and PBDEs. The present levels of DDTs in cormorant tissues are lower than levels measured in cormorant eggs sampled from the Danube Delta in 1982 and 1997, respectively. The variance of delta15N for herbivores was much greater than for carnivores, while carp and bream showed higher delta15N signatures than expected, probably due to a higher dietary proportion of benthos, typically more delta15N enriched relative to pelagic biota.     

Genotoxic and teratogenic potential of marine sediment extracts investigated with comet assay and zebrafish test

Organic extracts of marine sediments from the North Sea and the Baltic Sea were investigated with two toxicity assays. The comet assay based on the fish cell line Epithelioma papulosum cyprini (EPC) was applied to determine the genotoxic potential; zebrafish embryos (Danio rerio) were used to quantify the teratogenic potential of the samples. EC(50) values were calculated from dose-response curves for both test systems. Highest teratogenic and genotoxic effects normalised to total organic carbon (TOC) content were detected in sediment samples of different origins. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) are not likely to be the causes of the observed effects, as demonstrated by a two-step fractionation procedure of selected extracts. The toxic potential was more pronounced in fractions having polarity higher than those possessed by PAHs and PCBs. The suitability of the two in vitro test systems for assessing genotoxic and teratogenic effects of marine sediment extracts could be demonstrated.     

Application of an ELISA for PCB 118 to the screening of dioxin-like PCBs in retail fish

A commercially available enzyme-linked immunosorbent assay (ELISA) kit was evaluated for the determination of toxic equivalents (TEQs) of dioxin-like polychlorinated biphenyls (PCBs) in retail fish. The ELISA was highly specific for 2,3',4,4',5-pentachlorobiphenyl (PCB 118), which is generally the most abundant dioxin-like PCB isomer found in fish. The quantitative limit of the ELISA (using 3,3',4'-trichloro-4-methoxybiphenyl as a surrogate standard for PCB 118) was 10 ng ml(-1) (125 pg assay(-1)) in the standard curve, corresponding to 50 pg PCB 118 g(-1) in the tested sample. Good recoveries of PCB 118 (78.7-112.3%) were obtained for spiked purified fish extracts according to the ELISA. Good linearity was also obtained in dilution tests using purified fish extracts. No significant interference of the matrix was observed in the ELISA when this purification procedure was used. Recovery tests in which PCB 118 was added to fish samples also resulted in acceptable recoveries (60.2-82.3%) in the ELISA following purification. The ELISA results for fish samples correlated well with the TEQ concentrations of dioxin-like PCBs obtained by high-resolution gas chromatography/high-resolution mass spectrometry (r = 0.92, n = 26). These data indicate that the ELISA kit is suitable for screening retail fish for the TEQs of dioxin-like PCBs.     

Age dependence of the accumulation of organochlorine pollutants in brown trout (Salmo trutta) from a remote high mountain lake (Redó, Pyrenees)

Polychlorobiphenyls (PCBs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB) and DDT were examined in the muscle of brown trout (Salmo trutta) from a high mountain lake located in the Pyrenees (Catalonia, Spain) that was used as a model of these lacustrine environments. Results indicate that fish age is the main factor of variability among specimens in this population that is subjected to atmospheric inputs of the organochlorine compounds (OC). Increases of 2- and 20-fold between fish aged 1 year and 15 years old are found. The observed pattern cannot be explained in terms of fish size, condition factor, or muscle lipid content. Higher molecular weight compounds (higher lipophilicity) are better correlated with fish age than low molecular weight compounds. A transformation from 4,4'-DDT to 4,4'-DDE occurs in fish after ingestion; this results in amplified age-dependent signals, especially in male specimens. In contrast, PCB congener #180 has lower age dependence than the general OC group, which could be due to its high hydrophobicity (log K(ow) > 7). In any case, selective accumulation of hydrophobic compounds is already observed among younger fish (age, 1 year). Due to this effect, the relative OC composition does not reflect the main OC pollutants in the lake waters.     

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.     

Organochlorine pesticides and PCBs in fish from lakes of the Tibetan Plateau and the implications

High mountains may play significant roles in the global transport of persistent organic pollutants (POPs). This work aims to investigate the levels, patterns and distribution of semi-volatile organoclorine pollutants and to improve the understanding of the long-range atmospheric transport and fate of contaminants on the Tibetan Plateau. A total of 60 fish samples were collected from eight lakes located between 2813 and 4718 m above sea level across the Plateau. Concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) including dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) were measured in fish muscle. The results showed that concentrations of DDT, HCH and HCB were comparable to or lower than those found in remote mountains of Europe, Canada and US, while PCB concentrations in fish were, on average, about 4-150 times lower on Tibet than at other mountain areas. The transport and fate of contaminants in the Plateau are significantly influenced by the unique climatological and meteorological conditions, particularly by the summer Indian monsoon and winter westerly jet stream.     

Endocrine effects generated by photooxidation of coplanar biphenyls in water using titanium dioxide

The oxidative photodegradation behaviors of selected three coplanar polychlorinated biphenyls (PCBs), (CB77, CB81, and CB169) using titanium dioxide (TiO(2)) in water were investigated. The main purposes were to clarify the structural relation between the original PCBs and the intermediates derived by TiO(2) oxidation and to evaluate the estrogenic and thyroid hormonal activity in the treated three coplanar PCBs during the oxidative reactions. Approximately 90% of the three coplanar PCBs decomposed within 180 min. Intermediates from the decomposition of the three coplanar PCBs, such as some hydroxylated-PCBs (OH-PCBs), carboxylic intermediates, phenolic intermediates, and other intermediates produced by the cleavage of a benzene ring were identified and quantified. In the degradation pathways, the produced amounts of OH-PCBs increased within 60 min of irradiation time. The estrogenic activity and thyroid hormonal activity of the intermediates from the three coplanar PCBs in water at 0, 60, 120, 180 and 240 min of irradiation time were assessed by using a yeast two-hybrid assay system for human estrogen receptor alpha (hERalpha) and human thyroid hormone receptor alpha (hTRalpha). The maximal estrogenic activities were induced by the solutions of decomposed PCBs with irradiation time at 60-120 min similar and slightly lower than those after the irradiation time. We found that the solutions occuring during the irradiation times of 60-120 min contained several 4-OH-PCBs substituted with OH and Cl at para- and para'-positions having estrogenic activity. The thyroid hormonal activity was not detected in the decomposed three coplanar PCBs solutions.     

Is meltwater from Alpine glaciers a secondary DDT source for lakes?

A sharp increase in 2005 of pp'DDT and its metabolites was observed in mussels and fish from lakes Como and Iseo, the main glacier-fed southern Alpine lakes. DDTs in zebra mussels (Dreissena polymorpha) were more than 150 times higher than levels in 2003, and concentrations in pelagic fish (0.12 mgkg(-1) w.w.) exceeded the Italian safety threshold for human consumption (0.05 mgkg(-1) w.w.). The histological examination of the ovaries revealed many mussels with oocyte degeneration throughout the studied period. Prior to being banned in Italy in 1978, DDT was used in large amounts for fruit-tree treatment from the 1950s to 1970s in valleys just below the glaciers. Since glacier volume was increasing at that time and then continuously retreated, meltwater should be the main cause of the pollution peak recently observed in biota of downstream lakes. PCBs did not peak in biota tissues to a comparable extent probably because local sources were not as important as for DDTs.     

Environmental PCBs in Guánica Bay,Puerto Rico: implications for community health

Guánica Bay, located in southwestern Puerto Rico, has suffered oil spills and other pollution discharges since the 1960s. Previous research showed elevated concentrations of polychlorinated biphenyls (PCBs) in coral reef and sediment. This research examined PCB concentrations in sediment and fish. Sediment and fish sampling in the bay was facilitated by community members. This study identified the second highest reported PCB level (129,300 ng/g) in sediment in the USA. Fish samples also showed elevated concentrations (1623 to 3768 ng/g), which were higher than the thresholds of safe levels of PCBs in fish for human consumption. The alarmingly high concentration of PCBs calls for proactive community engagement to bring awareness about contamination of the bay and more extensive sampling to test for the concentration of PCBs in seafood and the people of Guánica. This study also underscores the value of the involvement of local communities during sampling design aimed at identifying hot spots of contaminants.     

Organochlorine compounds (PCBs, PCDDs and PCDFs) in seafish and seafood from the Spanish Atlantic Southwest Coast

Concentrations and congener specific profiles of PCDD/Fs and PCBs were determined in edible fish and seafood species from the Coast of Huelva, in the Spanish southwest Atlantic coast. Five fish species, namely wegde sole (Dicologoglossa cuneata), common sole (Solea vulgaris), white seabream (Diplodus sargus), sardine (Sardina pilchardus), angler fish (Lophius piscatorius), two shellfish species (Donax trunculus and Chamelea gallina), common cuttlefish (Sepia officinalis) and prawns (Parapenaeus longirostris), frequently found and consumed in the area were analysed. Concentrations ranged from 861 to 23787pg/g wet weight for total PCBs, while 2,3,7,8-PCDD/Fs showed concentrations ranging from 0.2 to 1.18pg/g wet weight. WHO-TEQ concentrations ranged from 0.038 to 0.186pg WHO-TEQ(PCDD/Fs)/g wet weight, values well below the maximum concentrations established by the EU. When non- and mono-ortho PCBs were included the values increased to a maximum of 0.99pg WHO-TEQ(PCDD/Fs+PCBs)/g wet weight. The PCB and PCDD/F accumulation pattern found in the samples analysed showed a distribution typically reported for marine samples, and no remarkable differences were found between species. The PCBs were the ones contributing with the highest percentage to the total TEQ content in most species studied. Concerning the seafood, specially prawns and shellfish, the opposite was observed and PCDD/Fs were found to contribute with a higher percentage than PCBs. The congener specific contribution to the TEQ showed PCB 126 followed by 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF as the most abundant ones.     

Influence of trophic status on PCB distribution in lake sediments and biota

We investigated the relationship between trophic status and polychlorinated biphenyl (PCB) distribution in 19 Swedish lakes. We analyzed PCB in water, phytoplankton, zooplankton, fish and sediment during two sampling periods, in spring and summer. The mass of sigma PCB in the lake sediments was positively related to lake trophy, i.e. more PCBs were accumulated and buried in the sediment of eutrophic lakes than in oligotrophic lakes. In the oligotrophic lakes a greater fraction of the total PCB load was dissolved in water. We conclude that this is a result of higher sedimentation rates in eutrophic lakes and relatively lower turnover of organic carbon in the water column of the shallow, eutrophic lakes. In the stratified lakes, the amount of PCB per cubic meter in the epilimnion decreased from spring to summer. We suggest that sedimentation of plankton beneath the thermocline during stratification act as a sink process of PCBs from the epilimnion.     

Concentration of polychlorinated biphenyls and organochlorine pesticides in mullet (Mugil cephalus) and sea bass (Dicentrarchus labrax) from Bizerte Lagoon (Northern Tunisia)

Concentrations of polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) were determined in two fish species, mullet (Mugil cephalus) and sea bass (Dicentrarchus labrax), collected from Bizerte Lagoon and the Mediterranean Sea. In all samples, PCBs were found in higher concentrations than OCPs. The highest concentrations of OCPs and PCBs were found in sea bass, and in Bizerte Lagoon. Concentrations of DDTs and PCBs detected in this study were generally comparable or slightly higher than those found in studies from other Mediterranean and non-Mediterranean regions subject to a high anthropogenic impact. ∑PCBs, ∑HCHs and HCB levels were negatively correlated with lipid content, while no such correlation was seen for ∑DDTs. A significant correlation between levels and length and between levels and weight existed only for ∑PCBs. The daily intake of PCBs and OCPs ingested by people living in Bizerte through the studied fish species was estimated and compared with those observed in other areas.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

The combined use of chemical and biochemical markers to assess water quality along the Ebro River

Carp (Cyprinus carpio) and barbel (Barbus graellsii) were collected from five sites along the Ebro River. The study was designed to assess levels of persistent organic pollutants and metals bioaccumulated by fish, and some biochemical responses (cytochrome P450 system, phase II activities, and metallothioneins) against those pollutants. The highest levels of PCBs and DDTs were detected in carp from industrialised areas, which also showed high levels of mercury and cadmium in the liver, and high levels of nonylphenol in bile. Significant alterations in some biochemical markers were observed and associated to combined exposure to pollutants. The activity 7-ethoxyresorufin O-deethylase ranged from 69 pmol/min/mg protein in carp from the reference site to 415 pmol/min/mg protein in those from polluted sites. Carp from the Ebro Delta, an agricultural area, had depressed acetylcholinesterase in muscle tissue. Metallothionein concentrations were positively correlated with copper residues, but no significant differences among sampling points were observed.     

PCB and DDT contamination in cultivated and wild sea bass from Ria de Aveiro, Portugal

Polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDT) and metabolites were quantified in muscle and liver of sea bass (Dicentrarchus labrax) collected in Ria de Aveiro and in two fish farms. Sea bass from natural environment showed lower levels than fish from farming, which may be partly attributed to the higher lipid content of cultivated fish. PCB congener distribution in tissues of sea bass from the two farms resembled that of diet pellets suggesting that commercial diet is a major source of PCBs. However, fish in the two sites were fed with diet of similar PCB and DDT contamination but showed distinct levels in its tissues not explained by lipid content.     

Monitoring of persistent organic pollutants (POPs): examples from Lake Vättern, Sweden

Lake V?ttern in southern Sweden is a large oligotrophic lake with high surface to catchment area ratio (ca. 0.4) and a water residence time of 60 years. The lake combines sensitivity to atmospheric POP-pollution with general susceptibility for effects of POPs and slow concentration decline. Time series, from the 1960s until 1996, of PCBs and DDT in fish and data on TCDD in sediment of L. V?ttern are presented and compared to other large lakes. The long time dataset of POPs in Arctic char (Salvelinus salvelinus) shows a significant annual decline of about 5% for PCBs and 13% for DDT. These rates are in agreement with other studies. Nutrients as well as biological effects and factors affecting the fate of POPs in oligotrophic lakes with long residence times are discussed. We propose that oligotrophic clear lakes are important ecosystems for monitoring POPs in biota.     

Screening for potential effects of endocrine-disrupting chemicals in peri-urban creeks and rivers in Melbourne, Australia using mosquitofish and recombinant receptor–reporter gene assays

Sexually mature male mosquitofish (Gambusia holbrooki) were collected from various sites around Melbourne in 2009 to evaluate the performance of gonopodial indices as a biomarker for endocrine disruption in Melbourne's waterways. The mosquitofish indices assessed were body length (BL), gonopodial length (GL)/BL ratio, ray 4:6 ratio and the absence or presence of hooks and serrae, and these varied between sites. The study was complemented by measurements of estrogenic, retinoid, thyroid and aryl hydrocarbon (AhR) receptor activities of the water. Male mosquitofish were 16.3–21.5 mm in length, and although there was a statistically significant positive relationship showing that bigger fish had longer gonopodia than small fish (r2 = 0.52, p < 0.001), there were few significant differences in GL/BL ratio of fish between sites. Measured estrogenic activity was mostly in the range 0.1–1.7 ng/L EEQ, with one site having much higher levels (~12 ng/L EEQ). Aryl hydrocarbon (AhR) receptor activity was observed in all water samples (7–180 ng/L βNF EQ), although there was no consistent pattern in the level of AhR activity observed, i.e., ‘clean’ sites were as likely to return a high AhR activity response as urban or wastewater treatment plant (WWTP)-impacted sites. There was no correlation between measurements of receptor actvity and gonopodial length (GL):BL ratio and BL. We conclude that the mosquitofish gonopodia only fulfills part of the criteria for biomarker selection for screening. The mosquitofish indices assessed were cheap and easy-to-perform procedures; however, there is no baseline data from the selected sites to evaluate whether differences in the morpholical indices observed at a site were a result of natural selection in the population or due to estrogenic exposure.