Persistent organic pollutants (POPs) in killer whales (Orcinus orca) from the Crozet Archipelago, southern Indian Ocean

Persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs), are ubiquitous environmental contaminants of which significant concentrations are reported in upper trophic level animals. In 1998, we collected blubber biopsy samples (n = 11) from killer whales (Orcinus orca) inhabiting the coastal waters around Possession Island, Crozet Archipelago, southern Indian Ocean, for contaminant analyses. Despite inhabiting an isolated region far removed from industrial activities, these killer whales can presently be considered among the most PCB-contaminated cetaceans in the southern hemisphere, with concentrations ranging from 4.4 to 20.5 mg/kg lipid weight (lw). PCDD levels ranged from below the detection limit (5 ng/kg) to 77.1 ng/kg lw and PCDF levels from below the detection limit (7 ng/kg) to 36.1 ng/kg lw. Over 70% of our study animals had PCB concentrations which exceeded a 1.3 mg/kg PCB threshold established for endocrine disruption and immunotoxicity in free-ranging harbour seals, suggesting that organic contaminants cannot be ruled out as an additional threat to this declining population.     

Indications of P450 monooxygenase activities in beluga (Delphinapterus leucas) and narwhal (Monodon monoceros) from patterns of PCB, PCDD and PCDF accumulation

Selective accumulation of PCDDs, PCDFs and PCB congeners was investigated in beluga (Delphinapterus leucas), narwhal (Monodon monoceros) and several species at the same trophic level in two areas of Canada. There was a much higher relative abundance of meta-para-unsubstituted PCBs in the cetaceans compared with other species. This suggests that activity of cytochrome P450 monooxygenase enzymes causing CYP2B-type metabolism was relatively low in beluga and narwhal. Lower relative levels of 2,3,7,8-TCDD occurred in beluga from both areas, and selective reduction of toxic non-ortho PCBs occurred in the highly PCB-contaminated St Lawrence beluga. These compounds are potent inducers of cytochrome P450 CYP 1A-type enzymes, suggesting that such an enzyme with the capability of metabolizing TCDD-like substrates is present in beluga and narwhal. SIMCA principal components analysis of PCB congener patterns showed that the two cetaceans were in a statistically significant different class than the other species. Variables (congeners) with the greatest separation power between classes were mainly those defined by the selective metabolism rules.     

中华白海豚(Sousa chinensis)组织中多氯联苯的研究

以珠江口海域的两头中华白海豚为研究对象,采用气相色谱法分析了海豚组织中多氯联苯（PCBs）的含量分布特征和毒性水平。结果表明,PCBs在海豚10种不同组织中的含量范围为25．1—85567．3ng／g,PCBs含量最高的组织为额隆和皮肤,其次为肝脏、肌肉、心脏、睾丸和脑,最低的为肺、胃和肾脏;PCBs同系物和同族物在海豚不同组织中的分布特征相似,同系物中以PCB101＋113和PCB153所占总量的百分比最大,在10．25％-51．70％之间;在同族物中以含在同族物中以5个氯原子和6个氯原子的PCBs为主,所占百分比均在23．53％-60．06％之间;运用二蛞哄毒性当量（TEQ）评价了中华白海豚不同组织中PCBs的毒性,其TEQs范围为55．9—68191．0pg／g,其中皮肤TEQs含量最高。TEQs主要来自非邻位取代的PCBs,占总量的74．15％-99．62％,其中来自PCB126的占34．11％-96．5I％。与世界其他海域海豚的PCBs污染水平相比,成年中华白海豚受PCBs污染严重,其体内的PCBs含量和毒性当量均已超出安全浓度范围,对其健康已造成威胁。     

Assessment of toxicological status of a SW Mediterranean segment population of striped dolphin (Stenella coeruleoalba) using skin biopsy

Various studies have revealed high concentrations of contaminants such as organochlorines (OCs) and heavy metals in Mediterranean cetaceans. A geographical trend of contamination (PCBs and DDTs) has been found for striped dolphin (Stenella coeruleoalba). In this study we used a non-lethal approach (skin biopsy) to investigate bioaccumulation of OCs, including polychlorobiphenyls (PCBs), DDTs, polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), trace elements (Hg, Cd, Pb) and CYP1A activity (BPMO) in nine striped dolphins sampled in the Aeolian area (Sicily - Italy) in summer 2002. The arithmetic mean value of BPMO activity in this group was 43.46 AUF/g tissue/h. This value is approximately 3 times and 5 times lower, respectively, than the value found in the Ionian and in the Ligurian groups. Skin biopsies of striped dolphins emerged as a suitable material for assessing the toxicological status of the various Mediterranean groups.     

PCB uptake and accumulation by oysters (Crassostrea virginica) exposed via a contaminated algal diet.

Reproductively active oysters were fed daily with 0.2 g algal paste containing 0, 0.1, and 1.0 microgram polychlorinated biphenyls (PCBs) (1:1:1 mixture of Aroclor 1242, 1254 and 1260) for either 15 or 30 days, and accumulation of PCBs in different organ tissues and eggs assessed. The effects of PCB exposure on lipid content, lipid class and fatty acid composition were also evaluated. PCBs were accumulated by the oysters and transferred to the eggs. PCB accumulation in oysters was dose, time and tissue dependent. Mean PCB contents were 3150, 1970, and 250 ng/g dry wt., respectively, in the visceral mass, gills + mantle and muscle of oysters fed algal paste containing 1.0 microgram PCBs for 30 days. The PCBs in the eggs from the same oysters reached 671 ng PCBs/g dry wt. Feeding oysters with PCB-sorbed algal paste for 30 days significantly increased phospholipid and free fatty acid contents in gills + mantle tissue compared to the same tissues in the undosed control.     

Apparent lack of CYP1A response to high PCB body burdens in fish from a chronically contaminated PCB site

Chronic exposure to organic contaminants such as polychlorinated biphenyls (PCBs) can lead to the development of resistance to these chemicals, a condition associated with reduced response of CYP1A1, a pollutant-inducible biomarker. We measured CYP1A activity (ethoxyresorufin o-deethylase, EROD) and PCB concentrations in feral fish from the Town Branch/Mud River system (Logan County, KY), a stream historically contaminated with PCBs and partially remediated. As a first step in evaluating the possible development of resistant populations in this system, we measured CYP1A expression and PCB body burdens in resident fish from sites we previously characterized as containing biologically significant levels of CYP1A inducing compounds. Mean PCB concentrations in edible flesh ranged from 75.2 to 16.7 microg/g in fish collected from Town Branch remediated sites and were relatively low (1.23 microg/g) in Town Branch reference site fish. However, hepatic CYP1A activity was similar among individuals of most species collected from reference and contaminated/remediated sites. The absence of elevated CYP1A levels in resident fish species despite the presence of significant PCB body burdens may indicate these fish have developed reduced sensitivity to CYP1A induction, a condition associated with acquired resistance to toxicants.     

PCB uptake and accumulation by oysters (Crassostrea virginica) exposed via a contaminated algal diet

Reproductively active oysters were fed daily with 0.2 g algal paste containing 0, 0.1, and 1.0 μg polychlorinated biphenyls (PCBs) (1:1:1 mixture of Aroclor 1242, 1254 and 1260) for either 15 or 30 days, and accumulation of PCBs in different organ tissues and eggs assessed. The effects of PCB exposure on lipid content, lipid class and fatty acid composition were also evaluated. PCBs were accumulated by the oysters and transferred to the eggs. PCB accumulation in oysters was dose, time and tissue dependent. Mean PCB contents were 3150, 1970, and 250 ng/g dry wt., respectively, in the visceral mass, gills+mantle and muscle of oysters fed algal paste containing 1.0 μg PCBs for 30 days. The PCBs in the eggs from the same oysters reached 671 ng PCBs/g dry wt. Feeding oysters with PCB-sorbed algal paste for 30 days significantly increased phospholipid and free fatty acid contents in gills+mantle tissues compared to the same tissues in the undosed control.     

Effects of PCBs sorbed to algal paste and sediments on the stress protein response (HSP70 family) in the eastern oyster, Crassostrea virginica.

This study examined the stress protein response (HSP70 family) of reproductively inactive oysters fed 0.7 g algal paste containing 0, 0.35 and 3.5 micrograms polychlorinated biphenyls (PCBs) daily. A second set of treatment groups investigated the combined effect of PCBs and sediments (0.3 g sediments daily per oyster) on HSP70 response. After 8 weeks of PCB exposure, oyster tissues (mantle and gill) were sampled and analyzed for HSP70. Preliminary results did not show a significant effect in HSP70 response in oysters fed PCB sorbed to algal paste, albeit PCBs accumulated up to 1342 ng/g dry weight in the mantle, and up to 180 ng/g dry weight in gill tissues. However, the addition of sediments caused a significant increase in HSP70 levels of gills and mantle, although the mantle was less sensitive to the sediments.     

Spatial Distribution of Polychlorinated Biphenyls （PCBs） Contaminants in the Tidal-flat Sediments of Yangtze Estuary

1 IntroductionYangtze River estuary is the biggest one in China, and there are domestic and manufactural rubbish disposal sites for Shanghai city in this tidal-flat. The Shanghai city, the whole Yangtze delta, or even all the Yangtze basin, will be PCBs contaminant sources of Yangtze estuary tidal-flat[1]. According to literatures so far, only two investigations for waters have included PCBs in the Yangtze estuary[2, 3]. No PCBs pollution of the tidal-flat sediments has been reported…     

Polychlorinated biphenyls and organochlorine compounds in brain,liver and muscle of beluga whales (Delphinapterus leucas) from the Arctic and St. Lawrence estuary

Brain, liver and muscle samples from seven male beluga whales, Delphinapterus leucas, from Hendrickson Island in the Canadian Arctic (n=3) and the St. Lawrence River estuary (n=4), were analyzed for polychlorinated biphenyls (PCBs) and other organochlorine (OC) compounds to determine whether there are differences in the distribution of these contaminants in beluga tissues and between geographic locations. Wet weight concentrations of ΣPCB, ΣDDT, Σchlordane and mirex were significantly higher (p<0.05) in St. Lawrence samples. Principal component analysis (PCA) of the PCB and OC data indicated that contaminant profiles in belugas from the St. Lawrence reflect point-source inputs of these compounds while Arctic samples appear to be dominated by PCB congeners and OC compounds subject to long-range transport and deposition. Discriminant functions analysis of the contaminant data for the brain, liver and muscle tissues indicated that the distributions of OC compounds in the liver and muscle tissues were very similar, while brain samples could be distinguished from other tissues by differences in PCB congener patterns and higher concentrations of Σhexachlorocyclohexane (ΣHCH), primarily αHCH.     

A description of chloride cell and kidney tubule alterations in the flatfish Solea senegalensis exposed to moderately contaminated sediments from the Sado estuary (Portugal)

The effects of sediment-bound contaminants on kidney and gill chloride cells were surveyed in juvenile Solea senegalensis exposed to fresh sediments collected from three distinct sites of the Sado Estuary (Portugal) in a 28-day laboratorial assay. Sediments were analyzed for metallic contaminants, polycyclic aromatic hydrocarbons and organochlorines as well as for total organic matter, redox potential and fine fraction. The potential for causing adverse biological effects of each surveyed sediment was assessed by comparison of contaminant levels to available guidelines for coastal sediments, namely the Threshold Effects Level (TEL) and the Probable Effects Level (PEL). The Sediment Quality Guideline Quotient indices (SQGQ) were calculated to compare the overall contamination levels of the three stations. A qualitative approach was employed to analyze the histo/cytopathological traits in gill chloride cells and body kidney of fish exposed to each tested sediment for 0, 14 and 28 days. The results showed that sediment contamination can be considered low to moderate and that the least contaminated sediment (from a reference site, with the lowest SQGQ) caused lesser changes in the surveyed organs. However, the most contaminated sediment (by both metallic and organic xenobiotics, with highest SQGQ) was neither responsible for the highest mortality nor for the most pronounced lesions. Exposure to the sediment presenting an intermediate SQGQ, essentially contaminated by organic compounds, caused the highest mortality (48%) and the most severe damage to kidneys, up to full renal necrosis. Chloride cell alterations were similar in fish exposed to the two most contaminated sediments and consisted of a pronounced cellular hypertrophy, likely involving fluid retention and loss of mitochondria. It can be concluded that sediment contamination considered to be low or moderate may be responsible for severe injury to cells and parenchyma involved in the maintenance of osmotic balance, contributing for the high mortality levels observed. The results suggest that sediment-bound organic contaminants such as PAHs (polycyclic aromatic hydrocarbons) and PCBs (polychlorinated biphenyls) may be very toxic to the analyzed organs, especially the kidney, even when present in low-risk concentrations.     

A description of chloride cell and kidney tubule alterations in the flatfish Solea senegalensis exposed to moderately contaminated sediments from the Sado estuary (Portugal)

The effects of sediment-bound contaminants on kidney and gill chloride cells were surveyed in juvenile Solea senegalensis exposed to fresh sediments collected from three distinct sites of the Sado Estuary (Portugal) in a 28-day laboratorial assay. Sediments were analyzed for metallic contaminants, polycyclic aromatic hydrocarbons and organochlorines as well as for total organic matter, redox potential and fine fraction. The potential for causing adverse biological effects of each surveyed sediment was assessed by comparison of contaminant levels to available guidelines for coastal sediments, namely the Threshold Effects Level (TEL) and the Probable Effects Level (PEL). The Sediment Quality Guideline Quotient indices (SQGQ) were calculated to compare the overall contamination levels of the three stations. A qualitative approach was employed to analyze the histo/cytopathological traits in gill chloride cells and body kidney of fish exposed to each tested sediment for 0, 14 and 28 days. The results showed that sediment contamination can be considered low to moderate and that the least contaminated sediment (from a reference site, with the lowest SQGQ) caused lesser changes in the surveyed organs. However, the most contaminated sediment (by both metallic and organic xenobiotics, with highest SQGQ) was neither responsible for the highest mortality nor for the most pronounced lesions. Exposure to the sediment presenting an intermediate SQGQ, essentially contaminated by organic compounds, caused the highest mortality (48%) and the most severe damage to kidneys, up to full renal necrosis. Chloride cell alterations were similar in fish exposed to the two most contaminated sediments and consisted of a pronounced cellular hypertrophy, likely involving fluid retention and loss of mitochondria. It can be concluded that sediment contamination considered to be low or moderate may be responsible for severe injury to cells and parenchyma involved in the maintenance of osmotic balance, contributing for the high mortality levels observed. The results suggest that sediment-bound organic contaminants such as PAHs (polycyclic aromatic hydrocarbons) and PCBs (polychlorinated biphenyls) may be very toxic to the analyzed organs, especially the kidney, even when present in low-risk concentrations.     

Biotransformation enzyme activities and PCDD/PCDF levels in pike caught in a Swedish Lake

Recently, analysis of organochlorines in sediment and in pike from Lake Vänern, Sweden, showed a north-south gradient of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). In the present study, good correlations were found between muscle 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents and liver ethoxyresorufin-O-deethylase (EROD) activities (and P4501A levels) in pike caught at three sampling sites along the north-south gradient in the lake. This comparison between tissue levels of PCDD/PCDF and EROD activity (and P4501A) may indicate that TCDD or structural analogs could be responsible for the observed induction of the pike P450 system. It must, however, be taken into account that the analysed contaminants often do not appear alone but are, rather, accompanied by a range of other substances which may be inducers or antagonists.     

Assessment of toxicological status of a SW Mediterranean segment population of striped dolphin (Stenella coeruleoalba) using skin biopsy

Various studies have revealed high concentrations of contaminants such as organochlorines (OCs) and heavy metals in Mediterranean cetaceans. A geographical trend of contamination (PCBs and DDTs) has been found for striped dolphin (Stenella coeruleoalba). In this study we used a non-lethal approach (skin biopsy) to investigate bioaccumulation of OCs, including polychlorobiphenyls (PCBs), DDTs, polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), trace elements (Hg, Cd, Pb) and CYP1A activity (BPMO) in nine striped dolphins sampled in the Aeolian area (Sicily – Italy) in summer 2002. The arithmetic mean value of BPMO activity in this group was 43.46 AUF/g tissue/h. This value is approximately 3 times and 5 times lower, respectively, than the value found in the Ionian and in the Ligurian groups. Skin biopsies of striped dolphins emerged as a suitable material for assessing the toxicological status of the various Mediterranean groups.     

Evaluation of non-specific immune functions in dab,Limanda limanda L., following short-term exposure to sediments contaminated with polyaromatic hydrocarbons and/or polychlorinated biphenyls

Experimental exposure tanks were set up containing 'clean' marine sediment spiked with set doses of polyaromatic hydrocarbons (PAH), or polychlorinated biphenyls (PCB), or both. Reference tanks contained only 'clean' sediment. Female dab Limanda limanda L., exposed to these sediments for 7 days showed no differences in serum total protein concentration, serum lysozyme activity or body growth. Their kidney leucocytes were assayed for extracellular production of reactive oxygen species of the phagocytic respiratory burst. No significant differences in superoxide anion (O2-) production were found between fish exposed to the 'spiked' sediments and those on the 'clean' reference sediment. The production of hydrogen peroxide (H2O2) was, however, reduced in the fish held on the PAH and PAH/PCB spiked sediments. H2O2 levels for fish exposed to PCBs alone, did not differ significantly from those of control fish. Our results suggest that the decrease in H2O2 production was due to exposure to PAHs, rather than to PCBs.     

Spatial distribution of persistent organochlorines in ringed seal (Phoca hispida) blubber

Blubber samples, taken through the entire blubber column, were collected from three different anatomical locations on ringed seals (Phoca hispida). The outer and inner layers of these samples were analysed for concentrations of sigma PCBs (sum of the analysed congeners, polychlorinated biphenyls) and p,p'-DDE (4,4'-dichlorodiphenyldichloroethylene). No significant differences were found in blubber thickness or in per cent extractable lipid when comparing age- and sex-groups, or in extractable lipid content when comparing anatomical locations of the blubber or blubber depth. No significant differences were found between the three different anatomical locations with respect to the concentrations of sigma PCBs or p,p'-DDE. However, the concentrations of both sigma PCB and p,p'-DDE were significantly higher in the outer blubber layer compared to the inner. Higher levels of both sigma PCB and p,p'-DDE were found in males compared to females and juveniles in both the inner and outer parts of the blubber column. The most commonly used blubber sampling devices are biopsy tools that penetrate only the outer layer of the blubber. Analyses of such samples will not reflect the real body burden of organochlorines. Standard methods for sampling blubber of marine mammals should be developed so that comparative studies and longitudinal monitoring programs of pollutants in marine mammals can be conducted in a meaningful way.     

Enrichment of organochlorine contaminants in the sea surface microlayer: An organic carbon-driven process

Over 50 seawater samples from two different sites—Barcelona (Spain) and Banyuls-sur-Mer (France)—were analyzed in order to study the extent and postulate the processes driving the enrichment of hydrophobic organic pollutants in the sea surface microlayer (SML). A number of individual polychlorinated biphenyl (PCB) congeners (41) were measured to study their partitioning between the particulate (fraction > 0.7 μm) and the dissolved + colloidal phases (fraction < 0.7 μm), with the latter being differentiated into estimated dissolved and colloidal phases. In addition, several organochlorine pesticides were also measured, namely, HCB, α-HCH, γ-HCH, 4,4′-DDE, 4,4′-DDD and 4,4′-DDT. The presence of PCB congener profiles found in the SML suggests a dynamic coupling with the atmosphere in Banyuls sampling site, whereas offshore Barcelona the presence of highly chlorinated congeners was due to persistent sediment resuspension. The average PCB concentration in the SML dissolved + colloidal phase were higher in Banyuls (7.8 ng L^{− 1}) than in Barcelona (3.6 ng L^{− 1}) samples, but in the particulate phase concentrations were higher in Barcelona (3.2 ng L^{− 1}) to that of Banyuls (1.4 ng L^{− 1}). However, PCB concentrations in the SML generally also showed large variability. Enrichment factors of PCBs and other organochlorine compounds in the SML with respect to the underlying water column ranged from 0.2 to 7.4. This may be explained for both the dissolved + colloidal and particulate phases by the enrichment in the SML of organic carbon (OC) as discerned from particle–water and colloid–water partitioning.     

Trace organic contaminants and their sources in surface sediments of Santa Monica Bay,California, USA

Spatial distribution of selected contaminants in the surface sediments of Santa Monica Bay (SMB), California was investigated. Sediments were analyzed for DDTs (DDT and metabolites), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), linear alkylbenzenes (LABs) and coprostanol. Effluent samples from the Hyperion Treatment Plant (HTP), which discharges treated municipal wastewater effluents into SMB, were also analyzed. The inter-correlation in the distribution trends of contaminants was examined. The concentrations of contaminants were interpolated in a geographic information system to visualize their spatial distribution in the Bay. Inventories of the contaminants were also estimated.The concentrations of coprostanol, LABs and PCBs are very high only in the vicinity of the sewage outfall whereas PAHs and DDTs occur widespread in the Bay. The poor correlation of DDTs with LABs, PAHs or coprostanol content confirms the historic origin of DDTs and their absence in the contemporary wastewaters. Moderate correlation of DDTs with PCBs implies historic deposits as a major origin of PCBs. There are hot spots of DDTs at water depths of 60 and 100 m and the inventory of DDTs in Bay sediments is insignificant compared to that estimated in the Palos Verdes Shelf which extends from the southern edge of Redondo Canyon around Palos Verdes Peninsula. The concentration of toxic contaminants was examined according to published sediment quality guidelines. About 20 stations contain p, p′-DDE and/or total DDTs above ERM and, PCBs between ERL and ERM indicating potential for adverse biological effects.     

Internal recycling of particle reactive organic chemicals in the Chesapeake Bay water column

Hydrophobic organic contaminants (HOCs) may be used as tracers of particle dynamics in aquatic systems. Internal cycling of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were studied in the mesohaline Chesapeake Bay to assess the role of resuspension in maintaining particle and contaminant inventories in the water column, and to compare settling and suspended particle characteristics. Direct measurements of sediment resuspension and settling conducted in conjunction with one of the sediment trap deployments indicate reasonable agreement between measurements of particle flux using the two different methods. Organic carbon and PCB concentrations in settling solids collected in near-surface sediment traps were remarkably lower than concentrations in suspended particles collected by filtration during the trap deployments, but higher PAH concentrations were found in the settling particles. The different behaviors of PAHs and PCBs in the settling particles are due to their different source types and association to different types of particles. Sediment trap collections in near bottom waters were dominated by resuspension. Resuspension fluxes of HOCs measured 2 m above the bay bottom were as high as 2.5 μg/m² day for total PCBs and 15 μg/m² day for fluoranthene, and were 25 and 10 times higher than their settling fluxes from surface waters, respectively. HOC concentrations in the near bottom traps varied much less between trap deployments than HOC concentrations in the surface traps, indicating that the chemical composition of the resuspended particles collected in the near bottom traps was more time-averaged by repeated resuspension than the surface particles.     

Bioaccumulation of PCB congeners in marine benthic infauna

Field concentrations of polychlorinated biphenyls (PCBs) were measured in sediment and nine marine soft bottom invertebrate species. Lipid- and organic carbon normalised biota-sediment accumulation factors (BSAFs) were determined for 29 nonplanar and 11 coplanar congeners. To investigate whether the bioaccumulation was in thermodynamic equilibrium with the sediment, the determined BSAFs were compared to theoretically calculated ones to obtain a BSAFdet./BSAFtheor-ratio. Large interspecific variations were found: one suspension feeding and one deposit feeding species of brittle stars (Amphiura filiformis and A. chiajei), and one predatory polychaete (Glycera rouxii) had ratios>1 for congeners with logKow>6.5. In these species there was also a linear relationship between logKow and BSAF, both for coplanar and for planar congeners but with lower values for coplanar ones. For other species the pattern was more scattered. Only the deposit feeding polychaete Melinna cristata had BSAFdet./BSAFtheor-ratios<1 for all congeners. Thus, the interspecific variations in bioaccumulation did not correlate with differences in feeding strategies, but may be caused by differences in biotransformation, and in age and size of the analysed specimens.