Persistent organochlorine residues and toxic evaluation of polychlorinated biphenyls in sharks from the Mediterranean Sea (Italy)

Persistent organochlorines such as polychlorinated biphenyls including coplanar congeners, DDT compounds and HCB were measured in different tissues (muscle, liver and eggs) of two Mediterranean shark species: namely Centrophorus granulosus and Squalus blainvillei. The concentrations of organochlorines in the tissues and organs of both species were in the order DDTs>PCBs>HCB. The highest values of DDTs, PCBs and HCB were found in liver followed by eggs and muscle. Among DDTs the compound found in greatest concentration was p,p^′-DDE. The PCB profiles were dominated by congeners 138, 153, and 180. The isomers with higher TEQs values were non- and mono-ortho congeners than di-ortho ones in muscle, liver and eggs of both species. Among the non-ortho, PCB 126 was the major contributing individual to the total TEQs in both species.     

Polychlorinated biphenyl and organochlorine pesticide residues in Lophius budegassa from the Mediterranean Sea (Italy)

Persistent organochlorines, such as polychlorinated biphenyls, including coplanar congeners and DDT compounds, were measured in the liver of a teleost species: namely, Lophius budegassa. The mean concentrations of PCBs (1249 ng/g wet wt) were comparable with DDTs mean levels (1459 ng/g wet wt). Among DDTs the compound found at the highest concentration was p,p'-DDE representing 76% of the total DDT burden. The PCB profiles were dominated by congeners 153, 180, and 138 accounting for 49.8%, 16.0% and 13.7% of the total PCBs. The total 2,3,7,8-TCDD toxic equivalent (TEQs) of six coplanar PCBs, including mono- and non-ortho congeners, was 0.98 pg/g wet wt. The congeners with highest TEQs values were non-ortho-congeners followed by mono-ortho ones.     

PCBs and organochlorine pesticide residues in eggs of Audouin's gull (Larus audouinii) in the north-eastern Mediterranean.

Levels of eight PCB congeners (IUPAC 8, 20, 28, 52, 101, 118, 138, 180) and 13 organochlorine pesticides (alpha-BHC, beta-BHC, lindane (gamma-BHC), heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, 2,4'-DDT, 2,4'-DDD, 4,4'-DDT, 4,4'-DDD, 4,4'-DDE) were measured in unhatched Audouin gull eggs from Aegean Sea (northeastern Mediterranean) colonies in 1997 and 1998. Levels of more persistent congeners 138, 180 and in some colonies 118, predominated among PCBs. Between years significant differences were found in the levels of a variety of contaminants in the same regional colonies (Lipsos, Agathonisi, and Fourni) attributable to temporal changes in diet. Within years differences were limited (1997: PCB congeners 52, 118, 180, heptachlor and 4,4'-DDD; 1998: PCB congener 8 and heptachlor epoxide) which in combination with cluster analysis suggest a temporal rather than spatial pattern of pollution in the Aegean Sea. Maximum median levels of five PCB congeners, total PCBs and eight organochlorine pesticides were found in the Agathonisi and Fourni colonies suggesting an elevated nearby pollution probably from the polluted Menderez River. Levels of all contaminants were too low to have any adverse reproductive effects on the Audouin's gull of the Aegean colonies.     

ANAEROBIC DECHLORINATION OF PCBs IN SEDIMENTS OF KINNICKINNIC RIVER, WISCONSIN

1 INTRODUCTION Polychlorinated biphenyls (PCBs) have been used for several decades in a variety of industrial applications such as for transformers, capacitors, and hydraulic fluids (Rachdawong and Christensen, 1997). Because of their stability and desirable hydraulic and dielectric properties, PCBs were used extensively. However, later it became clear that they can be toxic and can have deleterious reproductive effects on biota and humans. They may also display dioxin-like toxicity…     

Contamination by Persistent Organochlorines in Small Cetaceans from Hong Kong Coastal Waters

Blubber samples of 2 cetacean species, the Indo-Pacific hump-backed dolphin (Sousa chinensis) (n=11) and finless porpoise (Neophocaena phocaenoides) (n=9), collected from Hong Kong coastal waters were analysed for persistent organochlorines. Mean concentration in the blubber of DDTs was ranked first (46 μg/g wet wt.), followed by PCBs (24 μg/g wet wt.), HCHs (0.76 μg/g wet wt.), chlordane compounds (0.38 μg/g wet wt.) and HCB (0.07 μg/g wet wt.). The present cetacean species may potentially be faced with high risk due to the elevated level of DDTs and PCBs. Relatively high concentrations of PCBs and DDTs can be attributed to the continuous environmental input of these compounds in the Far East region including Hong Kong. Highly chlorinated PCBs such as IUPAC Nos. 138, 153, 180 were the prominent congeners, accounting for 39% of the total PCBs. Mean concentrations of 6 non- and mono-ortho coplanar congeners were 2.1 and 2.8 μg/g wet wt. in the hump-backed dolphin and finless porpoise, respectively. Among highly toxic coplanar PCBs, mono-ortho congener IUPAC No. 118 and non-ortho congener IUPAC No. 126 were estimated to have the greatest toxicity contribution. Tris(4-chlorophenyl) methane (TCPMe) and tris(4-chlorophenyl) methanol (TCPMeOH), which have been the most recently identified microcontaminants, were also detected with the highest concentration of 290 and 300 ng/g (wet wt. basis), respectively. The concentrations of TCPMe relative to TCPMeOH in cetaceans from Hong Kong coastal waters were significantly higher than those found in various seals collected from other parts of the world, suggesting the different metabolic system of these two compounds between seals and cetaceans. Correlations between the concentrations of tris-chlorophenyl compounds with other persistent organochlorines such as HCHs, CHLs, DDTs and PCBs were significant, suggesting their accumulation nature similar to these organochlorines.     

Alteration of gene expression profiles in the brain of Japanese medaka (Oryzias latipes) exposed to KC-400 or PCB126

Polychlorinated biphenyls (PCBs) are known as neurotoxic chemicals and possibly alter animal behavior. We previously reported that PCB-exposure induced abnormal schooling behavior in Japanese medaka (Oryzias latipes). This abnormal behavior might be caused by the functional alteration of central or terminal nervous system. To understand the mechanism(s) of behavioral change by PCB-exposure, we analyzed the gene expression profiles in the brain of medaka exposed to 3,3',4,4',5-pentachlorobiphenyl (PCB126) or a PCB mixture (Kanechlor-400: KC-400) using a cDNA microarray that we constructed. Twelve FLF-II strain medaka (six individuals per treatment) were dietary exposed to PCB126 (0.01 microg/g b.w./day) or KC-400 (1 microg/g b.w./day) for three weeks. For the control, six fish were fed a control diet. After the exposure period, fish were dissected, and the brain samples were collected. The samples from control fish were pooled and used as a common reference in the microarray experiment. Microarray data were normalized by the LOWESS method, and we screened the genes whose expression levels were altered more than 1.5-fold. Gene expression profiling showed 97 down-regulated and 379 up-regulated genes in the brain of medaka exposed to PCB126. KC-400 exposure suppressed 15 genes and induced 266 genes in medaka brain. Among these genes, the expression levels of 7 and 188 genes were commonly down- or up-regulated, respectively in both treatment groups. On the other hand, 31 gene expressions were significantly different between PCB126 and KC-400 treatment groups, and three out of 31 genes were received opposite effects. In addition, the microarray data showed that thyroid hormone-responsive genes were up-regulated by PCB-exposure, which may imply that PCBs or their metabolites mimic thyroid hormone effects in the brain of PCB-exposed medaka.     

Alteration of gene expression profiles in the brain of Japanese medaka (Oryzias latipes) exposed to KC-400 or PCB126

Polychlorinated biphenyls (PCBs) are known as neurotoxic chemicals and possibly alter animal behavior. We previously reported that PCB-exposure induced abnormal schooling behavior in Japanese medaka (Oryzias latipes). This abnormal behavior might be caused by the functional alteration of central or terminal nervous system. To understand the mechanism(s) of behavioral change by PCB-exposure, we analyzed the gene expression profiles in the brain of medaka exposed to 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) or a PCB mixture (Kanechlor-400: KC-400) using a cDNA microarray that we constructed. Twelve FLF-II strain medaka (six individuals per treatment) were dietary exposed to PCB126 (0.01 μg/g b.w./day) or KC-400 (1 μg/g b.w./day) for three weeks. For the control, six fish were fed a control diet. After the exposure period, fish were dissected, and the brain samples were collected. The samples from control fish were pooled and used as a common reference in the microarray experiment. Microarray data were normalized by the LOWESS method, and we screened the genes whose expression levels were altered more than 1.5-fold. Gene expression profiling showed 97 down-regulated and 379 up-regulated genes in the brain of medaka exposed to PCB126. KC-400 exposure suppressed 15 genes and induced 266 genes in medaka brain. Among these genes, the expression levels of 7 and 188 genes were commonly down- or up-regulated, respectively in both treatment groups. On the other hand, 31 gene expressions were significantly different between PCB126 and KC-400 treatment groups, and three out of 31 genes were received opposite effects. In addition, the microarray data showed that thyroid hormone-responsive genes were up-regulated by PCB-exposure, which may imply that PCBs or their metabolites mimic thyroid hormone effects in the brain of PCB-exposed medaka.     

Polychlorinated biphenyl (PCB) concentrations and congener composition in masu salmon from Japan: A study of all 209 PCB congeners by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS)

We collected two subspecies of masu salmon: Oncorhynchus masou masou from four localities (southern Sea of Japan northward to Hokkaido) and O. masou ishikawae from upstream from Ise Bay close to a heavy industrial area. All 209 PCB congeners were analyzed using HRGC/HRMS. PCA ordination of congener concentrations divided data into three groups: (i) ssp. masou from Hokkaido, (ii) ssp. masou from the other regions and (iii) ssp. ishikawae. The highest ∑ PCB concentration (40.39 ng/wet wt) was in ssp. ishikawae followed by ssp. masou from southern waters; however the TEQ_{dioxin-like PCBs} was highest in ssp. masou from southern water (1.96 pg-TEQ_{dioxin-like PCBs}/g wet wt.) due to the high proportion of congener #126 in its complement (#126 has the highest toxic equivalency factor among congeners). There is likely a contamination source offshore in the southern Sea of Japan and/or along the migratory route of ssp. masou.     

Alteration of gene expression profiles in the brain of Japanese medaka (Oryzias latipes) exposed to KC-400 or PCB126

Polychlorinated biphenyls (PCBs) are known as neurotoxic chemicals and possibly alter animal behavior. We previously reported that PCB-exposure induced abnormal schooling behavior in Japanese medaka (Oryzias latipes). This abnormal behavior might be caused by the functional alteration of central or terminal nervous system. To understand the mechanism(s) of behavioral change by PCB-exposure, we analyzed the gene expression profiles in the brain of medaka exposed to 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) or a PCB mixture (Kanechlor-400: KC-400) using a cDNA microarray that we constructed. Twelve FLF-II strain medaka (six individuals per treatment) were dietary exposed to PCB126 (0.01 μg/g b.w./day) or KC-400 (1 μg/g b.w./day) for three weeks. For the control, six fish were fed a control diet. After the exposure period, fish were dissected, and the brain samples were collected. The samples from control fish were pooled and used as a common reference in the microarray experiment. Microarray data were normalized by the LOWESS method, and we screened the genes whose expression levels were altered more than 1.5-fold. Gene expression profiling showed 97 down-regulated and 379 up-regulated genes in the brain of medaka exposed to PCB126. KC-400 exposure suppressed 15 genes and induced 266 genes in medaka brain. Among these genes, the expression levels of 7 and 188 genes were commonly down- or up-regulated, respectively in both treatment groups. On the other hand, 31 gene expressions were significantly different between PCB126 and KC-400 treatment groups, and three out of 31 genes were received opposite effects. In addition, the microarray data showed that thyroid hormone-responsive genes were up-regulated by PCB-exposure, which may imply that PCBs or their metabolites mimic thyroid hormone effects in the brain of PCB-exposed medaka.     

Effects of individual polybrominated diphenyl ether (PBDE) congeners on harbour seal immune cells in vitro

Effects of polybrominated diphenyl ethers (PBDEs) on the immune system of marine mammals are poorly understood. One important innate immune function of granulocytes is the respiratory burst which generates reactive oxygen species (ROS) used to kill engulfed microorganisms. The present study investigates in vitro the effects of BDE-47, -99 and -153, on the formation of ROS, on intracellular level of thiols, on activity and efficiency of phagocytosis and on apoptosis in granulocytes of harbour seals. Compounds were tested at four different concentrations ranging from 1.5 to 12 μM. Results showed that ROS levels, thiol levels and phagocytosis were all affected when harbour seal cells were exposed to the highest concentration (12 μM) of PBDE congeners. Apoptosis was not affected by PBDEs. The observed effects were similar in adults, pups and in the 11B7501 cell line of harbour seals.     

Bioconcentration and biomagnification of polybrominated diphenyl ethers (PBDEs) through lower-trophic-level coastal marine food web

Bivalves, crabs, fishes, seawater, and sediment collected from the inner part of Tokyo Bay, Japan, were measured for 20 polybrominated diphenyl ether (PBDE) and 5 polychlorinated biphenyl (PCB) congeners. To determine the trophic levels of the organisms, carbon and nitrogen stable isotope ratios (δ¹³C and δ¹⁵N) were also measured. Bioconcentration factors of PBDE and PCB congeners increased as the octanol-water partition coefficient (K_ow) rose to log K_ow = 7, above which they decreased again. Biomagnification of PCBs and several PBDE congeners (BDE47, 99, 100, 153 and 154) up the trophic ladder was confirmed by a positive correlation between their concentrations and δ¹⁵N. Other PBDE congeners showed a negative or no correlation, suggesting their biotransformation through metabolism. The more hydrophobic congeners of both PBDEs (Br = 2-6) and PCBs (Cl = 6-9) were biomagnified more. It thus appears that PBDEs are less biomagnified than PCBs.     

Determination of HBCD, PBDEs and MeO-BDEs in California sea lions (Zalophus californianus) stranded between 1993 and 2003

Blubber samples from male California sea lions (Zalphophus californianus) stranded between 1993 and 2003 were analyzed for 27 polybrominated diphenyl ether (PBDE) congeners, three isomers of hexabromocyclododecane (HBCD) and 14 methoxylated polybrominated diphenyl ether (MeO-BDE) congeners. Total PBDEs ranged from 450 ng/g to 4740 ng/g wet mass and total HBCD ranged from < 0.3 ng/g to 12 ng/g wet mass. The concentration of HBCD increased from 0.7 ng/g to12.0 ng/g wet mass in sea lion blubber between 1993 and 2003. However, no significant temporal trend was observed for any of the other brominated compounds over this 10 year period. Only one of the 14 MeO-BDE congeners was detected in the blubber samples, 6-methoxy-2,2',4,4'-tetrabromodiphenyl ether (6-MeO-BDE 47), and concentrations ranged from < 0.2 ng/g to 12 ng/g wet mass. A bromo-, chloro-heterocyclic compound, 1,1'-dimethyl-tetrabromo-dichloro-2,2'-bipyrrole (DBP-Br4Cl2), previously reported in marine species along the Pacific coast, was also identified in the sea lion blubber. DBP-Br4Cl2 ranged from 44 ng/g wet mass to 660 ng/g wet mass and was present at concentrations rivaling the dominant PBDE congener, BDE 47 (2,2',4,4'-tetrabromodiphenyl ether). Concentrations of DBP-Br4Cl2 were positively correlated with 6-MeO-BDE 47 (r = 0.7; p < 0.05). Both of these compounds have been identified in marine algae and sponges, and studies suggest they are both produced from natural sources. This study demonstrates that brominated compounds from both anthropogenic and biogenic sources can accumulate to similar levels in marine mammals. In addition, HBCD concentrations appear to be increasing in California sea lion populations, whereas PBDE concentrations, between 1993 and 2003, were highly variable.     

Assessment of temporal variation and sources of PCBs in the sediments of Mediterranean Sea, Mersin Bay, Turkey

Information on temporal distribution of polychlorinated biphenyls (PCBs) in the coastal sediments of Mediterranean Sea, Mersin was compiled using data published between 1980 and 2009, and the present study. The first congener specific PCB results from the region yield concentration levels of Σ₄₁PCBs in sediments ranging from 0.61 to 1.04 ng g⁻¹. Sediment profiles show penta-, hexa- and hepta-chlorobiphenyls, specifically, #149 and 153 as the most abundant congeners in all samples. Comparison of total PCB concentrations over time suggests no recent PCB input to the region. Using congener specific PCB data for the region, identity and contribution of PCB sources were also predicted using a chemical mass balance -based (CMB) receptor model. The CMB model identified Aroclor 1260 to be the major PCB source in coastal sediments. The potential sources for the PCBs were briefly discussed in terms of their use in various industrial applications.     

Specific profiles of polybrominated diphenylethers (PBDEs) and polychlorinated biphenyls (PCBs) in fish and tucuxi dolphins from the estuary of Paraíba do Sul River, Southeastern Brazil

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) are ubiquitous pollutants in the environment and subject of several studies due to their adverse effects as endocrine disruptors. Despite the concern over widespread distribution of PBDEs even in sparsely populated regions of the world, few studies have reported their occurrence in Brazil. In this study, PBDEs and PCBs levels were measured in selected fish species and dolphins from Paraiba do Sul River, Brazil. BDE 47 and 85 were the predominant congeners. Low chlorinated congeners showed the highest concentrations in fish; however dolphins presented the highest proportion of PCBs 153, followed by 138 and 180. The daily intake of PBDEs and PCBs was estimated for the population of this region. PCB daily intake through consumption of croaker was above the limits set by the Brazilian Ministry of Agriculture, raising great concern over the existence of a source of PCB contamination in Brazil.     

PCB, PCDD/F and PBDE levels and profiles in crustaceans from the coastal waters of Brittany and Normandy (France)

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analysed in the muscle of various edible marine crustaceans (spider crab, edible crab, velvet swimming crab and Norway lobster) from the Brittany and Normandy coasts (France). The highest concentrations were measured in species collected from Antifer (Seine Bay). PCB and PBDE patterns in crustacean muscles were similar and independent of the geographical area with the predominance of the high chlorinated PCBs (CB153, 138, 118 and 180), and of a few PBDE congeners (BDE47, BDE99, BDE100 and BDE28). Oppositely, dioxin contamination differed with site. The major component in crustaceans from the Seine Bay was 2378-TCDF, whereas specimens from cleaner areas had higher relative concentrations of OCDD. Finally, the comparison of the spider crab contaminant profiles to those measured in mussel and sea bass highlighted two different trends: decapod crustaceans possess relatively strong capacity to metabolise PCBs and PBDEs; however these species might be used as bioindicators for dioxin pollution monitoring in the marine coastal environment.     

Screening of Mercury and Persistent Organochlorine Pollutants in Long-Finned Pilot Whale (Globicephala melas) in the Faroe Islands

Results of mercury and organochlorine analyses in pooled muscle and blubber samples representing in all 417 long-finned pilot whales (Globicephala melas) sampled in 1997 in the Faroe Islands are presented. The 28 pooled muscle samples from (in all) 9 pods were analysed for total mercury and the same number of pooled blubber samples were analysed for PCB (IUPAC CBs no. 28, 52, 99, 101, 105, 118, 128, 138, 153, 170, 180, 183 and 187), p,p′-DDT and metabolites and o,p′-DDT and metabolites, cis () and trans (γ)-chlordane, cis- and trans-nonachlor, oxychlordane, mirex, hexachlorobenzene, β-HCH and toxaphene (Parlars no. 26 (T2), 32, 50 (T12), 62 (T20) and 69.     

PCBs in fish from the southern Baltic Sea: levels, bioaccumulation features, and temporal trends during the period from 1997 to 2006

Levels of seven marker polychlorinated biphenyls (PCBs) have been determined in five species of Baltic fish collected during 1997-2006. Downward time trends in the concentrations of heavier congeners of PCBs in different Baltic fish, with the exception of cod, have been observed between 1997 and 2001. In case of sprat and herring samples, the statistical significance of the time trends of the PCBs: 101, 118, 153, 138 and 180 concentrations has been proved. Species-specific bioaccumulation of PCBs has been indicated, and the lowest and highest levels of PCBs (expressed on the basis of lipid weight) have been observed in sprat and salmon samples, respectively. PCB profiles have been found to be similar in all the fish species tested. Sampling location has not been a crucial factor for the observed levels of various PCBs. In some fish species, PCB concentrations are negatively correlated with the fat content but have no relation with the fish length.     

Analyses of organic and inorganic contaminants in Salton Sea fish

Chemical contamination of fish from the Salton Sea, a quasi-marine lake in Southern California, could adversely impact millions of birds using the Pacific Flyway and thousands of humans using the lake for recreation. Bairdiella icistia (bairdiella), Cynoscion xanthulus (orangemouth corvina), and Oreochromis spp. (tilapia) were sampled from two river mouths and two nearshore areas of the Salton Sea. Muscle tissues were analyzed for a complete suite of 14 trace metals and 53 pesticides. Fish muscle tissues had concentrations of selenium ranging between 1.89 and 2.73 microg/g wet weight. 4,4'-DDE accounted for 94% of the total DDT metabolites. Total DDTs ranged between 17.1 and 239.0 and total PCBs between 2.5 and 18.6 ng/g wet weight. PCB congeners 132, 138, 153, 168, and 180 comprised over 50% of the total PCBs. Given the potential implementation of a commercial fishing at the Salton Sea in the future, the presence of persistent organic pollutants and selenium warrants further research into the effects of these mixtures on fish populations, and on wildlife and humans consuming fish.