Persistency of highly toxic coplanar PCBs in aquatic ecosystems: uptake and release kinetics of coplanar PCBs in green-lipped mussels (Perna viridis Linnaeus)

The bioaccumulation potential of three highly toxic coplanar PCB isomers [3,3',4,4'-tetrachlorobiphenyl (T(4)CB); 3,3',4,4',5-pentachlorobiphenyl (P(5)CB); and 3,3',4,4',5,5'-hexachlorobiphenyl (H(6)CB)] was investigated using green-lipped mussels (Perna viridis Linnaeus) as a bioindicator, through a transplantation experiment at two locations in Hong Kong waters. By contrast to the relatively rapid uptake and release of many other PCB isomers, the non-ortho chlorine substituted coplanar PCB congeners exhibited slow uptake and clearance. The kinetic parameters of coplanar PCBs based on lipid weight-related data, and the degree of bioaccumulation based on the proportion of coplanar PCBs in total PCBs in mussels, clearly indicate that coplanar PCBs are highly bioaccumulative in lower organisms. On the assumption that mussels are unlikely to be particularly unusual with respect to their bioaccumulation of coplanar PCBs, it appears most likely that these highly toxic and persistent PCB congeners are concentrated by all aquatic organisms, and may reach higher consumers (including humans) in quantities of toxicological concern.     

Polychlorinated biphenyls (PCBs) in sediments in Hong Kong: a congener-specific approach to the study of coplanar PCBs in aquatic ecosystems

Patterns of contamination by polychlorinated biphenyls (PCBs) were investigated in fourteen samples of coastal sediments from Hong Kong. Congener-specific analyses revealed nine sediment samples from Junk Bay to contain PCBs at concentrations ranging from 31 to 2200 ng g(-1) dry weight, concentrations generally increasing with distance north in the Bay. By contrast, five sediments from the Tolo area to the north-east of Hong Kong exhibited total PCB levels of only 6.6 to 45 ng g(-) dry weight. The patterns of relative abundance of PCB congeners in the northern Junk Bay sediments suggested the existence of ongoing source(s) of PCBs in this area; biphenyls of lower chlorination were present at high concentration in these samples. Three coplanar PCBs (3', 4, 4'-tetrachlorobiphenyl; 3,3',4,4',5-pentachlorobiphenyl; and 3,3',4,4',5,5'-hexachlorobiphenyl) were found to be present in Junk Bay sediments; these are highly toxic and are cause for concern in aquatic environments. The abundance of the three coplanar PCBs in the sediments studied was similar to that in commercial PCB mixtures, suggesting that these congeners are not enriched over other PCBs by the sediments of coastal ecosystems. It is concluded that the preferential enrichment of coplanar PCBs occurs in the biosphere, rather than in sediments.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

Comparison of seven indicator PCBs and three coplanar PCBs in beef, pork, and chicken fat

The risk assessment of polychlorinated biphenyls (PCBs) is difficult since complex congeners were used in many industrial applications for a long period of time and the residue monitoring in foods of animal origin and the environment were not established in comparable systems. The relationships of determined concentrations in indicator PCB congeners (mono- and di-ortho PCBs) and coplanar PCB congeners (non-ortho PCBs) in livestock products are presented in this study. The concentrations of seven indicator PCBs were compared with three coplanar PCBs in beef, pork, and chicken fat. Distributions of concentration for the indicator PCBs in three different animal species were similar except for that of PCB-118 (2,3',4,4',5-pentachlorobiphenyl) in pork fat. The congeners with the highest concentration were PCB-138 (2,2',3,4,4',5'-hexachlorobiphenyl) in beef and pork fat and PCB-28 (2,4,4'-trichlorobiphenyl) in chicken fat. The bioaccumulation and metabolism of PCBs in animal species represent different congener profiles in livestock products. The percentage of the total concentration of three coplanar PCBs was about 2% of the total concentration of the seven indicator PCBs. Relatively high concentration of mono-ortho and di-ortho PCBs in fat samples of livestock products may be calculated with the concentration of coplanar PCBs that can be usually determined on a sequential procedure with dioxin analysis. Therefore, the relationship of the amounts between seven indicator PCBs and three coplanar PCBs may be useful to derive the composition and level of contaminants in beef, pork, and chicken.     

Bioaccumulation profiles of polychlorinated biphenyls including coplanar congeners and possible toxicological implications in Baikal seal (Phoca sibirica)

Isomer specific concentrations of individual polychlorinated biphenyls (PCBs) including toxic non-ortho (IUPAC 77, 126, 169), mono-ortho (105, 118, 156) and di-ortho (137, 138, 153, 180) coplanar congeners were determined in the blubber of 40 Baikal seals (Phoca sibirica) and as their fish diet collected from Lake Baikal, Siberia. Residue levels of total PCBs in Baikal seals were noticeably high and comparable to those reported for seals from the North Sea, suggesting the recent usage of this compound in the watershed of Lake Baikal. Non-, mono-, and di-ortho coplanar congeners were also detected in Baikal seals and fish. An approach to estimate bioaccumulation profiles of PCB congeners revealed that the non-ortho PCBs, IUPAC 77, 126 and 169 seemed to be less persistent than other congeners. Furthermore, selective biotransformation of PCB congeners having either meta-para vicinal H atoms or both adjacent chlorinated meta-para and ortho-meta positions has been suggested. Comparison of 2,3,7,8-TCDD toxic equivalents (TEQ) of non-, mono- and di-ortho coplanar congeners in Baikal seals with those for other marine mammals suggested higher enrichment of mono-ortho congeners, particularly IUPAC 105 and 118, which contributed significantly to the total TEQs in Baikal seals. Results imply that the TCDD-like toxicity is relatively serious in Baikal seals, because of the enrichment of these toxic PCB congeners in tissues.     

Individual PCBs as predictors for concentrations of non and mono-ortho PCBs in human milk

32 Dutch human milk samples were analyzed for PCBs with either HRGC-ECD or HRGC-LRMS in the NCI mode. Samples were collected from three different locations in The Netherlands: Amsterdam, Rotterdam and Groningen. Quantitatively, no differences could be observed between the three localities, while in addition the congener specific pattern showed a striking similarity for all individual samples. Only principal component analysis revealed slight individual differences. Based on similarities in the PCB profiles, linear relationships were calculated between 2,3′4,4′,5-PnCB (#118) or 2,2′4,4′5,5′HxCB (#153) and the most relevantnon andmonoortho PCBs exhibiting dioxinlike activity. These PCBs included 2,3,3′,4,4′-PnCB (#105), 3,3′,4,4′5-PnCB (#126) 2,3,3′,4,4′,5-HxCB (#156), 2,3,3′,4,4′,5′-HxCB (#157), 2,3′,4,4′,5,5′-HxCB (#167) and 3,3′,4,4′,5′5-HxCB (#169). Good linear relationships were observed between individual PCBs. Based on the results of this study, PCB #118 can be used to predict concentrations of the PCBs #105 and #126. PCB #153 can be used as a predictor for the PCBs #156, #157, #167 and #169, but also for the total toxic equivalencies (TEQs) ofnon andmonoortho PCBs present in human milk. This method using certain PCBs as predictors for other toxicological relevant congeners, can be useful and cost effective, e.g. for epidemiological studies. However, before applied a number of conditions should be met. These are:

1. A stable composition of the PCB matrix should be established.
2. A possible time dependent change in composition of the matrix should first be excluded when used over different time periods.

     

Persistent organochlorines in beluga whales (Delphinapterus leucas) from the St Lawrence River estuary--I. Concentrations and patterns of specific PCBs, chlorinated pesticides and polychlorinated dibenzo-p-dioxins and dibenzofurans

Blubber samples from beluga whales (Delphinapterus leucas) in the St Lawrence River estuary were analysed for PCB congeners (ortho- and non-ortho-substituted) and other persistent organochlorines as well as chlorinated dibenzo-dioxins/furans (PCDD/Fs). Major individual components (mean concentrations > 1 microg g(-1)) were 4,4'-DDE, -DDD and -DDT, T12 (a toxaphene-related compound), trans-nonachlor, oxychlordane, mirex, HCB, tris(p-chlorophenyl) methane and dieldrin. Concentrations of SigmaPCBs (8.3-412 microg g(-1)), SigmaDDT (3.36-389 microg g(-1)) and mirex (0.18-6.8 microg g(-1)) were particularly elevated relative to other odontocetes in Canadian waters. SigmaDDT, PCBs (as Aroclor), mirex and T12 concentrations were positively correlated with age of adult females (> 10 years) but only weakly, or not significantly, correlated with age of adult males. PCDD/Fs were present at low ng kg(-1) levels and consisted mainly of penta- and hexachlorofurans, and hepta- and octachlorodioxin. CB126 (3,3',4,4',5-PCB) was the most prominent non-ortho-substituted PCB congener in beluga blubber. Total TCDD toxic equivalents averaged 330 ng kg(-1) in females and 1400 ng kg(-1) in males and were dominated by CB126, and the mono-ortho-substituted congeners CB105 and CB118. Biomagnification factors (BMFs) for mirex and SigmaPCB from fish to beluga ranged from 11 to 16, and were similar to BMFs in Arctic animals, indicating that elevated levels in St Lawrence animals are a consequence of relatively high levels of recalcitrant organochlorines in prey of the beluga in the St Lawrence river system.     

Congener-specific analysis of non-dioxin-like polychlorinated biphenyls in blood collected from 127 elderly residents in Nakagawa Town, Fukuoka Prefecture, Japan

We conducted congener-specific analysis of non-dioxin-like polychlorinated biphenyls (non-dioxin-like PCBs) in blood collected in February 2004 from 127 elderly residents living in Nakagawa Town, Fukuoka Prefecture, Japan. The present study is one of the few studies in which 56 non-dioxin-like PCBs congeners were measured in human blood. Of the 127 elderly residents, 51 were men (mean: 68.1 years) and 76 were women (mean: 68.1 years). Among 197 non-dioxin-like PCB congeners, 56 were identified in the blood of elderly residents. The arithmetic mean total concentrations of 56 non-dioxin-like PCBs congeners in the blood of elderly men and women in Nakagawa Town were 419 (median: 378) and 363 (median: 323)ngg(-1)lipid, respectively, and the concentrations were in the range of 172-1102 and 119-1226ngg(-1)lipid, respectively, indicating that the total concentrations in elderly men are significantly higher than those in elderly women. The contamination of non-dioxin-like PCBs in the blood of elderly men and women in Fukuoka Prefecture was found to have decreased compared to past levels. The ratios of hexachlorinated biphenyls (hexaCBs) to the total concentrations of 56 non-dioxin-like PCBs congeners in the blood of elderly men and women were 44.6% and 45.6%, respectively, which was particularly high compared with those of other congeners. 2,2',4,4',5,5'-HexaCB (#153) among hexaCBs congeners, the most abundant congener in the blood of elderly men and women, contributed approximately 23.0% and 23.5% to the total concentrations of 56 non-dioxin-like PCBs congeners, respectively. Furthermore, 2,2',3,4,4',5'-hexaCB (#138), 2,3,3',4',5,6-hexaCB (#163)/2,3,3',4',5',6-hexaCB (#164), 2,2',3,4,4',5,5'-heptaCB (#180), and 2,2',3,4,4',5,6'-heptaCB (#182)/2,2',3,4',5,5',6-heptaCB (#187) also showed high ratios to the total concentrations of 56 non-dioxin-like PCBs congeners detected in the blood of elderly men and women. A statistical examination of the relationship between the total concentrations of 56 non-dioxin-like PCBs congeners in blood and the age of elderly residents who were over 60 years indicated statistically significant correlations between the total concentrations of these PCBs congeners and the age of elderly women. However, similar correlations were not observed in elderly men. The results of the present study have indicated the current levels of non-dioxin-like PCBs in the blood of elderly men and women in Fukuoka Prefecture, Japan and can be used as baseline data for those over age 60.     

Accumulation properties of polychlorinated biphenyl congeners in Yusho patients and prediction of their cytochrome P450-dependent metabolism by in silico analysis

In what has become known as the Yusho incident, thousands of people in western Japan were poisoned by the accidental ingestion of rice bran oil contaminated with polychlorinated biphenyls (PCBs) and various dioxins and dioxin-like compounds. In this study, we investigated the accumulation patterns of 69 PCB congeners in the blood of Yusho patients in comparison with those of non-exposed controls. The blood samples were collected at medical check-ups in 2004 and 2005. To compare the patterns of PCB congeners, we calculated the concentration ratio of each congener relative to the 2,2′,4,4′,5,5′-hexaCB (CB153) concentration. The concentration ratios of tetra- and penta-chlorinated congeners in the blood of Yusho patients were significantly lower than those of controls. To examine the cytochrome P450 (CYP)-dependent metabolic potential of the 2,3′,4,4′5-pentaCB (CB118), CB153, and 2,3,3′,4,4′5-hexaCB (CB156) congeners, we conducted PCB-CYP (CYP1A1, CYP1A2, CYP2A6, and CYP2B6) docking simulation by in silico analysis. The docking models showed that human CYP1A1, CYP2A6, and CYP2B6 isozymes have the potential to metabolize CB118 and CB153. On the other hand, it was inferred that CB156 is difficult to be metabolized by these four CYP isozymes. These results indicate that CYP1 and CYP2 isozymes may be involved in the characteristic accumulation patterns of PCB congeners in the blood of Yusho patients.     

Congener specific accumulation and toxic assessment of polychlorinated biphenyls in common cormorants, Phalacrocorax carbo, from Lake Biwa, Japan

Isomer-specific accumulation of polychlorinated biphenyls (PCBs) including di-, mono- and non-ortho congeners and hepatic P-450 activities were determined in adult common cormorants from Lake Biwa, Japan. The mean total PCB levels in male and female birds were 7.2 +/- 6.1 and 2.1 +/- 0.74 microg g(-1) wet wt, respectively, in the liver. The highly biomagnified congeners were IUPAC 126, 153, 169, 180 and 194, whereas a higher degree of biotransformation could be observed in both meta-para chlorine unsubstituted congeners in the cormorant liver. The estimated metabolic index also showed that common cormorants had higher PB-type enzyme activities than some avian and marine mammals but poor MC-type enzyme activities. The concentrations of non-ortho coplanar congeners were in the order of IUPAC 126 > IUPAC 169 > IUPAC 77 with mean values 6.1 +/- 5.9, 1.3 +/- 1.4 and 0.43 +/- 0.26 ng g(-1) wet wt, respectively. The calculated mean 2,3,7,8-TCDD toxic equivalent (TEQ) concentration in cormorants was 1.8 +/- 1.7 ng g(-1) wet wt and was dominated by IUPAC 118, followed by IUPAC 126. A significant increase of ethoxyresorufin-O-deethylase (EROD) and pentoxyresorufin-O-deethylase (PROD) activities was observed with estimated TEQ of PCBs in the cormorants, suggesting that the current contamination level is sufficient for altering their biochemical responses.     

Examination of the bioaccumulation of halogenated dimethyl bipyrroles in an Arctic marine food web using stable nitrogen isotope analysis.

Concentrations of four possibly naturally produced organohalogens--1,1'-dimethyl-3,3',4-tribromo-4,5,5'-trichloro-2,2'-bipyrrole (DBP-Br3Cl3), 1,1'-dimethyl-3,3',4,4'-tetrabromo-5,5'-dichloro-2,2'-bipyrrole (DBP-Br4Cl2), 1,1'-dimethyl-3,3',4,4',5-pentabromo-5'-chloro-2,2'-bipyrrole (DBP-Br5Cl) and 1,1'-dimethyl-3,3',4,4',5,5'-hexabromo-2,2'-bipyrrole (DBP-Br6)--were quantitated and the extent of their magnification through an entire Arctic marine food web [measured as integrated trophic magnification factors (TMFs)] were calculated. The food web consisted of three zooplankton species (Calanus hyperboreus, Mysis oculata, and Sagitta sp.), one fish species [Arctic cod (Boreogadus saida)], four seabird species [dovekie (Alle alle), black guillemot (Cepphus grylle), black-legged kittiwake (Rissa tridactyla), and glaucous gull (Larus hyperboreus)], and one marine mammal species [ringed seal (Phoca hispida)]. Trophic levels in the food web were calculated from ratios of stable isotopes of nitrogen (15N/14N). All halogenated dimethyl bipyrrole (HDBP) congeners were found to significantly (P<0.02) biomagnify, or increase in concentration with trophic level in the invertebrate--fish--seabird food web. DBP-Br4Cl2 (TMF= 14.6) was found to biomagnify to a greater extent than DBP-Br3Cl3 (TMF = 5.2), DBP-Br5Cl (TMF = 6.9), or DBP-Br6 (TMF = 7.0), even though the Kow of DBP-Br4CI2 was predicted to be lower than those of DBP-Br5Cl and DBP-Br6. None of the four HDBP congeners in ringed seals followed the general trend of increasing concentration with trophic level, which was possibly due to an ability of the seals to metabolize HDBPs.     

Comparative toxicities of the polychlorinated dibenzofuran (PCDF) and biphenyl (PCB) mixtures which persist in Yusho victims

The toxic Yusho oil contained a mixture of polychlorinated biphenyls (PCBs) which were contaminated by other halogenated aromatics including the highly toxic polychlorinated dibenzofurans (PCDFs). It has been reported that the PCBs and PCDFs which persist in the liver of victims still suffering from Yusho poisoning include the following compounds; 2,3′,4,4′,5-penta-,2,2′,4,4′,5,5′-,2,2′,3′,4,4′,5- and 2,3,3′,4,4′,5-hexa, 2,2′,3,4,4′,5,5′- and 2,2′,3,3′,4,4′,5-heptachlorobiphenyls and the 2,3,7,8-tetra-, 1,2,4,7,8-, 1,2,3,7,8- and 2,3,4,7,8-penta- and 1,2,3,4,7,8-hexachlorodibenzofurans. All of these PCBs and PCDFs have been synthesized and reconstituted to approximate their composition in human liver. A comparison of the dose-response effects of the reconstituted PCB and PCDF mixtures in causing weight loss, thymic atrophy and the induction of cytochrome P-448-dependent monooxygenases indicated that the PCDF mixture was at least 700 times more active than the PCBs. Since the ratio of PCBs/PCDFs persisting in Yusho patients' blood and liver was less than 600:1 and 5:1 respectively, the results suggest that the PCDFs are the major etiologic agent in Yusho poisoning.     

PCB problems in the future: foresight from current knowledge

The present paper overviews the forthcoming PCB problems from current knowledge of their use, environmental contamination and toxicology. From a global point of view, PCB levels in the environmental media and biota are unlikely to decline in the near future due to the greater quantities of PCBs still in use than the quantity that has already escaped into the open environment. Considering all the information on the occurrence, distribution and behaviour of PCBs in the ecosystems, the marine mammals are probably the most vulnerable and possible target organisms in forthcoming long-term PCB toxicity. The recent isomer-specific analyses suggest that the intrinsic toxicity of PCBs principally resulted from the coplanar PCB congeners which may impose a greater toxic threat than chlorinated dioxins and furans to humans and wildlife. The measures necessary to reduce further discharge of PCBs into the environment should be set in motion immediately, otherwise there may be a subsequent deleterious biological impact.     

Monobromo and higher brominated congeners of the marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1)

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) is widely distributed in the environment. In this study, we screened samples which have previously been found to contain remarkably high residues of Q1 (blubber of marine mammals from Australia, samples from Antarctica, human milk from the Faroe Island) for the additional presence of mixed chlorinated and brominated congeners. Using GC/ECNI-MS, all samples tested were positive and many contained four out of five possible bromohexachloro congeners (BrCl6-MBPs), five out of 14 possible dibromopentachloro congeners (Br2Cl5-MBPs), five of 21 possible tribromotetrachloro-congeners (Br3Cl4-MBPs), as well as several higher brominated congeners. About 20 heptahalo congeners of Q1 are described for the first time in the scientific literature. Isomers eluted within about one minute, respectively. Hence it is possible, that the peak clusters identified may be composed of more, co-eluting congeners. Similarities in the GC/ECNI-MS mass spectra with polychlorinated biphenyls (PCBs) were addressed. We also suggest an acronym system similar to that in use for polychlorinated biphenyls that may simplify the use of this substance class in scientific papers. In the samples from Australia, BrCl6-MBPs and Br2Cl5-MBPs amounted for 7-27.5% and 0.4-4.2% of Q1, respectively whereas Br3Cl4-MBPs and higher brominated MBPs were found in the range of <1% of Q1 or less.     

Polychlorinated dibenzo-p-dioxins and related compounds in breast milk of Japanese primiparas and multiparas

We analyzed polychlorinated dibenzo-p-dioxins and related compounds in the breast milk of primiparas and multiparas, and estimated the levels transferred to newborns by breast milk in Western Japan. 2,3,7,8-TeCDD equivalents (TEQ) of the chemicals in primiparas decreased slightly from 1994 to 1996. In particular, decreases of the TEQs of total PCDDs and total coplanar PCBs were higher than that of total PCDFs. In 2,3,7,8-TeCDD, 1,2,3,7,8-PeCDD, 1,2,3,6,7,8-HxCDD, 1,2,3,7,8,9-HxCDD, 2,3,4,7,8-PeCDF, 1,2,3,6,7,8-HxCDF, 3,3',4,4',5-PeCB and 3,3',4,4',5,5'-HxCB concentrations, those in the breast milk of multiparas were significantly lower than those in the breast milk of primiparas (p < 0.05, lipid basis). Based on the assumption that newborns ingest 120 g of breast milk per kg body weight per day, the amounts converted to TEQ values were 121 pg/kg/day (primiparas) and 97.2 pg/kg/day (multiparas).     

PCDDs, PCDFs, and coplanar PCBs in wild terrestrial mammals from Japan: congener specific accumulation and hepatic sequestration

The present study determined the contamination levels and congener-specific accumulation features of dioxins and related compounds (DRCs) in wild terrestrial mammals such as large Japanese field mice (LJFM), lesser Japanese moles (LJMs), and raccoon dogs (RDs) collected from Kanto region in Japan during 2001. The toxic equivalent quantity (TEQ) levels in the carcasses or adipose tissues were in the order of RDs > or = LJMs > LJFM. Comparison of DRC congener profiles in the three species and principal component analysis (PCA) demonstrated a higher contribution of OCDD, T4CB77, and P5CB118 in LJMs. Analysis of liver-adipose distribution of DRC congeners in RDs showed that livers contained significantly higher TEQs than adipose tissues, indicating that liver is a depository organ and critical for determining the toxicokinetics of DRCs. As for most T4, P5, H6CDD/DFs and for P5CB126, H6CB169 and mono-ortho PCB congeners, their liver/adipose concentration ratios in RDs revealed a tendency to increase with hepatic TEQ levels, suggesting TEQ-dependent hepatic sequestration.     

Organochlorine pesticides and polychlorinated biphenyl congeners in wild terrestrial mammals and birds from Chubu region, Japan: Interspecies comparison of the residue levels and compositions

In order to understand the residue levels of organochlorine compounds (OCs) and their accumulation patterns in wildlife inhabiting Chubu region, Japan, the concentrations of polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), DDT compounds (DDTs) and hexachlorobenzene (HCB) were measured in 8 species of terrestrial mammals and 10 species of birds. In view of feeding habits, the contamination levels of OCs were found to be higher in omnivorous mammals than in herbivorous ones, and in fish-eating ones and raptores than in omnivorous birds. In fox and dog, PCB-180 (2, 2′, 3, 4, 4′, 5, 5′-heptachlorobiphenyl) was the most dominant PCB congener, while in the other species PCB-153 (2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl) was the most persistent. The ratios of lower chlorinated PCB congeners (tri- to tetra-) to total PCBs were larger in fish-eating birds than in the other birds. The results indicate that the compositions of PCB congeners would reflect the differences of feeding habits and xenobiotic metabolizing systems among each species.     

Development and calibration of epiphytic lichens as saltfall biomonitors--dry-deposition modelling

Blubber collected from beluga whales and ringed seals during subsistence hunts in the southern Baffin Island region of the Canadian Arctic were analysed for polychlorinated naphthalenes and eight planar PCB congeners (mono-ortho PCBs: 105, 114, 118 and 156; non-ortho PCBs: 77, 81, 126, 169). SigmaPCN (3-7 Cl) concentrations in blubber ranged from 35.9-383 pg/g (lipid weight; lw) in beluga and 35.4-71.3 pg/g (lw) in ringed seal. These represent the first measurements of PCNs in marine mammals in the Canadian Arctic, mammals which are an important part of the traditional diet of the indigenous population. SigmaCoplPCB concentrations were much higher, ranging from 15.5-317 ng/g (lw) in beluga whale blubber and 16.5-40.9 ng/g (lw) in ringed seal blubber. PCNs and coplanar PCBs both exhibit dioxin-like toxicity. Although average sigmaPCN concentrations were less than 1% of sigmaCoplPCBs, PCNs contribute up to 11% of TEQ relative to the coplanar PCBs based on TEFs determined by H4IIE enzyme assays.     

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.     

Pathways and products of the degradation of PCBs by the sodium dispersion method

Nine polychlorinated biphenyl (PCB) congeners (2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 2,3,4-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl, 2,3',4,4',5-pentachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl, 2,2',4,4',5,5'-hexachlorobiphenyl, and decachlorobiphenyl) were dechlorinated by the sodium dispersion method (SD) at low temperature (60 degrees C). The dechlorination of 4-chlorobiphenyl was the fastest among the three monochlorobiphenyls. As for the other six congeners, we investigated the major dechlorination pathways. Although reaction selectivity was not very sensitive to the position of the chlorine substituent, the chlorines at the para position were slightly easier to dechlorinate than those at the ortho or meta positions. The decomposition rate increased with the total numbers of chlorine substituents. A chlorine situated between two other chlorines showed a high reactivity. When the numbers of chlorines on each of the phenyl rings were different, the reactions occurred on the more substituted ring. In the degradation of 4-chlorobiphenyl at elevated temperature (160 degrees C), we investigated the structures of the polymerized products and whether all the organic chlorinated compounds degraded finally or not. As for the dimers, p-quarterphenyl (QP) and m,p-QP were detected but not o-QP, m-QP, o,p-QP, o,m-QP, or the mono- to tetra-chlorinated QPs. Compounds with a molecular weight of 534.4183 or 758.6713 were detected. They were considered to have C40H54 or C56H86 as their molecular formula. The compounds were most probably the polymerized products resulting from coupling of hexadecane or two hexadecanes and two phenylcyclohexadienes. It was thought the dechlorination and the polymerization were the main reactions. All of many detected compounds were hydrocarbons without chlorines, and no peaks originating from organic chlorinated compounds were observed by mass spectroscopic (MS) methods.