Levels and trends of organochlorines and brominated flame retardants in ivory gull eggs from the Canadian Arctic, 1976 to 2004

The ivory gull (Pagophila eburnea) is a circumpolar marine bird which has recently been listed as an endangered species in Canada. To determine whether contaminants may be playing a role in the population decline of this species, ivory gull eggs collected in 1976, 1987 and 2004 from Seymour Island in the Canadian Arctic were analyzed for organochlorines, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs. This study also provides the first account of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs) and polybrominated biphenyls (PBBs) in ivory gulls. The most quantitatively abundant legacy organochlorines found in the ivory gull eggs were p,p'-DDE, SigmaPCB and oxychlordane. Concentrations of the organochlorines analyzed either decreased or showed little change between 1976 and 2004. Concentrations of SigmaPCDD in ivory gull eggs were greater than SigmaPCDF, and the non-ortho PCBs (primarily PCB-126) contributed the largest fraction to the total TEQ value in all years sampled. Concentrations of PCDDs, PCDFs and SigmaTEQ decreased from 1976 to 2004. In contrast, concentrations of the PBDEs steadily increased between 1976 and 2004 driven primarily by increases in BDE-47. Although concentrations of the persistent chlorinated compounds (i.e. organochlorine pesticides, PCBs, PCDDs, PCDFs) reported in this study were below published toxicological threshold values for eggs of wild birds, we cannot rule out the possibility of synergistic/additive, sublethal effects. Very few studies have been carried out to evaluate the exposure-effect relationship of the persistent brominated compounds in avian species. Given the scarcity of information on toxicity threshold levels for PBBs and PBDEs in avian species, coupled with the trend toward increasing concentrations in ivory gulls, continued monitoring and further toxicological studies of these compounds are warranted.     

Chlorinated hydrocarbon contaminants in feces of river otters from the southern Pacific coast of Canada, 1998-2004

Chlorinated hydrocarbon contaminants in coastal river otters (Lontra canadensis) were evaluated by sampling feces (scats) collected on the south coast of British Columbia, Canada. A broad survey of industrialized areas of the Strait of Georgia region was conducted in 1998, and a subsequent survey of working harbours in 2004. Samples from 1998 were analyzed for polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides, and polychlorinated dioxins (PCDDs) and furans (PCDFs), while in 2004, chemistry was confined to summation operatorPCBs and OC pesticides. Concentrations of OC pesticides were low in both years, with only dichlorodiphenyldichloroethylene (DDE; range: 0.01-2.12 mg/kg lw) and hexachlorocyclobenzene (HCB; range: 0.003-0.25 mg/kg lw) detected in all samples. In 1998, octachlorodibenzo-p-dioxin (OCDD) and other higher chlorinated PCDD/Fs were found in most samples, with OCDD ranging from 120 ng/kg lw in Clayoquot Sound to 19,100 ng/kg lw in a pooled sample from two latrines in Nanaimo. PCBs were present in all samples. In 1998 geometric mean concentrations of the sum of 59 PCB congeners ranged from 0.49 mg/kg lw in Nanaimo to 12.3 mg/kg lw in Victoria Harbour. Six years later, mean summation operatorPCBs remained elevated (geometric mean 9.5 mg/kg lw) in Victoria Harbour. Geometric mean concentrations of summation operatorPCBs from Victoria Harbour in 1998 and 2004 were >9 mg/kg lw, a published adverse effect level for reproduction. At some latrines in both Victoria and Esquimalt Harbours, concentrations of TCDD-toxic equivalents exceeded 1500 ng/kg lw, a value for health effects in otters that we derived using published information. As shown in previous studies, analysis of scats provides an efficient and non-intrusive approach to assessing contaminant threats to otter populations, and to documenting spatial trends in residues.     

Trace elements, PCBs and organochlorine pesticides in New Zealand common dolphins (Delphinus sp.)

Trace elements, polychlorinated biphenyls (PCBs) and organochlorine (OC) pesticide levels were determined in tissues collected from stranded and bycaught common dolphins (Delphinus sp.) from New Zealand waters between 1999 and 2005. The concentrations of mercury (Hg), selenium (Se), chromium (Cr), zinc (Zn), nickel (Ni), cadmium (Cd), cobalt (Co), manganese (Mn), iron (Fe), copper (Cu), tin (Sn), lead (Pb), arsenic (As) and silver (Ag) were determined in blubber, liver and kidney tissue. PCBs (45 congeners) and a range of OC pesticides including dieldrin, hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) and its metabolites DDE and DDD were determined in blubber samples. Cr and Ni were not detected in any of the samples and concentrations of Co, Sn and Pb were generally low. Concentrations of Hg ranged from 0.17 to 110 mg/kg wet weight. Organochlorine pesticides dieldrin, HCB, o,p'-DDT and p,p'-DDE were present at the highest concentrations. Sum DDT concentrations in the blubber ranged from 17 to 337 and 654 to 4430 microg/kg wet weight in females and males, respectively. Similarly, Sigma45CB concentrations ranged from 49 to 386 and 268 to 1634 microg/kg wet weight in females and males, respectively. The mean transmission of SigmaDDTs and ICES7CBs between a genetically determined mother-offspring pair was calculated at 46% and 42%, respectively. Concentrations of organochlorine pesticides determined in the present study are within similar range to those reported for Hector's dolphins (Cephalorhyncus hectori) from inshore New Zealand waters.     

Organochlorine contaminants in endangered Steller sea lion pups (Eumetopias jubatus) from western Alaska and the Russian Far East

Investigations into the cause of the Steller sea lion population decline have focused on numerous factors, including exposure to toxic contaminants such as organochlorines (OCs). OCs, such as polychlorinated biphenyls (PCBs), 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, or dichlorodiphenyltrichloroethane (DDT), have been associated with various biological effects in marine mammals. We measured these compounds in whole blood of free-ranging Steller sea lion pups in order to determine the extent and magnitude of contamination across their geographical range. Of 212 pups analyzed for OCs, 76 pups (36 females and 40 males) were from western Alaska and the other 136 (63 females and 73 males) were from the Russian Far East. Concentrations of summation SigmaPCBs in the whole blood of pups from western Alaska ranged from 0.21 to 13 ng/g wet weight with a mean of 2.1+/-0.27 ng/g wet weight. In the Russian animals, summation SigmaPCB concentrations in the whole blood of pups ranged from 0.33 to 36 ng/g wet weight with a mean of 4.3+/-0.44 ng/g wet weight. summation SigmaDDT concentrations in the whole blood of pups from western Alaska ranged from 0.18 to 11 ng/g wet weight with a mean of 1.6+/-0.23 ng/g wet weight. In Russia, summation SigmaDDT in the whole blood of pups ranged from undetectable to 26 ng/g wet weight with a mean of 3.3+/-0.36 ng/g wet weight. Average OC concentrations were significantly higher in the blood of Russian animals compared to western Alaska (for PCBs and DDTs, p<0.001) and in both areas females had higher concentrations than males. Male pups from western Alaska had significantly lower levels of summation SigmaPCBs and summation SigmaDDT when compared to male pups from Russia (for PCBs and DDTs p<0.001). Female pups from western Alaska were significantly lower in summation SigmaPCBs than Russian female pups (for PCBs p=0.009) as were female pups for summation SigmaDDT levels between areas (for DDTs p=0.026). OC contaminants data indicate that Steller sea lion pups have measurable concentrations of these synthetic chemicals. While any physiological effect and the specific role these chemicals may have in either the decline or the failure of the endangered Steller sea lion population to recover needs to be further investigated, this study indicates specific areas and animals that may be most at risk.     

Geographic variation of chlorinated pesticides,toxaphenes and PCBs in human milk from sub-arctic and arctic locations in Russia

The concentrations of HCB, alpha-, beta- and gamma-HCH, 3 chlordanes (CHLs), p,p'-DDE, p,p'-DDD, p,p'-DDT, and 30 PCBs (polychlorinated biphenyls) were determined in 140 human milk samples from Kargopol (n=19), Severodvinsk (n=50), Arkhangelsk (n=51) and Naryan-Mar (n=20). Pooled samples were used for determination of three toxaphenes (chlorobornanes, CHBs). The concentrations of HCB, beta-HCH and p,p'-DDE in Russian human milk were 2, 10 and 3 times higher than corresponding levels in Norway, respectively, while concentrations of sum-PCBs and sum-TEQs (toxic equivalent quantities) of the mono-ortho substituted PCBs were in the same range as corresponding levels in Norway. The PCB-156 contributed most to the sum-TEQs. Highest mean concentrations of HCB (129 microg/kg milk fat) and sum-PCBs (458 microg/kg milk fat) were detected in Naryan-Mar, while highest mean concentrations of sum-HCHs (408 microg/kg milk fat), sum-CHLs (48 microg/kg milk fat), sum-DDTs (1392 microg/kg milk fat) and sum-toxaphenes (13 microg/kg milk fat) were detected in Arkhangelsk. An eastward geographic trend of increasing ratios of alpha/beta-HCH, gamma/beta-HCH, p,p'-DDT/p,p'-DDE and PCB-180/28 was observed. In all areas the levels of sum-HCHs decreased with parity (number of children born). Considerable variation in levels of the analysed organochlorines (OCs) was found in all the studied areas. Breast milk from mothers nursing their second or third child (multiparas) in Naryan-Mar showed a significant different PCB profile compared to mothers giving birth to their first child (primiparas) from the same area and to primi- and multiparas in the other areas. Both p,p'-DDE and p,p'-DDT showed a significant, but weak, negative correlation with the infants birth weight.     

Organochlorines in the free-ranging Hawaiian monk seal (Monachus schauinslandi) from French Frigate Shoals, North Pacific Ocean

The Hawaiian monk seal (Monachus schauinslandi) is an endangered species found only in the Hawaiian Island chain. The largest subpopulation, at French Frigate Shoals, has been in decline since 1989. In order to assess organochlorine (OC) levels in the Hawaiian monk seals, whole blood and blubber samples were collected in 1999 from 46 free-ranging Hawaiian monk seals at French Frigate Shoals, and were analyzed for eight dioxin-like polychlorinated biphenyls (PCBs) as well as six other PCB congeners, DDT and DDT metabolites. Average levels of the total PCBs in blood samples from adult male, juvenile and reproductive female groups were 4800, 4000 and 3000 ng/g lipid wt., respectively, whereas 3200, 1300 and 1200 ng/g, respectively, in blubber from the three corresponding groups. p,p'-DDE was the only DDT detected in blubber samples, and no DDTs were detected in blood samples. Concentrations of the total PCBs in adult males were significantly higher than the levels measured in either reproductive females or juveniles. There were significant correlations between age and blubber p,p'-DDE, estimated mass and total blood PCBs or blubber p,p'-DDE, and body condition and total blood PCBs. Although it is clear that the Hawaiian monk seal has been exposed to OCs, it is unclear what biological effects, if any, these xenobiotics may have on the animals.     

Ratio variation of congener profiles of PCDD/Fs and dioxin-like PCBs in human milk during lactation

This study investigates the compositional variations, changes in concentrations and contribution of particular congeners of PCDDs, PCDFs, non-ortho PCBs and mono-ortho PCBs in human milk from two mothers sampled during the 12-month lactation period. Total PCDD/F and dioxin-like PCB concentration in milk sampled from the primiparous mother on day 5 after delivery was 37 pg TEQ/g fat, and this value decreased significantly by 43% at 12 months. In milk sampled from the multiparous mother nursing her second child on day 5 after delivery was 12 pg TEQ/g fat, and this value decreased by 40% at 12 months. The decrease was statistically significant not for PCDD/Fs, but for dioxin-like PCBs. The ratio variance of the congener profiles of PCDD/Fs and dioxin-like PCBs in the milk remained similar during lactation. Moreover, the congener profiles of PCDD/Fs and dioxin-like PCBs in the milk showed similar percentages for both mothers independent of the lactation event and the number of previous births. The mean daily intake of dioxins by the infant nursed by the primiparous mother and the infant nursed by the multiparous mother up to six months of age was 140 and 46 pg TEQ/kg body weight, respectively. From seven to twelve months of age, the mean daily intake was 37 and 13 pg TEQ/kg body weight, respectively. Both values decreased by approximately 70%. The reasons why the mothers' body burden of dioxins decreased by breastfeeding and why the infants' daily intake of human milk per body weight decreased as the infant grows older consequently decreased were considered.     

Bioaccumulation of PCBs and chlorinated pesticides in seals,fishes and invertebrates from the White Sea,Russia

Persistent organochlorines (OC) contaminants, including polychlorinated biphenyl (PCB) congeners, Dichlorophenyltrichloroethane (DDT)- and chlordane (CHL) related compounds, hexachlorocyclohexanes (HCH) isomers and chlorobenzenes (CBz) were determined in blubber of harp seals (Phoca groenlandica), ringed seals (Phoca hispida) and bearded seals (Eringnathus barbatus) as well as in fishes and invertebrates from the White Sea, in northwest Russia. Highest summation operator PCB and summation operator DDT concentrations were found in samples from two male bearded seals (means of 4150 ng/g lw and 3950 ng/g lw, respectively). Female harp seals had mean summation operator PCB and summation operator DDT concentrations of 1070+/-504 ng/g lw and 619+/-328 ng/g lw, respectively. Male and female adult ringed seals had similar mean summation operator PCB concentrations as harp seals (955+/-385 ng/g lw and 999+/-304 ng/g lw, respectively). summation operator CHL concentrations ranged from 63+/-29 ng/g lw in blubber of female adult ringed seals, to 322+/-156 ng/g lw in adult harp seals and averaged 465 ng/g lw in bearded seals. HCH isomers, mirex and chlorobenzenes were detected in all seal samples but were present at lower levels than summation operator CHL, summation operator DDT and summation operator PCB. Concentrations of summation operator CHL, summation operator DDT and summation operator PCB in ringed seals from the White Sea were within the range reported for the Barents Sea but lower than in ringed seals from the Kara Sea. Temporal trends were investigated by comparing concentrations of OCs in blubber of harp seal pups collected in 1992 with pups of the same age collected in 1998. The declines over the 6 year period ranged from approximately 33% for summation operator DDT to 60% for summation operator PCB. These declines are consistent with reports of declining concentrations summation operator DDT in seawater from the White Sea and inflowing rivers in the 1980's and early 1990s. The major OC contaminants in fishes from the White Sea were DDT-related compounds and PCBs. Navaga (Eleginus navaga) had the highest concentrations of the 5 fish species studied with mean summation operator PCB of 41+/-6 ng/g wet wt. while lowest mean concentrations were present in cod muscle (16+/-8 ng/g ww). Concentrations of hexachlorobenzene (HCB), DDT, CHL-related compounds and PCB congeners were strongly correlated with trophic level of the organisms assigned using delta(15)N values, while beta-HCH, gamma-HCH and cis-chlordane showed no relationship with trophic level. Food web magnification factors (FWMFs) for p,p'-DDE, alpha-HCH, oxychlordane and trans-nonachlor the White Sea were similar to those from marine food webs in the Barents Sea and the Canadian arctic, while FWMFs for HCB and PCBs were generally lower. Overall the results suggest that the White Sea marine food differs in terms of the availability of contaminants in comparison to studies of open ocean arctic food webs due to proximity to urban/industrial areas and greater importance of benthic food sources.     

Accumulation and distribution of organochlorines (PCBs and DDTs) in various organs of Stenella coeruleoalba and a Tursiops truncatus from Mediterranean littoral environment (France)

The objective of the present study is to determine the levels of contamination by PCBs, DDT and its metabolites in dolphins failed on the coasts of the Mediterranean sea. Samples are represented by six Stenella coeruleoalba and a Tursiops truncatus collected in 2000 and 2003. The studies are achieved on the blubber, the heart, the liver, the kidney, the muscle and the lung. The concentrations of PCBs and DDT are very high in all tissues and organs analyzed. For the PCBs, the concentrations vary between 43,838 and 110,343 microg/kg lipid basis in the blubber, 601 and 39444 microg/kg dried weight in the liver, 1375 and 34512 microg/kg dried weight in the muscle, 3151 and 17082 microg/kg dried weight in the heart, 674 and 12365 microg/kg dried weight in the kidney and finally between 648 and 4118 microg/kg dried weight in the lung. These values are comparable to those previously obtained in our laboratory and by other authors during the years 1990 on the Mediterranean environment. Significant differences in concentrations are noted in tissues and organs, neither according to the age, nor according to the gender. In all the analyzed samples, the contents in PCBs are higher than those of DDT. The average ratios of pp'-DDE/SigmaDDT are close to 0.6 which shows the metabolization of these compounds along the years. The examination of the profiles of congeners shows that the hexachlorinated molecules are dominating in all tissues and organs which supposes the different animals were especially exposed to Pyralen-type compounds of transformer (Dp6).     

Determination of dioxins and polychlorinated biphenyls in breast milk, maternal blood and cord blood from residents of Tohoku, Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are bioaccumulative chemicals that are considered to be toxic contaminants based on several epidemiological studies. To elucidate exposure levels of these chemicals in the present study, concentrations of PCDD/DFs, dioxin-like PCBs (DL-PCBs) and PCBs in breast milk, maternal blood and cord blood obtained from the same participants registered in a birth cohort study in Tohoku, Japan, were measured. Congener-specific analysis revealed several differences in minor congeners of these compounds among the three specimen types, although major congeners were detected in the specimens. The toxicity equivalence quantity concentrations (1998 WHO-TEF) and PCBs in breast milk, maternal blood and cord blood on the whole and on a lipid basis were in the order of breast milk > maternal blood > cord blood. Pearson's correlation coefficients of TEQs and total PCBs among the three specimens were high, with the correlation coefficient of TEQ between breast milk and maternal blood being the highest (r=0.94, p<0.001). On the other hand, the TEQ between breast milk and cord blood was the lowest (r=0.79, p<0.001). Pearson's correlation coefficient between the TEQ and PCBs in each specimen was also high (r=0.82-0.95, p<0.001). The associations of chemical concentrations with maternal age, parity, fish intake, BMI and the rate of body weight increase during pregnancy were analyzed with multiple linear regression analysis. TEQ concentrations and PCBs were negatively associated with parity (p<0.05), and maternal age was positively associated with PCBs (p<0.05). However, the associations with BMI and fish intake during pregnancy were not significant. These results suggest that parity is an important factor affecting the concentrations of dioxins and PCBs in these specimens.     

Fish intake and serum levels of organochlorines among Japanese women

This study evaluates background serum levels of selected organochlorine compounds among Japanese women of reproductive age and investigates whether lifestyle factors, especially dietary factors, may be associated with these levels. A cross-sectional study was performed on 80 Japanese women, aged 26-43 years, who complained of infertility and were confirmed not to have endometriosis. The serum levels of total toxic equivalency (TEQ), 18 polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs), 4 coplanar polychlorinated biphenyls (cPCBs), 36 ortho-substituted polychlorinated biphenyls (PCBs), and 13 chlorinated pesticides or their metabolites were measured and data were collected on the women's age, residence, occupation, body mass index (BMI), smoking and alcohol habit and 6 dietary intakes (fish, meats, rice, vegetables, fruits and dairy products). The serum median level of total TEQ was 25.1 pg TEQ/g lipid, that of PCDDs/PCDFs/cPCBs was 11.5 pmol/g lipid, that of PCBs was 0.46 nmol/g lipid, and that of total pesticides was 1.32 nmol/g lipid. The serum levels of total TEQ, PCDDs/PCDFs/cPCBs, PCBs and pesticides were positively associated with age (P for trend=0.003, 0.01, 0.005 and 0.01, respectively) and frequent fish consumption (P for trend=0.002, 0.003, 0.0003 and 0.006, respectively). Other lifestyle factors were not associated with serum organochlorine levels. The present study suggests that Japanese women who consume fish frequently in their reproductive period tend to accumulate organochlorines in their bodies.     

Polychlorobiphenyls (PCBs), polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs) in human milk, blood and adipose tissue

Persistent and toxic chemicals such as polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans are able to accumulate in human tissues, especially in fats. In recent years PCBs have frequently been detected in human milk, blood and adipose tissue from the general population and levels in different tissues correspond to the fat content of the samples. In recent years the very rapid development of analytical methods and the lowering of detection limits have resulted in the detection of PCDDs and PCDFs in human tissues from the general population. The levels of PCBs are approximately 10,000 times higher than the sum of the levels of PCDDs and PCDFs, but the latter substances are much more toxic. Accidental or occupational exposures have resulted in much higher tissue levels in exposed individuals than in the general population. The relatively high levels in breast milk result in very high daily intakes of such chemicals by breast-fed infants, and a potential hazard to this risk group. The origin of the residues seems mainly to be environmental pollution from waste disposal, incineration or other high-temperature operations.     

Prenatal exposures to persistent organic pollutants as measured in cord blood and meconium from three localities of Zhejiang, China

Prenatal exposures to persistent organic pollutants were assessed using the levels of PCBs and organochlorine pesticides (OCPs) measured in cord blood and meconium samples from Luqiao and two other localities of the Zhejiang province in China. Luqiao is a town with the largest site for disassembly of PCB-containing obsolete transformers and electrical waste in China. The other two localities Pingqiao (100 km NW of Luqiao) and Lin'an (500 km NW of Luqiao) are towns without known electronic or electrical waste sites. A total of 23 PCB congeners (including 12 dioxin-like) and 6 OCPs were measured using the traditional GC-muECD technique. Micro-EROD bioassay was additionally used to measure TCDD-based TEQ levels of the 12 dioxin-like PCBs. Significant correlations were found between the TEQs measured by the two methods, supporting the application of micro-EROD as a practical tool for complementing the chemical analysis. The data showed that beta-HCH, p,p'-DDE, and 6 PCB congeners (101, 138, 153, 180, 183, and 187) were the predominant pollutants, with PCB138 being the best indicator (predictor) for total PCB levels. Cord blood and meconium from Luqiao have higher levels of PCBs than those from the other two localities, suggesting that a disassembly site for electronic and electric waste would provide an environment for greater exposure to these chemicals. The cord blood or meconium levels of beta-HCH, though likewise considerably high, were comparable in the three localities. Similar findings were observed for p,p'-DDE. Pollution by these OCPs might have come from past use of agricultural pesticides in the three localities.     

Characterization of aryl hydrocarbon receptor agonists in sediments of Wenyu River, Beijing, China

Aryl hydrocarbon receptor agonistic (Ah-agonistic) effects of 23 sediments from Wenyu River in Beijing, China were evaluated using the H4IIE cell bioassay. Five samples were selected for chemical analysis of most concerned Ah-agonists, i.e. polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). All raw sediment extracts induced significant Ah-agonistic effects, and the bioassay-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents of raw extracts (TEQ_raws) ranged from 8.5 to 336.0 pg/g dry weight (dw). Chemical analysis-derived TEQs (TEQ_chems) ranged from 20.5 to 64.8 pg/g dw. When raw extracts were purified by sulphuric acid silica gel column to derive acid stable fraction, the TCDD equivalents in this fraction (TEQ_stables) ranged from 2.7 to 63.8 pg/g dw. PCBs, PCDDs and PCDFs contributed about 51.4-72.1%, 1.2-7.3%, and 16.4-34.8% of TEQ_stables, respectively, and the sum was 69.1-108.6%. Therefore, about 65.0% of TEQ_raws could be attributed to acid labile fraction and only 3.3-9.6% to PAHs. These observations suggested that acid stable fraction and labile fraction contributed together to total Ah-agonistic effects in the sediments, and PCBs and PCDFs might be the two main components in acid stable Ah-agonists. The proposed approach using both H4IIE cell bioassay and chemical analysis could be used for characterization and prioritization of Ah-agonists in river sediments and helpful to the following progression of ecological remediation.     

A source inventory and budget for chlorinated dioxins and furans in the United Kingdom environment.

Polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs) are ubiquitous in the environment. This paper estimates the present UK environmental loading of PCDD/Fs in soils, vegetation, air, water and sediments. Greater than 95% of the estimated total PCDD/F loading of 5.7 t in the UK environment is present in surface soils. Annual emissions from known primary sources of PCDDs and PCDFs are estimated. The most important of these include: municipal waste incinerator stack emissions (10.9 kg sigma PCDD/F per annum); industrial (7.7 kg/year) and domestic (5.1 kg/year) combustion of coal; clinical waste incinerators (1.7 kg/year); volatilisation from chlorophenol-treated substrates (1.7 kg/year) and combustion of leaded petrol by motor vehicles (0.7 kg/year). These sources are generally easy to define and reasonably reliable national estimates can be obtained. More difficult to quantify are secondary releases from the large UK stock of pentachlorophenol (PCP) and PCP-treated products, which may represent quantitatively one of the most important sources of total PCDD/Fs to the environment. Estimates of homologue-specific emissions indicate that combustion processes represent a far more significant source of tetra and penta CDD/Fs than do chlorophenols, which in turn constitute a greater source of hepta- and octachlorinated congeners. Direct emission of PCDD/Fs into the atmosphere from combustion processes facilitates their atmospheric transport to remote locations. This, coupled with the diffuse nature of combustion processes, means that the effects of PCDD/F contamination originating from anthropogenic combustion are more widespread than those from the use and disposal of chlorophenols. Contamination from chlorophenols will be more localised, owing to the insignificance of direct atmospheric release pathways for this source. Although there is reasonable agreement between the estimated current annual flux and the present UK environmental loading of PCDDs and PCDFs, a large discrepancy exists between the sum of the annual contributions from primary sources and this annual flux. Whilst the existence of an as yet unidentified source or sources or gross underestimates of known sources cannot be excluded, it is proposed that much of this discrepancy may be accounted for by secondary releases from the use and disposal of chlorophenols and the long-range transport, continued remobilisation and subsequent redeposition of PCDDs and PCDFs already present in the environment. Despite limited evidence for a modest decline in levels of PCDDs and PCDFs in some environmental compartments over the last 20 years, the environmental persistence of these chemicals means that they will remain in the UK environment for the foreseeable future despite recent action to curb primary emissions.     

Decabromodiphenyl ether (BDE-209) enters the food web of the River Po and is metabolically debrominated in resident cyprinid fishes

Decabromodiphenyl ether (BDE-209), the primary constituent of a widely used flame retardant formulation, is present at relatively high levels in sediments and macroinvertebrates of the River Po. Since it was demonstrated that BDE-209 can be biotransformed to smaller and more toxic polybrominated dipheyl ethers (PBDEs), the main objective of this study was to assess whether the large quantities of BDE-209 present in the River Po are bioavailable to the higher levels of the food web and are biotransformed in feral fishes. To this aim, 23 cyprinids, mainly common carp, were analysed for the hepatic contents of PBDEs. Contrary to sediments and invertebrates of the same area, no fish sample contained detectable levels of BDE-209. All fishes contained typical PBDE representatives, e.g. BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154, but more importantly they contained three congeners, i.e. BDE-179, BDE-188 and BDE-202, which are not present in any technical formulations and are known products of BDE-209 debromination in fish. The age of carps had no effects on the bioaccumulation of PBDEs. Conversely, the contents of PCBs, which also were determined in the same fish samples, showed a positive correlation with age. Both groups of chemicals displayed a tendency to a higher contamination in male fish. This study shows that BDE-209 enters the food web of the River Po contributing to the load of lower brominated PBDEs and thus to the load of chemical stressors threatening the aquatic life of the major Italian watercourse.     

Bioaccumulation of polybrominated diphenyl ethers and hexabromocyclododecane in the northwest Atlantic marine food web

Seven species of teleost fishes comprising major prey of northwest Atlantic harbor seals were analyzed for polybrominated diphenyl ethers (PBDEs). PBDE concentrations in whole fish samples (n = 87) were compared with those measured previously in harbor seal blubber to evaluate the transfer of PBDEs from prey to predator. Hexabromocyclododecane (HBCD) concentrations were measured in three fish species to provide an initial estimation of HBCD contamination in this ecosystem. HBCD was detected in 87% of the fish samples at concentrations ranging from 2.4 to 38.1 ng/g, lw (overall mean 17.2 ± 10.2 ng/g, lw). ∑PBDE concentrations in fish ranged from 17.9 to 94 ng/g, lw (overall mean 62 ± 34 ng/g, lw). ∑PBDE concentrations in the harbor seals were two orders of magnitude higher than levels in the fish. Biomagnification factors (BMFs) from fish to seals averaged from 17 to 76, indicating that tetra- to hexa-BDEs are highly biomagnified in this marine food web. BDE-47 was the dominant congener in all samples, suggesting exposure to the penta-BDE mixture. The presence of higher brominated congeners including BDE-209 at measurable levels in fish and seal tissue, along with the very high biomagnification of BDE-153, as well as − 155, and − 154, suggests recent exposure to the octa- and deca-BDE formulations in this US coastal marine food web, as well as the additional contribution of BDE-209 debromination in fish to the loading of persistent PBDEs in the seals. This is the first study to report the occurrence of BDE-209 and other higher BDEs in commercially important marine fishes from the northwest Atlantic.     

Seasonal and temporal trends in polychlorinated biphenyls and organochlorine pesticides in East Greenland polar bears (Ursus maritimus), 1990-2001

Persistent organochlorine (OC) contaminants (PCBs, DDTs, chlordanes (CHLs), dieldrin, hexachlorocyclohexanes (HCHs), chlorobenzenes (CBzs)) were determined in adipose tissue of 92 polar bears (Ursus maritimus) sampled between 1999 and 2001 in central East Greenland (69 degrees 00'N to 74 degrees 00'N). OC data were presented from subadults (S: females: x 5 years and males: x 6 years), adult females (F: x 5 years) and adult males (M: x 6 years). Summed chlorobiphenyl (SigmaCBs) concentrations (41 congeners including co-eluters), SigmaCHLs and SigmaDDTs were the dominant classes of OCs. SigmaCBs concentrations were found to be 6470, 8240 and 9100 ng/g lipid weight (lw) i subadults, adult females and adult males, respectively. The corresponding figures were: 2010 (S), 2220 (F) and 1710 (M) ng/g lw for SigmaCHLs and 462 (S), 462 (F) and 559 (M) ng/g lw for SigmaDDTs. The dominant CB congeners were CB153 (32.3%), CB180 (21.4%), CB170 (12.2%) and CB138 (11.0%). The metabolite p,p'-DDE (88.2%) dominated the SigmaDDTs, while oxychlordane was the dominant (57.1%) CHL-related compound. Concentrations of SigmaCBs, SigmaCBzs, SigmaDDTs, mirex and dieldrin were highest in adult males, whereas concentrations of SigmaHCHs were lower than in adult females but not than those in subadults. Adult females had the lowest concentrations of SigmaCBzs, mirex and dieldrin. Concentrations of SigmaCHLs were lowest in adult males, intermediate in subadults and highest in adult females. SigmaCB, SigmaHCH and SigmaCHL concentrations showed high seasonal variability in adult females but remained relatively constant in adult males and subadults. In general, the OC levels in females appeared to be highest in March and lowest in January or September. Concentrations of SigmaCBzs and dieldrin showed seasonal variability in all three groups, with a maximum in March in adult females. SigmaCBz concentrations in adult males and subadults of both sexes peaked in April-July, and dieldrin concentrations peaked in April-July in subadults, but not until August in adult males. SigmaDDT concentrations increased from January to a maximum in April-July for subadults and in August for adults. Temporal trends within the last decade were examined by comparing the present data to the concentrations reported in samples from 1990 from the same region. SigmaCB, p,p'-DDE and SigmaHCH concentrations in 1999-2001 were 22.1%, 66.3% and 39.3% lower than the 1990 concentrations, respectively. in contrast, SigmaCHL and dieldrin concentrations showed differences amongst sex and age groups in the temporal trends, where present concentrations are between 24.4% to 69.3% and 27.0% to 69.0% lower, respectively, relative to the 1990 levels. However, power analysis suggested that firm conclusions could not be drawn regarding the general time trend based on these two sampling periods. The range of half-lives of the various OC classes were estimated to lie between 4.5 and 20.6 years depending on the age and sex groups considered.     

Artificial-turf playing fields: contents of metals, PAHs, PCBs, PCDDs and PCDFs, inhalation exposure to PAHs and related preliminary risk assessment

The artificial-turf granulates made from recycled rubber waste are of health concern due the possible exposure of users to dangerous substances present in the rubber, and especially to PAHs. In this work, we determined the contents of PAHs, metals, non-dioxin-like PCBs (NDL-PCBs), PCDDs and PCDFs in granulates, and PAH concentrations in air during the use of the field. The purposes were to identify some potential chemical risks and to roughly assess the risk associated with inhalation exposure to PAHs. Rubber granulates were collected from 13 Italian fields and analysed for 25 metals and nine PAHs. One further granulate was analysed for NDL-PCBs, PCDDs, PCDFs and 13 PAHs. Air samples were collected on filter at two fields, using respectively a high volume static sampler close to the athletes and personal samplers worn by the athletes, and at background locations outside the fields. In the absence of specific quality standards, we evaluated the measured contents with respect to the Italian standards for soils to be reclaimed as green areas. Zn concentrations (1 to 19 g/kg) and BaP concentrations (0.02 to 11 mg/kg) in granulates largely exceeded the pertinent standards, up to two orders of magnitude. No association between the origin of the recycled rubber and the contents of PAHs and metals was observed. The sums of NDL-PCBs and WHO-TE PCDDs + PCDFs were, respectively, 0.18 and 0.67 × 10^− 5 mg/kg. The increased BaP concentrations in air, due to the use of the field, varied approximately from < 0.01 to 0.4 ng/m³, the latter referring to worst-case conditions as to the release of particle-bound PAHs. Based on the 0.4 ng/m³ concentration, an excess lifetime cancer risk of 1 × 10^− 6 was calculated for an intense 30-year activity.     

PCDD/Fs and dioxin-like PCBs in home-produced eggs from Belgium: Levels, contamination sources and health risks

This paper discusses the dioxin TEQ levels as determined by the chemically activated luciferase gene expression assay (CALUX) and by HRGC-HRMS in eggs, soils, faeces and kitchen waste samples obtained in the CONTEGG study. The samples were collected in each Belgian province at private homes and in small gardens where chickens are held. The CALUX levels for eggs sampled in autumn were higher than the levels in eggs obtained at the same locations in spring (median values of 5.86 and 4.08 pg CALUX TEQ/g fat, respectively). The total WHO-TEQ levels in eggs, determined by HRGC-HRMS, ranged from 3.29 to 95.35 pg TEQ/g fat in autumn and from 1.50 to 64.79 pg TEQ/g fat in spring. In the soils on which the chickens forage, levels of 2.51-11.35 pg I-TEQ/g in autumn and 2.00-7.86 pg I-TEQ/g in spring were found. The congener pattern of PCDD/Fs in the eggs, soils and faeces was dominated by OCDD, in addition to 1,2,3,4,6,7,8-HeptaCDD, OCDF and 1,2,3,4,6,7,8-HeptaCDF. The predominant dioxin-like PCBs were PCB118, PCB 105 and PCB 156. The dioxin-like PCBs contributed on average 47%, 14% and 20% to the total WHO-TEQ in eggs, soils and faeces, respectively. Kitchen waste samples were very low-contaminated with dioxin-like compounds. The present results showed a good agreement between egg and soil TEQ levels for PCDD/Fs but not for dioxin-like PCBs. This study showed that current soil levels found in some private gardens do not lead to egg levels below the current EU maximal level of 6 pg total TEQ/g fat for dioxins and dioxin-like PCBs. The consumers of the analysed eggs attained 5-79% of the tolerable weekly intake (TWI) of 14 pg TEQ/kg bw for dioxins and dioxin-like PCBs by exposure to their home-produced eggs only.