Anuschka Polder

Chlorinated hydrocarbons in glaucous gulls (Larus hyperboreus) in the southern part of Svalbard

Abstract In 1989, a number of glaucous gulls ( Larus hyperboreus ) were found dead near a seabird cliff at south Svalbard. In an effort to clucidate the course of death, 12 individuals were sent to the Central Veterinary Institute for autopsy and analysis of chlorinated pesticides and polychlorinated biphenyls (PCBs) in samples of liver, kidney, brain and muscle. Eggs of common and Bru¨nnichs guillemots constitute important food for glaucous gulls during the nestling period, thus 13 eggs (3 eggs from common and 10 eggs from Bru¨nnichs guillemots) from the same area were also analyzed for organochlorines. The autopsy of the birds did not reveal any specific cause of death. The following chlorinated pesticides were analyzed: hexachlorobenzene (HCB), hexachlorocyclohexanes (α-, β-, γ-HCH), chlordanes (oxychlordane, trans -nonachlor, heptachlor and heptachlor epoxide), the drin group (aldrin, dieldrin) and the DDT group ( o,p′, p,p′DDT, DDD and DDE). Relatively low hepatic concentrations of dieldrin were found (n.d.−0.17 mg/kg wet weight (w.w.), mean 0.04), ∑HCH (n.d.−0.14 mg/kg w.w., mean 0.02), HCB (0.03-1.01 mg/kg w.w., mean 0.51), oxychlordane (0.01-1.85 mg/kg w.w., mean 1.05), p,p′DDE (0.81-5.41 mg/kg w.w., mean 2.98), o,p′DDD (0-0.52 mg/kg w.w., mean 0.14) and ∑DDT (0.9-6.25 mg/kg w.w., mean 2.92). Levels of the other chlorinated pesticides were below the quantification level. Very high concentrations of PCBs were found. The ∑PCB (sum of wet weight concentrations of the 21 individual congeners, the IUPAC nos. 28, 52, 74, 99, 101, 110, 118, 114, 153, 105, 141, 138, 183, 128, 187, 156, 157, 180, 170, 194 and 209) in hepatic tissue was 0.8–32.3 mg/kg w.w. (mean 16.0), in brain 0.9–29.5 mg/kg w.w. (mean 14.8), in kidney 0.4–21.4 mg/kg w.w. (mean 9.7) and in muscle 0.5–6.0 mg/kg w.w. (mean 3.1). The concentrations of the individual PCB congeners are also given. Relatively low concentrations of all the organochlorines were found in guillemot eggs, mean concentrations of ∑DDT and PCBs were 0.25 and 0.47 mg/kg w.w., respectively. A toxicological evaluation of the PCB results is difficult; however, it cannot be excluded that PCBs might have contributed to the death of the gulls.

Levels and temporal trends of chlorinated pesticides, polychlorinated biphenyls and brominated flame retardants in individual human breast milk samples from Northern and Southern Norway.

Human breast milk samples from primipara women from Northern (Tromsø) (N=10) and Southern Norway (Oslo) (N=19) collected in 2000-2001 were analysed with respect to hexachlorobenzene (HCB), hexachlorocyclohexane (HCHs), chlordanes (CHLs), DDTs, mirex, toxaphenes (CHBs), polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCD). CHBs, PBDEs and HBCD were only analysed in the Tromsø samples. Sum-PCBs and sum-DDTs were the major organochlorines (OCs) (170 and 110 ng g(-1) lipid weight (lw), respectively). Other OCs were found in levels of approximately 10- to 300-fold lower than sum-PCBs. Overall, the concentrations of OCs followed the decreasing order of PCBs>DDTs>HCB>HCHs approximately CHLs>CHBs>mirex. Concentrations of sum-HCHs were significantly higher in breast milk from Oslo compared to Tromsø (p<0.05). The PCB profile was dominated by PCB-153, -138 and -180. The PBDE pattern was dominated by PBDE-47 and PBDE-153. The median level of sum-PBDEs was 4.1 ng g(-1) lw. PBDE-209 was detected in all analysed samples (median 0.13 ng g(-1) lw). The estimated daily intake (EDI) for the median (range) of sum mono-ortho (mo) PCBs(8) was 3.7 (1-9) pg TEQ kg(-1) body weight per day for breast fed infants in Norway. This exceeded the TDI by a factor of 1.8 (1-4) based only on intake of mono-ortho PCBs. The present study shows that concentrations of OCs in primipara breast milk have decreased 50-60% since 1991, and that this trend is continuing.

Human health risk associated with brominated flame-retardants (BFRs)

The purposes of this review are to assess the human exposure and human and experimental evidence for adverse effects of brominated flame-retardants (BFRs) with specific focus on intake from seafood. The leakage of BFRs from consumer products leads to exposure of humans from fetal life to adulthood. Fish and fish products contain the highest levels of BFRs and dominate the dietary intake of frequent fish eaters in Europe, while meat, followed by seafood and dairy products accounted for the highest US dietary intake. House dust is also reported as an important source of exposure for children as well as adults. The levels of BFRs in the general North American populations are higher than those in Europe and Japan and the highest levels are detected in infants and toddlers. The daily intake via breast milk exceeds the RfD in 10% of US infants. BFRs including PBDEs, HBCDs and TBBP-A have induced endocrine-, reproductive- and behavior effects in laboratory animals. Furthermore, recent human epidemiological data demonstrated association between exposure to BFRs and similar adverse effects as observed in animal studies. Fish including farmed fish and crude fish oil for human consumption may contain substantial levels of BFRs and infants and toddlers consuming these products on a daily basis may exceed the tolerable daily intake suggesting that fish and fish oil alone represent a risk to human health. This intake comes in addition to exposure from other sources (breast milk, other food, house dust). Because potential harmful concentrations of BFRs and other toxicants occur in fish and fish products, research on a wider range of products is warranted, to assess health hazard related to the contamination of fish and fish products for human consumption.

Polybrominated diphenyl ethers and HBCD in bird eggs of South Africa

In this paper, the first data on brominated flame retardants (BFRs), in particular polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in eggs of bird species from South Africa are described (N=43). Concentrations of PBDEs were detected in all the studied species and in all the geographic areas. Highest concentrations of PBDEs were measured in bird eggs from the Vaal River, which is situated downstream of the most industrialized area in South Africa. Sum-PBDE concentrations were highest in eggs of one African sacred ibis (396 ng g(-1) lipid weight (lw)), possibly due to foraging on dumping sites. Lowest mean level of sum-PBDEs (2.3 ng g(-1) lw) was measured in cattle egrets (N=11) from Barberspan Sanctuary, a Ramsar site. The PBDE congener pattern showed large differences, reflecting different trophic levels, migratory behavior, distance to the source, and, exposure to different PBDE mixtures, among others. HBCD was detected only in four species, and highest levels were measured in one egg of African sacred ibis (71 ng g(-1) lw). In most species, levels of PBDEs were one to several orders of magnitude lower than levels of DDTs and PCBs. PBDEs correlated strongly with DDTs, PCBs and some other organochlorines (OCs), indicating the same source. The widespread occurrence of PBDEs in the South African avian species showed a strong need for further investigations of PBDEs in the Southern African environment.

Levels and patterns of Persistent Organic Pollutants (POPS) in selected food items from Northwest Russia (1998–2002) and implications for dietary exposure

Residues of persistent organic pollutants (POPs) were analysed in 70 selected food items from Northwest Russia in 1998-2002. Levels of PCBs ranged from 0.2 to 16ng/g wet weight (ww) in dairy products and fats, 0.2 to 23ng/g ww in meat products, 0.5 to 16ng/g ww in eggs and 0.3 to 30ng/g ww in fish. High levels of DDT (16ng/g ww) were found in locally produced butter from Kola Peninsula, in pork fat from Arkhangels region (10 to 130ng/g ww) and in some fish samples from White Sea and Kargopol region (17 and 30ng/g ww). Findings of low DDE/DDT ratios in many of the studied food items indicated recent contamination to DDTs. Mean levels of sum TEQs(WHO1998) of dioxin-like mono-ortho PCBs: PCBs 105, 118, 156 and 157 (∑mo-PCBs-TEQs(WHO1998)) were highest in dairy products, chicken eggs and fish, with levels of 0.292, 0.245 and 0.254pg/g ww, respectively. The estimated daily intake (EDI) for ∑mo-PCBs-TEQs(WHO1998) was 0.74pg/kgbw/day and in the same range as in Sweden and Denmark. Fish, dairy products, eggs and meat were the main contributors to the EDI of ∑mo-PCBs-TEQs(WHO1998). The EDIs of DDTs, HCHs and HCB were several times higher than in Sweden and Denmark. Consumption of meat and poultry were important sources for intake of DDTs and HCHs, respectively. Contamination of animal feed and agricultural practice were assumed the most important causes for the results in the present study. However, increased control on maximum residue levels in food and feed may have resulted in large changes on levels and patterns of POPs in food in the studied areas.

Increasing levels of long-chain perfluorocarboxylic acids (PFCAs) in Arctic and North Atlantic marine mammals, 1984-2009

Temporal variations in concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs), including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) structural isomers, were examined in livers of pilot whale (Globicephala melas), ringed seal (Phoca hisida), minke whale (Balaenoptera acutorostrata), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), Atlantic white-sided dolphin (Lagenorhynchus acutus) and in muscle tissue of fin whales (Balaenoptera physalus). The sampling spanned over 20 years (1984-2009) and covered a large geographical area of the North Atlantic and West Greenland. Liver and muscle samples were homogenized, extracted with acetonitrile, cleaned up using hexane and solid phase extraction (SPE), and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). In general, the levels of the long-chained PFCAs (C9-C12) increased whereas the levels of PFOS remained steady over the studied period. The PFOS isomer pattern in pilot whale liver was relatively constant over the sampling years. However, in ringed seals there seemed to be a decrease in linear PFOS (L-PFOS) with time, going from 91% in 1984 to 83% in 2006.

PCDDs, PCDFs, and PCBs in human milk from different parts of Norway and Lithuania

Concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) as well as 16 polychlorinated biphenyls (PCBs) have been determined in pooled samples of breast milk from 10-12 mothers living in three different geographical areas in both Norway and Lithuania. The results indicate no apparent dependency of the PCDD/PCDF levels, expressed as toxic equivalents (TEQs), and total PCB levels on the geographical residence of the donors within a country. This confirms the findings from a corresponding Norwegian study in 1985/1986 where individual samples from the same areas were analyzed. Teh total TEQs, including dioxin-like PCBs, ranged from 31 to 42 pg TEQs/g fat in Norway and from 45 to 49 pg TEQs/g fat in Lithuania. The mean concentration of PCDDs/PCDFs in teh Norwegian samples (10.4 pg TEQs/g fat) was slightly lower than in the Lithuanian samples (14.8 pg TEQs/g fat). Dioxin-like PCBs were found to contribute two to three times more to the total TEQs than the PCDDs and PCDFs. Major contributors among the dioxin-like PCBs were PCBs 126, 156, 114, 118, and 170. Comparison of the present data with those obtained in the Norwegian study in 1985/1986 shows that for PCDDs/PCDFs the mean TEQ levels have decreased by about 37% in the 7-yr time span, while the levels of total PCBs, as determined by packed-column gas chromatography, have remained unchanged or only slightly decreased. Future studies are necessary to confirm this potential temporal trend.

Chlorinated hydrocarbons in seabirds from the Barents Sea area

Abstract This study presents preliminary results on the levels of organochlorines (OCs) in three seabird species: common eider ( Somateria mollissima ), kittiwake ( Rissa tridactyla ) and glaucous gull ( Larus hyperboreus ) from the Barents Sea area, including Frans Josef Land, Ny-A˚lesund, Bjornoya and Hornoya, in July–August, 1991. Kittiwake was the only species collected at all four sampling areas, and all three species were sampled only at Ny-A˚lesund. Samples of liver, fat, muscle and brain tissue were analyzed for chlorinated pesticides, hexachlorobenzene (HCB), hexachlorocyclohexanes (α, β, γ-HCH), chlordanes (oxychlordane, trans -nonachlor and heptachlor epoxide), the DDT group ( op′ , pp′ DDT, DDD and DDE) and the industrial chemical polychlorinated biphenyls (PCBs). In all species, the highest OC levels were found in fat tissue, followed by liver, muscle and brain. PCBs were the major OC contaminants, followed by the DDT group, the chlordane group, HCB and the HCHs. Only low levels of HCHs were found. The lowest mean level of ΣPCB — sum of concentrations of the 19 individual congeners (2.8 μg/kg wet weight (w.w.)) — was found in the liver of juvenile common eider from Frans Josef Land. The highest mean level of ΣPCB (15 980 μg/kg w.w.) was found in the fat of adult glaucous gulls from Ny-A˚lesund. There were no significant geographical trends in OC contamination in the species investigated. However, the OC levels in kittiwake were highest at Bjornoya. The OC contamination levels in seabirds from the Barents Sea region are in general lower in the 1990s than in past decades.

Dioxins, PCBs and some chlorinated pesticides in human milk from the Kola Peninsula, Russia

In 1993, 30 individual human milk samples were collected in Murmansk and Monchegorsk, and analysed for 23 polychlorinated biphenyl congeners, PCBs (IUPAC nos.) 28, 52, 66, 74, 99, 101, 105, 110, 114, 118, 128, 138, 141, 149, 153, 156, 157, 170, 180, 187, 194, 206, and 209. In addition, the following organochlorine pesticides (OCPs): hexachlorobenzene (HCB), the alpha-, beta-, gamma-isomers of hexachlorocyclohexane (HCH), the chlordanes: oxychlordane, trans-chlordane, cis-chlordane, trans-nonachlor, and cis-nonachlor, and the DDT-compounds: pp-DDE, pp-DDD, op-DDT and pp-DDT were detected. From each city, a pooled sample was made and analysed for non-ortho PCBs, dibenzodioxins (PCDDs) and dibenzofurans (PCDFs). In addition one individual sample from Monchegorsk was analysed for PCDDs/PCDFs because of the very high levels of PCBs in this sample. High levels of pp-DDE and beta-HCH were found in Murmansk and Monchegorsk (in parenthesis) with mean levels of 1269, (892) and 853, (739) micrograms/kg milk fat respectively. Highest individual levels of pp-DDE (2816 micrograms/kg milk fat) and beta-HCH (1988 micrograms/kg milk fat) were found in Murmansk. Significant differences were found between the levels of gamma-HCH, cis-chlordane, trans-nonachlor, cis-nonachlor, pp-DDE, and the PCBs 28, 52, 74, 66, 110, 118, 105, 128, 206, and 209, between the two areas. No geographic differences in the concentrations of PCDDs/PCDFs and non-ortho PCBs in the sample pools from the two Russian areas were observed.

Polybrominated diphenyl ethers (PBDEs) in marine mammals from Arctic and North Atlantic regions, 1986-2009.

A selection of PBDE congeners was analyzed in pooled blubber samples of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), fin whale (Balaenoptera physalus), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata) and Atlantic white-sided dolphin (Lagenorhynchus acutus), covering a time period of more than 20 years (1986-2009). The analytes were extracted and cleaned-up using open column extraction and multi-layer silica gel column chromatography, and the analysis was performed on a GC-MS system operating in the NCI mode. The highest PBDE levels were found in the toothed whale species pilot whale and white-sided dolphin, and the lowest levels in fin whales and ringed seals. One-sided analyses of variance (ANOVA) followed by Tukey comparisons of means were applied to test for differences between years and sampling areas. Due to inter-year sampling variability, only general comparisons of PBDE concentrations between different sampling areas could be made. Differences in PBDE concentrations between three sampling periods, from 1986 to 2007, were evaluated in samples of pilot whales, ringed seals, white-sided dolphins and hooded seals. The highest PBDE levels were found in samples from the late 1990s or beginning of 2000, possibly reflecting the increase in the global production of technical PBDE mixtures in the 1990s. The levels of BDE #153 and #154 increased relative to the total PBDE concentration in some of the species in recent years, which may indicate an increased relative exposure to higher brominated congeners. In order to assess the effect of measures taken in legally binding international agreements, it is important to continuously monitor POPs such as PBDEs in sub-Arctic and Arctic environments.