Passive air sampling of polychlorinated biphenyls and organochlorine pesticides at the Korean Arctic and Antarctic research stations: implications for long-range transport and local pollution

To assess levels and patterns of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in polar regions, XAD-resin based passive air samplers were deployed for one year at the Korean polar research stations at Ny-Alesund, Norway (2005-2006) and King George Island, Antarctica (2004-2005). Backward trajectories suggest that these stations are affected by long-range transport from source regions in Northern Europe and Russia and the southern tip of South America, respectively. Relatively high levels of PCB-11, averaging 60 pg x m(-3), were observed in Antarctica, suggesting an unusual source of PCB-11 to the Southern Hemisphere. Reflecting the hemispheric distribution of global PCB emissions, the average level of sigma205PCB (excluding three mono-CBs and PCB-11) was five times higher in the Arctic (95 pg x m(-3)) than in the Antarctic (19 pg x m(-3)). Levels of sigma9PCB at Ny-Alesund were similarto those reported for other Arctic sites, while levels at King George Island were lower than at other sites on the Antarctic Peninsula but 1 order of magnitude higher than background levels measured at a more remote Antarctic site. Light homologues were predominant in all samples (except for one Arctic sample), consistent with the hypothesis of global fractionation and predictions of long-range transport potential. Dominance of heavy PCBs on the roof of the main building at Ny-Alesund and a concentration gradient with distance from the main building at King George Island strongly indicated the influence of local sources. OCP levels were also influenced by long-range transport but not by local sources. This study highlights the feasibility of using passive air sampling to assess both long-range transport and local pollution in remote regions.     

Residues of persistent organochlorine contaminants in southern elephant seals (Mirounga leonina) from Elephant Island, Antarctica

Contamination of blubber tissues by organochlorine pesticides (OC) and PCBs was assessed in female and male pups and juveniles, as well as in adult females and subdominant adult males of the Southern elephant seal, Mirounga leonina, from Elephant Island in the Antarctic Peninsula. All residues of persistent organochlorine contaminants analyzed were found in blubber samples, except for beta-HCH, endosulfan II, endrin, heptachlor, and aldrin. The relative concentrations of the analytes detected were sigmaDDT > sigmaPCB > sigmachlordane > mirex > dieldrin > HCB> sigmaendosulfan > methoxychlor > sigmaHCHs > other OC pesticides. OC and PCBs concentrations were 1 or 2 orders of magnitude lower than those found in pinnipeds from northern hemisphere. The ratio sigmaDDT/sigmaPCB was higher in southern elephant seals. The relative importance of some OC residues indicates that pesticides used either currently or in the recent past in countries in the southern hemisphere are the sources of contamination in the Antarctic region. Data showed that concentrations of contaminants generally increased from pups < juveniles < adults and suggested that pups accumulated contaminants through transfer from the mother seals via transplacental and lactational routes.     

Halogenated natural products in five species of Antarctic sponges: compounds with POP-like properties?

Purified extracts of five species of Antarctic sponges (Demospongiae: Kirkpatrickia variolosa, Artemisina apollinis, Phorbas glaberrima, and Halichondria sp. and Calcarea: Leucetta antarctica) from King George Island were analyzed by GC/MS for the presence of persistent and lipophilic halogenated compounds to identify bioaccumulative halogenated natural products. Sample extracts were prepared using methods identical for the determination of POPs, namely, microwave-assisted extraction with organic solvents, gel permeation chromatography, and column chromatography on deactivated silica. In addition, samples were treated with sulfuric acid to remove acid-destructible compounds. PCBs were not detectable and only traces of lindane, p,p'-DDE, and alpha-HCH were detected in these samples in decreasing order of abundance, underscoring their uncontaminated state. In contrast, 146 brominated compounds were identified by correct isotopic ratios m/z 79 and 81, 50% of which eluted prior to lindane including the most abundant peaks. Each sponge sample contained > or = 35 brominated compounds of natural origin, 14 of which were detected in all species. Estimated concentrations ranged from the high ng/kg to mg/kg (air-dried weights) and relative distributions of the same compounds in different sponges were highly variable. The high abundance of these compounds relative to known anthropogenic pollutants strongly suggests a natural origin. Multiple mode (EI-, ECNI-, and PCI-) GC/MS enabled identification of an aliphatic ketone tentatively identified as 1,1,2-tribromo-oct-1-en-3-one, present in all species but highest in Phorbas glaberrima. Several halogenated phenols including 2,4,6-tribromophenol were also abundant in Phorbas glaberrima as were halogenated anisoles in lower relative abundances. The halogenated phenols were analyzed without derivatization. The sample of Halichondria sp. contained the dibromotrichloro monoterpene MHC-1, a recently described environmental contaminant in fish and seals. Retrospective analysis of other marine samples confirmed that 2,4,6-tribromophenol was present in seal blubber from both the Arctic and the Antarctic. The presence of naturally occurring organohalogens such as 2,4,6-tribromophenol and MHC-1 in Antarctic marine invertebrates thus provides a link to their occurrence in marine mammals.     

Polychloronaphthalenes and other dioxin-like compounds in Arctic and Antarctic marine food webs

Here we report accumulation patterns of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and pesticides (HCB, p,p'DDE) in polar organisms (polar bear from Alaskan Arctic and krill, sharp-spined notothen, crocodile icefish, Antarctic silverfish, Adélie penguin, South polar skua, and Weddell seal from the Ross Sea, Antarctica). PCNs, found in most of the samples, ranged from 1.5 pg/g in krill to 2550 pg/g in South polar skua on a wet weight basis. Lower chlorinated PCNs were the predominant congeners in organisms except skua and polar bear that showed similar PCN homologue patterns. PCDD/F concentrations were <90 pg/g wet wt in polar organisms; PCDD congeners showed peculiar accumulation patterns in different organisms. Correlation existed between PCN and PCB concentrations. PCB, HCF, and p,p'DDE levels were the highest in skua liver (11,150 ng/g wet wt, 345 ng/g wet wt, and 300 ng/g wet wt, respectively). Contribution of PCNs to 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ) was negligible (<0.1%) because of the lack of most toxic congeners. The highest TEQ was found in South polar skua liver (45 pg/g, wet weight). This is the first study to document the occurrence of PCNs in Antarctic organisms. High levels of dioxin-like chemicals in skua suggest the importance of intake via diet and migration habits, thus POP detection can be useful to trace migration behavior. Moreover, POP concentrations in penguin and skua eggs prove their transfer from the mother to eggs.     

Synthesis and characterization of 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and structurally related compounds evidenced in seal blubber and brain

The unknown compound UBC-1 previously described as the major organobromine contamination in the blubber extract of a hooded seal (Cystophora cristata) from the Barents Sea was identified as 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE). DPTE, which is the main component of the brominated flame retardant (BFR) Bromkal 73-5 PE, was synthesized by electrophilic addition of bromine to allyl-2,4,6-tribromophenyl ether (ATE). The chirality of DPTE was proven by gas chromatographic enantioseparation of the synthesized racemate. On the basis of GC/ECNI-MS ion chromatograms (m/z79 and 81), DPTE was the dominating organobromine compound in blubber and brain samples of hooded seals and harp seals (Phoca groenlandica) from the Barents and Greenland Seas. The concentrations of DPTE in blubber and brain were up to 470 and 340 microg/kg wet weight. Next to DPTE, the natural dibromo-trichloromonoterpene (MHC-1), the anthropogenic BDE 47 and BDE 99, as well as ATE, 3,5-dibromo-2-(2',4'-dibromo)-phenoxyanisole (6-MeO-BDE 47), 2-bromoallyl-2,4,6-tribromophenyl ether (BATE), and 4,6-dibromo-2-(2',4'-dibromo)-phenoxyanisole (2'-MeO-BDE 68) were present with decreasing relevance. BATE, which was detected for the first time in environmental samples, was synthesized from DPTE by E2 elimination. In brain samples of the harp seals, DPTE, ATE, and BATE were the most abundant organobromine compounds, whereas polybrominated diphenyl ethers (PBDEs) and MHC-1 were virtually absent. This indicated that DPTE, ATE, and BATE were able to penetrate the blood-brain barrier. The general co-occurrence of ATE and BATE in samples contaminated with DPTE support the hypothesis that these compounds are biotransformation products of DPTE. Anaerobic transformation studies of DPTE with super-reduced corrinoids resulted in the formation of ATE. Furthermore, 2,4,6-tribromophenol (TBP) and two other unknown minor transformation products were detected.     

Exponential increases of the brominated flame retardants,polybrominated diphenyl ethers,in the Canadian Arctic from 1981 to 2000

A suite of 37 polybrominated diphenyl ether (PBDE) congeners and all of the homologue groups from mono- to deca-brominated were determined in ringed seal (Phoca hispida) blubber collected from subsistence hunts in the Canadian Arctic in 1981, 1991, 1996, and 2000. Total PBDE (sum(PBDE)) concentrations have increased exponentially over this period in male ringed seals aged 0-15 years. Penta- and hexa-BDEs are increasing at approximately the same rate (t2 = 4.7 and 4.3 years, respectively) and more rapidly than tetra-BDEs (t2 = 8.6 years) and tri-BDEs (t2 = infinity) in this age/sex grouping. In contrast to declining PBDE concentrations since 1997 in human milk from Sweden, sum(PBDE) concentrations in arctic ringed seals continue to increase exponentially similar to worldwide commercial penta-BDE production. PBDE congener profiles in male ringed seals aged 0-15 years from 1991 to 2000 also differ significantly from other aquatic organisms and semipermeable membrane devices collected from temperate coastal regions of British Columbia. While PBDE concentrations are 50 times lower than those of mono-ortho and non-ortho PCBs, and approxiamately 500 times higher than PCDD/Fs, our data indicate that, at current rates of bioaccumulation, PBDEs will surpass PCBs to become the most prevalent organohalogen compound in Canadian arctic ringed seals by 2050.     

Toxicokinetics of PCDD, PCDF, and coplanar PCB congeners in Baikal seals, Pusa sibirica: age-related accumulation, maternal transfer, and hepatic sequestration

To assess the toxicokinetic behavior and potential toxicity of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (PCBs) in Baikal seals, congener-specific levels and tissue distribution were evaluated in the liver and blubber, and the effects of biological factors including sex and growth were assessed. Total 2,3,7,8-TCDD toxic equivalents (TEQs) were in the range of 210-920 pgTEQ/g fat wt (180-800 pgTEQ/g wet wt) in the blubber and 290-7800 pgTEQ/g fat wt (10-570 pgTEQ/wet wt) in the liver. Non-ortho coplanar PCB126 was the most TEQ-contributed congener accounting for 37-59% of the total TEQs in the liver. From the unique congener profiles, weak metabolic properties of Baikal seals for 2,3,7,8-TCDF and 1,2,3,7,8-P5CDF are suggested. Concentrations of most congeners linearly increased with age in male seals, whereas in adult females the levels revealed an age-related decline. The increasing and declining rates were congener-specific. Maternal transfer rates of 5 representative congeners from adult female to pup through lactation, which was estimated from male-female differences in the body burden, was 1.1 ngTEQ/kg/day for the first pup and decreased with every lactational epoch. The liver-blubber distribution of 1,2,3,4,7,8-H6CDD, 1,2,3,6,7,8-H6CDD, PCB81, PCB126, and PCB169 was dependent on the hepatic total TEQ, indicating hepatic sequestration by induced cytochrome P450 (CYP). These results indicate that congener profile in Baikal seals is governed by complex factors including sex, tissue concentration, binding to CYP, and rates of absorption and metabolism/excretion.     

Hexabromocyclododecane in white-sided dolphins: temporal trend and stereoisomer distribution in tissues

Hexabromocyclododecane (HBCD) is a brominated flame retardant used primarily in expanded polystyrene foams and other styrene resins. Samples of blubber (n = 57) and liver (n = 16) from Atlantic white-sided dolphins, Lagenorhynchus acutus, that stranded on the eastern coast of United States between 1993 and 2004 were obtained from the National Marine Mammal Tissue Bank (NMMTB). Blubber samples from most of these animals (n = 47) were previously analyzed for polybrominated diphenyl ethers (PBDE), polychlorinated biphenyls (PCB), and several toxaphene congeners. The three most abundant diastereomers in the technical HBCD mixture (alpha-HBCD, beta-HBCD, and gamma-HBCD) and their enantiomers were determined using liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS). alpha-HBCD was found in all blubber and liver samples while beta-HBCD and gamma-HBCD were not detected in any samples. The alpha-HBCD concentration in blubber and liver ranged from 14 ng/g wet mass (19 ng/g lipid) to 280 ng/g wet mass (380 ng/g lipid) and 0.051 ng/g wet mass (2.9 ng/g lipid) to 3.6 ng/g wet mass (140 ng/g lipid), respectively. Concentrations of alpha-HBCD were 2 to 3 orders of magnitude lower than previously reported PBDE, PCB, and toxaphene concentrations in these same animals. There was not a significant temporal trend for these compounds in white-sided dolphin blubber. The enantiomeric fractions (EF) measured in blubber and liver were not statistically different and ranged from 0.34 to 0.53. Blubber EFs were significantly correlated with both alpha-HBCD concentrations and white-sided dolphin body length. In general, concentrations of HBCDs were lower in these white-sided dolphins than in cetaceans from Western Europe.     

Enantiomeric specificity of methylsulfonyl-PCBs and distribution of bis(4-chlorophenyl) sulfone, PCB, and DDE methyl sulfones in grey seal tissues

PCB methyl sulfones (MeSO2-PCBs) are lipophilic PCB metabolites of which five of the environmentally relevant meta/para pairs are chiral (i.e., exist as atropisomeric pairs). Methylsulfonyl-DDE (MeSO2-DDE) is a DDE metabolite, while bis(4-chlorophenyl) sulfone (BCPS) is a commercial monomer used for thermoplastic production. All these sulfones are well-known environmental contaminants. In this study, liver, lung, and adipose tissue in grey seals (Halichoerus grypus) from the Baltic Sea, naturally exposed to organochlorines via their food, were analyzed for the compounds mentioned. MeSO2-PCBs, 3-MeSO2-DDE, and BCPS were all found in significantly higher concentrations in the liver than in lung and blubber. Their strong liver retention, represented by a median of 42 microg/g l.w. of sigmaMeSO2-PCBs, has previously been mainly neglected in assessments of exposure. The highest concentrations of PCBs and DDE were still found in the grey seal blubber. The atropisomeric composition of MeSO2-PCB congeners was determined, and their enantiomeric fractions were calculated and compared in blubber, liver, and lung tissues. The enantiomeric specificity was equal in all tissues. A notably high abundance (>94%) was observed for one atropisomer in each chiral MeSO2-PCB pair. The first eluting atropisomer (A1) was dominating for all para-substituted MeSO2-PCBs studied, while the second eluting atropisomers (A2) were as dominant in all meta-substituted MeSO2-PCBs in all samples analyzed. In the liver, as much as 50% of sigmaMeSO2-PCBs consisted of the second eluting atropisomer (A2) of 5-MeSO2-CB149. The results imply that the sulfone group is crucial for the specific liver retention of MeSO2-PCBs, 3-MeSO2-DDE, and BCPS.     

Three-year atmospheric monitoring of organochlorine pesticides and polychlorinated biphenyls in polar regions and the South Pacific

XAD-2 resin based passive air samplers (PAS) were deployed for three one-year periods at the Korean polar and South Pacific research stations at Ny-?lesund (2005-2009), King George Island (2005-2007), and Chuuk (2006-2009) to investigate long-range transport, local sources, and temporal trends of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The highest hexachlocyclohexane (HCH) concentration (35.2-78.9 pg·m(-3)) over the entire sampling period was detected at Ny-?lesund, in the Arctic. α-HCH was the dominant OCP (31.1-67.1 pg·m(-3)), contributing about 50% of the total OCP load. Additionally, a high and consistent α/γ-HCH ratio was observed at Ny-?lesund. HCHs might reach Arctic sites more easily than other OCPs from surrounding countries through long-range atmospheric transport (LRAT). Interestingly, high levels of the current-use OCP endosulfan-particularly endosulfan-I--were detected at almost all sampling sites, including in Antarctica, ranging 12.2-88.5, 17.7-130, and ND-59.7 pg·m(-3) at King George Island, Ny-?lesund, and Chuuk, respectively. Specific OCP and PCB patterns, such as low trans/cis-chlordane ratios and a prevalence of lighter PCB congeners, were observed in all three regions (excepting one site at Ny-?lesund and one site in the South Pacific affected by local sources) during all sampling periods. This indicates that these Polar and remote South Pacific sites are mainly influenced by LRAT. Over the entire sampling period, a decreasing trend of HCHs (α- and γ-HCH) and an increasing trend of endosulfan-I were observed at the Ny-?lesund sites.     

Bottlenose dolphins as indicators of persistent organic pollutants in the western North Atlantic Ocean and northern Gulf of Mexico

Persistent organic pollutants (POPs) including legacy POPs (PCBs, chlordanes, mirex, DDTs, HCB, and dieldrin) and polybrominated diphenyl ether (PBDE) flame retardants were determined in 300 blubber biopsy samples from coastal and near shore/estuarine male bottlenose dolphins (Tursiops truncatus) sampled along the U.S. East and Gulf of Mexico coasts and Bermuda. Samples were from 14 locations including urban and rural estuaries and near a Superfund site (Brunswick, Georgia) contaminated with the PCB formulation Aroclor 1268. All classes of legacy POPs in estuarine stocks varied significantly (p < 0.05) among sampling locations. POP profiles in blubber varied by location with the most characteristic profile observed in bottlenose dolphins sampled near the Brunswick and Sapelo estuaries along the Georgia coast which differed significantly (p < 0.001) from other sites. Here and in Sapelo, PCB congeners from Aroclor 1268 dominated indicating widespread food web contamination by this PCB mixture. PCB 153, which is associated with non-Aroclor 1268 PCB formulations, correlated significantly to human population indicating contamination from a general urban PCB source. Factors influencing regional differences of other POPs were less clear and warrant further study. This work puts into geographical context POP contamination in dolphins to help prioritize efforts examining health effects from POP exposure in bottlenose dolphins.     

Single-particle characterization of summertime Antarctic aerosols collected at King George Island using quantitative energy-dispersive electron probe X-ray microanalysis and attenuated total reflection Fourier transform-infrared imaging techniques

Single-particle characterization of Antarctic aerosols was performed to investigate the impact of marine biogenic sulfur species on the chemical compositions of sea-salt aerosols in the polar atmosphere. Quantitative energy-dispersive electron probe X-ray microanalysis was used to characterize 2900 individual particles in 10 sets of aerosol samples collected between March 12 and 16, 2009 at King Sejong Station, a Korean scientific research station located at King George Island in the Antarctic. Two size modes of particles, i.e., PM(2.5-10) and PM(1.0-2.5), were analyzed, and four types of particles were identified, with sulfur-containing sea-salt particles being the most abundant, followed by genuine sea-salt particles without sulfur species, iron-containing particles, and other species including CaCO(3)/CaMg(CO(3))(2), organic carbon, and aluminosilicates. When a sulfur-containing sea-salt particle showed an atomic concentration ratio of sulfur to sodium of >0.083 (seawater ratio), it is regarded as containing nonsea-salt sulfate (nss-SO(4)(2-)) and/or methanesulfonate (CH(3)SO(3)(-)), which was supported by attenuated total reflection Fourier transform-infrared imaging measurements. These internal mixture particles of sea-salt/CH(3)SO(3)(-)/SO(4)(2-) were very frequently encountered. As nitrate-containing particles were not encountered, and the air-masses for all of the samples originated from the Pacific Ocean (based on 5-day backward trajectories), the oxidation of dimethylsulfide (DMS) emitted from phytoplanktons in the ocean is most likely to be responsible for the formation of the mixed sea-salt/CH(3)SO(3)(-)/SO(4)(2-) particles.     

Western Canadian Arctic ringed seal organic contaminant trends in relation to sea ice break-up

The association between changing sea ice conditions and contaminant exposure to Arctic animals interests Inuvialuit harvesters, communities, and researchers. We examined organochlorine contaminant (OC) concentrations in the blubber of 90 male adult ringed seals (Phoca hispida) sampled from the subsistence harvest in Ulukhaktok (formerly Holman), NT, Canada, just prior to break-up of the sea ice (1993-2008). OC blubber concentrations were assessed with respect to year and sea ice break-up date. HCB and age- and blubber-adjusted concentrations of p,p'-DDT and ΣCHB (chlorobornane) significantly decreased over the study period. With respect to the timing of the spring break-up, highly lipophlic OCs, such as p,p'-DDE and PCB 153, were higher during years of early ice clearing (at least 12 days earlier than the mean annual break-up date), whereas no trends were observed for α, β, and γ isomers of HCH, trans- and cis-chlordane, oxychlordane, or ΣCHB. The higher contaminant concentrations found in earlier break-up years is likely due to earlier and/or increased foraging opportunities. This situation also has potential for enhancing bioaccumulation and biomagnification of contaminants over the long-term if projected changes continue to result in lighter and earlier ice conditions.     

Enantiomer-specific accumulation of PCB atropisomers in the bowhead whale (Balaena mysticetus)

Blubber (n = 40) and liver (n = 20) samples from the bowhead whale (Balaena mysticetus) were collected during the 1997-1998 Native (Inuit) subsistence harvests in Barrow, AK. Bowhead tissues and zooplankton were analyzed for polychlorinated biphenyl (PCB) concentrations and the enantiomeric fractions (EFs) of eight chiral PCB congeners (PCB-91, 95, 135, 136, 149, 174, 176, and 183) to quantify the enantiomer-specific accumulation of PCBs in this cetacean. PCB concentrations in bowhead blubber were low (mean +/- 1 SE: 610 +/- 54 ng g(-1) lipid) relative to other cetaceans. The accumulation of several chiral PCBs (PCB-91, 135, 149, 174, 176, and 183) in bowhead blubber was enantiomer-specific relative to bowhead liver and zooplankton, suggesting that biotransformation processes within the bowhead whale are enantioselective. The EFs for PCB-95 and 149 were significantly correlated with body length in male and female whales, while EFs for PCB-91 correlated with length in males only. Despite evidence for enantioselective biotransformation, all three congeners bioaccumulated in the bowhead relative to PCB-153. Results suggest that enantioselective accumulation of PCB-91, 95, and 149 is influenced by PCB concentrations, age, and/or the modification of an uncharacterized stereoselective process (or processes) during sexual maturity.     

Perfluorooctanesulfonate and related fluorinated hydrocarbons in marine mammals,fishes, and birds from coasts of the Baltic and the Mediterranean Seas

Perfluorooctanesulfonate (PFOS; C8F17SO3-), perfluorooctanesulfonamide (FOSA; C8F17SO2NH2), perfluorohexanesulfonate (PFHxS; C6F13SO3-), and perfluorooctanoate (PFOA; C7F15CO2-) were detected in 175 samples of liver and blood of bluefin tuna (Thunnus thynnus), swordfish (Xiphias gladius), common cormorants (Phalacrocorax carbo), bottlenose dolphins (Tursiops truncatus), striped dolphins (Stenella coeruleoalba), common dolphins (Delphinus delphi), fin whales (Balenoptera physalus), and long-finned pilot whales (Globicephala melas) from the Italian coast of the Mediterranean Sea and in livers of ringed seals (Phoca hispida), gray seals (Halichoerus grypus), white-tailed sea eagles (Haliaeetus albicilla), and Atlantic salmon (Salmo salar) from coastal areas of the Baltic Sea. PFOS was detected in all of the wildlife species analyzed. Concentrations of PFOS in blood decreased in order of bottlenose dolphins > bluefin tuna > swordfish. Mean PFOS concentrations (61 ng/ g, wet wt) in cormorant livers collected from Sardinia Island in the Mediterranean Sea were less than the concentrations of PFOA (95 ng/g, wetwt). PFOS concentrations in cormorant livers were significantly correlated with those of PFOA. FOSA was found in 14 of 19 livers or blood samples of marine mammals from the Mediterranean Sea. The highest concentration of 878 ng FOSA/g, wet wt, was found in the liver of a common dolphin. Livers of ringed and gray seals from the Bothnian Bay in the Baltic Sea contained PFOS concentrations ranging from 130 to 1,100 ng/g, wet wt. No relationships between PFOS concentrations and ages of ringed or gray seals were observed. Concentrations of PFOS in livers of seals were 5.5-fold greater than those in corresponding blood. A significant positive correlation existed between the PFOS concentrations in liver and blood, which indicates that blood can be used for nonlethal monitoring of PFOS. Trend analysis of PFOS concentrations in livers of white-tailed sea eagles collected from eastern Germany and Poland since 1979 indicated an increase in concentrations during the 1990s. Livers of Atlantic salmons did not contain quantifiable concentrations of any of the fluorochemicals monitored. PFOS is a widespread contaminant in wildlife from the Baltic and the Mediterranean Seas, while FOSA and PFOA were detected only in certain locations indicating their sporadic spatial distribution.     

Brominated flame retardants and halogenated phenolic compounds in North American west coast bald eaglet (Haliaeetus leucocephalus) plasma

We report on the identity, characterization, and spatial trends of several brominated flame retardants and hydroxylated (OH-) and methoxylated (MeO-) organohalogen contaminants in bald eagle (Haliaeetus leucocephalus) nestling plasma collected from sites along the west coast of North America. Samples were from four southwestern British Columbia (BC) locations, a reference site in northern BC (Fort St. James; FSJ), and from Santa Catalina Island, CA (SCI), an area of high DDT and PCB contamination. Mean concentrations of sigma polybrominated diphenyl ether (sigma PBDE (8 congeners monitored); 1.78-8.49 ng/g), sigma OH-polychlorinated biphenyl (sigma OH-PCB (30 congeners monitored); 0.44-0.87 ng/g), and sigma OH-PBDE (14 congeners monitored; 0.31-0.92 ng/g) were similar in eaglets from southwestern BC yet lower than for SCl and significantly higher than for FSJ. Dominant PBDE congeners were BDE47, BDE99, and BDE100, but SCl eaglets also contained low levels of higher brominated congeners. 4-OH-CB187 and 4'-OH-CB202 accounted for 65-100% of sigma OH-PCB in all BC eaglets, with 4'-OH-CB202 as well as 3'-OH-CB138 and 4-OH-CB146 dominating in SCl eaglets. Ostensibly of biogenic origin, 6'-OH-BDE49 and 6-OH-BDE47 were found in BC nestlings. Only 4'-OH-BDE49 (2.10 ng/g) was found in SCl eaglets. MeO-PBDEs and total hexabromocyclododecane (HBCD) were not found in any birds, but the polybrominated biphenyl BB101 was detected in southwestern BC samples. This study demonstrates that west coast North American bald eagles contain previously unreported organohalogens, which have the potential to impact the health and survival of these raptors.     

Measurements of atmospheric mercury species at a coastal site in the Antarctic and over the south Atlantic Ocean during polar summer

Mercury and many of its compounds behave exceptionally in the environment because of their volatility, capability for methylation, and subsequent biomagnification in contrast with most of the other heavy metals. Long-range atmospheric transport of elemental mercury, its transformation to more toxic methylmercury compounds, the ability of some to undergo photochemical reactions, and their bioaccumulation in the aquatic food chain have made it a subject of global research activities, even in polar regions. The first continuous high-time-resolution measurements of total gaseous mercury in the Antarctic covering a 12-month period were carried out at the German Antarctic research station Neumayer (70 degrees 39' S, 8 degrees 15' W) between January 2000 and February 2001. We recently reported that mercury depletion events (MDEs) occur in the Antarctic after polar sunrise, as was previously shown for Arctic sites. These events (MDEs) end suddenly during Antarctic summer. A possible explanation of this phenomenon is presented in this paper, showing that air masses originating from the sea-ice surface were a necessary prerequisite for the observations of depletion of atmospheric mercury at polar spring. Our extensive measurements at Neumayer of atmospheric mercury species during December 2000-February 2001 show that fast oxidation of gaseous elemental mercury leads to variable Hg0 concentrations during Antarctic summer, accompanied by elevated concentrations, up to more than 300 pg/m3, of reactive gaseous mercury. For the first time in the Southern Hemisphere, atmospheric mercury species measurements were also performed onboard of a research vessel, indicating the existence of homogeneous background concentrations over the south Atlantic Ocean. These new findings contain evidence for an enhanced oxidizing potential of the Antarctic atmosphere over the continent that needs to be considered for the interpretation of dynamic transformations of mercury during summertime.     

Persistent organic pollutants in Mediterranean seawater and processes affecting their accumulation in plankton

The Mediterranean and Black Seas are unique marine environments subject to important anthropogenic pressures due to riverine and atmospheric inputs of organic pollutants. Here, we report the results obtained during two east-west sampling cruises in June 2006 and May 2007 from Barcelona to Istanbul and Alexandria, respectively, where water and plankton samples were collected simultaneously. Both matrixes were analyzed for hexaclorochyclohexanes (HCHs), hexachlorobenzene (HCB), and 41 polychlorinated biphenyl (PCB) congeners. The comparison of the measured HCB and HCHs concentrations with previously reported dissolved phase concentrations suggests a temporal decline in their concentrations since the 1990s. On the contrary, PCB seawater concentrations did not exhibit such a decline, but show a significant spatial variability in dissolved concentrations with lower levels in the open Western and South Eastern Mediterranean, and higher concentrations in the Black, Marmara, and Aegean Seas and Sicilian Strait. PCB and OCPs (organochlorine pesticides) concentrations in plankton were higher at lower plankton biomass, but the intensity of this trend depended on the compound hydrophobicity (K(OW)). For the more persistent PCBs and HCB, the observed dependence of POP concentrations in plankton versus biomass can be explained by interactions between air-water exchange, particle settling, and/or bioaccumulation processes, whereas degradation processes occurring in the photic zone drive the trends shown by the more labile HCHs. The results presented here provide clear evidence of the important physical and biogeochemical controls on POP occurrence in the marine environment.     

Fine-scale spatial variation of persistent organic pollutants in bottlenose dolphins (Tursiops truncatus) in Biscayne Bay, Florida

Bottlenose dolphins (Tursiops truncatus) are long-term residents and apex predators in southeast U.S. estuaries and are vulnerable to bioaccumulation of persistent organic pollutants (POPs). Dart biopsy samples were collected from 45 dolphins in Biscayne Bay (Miami, FL), 34 of which were matched using fin markings to a photo identification catalogue. Blubber samples were analyzed for 73 polychlorinated biphenyl (PCB) congeners, six polybrominated diphenyl ether (PBDE) congeners, and organochlorine pesticides including dichloro-diphenyl-trichloroethane (DDT) and metabolites, chlordanes, and dieldrin. Total PCBs (sigma 73PCBs) were present in the highest concentrations and were 5 times higher in males with sighting histories in the northern, metropolitan area of Biscayne Bay than males with sighting histories in the southern, more rural area [geometric mean: 43.3 (95% confidence interval: 28.0-66.9) vs 8.6 (6.3-11.9) microg/g wet mass, respectively]. All compound classes had higher concentrations in northern animals than southern. The differences in POP concentrations found on this small geographic scale demonstrate that differential habitat use can strongly influence pollutant concentrations and should be considered when interpreting bottlenose dolphin POP data. The PCB concentrations in northern Bay dolphins are high as compared to other studies of estuarine dolphins and may place these animals at risk of reproductive failure and decreased immune function.     

Contamination of human fat from Rostock residents with DDT and polychlorinated biphenyls in 1979)

70 fat samples collected from Rostock men and women, aged between 20 and 90 years, were analysed by gas chromatography for total DDT and polychlorinated biphenyls (PCB). It was found that the mean value for DDT and also that for PCB increased with the increase in age, the mean values for all the subjects being 4.0 +/- 0.5 mg/kg (PCB). There were no statistically significant differences among the residue values found in men and women.