Spatial and temporal trends of perfluorinated compounds in Beluga Whales (Delphinapterus leucas) from Alaska

Wildlife from remote locations have been shown to bioaccumulate perfluorinated compounds (PFCs) in their tissues. Twelve PFCs, consisting of perfluorinated carboxylic (PFCA) and sulfonic (PFSA) acids as well as the perfluorooctane sulfonate (PFOS) precursor perfluorooctane sulfonamide (PFOSA), were measured in livers of 68 beluga whales (Delphinapterus leucas) collected from two subpopulations, Cook Inlet and eastern Chukchi Sea, in Alaska between 1989 and 2006. PFOS and PFOSA were the dominant compounds measured in both beluga stock populations, with overall median concentrations of 10.8 ng/g and 22.8 ng/g, respectively. Long-chain perfluorocarboxylates, PFCAs (9 to 14 carbons), were detected in more than 80% of the samples. Perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTriA) made up a large percentage of the PFCAs measured with median concentrations of 8.49 ng/g and 4.38 ng/g, respectively. To compare differences in location, year, sex, and length, backward stepwise multiple regression models of the individual and total PFC concentrations were used. Spatially, the Cook Inlet belugas had higher concentrations of most PFCAs and PFOS (p < 0.05); however, these belugas had a lower median concentration of PFOSA when compared to belugas from the eastern Chukchi Sea (p < 0.05). Temporal trends indicated most PFCAs, PFHxS, PFOS, and PFOSA concentrations increased from 1989 to 2006 (p < 0.05). Males had significantly higher concentrations of PFTriA, ΣPFCA, and PFOS (p < 0.05). Perfluorononanic acid (PFNA) and PFOS showed a significant decrease in concentration with increasing animal length (p < 0.05). These observations suggest the accumulation of PFCs in belugas is influenced by year, location, sex, and length.     

Tissue distribution of perfluorinated chemicals in harbor seals (Phoca vitulina) from the Dutch Wadden Sea

Perfluorinated acids (PFAs) are today widely distributed in the environment, even in remote arctic areas. Recently, perfluorooctane sulfonate (PFOS) has been identified in marine mammals all over the world, but information on the compound-specific tissue distribution remains scarce. Furthermore, although longer perfluorinated carboxylic acids (PFCAs) are used in industry and were shown to cause severe toxic effects, still little is known on potential sources or their widespread distribution. In this study, we report for the first time on levels of longer chain PFCAs, together with some short chain PFAs, perfluorobutane sulfonate (PFBS) and perfluorobutanoate (PFBA), in liver, kidney, blubber, muscle, and spleen tissues of harbor seals (Phoca vitulina) from the Dutch Wadden Sea. PFOS was the predominant compound in all seal samples measured (ranging from 89 to 2724 ng/g wet weight); however, large variations between tissues were monitored. Although these are preliminary results, it is, to our knowledge, the first time that PFBS could be found at detectable concentrations (2.3 +/- 0.7 ng/g w wt) in environmental samples. PFBS was only detected in spleen tissue. PFCA levels were much lower than PFOS concentrations. The dominant PFCA in all tissues was PFNA (perfluorononanoic acid), and concentrations generally decreased in tissues for all other PFCA homologues with increasing chain length. No clear relationship between PFOS levels in liver and kidney was observed. Furthermore, hepatic PFDA (perfluorodecanoic acid) levels increased with increasing body length, but in kidney tissue, PFDA levels showed an inverse relationship with increasing body length. These data suggest large differences in tissue distribution and accumulation patterns of perfluorinated compounds in marine organisms.     

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.     

Nutritional composition of blubber and meat of hooded seal (Cystophora cristata) and harp seal (Phagophilus groenlandicus) from Greenland

Seal blubber and skin are widely used, but the utilisation of blubber and meat for human consumption is limited. The aim of this study was to evaluate the nutritional composition of seal blubber and meat. The fatty acid composition, selected minerals and trace-elements, vitamins, amino acids and proximal composition of blubber and meat from hooded seal (Cystophora cristata) and harp seal (Phagophilus groenlandicus) from the “West Ice” near Greenland were analysed. The results showed that seal blubber is an excellent source of long- and very long-chain (VLC) n − 3 polyunsaturated fatty acids (PUFAs), in addition to long- and VLC monounsaturated fatty acids (MUFAs). Eicosapentaenoic acid (EPA) content contributed to a clear separation between blubber and meat from the two species. The blubber of harp seal showed the highest EPA (9.2%), whereas the muscle of harp seal showed the lowest EPA (3%) content. Seal meat is lean with less than 2% total fat, mainly composed of MUFAs, long- and VLC n − 3 PUFAs. In addition, the meat contains a high amount of proteins with a well-balanced amino acid composition. The trace-element content of seal meat is very high, particularly iron (379 μg/g muscle in hooded seal) and zinc (30 μg/g muscle in harp seal), as also is the vitamin content, especially vitamins A, D₃ and B₁₂. The seals included in this study varied greatly in age and size, which in turn may be the principal reason for the great individual variation observed in nutritional composition. On average, however, consumption of only 40 g seal meat covers the recommended daily intakes of iron and vitamin B₁₂ for young women. In conclusion, as long as the products fulfil the amending legislations regarding contaminants, both seal blubber and meat, from the present species, represent high quality food regarding nutrients and bioactive components beneficial for human health.     

Temporal trends of perfluoroalkyl compounds with isomer analysis in lake trout from Lake Ontario (1979-2004)

The temporal trends of perfluoroalkyl compounds (PFCs), including C7-C15 perfluorocarboxylates (PFCAs), perfluorosulfonates (PFSAs) and heptadecafluorooctane sulfonamide (PFOSA), were determined in lake trout collected between 1979 and 2004 from Lake Ontario. The average concentrations of total PFSAs (+/- standard error of the mean; range) increased from 20 ng g(-1) wet weight (+/- 4; 8-26) in 1979, peaked at 70 ng g(-1) (+/- 7; 58-91) in 1993, and were 46 ng g(-1) (+/- 10; 30-83) in 2004, with perfluorooctane sulfonate (PFOS) asthe most abundant PFC. The PFCAs exhibited similar temporal variation, with concentrations increasing from 1.4 ng g(-1) (+/- 0.1; 0.9-1.9) in 1979 to 9.4 ng g(1) (+/- 3.1; 3-17) in 1988, and were 6.8 ng g(-1) (+/- 1.0; 4.5-9.8) in 2004. Individual mean PFCA concentrations varied between 0.2 and 2 ng g(-1) (wet weight). Perfluorodecane sulfonate (PFDS) and PFOSA were the only compounds showing a declining trend in the past decade, after reaching a peak value in 1993. Branched C11 and C13 PFCA isomers were detected in the lake trout and confirmed in Niagara River suspended sediments, with trends in both matrices suggesting that declining emissions or use of products containing these isomers in part account for the observed PFCA trends in the mid-1990s. However, the most recent samples, comprised almost exclusively of linear isomers, indicate that current PFCA sources to Lake Ontario result from the telomerization process of linear telogens.     

Temporal trends and pattern of polyfluoroalkyl compounds in Tawny Owl (Strix aluco) eggs from Norway, 1986-2009

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in tawny owl (Strix aluco) eggs collected in Central Norway over a period of 24 years (1986-2009). Concentrations of 12 PFCs, including C(6)-C(8), C(10) perfluoroalkyl sulfonates (PFSAs), perfluorooctane sulfonamide (PFOSA), and C(8)-C(14) perfluoroalkyl carboxylates (PFCAs), were measured, whereas saturated and unsaturated fluorotelomer carboxylates and shorter chain PFSAs and PFCAs were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (geometric mean 10.1 ng/g wet weight (ww)), followed by perfluorotridecanoate (PFTriDA) (0.36 ng/g ww) and perfluoroundecanoate (PFUnDA) (0.19 ng/g ww). Significant decreasing concentrations were found for PFOS with an annual decrease of 1.6% (1986-2009), while, conversely, the C(10)-C(13) PFCA concentrations increase significantly with an annual increase of 4.2-12% (1986-2009). Consequently, the contribution of PFOS to the ∑PFCs decreased, whereas the contribution of the ∑PFCAs increased over the time. Toxicological implications for tawny owls are limited, but the maximal PFOS concentration found in this stu0dy is about 20 times lower than the predicted avian no effect concentration (PNEC) which suggest adverse effects caused by PFOS are unlikely. However, tawny owls are exposed to a mixture of various PFCs, and PFCA concentrations still increase.     

Temporal and spatial trends of organochlorine pesticides in Great Lakes precipitation

Organochlorine pesticide concentrations in precipitation samples collected from 1997 to 2003 at seven Integrated Atmospheric Deposition Network sites around the Great Lakes are reported. The 28-day volume weighted mean concentrations of several pesticides, including gamma-hexachlorocyclohexane (HCH), endosulfan, hexachlorobenzene, chlordane, and DDE, showed significant seasonal trends. For current-use pesticides (endosulfan and gamma-HCH), their concentrations peaked in late spring to summer just after their agricultural application. For the banned pesticides, higher concentrations were observed in the winter due to their enhanced partitioning to particles and scavenging by snow. Long-term decreasing trends were observed for several pesticides such as gamma-HCH and DDE. On the other hand, beta-HCH showed significant increasing concentrations as a function of time at Brule River, Eagle Harbor, and Sleeping Bear Dunes. Generally, Chicago had the highest concentration of chlordanes, dieldrin, and DDT, indicating that urban areas could be a source for these compounds to precipitation. For gamma-HCH and endosulfans, Point Petre had the highest concentrations due to the application of these pesticides in the surrounding areas.     

Temporal trends and spatial distributions of brominated flame retardants in archived fishes from the Great Lakes

To explore the geographical distribution and temporal trends of polybrominated diphenyl ethers (PBDEs) in the Great Lakes, lake trout from Lakes Superior, Michigan, Huron, and Ontario and walleye from Lake Erie, collected during the period of 1980-2000, were analyzed. The concentrations of fifteen PBDE congeners and one polybrominated biphenyl (PBB-153) were determined in each fish sample. Lake trout from Lakes Michigan and Ontario had the highest sigmaPBDE concentrations during the years investigated. The sigmaPBDE concentrations in fishes from the five lakes increased exponentially with time, doubling every 3-4 years. The relative proportion of BDEs-47, -99, and -100 compared to BDEs-153 and -154 increased significantly as a function of time. Over the period 1980-2000, the concentrations of PBB-153, which was a component of a flame retardant banned in the 1970s, generally remained the same in these Great Lakes fishes, except for lake trout from Lake Huron, where the PBB-153 concentrations decreased significantly, but slowly.     

Polybrominated diphenyl ethers, perfluorinated compounds and chlorinated pesticides in swordfish (Xiphias gladius) from the Mediterranean Sea

The relative isolation of the Mediterranean population, their feeding habits, and the widespread use of their fillets for human consumption make the Mediterranean swordfish, Xiphias gladius, an interesting species from an ecotoxicological and commercial point of views. High resolution gas chromatography and tandem mass spectrometry detected 19 PBDE congeners, perfluorooctane sulfonate (PFOS), and perfluorooctanoic acid (PFOA), hexachlorobenzene (HCB), p,p' and o,p' isomers of DDT, DDE, and DDD in all samples. The presence of PBDEs was reported for the first time in Mediterranean swordfish from the South Tyrrhenian Sea; total PBDE concentrations were 2218 +/- 3291 and 612 +/- 598 pg/g wet wt in the liver and in the muscle, respectively. Significant correlations were identified between BDE47 and sigmaPBDE liver concentrations versus sex and sexual maturity of specimens. The lipid-normalized concentrations ratio BDEn(liver)/BDEn(muscle+liver) suggested that this species mostly accumulates POPs in the liver. PFOS and PFOA were below the LOD (1.5 and 3 ng/g wet wt, respectively) in all the samples. The sigmaDDTs was 155 +/- 125 and 309 +/- 273 ng/g wet wt in the muscle and the liver, respectively. The estimated daily ingestion of PBDEs and DDTs through diet was lower than the acceptable weekly intakes proposed by the World Health Organization.     

Temporal development of brominated flame retardants in peregrine Falcon (Falco peregrinus) eggs from South Greenland (1986-2003)

A time trend between 1986 and 2003 was found for brominated flame retardants in peregrine falcon eggs from South Greenland, with significantly increasing concentrations of the polybrominated diphenyl ethers (PBDEs) 99, 100, 153, 154, and 209. For BDE-99 and -100, the concentration increased approximately 10% per year. The concentrations of PBDEs were among the highest detected in wildlife so far and ranged from 300 to 12,900 ng/g lipid weight (lw) for sigmaPBDE. While tetrabromobisphenol A (TBBPA) was below the limit of detection in all eggs, hexabromocyclododecane (HBCD), dimethyl-TBBPA, and brominated biphenyl BB-153 were detected in a majority of eggs, with median concentrations of 2.4, 230, and 550 ng/g lw, respectively. Analyses of eggs of the same bird showed no significant intra-clutch variation for PBDEs, BB-153, and HBCD but larger variations for dimethyl-TBBPA. Inter-clutch variations with increasing time trends exist for the BDEs 99, 100, 153, 154, and 209, while a decreasing contamination with the BDEs 183, 49, 47, 66 and 153 was indicated in a subset of eggs.     

Enzyme-catalyzed synthesis of structured lipids via acidolysis of seal (Phoca groenlandica) blubber oil with capric acid

A structured lipid (SL) containing n-3 fatty acids (eicosapentaenoic acid, 20:5n-3; docosahexaenoic acid, 22:6n-3) and capric acid (10:0; a medium chain fatty acid) was prepared using lipase-catalyzed acidolysis of seal blubber oil with capric acid. An immobilized lipase, Lipozyme-IM from Mucor miehei, was used as the biocatalyst. Acidolysis reactions were carried out in hexane and the products were analyzed by gas chromatography. Incorporation of capric acid was affected by mole ratio of substrates, type of organic solvent, reaction temperature, reaction time, water content and the amount of lipase. The optimum reaction mixture and conditions were oil/fatty acid mole ratio of 1:3, hexane, 45 °C, 24 h, 1% (w/w of substrates) water and 10% (w/w of substrates) Lipozyme-IM lipase. Under these conditions, a SL containing 2.3% 20:5n-3, 7.6% 22:6n-3 and 27.1% 10:0 was obtained. Solvents with log P values between 2.5 and 4.5 performed the acidolysis reaction better than those with log P values of less than 2.5. However, in the absence of any organic solvent, Lipozyme-IM afforded a satisfactory incorporation of capric acid into seal blubber oil.     

Temporal changes in the levels of perfluorinated compounds in California women's serum over the past 50 years

Serum samples collected from California women at different time periods: 1960s (n = 40), 1980s (n = 30), and 2009 (n = 35) were examined for the presence of 12 perfluorinated compounds (PFCs) using an online SPE-HPLC-MS/MS method. At each time period, perfluorooctane sulfonate (PFOS) was present at the highest concentration, followed by perfluorooctanoic acid (PFOA, except in the 1960s). We found the highest levels of PFOS (median = 42.1 ng/mL) and perfluorohexane sulfonate (PFHxS, median = 1.56 ng/mL) in the 1960s samples, possibly reflecting widespread use of precursor PFCs. PFOS showed a statistically significant drop from the 1960s to the 1980s (28.8 ng/mL ) and to 2009 (9.0 ng/mL ), the latter being in agreement with national data. For PFOA, there was an approximately 10-fold increase in median concentrations from the 1960s (0.27 ng/mL) to the 1980s (2.71 ng/mL), and a slight drop in the 2009 samples (2.08 ng/mL). For longer chain perfluorocarboxylic acids (PFCAs), there was a continuous build-up in serum from the 1960s to 2009. To our knowledge, this is the first study to investigate temporal changes of PFCs over the past 50 years.     

Monitoring of perfluorinated compounds in edible fish from the Mediterranean Sea

Perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS) are environmental contaminants belonging to a chemical group known as perfluorinated compounds (PCFs). The United States Environmental Protection Agency (US EPA) considers both compounds to be carcinogenic. The goal of the present study was to evaluate the contamination levels of PFOS and PFOA in edible fish of the Mediterranean Sea. Twenty six fish muscles, 17 fish livers, five series of cephalopods (each composed of ten specimens) and thirteen series of bivalves (each composed of about 50 specimens) were used for the investigation. A fast sample treatment, followed by an LC–ESI–MS/MS method is described for the identification, and quantification of PFOA and PFOS in fish. The method was in-house-validated through the determination of precision, accuracy, specificity, calibration curve, decision limit (CCα), and detection capability (CCβ). The results showed PFOA and PFOS levels in fishes and molluscs lower than those reported for analogue matrices in different geographic areas. Therefore, our biomonitoring results did not show that the Mediterranean Sea had any particularly alarming pollution by PFCs, although it is located in a semi-closed basin with scarce water change. Nonetheless, a worrying element is that a few fish showed extremely high contamination by PFOA and PFOS. This finding needs further clarification in order to assess whether such unusual contamination is linked to “dot-like” pollutant release, which could explain the anomaly.     

Temporal and spatial trends of atmospheric polychlorinated biphenyl concentrations near the Great Lakes

Polychlorinated biphenyl (PCB) concentrations were measured in the atmosphere at six regionally representative sites near the five Great Lakes from 1990 to 2003 as part of the Integrated Atmospheric Deposition Network (IADN). Concentration data for several individual PCB congeners and for total PCBs were analyzed for temporal and spatial trends after correcting for the temperature dependency of the partial pressures. Atmospheric PCB concentrations are decreasing relatively slowly for tetra- and pentachlorinated congeners, an observation that is in agreement with primary emissions modeling. Relatively rapid decreases in PCB concentrations at the sites near Lakes Michigan and Ontario may reflect successful reduction efforts in Chicago and Toronto, respectively. Atmospheric PCB concentrations near Lakes Superior and Huron are now so low that the air and water concentrations may be close to equilibrium. Atmospheric PCB concentrations at sites near Lakes Michigan, Erie, and Ontario are relatively higher than those measured at sites near Lakes Superior and Huron. The highest PCB level was observed at the site near Lake Erie, most likely due to nearby urban activity. However, this relatively higher concentration is still 6-10 times lower than that previously reported at the Chicago site. A correlation between average gas-phase PCB concentration with local population indicates a strong urban source of PCBs. The temperature dependence of gas-phase PCB concentrations is similar at most sites except at Burnt Island on Lake Huron, where very low concentrations, approaching virtual elimination, prevent reliable temperature correlation calculations.     

鸡蛋中全氟化合物残留特征及其风险评估

为探究鸡蛋中全氟化合物(perfluorinated compounds,PFCs)的残留特征及其健康风险,采用离子对萃取与高效液相色谱质谱联用相结合的方法,对全国11个省(直辖市)产地鸡蛋中12种PFCs进行了分析,结果显示:全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)与全氟辛酸(perfluorooctanoic acid,PFOA)是鸡蛋中主要残留物,东部沿海产鸡蛋中ΣPFCs高于内陆,北方产鸡蛋中PFOS含量较高,煮鸡蛋中ΣPFCs仅为生鸡蛋11%。PFOS、PFOA风险评估结果显示,鸡蛋中PFCs对人体不具即时危害。     

Time trends of selected persistent organic pollutants in lake sediments from Greenland

Sediments from seven lakes in West Greenland were used as natural archives to study past and present levels of PCBs (polychlorinated biphenyls, tri- to decachlorinated), tetra-BDE #47 (2,2',4,4'-bromodiphenyl ether), chlordane (cis- and trans-octachlordane) and HxCBz (hexachlorobenzene). The concentrations found are lower than or comparable to concentrations found in sediments from other Arctic regions and one to 2 orders of magnitude lower than concentrations typically found in sediments at lower latitudes. The observed temporal trends (direct and indirect dating) show a decreasing total PCB concentration. Even though local contamination sources exist, the POP deposition in the studied area is most likely a result from long-range transport. The hypothesis about "cold condensation" suggests a latitudinal fractionation to occur between different volatile compounds during the transport toward the pole. In this study a time delay in the deposition for the low-chlorinated PCBs (tri- and tetrachlorinated), compared to their emission histories and compared to higher chlorinated PCBs, was indicated. Although very low tetra-BDE #47 concentrations are observed in this study, there are indications for an increasing concentration in recent sediment layers that may reflect increasing environmental concentrations at lower latitudes. The investigated pesticides are still in use at lower latitudes, however neither chlordane nor HxCBz show any distinct temporal trend of increasing or decreasing concentration toward the sediment surface.     

Temporal trends (1986-2004) of organochlorines and brominated flame retardants in tawny owl eggs from northern Europe

Eggs (n = 139) from tawny owls (Strix aluco) were collected annually (1986-2004) in Central Norway and analyzed for organochlorines (OCs) and brominated flame retardants (BFRs). p,p'-DDE (2,2-bis(4-chlorophenyl)-1,1-dichloroethene) and polychlorinated biphenyls (PCBs) were the dominating contaminants (mean/median = 2.7/1.7 and 2.9/1.6 microg/g, lipid weight [l.w.], respectively), comprising 90% of the contaminant burden. Other OCs (hexachlorobenzene [HCB], hexachlorocyclohexanes [HCHs], trans-nonachlor and oxychlordane) comprised less than 4% of the contaminant burden. Concentrations of OCs dropped 74-96% during the study period; p,p'-DDE, HCB, beta-HCH, oxychlordane, and PCBs decreased rapidly in the early (1986-1989) study period (23-34% per year; mean = 27.4%), but leveled off to less than 7% (mean = 3.6%) in the late period (2001-2004). The decrease in p,p'-DDE concentrations leveled off in the early 1990s, possibly due to an early ban on the use of DDT. alpha-HCH showed the strongest decline (always > 20% per year), while trans-nonachlor and gamma-HCH dropped at a constant rate of 9% per year. Toxaphene made up less than 0.6% of the measured contaminants (mean/median = 39/13 ng/ g, l.w.), and the concentrations of these compounds were lower in the late period compared to the early period, but not significant. BFRs, including hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (sigmaPBDE: mean/median = 182/ 85 ng/g, l.w.) made up about 3% of the measured contaminants. sigmaPBDE declined significantly over the study period (62%). Most PBDE congeners declined: significantly for BDE-47 (80% reduction) and BDE-153 (50% reduction), but the patterns differed; i.e., congeners associated with PentaBDE mixtures showed a rapid annual decline early (22-26%) and a slower decline late in the study period (6-12%), while the PBDEs associated with OctaBDE declined at a constant rate (1-4%). This may result from a larger reduction in the use of PentaBDE compared to other PBDE products in Europe.