Bioaccumulation and biotransformation of brominated and chlorinated contaminants and their metabolites in ringed seals (Pusa hispida) and polar bears (Ursus maritimus) from East Greenland

We report on the comparative bioaccumulation, biotransformation and/or biomagnification from East Greenland ringed seal (Pusa hispida) blubber to polar bear (Ursus maritimus) tissues (adipose, liver and brain) of various classes and congeners of persistent chlorinated and brominated contaminants and metabolic by-products: polychlorinated biphenyls (PCBs), chlordanes (CHLs), hydroxyl (OH-) and methylsulfonyl (MeSO₂-) PCBs, polybrominated biphenyls (PBBs), OH-PBBs, polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants and OH- and methoxyl (MeO-) PBDEs, 2,2-dichloro-bis(4-chlorophenyl)ethene (p,p′-DDE), 3-MeSO₂-p,p′-DDE, pentachlorophenol (PCP) and 4-OH-heptachlorostyrene (4-OH-HpCS). We detected all of the investigated contaminants in ringed seal blubber with high frequency, the main diet of East Greenland bears, with the exception of OH-PCBs and 4-OH-HpCS, which indicated that these phenolic contaminants were likely of metabolic origin and formed in the bears from accumulated PCBs and octachlorostyrene (OCS), respectively, rather than being bioaccumulated from a seal blubber diet. For all of the detectable sum of classes or individual organohalogens, in general, the ringed seal to polar bear mean BMFs for ΣPCBs, p,p′-DDE, ΣCHLs, ΣMeSO₂-PCBs, 3-MeSO₂-p,p′-DDE, PCP, ΣPBDEs, total-(α)-HBCD, ΣOH-PBDEs, ΣMeO-PBDEs and ΣOH-PBBs indicated that these organohalogens bioaccumulate, and in some cases there was tissue-specific biomagnification, e.g., BMFs for bear adipose and liver ranged from 2 to 570. The blood-brain barrier appeared to be effective in minimizing brain accumulation as BMFs were ≤ 1 in the brain, with the exception of ΣOH-PBBs (mean BMF = 93 ± 54). Unlike OH-PCB metabolites, OH-PBDEs in the bear tissues appeared to be mainly accumulated from the seal blubber rather than being metabolic formed from PBDEs in the bears. In vitro PBDE depletion assays using polar bear hepatic microsomes, wherein the rate of oxidative metabolism of PBDE congeners was very slow, supported the probability that accumulation from seals is the main source of OH-PBDEs in the bear tissues. Our findings demonstrated from ringed seal to polar bears that organohalogen biotransformation, bioaccumulation and/or biomagnification varied widely and depended on the contaminant in question. Our results show the increasing complexity of bioaccumulated and in some cases biomagnified, chlorinated and brominated contaminants and/or metabolites from the diet may be a contributing stress factor in the health of East Greenland polar bears.     

淀山湖水生生物中有机氯化合物的浓度与富集特征

为研究淀山湖水生生物中有机氯化合物的浓度与富集特征,测定了该湖水生生物样品(铜锈环棱螺、日本沼虾、鱼类)中滴滴涕(DDTs)、六六六(HCHs)、六氯苯(HCB)、多氯联苯(PCBs)的浓度。研究结果显示,在所有生物样品中均检测到了DDTs、HCHs、HCB,各生物体内的有机氯农药含量有很大差异。在8种生物样品中,乌鳢体内的有机氯化合物含量最高,这可能与乌鳢处于较高营养级,且为肉食性鱼类,体内脂肪较多有关。∑DDTs、∑HCHs、HCB的含量范围分别是55~1 135、0.5~24、6.9~91ng/g lw,其中DDTs为最主要的有机氯农药。4,4’-DDE和α-HCH在各自同系物中所占比例最高,说明淀山湖历史上曾经使用过有机氯农药,而近期没有新的污染源输入。以铜锈环棱螺为参照,有机氯农药的生物放大系数(BMFs)范围是1.2(泥鳅)~23(乌鳢);PCBs的生物放大系数范围是5.9(河川沙塘鳢)~55(乌鳢)。亲脂疏水性、低生化降解速率导致有机氯化合物能在生物组织中富集并通过食物链逐级放大。研究结果表明,有机氯化合物会沿着食物链积累放大,可能会对人体健康存在潜在的威胁。     

Organochlorine levels in edible fish from the Marmara Sea, Turkey

Samples of 12 edible fish species from the Marmara Sea were analyzed for organochlorines (PCBs, DDTs, HCB, HCHs, toxaphene, etc.). The results showed that the total concentrations ranged from 329.41 ng/g fat to 1453.87 ng/g fat. DDT group components made up almost half or more of organochlorine contamination. Levels in red mullet were compared with those from neighbor seas. The sum of DDTs as well as HCHs concentrations were markedly lower than in the Black Sea but higher in the Aegean Sea and Mediterranean. Thus, inflow from the Black Sea might be considered as a contamination source for DDT and HCH contamination. On the other hand, total PCB concentration (sum of congeners 28, 52, 101, 118, 138, 153 and 180) detected in this study was comparable or lower than those from the Aegean Sea and Mediterranean. Toxaphene was a minor contaminant. Measured values were below maximum residue levels for human consumption.     

Tissue-specific accumulation of polybrominated diphenyl ethers (PBDEs) including Deca-BDE and hexabromocyclododecanes (HBCDs) in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) are widely used flame retardants that enter coastal waters from multiple sources and biomagnify in marine food webs. PBDEs have been detected at relatively high concentrations in harbor seals, apex predators in the northwest Atlantic. Whereas tri- to hexa-BDEs readily biomagnified from prey fishes to seal blubber, Deca-BDE (BDE-209) did not biomagnify in blubber. To explore tissue-specific differences in the accumulation/biomagnification of BFRs, we analyzed tri- to Deca-BDES in liver of 56 harbor seals (6 adult males, 50 pups), and compared hepatic concentrations and biomagnification potential with those in blubber. HBCDs were analyzed in seal liver and blubber to enable similar comparisons. Hepatic ΣPBDE (tri- to Octa-BDE) concentrations (range 35–19,547 ng/g lipid weight, lw) were similar to blubber concentrations, while α-HBCD levels in seal liver (range 2–279 ng/g lw) were significantly higher than levels in blubber. Tissue distribution of PBDEs and α-HBCD varied significantly by age and, surprisingly, by gender among the pups. Biomagnification of α-HBCD from fish to seal liver and blubber was negligible to low, implying that harbor seals can metabolize this persistent isomer. Similar to the patterns in blubber, tri- through hexa-BDEs were highly biomagnified from fish to seal liver. In contrast, BDE-209 concentrations in liver were up to five times higher than those in blubber, which is consistent with observations that BDE-209 migrates to perfused tissues such as the liver in biota. Although detection frequency was low, BDE-209 levels in seal liver were up to ten times higher than those in their prey fish, suggesting that the accumulation/biomagnification of Deca-BDE in marine food webs is tissue-specific. As BDE-209 is the dominant PBDE found in marine sediments, its biomagnification in marine ecosystems is of concern.     

Chlorinated biphenyls and pesticides in migrating and resident seabirds from East and West Antarctica

The unhatched eggs of the following seabirds were analyzed to quantify PCBs, hexachlorobenzene (HCB), α-, β-, γ-, δ-hexachlorocyclohexanes (HCHs), o,p' and p,p' isomers of DDT, DDD and DDE: resident Adèlie (Pygoscelis adèliae, ADPE) and Emperor (Aptenodytes forsteri, EMPE) penguins, migrating snow petrel (Pagodroma nivea, SNPT) and South Polar skua (Catharacta maccormicki, SPSK) from the Ross Sea (East Antarctica); and migrating Brown skua (Catharacta antartica, BRSK) and resident ADPE from the Brainsfield Strait (West Antarctica). The general aims were to evaluate the contaminant accumulation in eggs of migrating and resident species in the two study areas, and to compare levels in penguins and skuas nesting in East and West Antarctica. PCB congener and HCH and DDT isomer profiles were also assessed. Comparisons were evaluated using seven PCB congeners (IUPAC nos. 28, 52, 101, 118+149, 138, 153, and 180), p,p'-DDE, ΣDDTs, and ΣHCHs. Higher contaminant concentrations were detected in migrating seabirds (South polar skua and brown skua)>sub-Antarctic species (snow petrel)>Antarctic species (penguins) from both the sampling sites, suggesting contamination events at lower latitudes for those birds migrating northward. HCHs showed the lowest concentrations in all species (from 0.03±0.03 ng/g wet wt in SPSK to 1.81±1.23 ng/g wet wt in ADPE from West Antarctica), and PCBs were the most abundant contaminants (from 4.34±2.15 ng/g wet wt. in EMPE to 53.41±19.61 ng/g wet wt. in brown skua). Among pesticides, it is relevant the detection of p,p'-DDT in Adèlie penguin from West Antarctica and in both species of skua; the detection of this pesticide can confirm its actual use in certain malaria-endemic countries from where it is transferred through the long range transport to the polar regions. Contaminants did not show any significant temporal trend during a ten year time span, from 1994/95 to 2004/05, in organisms collected in East Antarctica and they did not indicate any latitudinal gradient along the Ross Sea coasts.     

Levels of organohalogenated persistent pollutants in human milk from Kahramanmaraş region, Turkey

The levels of 1,1,1-trichloro-bis-2,2'-(4-chlorophenyl) ethane (p,p'-DDT) and its metabolites, hexachlorobenzene (HCB), hexachlorocyclohexane isomers (HCHs), chlordanes (trans- and cis-chlordane, oxychlordane and trans-nonachlor), 11 polychlorinated biphenyl (PCB) congeners, and 7 polybrominated diphenyl ether (PBDE) congeners were measured in 37 individual human milk samples from Kahramanmara? region, Turkey. Organochlorine pesticides were the major contaminants in the milk samples. p,p'-DDE and p,p'-DDT were detected in all samples, while beta-HCH had a detection frequency of 97%. The sum of the DDTs in human milk samples varied between 0.52 and 315.8 ng/g wet weight (ww) with a mean ratio between p,p'-DDE and p,p'-DDT equal to 31.1. p,p'-DDD could be measured only in six samples. beta-HCH was the most prevalent HCH isomer with a mean value of 2.08 ng/g ww. The mean concentration of gamma-HCH was 0.38 ng/g ww, while alpha-HCH was not detected in any sample. HCB is found in 95% of the milk samples with a mean concentration of 0.30 ng/g ww. The mean value for the sum of chlordanes was 0.39 ng/g ww, with oxychlordane and trans-nonachlor being the principal contributors. PCBs could be measured only in 8 out of 37 samples and their concentration ranged between <0.15 and 1.92 ng/g ww for the sum of PCBs. PCB profiles were dominated by congeners 153, 180 and 138. PBDEs were detected only in 3 out of 37 samples, with the highest value being 0.014 ng/g ww (0.40 ng/g lipid weight) and BDE 47 was the dominant congener. Although the number of samples is relatively low and they are not representative for the whole Turkish population, the results of the present study are important to provide additional data on the concentrations of persistent organochlorinated pollutants in Turkey and show as first the PBDE levels in Turkish population.     

Levels of organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in fish species from Kahramanmaras, Turkey

The levels of organohalogenated contaminants, such as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were measured in four fish species (Acanthobrama marmid (kalashpa), Cyprinus carpio (carp), Chondrostoma regium (nose-carp), and Silurus glanis (wels)) from the Sir Dam Lake, Kahramanmaras, Turkey. These species were selected for their characteristic feeding behaviour and their importance to local human fish consumption. DDTs were the predominant organohalogenated contaminants in all species, with the p,p'-DDE contributing to more than 90% to the total DDTs. Other OCPs, such as hexachlorocyclohexane (HCH) isomers, chlordanes and hexachlorobenzene (HCB) were found at much lower levels in all five species. The levels of PCBs and PBDEs (on wet weight basis) were lower than in similar species from European or American freshwater systems. PBDE data were measured for the first time in fish species from Turkish environment. Lipid-based concentrations of OCPs, PCBs and PBDEs were higher in wels than in the other species and this was related to its piscivorous feeding mode and to its higher lipid content. Contrarily, concentrations of pollutants in nose-carp were the lowest, in agreement with its more herbivorous diet. A preferential accumulation in muscle compared to liver was observed for all OCPs, PCBs, and PBDEs in wels and carp, while in nose-carp, a preferential accumulation in liver was observed only for PBDEs, p,p'-DDT and PCBs. Racemic amounts for alpha-HCH were measured in all investigated muscle and liver samples, except for carp muscle.     

Levels and distribution of organochlorines in fish from Indonesia

Organochlorines such as PCBs, DDTs, HCHs, CHLs and HCB were determined in pooled whole body homogenized of fish samples collected from five locations during 1998 and 2003 in order to understand their contamination status, temporal and spatial variation in Indonesian waters. PCBs and DDTs were the predominant contaminants with concentrations from 9.7 to 2700 ng/g lipid wt. and 12 to 1100 ng/g lipid wt., respectively, while HCHs (nd-24 ng/g lipid wt.), CHL compounds (nd-81 ng/g lipid wt.) and HCB (0.22-28 ng/g lipid wt.) were one to two orders of magnitude lower. Among the locations, PCBs and CHLs were higher in the samples from highly industrialized and thickly populated-locations, whereas OC pesticides such as DDTs and HCHs were particularly more prominent in suburban and rural areas. Levels of OCs observed in the waters surrounding Java Island were higher than those in Sumatra Island, implying significant use of OCs in highly populated Java Island. Concentrations of PCBs and DDTs in fish from Jakarta Bay were significantly lower in the samples collected in 2003 as compared to fish in 1998, indicating decreasing trend of these compounds in the Indonesian environment. Recent estimated average daily intakes of PCBs (0.81 microg/person/day), DDTs (1.1 microg/person/day), HCHs (0.018 microg/person/day), CHLs (0.010 microg/person/day) were much lower than the threshold values recommended by various agencies, suggesting minimal risk of this compound via fish ingestion to Indonesians.     

Biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in harbour seals and harbour porpoises from the Southern North Sea

Harbour seals and harbour porpoises are top predator species from the North Sea, have long life spans and hence, are known to accumulate high levels of anthropogenic contaminants. To gain knowledge about the behaviour of naturally-produced compounds in these marine mammals, the biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) was assessed. The biomagnification of MeO-PBDEs (2′-MeO-BDE 68 and 6-MeO-BDE 47) was lower in harbour seals (all biomagnification factors (BMFs) < 1) compared to the same age–gender groups of the harbour porpoises (all BMFs > 1). This may indicate a better metabolic breakdown of MeO-PBDEs in harbour seals, as was previously suggested for polybrominated diphenyl ethers (PBDEs). In both predators, 6-MeO-BDE 47 had the highest concentrations (range: 45–483 ng/g lw and 2–38 ng/g lw for harbour porpoises and seals, respectively) compared to 2′-MeO-BDE 68 (range: 2–28 ng/g lw and 1–6 ng/g lw for harbour porpoises and seals, respectively). In general, the highest concentrations were found in juveniles, suggesting an increased biotransformation capacity with age or the influence of dilution by growth for both species. Here we show that naturally-produced brominated organic compounds can biomagnify and accumulate in North Sea top predators, although to a lesser extent than anthropogenic lipophilic contaminants, such as polychlorinated biphenyls (PCBs) or PBDEs.     

Maternal transfer of organochlorines and brominated flame retardants in blue tits (Cyanistes caeruleus)

Although eggs have frequently been used as a biomonitoring tool for contamination with organohalogenated pollutants (OHPs), few studies have investigated the processes of maternal transfer in birds. Here, maternal transfer of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was investigated through comparison of the concentrations and profiles between whole homogenised female blue tits (Cyanistes caeruleus) and their eggs. In addition, we examined if there was an effect of laying order on the concentrations of PCBs, OCPs and PBDEs. PCBs were the most abundant contaminants in female blue tits and their eggs, followed by OCPs and PBDEs. Among the OCPs, p,p'-DDE was the most dominant compound and accounted for more than 80% of the sum OCPs. Egg concentrations decreased significantly in relation to the laying order from 1623+/-148 ng/g lipid weight (lw) to 1040+/-47 ng/g lw for the sum PCBs, from 342+/-24 ng/g lw to 235+/-17 ng/g lw for the sum OCPs and from 49+/-5 ng/g lw to 27+/-5 ng/g lw for the sum PBDEs. When reviewing all studies investigating laying order effects of OHPs in birds, no clear patterns emerged, which may be due to differences in study species and methodology among studies. Despite the fact that there were laying order effects in blue tit clutches, the variance in concentrations of PCBs and PBDEs was larger among clutches than within clutches. Variance in OCP concentrations among clutches was similar to the variance within clutches. These results suggest that one randomly collected blue tit egg from a clutch is useful as biomonitoring tool for PCBs and PBDEs, while for OCPs it is recommended to consistently use the same egg from the laying sequence as a biomonitoring tool. Lipid-normalized concentrations of sum PCBs, sum OCPs and sum PBDEs in female blue tits after clutch completion were comparable to the concentrations in the first-laid eggs. The egg/female lipid concentration ratios for sum PCBs, sum OCPs and sum PBDEs decreased significantly from 1.0+/-0.09 to 0.7+/-0.003, 1.1+/-0.1 to 0.7+/-0.02 and 1.2+/-0.14 to 0.8+/-0.05, respectively, during the course of egg laying. The profiles of the females and eggs differed significantly for the PCBs, OCPs and PBDEs. There was a higher contribution of lower chlorinated PCB congeners (CB 28, CB 52, CB 95, CB 101 and CB 110), BDE 183, p,p'-DDT and other less persistent OCPs in the females compared to their eggs. Maternal transfer in blue tits seemed to be selective for the more bioaccumulative and persistent congeners/compounds.     

三峡库区水体有机氯农药污染特征

在长江三峡库区采集了111件水体样品,并用气相色谱(GC ECD)内标法分析其有机氯农药(OCPs)的含量,探讨了研究区水体中OCPs的残留水平、分布及来源。结果表明：水体中OCPs指标,检出率为100%。HCH四种同分异构体含量范围分别为α HCH 010~608 ng/L,β HCH 048~1020 ng/L,γ HCH 009~843 ng/L,δ HCH 007~1053 ng/L;DDT类化合物检出率普遍较低,含量范围是：p,p' DDE 001~1914 ng/L,p,p' DDD 0.04~213 ng/L,p,p' DDT 007~164 ng/L。两类农药中HCHs在多数采样点上都能被检测到,在总体含量上干流断面HCHs普遍高于DDTs。长江干流重点位置与库区断面含量相比,HCHs高于断面,DDTs低于断面。HCHs在水库水体干流中的分布呈跳跃式波动,且每次含量波动幅度都要比前一次高。库区干流重点位置水体以β HCH为主,但δ HCH普遍存在。库区重点位置水体未能检测到DDT,表明其对库区水体DDTs的贡献较小。通过比值分析得出大气输入是库区水体DDT类物质的主要来源     

Distribution of persistent organic pollutants in two different fat compartments from obese individuals

There are only few studies defining persistent organic pollutant (POP) concentrations in various fat compartments from living obese individuals. The present study has therefore determined the concentrations of various classes of organohalogenated compounds, such as dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in visceral fat (VF: n = 52) and subcutaneous abdominal fat (SF: n = 52) samples collected in 2010–2012 from obese individuals in Belgium. Organohalogen compounds were detected in all fat samples in the decreasing order of their concentrations: PCBs > DDTs > HCHs > CHLs > HCB > HBCDs > PBDEs, suggesting that Belgians have been widely exposed to these contaminants. The levels and the patterns of POP distribution in VF and SF tissue depots were not significantly different. Concentrations of PCBs (VF/SF; median: 285/275 ng/g lw) and DDTs (VF/SF; median: 150/155 ng/g lw) were the major POPs in all fat samples. Concerning PCBs, PCB 153 (VF/SF: 27/26%) was the most dominant congener, followed by PCB 180 (VF/SF: 17/18%), PCB 138 (VF/SF: 15/14.5%) and PCB 170 (VF/SF: 8.1/8.4%) to the sum PCBs, respectively. Levels of HBCDs (VF/SF; median: 4.0/3.7 ng/g lw) and PBDEs (VF/SF; median: 2.6/2.7 ng/g lw) were 1–2 orders of magnitude lower than those of PCBs and DDTs. Among PBDEs, BDE 153 (VF/SF: 31/34%) was the dominant congener, followed by BDE 47 (VF/SF: 26/23%), BDE 154 (VF/SF: 16/16%), BDE 100 (VF/SF: 10/11%) and BDE 99 (VF/SF: 9/9%). To our knowledge, this is the first report on HBCD concentrations in Belgian human fat tissues. Total PBDE and HBCD levels in human fat samples could not be correlated with age. In agreement with the literature, a significant correlation (p < 0.05) between age and the concentration of PCBs (r = 0.828), DDTs (r = 0.640), HCHs (r = 0.666), CHLs (r = 0.534) and HCB (r = 0.754), was observed in the present study. Levels of DDTs, HCHs, HCB and CHLs were also significantly correlated to each other, suggesting that they share similar exposure routes. Correlation with computed tomography (CT) scan data revealed that VF and VF/SF ratios are positive for most of the POPs, such as PCBs, PBDEs, p,p′DDE, CHLs, β-HCH, and HCB. To our knowledge, this study is the first to assess the relationship between POP levels in adipose tissue and markers of abdominal adiposity, determined by CT.     

Persistent organochlorine compounds in peregrine falcon (Falco peregrinus) eggs from South Greenland: levels and temporal changes between 1986 and 2003

Thirty-seven addled peregrine falcon eggs collected in South Greenland between 1986 and 2003 were analysed for their content of the organochlorine compounds polychlorinated biphenyls (PCBs), dichlorodiphenyl tricloroethane (DDT) and its degradation products, hexachlorocyclohexane (HCH) isomers and hexachlorobenzene (HCB). PCBs and DDT (including metabolites) were by far the most abundant OC groups, with median concentrations of 55 and 40 microg/g lw, respectively. The concentrations were high in an Arctic context, but similar to previously reported levels from Alaska and Norway and slightly lower than concentrations measured in eggs from industrialised regions. Geographical differences may be of importance, considering the migration of peregrine falcons and their prey. SigmaHCH and HCB had median concentrations of 0.39 and 0.17 microg/g lw, respectively. On average, DDE accounted for 97% of SigmaDDT, but was below critical levels for eggshell thinning. All compound groups showed a weak decreasing trend over the study period, which was statistically significant for HCB and close to being significant for SigmaHCH. The weak decrease of SigmaPCB and SigmaDDT is different from other time trend studies from Greenland, usually showing a more pronounced decrease in the beginning of the study period, followed by a certain stabilisation in recent years.     

Organochlorine pesticide and polychlorinated biphenyl residues in feathers of birds from different trophic levels of South-West Iran

Persistent organochlorine pesticides (OCPs), such as dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), alpha, beta and gamma-hexachlorocyclohexane (HCH) isomers, together with polychlorinated biphenyl (PCB) congeners (IUPAC Nos. 28, 52, 101, 138, 153 and 180), were determined in tail feathers from 37 birds belonging to 18 species, all originating from the South-West of Iran (Khuzestan, coast of the Persian Gulf). This is the first report on organochlorine contaminants in feathers from museum collections and it is an indication of the concentrations of OCPs and PCBs in the past (1991-1996). Median concentrations of HCHs, DDTs, PCBs and HCB were 22, 14, 11 and 10 ng/g feather, respectively. Significant correlations (p<0.05) were calculated between OCPs (except HCB) and PCBs in the bird feathers. p,p'-DDE and gamma-HCH were the most abundant OCPs, while CB 180, CB 138 and CB 101 were the predominant PCB congeners in almost all species. Significant differences (p<0.05) in the mean concentrations of DDTs and PCBs were detected among species grouped according to their feeding habits. Levels of DDTs and PCBs were highest in the carnivorous species and lowest in the herbivorous species. Levels of OCPs and PCBs in feathers of bids in the 1990s were generally below the thresholds reported to affect reproduction.     

Flame retardants and legacy contaminants in polar bears from Alaska, Canada, East Greenland and Svalbard, 2005-2008

Flame retardants and legacy contaminants were analyzed in adipose tissue from 11 circumpolar polar bear (Ursus maritimus) subpopulations in 2005-2008 spanning Alaska east to Svalbard. Although 37 polybrominated diphenyl ethers (PBDEs), total-(α)-hexabromocyclododecane (HBCD), 2 polybrominated biphenyls (PBBs), pentabromotoluene, pentabromoethylbenzene, hexabromobenzene, 1,2-bis(2,4,6-tribromophenoxy(ethane) and decabromodiphenyl ethane were screened, only 4 PBDEs, total-(α-)HBCD and BB153 were consistently found. Geometric mean ΣPBDE (4.6-78.4 ng/g lipid weight (lw)) and BB153 (2.5-81.1 ng/g lw) levels were highest in East Greenland (43.2 and 39.2 ng/g lipid weight (lw), respectively), Svalbard (44.4 and 20.9 ng/g lw) and western (38.6 and 30.1 ng/g lw) and southern Hudson Bay (78.4 and 81.1 ng/g lw). Total-(α)-HBCD levels (<0.3-41.1 ng/g lw) were lower than ΣPBDE levels in all subpopulations except in Svalbard, consistent with greater European HBCD use versus North American pentaBDE product use. ΣPCB levels were high relative to flame retardants as well as other legacy contaminants and increased from west to east (1797-10,537 ng/g lw). ΣCHL levels were highest among legacy organochlorine pesticides and relatively spatially uniform (765-3477 ng/g lw). ΣDDT levels were relatively low and spatially variable (31.5-206 ng/g lw). However, elevated proportions of p,p'-DDT to ΣDDT in Alaska and Beaufort Sea relative to other subpopulations suggested fresh inputs from vector control use in Asia and/or Africa. Comparing earlier circumpolar polar bear studies, ΣPBDE, total-(α)-HBCD, p,p'-DDE and ΣCHL levels consistently declined, whereas levels of other legacy contaminants did not. International regulations have clearly been effective in reducing levels of several legacy contaminants in polar bears relative to historical levels. However, slow or stalling declines of certain historic pollutants like PCBs and a complex mixture of "new" chemicals continue to be of concern to polar bear health and that of their arctic marine ecosystems.     

Bioaccumulation of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in wild aquatic species from an electronic waste (e-waste) recycling site in South China

Water and several wild aquatic species including Chinese mysterysnail, prawn, fish, and water snake were collected from a reservoir surrounded by several e-waste recycling workshops in South China. The samples were examined to investigate the levels and bioaccumulation extent of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) released from electronic waste (e-waste) which was processed by crude recycling method. Elevated levels of PBDEs [52.7 to 1702 ng/g wet weight (ww)] and PCBs (20.2-25958 ng/g ww) were found in the collected biota species compared to that in the reference samples (13.0-20.5 ng/g ww for PBDEs and 75.4-82.8 ng/g ww for PCBs). log BAF (bioaccumulation factor) ranged from 2.9 to 5.3 for PBDEs and from 1.2 to 8.4 for PCBs, depending on congeners and species. The relationship between log BAFs and log K(OW) (octanol-water partition coefficient) can be adequately described by species-specific parabolic models wherein log BAFs generally increased at log K(OW)<7 then decreased with further increasing log K(OW) both for PBDEs and PCBs. The exceptions were for Chinese mysterysnail and prawn, in which the log BAFs showed a positive linear correlation with log K(OW) for PBDEs. Some PBDE and PCB congeners showed BAF values declining from the general trend predicted by K(OW), largely attributing to metabolism of these congeners in species sampled.     

Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

Polybrominated diphenyl ethers, polychlorinated biphenyls and organochlorine pesticides in sediment cores from the Western Scheldt river (Belgium): analytical aspects and depth profiles

A rapid and simple analytical method for the determination of organochlorines, such as polychlorinated biphenyls (PCBs) and selected organochlorinated pesticides (OCPs) and organobromines, such as polybrominated diphenyl ethers (PBDEs), in sediment samples was optimised using CRM 536 (PCBs in freshwater sediment). The method involved a hot Soxhlet extraction that reduced the extraction time to 2 h. Elemental sulphur, which is present in sediments and may interfere during the analysis, was removed by means of copper powder added to the sediment during extraction and into the clean-up cartridge. The analysis of PCBs and OCPs was accomplished by gas chromatography with electron capture or mass spectrometric detection. Similar quantitative results for PCB congeners in CRM 536 were obtained using a 50-m capillary column and a 10-m narrow bore column suited for fast analysis. The analysis of PBDEs was done by mass spectrometry in negative chemical ionisation mode. Concentrations of organic pollutants in two sediment cores (approximately 50 cm depth) from the Scheldt river (south of Antwerp, Belgium) showed a relative steady state for PCBs and DDTs, with a slight decrease in the top layers, suggesting a slight decline in their concentrations due to restrictions in their usage. On the contrary, PBDEs were showing an increase in their concentrations in the top layers (up to 270 and 8400 ng/g dry weight for sum of tri- to hexa-BDE congeners and for BDE 209, respectively). This suggests an increasing trend in the concentrations of PBDEs in the Belgian environment.     

Chlorinated biphenyls and pesticides in migrating and resident seabirds from East and West Antarctica

The unhatched eggs of the following seabirds were analyzed to quantify PCBs, hexachlorobenzene (HCB), α-, β-, γ-, δ-hexachlorocyclohexanes (HCHs), o,p′ and p,p′ isomers of DDT, DDD and DDE: resident Adèlie (Pygoscelis adèliae, ADPE) and Emperor (Aptenodytes forsteri, EMPE) penguins, migrating snow petrel (Pagodroma nivea, SNPT) and South Polar skua (Catharacta maccormicki, SPSK) from the Ross Sea (East Antarctica); and migrating Brown skua (Catharacta antartica, BRSK) and resident ADPE from the Brainsfield Strait (West Antarctica). The general aims were to evaluate the contaminant accumulation in eggs of migrating and resident species in the two study areas, and to compare levels in penguins and skuas nesting in East and West Antarctica. PCB congener and HCH and DDT isomer profiles were also assessed. Comparisons were evaluated using seven PCB congeners (IUPAC nos. 28, 52, 101, 118 + 149, 138, 153, and 180), p,p′-DDE, ΣDDTs, and ΣHCHs. Higher contaminant concentrations were detected in migrating seabirds (South polar skua and brown skua) > sub-Antarctic species (snow petrel) > Antarctic species (penguins) from both the sampling sites, suggesting contamination events at lower latitudes for those birds migrating northward. HCHs showed the lowest concentrations in all species (from 0.03 ± 0.03 ng/g wet wt in SPSK to 1.81 ± 1.23 ng/g wet wt in ADPE from West Antarctica), and PCBs were the most abundant contaminants (from 4.34 ± 2.15 ng/g wet wt. in EMPE to 53.41 ± 19.61 ng/g wet wt. in brown skua). Among pesticides, it is relevant the detection of p,p′-DDT in Adèlie penguin from West Antarctica and in both species of skua; the detection of this pesticide can confirm its actual use in certain malaria-endemic countries from where it is transferred through the long range transport to the polar regions. Contaminants did not show any significant temporal trend during a ten year time span, from 1994/95 to 2004/05, in organisms collected in East Antarctica and they did not indicate any latitudinal gradient along the Ross Sea coasts.     

Evaluation of the concentration of HCH, DDT, HCB, PCB and PAH in the sediments along the lower stretch of Hugli estuary, West Bengal, northeast India

Detailed analyses of persistent organic pollutants (POPs) such as hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs), hexachlorobenzene (HCB) and congeners of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in surface sediments from the coastal estuarine environment of West Bengal, northeast India allowed the evaluation of the contamination status, distribution and possible pollution sources. HCH, DDT, HCB, PCB and PAH were identified compounds in all the samples, whereas the concentrations of chlorinated pesticides (trans-eptachlorepoxide, dieldrin, endrin, metaoxychlor and mirex) were below the detection limits and were not of great concern. The pesticides did demonstrate markedly different distributions reflecting different agricultural and domestic usage in the region. The range of concentrations of HCH, HCB, DDT and PCBs in the sediments were 0.11-0.40, <0.05-0.98, 0.18-1.93 and 0.18-2.33 ng/g dry wt, respectively. Overall elevated levels of HCB, DDT and PCB were recorded at Babughat, a very closely located site of the metropolitan megacity Calcutta. Fluoranthene (flu) and pyrene (py), the dominant 4-ring PAHs, also showed an abrupt elevated concentrations at Babughat with values of 214 and 144 ng/g dry wt, respectively. Among the isomers and metabolites of HCH, DDT and PCB, alpha-HCH, pp'-DDT and PCB (101), PCB (118), PCB(153) and PCB (138) were found to be dominant. High ratios of metabolites of DDT to SigmaDDTs reveal recent use of DDT in this coastal environment. Fluoranthene, pyrene, 1,2-benzo(a)anthracene and chrysene formed the dominant congeners out of 19 identified PAHs. The sources of contamination are closely related to human activities such as domestic and industrial discharge, automobile exhausts, street runoff, slum sewage, agricultural chemicals and soil erosion due to deforestation as well as atmospheric transport. This study is compared to other coastal and estuarine environments in India and abroad. The baseline data can be used for regular ecological monitoring, considering the industrial and agricultural growth around this important estuarine ecosystem.