Organohalogen compounds in human breast milk from Republic of Buryatia, Russia

Human breast milk samples collected during 2003/04 in Buryatia, a Russian autonomous republic, were analyzed in order to assess human exposure to organohalogen compounds including organochlorine pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). When compared with available worldwide data, levels of HCB (23-880 ng/g lipid wt.), PCBs (69-680 ng/g lipid wt.), and HCHs (100-3700 ng/g lipid wt.) were relatively high, indicating elevated human exposure to these organochlorines (OCs) in Buryatia. In contrast to OCs, PBDE concentrations were low (0.46-1.7 ng/g lipid wt.). Out of 14 BDE congeners analyzed, BDE-28, BDE-47, BDE-100, BDE-153, BDE-197, and BDE-207 were detected. Estimated daily intakes (EDIs) of HCHs, HCB, CHLs, and PCBs by infants solely from human milk for 100%, 43%, 34%, and 17% of the samples, respectively, exceeded guideline thresholds. Although high EDIs raise concern for possible toxic effects of OCs, women in Buryatia are recommended to breastfeed due to numerous advantages of breastfeeding for mother and child.     

Geographical distribution of polybrominated diphenyl ethers (PBDEs) and organochlorines in small cetaceans from Asian waters

Polybrominated diphenyl ethers (PBDEs) are one of the flame retardants widely used in plastics, textiles, electronic appliances, and electrical household appliances. In this study, PBDEs and organochlorine compounds (OCs) were determined in the archived samples from the Environmental Specimen Bank for Global Monitoring (es-BANK) at Ehime University. The blubber of cetaceans found stranded along the coasts of Japan, Hong Kong, the Philippines and India during the period from 1990 to 2001 were employed for chemical analysis to understand the present status of contamination and the specific accumulation of PBDEs. PBDEs were detected in all the cetacean samples analyzed, and concentrations were one or two orders of magnitude lower than for PCBs and DDTs. Concentrations of PBDEs ranged from a low value of 6.0 ng/g lipid wt. in spinner dolphin (Stenella longirostris) from India to a high value of 6000 ng/g lipid wt. in Indo-Pacific humpback dolphin (Sousa chinensis) from Hong Kong. No difference in PBDE levels between coastal and offshore species from Japan was observed, implying the existence of pollution sources in this region other than Japan. Highest concentrations of PBDEs were found in animals from Hong Kong, followed by Japan, and much lower levels from the Philippines and India, suggesting that developing nations may also have pollution sources of PBDEs. Geographical distribution of PBDEs in Asian waters was different from PCBs but similar to DDTs.     

Spatial distribution and accumulation of brominated flame retardants, polychlorinated biphenyls and organochlorine pesticides in blue mussels (Mytilus edulis) from coastal waters of Korea

Blue mussels (Mytilus edulis) from 20 locations along the coastal waters of Korea were analyzed to elucidate the characteristic distribution and contamination status of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), polychlorinated biphenyls (PCBs) and organochlorine pesticides. To our knowledge, this is the first study to report on the contamination status of HBCDs from Korea. PBDEs and HBCDs were found in mussels at levels ranging from 6.6 to 440 and from 6.0 to 500 ng/g lipid wt., respectively. Concentrations of PBDEs in mussels from Korea were higher or comparable to available data in mussels from other countries. Among the organochlorine compounds (OCs) analyzed, levels of PCBs and DDTs were the highest followed by CHLs, HCHs and hexachlorobenzene. For all the compounds, higher concentrations were found in mussels from southeastern coast of Korea. The present study shows the importance of mussels as bioindicators for monitoring contaminants in coastal waters.     

Contamination by polybrominated diphenyl ethers of sediments from the Lake Maggiore basin (Italy and Switzerland)

Polybrominated diphenyl ethers (PBDEs) are characterized by chemical properties and toxicological profiles similar to other POPs (persistent organic pollutants) included in the EU Priority Pollutant List (2455/01/CE). However, limited data have been available for these compounds thus far for Italian freshwater abiotic matrices. Lake Maggiore basin, a heavily industrialized and densely populated area, was selected for studying PBDE contamination in Italy. PBDEs and OCs (organochlorine compounds) in the basin were quantified by analysing both sediment cores collected in 2005 from the lake and grab samples from the main tributaries and the emissary. Fourteen PBDEs, from tri-BDE to hepta-BDE congeners and BDE209, were compared with some organochlorine POPs (PCBs and DDTs) characterizing Lake Maggiore basin contamination. Analyses of tri-to hepta-BDEs, PCBs and DDTs were undertaken by GC-MS/MS, while BDE-209 was analysed by GC/ECD. Results showed a dominant presence of BDE-209 (>95% of SigmaBDE) and limited amounts of BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154. Lake core profiles highlighted a decreasing trend in PCB concentrations starting from the year 2000, while PBDEs showed greater concentrations after the beginning of the 1990s (up to 30 ng g(-1)d.w.). Among the tributaries, the Bardello and Boesio rivers were the most PBDE-contaminated (up to 290 ng g(-1)d.w.).     

Brominated flame retardants and organochlorine pollutants in eggs of little owls (Athene noctua) from Belgium

Residues of brominated diphenylethers (PBDEs), organochlorinated pesticides (OCPs) and polychlorinated biphenyls (PCBs) were measured in 40 eggs of little owls (Athene noctua), a terrestrial top predator from Belgium. The major organohalogens detected were PCBs (median 2,600 ng/g lipid, range 790-23 000 ng/g lipid). PCB 153,138/163, 170, 180 and 187 were the predominant congeners and constituted 71% of total sum PCBs. PBDEs were measurable in all samples, but their concentrations were much lower than for PCBs, with a range from 29-572 ng/g lipid (median 108 ng/g lipid). The most prevalent PBDE congeners in little owl egg samples were BDE 47, 99 and 153. This profile differs from the profile in marine bird species, for which BDE 47 was the dominant congener, indicating that terrestrial birds may be more exposed to higher brominated BDE congeners than marine birds. The fully brominated BDE 209 could be detected in one egg sample (17 ng/g lipid), suggesting that higher brominated BDEs may accumulate in terrestrial food chains. Brominated biphenyl (BB) 153 was determined in all egg samples, with levels ranging from 0.6 to 5.6 ng/g lipid (median 1.3 ng/g lipid). Additionally, hexabromocyclododecane (HBCD) could be identified and quantified in only two eggs at levels of 20 and 50 ng/g lipid. OCPs were present at low concentrations, suggesting a rather low contamination of the sampled environment with OCPs (median concentrations of sum DDTs: 826 ng/g lipid, sum chlordanes: 1,016 ng/g lipid, sum HCHs: 273 ng/g lipid). Hexachlorobenzene (HCB) and octachlorostyrene (OCS) were also found at low median levels of 134 and 3.4 ng/g lipid, respectively. Concentrations of most analytes were significantly higher in eggs collected from deserted nests in comparison to addled (unhatched) eggs, while eggshell thickness did not differ between deserted and addled eggs. No significant correlations were found between eggshell thickness and the analysed organohalogens.     

Brominated flame retardants and organochlorine pollutants in aquatic and terrestrial predatory birds of Belgium: levels, patterns, tissue distribution and condition factors

Liver and muscle samples from 7 species of aquatic and terrestrial predatory birds from Flanders (Belgium) were analysed for polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and organochlorine pesticides (OCPs). PCBs were the predominant compounds in our samples, which showed highest concentrations in the liver of barn owl (Tyto alba) and sparrowhawk (Accipiter nisus) (up to 1000 microg/g lipid weight). PBDEs could be determined in most samples at lower concentrations than PCBs (up to 64 microg/g lipid in sparrowhawk liver). Sparrowhawks had the highest levels of hexachlorobenzene, DDTs and PBDEs. In contrast, kestrels (Falco tinnunculus) had relatively low levels of most measured organochlorines. BDE 47 was the most abundant congener in heron (Ardea cinerea) and grebe (Podiceps cristatus), while BDE 47, 99 and 153 were equally important in the terrestrial species. BDE 183 and BDE 209 were only measured in the terrestrial birds. These results indicate that terrestrial birds may be more exposed to higher brominated BDE congeners than aquatic species.     

Polybrominated diphenyl ethers (PBDEs) and organochlorines in melon-headed whales, Peponocephala electra, mass stranded along the Japanese coasts: maternal transfer and temporal trend

Polybrominated diphenyl ethers (PBDEs) and organochlorine compounds (OCs) were determined in the blubber of 55 melon-headed whales (Peponocephala electra) mass stranded along the Japanese coasts since 1982. DDTs and PCBs were predominant in all the specimens investigated. In whales that died during the latest event in 2006, concentrations of PBDEs (190–510 ng/g lipid wt) were approximately two orders of magnitude lower than DDTs and PCBs, but comparable with HCHs and HCB. Maternal transfer of PBDEs to offspring through the whole reproductive process was estimated to be 85% of the mother's body burden, while that occurring during gestation was much lower (2.6–3.5%). Concentrations of PCBs, DDTs, and HCB were lower in melon-headed whales stranded after the year 2000 than those stranded in 1982, whereas PBDE and CHL levels showed a temporal increase during the past 20 years, suggesting that the peak of their usage and contamination occurred after the year 1982.     

Inter-species differences for polychlorinated biphenyls and polybrominated diphenyl ethers in marine top predators from the Southern North Sea: Part 2. Biomagnification in harbour seals and harbour porpoises

Harbour porpoises (Phocoena phocoena) and harbour seals (Phoca vitulina) were found to differ in the ability to metabolize polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Biomagnification factors (BMFs), calculated between both predators and their prey (sole - Solea solea and whiting - Merlangius merlangus), had a large range of variation (between 0.5 and 91 for PCBs and between 0.6 and 53 for PBDEs). For the higher chlorinated PCBs and the highest brominated PBDEs, the BMF values in adult males were significantly higher than in the juvenile individuals of both species. BMF values of hexa- to octa-PCBs were the highest, suggesting reduced ability to degrade these congeners. Harbour porpoises had higher BMFs for lower chlorinated PCBs and for all PBDEs compared to harbour seals. Other factors, which may influence biomagnification, such as the octanol-water partition coefficients and the trophic level position measured through stable isotope (δ¹⁵N) analysis, were found to be of lesser importance to predict biomagnification in the studied food chain.     

Distribution of polychlorinated biphenyls and polybrominated diphenyl ethers in birds of prey from Switzerland

Polychlorinated biphenyls (PCBs) and the structurally related polybrominated diphenyl ethers (PBDEs) have been associated with chronic neurotoxicity involving reduced motor activity and impaired attentiveness. Such neurobehavioral effects indicate that the central nervous system may represent an important target organ for the action of these persistent contaminants in wildlife. As a consequence, the brain of different terrestrial and aquatic birds collected in Switzerland was analysed for PCBs and PBDEs. In parallel, the same contaminants were examined in the accompanying adipose tissue. After clean-up by means of glass columns containing acidified silica, deactivated alumina and anhydrous sodium sulphate, the samples were analysed by high resolution gas chromatography/tandem mass spectrometry (HRGC-MS/MS). Median PCB concentrations in the brain (sum of PCB 28, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 and PCB 180) ranged between 13 ng g(-1) wet weight (ww) in blackbirds (Turdus merula) and 428 ng g(-1) ww in sparrow hawks (Accipiter nisus). Median PBDE concentrations in the brain (sum of BDE 28, BDE 47, BDE 99, BDE 100, BDE 153, BDE 154 and BDE 183) ranged from below the decision limit in buzzards (Buteo buteo) and blackbirds, to 14 ng g(-1) ww in sparrow hawks. After correction for the respective lipid content, higher PCB or PBDE concentrations in brain compared to adipose tissue, were found in three sparrow hawks, four buzzards and in all investigated blackbirds. These results suggest that a deficit in the neuroprotective function of the blood-brain barrier may cause unexpected levels of PCBs and PBDEs in the central nervous system.     

Polybrominated diphenyl ethers and selected organochlorine chemicals in grey seals (Halichoerus grypus) in the North Sea

Blubber samples from grey seal (Halichoerus grypus) pups were collected in 1998 through to 2000. Twenty four newly weaned pups were sampled in November 1998, 13 of which were re-sampled during their first year of life, between March and December 1999, and an additional 48 and 25 samples (new cohorts) were obtained in 1999 (November-December) and 2000 (May-September) respectively. SimgaPBDE concentrations (sum of Di-HxBDEs) ranged from 45 to 1500 ng/g lipid, with a geometric mean of 290 ng/g lipid. BDE 47 dominated the congener profile, followed by BDEs 100, 99, 153 and 154. SimgaPCB concentrations (sum of 41 congeners) ranged from 100 to 93000 ng/g lipid, with a geometric mean of 4600 ng/g lipid, with CB congeners 153, 138 and 180 making up 84% of the total PCB concentrations. The predominant OC pesticides were p,p'-DDE (geometric mean=860 ng/g lipid, range=160-3800 ng/g lipid) and p,p'-DDT (geometric mean=120 ng/g lipid, range=30-670 ng/g lipid). No significant differences were found between males and females, probably due to the young age of the animals. Significant decreases (P<0.01 for PBDEs and P<0.05 for PCBs/OCs) were observed between newly weaned seals in 1998 and 1999, but not for the majority of juveniles in 1999 and 2000. Significant differences (P<0.01) were also found between the different seasons in 1999 newly weaned and juvenile seals, reflecting changes in blubber mass.     

Organohalogen compounds in human breast milk from mothers living in Payatas and Malate, the Philippines: Levels, accumulation kinetics and infant health risk

Human breast milk samples (n = 33) from primipara and multipara mothers from Payatas a waste dump site, and Malate a reference site in the Phillipines were collected in 2004 and analyzed for eight organohalogen compounds, viz., PCBs, DDTs, CHLs, HCHs, HCB, TCPMe, PBDEs and HBCDs. DDTs and PCBs were predominant in all the samples. Overall mean concentrations of PBDEs found in our study were higher (7.5 ng/g lipid wt.) than those reported for Japan and many other Asian countries. Primipara mothers had significantly higher levels of DDTs, CHLs and HCHs than multipara mothers, but not PBDEs and HBCDs. A few individuals accumulated CHLs close to or even higher than the tolerable daily intake guidelines proposed by Health Canada.     

Inter-species differences for polychlorinated biphenyls and polybrominated diphenyl ethers in marine top predators from the Southern North Sea: Part 1. Accumulation patterns in harbour seals and harbour porpoises

Harbour porpoises (Phocoena phocoena) and harbour seals (Phoca vitulina) are two representative top predator species of the North Sea ecosystem. The median values of sum of 21 polychlorinated biphenyl (PCB) congeners and sum of 10 polybrominated diphenyl ether (PBDE) congeners were 23.1 μg/g lipid weight (lw) and 0.33 μg/g lw in blubber of harbour seals (n = 28) and 12.4 μg/g lw and 0.76 μg/g lw in blubber of harbour porpoises (n = 35), respectively. For both species, the highest PCB concentrations were observed in adult males indicating bioaccumulation. On the contrary, the highest PBDE concentrations were measured in juveniles, likely due to better-developed metabolic capacities with age in adults. A higher contribution of lower chlorinated and non-persistent congeners, such as CB 52, CB 95, CB 101, and CB 149, together with higher contributions of other PBDE congeners than BDE 47, indicated that harbour porpoises are unable to metabolize these compounds. Harbour seals showed a higher ability to metabolize PCBs and PBDEs.     

Evaluation of mitogen-induced responses in marine mammal and human lymphocytes by in-vitro exposure of butyltins and non-ortho coplanar PCBs

The effects of exposure to butyltin compounds (BTs: tributyltin; TBT, dibutyltin; DBT and monobutyltin; MBT) and non-ortho coplanar PCBs (IUPAC 77, 126 and 169) on marine mammals and human lymphocyte were evaluated. Peripheral blood mononuclear cells (PBMCs) isolated from Dall's porpoises (Phocoenoides dalli), bottlenose dolphins (Tursiops truncatus), a California sealion (Zalophus californianus), a larga seal (Phocoa largha) and humans (Homo sapiens) were exposed at varying concentrations of BTs and coplanar PCBs. Concanavalin A (Con A)-stimulated mitogenesis found significantly suppressed (P<0.01) when the cells were exposed at 300 nM (89 ng/ml) of TBT and 330 nM of DBT (77 ng/ml), while MBT showed little cytotoxicity at treatment levels of up to 3,600 nM (620 ng/ml). BTs concentrations in the liver of Dall's porpoises from Japanese coastal waters ranged between 81-450 ng/g for TBT and 200-1,100 ng/g (wet wt.) for DBTs, which is greater than the cytotoxic levels registered in this study. In contrast, non-ortho coplanar PCBs did not suppress cell proliferation at concentrations of up to 30 nM (10 ng/ml). The residue levels of coplanar PCBs in the blubber of Dall's porpoises were 0.12-1.3 ng/g, which were one order of lower than those levels that do cell proliferation. When cells were exposed to a mixture of TBT/DBTand coplanar PCBs, the proliferation was significantly reduced to 33 nM DBT plus 34 nM CB-77 and 33 nM DBT plus 28 nM CB-169 mixtures, respectively. The investigations relating the contaminant-induced immunosuppression in marine mammals have been focused on persistent organochlorines such as PCBs. pesticides and dioxin compounds. However, this study suggested the possibility of BTs could also pose a serious threat to the immune functions in free-ranging marine mammals and humans.     

Within- and among-clutch variation of organohalogenated contaminants in eggs of great tits (Parus major)

In this study we investigated the variation of organohalogenated compounds, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs), within and among clutches of a small insectivorous songbird, the great tit (Parus major), and determined whether egg laying order affects the concentrations of these compounds. PCBs were the major organohalogenated contaminants in the eggs of great tits (mean 4778 ng/g lipid weight), while PBDEs (mean 204 ng/g lipid weight) and DDTs (mean 601 ng/g lipid weight) were found at much lower concentrations. Within-clutch variability of PCBs, PBDEs, and DDTs residues in the egg samples was small (7%, 3%, and 22%, respectively) compared to among-clutch variability (93%, 97%, and 78%, respectively). The small within-clutch variability may be in part related to the small home range of great tits and low spatial heterogeneity of the contaminants. We found no laying order effects on the concentrations of PCBs, PBDEs, and DDTs. Our results show that random egg samples of great tits are suitable as a biomonitoring tool for contamination with persistent organohalogenated pollutants in terrestrial environments.     

Characterization of PBDEs in soils and vegetations near an e-waste recycling site in South China

The concentration and composition of PBDEs in the soils and plants near a typical e-waste recycling site in South China were investigated. The total concentration of PBDEs (ΣPBDEs) in soil ranged from 4.8 to 533 ng/g dry wt. The ΣPBDEs in vegetation were from 2.1 to 217 ng/g dry wt. For the vegetable, the highest concentration of 19.9 ng/g dry wt. was observed in the shoot of Brassica alboglabra L. BDE 209 was the predominant congener in all samples. In comaprison with other e-waste contaminated sites in China, lower concentrations of PBDEs and higher concentrations of PCBs were observed in both soils and plants suggesting different e-waste types involved in the present study. The PBDEs contaminated vegetables around the e-waste dismantling site may pose a potential health risk to the local inhabitants.     

Accumulation of hydroxylated polychlorinated biphenyls (OH-PCBs) and implications for PCBs metabolic capacities in three porpoise species

The present study investigated polychlorinated biphenyls (PCBs) and hydroxylated metabolites of PCBs (OH-PCBs) in blood from three porpoise species: finless porpoises (Neophocaena phocaenoides), harbor porpoises (Phocoena phocoena), and Dall’s porpoises (Phocoenoides dalli). The porpoises were found stranded or were bycaught along the Japanese coast. Concentrations of OH-PCB were the highest in Dall’s porpoises (58 pg g⁻¹ wet wt), second highest in finless porpoises (20 pg g⁻¹ wet wt), and lowest in harbor porpoises (8.3 pg g⁻¹ wet wt). The concentrations in Dall’s porpoises were significantly higher than the concentrations in finless porpoises and harbor porpoises (p < 0.05 and p < 0.01, respectively). There was a positive correlation between PCB and OH-PCB concentrations (r = 0.67, p < 0.001), suggesting the possible concentration-dependent induction of CYP enzymes. The three porpoise species may have exceptionally low metabolic capacities compared with other marine and terrestrial mammals, because low OH-PCB/PCB concentration ratios were found, which were 0.0016 for Dall’s porpoises, 0.0013 for harbor porpoises, and 0.00058 for finless porpoises. Distinct differences in the OH-PCB congener patterns were observed for the three species, even though they are taxonomically closely related.     

Geographical distribution and accumulation features of PBDEs in human breast milk from Indonesia

The present study reports concentrations of polybrominated diphenyl ethers (PBDEs) and organochlorines (OCs) in human breast milk from Indonesia covering urban, suburban and rural areas. PBDEs were detected in all the samples of the present study with total concentrations ranging from 0.49 to 13 ng/g lipid wt. Geographical distribution showed that concentrations of PBDEs were relatively uniform (p>0.05) and the levels were in the same order as those in Japan and some European countries, but were one or two order lower than North America. When compared to OCs, the level of total PBDEs was lower. The congener pattern was in accordance with other studies on human matrices, in which BDE-47 was the most abundant congener. Variations of PBDE congeners in human breast milk were further discussed to elucidate the potential exposure source(s) and pathways.     

Specific accumulation of polychlorinated biphenyls and organochlorine pesticides in Japanese common squid as a bioindicator

Organochlorines (OCs) representing Persistent Organic Pollutants (POPs) such as PCBs (polychlorinated biphenyls), DDTs (DDT and its metabolites), CHLs (chlordane compounds), HCHs (hexachlorocyclohexane isomers) and HCB (hexachlorobenzene) were determined in the liver of Japanese common squid (Todarodes pacificus) collected from the waters around Japan (Japan Sea and western North Pacific Ocean). Among OCs concentrations, PCBs (upto 5600 ng/g lipid wt.) were the highest, and those of other OCs were in the order of DDT> CHLs > HCHs > HCB. Studies on growth trend and seasonal variation of OCs in this species suggest a rapid reflection of the pollution levels in seawater where and when they were collected, regardless of body-length and time of collection. These results indicate that Japanese common squid is a suitable bioindicator for monitoring OCs pollution in waters around Japan. With regard to the geographical distribution of OCs in this species collected from waters around Japan, OCs concentrations in specimens from Japan Sea were higher than those from the Pacific Ocean. This result might reflect some existing of local pollution sources of OCs around Japan Sea, and slower water exchange between Japan Sea and open ocean.     

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

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