Hydroxylated and methoxylated polybrominated diphenyl ethers in a Canadian Arctic marine food web

Residues of hydroxylated (OH-) and methoxylated (MeO-) polybrominated diphenyl ethers (PBDEs) have been previously detected in precipitation, surface waters, wildlife, and humans. We report measured concentrations of OH-PBDEs, MeO-PBDEs, and Br3-Br7 PBDEs in sediments and biota from a Canadian Arctic marine food web. PBDEs exhibited very low trophic magnification factors (TMFs between 0.1-1.6), compared to recalcitrant PCBs (TMFs between 3 and 11), indicating biotransformation via debromination and/or cytochrome P450 mediated metabolism. OH-PBDEs were not detectable in samples of blood, muscle, and/or liver of fish and marine wildlife. Five OH-PBDEs were detected at very low concentrations (range: 0.01-0.1 ng x g(-1) lipid equivalent) in beluga whale blubber and milk. The data indicate negligible formation/retention of OH-PBDEs in these Arctic marine organisms. Appreciable levels of several MeO-PBDEs were observed in bivalves, Arctic cod, sculpin, seaducks, and beluga whales (mean range 0.1-130 ng x g(-1) lipid equivalent). 2'-MeO-BDE-68 and 6-MeO-BDE-47 exhibited the highest concentrations among the brominated compounds studied (including BDE-47 and BDE-99) and biomagnified slightly in the food web, with TMFs of 2.3 and 2.6, respectively. OH- and MeO-PBDEs in this Arctic marine food web may occur via metabolic transformation of PBDEs or bioaccumulation of PBDE degradation products and/or natural marine products. We observed no evidence of a local natural source of OH- or MeO-PBDEs, as no measurable quantities of those compounds were observed in ambient environmental media (i.e., sediments) or macroalgae. Further investigations of PBDEs and their hydroxylated and methoxylated analogues would be useful to better understand sources, fate, and mechanisms governing biotransformation and bioaccumulation behavior of these compounds.     

Trophic magnification of triphenyltin in a marine food web of Bohai Bay, North China: comparison to tributyltin

Organotins, especially tributyltin (TBT) and triphenyltin (TPT), are of particular concern due to their ubiquity in the aquatic environment and theirtoxicityto aquatic organisms. This study reports field studies on trophic magnification factors (TMF) of TBT and TPT in a marine food web. TBT, TPT, and their metabolites in plankton, five benthic invertebrate species, and six fish species collected from Bohai Bay, North China were determined, and it was found that the concentrations of TPT in marine fish were unexpectedly higherthan those of TBT. A positive relationship was found between trophic levels and concentrations of TPT, indicating trophic magnification of TPT in this food web. The TMF of TPT was calculated to be 3.70. On the other hand, concentrations of TBT, dibutyltin (DBT) and monobutyltin (MBT) did not exhibit statistically significant trends with trophic levels, and the TMF of TBT was 0.59. Analysis of organotins in the water and surface sediment from Bohai Bay revealed low inputs of TPT to the environment, which indicated that the high concentrations of TPT found in fish from Bohai Bay were due to the food web magnification of TPT.     

Elevated PBDE levels in pet cats: sentinels for humans?

Co-incident with the introduction of polybrominated diphenyl ethers (PBDEs) into household materials nearly 30 years ago, feline hyperthyroidism (FH) has increased dramatically. Risk of developing FH is associated with indoor living and consumption of canned catfood. We hypothesized that increases in FH were, in part, related to increased PBDE exposure, with key routes of exposure being diet and ingestion of house dust. This study was designed to determine whether body burdens of PBDEs in hyperthyroid (HT) cats were greater than that of young or sick non-HT cats. Serum samples and clinical information were collected from 23 cats. Serum and dry and canned cat food were analyzed for PBDEs. A spectrum of BDE congeners was detected in all cats, with BDE-47, 99, 207, and 209 predominating. Mean +/- standard error (and median) cumulative sigma PBDE serum concentrations of young, old non-HT, and HT cats were 4.3 +/- 1.5 (3.5), 10.5 +/- 3.5 (5.9), and 12.7 +/- 3.9 (6.2) ng/mL, respectively. Due to high variability within each group, no association was detected between HT cats and sigma PBDE levels. Indicative of age- or disease-dependent changes in PBDE metabolism, BDE-47/99 ratios were inversely correlated with age, and 47/99 and 100/ 99 ratios in HT cats were significantly lower than those in the other cats. Overall, sigma PBDE levels in cats were 20- to 100-fold greater than median levels in U.S. adults. Our results support the hypothesis that cats are highly exposed to PBDEs; hence, pet cats may serve as sentinels to better assess human exposure and adverse health outcomes related to low-level but chronic PBDE exposure.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in a marine foodweb of coastal Florida

Nine species of marine fish, including teleost fishes, sharks, and stingrays, and two species of marine mammals (dolphins) collected from Florida coastal waters were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) to evaluate biomagnification factors (BMF) of these contaminants in a coastal foodweb. In addition, bottlenose dolphins and bull sharks collected from the Florida coast during the 1990s and the 2000s were analyzed for evaluation of temporal trends in PBDE and PCB levels in coastal ecosystems. Mean concentrations of PBDEs in muscle tissues of teleost fishes ranged from 8.0 ng/g, lipid wt (in silver perch), to 88 ng/g, lipid wt (in hardhead catfish), with an overall mean concentration of 43 +/- 30 ng/g, lipid wt. Mean concentrations of PBDEs in muscle of sharks ranged from 37.8 ng/g, lipid wt, in spiny dogfish to 1630 ng/g, lipid wt, in bull sharks. Mean concentrations of PBDEs in the blubber of bottlenose dolphins and striped dolphins were 1190 +/- 1580 and 660 ng/g, lipid wt, respectively. Tetra-BDE 47 (2,2',4,4'-) was the major congener detected in teleost fishes and dolphin samples, followed by BDE-99, BDE-153, BDE-100, and BDE-154. In contrast, BDE-209 was the most abundant congener in sharks. Concentrations of PBDEs and PCBs in dolphins and sharks were 1-2 orders of magnitude greater than those in lower trophic-level fish species, indicating biomagnification of both of these contaminants in the marine foodweb. Based on the analysis of sharks and dolphins collected over a 10-year period, an exponential increase in the concentrations of PBDEs and PCBs has occurred in these marine predators. The doubling time of PBDE and PCB concentrations was estimated to be 2-3 years for bull sharks and 3-4 years for bottlenose dolphin.     

Development of a multichemical food web model: application to PBDEs in Lake Ellasjoen, Bear Island, Norway

A multichemical food web model has been developed to estimate the biomagnification of interconverting chemicals in aquatic food webs. We extended a fugacity-based food web model for single chemicals to account for reversible and irreversible biotransformation among a parent chemical and transformation products, by simultaneously solving mass balance equations of the chemicals using a matrix solution. The model can be applied to any number of chemicals and organisms or taxonomic groups in a food web. The model was illustratively applied to four PBDE congeners, BDE-47, -99, -100, and -153, in the food web of Lake Ellasj?en, Bear Island, Norway. In Ellasj?en arctic char (Salvelinus alpinus), the multichemical model estimated PBDE biotransformation from higher to lower brominated congeners and improved the correspondence between estimated and measured concentrations in comparison to estimates from the single-chemical food web model. The underestimation of BDE-47, even after considering bioformation due to biotransformation of the otherthree congeners, suggests its formation from additional biotransformation pathways not considered in this application. The model estimates approximate values for congener-specific biotransformation half-lives of 5.7,0.8,1.14, and 0.45 years for BDE-47, -99, -100, and -153, respectively, in large arctic char (S. alpinus) of Lake Ellasj?en.     

Bioaccumulation and metabolism of polybrominated diphenyl ethers in carp (Cyprinus carpio) in a water/sediment microcosm: important role of particulate matter exposure

Microcosms were built up to simulate a pond system with polybrominated diphenyl ether (PBDE) contaminated sediment and bioorganisms. The microcosms were divided into groups A and B. In group A, both benthic invertebrates (tubificid worms) and carp (Cyprinu carpio) were added, while in group B, only fish were added. After exposure for 20 d, the fish were sampled (exposure I). A net was fixed in the microcosms, and new fish were added (exposure II). These fish were prohibited from contacting the sediment by the net, and the accumulation and depuration of PBDEs in the fish were investigated. Among 11 monitored PBDE congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, BDE-206, BDE-207, BDE-208, and BDE-209), only 5 congeners (BDE-28, BDE-47, BDE-100, BDE-153, and BDE-154) were detected in the carp fillets and liver. BDE-99 and BDE-183 were not detected in the fish because of the efficient metabolic debromination in carp tissues. The uptake of PBDEs in exposure I was significantly higher/faster than that in exposure II, since the fish in exposure I had an opportunity to take in more of the highly contaminated particles. The uptake kinetics (k(s)) and elimination (k(e)) rate coefficients showed a general trend of decreasing with increasing log K(ow). No significant difference was observed in uptake/depuration kinetics between groups A and B, indicating that the tubificids' reworking does not affect the bioaccumulation of sediment-associated PBDEs in fish significantly. All the PBDE congeners, including nona- and deca-BDEs, were bioaccumulated in the tubificid worms. The PBDE concentrations in the worms were significantly higher than those in the fish, and the congener profile of the sevem major congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, and BDE-183) was distinctly different from that of fish tissues. The biota-sediment accumulation factors in the worms ranged from 0.01 to 5.89 and declined with increasing bromination and log K(ow.).     

Tracking polybrominated diphenyl ether releases in a wastewater treatment plant effluent, Palo Alto, California

Polybrominated diphenyl ethers (PBDEs) are commonly used flame-retardants that are now ubiquitous environmental contaminants. Wastewater treatment plants are one source of PBDEs to the environment through their discharge of treated effluent and land application of sewage sludge. Effluent and sludge were collected and analyzed for PBDEs at a wastewater treatment plant in California. The total concentration of PBDEs ranged from 61 to 1440 microg/kg dry wt in the sludge and from 4 to 29,000 pg/L in discharged effluent. The congeners with the highest abundance in sludge were BDE-47, BDE-99, and BDE-209, while in treated effluent BDE-47 and BDE-99 were the most abundant. BDE-47 and BDE-99 are major congeners of the penta-formulation, while BDE-209 composes the deca-formulation. The sum of the major congeners in the penta-formulation (BDE-47, 99, 100, 153, and 154) comprises 88% of the total PBDEs in the effluent, while BDE-209 is only 6%. Based on the loading analysis, the total PBDE concentrations loaded to the San Francisco Estuary through effluent discharge from this wastewater treatment plant is 2 lb/year (0.9 kg/year).     

Trophic dilution of polycyclic aromatic hydrocarbons (PAHs) in a marine food web from Bohai Bay, north China

Trophic transfer of polycyclic aromatic hydrocarbons (PAHs) in aquatic ecosystems is an important criterion for assessing their ecological risk. This study analyzed 18 PAHs in phytoplankton/seston, zooplankton, five invertebrate species, five fish species, and one seabird species collected from Bohai Bay, and trophic transfer of the PAHs was determined in the food web, of which the length was approximately 4 on the basis of stable nitrogen isotope values. The concentrations of PAHs (2-64.5 ng/g wet weight) in the marine ecosystem were moderate compared with other marine organisms worldwide, and the PAH compositions exhibited species-specific profiles that were related to trophic levels in some organisms. Significant negative relationships were also found between trophic levels and lipid-normalized concentrations for 10 PAH compounds (acenaphthylene, anthracene, fluoranthene, pyrene, chrysene, benz[a]anthracene, benzo[b]fluoranthene + benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, and perylene), and their trophic magnification factors (TMFs) ranged from 0.11 for fluoranthene to 0.45 for acenaphthylene. These results confirm that PAHs undergo trophic dilution in the marine food web, which is likely to be the combined results of low assimilation efficiencies and efficient metabolic transformation at higher trophic levels.     

Occurrences and fates of hydroxylated polybrominated diphenyl ethers in marine sediments in relation to trophodynamics

While occurrences and origins of hydroxylated (OH-) polybrominated diphenyl ethers (PBDEs) in organisms have been reported, the fates of these compounds in abiotic matrixes and related trophodynamics are unclear. The present study measured concentrations of nine OH-PBDEs, twelve methoxylated (MeO-) PBDEs, and eleven PBDEs in marine sediments and explored the trophodynamics of OH-PBDEs in five invertebrates, eight fish, and two species of birds from Liaodong Bay, north China. While concentrations of PBDEs were less than the limit of quantification in sediments, concentrations of ΣOH-PBDEs and ΣMeO-PBDEs were 3.2-116 pg/g dry weight (dw) and 3.8-56 pg/g dw, respectively. When the detected compounds were incubated in native marine sediments the interconversion between 6-OH-BDE47 and 6-MeO-BDE47 was observed. This result is consistent with the similar spatial distributions and significant correlation between the concentrations of these naturally occurring compounds. 6-OH-BDE47 and 2'-OH-BDE68 were detected as the two major congeners in organisms collected from Liaodong Bay, and concentrations were 0.24 ± 0.005 ng/g lw (lipid weight) and 0.088 ± 0.006 ng/g lw, respectively. Biota-sediment accumulation factors (BSAFs) for invertebrates of 6-OH-BDE47 and 2'-OH-BDE68 were 0.017-0.96 and 0.19-1.5 (except for short-necked clam: 6.3), respectively. Lipid-normalized concentrations of 6-OH-BDE47 and 2'-OH-BDE68 decreased significantly with trophic level with TMFs of 0.21 and 0.15, respectively. The fates of OH-PBDEs in sediment together with their trophodynamics in marine food webs suggested that OH-PBDEs are partitioned into sediment and undergo biodilution in the marine food web.     

Tris(2,3-dibromopropyl) isocyanurate, hexabromocyclododecanes, and polybrominated diphenyl ethers in mollusks from Chinese Bohai Sea

A novel brominated flame retardant (BFR), tris(2,3-dibromopropyl) isocyanurate (TBC), as well as hexabromocyclododecanes (HBCDs) and polybrominated diphenyl ethers (PBDEs), were analyzed in 11 species of mollusks collected from nine coastal cities around the Chinese Bohai Sea in 2009 and 2010. The detection frequencies were 100%, 99%, and 77% for PBDEs, HBCDs, and TBC, respectively. Concentrations of ∑HBCDs ranged from below detection limit (nd) to 28.8 ng g(-1) on a dry weight (dw) basis, followed by ∑(12)PBDE (0.01-20.4 ng g(-1) dw) and TBC (nd-12.1 ng g(-1) dw). Statistically significant linear correlations were found among the three BFRs. Positive correlations were found between BFRs concentrations and lipid content in mollusks. The concentrations tend to decrease with increasing trophic levels of the mollusks, implying trophic dilution rather than biomagnifications of the BFRs in the aquatic food chains of the sampling area. Among the 11 mollusks species, Mytilus edulis showed higher bioaccumulation capability than others and was therefore considered to be an appropriate bioindicator of contamination by the BFRs in the Chinese Bohai Sea, in agreement with its previous selection for the biomonitoring of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). A dramatic decrease in PBDE concentrations in mollusks of the area was found for the time period from 2003 to 2010, with a half-life of only 2.3 ± 1.7 years, reflecting a rapid response of mollusks to the change in pollution of the marine environment.     

Enantioselective bioaccumulation of hexabromocyclododecane and congener-specific accumulation of brominated diphenyl ethers in an eastern Canadian Arctic marine food web

The extent of trophic transfer of the three diastereoisomers of hexabromocyclododecane (HBCD) and seven brominated diphenyl ether (BDE) congeners was examined in components of an Arctic marine food web from eastern Canada. Alpha and gamma-HBCD diastereoisomers were detected in all species and total (sigma) HBCD concentrations ranged from 0.6 +/- 0.2 pg/g (geometric mean +/- 1 x standard error (SE), lipid weight (lw)) in arctic cod to 3.9 +/- 0.9 ng/g (lw) in narwhal. beta-HBCD was below method detection limits in all the samples. Mean sigmaBDE (sum of seven congeners) concentrations ranged from 0.4 +/- 0.2 ng/g (lw) in walrus to 73 +/- 10 ng/g (lw) in zooplankton. The relative trophic status of biota was determined by nitrogen stable isotopes (delta15N), and results indicated clear differences in HBCD isomer and BDE congener profiles with trophic level (TL). Trophic magnification was observed for the alpha-diastereoisomer and BDE-47 as concentrations increased with increasing TL in the food web, whereas there was trophic dilution of gamma-HBCD and BDE-209 through the food web. Only the (-)alpha-enantiomer showed a strong positive relationship between concentration and TL (p < 0.01) with a trophic magnification factor (TMF) value of 2.2. A small but significant increase in the enantiomeric fraction value of the alpha-enantiomers with TL was also observed (r2 = 0.22, p < 0.005), implying that there is an overall preferential enrichment of the (-)alpha-enantiomer relative to the (+)alpha-enantiomer likely due to the greater bioaccumulation potential of the (-)alpha-enantiomer and/or to the greater susceptibility of the (+)alpha-enantiomer to metabolism.     

Trophodynamic behavior of 4-nonylphenol and nonylphenol polyethoxylate in a marine aquatic food web from Bohai Bay, north China: comparison to DDTs

4-Nonylphenol (4-NP) is of particular concern because of its ubiquity in aquatic environment and its endocrine-disrupting effects in aquatic organisms. On the basis of its octanol-water partition coefficient (104.6), it has a potential to bioaccumulate in aquatic food webs. However, there are no reported field studies on the trophodynamics of 4-NP and its precursor, nonylphenol polyethoxylate (NPEOs) surfactants, in aquatic food webs. This study reports the trophodynamics of 4-NP and NPEOs (4 < s < 16) in a marine aquatic food web from Bohai Bay, North China. 4-NP and NPEOs (4 < s < 16) were determined in 14 marine species including plankton, benthic invertebrates, fish, and marine birds. This paper provides the first report on the occurrence of NPEOs with s > 5 in marine biota. Co-analysis of DDTs in all samples allowed a direct comparison of the bioaccumulation behavior of DDTs with that of NP and NPEOs. The lipid equivalent concentration of DDE and 2,2-bis(chlorophenyl)-1-chloroethylene (DDMU) increased with increasing trophic level, and the trophic level was determined by stable isotope ratios. The trophic magnification factors (TMFs) of DDE and DDMU were 3.26 and 3.7, respectively. Lipid equivalent concentrations of 4-NP and of all NPEOs did not exhibit a statistically significant correlation with trophic levels in the food web, and the TMF of NP was 0.83, which was similar to those of all NPEOs (0.45-1.22). These results show that in the studied aquatic food web, there was no trophic magnification for 4-NP and NPEOs, whereas DDE and DDMU biomagnified.     

Polybrominated diphenyl ethers, hydroxylated polybrominated diphenyl ethers, and measures of thyroid function in second trimester pregnant women in California

Prenatal exposure to polybrominated diphenyl ethers (PBDEs) may disrupt thyroid function and contribute to adverse neurodevelopmental outcomes. We conducted a pilot study to explore the relationship between serum concentrations of lower-brominated PBDEs (BDE-17 to -154), higher-brominated PBDEs (BDE-183 to -209), and hydroxylated PBDE metabolites (OH-PBDEs) with measures of thyroid function in pregnant women. Concentrations of PBDEs, OH-PBDEs, thyroid-stimulating hormone (TSH), total thyroxine (T(4)), and free T(4) were measured in serum samples collected between 2008 and 2009 from 25 second trimester pregnant women in California. Median concentrations of lower-brominated PBDEs and OH-PBDEs were the highest reported to date in pregnant women. Median concentrations of BDE-47 and the sum of lower-brominated PBDEs (ΣPBDE(5)) were 43.1 ng/g lipid and 85.8 ng/g lipid, respectively, and the sum of OH-PBDEs (ΣOH-PBDE(4)) was 0.084 ng/mL. We observed a positive association between the weighted sum of chemicals known to bind to transthyretin (ΣTTR binders) and TSH levels. We also found positive associations between TSH and ΣPBDE(5), ΣOH-PBDE(4), BDE-47, BDE-85, 5-OH-BDE47, and 4'-OH-BDE49, and an inverse association with BDE-207. Relationships with free and total T(4) were weak and inconsistent. Our results indicate that PBDE exposures are elevated in pregnant women in California and suggest a relationship with thyroid function. Further investigation is warranted to characterize the risks of PBDE exposures during pregnancy.     

Partitioning and bioaccumulation of PBDEs and PCBs in Lake Michigan

Water from Lake Michigan and fish from all five Great Lakes have been sampled and analyzed for a suite of six polybrominated diphenyl ether (PBDE) congeners and 110 polychlorinated biphenyl congeners (PCBs). The Lake Michigan dissolved phase PBDE congener concentrations (0.2 to 10 pg/L) are similar to dissolved phase PCB congener concentrations (nondetected to 13 pg/L). Partitioning of PBDEs between the particulate and dissolved phases exhibits behavior similar to that of PCBs. Organic-carbon-normalized water-particle partition coefficients (log K(OC)s) ranged from 6.2 to 6.5. Lake trout are depleted in BDE-99 relative to dissolved phase concentrations, and in contrast to what is expected from the PCB congener patterns. This reflects suspected debromination of BDE-99 in the food web of Lake Michigan. A regression of the log of the bioaccumulation factor (BAF) and the log of the octanol-water partition coefficent (K(OW)) indicated a positive relationship for both PCB congeners and PBDE congeners. BDE-99 does not appear to followthe same trend, a further indication that it is subject to biotransformation. Using the PBDE BAFs for Lake Michigan and the PBDE fish concentrations from the other Great Lakes it is expected that the dissolved phase concentrations of congeners in the other lakes would range from 0.04 to approximately 3 pg/L.     

Polybrominated diphenyl ethers in peregrine falcon (Falco peregrinus) eggs from the northeastern U.S

A total of 114 peregrine falcon eggs from nests in Connecticut, Massachusetts, Maine, New Hampshire, Rhode Island, and Vermont were analyzed for polybrominanted diphenyl ethers (PBDEs). Eggs were collected from 1996 to 2006, excluding 1997 and 1998. Total PBDE concentrations ranged from 74.5 to 6610 ng/g wet weight, with a median of 440. These levels were generally higher than those observed in European peregrine eggs, but comparable to those in North American seabird eggs. Congener patterns differed from such seabirds and were dominated by BDE-153, followed by BDE-99, -183, -209, -197, -207, -154, -100, and -196; with lesser contributions from BDE-47, -208, -203, -201, -206, -202, -138, and -119. Urban and rural falcon eggs contained similar total PBDE concentrations but different congener profiles. Urban eggs exhibited higher BDE-209 concentrations and greater percentages of other highly brominated congeners. BDE-209 was detectable in all eggs, with concentrations ranging from 1.4 to 420 ng/g wet weight Five octa- and three nona-brominated congeners were also frequently detected, some likely derived from the biodegradation of BDE-209. Temporal analyses indicated no significant changes in concentrations of total PBDEs, or most individual congeners, during the study period. An exception was BDE-209. It exhibited a significant increase, with a doubling time of 5 years. Current PBDE burdens may be insufficient to cause noticeable adverse effects at the population level, as the number of territorial pairs increased in the past decade. However, the high BDE-209 concentrations, short doubling time, and likely biodegradation observed in peregrine eggs from the northeastern U.S. may supportthe need for additional deca-BDE regulations.     

Indoor air is a significant source of tri-decabrominated diphenyl ethers to outdoor air via ventilation systems

Ventilation of indoor air has been hypothesized to be a source of PBDEs to outdoors. To study this, tri-decabrominated diphenyl ethers were analyzed in outgoing air samples collected inside ventilation systems just before exiting 33 buildings and compared to indoor air samples from microenvironments in each building collected simultaneously. Median ∑(10)PBDE (BDE- 28, -47, -99, -153, -183, -197, -206, -207, -208, -209) concentrations in air from apartment, office and day care center buildings were 93, 3700, and 660 pg/m(3) for outgoing air, and 92, 4700, and 1200 pg/m(3) for indoor air, respectively. BDE-209 was the major congener found. No statistically significant differences were seen for individual PBDE concentrations in matched indoor and outgoing air samples, indicating that outgoing air PBDE concentrations are equivalent to indoor air concentrations. PBDE concentrations in indoor and outgoing air were higher than published outdoor air values suggesting ventilation as a conduit of PBDEs, including BDE-209, from indoors to outdoors. BDE-209 and sum of BDE-28, -47, -99, and -153 emissions from indoor air to outdoors were roughly estimated to represent close to 90% of total emissions to outdoor air for Sweden, indicating that contaminated indoor air is an important source of PBDE contamination to outdoor air.     

Effect of municipal sewage treatment plant effluent on bioaccumulation of polychlorinated biphenyls and polybrominated diphenyl ethers in the recipient water

Water, sediment, and aquatic species including plankton, fish, and turtles were collected from a small lake in Beijing, which receives effluent discharged from a large sewage treatment plant (STP). The samples were examined to investigate polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) releases from a STP and their distributions in the lake. The accumulations of sigma 12PBDEs and BDE-209 in the sediment were 62.3 and 1150 ng/cm2, respectively, while that of sigma PCBs was 99.3 ng/cm2. BDE-209 was detected in more than 50% of the aquatic species. A strong linear correlation (R2 = 0.92) was found between sigma 12PBDEs and sigma PCBs levels in aquatic species but not in sediments. The different PBDE congener profiles in sediments and biota samples suggest metabolic debromination in the sampled fish. Bioaccumulations of PBDEs and PCBs were found in aquatic species.The logarithm bioaccumulation factor (BAF) decreases with the number of bromines in PBDEs molecules, while the log BAF versus the number of chlorines in PCBs appears to be parabolic. Biomagnifications of these compounds were not obvious in the food web by analysis of the relationship between sigma 12PBDEs or sigma PCBs levels and the trophic level of aquatic biota species.     

Spray irrigation of treated municipal wastewater as a potential source of atmospheric PBDEs

Spray irrigation facilities utilizing treated municipal wastewater are a potential source of polybrominated diphenyl ethers (PBDEs) to the atmosphere. PBDEs are used as flame retardants in many household items and have been found in wastewaters and biosolids. Evidence of PBDE release from spray irrigation facilities was discovered during a multiyear project to measure semivolatile organic chemical concentrations in air. Four BDE congeners (47, 99, 100, and 154) were monitored at three remote/ rural locations in Maryland and Delaware from 2001 to 2003. Average concentrations at two of the sites (BDE-47, 10-17 pg/m3; BDE-99, 5.3-7.7 pg/m3) reflect background levels. Average concentrations at the third location were 5-10 times higher (BDE-47, 175 pg/m3; BDE-99, 26 pg/m3) and were significantly correlated (p < 0.0001) with temperature indicating local source(s). Several spray irrigation facilities are located south and west of the third site, the prevailing wind direction during the spring and summer when most samples were collected. The fine mist released from the irrigation equipment may enhance release to the atmosphere via air-water gas exchange from water droplets. Temporal trends indicate that aerial concentrations of PBDEs in this area are increasing at an exponential rate; the atmospheric doubling times for the different congeners range from 1.1 to 1.7 yrs.     

Biomagnification of higher brominated PBDE congeners in an urban terrestrial food web in north China based on field observation of prey deliveries

As an important group of brominated flame retardants, polybrominated diphenyl ethers (PBDEs) persist in the wildlife food webs. However, the biomagnification of PBDEs has not been adequately studied in the terrestrial food webs. In this study, a terrestrial food web composed of common kestrels, sparrows, rats, grasshoppers, and dragonflies in the urban environment from northern China was obtained. A field prey delivery study, reinforced by δ13C and δ1?N analyses, indicates that sparrows are the primary prey items of common kestrels. Concentrations of PBDEs were in the following order: common kestrel > sparrow > rat > grasshopper and dragonfly with BDE-209 as the dominant congener. Biomagnification factors (BMFs) were calculated as the ratio between the lipid normalized concentrations in the predator and prey. The highest BMF (6.9) was determined for BDE-153 in sparrow/common kestrel food chain. Other higher brominated congeners, such as BDE-202, -203, -154, -183, -197, and -209, were also biomagnified in this terrestrial food chain with BMF of 1.3-4.7. BDE-47, -99, and -100 were found to be biodiluted from sparrow to common kestrel (BMFs < 1). Measured BMF values for BDE-153, -47, -99, and -100 were consistent with predicted values from a nonsteady-state model in American kestrels from another study. Retention factors and metabolism of BDE congeners may be confounding factors influencing the measured BMFs in this current study.     

Distribution of polybrominated diphenyl ethers in sediments of the Pearl River Delta and adjacent South China Sea

Spatial and temporal distributions of polybrominated diphenyl ethers (PBDEs) in sediments of the Pearl River Delta (PRD) and adjacent South China Sea (SCS) of southern China were examined. A total of 66 surface sediment samples were collected and analyzed to determine the concentrations of 10 PBDE congeners (BDE-28, -47, -66, -100, -99, -154, -153, -138, -183, and -209). The concentrations of BDE-209 and SigmaPBDEs (defined as the sum of all targeted PBDE congeners except for BDE-209) ranged from 0.4 to 7340 and from 0.04 to 94.7 ng/g, respectively. The SigmaPBDEs concentrations were mostly < 50 ng/g, within the range for riverine and coastal sediments around the world, whereas the BDE-209 concentrations at the most contaminated sites were at the high end of the worldwide figures. Congener compositions were dominated by BDE-209 (72.6 - 99.7%), with minor contributions from penta- and octa-BDEs. Slightly different PBDE compositions were observed among samples collected from different locations, attributable to possible decomposition of highly brominated congeners and/or redistribution between particles of various sizes during atmospheric or fluvial transportation. The PBDE patterns in the SCS and Pearl River Estuary sediments were similar to those in sediments of the Zhujiang and Dongjiang Rivers, reflecting the widespread influence from local inputs. Analyses of two short sediment cores collected from the Pearl River Estuary showed that concentrations of BDE-209 rapidly increased in the upper layers of both cores, coincident with the growth of the electronics manufacturing capacities in the PRD region. The major sources of PBDEs were probably waste discharges from the cities of Guangzhou, Dongguan, and Shenzhen, the three fastest growing urban centers in the PRD.