Food Web Bioaccumulation Model for Resident Killer Whales from the Northeastern Pacific Ocean as a Tool for the Derivation of PBDE-Sediment Quality Guidelines.

Resident killer whale populations in the NE Pacific Ocean are at risk due to the accumulation of pollutants, including polybrominated diphenyl ethers (PBDEs). To assess the impact of PBDEs in water and sediments in killer whale critical habitat, we developed a food web bioaccumulation model. The model was designed to estimate PBDE concentrations in killer whales based on PBDE concentrations in sediments and the water column throughout a lifetime of exposure. Calculated and observed PBDE concentrations exceeded the only toxicity reference value available for PBDEs in marine mammals (1500 µg/kg lipid) in southern resident killer whales but not in northern resident killer whales. Temporal trends (1993-2006) for PBDEs observed in southern resident killer whales showed a doubling time of ≈5 years. If current sediment quality guidelines available in Canada for polychlorinated biphenyls are applied to PBDEs, it can be expected that PBDE concentrations in killer whales will exceed available toxicity reference values by a large margin. Model calculations suggest that a PBDE concentration in sediments of approximately 1.0 µg/kg dw produces PBDE concentrations in resident killer whales that are below the current toxicity reference value for 95 % of the population, with this value serving as a precautionary benchmark for a management-based approach to reducing PBDE health risks to killer whales. The food web bioaccumulation model may be a useful risk management tool in support of regulatory protection for killer whales.

Anthropogenic (PBDE) and naturally-produced (MeO-PBDE) brominated compounds in cetaceans--a review.

This paper reviews the available data on brominated flame retardants, the polybrominated diphenyl ethers (PBDEs), as well as on the naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in cetacean tissues around the world. Levels and possible sources of both compound classes are discussed. Odontocete cetaceans accumulate higher PBDE concentrations than mysticete species. PBDE contamination was higher in cetaceans from the Northern hemisphere, whereas MeO-PBDE levels were higher in animals from the Southern hemisphere. Southern resident killer whales from NE Pacific presented the highest levels reported in biota, followed by bottlenose dolphins from North Atlantic (U.K. and U.S. coast). Many species presented PBDE concentrations above threshold levels for health effects in odontocetes. Time trend studies indicate that PBDE concentrations in odontocetes from Japan, China, U.S. and Canada coastal zones have increased significantly over the past 30 years. Studies from U.K. waters and NE Atlantic showed a decrease and/or stability of PBDE levels in cetacean tissues in recent decades. The highest MeO-PBDE concentrations were found in dolphins from Tanzania (Indian Ocean), bottlenose dolphins from Queensland, Australia (SW Pacific), and odontocetes from coastal and continental shelf waters off southeastern Brazil (SW Atlantic). The upwelling phenomenon and the presence of coral reef complexes in these tropical oceans may explain the large amounts of the naturally-produced organobromines. Considering that these bioaccumulative chemicals have properties that could cause many deleterious effects in those animals, future studies are required to evaluate the potential ecotoxicological risks.

Concentrations of polybrominated diphenyl ethers in matched samples of indoor dust and breast milk in New Zealand.

Polybrominated diphenyl ethers (PBDEs) are present in many consumer goods. There is evidence that PBDEs are toxic to humans, particular young children. The purpose of this study was to assess indoor dust as an exposure source for PBDEs. Concentrations of 16 PBDEs were determined in dust samples from 33 households in New Zealand, and in breast milk samples from 33 mothers living in these households. Associations between dust and breast milk PBDE concentrations were assessed, and children's PBDE intake from breast milk and dust estimated. Influences of household and demographic factors on PBDE concentrations in dust were investigated. Indoor dust concentrations ranged from 0.1ng/g for BDE17 to 2500ng/g for BDE209. Breast milk concentrations were positively correlated (p<0.05) with mattress dust concentrations for BDE47, BDE153, BDE154, and BDE209 and with floor dust for BDE47, BDE183, BDE206, and BDE209. The correlation for BDE209 between dust and breast milk is a novel finding. PBDE concentrations in floor dust were lower from households with new carpets. The estimated children's daily intake of PBDEs from dust and breast milk was below U.S. EPA Reference Dose values. The study shows that dust is an important human exposure source for common PBDE formulations in New Zealand.

Body burden of metals and persistent organic pollutants among Inuit in the Canadian Arctic.

Inuit living in the Arctic are exposed to elevated levels of environmental contaminants primarily due to long-range atmospheric transport. Blood sampling and contaminant biomonitoring was conducted as part of the International Polar Year Inuit Health Survey in 2007-2008. The body burden of metals (e.g. Cd, Pb) and persistent organic pollutants (e.g. PCBs, DDT & DDE, toxaphene, chlordane, PBDEs) were measured for Inuit participants (n=2172) from 36 communities in Nunavut, Nunatsiavut, and the Inuvialuit Settlement Region, in Canada. The geometric mean of blood concentrations for Cd, Pb, PCBs, DDE & DDT, toxaphene, and chlordane were higher than those in the Canadian general population. A total of 9% of study participants exceeded the intervention guideline of 100µgL(-1) for Pb, 11% of participants exceeded the trigger guideline of 5µgL(-1) for Cd, and 1% exceeded the intervention guideline of 100µgL(-1) for PCBs. Also, 3% of women of child-bearing age exceeded blood Pb of 100µgL(-1) while 28% of women of child-bearing age exceeded 5µgL(-1) of PCBs. This work showed that most Inuit Health Survey participants were below blood contaminant guidelines set by Health Canada but that metal and POP body burdens commonly exceed exposures observed in the general population of Canada.

Monitoring micropollutants in marine waters, can quality standards be met?

The environmental risks of 33 micropollutants occurring in Belgian coastal zone were assessed as single-substances and as mixtures. Water and sediment samples were taken in harbors, coastal waters and the Scheldt estuary during 2007-2009. Measured environmental concentrations were compared to quality standards such as Predicted No Effect Concentrations (PNECs), Environmental Quality Standards (EQSs), and Ecotoxicological Assessment Criteria (EAC). Out of a total of 2547 samples analyzed, 232 and 126 samples exceeded the EQS and EAC, respectively. Highest risks were observed for TBT, PBDEs, PCBs and the PAHs anthracene, indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, benzo(k)fluoranthene, and benzo(b)fluoranthene in the water compartment and for TBT and PCBs in the sediment compartment. Samples taken at all stations during the April 2008 campaign indicate a potential risk of the contaminant mixtures to the aquatic environment (except W06 station). This study argues the need to revise quality standards when appropriate and hence the overall regulatory implication of these standards.

Blood plasma clinical-chemical parameters as biomarker endpoints for organohalogen contaminant exposure in Norwegian raptor nestlings.

Raptors are exposed to biomagnifying and toxic organohalogenated compounds (OHCs) such as organochlorines, brominated flame retardants and perfluorinated compounds. To investigate how OHC exposure may affect biochemical pathways we collected blood plasma from Norwegian northern goshawk (n=56), golden eagle (n=12) and white-tailed eagle (n=36) nestlings during three consecutive breeding seasons. We found that blood plasma concentrations of calcium, sodium, creatinine, cholesterol, albumin, total protein, urea, inorganic phosphate, protein:creatinine, urea:creatinine and uric acid:creatinine ratios and liver enzymes ALKP and ALAT were positively correlated to PCBs, chlordanes, p,p'-DDE, HCB, PFCs and/or PBDEs. Total bilirubin and glucose were negatively correlated to PCBs while magnesium and potassium were negatively correlated to HCB and p,p'-DDE. In addition, protein:creatinine and ALAT were also negatively correlated to PCBs and PFCs, respectively. The most significant relationships were found for the highly contaminated northern goshawks and white-tailed eagles. The statistical relationships between OHCs and BCCPs indicate that biochemical pathways could be influenced while it is uncertain if such changes have any health effects. The OHC concentrations were below concentrations causing reproductive toxicity in adults of other raptor species but similar to those of concern for endocrine disruption of thyroid hormones in e.g., bald eagles.

PBDD/F impurities in some commercial deca-BDE.

The study presented the concentrations and distributions of polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans (PBDD/Fs) as impurities in some commercial decabromodiphenyl ether (DBDE) mixtures that were produced by several manufacturers. The total concentrations of 12 2,3,7,8-substituted tetra- to octa-BDD/F congeners were found to be in the range of 3.4-13.6 (mean 7.8) µg/g, averagely accounting for 99% of total PBDD/Fs. OBDF was the prevailing congener, followed by 1,2,3,4,6,7,8-HpBDF. In addition, OBDD and 1,2,3,4,7,8-HxBDF were also obviously detectable. The total concentrations of PBDD/Fs varied both between the manufacturers and between the lots. On the basis of the global demand for the commercial DBDE in 2001, the annual potential emissions of PBDD/Fs were calculated coarsely to be 0.43 (range: 0.21-0.78) tons. The major dioxin congeners, OBDF and 1,2,3,4,6,7,8-HpBDF, presenting in DBDE, were estimated to be formed from BDE-209, BDE-206, and/or BDE-207 via an intra-molecular elimination of Br2/HBr.

pK(a) values of the monohydroxylated polychlorinated biphenyls (OH-PCBs), polybrominated biphenyls (OH-PBBs), polychlorinated diphenyl ethers (OH-PCDEs), and polybrominated diphenyl ethers (OH-PBDEs).

The SPARC software program aqueous pK(a) prediction module was validated against corresponding experimental acidity constants for chlorinated and brominated phenols and the limited experimental aqueous pK(a) data sets for monohydroxylated polychlorinated biphenyls (OH-PCBs), polychlorinated diphenyl ethers (OH-PCDEs), and polybrominated diphenyl ethers (OH-PBDEs). pK(a) values were then estimated for all 837 monohydroxylated mono- through nona-halogenated congeners in each of the OH-PCB, OH-PCDE, and OH-PBDE classes, as well as for the monohydroxylated polybrominated biphenyls (OH-PBBs), giving a total of 3348 compounds. Large intrahomolog pK(a) variation by up to six units is expected within each contaminant class, with pK(a) values ranging from about 4 to 11 dependent on the degree and pattern of halogenation. Increasing halogenation generally decreased the average pK(a) within each homolog group. Significant intrahomolog differences in pK(a) values exist between OH-PCB, OH-PBB, OH-PCDE, and OH-PBDE congeners, including large acidity constant variation between isomers with equivalent halogenation patterns but varying location of the hydroxy moiety. Congener specific pH dependent investigations into the partitioning and degradation behaviors of these compounds are necessary, including greater consideration of analyte ionization effects during their extraction and analysis.

Determination of environmentally relevant exposure concentrations of polybrominated diphenyl ethers for in vitro toxicological studies.

Toxicological studies at environmentally relevant concentrations are essential for understanding ecotoxic and health risks of pollutants such as polybrominated diphenyl ethers (PBDEs). However, no information is available on what exposure levels of PBDEs in vitro studies are environmentally relevant. We exposed MCF-7, HepG2, H295R and PC12 cells to BDE-47, and measured BDE-47 concentrations in the cells after exposure. We also used the percentile method to summarize literature data on environmental exposure levels of biotic tissues to PBDEs. The exposure concentration that resulted in a BDE-47 burden in cells close to the 90th percentile of PBDEs levels in tissues was assigned as the upper limit for the environmentally relevant concentration. Exposure to 1nM BDE-47 resulted in PBDEs burdens in MCF-7, HepG2 and H295R cells close to the 90th percentile but PBDEs burdens in PC12 cells were higher than the 90th percentile. In consideration of the high exposure levels in PBDE-polluted areas, we concluded that the highest environmentally relevant exposure concentration of PBDEs in culture media should be approximately 10nM for MCF-7, HepG2 and H295R cells, and<10nM for PC12 cells. These results provide an approximate reference for setting environmentally relevant exposure concentrations of PBDEs for studies in vitro.

Toxicology and human health assessment of decabromodiphenyl ether.

We evaluated the available pharmacokinetic data and human and animal toxicity data for 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE-209) (CASRN 1163-19-5) with the objective of deriving a reference dose (RfD) based on the best available science. The available studies for deriving an RfD were first screened using the Klimisch criteria and further evaluated using the United States Environmental Protection Agency's general assessment factors for data quality and relevance (i.e., soundness, applicability and utility, clarity and completeness, uncertainty and variability, and evaluation and review). The chronic 2-year dietary feeding study conducted by the United States National Toxicology Program ( NTP, 1986 , Technical Report Series No. 309) was selected for RfD derivation. Hepatocellular degeneration in male rats was chosen as the critical endpoint in the development of an RfD. For dose-response characterization, we applied benchmark-dose modeling to animal data and determined a point of departure (the 95% lower confidence limit for a 10% increase in hepatocellular degeneration) of 419 mg/kg-day for oral exposures. Based on the similar pharmacokinetic characteristics of BDE-209 across species, this value was converted to a human equivalence dose of 113 mg/kg-day by applying a dosimetric adjustment factor based on body weight scaling to the (3/4) power. An oral RfD of 4 mg/kg-day was calculated by using a composite uncertainty factor of 30, which consisted of 10 for intraspecies uncertainty, 3 for interspecies uncertainty (i.e., 3 for toxicodynamics x 1 for toxicokinetics), and 1 for deficiencies with the database. We consider the RfD to be adequately protective of sensitive subpopulations, including women, their fetuses, children, and people with hepatocellular diseases.

Selective pressurized liquid extraction of polybrominated diphenyl ethers in fish.

A fast and simple method for the analysis of polybrominated diphenyl ethers (PBDEs) in fish samples was developed using a one-step extraction and clean-up by means of pressurized liquid extraction (PLE) combined with gas chromatography-ion trap tandem mass spectrometry (GC-ITMS-MS). The selective PLE method provided to obtain ready-to-analyse extracts without any additional clean-up step, using a sorbent as fat retainer inside the PLE cell. Several PLE operating conditions, such as solvent type, extraction temperature and time, number of cycles and type of fat retainer, were studied. Using Florisil as fat retainer, maximum recoveries of PBDEs (83-108%) with minimum presence of matrix-interfering compounds were obtained using a mixture of n-hexane:dichloromethane 90:10 (v/v) as solvent, an extraction temperature of 100 degrees C and a static extraction time of 5 min in combination with three static cycles. Quality parameters of the method were established using standards and fish samples. Limits of detection and quantification ranged from 10 to 34 pg g(-1) wet weight and between 34 and 68 pg g(-1) wet weight, respectively. In addition, good linearity (between 1 and 500 ng ml(-1)) and high precision (RSD %<15%) were achieved. The method was validated using the standard reference material SRM-1945 (whale blubber) and was then applied to the analysis of PBDEs in fish samples.