Peregrine Falcon Eggs Research Articles

Exposure of Peregrine Falcons to Halogenated Flame Retardants: A 30 Year Retrospective Biomonitoring Study across North America.

Compared to aquatic ecosystem, terrestrial systems have been subjected to fewer investigations on the exposure to halogenated flame retardants (HFRs). Our study utilized peregrine falcon eggs collected from multiple habitats across North America to retrospectively explore both spatial distribution and temporal changes in legacy (e.g., polybrominated diphenyl ethers) and alternative HFRs over a 30 year period (1984-2016). The results reveal intensive HFR exposure in terrestrial ecosystems and chemical-specific spatiotemporal distribution patterns. The correlations between egg levels of the selected HFRs and human population density clearly illustrated a significant urban influence on the exposure of this wildlife species to these HFRs and subsequent maternal transfer to their eggs. Temporal analyses suggest that, unlike aquatic systems, terrestrial ecosystems may undergo continual exposure to consistently high levels of legacy HFRs for a long period of time. Our findings collectively highlight the effectiveness of using peregrine eggs to monitor terrestrial exposure to HFRs and other bioaccumulative chemicals and the need for continuous monitoring of HFRs in terrestrial ecosystems.

Novel Dechlorane Analogues and Possible Sources in Peregrine Falcon Eggs and Shark Livers from the Western North Atlantic Regions

During the investigation of dechlorane-related chemicals in North American wildlife, two unknown polychlorinated compounds (referred to as U1 and U2) were discovered. After extensive sample cleanup, structural information on U1 and U2 was characterized by gas chromatography (GC) coupled with single quadrupole mass spectrometer (MS) or GC-quadrupole time-of-flight (QToF) MS. Mass spectral evidence suggests that both U1 and U2 are structurally related to Dechlorane 603 (Dec603; C17H8Cl12), an analogue of the chlorinated flame retardant Dechlorane Plus. From the results we suspect U1 (C17H9Cl11) to be a monohydro analogue of Dec603 (i.e., one chlorine atom in Dec603 is replaced by a hydrogen atom). U1 may be formed via the degradation of Dec603's stereoisomers or present as an impurity in commercial Dec603 products. Mass spectral characterization of U2 (C17H7OCl11) suggests it is a carbonylic derivative of Dec603, likely formed via metabolic transformation of Dec603 or its photoisomer. Semiquantitative measurement revealed that U1 and U2 were present at estimated median concentrations of 49 ng/g lipid weight (lw) and 59 ng/g lw in peregrine falcon ( Falco peregrinus) eggs, from the mid-Atlantic region of the United States, and 4.6 and 3.0 ng/g lw in shortfin mako shark ( Isurus oxyrinchus) livers from the western North Atlantic Ocean, respectively. Our results demonstrate the occurrence of these two novel Dec603-related chemicals in both terrestrial and aquatic ecosystems.

Perfluoroalkyl substances (PFASs) and polychlorinated naphthalenes (PCNs) add to the chemical cocktail in peregrine falcon eggs

A suite of perfluoroalkyl substances (PFASs) and polychlorinated naphthalenes (PCNs) were determined in 41 peregrine falcon eggs collected in South Greenland between 1986 and 2014. Median concentrations of perfluorinated sulfonic acids (ΣPFSA) and perfluorinated carboxylic acids (ΣPFCA) were 303 ng/g dry weight (dw) (58 ng/g wet weight, ww) and 100 ng/g dw (19 ng/g ww), respectively, which was comparable to other studies. Perfluorooctane sulfonate (PFOS) accounted for 94% on average of all PFSAs, but did not show a significant time trend. Perfluorohexane sulfonate (PFHxS), perfluoroheptane sulfonate (PFHpS) and perfluorodecane sulfonate (PFDS) showed non-linear decreases over the study period, while some long-chain PFCAs increased significantly. The PCN profile was dominated by the penta-, hexa- and tetrachlorinated congeners CN-52/60, CN-66/67 and CN-42. CN-54, an indicator of combustion, accounted for 2.4% of ΣPCN on average. All PCN congeners showed a decreasing tendency, which was significant for lipid-normalized concentrations of CN-53, CN-54 and CN-63. The ΣPCN median concentration was 21 ng/g lipid weight, which is in the high end of concentrations reported for bird eggs. The PCN and PFAS concentrations add to an already high contaminant burden and a complex chemical cocktail in the peregrine falcon population in Greenland, mainly reflecting contaminant exposure during migration and winter stays in Central and South America.

Regulated and Unregulated Halogenated Flame Retardants in Peregrine Falcon Eggs from Greenland.

Median levels of regulated flame retardants, i.e., polybrominated diphenyl ethers (PBDEs), brominated biphenyl (BB)-153, and hexabromocyclododecane (HBCD), in 33-48 eggs of peregrine falcons (Falco peregrinus) from Greenland were 1909, 359, and 5.98 ng/g lipid weight (lw), respectively, and generally intermediate to levels in North America and Europe. Unregulated flame retardants had lower median concentrations of 1.06 (2-ethylhexyl-2,3,4,5-tetrabromobenzoate, EH-TBB), 2.42 (1,2-bis(2,4,6-tribromophenoxy)-ethane, BTBPE), 0.52 (2,4,6-tribromophenyl 2,3-dibromopropyl ether, DPTE), and 4.78 (dechlorane plus) ng/g lw. Although these compounds are often described as recent replacements for PBDEs, they were also present in eggs from the 1980s. BDE-209 was the only compound with a significant increase (+7.2% annual change) between 1986 and 2014, while BB-153 and DPTE decreased significantly (-8.0% and -2.8% annual change, respectively). Dechlorane plus showed a nonsignificant increase. Individual birds, equipped with light-logging geolocators, confirmed the contaminant exposure over a large geographical area as the birds spent nearly equal time periods in their breeding and wintering grounds in Greenland and Central/South America, respectively, interrupted by 5-6 weeks of migration through North America.

Brominated flame retardants (BFRs) in eggs from birds of prey from Southern Germany, 2014

In Southern Germany, peregrine falcons (Falco peregrinus), which almost exclusively prey on other birds, are top predators of the terrestrial food chain. These animals accumulate persistent organic pollutants (POPs) and halogenated flame retardants (HFRs) with mothers transferring these lipophilic contaminants to their eggs. Here we analyzed unhatched eggs of eleven peregrine falcons and six of other species, and report concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), hexabromobenzene (HBB), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and its metabolites, pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and tribromophenol (TBP). The extract of one purified peregrine falcon egg sample was comprehensively analyzed in a non-target (NT) approach by gas chromatography with mass spectrometry in the electron capture negative ion mode. A total of ∼400 polyhalogenated compounds were detected, among them dechloranes and possibly transformation products, two tetrabrominated metabolites of PBT and several compounds unknown to us which could not be identified.

The occurrence of Dechlorane Plus and related norbornene-based flame retardants in Baltic wild salmon (Salmo salar)

Twenty five Baltic wild salmon (Salmo salar) specimens were analysed for the content of Dechlorane-related compounds (DRCs). Out of the ten analysed DRCs, seven compounds were detected in the muscle tissues of salmon, including Dechlorane (Dec) 602, Dec 603, syn- and anti-stereoisomers of Dechlorane Plus (DP), Dechlorane Plus monoadduct (1,3-DPMA), hexachlorocyclopentadienyl-dibromocyclooctane (DBHCTD), and Mirex. The concentrations of Dec 604 and two DP dechlorinated compounds – decachloropentacyclooctadecadiene (Cl10DP) and undecachloropentacyclooctadecadiene (Cl11DP) – were below the limit of detection in all samples. The aggregated concentrations of DRCs (ΣDRC) were in the range of 551–3339 pg g−1 fresh weight (f.w.) with 1,3-DPMA being the predominant DRC component contributing up to 70% to the ΣDRC. The fractional abundance of syn- and anti-DP stereoisomers showed a pronounced enrichment of anti-DP and was close to the composition of OxyChem® DP commercial product. The obtained concentrations of DRCs were substantially lower than those reported in previous studies of biotic samples (among them fish, mollusks, white stork and peregrine falcon eggs) from inland freshwater reservoirs in more industrialised areas throughout Europe and North America. A statistically significant relationships between the concentrations of Dec 602 and the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) was observed.

Peregrine falcon egg pollutants

ABSTRACTThe role of the peregrine falcon (Falco peregrinus) as a bioindicator for the accumulation of organohalogen compounds and other persistent organic pollutants has been established in field studies. Biometric indices for damage caused by pollutants such as the shell thickness and the shell index were determined and the egg contents were analyzed for various pollutants by gas chromatography/mass spectrometry. A wide range of chemically activated luciferase expression (CALUX®) bioassays were performed on subsamples of the eggs.The following organohalogen compounds were found in the eggs of 2009: dichlorodiphenyltrichloroethane (DDT) and dichlorodiphenyldichloroethane, heptachlor epoxide, hexachlorobenzene, dieldrin, hexachlorocyclohexane, polychlorobiphenyls and polychlorodibenzodioxins and polychlorodibenzofurans, polybromodiphenyl ethers, hexabromocyclododecane, tetrabromobisphenyl A, perfluoro compounds, and mercury. The DDT metabolite, dichlorodiphenyldichloroethene (DDE) (11,800 ng/g dry matter), was found to be the most highly concentrated egg contaminant followed by 2,2′,4,4′,5,5′-hexachlorobiphenyl (3800 ng/g). After a past general drop in pollution level, most egg contaminants presently plateau at levels that may still exceed limit values in foods of animal origin (DDE) or even toxicological thresholds (polychlorobiphenyls + polychlorodibenzodioxins, polybromodiphenyl ethers, perfluorooctanesulfonate, methylmercury).Accumulation of DDE could be shown in peregrine falcon eggs from the uplands of Southwest Germany with elevations up to 1500 m, presumably due to its global distribution and its cold condensation in higher altitudes. In contrast, the concentration of polychlorobiphenyls in falcon eggs decreases with elevation, indicating that these pollutants originate mainly from conurbations and local industrial sites.Significant negative correlations were found between both shell index and thickness and the concentration of Hg. A deleterious effect is also evident from a no-observed-adverse-effect level of 120 ng MeHg per gram egg determined by other authors in chronic feeding studies with ibises, which resulted in decreased egg productivity and male homosexual nesting and courtship behavior. The average Hg concentration in the peregrine falcon eggs from 2009 is almost four times higher than this level. MeHg accounted for 82.5% of the Hg present in the eggs of 2009 and 2010.The cell test DR CALUX® for screening of dioxin-like activities can be used to detect not only the 29 regulated dioxin-like substances but also many other persistent organic pollutants with dioxin-like potencies, such as mixed halogenated dioxins/biphenyls. In our case, the results of bioanalytical screening methods showed no additional effect of other compounds with dioxin-like activity.Ninety-three out of 177 analytes sought could be detected in the eggs. Chlorinated paraffins, organotin compounds, some pesticides that are still in use, and phthalic esters with the exception of traces of diethylhexyl phthalate could be excluded. All pollutants found in the eggs belong to substance classes banned by the Stockholm and Minamata Conventions.

Peregrine falcon egg pollutants: Mirror Stockholm POPs list including methylmercury

The role of the peregrine falcon (Falco peregrinus) as a bioindicator for the accumulation of organohalogen compounds and other persistent organic pollutants has been established in field studies. Biometric indices for damage caused by pollutants such as the shell thickness and the shell index were determined and the egg contents were analyzed for various pollutants by gas chromatography/mass spectrometry. A wide range of chemically activated luciferase expression (CALUX®) bioassays were performed on subsamples of the eggs.The following organohalogen compounds were found in the eggs of 2009: dichlorodiphenyltrichloroethane (DDT) and dichlorodiphenyldichloroethane, heptachlor epoxide, hexachlorobenzene, dieldrin, hexachlorocyclohexane, polychlorobiphenyls and polychlorodibenzodioxins and polychlorodibenzofurans, polybromodiphenyl ethers, hexabromocyclododecane, tetrabromobisphenyl A, perfluoro compounds, and mercury. The DDT metabolite, dichlorodiphenyldichloroethene (DDE) (11,800 ng/g dry matter),...

Levels and trends of toxaphene and chlordane-related pesticides in peregrine falcon eggs from South Greenland

Peregrine falcon eggs were collected in South Greenland between 1986 and 2003 and analysed for 6 congeners of toxaphene and 5 chlordane-related pesticides (cis-chlordane, trans-chlordane, cis-nonachlor, trans-nonachlor and oxychlordane). Oxychlordane had the highest median concentration of 1448ng/g lipid weight (lw) or 79ng/g wet weight (ww) of all compounds. Of the toxaphene congeners, CHB-50 was the predominant congener, with a median concentration of 215ng/g lw (15.5ng/g ww). Chlordane-related concentrations were comparable with results from the USA, but lower than those from Canada and Norway. Toxaphene was considerably higher than in eggs of Norwegian peregrine falcon eggs, possibly reflecting different toxaphene usage in the areas of peregrine falcon migration. Toxaphene information in birds of prey is limited and comparisons with other species indicate differences in concentrations and organochlorine pattern. Temporal trends showed significant log-linear decreases for cis-chlordane and trans-chlordane, but no significant trends for other chlordanes or the toxaphene congeners, probably affected by the large variation between eggs, also of the same bird. Correlations between chlordanes and toxaphene in the Greenland peregrine falcon eggs might suggest similar sources of exposure.

Modelling interactions of toxicants and density dependence in wildlife populations

Summary A major challenge in the conservation of threatened and endangered species is to predict population decline and design appropriate recovery measures. However, anthropogenic impacts on wildlife populations are notoriously difficult to predict due to potentially nonlinear responses and interactions with natural ecological processes like density dependence. Here, we incorporated both density dependence and anthropogenic stressors in a stage‐based matrix population model and parameterized it for a density‐dependent population of peregrine falcons Falco peregrinus exposed to two anthropogenic toxicants [dichlorodiphenyldichloroethylene (DDE) and polybrominated diphenyl ethers (PBDEs)]. Log‐logistic exposure–response relationships were used to translate toxicant concentrations in peregrine falcon eggs to effects on fecundity. Density dependence was modelled as the probability of a nonbreeding bird acquiring a breeding territory as a function of the current number of breeders. The equilibrium size of the population, as represented by the number of breeders, responded nonlinearly to increasing toxicant concentrations, showing a gradual decrease followed by a relatively steep decline. Initially, toxicant‐induced reductions in population size were mitigated by an alleviation of the density limitation, that is, an increasing probability of territory acquisition. Once population density was no longer limiting, the toxicant impacts were no longer buffered by an increasing proportion of nonbreeders shifting to the breeding stage, resulting in a strong decrease in the equilibrium number of breeders. Median critical exposure concentrations, that is, median toxicant concentrations in eggs corresponding with an equilibrium population size of zero, were 33 and 46 μg g−1 fresh weight for DDE and PBDEs, respectively. Synthesis and applications. Our modelling results showed that particular life stages of a density‐limited population may be relatively insensitive to toxicant impacts until a critical threshold is crossed. In our study population, toxicant‐induced changes were observed in the equilibrium number of nonbreeding rather than breeding birds, suggesting that monitoring efforts including both life stages are needed to timely detect population declines. Further, by combining quantitative exposure–response relationships with a wildlife demographic model, we provided a method to quantify critical toxicant thresholds for wildlife population persistence.

Emerging and historical brominated flame retardants in peregrine falcon (Falco peregrinus) eggs from Canada and Spain

Comparisons of brominated flame retardants (BFRs) in the eggs of peregrine falcons (Falco peregrinus) recently collected (2003–2007), are made between Canada (N=12) and Spain (N=13). Overall, concentrations of sum (Σ) polybrominated diphenyl ethers (PBDEs; 16 di-deca-BDE congeners) exceeded Σhexabromocyclododecane (HBCD) and were an order of magnitude higher than 2,2′4,4′,5,5′-hexabromobiphenyl (BB-153)>hexachlorocyclopentenyl-dibromocyclooctane (HCBDCO)>1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)>decabromodiphenylethane (DBDPE)>octabromotrimethylphenyllindane (OBIND)>hexabromobenzene (HBB)>bis(2-ethyl-1hexyl)tetrabromophthalate (BEHTBP). This is the first report of detectable HBCDCO and BEHTBP concentrations in biota, and the highest in ovo concentration of ∑HBCD (14,617ng/glw; Montreal, Canada) to date. There were significantly greater egg concentrations of BB-153, ΣHBCD, and ΣPBDE including BDE-153, -99, -100 and -183, in Canadian than Spanish peregrines with a terrestrial diet. HBB, BTBPE, and OBIND were detected in eggs from both countries, but only Canadian peregrine eggs had detectable levels of HCDBCO (25%) and DBDPE (N=1). The in ovo PBDE congener profile was dominated by BDE-153>BDE-99>BDE-47>BDE-183>BDE-100>BDE-209, with the isomeric HBCD pattern being α-HBCD>γ-HBCD (β-HBCD undetected). The Canadian peregrine eggs had lower enantiomeric HBCD values consistent with their higher fractions of (−) α-HBCD, suggesting selective enantiomeric enrichment or that the (+) α-isomer is more readily metabolized and so deposited in the egg through maternal transfer. Continental differences in egg burdens of peregrines are discussed relative to BFR usage patterns and exposure of peregrines on their breeding grounds.

Temporal trends of polybrominated diphenyl ethers and hexabromocyclododecane in Swedish Peregrine Falcon (Falco peregrinus peregrinus) eggs

A temporal trend study of brominated flame retardants in eggs from peregrine falcon ( Falco peregrinus peregrinus), a terrestrial bird of prey, is presented. Eggs collected between 1974 and 2007 were analyzed for the major constituents of the Penta-, Octa- and Decabromodiphenyl ether technical products (BDE-47, -99, -100, -153, -183 and -209), and hexabromocyclododecane (HBCD). Concentrations of BDE-99, -100, -153, -183, -209 and HBCD increased from 1974 to 2000. After the early 2000s, BDE-99, -100, -153 and -183 concentrations decreased, whereas BDE-209 and HBCD concentrations continued to increase. No temporal trend was detected for BDE-47. Rates of increase also differed, with BDE-99 and -100 increasing 3-fold between the 1980s and mid-1990s, and BDE-153 and -183 increasing approximately 10-fold during the same period. The average yearly increase was 15% and 11% for BDE-209 and HBCD, respectively, based on log-linear regression trends. There is a change in BDE congener patterns over time, with a shift from the predominance of BDE-99 and -47 until the late 1980s, to BDE-153 becoming the predominant congener later on. BFR temporal trends in Swedish peregrine falcon eggs reflect European BFR usage patterns.

Dechlorane Plus and Related Compounds in Peregrine Falcon (Falco peregrinus) Eggs from Canada and Spain

Concentrations of Mirex, Dechlorane (Dec) Plus (DP), Dec 602, Dec 603, and Dec 604 were significantly higher in peregrine falcon (Falco peregrinus) eggs from Canada than Spain, with the former having the only measurable concentrations of the dechlorinated DP products, decachloropentacyclooctadecadiene (aCl10DP) and undecachloropentacyclooctadecadiene (aCl11DP). Large variations also occurred in the in ovo concentrations of the DP monoadduct, DPMA. This is the first study to report the accumulation and metabolism of DP by peregrines, both DP and dechloranes in European biota, as well as dechloranes in a terrestrial organism and one at the top of the food web. The geographical differences in the measured in ovo concentrations reflect local exposure of the adult peregrines on their breeding grounds, likely differences in diet of the adults, the production of DP on the Niagara River, and the greater use of Mirex and dechloranes as flame retardants in North America than Europe.

Decabromodiphenylether and hexabromocyclododecane in wild birds from the United Kingdom, Sweden and The Netherlands: Screening and time trends

The brominated flame retardant decabromodiphenylether (DBDE) was analysed in wild birds to identify the most suitable species for monitoring time trends in DBDE contamination. This information was later used for the design of a 10-year trend study on DBDE in the European Union. DBDE was measured in muscle tissue, liver, and eggs from 10 terrestrial and four aquatic bird species. DBDE was detected in 47% of the terrestrial bird samples (nine species) and in 9% of the aquatic bird samples (six species). Peregrine falcon and sparrowhawk specimens were selected as most suitable species to determine temporal trends of DBDE. For sparrowhawks, no significant change in DBDE concentrations between 1973 and 2001 was found, although in later years more DBDE concentrations were above the detection limit. Peak DBDE levels measured in peregrines in 1995, were followed by a decline in concentrations until 2001. The same species were used for a trend study on hexabromocylcododecane (HBCD). Twenty-four percent of peregrine falcon eggs and 12% of sparrowhawk muscle samples demonstrated measurable HBCD residues. Three diastereomers of HBCD were analysed and the α-diastereomer was the predominant one in most samples. No clear time trends were observed for HBCD in either species. This study demonstrated that these DBDE and HBCD are bioavailable to birds of Northern Europe, although bioaccumulation seems to occur to a limited extent.

Polybrominated Diphenyl Ether (PBDE) Levels in Peregrine Falcon (Falco peregrinus) Eggs from California Correlate with Diet and Human Population Density

Peregrine falcons are now considered a conservation success story due in part to the phasing out of harmful contaminants that adversely affected reproduction. Recent studies have shown that peregrine eggs collected from California cities, however, have high levels of the higher-brominated polybrominated diphenyl ethers (SigmaPBDE(183-209)), a class of industrial flame retardants, in comparison to published data for other wildlife. Sources of these high PBDE levels and unusual PBDE profiles are unknown. Here we analyzed the stable carbon (delta(13)C), hydrogen (deltaD), and nitrogen (delta(15)N) isotope composition of peregrine eggs collected from urban and nonurban habitats. We found that delta(13)C values were significantly higher in urban versus nonurban eggs, suggesting that urban peregrines indirectly receive anthropogenic subsidies via their consumption of prey reliant on corn-based anthropogenic foods. delta(15)N and deltaD values were significantly lower in urban versus nonurban eggs, reflecting differences in dietary diversity and food/water sources available to peregrines in each habitat. These patterns suggest a link between an anthropogenic diet and high levels of SigmaPBDE(183-209) in California peregrines, and identify anthropogenic food as a potentially important PBDE exposure pathway for urban wildlife. If diet is an important PBDE exposure pathway for peregrines, continued high body burdens of SigmaPBDE(183-209) may be a potential risk to ongoing peregrine conservation efforts in California.

Temporal Trends of Perfluorinated Surfactants in Swedish Peregrine Falcon Eggs (Falco peregrinus), 1974−2007

Perfluorinated alkyl substances (PFAS) are today known to be globally distributed environmental contaminants. In the present study, concentrations of PFAS were analyzed in Swedish peregrine falcon eggs (Falco peregrinus), collected between 1974 and 2007. Analytes included in the study were perfluorinated carboxylates (PFCAs; carbon chain lengths C6-C15), perfluorinated sulfonates (PFSAs; C4, C6, C8, and C10), and perfluorooctane sulfonamide (PFOSA). The predominant PFAS was perfluorooctane sulfonate, PFOS (83 ng/g wet weight (w wt) mean concentration in samples from 2006), followed by perfluorotridecanoate, PFTriA (7.2 ng/g w wt) and perfluoroundecanoate, PFUnA (4.2 ng/g w wt). PFCA concentrations increased exponentially over the studied time. In contrast, concentrations of PFOS and perfluorohexane sulfonate (PFHxS) increased initially but leveled off after the mid 1980s. This is different from previously observed temporal trends in marine organisms. The present study is the first to establish temporal trends for PFAS in terrestrial biota. The results indicate potential differences between marine and terrestrial biota regarding sources of PFAS exposure and response to emission changes. The toxicological implications of PFAS exposure for the falcons are not known, but according to recent findings impaired hatching success and sublethal toxicological effects from PFOS exposure in the Swedish peregrine falcon cannot be ruled out.

Time-Trends and Congener Profiles of PBDEs and PCBs in California Peregrine Falcons (Falco peregrinus)

High levels (microg/g lw) of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in peregrine falcon eggs from California (n = 90 eggs from 52 birds, 38 nest sites, collected 1986-2007, SigmaPBDEs median = 4.53, range = 0.08-53.1). Over the past 22 years, PBDE levels more than tripled each decade in the eggs, whereas PCB levels had no significant changes. PBDE levels were highest in eggs from major California cities ("Big Cities"), whereas PCBs showed no difference across the regions. For PBDEs, Big City eggs had markedly different patterns from Coastal eggs: BDE-209 and the higher brominated PBDEs (hexa-nona) were dominant congeners in Big City eggs, while BDE-47 and -99 were dominant in Coastal eggs. In many of the birds that gave multiple eggs over time ("time series"), PBDE patterns changed over time: the high proportions of BDE-209 and higher brominated PBDEs (short half-lives) in young birds contrasted with increasingly higher proportions of BDE-153 (long half-life) and other lower brominated PBDEs as the birds aged. These data are consistent with metabolic debromination of BDE-209 (t(1/2) = 1-2 weeks) to the lower brominated PBDEs, with accumulation over time of BDE-153 (t(1/2) = 3-4 years). In contrast, PCB patterns showed no differences by locations, and did not change over time. Diet (prey birds) may explain the urban PBDE pattern, as the patterns in urban pigeons and peregrines were similar, with high proportions of BDE-209 and the higher-brominated PBDEs. Also, our prey data (feathers from peregrine nests) showed urban peregrines having a higher proportion (>2 fold) of granivorous/opportunistic birds (e.g., "introduced feral" pigeons, mourning doves, starlings) in their diet than coastal peregrines. In summary, these data indicate that BDE-209 exits consumer products as an environmental contaminant to be taken up by wildlife (particularly in urban locations), and undergoes metabolic debromination to the banned lower-brominated PBDEs. High levels of the higher-brominated PBDE congeners, especially in urban locations, permitted accurate measures of relative proportions of homologues in each of the hexa-nona congener classes. Using the major hexa-nona homologues in each of these classes, we propose a pathway for the stepwise, metabolic debromination of BDE-209.

Unusual hepta‐ and octabrominated diphenyl ethers and nonabrominated diphenyl ether profile in California, USA, peregrine falcons (Falco peregrinus): More evidence for brominated diphenyl ether‐209 debromination

High (maximum of 4.1 ppm lipid weight) levels of BDE-209 and other higher brominated diphenyl ethers (BDEs) found in California, USA, peregrine falcon (Falco peregrinus) eggs (n = 95) provided an opportunity to examine homolog profiles of nona-, octa-, and hepta-BDEs as possible evidence for biological debromination of BDE-209. We found two congeners in eggs, an unidentified hepta-BDE (BDE-heptaUNK) and BDE-202 (octa-BDE) that are not present in commercial mixtures. In addition, BDE-208 (nona-BDE) was present at much higher (10-fold) proportions in eggs than in commercial mixtures. To examine whether these unusual homolog patterns arose from assimilation of environmentally degraded BDE commercial mixtures, we compared nona-hepta-BDE homolog profiles of peregrine falcon eggs with those of weathered BDEs present in various abiotic matrices (sludge, sediment, and dusts). We found the profiles differed significantly: BDE-207 was the major nona-BDE in eggs, whereas BDE-206 was the major nona-BDE in abiotic matrices. Thus, the evidence for the biological debromination of BDE-209 in peregrine falcons is twofold: Eggs have two congeners (BDE-202 and -heptaUNK) that are not reported for any commercial mixtures nor in the abiotic matrices examined thus far, and eggs have higher-brominated BDE homolog patterns that are different from those found in commercial mixtures or environmental matrices.

Environmentally Relevant Concentrations of DE-71 and HBCD Alter Eggshell Thickness and Reproductive Success of American Kestrels

Polybrominated diphenyl ethers (PBDEs) and total alpha-hexabromocyclododecane (HBCD) are flame-retardant additives that are commonly used in household and commercial applications. PBDE congeners, which are comprised of technical mixtures such as DE-71, are globally persistent and their concentrations are increasing in many species. Captive American kestrels (Falco sparverius) were exposed by diet to vehicle (safflower oil), or one of two environmentally relevant concentrations of DE-71 and unintentionally to HBCD. This exposure resulted in the birds laying eggs that contain PBDE and HBCD concentrations currently found in wild herring gull (Larus argentatus) and peregrine falcon (F. peregrinus) eggs, and compared to control kestrels, resulted in delayed egg laying and smaller eggs being laid, caused thinner eggshells and differential weight loss during embryonic development, and reduced fertility and reproductive success. The thickness of the eggshell declined as the concentrations of all measured PBDE and the total amount of a-HBCD congeners (except BDE-183 and BDE-209) increased; increasing concentrations of BDE-153, BDE-154, BDE-28, BDE-17, delayed egg laying, reduced eggshell mass (plus sigmaPBDEs), and reduced fledging success (BDE-153 and BDE-154 only). BDE-153 is the dominant congener recently found in peregrine eggs. The results of this study are consistent with the PBDE-associated brood reduction in wild European peregrines and may partially explain the decline of kestrels in North America.

POLYBROMINATED DIPHENYL ETHER FLAME RETARDANTS IN CHESAPEAKE BAY REGION, USA, PEREGRINE FALCON (FALCO PEREGRINUS) EGGS: URBAN/RURAL TRENDS

A total of 23 peregrine falcon (Falco peregrinus) eggs were obtained between 1993 and 2002 from 13 nests, encompassing 11 locations in the Chesapeake Bay region, U.S.A. When multiple eggs were available from the same clutch, average clutch contaminant concentrations were calculated. An overall median total polybrominated diphenyl ether (PBDE) level of 201 ng/g wet weight was determined for the eggs/clutches examined. The maximum in an individual egg, from an urban highway bridge site, was 354 ng/g. This egg also exhibited the highest BDE 209 burden (48.2 ng/g). Compared to distributions reported in fish and piscivorous birds, falcon eggs were enriched in the more brominated congeners. The BDE congeners 153, 99, and 100 constituted 26.0, 24.8, and 13.1%, respectively, of total PBDEs. In most aquatic species, BDE 47 is the most abundant congener reported; however, it constituted only 4.4% of total PBDEs in the eggs of the present study. The median BDE 209 concentration was 6.3 ng/g. The sum of the octa- to nonabrominated congeners (BDEs 196, 197, 206, 207, and 208) contributed, on average, 14.0% of total PBDEs, exceeding the contribution of BDE 209 (5.9%). Concentrations of polychlorinated biphenyls (PCBs) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (4,4'-DDE) also were determined in a subset of 16 eggs (collected in 2001-2002 from six nests) and were an order of magnitude greater than the corresponding PBDEs. Median BDE 209 concentrations were significantly correlated (p < 0.01, Spearman R = 0.690) with the human population density of the area surrounding the nest. Total PBDEs, total PCBs, and 4,4'-DDE levels were not correlated to human population density.