Trophic transfer of polybrominated diphenyl ethers in a recently modified freshwater food web from the St. Lawrence River, Canada.

Introduction of invasive species can have a profound impact on food web structure and therefore on trophic transfer of contaminants. In the St. Lawrence River (Canada), 20 years after its first detection in the system, invasive round goby (Neogobius melanostomus) has become the main prey for several piscivorous species. To evaluate the accumulation, trophic transfer, and the ecological risk of polybrominated diphenyl ethers (PBDEs) in this recently modified freshwater food web, samples of sediment, invertebrates, fish and aquatic bird eggs and plasma were collected. Sampling sites were located upstream and at two locations downstream of the Montreal wastewater treatment plant outfall. The results suggest that the influence of the WWTP effluent on PBDEs concentrations varied among the various compartments of this recently modified freshwater food web. The results also suggest that although predatory fish have switched to consuming round goby as a prey item instead of native yellow perch, this new feeding behaviour is not expected to have important impacts on the level of transfer of PBDE within this food web. The biota-sediment accumulation factors (BSAFs) ranged from 0.6 to 436, whereas biomagnification factors (BMFs) varied between 0.2 and 475. Despite our conservative method of risk assessment, we calculated an important risk for piscivorous fish and gull eggs within this study area.

An investigation of physiological effects of the Deepwater Horizon oil spill on a long-distance migratory seabird, the northern gannet.

Exposure to oil can have long-term impacts on migratory birds. Following the 2010 Deepwater Horizon blowout in the Gulf of Mexico (GOM), we investigated potential impacts of oil exposure on a population of northern gannets (Morus bassanus) that breed on Bonaventure Island (Québec, Canada) and winter in GOM and along the U.S. Atlantic coast (AC). Blood and feather samples were collected from adults previously equipped with geolocators to determine wintering locations. Parent and alkylated polycyclic aromatic hydrocarbons (PAHs); trace metals; stable isotopes of carbon, nitrogen, and hydrogen; and immune, thyroid, steroid, retinoid, and genetic endpoints were measured. PAH and trace metal concentrations did not differ between gannets using different wintering sites. Feather stable isotope values varied significantly between birds from different wintering locations. Gannets wintering in GOM showed higher feather corticosterone and plasma thyroid hormone levels, which may indicate increased energetic demands and/or greater exposure to environmental stressors.

Perfluoroalkyl Acids in European Starling Eggs Indicate Landfill and Urban Influences in Canadian Terrestrial Environments.

Perfluoroalkyl acids (PFAAs) were determined in European starling ( Sturnus vulgaris) eggs collected between 2009 and 2014 from industrial, rural/agricultural, and landfill locations within five urban centers across Canada. Within each urban center, perfluoroalkyl sulfonic acid (PFSA) concentrations were generally greater in starling eggs collected from urban/industrial locations and PFSAs and perfluoroalkyl carboxylic acids (PFCAs) were generally greater at landfills compared to rural and remote locations. However, the relative importance of urban/industrial versus landfill locations as potential sources was chemical- and location-specific. PFSA concentrations in eggs collected from nonlandfills were positively correlated with human population. Despite the 2000 to 2002 phase-out of perfluorooctanesulfonic acid (PFOS) and its C8 precursors, leaching from consumer products during use likely continues to be a major source to the environment. In comparison, the concentrations of most PFCAs in eggs were not related to population, which supports the hypothesis that atmospheric transport and degradation of precursor chemicals are influencing their spatial trends. PFAA concentrations in eggs from landfills were not correlated with the quantity of waste received by a given landfill. The variability in PFAAs between landfills may be due to the specific composition of waste items.

Volatile Methylsiloxanes and Organophosphate Esters in the Eggs of European Starlings (Sturnus vulgaris) and Congeneric Gull Species from Locations across Canada.

Volatile methylsiloxanes (VMSs) and organophosphate esters (OPEs) are two suites of chemicals that are of environmental concern as organic contaminants, but little is known about the exposure of wildlife to these contaminants, particularly in birds, in terrestrial and aquatic ecosystems. The present study investigates the spatial distributions of nine cyclic and linear VMSs and 17 OPEs in the eggs of European starlings (Sturnus vulgaris) and three congeneric gull species (i.e., herring gull (Larus argentatus), glaucous-winged gull (L. glaucescens), and California gull (L. californicus)) from nesting sites across Canada. ∑VMS concentrations for all bird eggs were dominated by decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and octamethylcyclotetrasiloxane (D4). With European starlings, birds breeding adjacent to landfill sites had eggs containing significantly greater ∑VMS concentrations (median: 178 ng g-1 wet weight (ww)) compared with those from the urban industrial (20 ng g-1 ww) and rural sites (1.3 ng g-1 ww), indicating that the landfills are important sources of VMSs to Canadian terrestrial environments. In gull eggs, the median ∑VMS concentrations were up to 254 ng g-1 ww and suggested greater detection frequencies and levels of VMSs in aquatic- versus terrestrial-feeding birds in Canada. In contrast, the detection frequency of OPEs in all European starling and gull eggs was lower than 16%. This suggested that low dietary exposure or rapid metabolism of accumulated OPEs occurs in aquatic feeding birds and may warrant further investigation for the elucidation of the reasons for these differences.

Temporal trends of mercury and organohalogen contaminants in great blue heron eggs from the St. Lawrence River, Québec, Canada, 1991-2011, and relationships with tracers of feeding ecology.

Since 1991, great blue heron (Ardea herodias) eggs have been collected and analyzed for mercury (Hg), persistent organic contaminants (OCs), brominated and non-brominated flame retardants (FRs) as well as stable isotopes δ13C and δ15N. In the present study, temporal trends of contaminants were analyzed in eggs sampled in four regions along the St. Lawrence River (Quebec, Canada) and inland sites using new and previously published data. Most contaminants declined significantly over time in most regions. Globally, the highest annual change, -17.5%, was found for pp'-DDD, while the smallest annual decline, -0.54%, was observed for Hg. Concentrations of ΣDDT and ΣFR8 (sum of 8 congeners) decreased by -11.6% and -7.3%, respectively. Declines in ΣPCBs differed among regions, from -5.6% in the fluvial section to -14.7% in the inland region. The highest concentration of ΣFR8 was measured in eggs from Grande Ile in the fluvial section of the river in 1996 (2.39µg/g). Stable isotope ratios also showed temporal trends in some regions: δ13C decreased in the fluvial section and increased in Gulf region, while δ15N decreased in the fluvial section and increased in the upper estuary. Significant positive relationships were found between ΣDDT, ΣPCBs and ΣFRs and δ15N and δ13C in freshwater colonies, but not in estuarine or marine colonies. These results suggest that changes in trophic level and foraging areas over time were influential factors with respect to contaminant burden in great blue heron eggs in the fluvial section, but not in the other regions.

Spatiotemporal patterns and relationships among the diet, biochemistry, and exposure to flame retardants in an apex avian predator, the peregrine falcon.

Flame retardants (FR) are industrial chemicals and some are proven environmental contaminants that accumulate in predatory birds. Few studies have examined the influence of diet on FR profiles in nestling raptors and the possible physiological implications of such FR exposure. The objectives of this research were (1) to determine spatial patterns of ≤ 48 polybrominated diphenyl ether (PBDE) congeners and ≤ 26 non-PBDE FRs, including organophosphate esters (OPEs), in nestling peregrine falcons (Falco peregrinus) across the Canadian Great Lakes-St. Lawrence River Basin (GL-SLR; 2010) and in the eastern Canadian Arctic (2007); (2) to identify temporal changes in FR concentrations from the mid-2000s to 2010 in GL-SLR peregrine nestlings; (3) to investigate the role of diet using stable isotopes on exposure patterns of quantifiable FRs; and (4) to assess possible associations between circulating FRs and total (T) thyroxine (TT4) and triiodothyronine (TT3), tocopherol, retinol and oxidative status (isoprostanes). The summed concentrations of the top 5 PBDEs (Σ5) (BDE-47, -99, -100, -154, -153) were significantly higher in rural nestlings than urban nestlings in the GL-SLR, followed by the eastern Arctic nestlings. The PBDE congener profile of rural nestlings was dominated by BDE-99 (34‰), whereas BDE-209 (31‰) became dominant in the 2010 urban PBDE profile marking a shift since the mid-2000s. Low (ppb) concentrations of 25 novel non-PBDE FRs (e.g., 1,2-bis-(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenylethane (DBDPE)) were measured in the nestlings in at least one region, with the first report in peregrines of 15 novel non-PBDE FRs (e.g., 2-ethyl-1-hyxyl 2,3,4,5-tetrabromobenzoate (EHTBB), pentabromo allyl ether (PBPAE), tetrabromoethylcyclohexane (α-, ß-DBE-DBCH)) as well as of tris (2-butoxyethyl) phosphate (TBOEP) (0-7.5ng/g ww) > tris(2-chloroisopropyl) phosphate (TCIPP) (0.1-5.5ng/g ww) > tris(2-chloroethyl) phosphate (TCEP) (0.02-2.0ng/g ww) > tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (0-1.0ng/g ww). Within the GL-SLR, the urban nestlings' diet had significantly more terrestrial sources (greater δ13C values) than the broader, more aquatic-based diet of rural peregrines. Dietary source (δ13C) was significantly associated with concentrations of Σ5PBDE, BDE-209, EHTBB, and 2,2-4,4',5,5'-hexabromobiphenyl (BB-153), with trophic level (δ15N) also positively associated with BDE-209 levels. Compared to urban nestlings, the rural nestlings had significantly lower circulating concentrations of thyroxine (TT4), triiodothyronine (TT3), a greater proportion of TT3 relative to TT4 (TT3:TT4), tocopherol and oxidative status (isoprostanes), but higher retinol levels; the most recalcitrant PBDE congener, BDE-153, in combination with low concentrations of some novel FRs, particularly octabromotrimethylphenyllindane (OBIND), may influence circulating thyroid hormones, especially TT4, and retinol levels of peregrine falcon nestlings. These associations of FR-endocrine-biochemical measures suggest possible exposure-related changes in these birds and further study is warranted.

Feather corticosterone during non-breeding correlates with multiple measures of physiology during subsequent breeding in a migratory seabird.

Carry-over effects in migratory birds are likely mediated by physiological processes that are activated in response to environmental variation. Such processes affect body condition and/or reproductive success, and can include corticosterone (CORT) because this hormone responds to environmental stressors and influences energy balance. Few studies have considered how CORT levels during non-breeding relate to a broader physiological profile during subsequent breeding, and fewer still have considered measures other than body condition. To explore CORT's potential role in carry-over effects, we investigated the relationship between CORT and foraging ecology of northern gannets (Morus bassanus) during the non-breeding period, and tested for associations between these factors and variation in a suite of physiological and biochemical metrics during subsequent breeding. Northern gannets are the largest seabird top predator in the North Atlantic and were among the hardest hit by the Deepwater Horizon oil blowout in the Gulf of Mexico in 2010. We used light-level geolocators to confirm winter origins of individuals in our study. No interrelationships were found among levels of CORT from feathers grown during non-breeding (CORTf) and variation in foraging ecology, measured by stable isotopes of carbon (δ13C) and nitrogen (δ15N) from the same feathers. CORTf was correlated negatively with hematocrit and positively with triglyceride measured during subsequent incubation, and explained more variation in these variables than did body mass during incubation. These findings provide support for the hypothesis that energy management, measured using CORTf, during non-breeding carries over to influence physiological measures other than body condition. Gannets that previously wintered within the Gulf of Mexico in the years following the Deepwater Horizon oil blowout had higher levels of CORTf compared to birds that wintered along the Atlantic coast, suggesting an increased energetic cost associated with visiting the Gulf of Mexico. Our results indicate that CORT during non-breeding is associated with a broader physiological profile during subsequent breeding than previously reported in birds.

Thyroid Hormones, Retinol and Clinical Parameters in Relation to Mercury and Organohalogen Contaminants in Great Blue Heron (Ardea herodias) Nestlings from the St. Lawrence River, Québec, Canada.

The exposure and effects of persistent environmental contaminants were investigated in great blue heron (Ardea herodias) nestlings sampled in 2001, 2002, 2006, and 2007 in freshwater and estuarine heronries along the St. Lawrence River, Québec (Canada). Biomarkers (retinoids, thyroid hormones, and clinical parameters) and contaminants (organochlorine contaminants, polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs), and mercury (Hg)) were analyzed in blood, and Hg was analyzed in feathers (generally 9 nestlings per colony and 4 colonies per year). Feather Hg and most contaminants detected in blood were found in higher concentrations in birds from freshwater than estuarine colonies more distant from the pollution sources. Among freshwater colonies, Ile aux Hérons showed the highest levels of contaminants, with mean Hg concentrations of 8.4 and 0.55 mg/kg in feathers and plasma, respectively, and plasma ΣBFRs of 19.6 ng/g ww. The highest mean ΣPCBs, 56.5 ng/g ww, was measured at Grande Ile in 2001. The levels of contaminants in heron nestlings were generally below critical thresholds for adverse effects observed on reproduction or survival. Retinol, dehydroretinol (DROH), and thyroid hormone concentrations differed significantly among colonies. Retinol concentrations were negatively related to ΣPCBs, whereas DROH concentrations were negatively related to Hg and total and free triiodothyronine (T3) concentrations were negatively related to ΣBFRs. These results indicate that contaminants from the St. Lawrence River could impair the development and fitness of great blue heron nestlings and emphasize the need for more research on the great blue heron population to assess their health and nutritional status.

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and flame retardants in northern gannet (Morus bassanus) eggs from Bonaventure Island, Gulf of St. Lawrence, 1994-2014.

Northern gannet (Morus bassanus) eggs from Bonaventure Island, Québec, Canada, were collected to monitor concentrations of contaminants. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) and non-ortho polychlorinated biphenyls (PCBs) were measured in eggs from 2004 and 2009, and several brominated and nonbrominated flame retardants (FRs) were measured every 2-5 years in eggs from 1994 to 2014. The sum (Σ) concentrations of PCDDs/Fs were significantly lower in 2009 relative to 2004, but the total toxic equivalent concentrations for PCDDs, PCDFs, and PCBs showed no significant differences (196 ng/kg wet weight (ww) in 2004 and 220 ng/kg ww in 2009). The mean ΣFR concentrations decreased significantly between 1994 and 2014, from 58 ng/g ww to 19 ng/g ww. Hexabromocyclododecane (HBCDD) was the principal nonbrominated FR detected in gannet eggs and ranged from <1.0 ng/g ww to 6.9 ng/g ww. The PCDD/F and nonortho PCB profiles were dominated by 2,3,7,8- tetrachloro-dibenzofuran (2,3,7,8-TCDF; from 26.2 ng/g ww to 34.8 ng/kg ww) and PCB-77 (from 1580 ng/g ww to 2650 ng/kg ww), respectively. Although the values of both ecological tracer stable isotopes of carbon (δ13C) and nitrogen (δ15N) showed differences among the years, no temporal trends were observed, which indicates relatively stable adults' diet and foraging area over this time period. The trends over time in concentrations of the studied contaminants likely reflect a decrease in environmental contamination. The mean 2012 eggshell thickness was 10% lower than the pre-DDT value and corresponded to a year of poor reproductive success.

Spatio-temporal trends and monitoring design of perfluoroalkyl acids in the eggs of gull (Larid) species from across Canada and parts of the United States.

A large spatial dataset of perfluoroalkyl acid (PFAA) concentrations in eggs of herring gulls (Larus argentatus or congeneric species) collected from late April to early June between 2009 and 2014 from 28 colonies across Canada and parts of the Unites States was used to evaluate location-specific patterns in chemical concentrations and to generate hypotheses on the major sources affecting PFAA distributions. The highly bioaccumulative perfluorooctane sulfonic acid (PFOS) as well as other perfluoroalkyl sulfonic acids (PFSAs) showed the greatest concentrations in eggs from the lower Great Lakes of southern Ontario as well as from the St. Lawrence River. Despite the 2000 to 2002 phase-out of PFOS and related C8 chemistry by the major manufacturer at the time, ongoing losses from consumer products during use and disposal in urban/industrial locations continue to be major sources to the environment and are influencing the spatial trends of PFOS in Canada. In comparison to PFOS, perfluoroalkyl carboxylic acids (PFCAs) were not as concentrated in eggs in close proximity to urbanized/industrialized centers, but had surprisingly elevated levels in relatively remote regions such as Great Slave Lake, NT and East Bay in Hudson Bay, NU. The present results support the hypothesis that atmospheric transport and degradation of precursor chemicals, such as the fluorotelomer alcohols 8:2 FTOH and 10:2 FTOH, are influencing the spatial trends of PFCAs in Canada. A power analysis conducted on a representative urbanized/industrialized colony in the Toronto Harbour, ON, and a relatively remote colony in Lake Superior, emphasized the importance of consistent and long-term data collection in order to detect the anticipated changes in PFAA concentrations in Canadian gull eggs.

Temporal trends of mercury, organochlorines and PCBs in northern gannet (Morus bassanus) eggs from Bonaventure Island, Gulf of St. Lawrence, 1969-2009.

Since 1969, northern gannet (Morus bassanus) eggs from Bonaventure Island, Québec, have been collected to monitor concentrations of contaminants. Levels of p,p'-DDE, which caused low breeding success of Bonaventure gannets in the 1960s, decreased by 99.4% from 1969 to 2009 (17.1-0.1 mg/kg ww), with concomitant improvement of hatching success. PCBs, most organochlorines and mercury also showed decreasing trends. Stable isotopes of carbon (δ(13)C) and nitrogen (δ(15)N) were measured to track the possible influence of diet changes on concentrations of contaminants over time. The confounding effect of the combustion of fossil fuels on baseline values of δ(13)C (the Suess effect) was taken into account. No temporal trends were observed in δ(13)C and δ(15)N values in gannet eggs. Hence trophic level or foraging area had a negligible influence on temporal trends of contaminants.

European starlings ( Sturnus vulgaris ) suggest that landfills are an important source of bioaccumulative flame retardants to Canadian terrestrial ecosystems.

Landfills are used as the primary means for the disposal of municipal solid waste in Canada. In the present study, polybrominated diphenyl ethers (PBDEs) and other flame retardants (FRs) were determined in fresh European starling ( Sturnus vulgaris ) eggs collected in 2009, 2010, and 2011 from nest boxes established within, adjacent to, and 10 and 40 km distant to five major urban centers across Canada, i.e., Vancouver, British Columbia (BC); Calgary, Alberta (AB); Hamilton, Ontario (ON); Montréal, Québec (QC); and Halifax, Nova Scotia (NS). Nest boxes were located in several land use types: urban industrial areas (districts of industrial activity within city limits), landfill sites (adjacent to cities), and rural (agricultural) sites located 10 and 40 km distant from the major urban centers, as well as a national reference site. Of the 14 PBDE congeners and 16 non-PBDE FR substances determined in the starling eggs, BDE-17, -28, -47, -49, -66, -85, -99, -100, -138, -153, -154, -183, and -209, Dechlorane Plus isomers (anti and syn), and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (BEHTBP) were most frequently quantifiable. The data revealed orders of magnitude greater PBDE concentrations in eggs from starlings nesting in landfill sites (median: 28-280 ng/g wet weight) relative to those from urban industrial and rural environments. However, the percent fractional composition of the PBDE congener patterns did not vary significantly between the types of land uses or between years. Additionally, the median ∑PBDE concentration in eggs from landfill sites and the human population density of the metropolitan region that the landfill serves were highly correlated (r(2) = 0.998, p < 0.001). As the first transcontinental effort in assessing FR contamination in Canadian terrestrial ecosystems, the present study strongly suggest that landfills are an important FR source to starlings nesting nearby and that other terrestrial organisms could also be similarly exposed.

Mercury trends in herring gull (Larus argentatus) eggs from Atlantic Canada, 1972-2008: Temporal change or dietary shift?

Mercury (Hg) is a pervasive contaminant that can adversely affect predatory wildlife. Bird eggs provide insights into breeding females' Hg burdens, and are easily collected and archived. We present data on Hg trends in herring gull (Larus argentatus) eggs from five sites in Atlantic Canada from 1972 to 2008. We found a significant decrease in Hg at Manawagonish Island, New Brunswick and Île du Corossol, Quebec, but after correcting Hg for dietary shifts using stable isotopes (δ(15)N), these trends disappeared. Decreasing temporal trends of stable isotopes in gull eggs were observed at four sites, suggesting shifts in gull diets. At Gull Island, Newfoundland, diet-adjusted Hg increased from 1977 to 1992, dropped sharply between 1992 and 1996, and rose again from 1996 to 2008. After adjusting Hg trends for dietary shifts of herring gulls, it appears that environmental Hg in coastal ecosystems has remained relatively constant at most sites in Atlantic Canada over the last 36 years.

Metals, trace elements, polychlorinated biphenyls, organochlorine pesticides, and brominated flame retardants in tissues of Barrow's goldeneyes (Bucephala islandica) wintering in the St. Lawrence marine ecosystem, eastern Canada.

The eastern North American population of Barrow's goldeneyes winters in the St. Lawrence Estuary and Gulf of St. Lawrence where the sediments and food web are known to be contaminated with inorganic and organic compounds. Therefore, there is a potential for contamination of this population, which is designated of Special Concern by the Committee on the Status of Endangered Wildlife in Canada. Specimens were collected during three consecutive winters (2005-2007) in three regions (Manicouagan, Charlevoix, and Chaleur Bay) and analysed for metals, trace elements, polychlorinated biphenyls (PCBs), organochlorine pesticides, and brominated flame retardants (BFRs). Liver mercury levels were greater in the St. Lawrence Estuary (4.4 mg/kg in Manicouagan, 3.8 mg/kg in Charlevoix) than in Chaleur (2.4 mg/kg), whereas selenium showed the opposite pattern (7.3 mg/kg in Manicouagan, 7.0 mg/kg in Charlevoix, and 36.9 mg/kg in Chaleur). Liver PCB levels were greater in specimens from Manicouagan (236 ng/g) than in those from the two other regions (72 ng/g in Charlevoix, 35 ng/g in Chaleur). DDT was greater in Chaleur (66 ng/g) versus 10 ng/g in Manicouagan and 16 ng/g in Charlevoix. BFRs were not compared among regions because of smaller sample sizes, but mean total concentration was low (4.02 ng/g). Overall, although significant differences were found across regions, levels of all contaminants measured are generally low and not of toxicological concern for this population.

Flame retardants in eggs of four gull species (Laridae) from breeding sites spanning Atlantic to Pacific Canada.

To compare legacy and emerging flame retardant (FR) contamination in Canadian marine and freshwater ecosystems, eggs of four gull species (Laridae) were collected from 26 colonies spanning Pacific to Atlantic Canada, including in the Great Lakes basin. Fourteen polybrominated diphenyl ether (PBDE) congeners and 20 non-PBDE FRs were analyzed, but BDE-47, -99, -100, -153, -154 and -209, hexabromocyclododecane (HBCD) and Dechlorane Plus (DP) syn- and anti-isomers were common, and where concentrations of ∑PBDEs (37-610 ng/g wet weight, ww) â‰« HBCD (0.5-12 ng/g ww) > ∑DP (not quantifiable-5.5 ng/g ww). All other FRs were generally not detectable. Stable nitrogen and carbon isotopes used as dietary tracers provided insights into the diet choice influences on the exposure sources and contamination patterns (e.g., PBDE congener compositions) for individual gulls from the same colony. Eggs from gulls breeding near metropolitan regions of higher human densities showed greater PBDE burdens than from other ecosystems.

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 (14,617 ng/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 (ß-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.

Perfluoroalkyl carboxylates and sulfonates and precursors in relation to dietary source tracers in the eggs of four species of gulls (Larids) from breeding sites spanning Atlantic to Pacific Canada.

In the present study, we identified and examined the spatial trends, sources and dietary relationships of bioaccumulative perfluorinated sulfonate (PFSA; C(6), C(8), and C(10) chain lengths) and carboxylate (PFCA; C(6) to C(15) chain lengths) contaminants, as well as precursor compounds including several perfluorinated sulfonamides, and fluorotelomer acids and alcohols, in individual eggs (collected in 2008) from four gull species [glaucous-winged (Larus glaucescens), California (Larus californicus), ring-billed (Larus delawarensis) and herring (Larus argentatus) gulls] from 15 marine and freshwater colony sites in provinces across Canada. The pattern of PFSAs was dominated by perfluorooctane sulfonate (PFOS; >89% of ΣPFSA concentration) regardless of egg collection location. The highest ΣPFSA concentrations were found in the eggs collected in the urbanized areas in the Great Lakes and the St. Lawrence River area [Big Chicken Island 308 ng/g ww, Toronto Harbour 486 ng/g ww, and Ile Deslauriers (HG) 299 ng/g ww]. Also, eggs from all freshwater colony sites had higher ΣPFSA concentrations, which were significant (p<0.05) in many cases, compared to the marine sites with the exception of the Sable Island colony in Atlantic Canada off the coast of Nova Scotia. C(6) to C(15) chain length PFCAs were detected in the eggs, although the pattern was variable among the 15 sites, where PFUnA and PFTrA dominated the pattern for most colonies. Like the ΣPFSA, the highest concentrations of ΣPFCA were found in the eggs from Big Chicken Island, Toronto Harbour, Ile Deslauriers (HG), and Sable Island, although not all freshwater sites had higher concentrations compared to marine sites. Dietary tracers [δ(15)N and δ(13)C stable isotopes (SIs)] revealed that PFSA and PFCA exposure is colony dependent. SI signatures suggested that gulls from most marine colony sites were exposed to PFCs via marine prey. The exception was the Mandarte Island colony in Pacific British Columbia, where PFSA and PFCA exposure appeared to be via terrestrial and/or freshwater prey consumption. The same was true for the freshwater sites where egg SIs suggested both aquatic and terrestrial prey consumption as the source for PFC exposure depending on the colony. Both aquatic (marine and freshwater) and terrestrial prey are likely sources of PFC exposure to gulls but exposure scenarios are colony-specific.

Second generation anticoagulant rodenticides in predatory birds: Probabilistic characterisation of toxic liver concentrations and implications for predatory bird populations in Canada.

Second-generation anticoagulant rodenticides (SGARs) are widely used to control rodent pests but exposure and poisonings occur in non-target species, such as birds of prey. Liver residues are often analysed to detect exposure in birds found dead but their use to assess toxicity of SGARs is problematic. We analysed published data on hepatic rodenticide residues and associated symptoms of anticoagulant poisoning from 270 birds of prey using logistic regression to estimate the probability of toxicosis associated with different liver SGAR residues. We also evaluated exposure to SGARs on a national level in Canada by analysing 196 livers from great horned owls (Bubo virginianus) and red-tailed hawks (Buteo jamaicensis) found dead at locations across the country. Analysis of a broader sample of raptor species from Quebec also helped define the taxonomic breadth of contamination. Calculated probability curves suggest significant species differences in sensitivity to SGARs and significant likelihood of toxicosis below previously suggested concentrations of concern (<0.1mg/kg). Analysis of birds from Quebec showed that a broad range of raptor species are exposed to SGARs, indicating that generalised terrestrial food chains could be contaminated in the vicinity of the sampled areas. Of the two species for which we had samples from across Canada, great horned owls are exposed to SGARs to a greater extent than red-tailed hawks and the liver residue levels were also higher. Using our probability estimates of effect, we estimate that a minimum of 11% of the sampled great horned owl population is at risk of being directly killed by SGARs. This is the first time the potential mortality impact of SGARs on a raptor population has been estimated.

Polybrominated diphenyl ethers, toxaphenes, and other halogenated organic pollutants in great blue heron eggs.

The great blue heron (Ardea herodias) has been used as a bioindicator of the state of the St. Lawrence River (Québec, Canada) since 1996. At 5-year intervals, selected breeding colonies along the River and its estuary are visited to estimate reproductive success and determine levels of contamination. Brominated flame retardants are found in many ecosystems and are increasing in concentration in the Great Lakes, which is the source of much of the water for the St. Lawrence River. In 2001 and 2002, in addition to polychlorinated biphenyls (PCBs) and chlorinated pesticides, the levels of polybrominated diphenyl ethers (PBDEs), polychlorinated bornanes (toxaphene) congeners and non-ortho-substituted PCBs were measured for the first time in pools of great blue heron eggs. The PBDE levels in great blue heron eggs (70-1,377 ng/g wet wt) were comparable to those measured in herring gull (Larus argentatus) eggs from the Great Lakes. Toxaphene was detected in great blue heron eggs at levels comparable to those of other major chlorinated pesticides. Major toxaphene congeners were octachlorobornane P44 and the nonachlorobornane P50. Environ.