Perfluoroalkyl Substances in Seabird Eggs from Canada's Pacific Coast: Temporal Trends (1973-2019) and Interspecific Patterns.

Whether perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs) are responding to legislative restrictions and showing decreasing trends in top marine predators that range across the eastern North Pacific Ocean is unclear. Here, we examined longer-term temporal trends (1973-2019) of 4 PFSAs and 13 PFCAs, as well stable isotopes of δ13C and δ15N, in the eggs of 4 seabird species sampled along a nearshore-offshore gradient; double-crested cormorants (Nannopterum auritum), pelagic cormorants (Urile pelagicus), rhinoceros auklets (Cerorhinca monocerata), and Leach's storm-petrels (Hydrobates leucorhous) from the Pacific coast of British Columbia, Canada. PFOS was the most abundant PFSA (79-94%) detected in all eggs regardless of colony and year, with the highest concentrations, on average, measured in auklet eggs (mean = 58 ng g-1, range = 11-286 ng g-1 ww). Perfluoroundecanoic acid (PFUdA) and perfluorotridecanoic acid (PFTriDA) were the dominant long-chain PFCAs (≥30% combined). The majority of PFSAs (including PFOS) are statistically declining (p < 0.001) in the eggs of all 4 species with PFOS half-lives ranging from 2.6 to 7.8 years. Concentrations of long-chain PFCAs exhibited a trajectory comprised of linear increases and second-order declines, suggesting that the rate of uptake of PFCAs is slowing or leveling off. These trends are consistent with the voluntarily ceased production of PFSAs by 3M circa 2000-2003 and are among the first from the northeast Pacific to indicate a positive response to several regulations and restrictions on PFCAs from facility emissions and product content.

Trends of polybrominated diphenyl ethers and hexabromocyclododecane in eggs of Canadian Arctic seabirds reflect changing use patterns.

Due to the substantial use and release of polybrominated diphenyl ether (PBDE) flame retardants in North America, PBDE concentrations in North American marine biota are among the highest in the world. In this study, we compared PBDE concentrations and congener patterns in eggs of five seabird species (thick-billed murres, northern fulmars, black guillemots, glaucous gulls, black-legged kittiwakes) breeding at a colony in the Canadian Arctic in 1993, 2008 and 2013. Temporal trends of PBDEs (1975-2014) and another flame retardant, hexabromocyclododecane (HBCD) (2003-2014), were also examined in eggs of two seabird species, the thick-billed murre and northern fulmar. BDE-47 generally dominated the BDE congener profiles in eggs of all five species. Glaucous gulls had the highest concentrations of both ΣPBDE and BDE-47, and northern fulmars, the lowest. ΣPBDE concentrations increased exponentially in eggs of both thick-billed murres and northern fulmars from 1975 to 2003 with doubling times of 9.1 years in the murres and 7.2 years in the fulmars. From 2003 to 2008/09, ΣPBDE decreased rapidly in the murres and fulmars to concentrations not significantly different from those recorded in 1975 and 1987 for each species. After 2008/09, ΣPBDE concentrations plateaued. BDE-47 followed a similar temporal trend to that of ΣPBDE concentrations. These concentration trends were consistent with the phase-out of the penta- and octa-BDE products from the North American market in the mid-2000s. There was an overall decline in concentrations of HBCD in murre eggs from 2003 to 2014, whereas concentrations in the fulmar eggs increased from 2003 to 2006 followed by a decline to 2014. The ratio of HBCD to BDE-47 suggests that northern fulmars showed more of a European contaminant signature, and thick-billed murres, more of a North American signature.

Integrated approach for the isotope trophic position of black-tailed gull (Larus crassirostris) eggs over a decade: Combining stable isotopes of amino acids and fatty acids composition.

Recently, compound-specific isotope analysis (CSIA) using the amino acid nitrogen stable isotope ratio (δ15NAAs) has been widely used for accurate estimation of trophic position (TP). In addition, a quantitative fatty acid signature analysis (QFASA) offers insights into diet sources. In this study, we used these techniques to estimate the TP for seabirds that rely on diverse food sources across multiple ecosystems. This allows for the proper combination of factors used in TP calculation which are different for each ecosystem. The approach involved the application of a multi-mixing trophic discrimination factor (TDF) and mixing ß which is a Δδ15N between trophic and source amino acid of primary producer. Since the black-tailed gulls (BTGs) are income-breeding seabirds, which rely on energy sources obtained around their breeding sites, they and their eggs could be useful bioindicators for environmental monitoring. However, the ecological properties of BTGs such as habitats, diets, and TP are not well known due to their large migration range for wintering or breeding and their feeding habits on both aquatic and terrestrial prey. In this study, the eggs were used for estimating TP and for predicting TP of mother birds to overcome difficulties such as capturing birds and collecting non-invasive tissue samples. Eggs, sampled over a decade from three Korean islands, showed spatial differences in diet origin. Considering both the food chain and physiology of BTG, the TP of eggs was estimated to be 3.3-4.0. Notably, the TP was significantly higher at site H (3.8 ± 0.1) than at site B (3.5 ± 0.2), which indicated a higher contribution of marine diet as confirmed by QFASA. Using a reproductive shift of δ15NAAs, the TP of the mother birds was predicted to be 3.6-4.3, positioning them as the top predator in the food web. The advanced integration of multiple approaches provides valuable insights into bird ecology.

Microbead beating extraction of avian eggs for polycyclic aromatic compounds.

Due to their relatively high trophic position and importance as a food source for many communities in the circumpolar north, seabird eggs are an important matrix for monitoring contaminant levels. In fact, many countries, including Canada, have established long-term seabird egg contaminant monitoring programs, with oil related compounds a contaminant of emerging concern for seabirds in several regions. Current approaches to measuring many contaminant burdens in seabird eggs are time-consuming and often require large volumes of solvent. Here we propose an alternative approach, based on the principle of microbead beating tissue extraction using custom designed stainless-steel extraction tubes and lids, to measure a suite of 75 polycyclic aromatic compounds (polycyclic aromatic hydrocarbons (PAHs), alkyl-PAHs, halogenated-PAHs and some heterocyclic compounds) comprising a wide-range of chemical properties. Our method was conducted in strict accordance with ISO/IEC 17025 guidelines for method validation. Accuracies for our analytes generally ranged from 70 - 120%, and intra and inter-day repeatability for most analytes were < 30%. Limits of detection/quantitation for the 75 target analytes were < 0.2/0.6 ng g-1. The level of contamination in our method blanks was significantly smaller in our stainless-steel tubes/lids relative to commercially available high-density plastic alternatives. Overall, our method meets our data quality objectives and results in a notable reduction in sample processing times relative to current approaches.

Temporal trends (1968-2019) of legacy persistent organic pollutants (POPs) in seabird eggs from the northeast Pacific: Is it finally twilight for old POPs?

Legacy persistent organic pollutants (POPs), such as organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs), are known to persist in the marine environment; however, whether concentrations of these POPs have decreased or stabilized from Canada's Pacific coast in recent years is unclear. Here, we examined temporal trends of various legacy POPs in the eggs of five seabird species; two cormorants (Nannopterum auritum and Urile pelagicus), an auklet (Cerorhinca monocerata), a murrelet (Synthliboramphus antiquus), and a storm-petrel (Hydrobates leucorhous), sampled 1968 to 2019 from 23 colonies along the Pacific coast of British Columbia, Canada. The contaminant profile in the eggs of all species and sampling years was dominated by ΣPCBs, followed by ΣDDT (mostly p,p'-DDE), ΣHCH (ß-HCH), ΣCHLOR (oxychlordane), and ΣCBz (HCB). ΣOC and ΣPCB concentrations were generally higher in double-crested cormorant eggs than in the other four species. The majority of legacy POPs are either significantly declining (e.g. p,p'-DDE, HCB, HE, oxychlordane, ΣPCBs) or showing no directional change over time (ΣMirex) in the eggs of our monitoring species. Contaminants such as α-HCH, cis- and trans-chlordane, p,p'-DDT, dieldrin, and octachlorostyrene also showed evidence of downward trends, largely influenced by non-detect values during more recent sampling periods. Increasing trends were observed for ß-HCH in the eggs of some species; however, mean concentrations eventually returned to early 2000 levels by the end of the study period. Although bulk δ15N and δ13C egg values varied interannually, compound-specific amino acid analyses suggested no major changes in trophic position or baseline food web signature. Temporal trends observed here were comparable to those found in other seabird species and pelagic food webs. As most legacy POPs in our data set were at very low levels in recent years, we support the general consensus that it is indeed the twilight years for old POPs, and we attribute these declines largely to voluntary regulations and international restrictions on the production and use of these compounds, and thus their release into the marine environment.

Polycyclic aromatic hydrocarbons (PAHs) in seabird eggs in Ireland.

Seabird eggs are considered a favourable matrix for monitoring marine pollutants and are widely used as higher trophic level indicators. Concentrations of Polycyclic aromatic hydrocarbons (Σ15PAH) were determined in the eggs of four piscivorous seabirds in Ireland from multiple colonies for the first time, Common Guillemot Uria aalge, Northern Gannet Morus bassanus, Common Tern Sterna hirundo and Arctic Tern S. paradisaea. PAH concentrations were generally lower than levels detected in eggs from other seabird studies and considerably lower than concentrations associated with no adverse effect in the eggs of domestic avian species. This study indicates potential site and species differences in PAH concentrations. Baseline data of PAHs in a range of seabird species from this study may provide an important reference point should a major pollution event occur in European waters, such as an oil spill.

Persistent organic pollutants in sea bird eggs from the Indian Ocean's Mascarene Basin.

We report the concentrations of persistent organic pollutants (POPs) in seabird eggs from St. Brandon's Atoll, a tropical island system in the western Indian Ocean. Ten eggs each of sooty terns (Onychoprion fuscatus), fairy terns (Gygis alba), and common noddies (Anous stolidus) were collected from the atoll. For a terrestrial reference, we analysed three feral chicken (Gallus gallus domesticus) eggs from the same location. Sooty tern eggs contained the highest mean concentrations of three chemical classes: Æ©CHL3 (0.21 ng/g wm; wet mass), Æ©PCB10 (1.5 ng/g wm), and Æ©PBDE6 (1.1 ng/g wm). Fairy tern eggs contained the highest mean concentrations of HCB (0.68 ng/g wm) and Æ©CHB5 (0.83 ng/g wm). The chicken eggs contained the highest mean concentrations of Æ©DDT3 (2.6 ng/g wm), while common noddy eggs contained the highest mean concentrations of Æ©HCH2 (0.5 ng/g wm). We surmise that the differences in chemical composition between species reflect different pollutant compositions in prey from the bird's different foraging ranges. The sooty terns foraging offshore contained higher POPs concentrations than the nearshore-foraging common noddies. Fairy tern eggs contained intermediate concentrations, commensurate with their intermediate foraging. Inter-island differences in contaminant concentrations were seen between eggs of the common noddies from St. Brandon's Atoll and Rodrigues Island, 520 km to the south-east. Concentrations of contaminants found in this study were lower than values quantified by other studies, making St. Brandon's Atoll an ideal reference site to monitor background concentrations of POPs in the tropical Indian Ocean.

Persistent pollutants in fresh and abandoned eggs of Common Tern (Sterna hirundo) and Arctic Tern (Sterna paradisaea) in Ireland.

Higher levels of persistent pollutants (Σ16PCB, Σ6PBDE, ΣHCH, ΣDDT, ΣCHL) were detected in fresh eggs of Common Terns Sterna hirundo from Rockabill Island near Dublin (Ireland's industrialised capital city) compared to Common and Arctic Terns S. paradisaea from Ireland's west coast. Intra-clutch variation of pollutant levels in Common Terns was shown to be low, providing further evidence that random sampling of one egg may be an appropriate sampling strategy. Significant differences in pollutant concentrations were detected between fresh and abandoned eggs on Rockabill. However, abandoned eggs can still provide a useful approximation of pollutants in bird eggs if non-destructive sampling is preferred. Levels of p,p' -DDE in tern eggs have decreased over time according to this study, in concurrence with worldwide trends. Results in this study fall below toxicological thresholds for birds and OSPARs EcoQO thresholds set for Common Tern eggs, except for mercury and HCH in the west coast.

Legacy and emerging contaminants in common guillemot Uria aalge eggs in Ireland and Wales.

Guillemot eggs from multiple Irish colonies and one Welsh colony were analysed for legacy pollutants such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and other organochlorine compounds (OCs), as well as metals. Stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) were measured in eggs to understand the influence of diet on contaminant levels detected. Wide-scope target and suspect screening techniques were used on a single guillemot egg, providing novel information on contaminants of emerging concern. Stable isotope ratio analysis showed that guillemots from Great Saltee Island and Lambay Island (Ireland's east coast) had a similar carbon source (δ13C) and fed at similar trophic levels (δ15N), pollutant levels were higher in eggs from Lambay Island near Dublin, Ireland's industrialised capital city. Guillemot eggs from Aughris Head (Atlantic west coast of Ireland), and Skomer Island (Wales) had differing isotopic niches to other colonies. Egg samples from Aughris Head had the lowest levels of pollutants in this study (with the exception of mercury) and amongst the lowest levels reported worldwide. In contrast, Skomer Island had the highest level of pollutants with higher concentrations of Σ16PCB, Σ6PBDE and HCB than Irish colonies, most likely a result of its proximity to historically industrial areas. Levels of PCBs, p,p' -DDE and mercury in guillemot eggs have decreased over time according to this study, in concurrence with worldwide trends. Levels of pollutants in guillemot eggs, in this study, fall below existing thresholds for adverse effects in other species, with the exception of mercury.

Persistent pollutants in Northern Gannet Morus bassanus eggs in Ireland: Levels and colony differences.

Seabird eggs are considered a favourable matrix for monitoring marine pollutants and are widely used as higher trophic level indicators. Persistent organic pollutants such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and other organochlorine compounds (OCs) as well as metals have been shown to have deleterious impacts on seabirds. The Northern Gannet Morus bassanus is an avian sentinel; the largest breeding seabird in Ireland and an obligate piscivore. Gannet eggs were collected from two island colonies off the east coast of Ireland in locations with divergent history of industrialisation. Contaminant levels were measured and differences in concentrations between colonies compared. Stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) were measured in each egg to understand the influence of diet and trophic position on contaminant levels detected. Significantly higher levels of Σ14PCBs, Σ7PBDEs and total mercury were detected in Gannet eggs from Lambay Island near Dublin (Ireland's industrialised capital city) compared to Great Saltee Island. No differences were observed in levels of other OCs (HCB, ΣHCH, ΣCHL, ΣDDT) between the two colonies. Though Gannets travel significant distances when foraging for food, tracking studies have demonstrated that birds from proximal breeding colonies maintain exclusive feeding areas. Stable isotope ratio analysis in this study demonstrated that Gannets at both locations occupy similar dietary niches, indicating that dietary differences may not be the driver of differing contaminant levels between colonies. Levels of persistent pollutants in the Gannet eggs fall below most existing thresholds for adverse effects and are within internationally reported values. Recent population growth and range expansion of Gannets in Ireland suggest that persistent pollutants are not having an immediate impact on the Gannet population. This study will inform potential monitoring programmes that can help Ireland achieve good environmental status under the European Union's Marine Strategy Framework Directive.

Polar bears are inefficient predators of seabird eggs.

Climate-mediated sea-ice loss is disrupting the foraging ecology of polar bears (Ursus maritimus) across much of their range. As a result, there have been increased reports of polar bears foraging on seabird eggs across parts of their range. Given that polar bears have evolved to hunt seals on ice, they may not be efficient predators of seabird eggs. We investigated polar bears' foraging performance on common eider (Somateria mollissima) eggs on Mitivik Island, Nunavut, Canada to test whether bear decision-making heuristics are consistent with expectations of optimal foraging theory. Using aerial-drones, we recorded multiple foraging bouts over 11 days, and found that as clutches were depleted to completion, bears did not exhibit foraging behaviours matched to resource density. As the season progressed, bears visited fewer nests overall, but marginally increased their visitation to nests that were already empty. Bears did not display different movement modes related to nest density, but became less selective in their choice of clutches to consume. Lastly, bears that capitalized on visual cues of flushing eider hens significantly increased the number of clutches they consumed; however, they did not use this strategy consistently or universally. The foraging behaviours exhibited by polar bears in this study suggest they are inefficient predators of seabird eggs, particularly in the context of matching behaviours to resource density.

Perfluoroalkyl substances (PFAS) in tern eggs from St. Brandon's Atoll, Indian Ocean.

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic fluorinated compounds of concern for human and environmental health. There is no data on PFAS concentrations in marine bird eggs from the Western Indian Ocean. We analysed eight PFAS in eggs of fairy terns (Gygis alba), sooty terns (Onychoprion fuscatus), and common noddies (Anous stolidus) from St. Brandon's Atoll. Fairy tern eggs contained the highest concentrations, followed by sooty terns and common noddies. Perfluoroundecanoic acid (PFUdA) had the highest mean concentration (2.3 ng/g wm), followed by perfluorooctane sulfonic acid (PFOS) (2.0 ng/g wm), and perfluorononanoic acid (PFNA) (0.93 ng/g wm) in fairy tern eggs. Concentrations of all PFAS were lower than values found in literature. PFOS and PFOA concentrations were three orders of magnitude lower than toxicity reference values and levels of lowest-observed-adverse-effect-level concentrations. Eggs from St. Brandon's would be useful to monitor background changes on a regional and perhaps global scale.

Temporal trends of legacy organochlorines in eggs of Canadian Arctic seabirds monitored over four decades.

We compared temporal trends of legacy organochlorine pesticides and PCBs in eggs of five seabird species breeding at Prince Leopold Island in the Canadian high Arctic. Concentrations of most of the major organochlorine groups/compounds have either declined (e.g. Σ35PCB, ΣDDT, ΣCBz, ΣCHL, octachlorostyrene) or shown no consistent directional change (e.g. heptachlor epoxide) since 1975 in eggs of thick-billed murres (Uria lomvia), northern fulmars (Fulmarus glacialis) and black-legged kittiwakes (Rissa tridactyla). Aside from ß-HCH, which increased in most species, the major organochlorine compounds either declined or showed no trend between 1993 and 2013 in eggs of five seabird species (thick-billed murre, northern fulmar, black-legged kittiwake, black guillemot Cepphus grylle, glaucous gull Larus hyperboreus). Most of the declines occurred during the 1970s to 1990s followed by little change during the 2000s. Glaucous gull eggs had the highest concentrations of almost all organochlorines in the five years compared (1993, 1998, 2003/04, 2008, 2013), and murre eggs generally had among the lowest concentrations. The primary organochlorines found in eggs of all five species were Σ35PCB, ΣDDT (mainly p,p'-DDE), ΣCBz (mainly hexachlorobenzene) and ΣCHL (mainly oxychlordane) although proportions varied by species and year. The major PCB congeners found in eggs of all five species were CB-153, -138, -118 and -180. The penta-, hexa- and heptachlorobiphenyl homologs comprised the largest proportion of Σ35PCB in all five species. Although levels of most legacy organochlorines have declined since 1975, the potential for climate change to alter chemical transport pathways as well as exposure pathways in the biotic environment could affect temporal trends. Therefore, it is important to continue to monitor these legacy contaminants in order to determine how these changes will affect the temporal trends observed to date.

Declining trends of polychlorinated dibenzo-p-dioxins, dibenzofurans and non-ortho PCBs in Canadian Arctic seabirds.

Polychorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (PCBs) such as the non-ortho PCBs (nPCBs) persist in the environment despite international measures to ban their emissions. We determined congener patterns and temporal trends for PCDDs, PCDFs, nPCBs as well as their toxic equivalents (TEQs) in eggs of thick-billed murres (Uria lomvia) and northern fulmars (Fulmarus glacialis) sampled from Prince Leopold Island in the Canadian Arctic between 1975 and 2014. The dominant PCDD congeners were 1,2,3,7,8-PnCDD, 2,3,7,8-TCDD and 1,2,3,6,7,8-HxCDD, and the dominant PCDF congener was 2,3,4,7,8-PnCDF. The nPCB profile was dominated by PCB-126. The TEQ profile in the murre eggs was dominated by nPCB-TEQ whereas in the fulmar eggs, the PCDF-TEQ contribution to ΣTEQ was slightly greater than that of nPCB-TEQ. Concentrations of ΣPCDD, ΣPCDF, ΣnPCB and ΣTEQ declined between 1975 and 2014 in both murre and fulmar eggs. Based on TEQ thresholds in the literature for other species, and taking into account the trend towards declining TEQ levels, it is unlikely that current levels of PCDDs, PCDFs or nPCBs are affecting the reproductive success of thick-billed murres or northern fulmars in the Canadian Arctic.