In this study, we measured the concentrations of 58 flame retardants (and related compounds) in bald eagle (Haliaeetus leucocephalus) egg and plasma samples from the Michigan. These analytes include polybrominated diphenyl ethers (PBDEs), novel flame retardants (nFRs), Dechlorane-related compounds (Decs), and organophosphate esters (OPEs). A total of 24 paired eaglet plasma and egg samples were collected from inland (IN, N = 13) and the Great Lakes (GL, N = 11) breeding areas from 2000 to 2012. PBDEs were the most abundant chemical group with a geometric mean of 181 ng/g wet weight (ww) in egg and 5.31 ng/g ww in plasma. Decs were barely found in plasma samples, but they were frequently found in eggs (geometric mean 23.5 ng/g ww). OPE levels were comparable to those of PBDEs in the plasma but lower than those of PBDEs in eggs. Dec and PBDE concentrations were significantly higher in GL than in IN (p < 0.05). The ratio of egg to plasma concentrations (lipid normalized) varied with chemicals and correlated with the chemical's octanol-water partition coefficient. The lipid normalized bald eagle egg and plasma concentrations from Lake Superior and Huron were one to three orders of magnitude higher than concentrations measured in composite lake trout (Salvelinus namaycush) from the same lake, implying that they biomagnify in the environment.

We examine the concentrations and food web biomagnification of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) using aquatic biota collected from Lake Erie. Concentrations of cVMS in biota were within the range reported for other studies of cVMS in aquatic biota. Trophic magnification factors (TMF) were assessed in various food web configurations to investigate the effects of food web structure. TMF estimates were highly dependent on the inclusion/exclusion of the organisms occupying the highest and lowest trophic levels and were >1 for D4 and D5, indicating biomagnification, in only 1 of the 5 food web configurations investigated and were <1 in the remaining 4 food web configurations. TMF estimates for PCB180 were also dependant on food web configuration, but did not correspond with those obtained for cVMS materials. These differences may be attributed to environmental exposure and/or lipid partitioning differences between PCB180 and cVMS.

Due to the complex sources and fate of perfluoroalkyl substance (PFAS), their source apportionment in the environment remains a challenge. A data set of 11 straight-chain PFAS in 139 samples of fish in the Great Lakes was analyzed using positive matrix factorization (PMF) to investigate their primary sources, whose spatial variations were examined against the surrounding environmental factors. PMF analysis produced five fingerprints. Factor 1 (72% of Σ₁₁PFAS, dominated by PFOS) probably represented emissions from primary sources (such as consumer products) and secondary sources (precursors), and increased in average abundance from west to east across the Great Lakes. Factor 2 (13% of Σ₁₁PFAS) and factor 3 (7% of Σ₁₁PFAS), highly loaded with long-chain PFAS and PFNA, respectively, were thought to represent PVDF manufacture or processing in metal plating. They showed higher contributions in sparsely populated Lakes Superior and Huron. Factor 4 (5% of Σ₁₁PFAS, highly loaded with PFOS and PFHxS) presented hot spots near current and former air force bases, suggesting it was related to aqueous film-forming foams (AFFFs). Factor 5 (4% of Σ₁₁PFAS) contained primarily PFOS and PFOSA, which may imply metabolism of precursors (PFOSA) to PFOS in vivo. Unexpectedly, the spatial trends of the five sources all showed abnormally low values near the more urbanized Chicago and Milwaukee in Lake Michigan, which may be due to their unique wastewater and stormwater infrastructure or may arise from atmospheric transport of precursors. Our study indicated that PMF was an effective tool to identify sources of PFAS in fish despite absorption, distribution, metabolism, and excretion (ADME) processes which might alter fingerprints in fish relative to their surrounding environment.

Decades of large-scale production of per- and polyfluoroalkyl substances (PFASs) have resulted in their ubiquitous presence in the environment worldwide. Similarly to other persistent and bioaccumulative organic contaminants, some PFASs, particularly the long-chain congeners, can be biomagnified via food webs, making top predators vulnerable to elevated PFAS exposure. In this study, we measured seven classes of PFASs in bald eagle (Haliaeetus leucocephalus) eggs for the first time. The eggs (n = 22) were collected from the North American Great Lakes in 2000–2012. The ranges of total concentrations of perfluoroalkyl sulfonic acids (∑PFSAs) and perfluoroalkyl carboxylic acids (∑PFCAs) were 30.5–1650 and 5.4–216 ng/g wet weight (ww), respectively. In addition to these traditional PFAS compounds, 6:2 fluorotelomer sulfonic acid (6:2 FTS; median: 15.7 ng/g ww), perfluoro-4-ethylcyclohexanesulfonic acid (PFECHS; 0.22 ng/g ww), and 8-chloro-perfluorooctanesulfonic acid (Cl-PFOS, detected in wildlife for the first time; 0.53 ng/g ww) were also frequently detected. Bald eagle eggs from breeding areas located less than 8 km from a Great Lake shoreline or tributary had significantly greater total PFAS concentrations (∑PFASs) than those from breeding areas located further than 8 km (p < 0.05). In these samples, ∑PFASs rivalled the total concentration of brominated flame retardants, and were significantly greater than those of several other organic contaminants, such as dechlorane-related compounds, organophosphate esters, and flame retardant metabolites.

Passive samplers are useful tools for monitoring hydrophobic, persistent, and potentially bioaccumulative contaminants in the environment. In this study, low density polyethylene passive samplers were deployed in urban-influenced and background nearshore freshwaters of northwestern Lake Ontario and analyzed for a broad range of both legacy halogenated organic contaminants (HOCs) and halogenated flame retardants (HFRs). Non-targeted analysis was conducted for screening additional halogenated substances. For most compounds, concentrations were greatest in the industrialized Hamilton Harbour and more generally at sites that have stronger influences of wastewater effluent discharges and stormwater run-off through rivers and creeks. Polychlorinated biphenyls (PCBs) remain the dominant class of HOCs in water, with dissolved-phase concentrations ranging from 10 to 4100 pg/L (ΣPCBs), followed by polybrominated diphenylethers (ΣPBDEs; 14–960 pg/L) and the organochlorine pesticides (OCPs; 22–290 pg/L). Several non-PBDE brominated flame retardants (nBFRs) and chlorinated Dechlorane-related compounds were detected, with hexabromocyclododecanes (ΣHBCDD; sum of 3 diastereoisomers) the most abundant (1.0–21 pg/L). Non-targeted screening of samples by high resolution mass spectrometry using Kendrick mass defect plots for data analysis indicated that several other halogenated compounds were present in waters at relatively high abundances compared to the flame retardants, based on semi-quantitative estimates. These included methyl-triclosan, four halogenated anisoles (2,4,6-tribromoanisole, dimethyl-trichloroanisole, pentachloroanisole, and pentachlorothioanisole), and pentachloro-aniline. Dissolved-phase methyl-triclosan was estimated to contribute up to approximately 40% of the summed target HOC concentrations. Polyethylene passive samplers provided an excellent medium for both non-targeted screening of HOCs not currently included in monitoring programs and tracking brominated and chlorinated chemicals slated for reductions in uses and emissions through international (Stockholm Convention) and binational (Great Lakes) agreements.

The occurrence and spatial distribution of selected pesticides were investigated along a 200-km reach of the St. Lawrence River (SLR) and tributaries in Quebec, Canada. Surface water samples (n = 68) were collected in the summer 2017 and analyzed for glyphosate, atrazine (ATZ), 8 systemic insecticides (acetamiprid, clothianidin, dinotefuran, fipronil, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam) and some metabolites. Overall, 99% of the surface water samples were positive to at least one of the targeted pesticides. The most recurrent compounds were glyphosate (detection frequency: 84%), ATZ (82%), thiamethoxam (59%), desethylatrazine (DEA: 47%), and clothianidin (46%). Glyphosate displayed variable levels (4–3,000 ng L−1), with higher concentrations in south tributaries (e.g., Nicolet and Yamaska). In positive samples, the sum of ATZ and DEA varied between 5 and 860 ng L−1, and the sum of 6 priority neonicotinoids between 1.5 and 115 ng L−1. From Repentigny to the Sorel Islands, the spatial distribution of pesticides within the St. Lawrence River was governed by the different upstream sources (i.e., Great Lakes vs. Ottawa River) due to the limited mixing of the different water masses. Cross-sectional patterns revealed higher concentrations of glyphosate and neonicotinoids in the north portions of transects, while the middle and south portions showed higher levels of atrazine. In Lake St. Pierre and further downstream, cross-sections revealed higher levels of the targeted pesticides near the southern portions of the SLR. This may be due to the higher contributions from south shore tributaries impacted by major agricultural areas, compared to north shore tributaries with forest land and less cropland use. Surface water samples were compliant with guidelines for the protection of aquatic life (chronic effects) for glyphosate and atrazine. However, 31% of the samples were found to surpass the guideline value of 8.3 ng L−1 for the sum of six priority neonicotinoids.

Long-term air monitoring data for POPs are required to determine the effectiveness of source reduction measures and factors controlling air concentrations. Air samples were collected between 1992 and 2012 at three sites with different geographical characteristics (Burnt Island, Egbert and Point Petre) in the Canadian Great Lakes Basin (GLB) using high-volume samplers and analyzed for organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). Spatial and temporal trends of gas-phase concentrations of OCPs, selected PCB congeners and ƩPCBs (84 congeners) were assessed. Egbert had the highest concentrations of some OCPs due to historical [dichlorodiphenyltrichloroethanes (DDTs), dieldrin, γ-hexachlorocyclohexane (γ-HCH)] and current (endosulfan) applications of these pesticides in the surrounding agricultural cropland. This shows that agricultural areas are a source of OCPs to the GLB. High o,p'-/p,p'-DDT ratios were determined and an increasing trend was observed at Point Petre and Burnt Island up to 2004; indicating that the GLB is influenced by dicofol-type DDT sources, which have higher o,p’-/p,p’-DDT ratios than technical DDT. Atmospheric PCB concentrations at Egbert and Point Petre are higher than those measured at Burnt Island, likely due to urban influence and greater populations. Loadings calculations suggest that the atmosphere is a source of α-endosulfan and p,p’-DDT to the lakes and the opposite is true for p,p’-DDE. Long-term decreasing trends were observed for both OCPs and PCBs; consistent with control measures implemented in North America. Atmospheric PCB concentrations are decreasing relatively slowly, with halflives in the range of 9–39 years. Chlordane, α-endosulfan, β-endosulfan, dieldrin, and DDT-related substances showed halflives in the range of 7–13 years. α-HCH and γ-HCH were decreasing rapidly in air, with halflives of 5 years. Long-term declining trends of PCBs and OCPs suggest that regulatory efforts to reduce emissions to the GLB environment have been effective, but emissions from primary and secondary sources might limit future declines.

Biomonitoring programs for persistent, bioaccumulative, and/or toxic chemicals of concern in fish tissues have been operated by the governments of Canada and the United States in the Great Lakes since the 1970's. The objectives of these programs are to assess concentrations of harmful chemicals in whole body top predator fish as an indicator of ecosystem health and to infer potential harm to fish and fish consuming wildlife in the Great Lakes Basin. Chemicals of interest are selected based upon national and binational commitments, risk assessment, and regulation, and include a wide range of compounds. This review summarizes all available data generated by Environment Canada and the United States Environmental Protection Agency for chemicals measured in whole body homogenates of Lake Trout (Salvelinus namaycush) and Walleye (Sander vitreus) for the time period spanning 2008 to 2012 from each of the five Great Lakes. The summary shows that concentrations of legacy compounds, such as, POPs listed in the Stockholm Convention and mercury continue to dominate the chemical burden of Great Lakes fish. This assessment, and others like it, can guide the creation of environmental quality targets where they are lacking, optimize chemical lists for monitoring, and prioritize chemicals of concern under agreements such as the Great Lakes Water Quality Agreement and the Stockholm Convention.

This study examined the temporal and spatial trends in wet deposition of 19 legacy and emerging brominated flame retardants (14 polybrominated diphenyl ethers (PBDEs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenylethane (DBDPE), hexabromocyclododecane (HBCD) and pentabromoethylbenzene (PBEB)) at 9 sites in the Canadian Great Lakes between 2004 and 2010. Concentrations of BDE-209 in wet deposition declined significantly. This indicates that the voluntary actions taken to phase out the use of BDE 209 in North America are having an immediate effect on its environment concentrations. The analysis also revealed the presence of 22 short-term high concentration events that dominated overall wet deposition loadings of current-use BFRs to the lakes. For instance, one sample in 2007 was responsible for 37% of the total loadings of HBCD to Lake Huron over the entire six-year sampling period. This questions the current paradigm of how we believe such pollutants enter the environment.

Accumulation of selenium (Se) by lesser and greater scaup (Aythya affinis, A. marila) at staging and wintering areas could have contributed to the decline in their continental population. We exposed lesser scaup to background (0.8 μg/g), moderate (8.1 μg/g) and high (20.7 μg/g) levels of dietary Se in captivity and measured survival rates and indices of health in relation to hepatic Se concentrations. There was 100% survival in scaup exposed to Se for 10-weeks (average staging duration at Great Lakes), but ducks in the high treatment group had less lipids. There was 93% survival after 23-weeks (average wintering duration at Great Lakes), but no differences among treatment groups in body composition. There were no effects of Se on oxidative stress and cell-mediated immunity; rather we recorded immuno-stimulatory effects on antibody production. Results from our captive study suggest Se alone did not cause the continental decline in scaup populations.