Legacy contaminant trends in the Great Lakes uncovered by the wildlife environmental quality index.

Since the 1970s, wildlife managers have prioritized the recovery of Great Lakes ecosystems from contamination by Persistent Organic Pollutants (POPs). Monitoring and quantifying the region's recovery is challenged by the diversity of legacy contaminants in the environment and the lack of benchmarks for their potential biological effects. We address this gap by introducing the Wildlife Environmental Quality Index (WEQI) based on prior water and sediment quality indices. The tool summarizes, in a single score, the exposure of wildlife to harmful levels of multiple contaminants - with harmful levels set by published guidelines for protecting piscivorous wildlife from biological impacts. We applied the new index to a combined Canadian and American dataset of Herring Gull (Larus argentatus) egg data to elucidate trends in wildlife for eight legacy industrial pollutants and insecticides in the Great Lakes. Environmental quality of the Great Lakes region (as indexed by WEQI) improved by 18% between 2002 and 2017. Improvement came from reductions in both the scope of contamination (the number of guideline-exceeding contaminants) and its amplitude (the average size of guideline exceedances) at bird colonies. But recovery was unequal among lakes, with Lake Erie showing no improvement at one extreme. Weakly- or non-recovering lakes (Erie, Ontario, Huron) were marked by inconsistent improvement in scope and amplitude, likely due to ongoing loading, sediment resuspension and other stressors reported elsewhere. Fast-recovering lakes (Superior and Michigan), meanwhile, improved in both scope and amplitude. Contrasting trends and contaminant profiles (e.g., exceedances of PCBs versus DDTs) highlight the importance of lake-specific management for equalizing recoveries. Lower environmental quality at American than Canadian colonies, particularly in Lake Huron, further suggest uneven success in - and opportunities for - the binational management of wildlife exposure to legacy contaminants.

Polycyclic aromatic compounds (PACs) in the Canadian environment: The challenges of ecological risk assessments.

Ecological risk assessments (ERAs) of polycyclic aromatic compounds (PACs), as single congeners or in mixtures, present technical challenges that raise concerns about their accuracy and validity for Canadian environments. Of more than 100,000 possible PAC structures, the toxicity of fewer than 1% have been tested as individual compounds, limiting the assessment of complex mixtures. Because of the diversity in modes of PAC action, the additivity of mixtures cannot be assumed, and mixture compositions change rapidly with weathering. In vertebrates, PACs are rapidly oxygenated by cytochrome P450 enzymes, often to metabolites that are more toxic than the parent compound. The ability to predict the ecological fate, distribution and effects of PACs is limited by toxicity data derived from tests of a few responses with a limited array of test species, under optimal laboratory conditions. Although several models are available to predict PAC toxicity and rank species sensitivity, they were developed with data biased by test methods, and the reported toxicities of many PACs exceed their solubility limits. As a result, Canadian Environmental Quality Guidelines for a few individual PACs provide little support for ERAs of complex mixtures in emissions and at contaminated sites. These issues are illustrated by reviews of three case studies of PAC-contaminated sites relevant to Canadian ecosystems. Interactions among ecosystem characteristics, the behaviour, fate and distribution of PACs, and non-chemical stresses on PAC-exposed species prevented clear associations between cause and effect. The uncertainties of ERAs can only be reduced by estimating the toxicity of a wider array of PACs to species typical of Canada's diverse geography and environmental conditions. Improvements are needed to models that predict toxicity, and more field studies of contaminated sites in Canada are needed to understand the ecological effects of PAC mixtures.

Polycyclic aromatic compounds (PACs) in the Canadian environment: Exposure and effects on wildlife.

Polycyclic aromatic compounds (PACs) are ubiquitous in the environment. Wildlife (including fish) are chronically exposed to PACs through air, water, sediment, soil, and/or dietary routes. Exposures are highest near industrial or urban sites, such as aluminum smelters and oil sands mines, or near natural sources such as forest fires. This review assesses the exposure and toxicity of PACs to wildlife, with a focus on the Canadian environment. Most published field studies measured PAC concentrations in tissues of invertebrates, fish, and birds, with fewer studies of amphibians and mammals. In general, PAC concentrations measured in Canadian wildlife tissues were under the benzo[a]pyrene (BaP) guideline for human consumption. Health effects of PAC exposure include embryotoxicity, deformities, cardiotoxicity, DNA damage, changes to DNA methylation, oxidative stress, endocrine disruption, and impaired reproduction. Much of the toxicity of PACs can be attributed to their bioavailability, and the extent to which certain PACs are transformed into more toxic metabolites by cytochrome P450 enzymes. As most mechanistic studies are limited to individual polycyclic aromatic hydrocarbons (PAHs), particularly BaP, research on other PACs and PAC-containing complex mixtures is required to understand the environmental significance of PAC exposure and toxicity. Additional work on responses to PACs in amphibians, reptiles, and semi-aquatic mammals, and development of molecular markers for early detection of biological responses to PACs would provide a stronger biological and ecological justification for regulating PAC emissions to protect Canadian wildlife.

Sub-lethal effects of calcium dinonylnaphthalenesulfonate on Western clawed frog embryos.

Naphthalene sulfonic acids (NSAs) are used as additives in lubricants, dyes, and greases and commonly act as surfactants in many industrial processes. The calcium salt of dinonyl NSA (calcium dinonylnaphthalenesulfonate; CaDNS) is listed among thousands of chemicals identified as priorities for assessment by the Government of Canada's Chemical Management Plan due to the limited toxicity data. The purpose of this study was two-fold: 1) to establish the toxicity of CaDNS to Western clawed frog (Silurana tropicalis) embryos and 2) to assess the sub-lethal effects and mechanisms of toxicity of CaDNS in amphibians through targeted gene expression and metabolite analyses. Frog embryos were exposed to water overlying sand spiked with a range of concentrations of CaDNS (17-1393 µg/g) over a 72-h period. Results indicated significantly higher mortality and presence of malformations in frog larvae exposed to over 672 µg/g CaDNS in the sand (14 ng/mL CaDNS in the water) compared to control treatments. An overall decrease in the glutathione redox cycle was observed, including decreases in relative mRNA levels of enzymes (glutathione S-transferase (gst), glutathione reductase (gsr), glutathione peroxidase (gpx)) and decreases in the glutathione (GSH) and glutathione disulfide (GSSG) metabolite concentrations. In addition, transcript levels of genes involved in antioxidant capacity and essential amino acid metabolites decreased significantly in embryos exposed to low levels of CaDNS. This is the first study to assess the toxicity of NSAs in amphibians, contributing important data to aid in the assessment of NSAs.

Assessment of Sublethal Effects of Neonicotinoid Insecticides on the Life-History Traits of 2 Frog Species.

Neonicotinoid insecticides are used extensively in agriculture and, as a consequence, are now detectable in nearby aquatic environments. Few studies have evaluated the effects of neonicotinoids on amphibians in these aquatic environments. In the present study, we examined the effects of 2 commercial formulations of neonicotinoids (active ingredients clothianidin and thiamethoxam) on survival and life-history traits of wood frogs (Lithobates sylvaticus) and northern leopard frogs (Lithobates pipiens). We used artificial pond mesocosms to assess the effects of these neonicotinoids, at nominal concentrations of 2.5 and 250 µg/L, on amphibian larval development through metamorphosis. We found no differences between controls and neonicotinoid exposure for any of the endpoints assessed for either wood frogs or leopard frogs. The present study suggests that concentrations meeting or exceeding observed levels of clothianidin and thiamethoxam in surface waters will not directly affect metamorphosis in 2 amphibians. Environ Toxicol Chem 2019;38:1967-1977. © 2019 SETAC.

Airborne polycyclic aromatic compounds contribute to the induction of the tumour-suppressing P53 pathway in wild double-crested cormorants.

Polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and PAH-like compounds are known or probable environmental carcinogens released into the environment as a by-product of incomplete combustion of fossil fuels and other organic materials. Studies have shown that exposure to PACs in the environment can induce both genotoxicity and epigenetic toxicity, but few studies have related PAC exposure to molecular changes in free ranging wildlife. Previous work has suggested that double-crested cormorants (Phalacrocorax auritus; DCCO) exhibited a higher incidence of genetic mutations when their breeding sites were located in heavily industrialized areas (e.g., Hamilton Harbour, Hamilton, ON, Canada) as compared to sites located in more pristine environments, such as in Lake Erie. The aim of this study was to determine if airborne PACs from Hamilton Harbour alter the tumour-suppressing P53 pathway and/or global DNA methylation in DCCOs. Airborne PACs were measured using passive air samplers in the Hamilton Harbour area and low-resolution mass spectrometry analysis detected PACs in livers of DCCOs living in Hamilton Harbour. Further hepatic and lung transcriptional analysis demonstrated that the expression of the genes involved in the DNA repair and cellular apoptosis pathway were up-regulated in both tissues of DCCOs exposed to PACs, while genes involved in p53 regulation were down-regulated. However, global methylation levels did not differ between reference- and PAC-exposed DCCOs. Altogether, data suggest that PACs activate the P53 pathway in free-ranging DCCOs living nearby PAC-contaminated areas.

Sensitivity of the early-life stages of freshwater mollusks to neonicotinoid and butenolide insecticides.

Neonicotinoid insecticides can be transported from agricultural fields, where they are used as foliar sprays or seed treatments, to surface waters by surface or sub-surface runoff. Few studies have investigated the toxicity of neonicotinoid or the related butenolide insecticides to freshwater mollusk species. The current study examined the effect of neonicotinoid and butenolide exposures to the early-life stages of the ramshorn snail, Planorbella pilsbryi, and the wavy-rayed lampmussel, Lampsilis fasciola. Juvenile P. pilsbryi were exposed to imidacloprid, clothianidin, or thiamethoxam for 7 or 28 d and mortality, growth, and biomass production were measured. The viability of larval (glochidia) L. fasciola was monitored during a 48 h exposure to six neonicotinoids (imidacloprid, thiamethoxam, clothianidin, acetamiprid, thiacloprid, or dinotefuran), or a butenolide (flupyradifurone). The 7-d LC50s of P. pilsbryi for imidacloprid, clothianidin, and thiamethoxam were ≥4000 µg/L and the 28-d LC50s were ≥182 µg/L. Growth and biomass production were considerably more sensitive endpoints than mortality with EC50s ranging from 33.2 to 122.0 µg/L. The 48-h LC50s for the viability of glochidia were ≥456 µg/L for all seven insecticides tested. Our data indicate that neonicotinoid and butenolide insecticides pose less of a hazard with respect to mortality of the two species of mollusk compared to the potential hazard to other non-target aquatic insects.

Bioaccumulation of pharmaceuticals and personal care products in the unionid mussel Lasmigona costata in a river receiving wastewater effluent.

Freshwater mussels are frequently found in rivers receiving effluent from wastewater treatment plants (WWTP), and there is strong evidence that poor water quality is deleterious to freshwater mussel populations. WWTPs are among the main sources of pharmaceuticals and personal care products (PPCPs) in surface waters. We monitored 145 PPCPs in wild and caged mussels both upstream and downstream of the Kitchener WWTP in the Grand River, Ontario, as well as 118 PPCPs in water samples. Our objectives were to characterize the seasonal changes in PPCP concentrations in water, to calculate bioaccumulation factors (BAFs) of PPCPs in mussels, and to determine the chemical and physical properties of PPCPs driving the bioaccumulation. Seventy PPCPs were detected in water, and concentrations were highest in the summer or early fall, which corresponded to low river flow. Forty-three PPCPs from many pharmaceutical classes were detected in mussel tissues, including stimulants, a contrasting agent, anti-inflammatory drugs, anti-bacterial agents, antibiotics, antidepressants, antihistamines, progestins, and illicit drugs such as cocaine and amphetamines. The BAFs ranged from 0.66 for metformin to 32,022 for sertraline. Using partial least squares to predict BAFs based upon chemical properties, log KOC, Log KOW, and fugacity ratio (sediment) all had similar and positive loadings with BAFs (R(2)X = 0.70; caged mussels). BAFs of PPCPs in mussels were predictable from fugacity models that estimate bioconcentration factors using log KOW. Our study demonstrated that mussels readily bioaccumulate PPCPs, in a manner consistent with expectations based upon BCF models and the chemical characteristics of each compound.

Microsatellite DNA mutations in double-crested cormorants (Phalacrocorax auritus) associated with exposure to PAH-containing industrial air pollution.

Hamilton Harbour, Ontario, Canada is one of the most polluted sites on the Great Lakes, and is subject to substantial airborne pollution due to emissions from both heavy industry and intense vehicle traffic. Mutagenic Polycyclic aromatic hydrocarbons (PAHs) are present at very high concentrations in the air and sediment of Hamilton Harbour. We used five variable DNA microsatellites to screen for mutations in 97 families of Double-crested Cormorants (Phalacrocorax auritus) from three wild colonies, two in Hamilton Harbour and one in cleaner northeastern Lake Erie. Mutations were identified in all five microsatellites at low frequencies, with the majority of mutations found in chicks from the Hamilton Harbour site closest to industrial sources of PAH contamination. Microsatellite mutation rates were 6-fold higher at the Hamilton Harbour site closest to the industrial sources of PAH contamination than the other Hamilton Harbour site, and both were higher than the reference colony. A Phase I metabolite of the PAH benzo[a]pyrene identified by LC-MS/MS in bile and liver from Hamilton Harbour cormorant chicks suggests that these cormorants are exposed to and metabolizing PAHs, highlighting their potential to have caused the observed mutations.

Highly elevated levels of perfluorooctane sulfonate and other perfluorinated acids found in biota and surface water downstream of an international airport, Hamilton, Ontario, Canada.

Per- and poly-fluorinated compounds (PFCs), which include perfluorinated carboxylates (PFCAs) and sulfonates (PFSAs) and various precursors, are used in a wide variety of industrial, commercial and domestic products. This includes aqueous film forming foam (AFFF), which is used by military and commercial airports as fire suppressants. In a preliminary assessment prior to this study, very high concentrations (>1 ppm wet weight) of the PFSA, perfluorooctane sulfonate (PFOS), were discovered in the plasma of snapping turtles (Chelydra serpentina) collected in 2008 from Lake Niapenco in southern Ontario, Canada. We presently report on a suite of C(6) to C(15) PFCAs, C(4), C(6), C(8) and C(10) PFSAs, several PFC precursors (e.g. perfluorooctane sulfonamide, PFOSA), and a cyclic perfluorinated acid used in aircraft hydraulic fluid, perfluoroethylcyclohexane sulfonate (PFECHS) in surface water from the Welland River and Lake Niapenco, downstream of the John C. Munro International Airport, Hamilton, Ontario, Canada. Amphipods, shrimp, and water were sampled from the Welland River and Lake Niapenco, as well as local references. The same suite of PFCs in turtle plasma from Lake Niapenco was compared to those from other southern Ontario sites. PFOS dominated the sum PFCs in all substrates (e.g., >99% in plasma of turtles downstream the Hamilton Airport, and 72.1 to 94.1% at all other sites). PFOS averaged 2223(±247.1SE) ng/g in turtle plasma from Lake Niapenco, and ranged from 9.0 to 171.4 elsewhere. Mean PFOS in amphipods and in water were 518.1(±83.8)ng/g and 130.3(±43.6) ng/L downstream of the airport, and 19.1(±2.7) ng/g and 6.8(±0.5) ng/L at reference sites, respectively. Concentrations of selected PFCs declined with distance downstream from the airport. Although there was no known spill event or publicly reported use of AFFF associated with a fire event at the Hamilton airport, the airport is a likely major source of PFC contamination in the Welland River.

Snapping turtles (Chelydra serpentina) as bioindicators in Canadian areas of concern in the Great Lakes Basin. II. Changes in hatching success and hatchling deformities in relation to persistent organic pollutants.

Hatching success and deformities in snapping turtle hatchlings (Chelydra serpentina) were evaluated using eggs collected from 14 sites in the Canadian lower Great Lakes, including Areas of Concern (AOC), between 2001 and 2004. Eggs were analyzed for PCBs, PBDEs, and pesticides. Between 2002 and 2004, hatchling deformity rates were highest in two AOCs (18.3-28.3%) compared to the reference sites (5.3-11.3%). Hatching success was poorest in three AOCs (71.3-73.1%) compared to the reference sites (86.0-92.7%). Hatching success and deformity rates were generally poorer in 2001 compared to 2002-2004, irrespective of the study location and could be due to egg handling stress in 2001. Hatching success and deformities were generally worst from the Wheatley Harbour, St. Lawrence River (Cornwall), Detroit River, and Hamilton Harbour AOCs. Associations between contaminant burdens with embryonic development were sufficiently poor that the biological relevance is questionable. Stressors not measured may have contributed to development abnormalities.

Snapping turtles (Chelydra serpentina) as bioindicators in Canadian areas of concern in the Great Lakes Basin. 1. Polybrominated diphenyl ethers, polychlorinated biphenyls, and organochlorine pesticides in eggs.

We examined the concentrations and spatial patterns of congeners of PBDEs, PCBs, and organochlorine pesticides in snapping turtle (Chelydra serpentina) eggs from Areas of Concern (AOCs) on the Canadian shores of Lake Ontario, St. Lawrence River, and connecting channels. Eggs from Lyons Creek (Niagara River AOC) reflected a local PCB source over a range of 7.5 km (3.2-10.8) from the Welland Canal. PCB contamination in eggs declined with increasing distance from the Welland Canal, whereas the relative contribution of congeners associated with Aroclor 1248/1254 increased with sigma PCB concentrations. Compared to turtle eggs from other sites in Lake Erie and Lake Ontario, eggs from Lyons Creek and Snye Marsh had PCB congener patterns that reflected a strong contribution from Aroclor 1254. PCBs in the eggs were associated with industrial sources and reflected the composition of different Aroclor technical mixtures. Organochlorine pesticides in eggs tended to be highest at Hamilton Harbour and Bay of Quinte AOCs, and were dominated by DDE, sigma chlordane, and mirex. In contrast, PBDE congener patterns in turtle eggs resembled PentaBDE technical formulations regardless of absolute concentrations or location, and were largely associated with urban environments.

Organochlorine pesticides, PCBs, dibenzodioxin, and furan concentrations in common snapping turtle eggs (Chelydra serpentina serpentina) in Akwesasne, Mohawk Territory, Ontario, Canada.

Subsamples of eight clutches of common snapping turtle eggs (Chelydra serpentina serpentina) were collected from four sites from the territory of the Mohawk Nation, Akwesasne, on the shore of the St. Lawrence River. Egg contents were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), dibenzodioxins, and furans. The sites were 2 to 13 km downstream from PCB-contaminated landfill sites. Maximum concentrations of total PCBs in snapping turtle clutches were extremely high, and ranged from 2 378.2 ng/g to 737 683 ng/g (wet weight) and are among the highest recorded in any tissue of a free-ranging animal. Similarly, in a pooled sample of eggs from all four sites, the summed concentrations of non-ortho PCBs (n = 6 congeners) was also very high at 54.54 ng/g and the summed dioxin and furan concentrations (n = 11 congeners) was 85.8 ng/g. Sum organochlorine pesticide levels varied from 28 to 2,264 ng/g among the four sites. The levels of PCBs found in turtle eggs exceed concentrations associated with developmental problems and reduced hatching success in snapping turtles and other species and also exceed the Canadian tissue residue guidelines for toxic equivalency concentrations. The extremely high levels of organochlorine contaminants demonstrate the high degree of contamination in the environment in the Akwesasne area.

Effect of dichlorodiphenyltrichloroethane on sex determination of the common snapping turtle (Chelydra serpentina serpentina).

Recent evidence indicates that 1,1,1-trichloro-2, 2-bis(p-chlorophenyl)ethane (DDT) and some of its metabolites alter reproductive and endocrine function in wildlife. Exposure to such endocrine-disrupting compounds during embryonic development can affect sexual differentiation. The authors tested the hypothesis that dichlorodiphenyltrichloroethane (p,p'-DDE) causes feminization of the common snapping turtle (Chelydra s. serpentina), a species with temperature-dependent sex determination, during embryonic development. Eggs from eight clutches (total eggs tested=237) were incubated at a male-producing temperature (26 degrees C). At stage 14 of embryonic development, p,p'-DDE was applied topically at four concentrations and estrogen (estradiol-17 beta) was applied as a positive control. Although application of estrogen did induce female development at this temperature, application of p,p'-DDE did not affect sex determination at the exposure levels used. Residue analysis indicated that the amount of p,p'-DDE detected in the eggs 72 h after application was considerably less than the concentrations applied. However, the amounts that penetrated the shells were comparable to levels which have been found in moderately contaminated sites in the Great Lakes. These results indicate that p, p'-DDE, at levels that exist in the environment in the Great Lakes, does not cause the feminization of snapping turtles during embryonic development.

Impact of organochlorine contamination on levels of sex hormones and external morphology of common snapping turtles (Chelydra serpentina serpentina) in Ontario, Canada.

Recent research has suggested that contaminants in the environment may influence sex differentiation and reproductive endocrine function in wildlife. Concentrations of organochlorine contaminants (total polychlorinated biphenyls, pesticides) were higher in the blood plasma of snapping turtles from contaminated sites than in those from reference sites. The ratio of the precloacal length to the posterior lobe of the plastron (PPR) is sexually dimorphic in snapping turtles. There were significant reductions in the PPR at three contaminated sites versus two reference sites. The magnitude of the response was such that a significantly higher proportion of PPRs of males from a contaminated site (Cootes Paradise) overlapped with those of females than PPRs of males from a reference site (Lake Sasajewun). Observers can incorrectly identify the sex of turtles at the contaminated site based on secondary sexual characteristics alone. Unlike the changes to the morphology, there were few changes in 17 beta-estradiol or testosterone levels, and where differences occurred, there was more variation among reference sites than between the reference and contaminated sites. Our results suggest that environmental contaminants may affect sexually dimorphic morphology in snapping turtles without affecting circulating testosterone or estrogen levels in the adults.