Temporal Trends of Legacy and Current-Use Halogenated Flame Retardants in Lake Ontario in Relation to Atmospheric Loadings, Sources, and Environmental Fate.

Since the phase-out of polybrominated diphenyl ethers (PBDEs), large amounts of alternative halogenated flame retardants (AHFRs) have been introduced to the market. Due to their persistence and toxicity, halogenated flame retardants (HFRs) have become a concern for the ecosystem and human health. However, there remains limited assessment of the atmospheric loadings, sources, and environmental fate of HFRs in Lake Ontario, which receives urban-related inputs and cumulative chemical inputs from the upstream Great Lakes from Canada and the United States. We combined long-term measurements with a modified multimedia model based on site-specific environmental parameters from Lake Ontario to understand the trends and fate of HFRs. All HFRs were detected in the air, precipitation, lake trout, and herring gull egg samples throughout the sampling periods. General decreasing trends were found for PBDEs, while the temporal trends for AHFRs were not clear. Physical-chemical properties and emissions significantly influence the levels, profiles, and trends. Using the probabilistic modeling, HFR concentrations in lake water and sediment were predicted to be close to the measurement, suggesting a good performance for the modified model. The loadings from tributaries and wastewater effluent were the primary input pathways. Transformations in the water and sedimentation were estimated to be the dominant output pathway for the three HFRs.

Organochlorine contaminants in wild mink from the lower Great Lakes basin, Canada, 1998-2006.

Organochlorine contaminants were measured in livers of wild mink (Neovison vison) trapped in the lower Great Lakes basin from 1998 to 2006. To assess exposure and potential risk in mink feeding on Great Lakes biota, concentrations of contaminants were compared in mink trapped within 7.8 km of the shoreline as well as at inland sites (i.e., 8-40 km). Overall, significant spatial variation in mean hepatic concentrations of sum PCBs and seven other organochlorines was found in mink from 13 Great Lakes sites, many of which are within the Great Lakes Areas of Concern. Mean sum PCB concentrations, on a lipid weight basis, ranged from 2 µg/g in mink from inland Lake Ontario sites to 44 µg/g in mink from western Lake Erie. Concentrations of other organochlorines in mink were generally low. Mink from western Lake Erie had the highest mean cumulative organochlorine burdens dominated largely by PCBs. A significant age effect was found with 1-year-old mink having significantly higher PCB burdens than mink less than 1 year in age. With respect to published PCB threshold effect concentrations, some mink exceeded those associated with effects on reproduction and survival as well as the presence of jaw lesions. This was most consistently found in western Lake Erie where the health of populations of wild mink may be adversely affected and where no mink 2 years of age or older were collected.

Testing for bias in a sentinel species: contaminants in free-ranging domestic, wild, and hybrid mink.

Sentinel species are important tools for studies of biodiversity and environmental health. The American mink (Neovison vison) has long been considered a sentinel of environmental contamination, since the species is known to be sensitive to a number of common contaminants, including polychlorinated biphenyls (PCB) and mercury. Mink may not always satisfy an important criterion of sentinels however--that they are continuous residents of the environment being sampled. This is because domestic mink commonly escape from farms, and can be confused with wild mink in areas where mink ranching is prevalent, biasing estimates of environmental contamination taken from free-ranging mink samples. We tested for bias in a sample of free-ranging mink from Ontario, Canada, where both genetic ancestry (domestic, wild, and domestic-wild hybrid) and contaminant burdens (PCBs and mercury) were known. Of 133 mink sampled for both contaminants and genetic ancestry, 9% were determined to be domestic and 10.5% hybrid animals. We found that including domestic and hybrid mink in our analysis resulted in overestimating mean PCB burdens in wild mink by 27%, and underestimating mercury by 13%. We also investigated morphological methods to aid in excluding domestic mink from free-ranging mink samples and found that we had the highest classification success using skull size (condylobasal length), which was 15% and 12% greater in male and female domestic than wild mink, respectively. Given the potential use of mink as sentinels, and also the potential for bias, we recommend that researchers take steps to exclude domestic mink from free-ranging mink samples in studies of environmental health.

Mercury and other heavy metals in free-ranging mink of the lower Great Lakes basin, Canada, 1998-2006.

Mercury concentrations were examined in livers of free-ranging mink (Neovison vison) trapped in the lower Great Lakes basin from 1998 to 2006. Significant geographic variation in total mercury levels was found in mink from 13 Great Lakes locations, many of which are within Great Lakes Areas of Concern (AOCs). Total mercury levels in mink from these locations were generally low to moderate, with means (±SE) ranging from 0.99 (±0.36) µg/g dry weight in mink from inland Lake Erie to 7.31 (±1.52) µg/g in mink from Walpole Island in the St. Clair River AOC. Overall, mercury exposure was highest in mink trapped in locations associated with large riverine wetlands. Total mercury concentrations were negatively related to the percentage of mercury present as methylmercury and positively related to selenium concentrations, consistent with increasing demethylation of methylmercury with increasing total mercury concentrations. One-year old mink had significantly higher levels of mercury and selenium than mink under 1 year but similar to mink 2 years of age and older. Mercury levels were below those associated with mercury toxicity. Concentrations of cadmium, lead and arsenic were low and largely associated with environmental background levels. Significant age and sex effects were found for cadmium. Lead levels were significantly lower in mink infected by the lung nematode parasite compared to uninfected animals. Further studies of biomagnification of methylmercury in wetland environments, where top predators such as mink may be an increased risk of exposure, are warranted.

Bisphenol A in the Canadian environment: A multimedia analysis.

Bisphenol A (BPA) is an industrial chemical that has been identified by some jurisdictions as an environmental concern. In 2010, Canada concluded that this substance posed a risk to the environment and human health, and implemented actions to reduce its concentrations in the environment. To support these activities, a multimedia analysis of BPA in the Canadian environment was conducted to evaluate spatial and temporal trends, and to infer mechanisms influencing the patterns. BPA was consistently detected in wastewater and biosolids across Canadian wastewater treatment plants (WWTPs) and in landfill leachate. In addition, BPA concentrations were significantly higher in surface water downstream compared to upstream of WWTPs in three of five urban areas evaluated. However, application of biosolids to Canadian agricultural fields did not contribute to elevated BPA concentrations in soil, earthworms, and European Starling (Sturnus vulgaris) plasma one and two years post-treatment. Spatial trends of BPA concentrations in surface water and sediment are influenced by human activity, with higher concentrations typically found downstream of industrial sources and WWTPs in urban areas. BPA was detected in bird plasma at locations impacted by WWTPs and landfills. However, spatial trends in birds were less clear and may have been confounded by metabolic biotransformation. In terms of temporal trends, BPA concentrations in surface water decreased significantly at 10 of 16 monitoring sites evaluated between 2008 and 2018. In contrast, recent temporal trends of BPA in six sediment cores were variable, which may be a result of biotransformation of the flame retardant tetrabromobisphenol A to BPA. Overall, our study provides evidence that Government of Canada actions have been generally successful in reducing BPA concentrations in the Canadian environment. Our results indicate that long-term monitoring programs using surface water are more effective than other media for tracking and understanding future environmental trends of BPA.

Potential endocrine disruption of sexual development in free ranging male northern leopard frogs (Rana pipiens) and green frogs (Rana clamitans) from areas of intensive row crop agriculture.

Intensive row crop agriculture (IRCA) for corn and soybean production is predominant in eastern and central North America. IRCA relies heavily on pesticide and nutrient inputs to maximize production under conventional systems. In 2003-2005, we assessed the occurrence of a suite of potential endocrine effects in amphibians inhabiting farm ponds and agricultural drains in IRCA areas of southwestern Ontario. Effects were compared to amphibians from two agricultural reference sites as well as four non-agricultural reference sites. Pesticide and nutrient concentrations were also determined in water samples from those sites. Atrazine and metolachlor were detected in most samples, exceeding 1 microg L(-1) at some sites. Blood samples were taken from northern leopard frogs (Rana pipiens) and green frogs (Rana clamitans) for analysis of circulating sex steroids and vitellogenin-like protein (Vtg-lp), a biomarker of exposure to environmental estrogens. Gonads were histologically examined for evidence of abnormalities. Some evidence of exposure to endocrine disrupting compounds was apparent from the data. The occurrence of testicular ovarian follicles (TOFS) in male R. pipiens was significantly higher (42%; p<0.05) at agricultural sites, particularly those in Chatham county compared to frogs from reference sites (7%). There was no difference in circulating sex steroid levels between frogs from agricultural and reference sites and sex steroid levels did not correlate with pesticide concentrations in the environment. No differences were detected in the gonadosomatic indices or stage of spermatogenesis between frogs from agricultural and non-agricultural regions (p>0.05). Plasma Vtg-lp was detected in only one male R. pipiens from an agricultural site. Neither gonad size, gonad maturity nor sex steroid levels differed between normal males and those with testicular oocytes. Although the proportion of testicular oocytes did not correlate directly with atrazine concentrations, it did correlate with a mixture of pesticides and nutrients, particularly atrazine and nitrate, while the number of pesticides detected at each site was also important.

Detection limits can influence the interpretation of pesticide monitoring data in Canadian surface waters.

Water quality monitoring programs rely on residue data that are frequently left censored, due to some observations occurring below the Method Detection Limit (MDL). Our objective was to determine the influence the MDL has on the interpretation of pesticide residues in surface waters. Water samples from tributaries in southern and central Ontario were collected by Environment Canada from 2003 to 2008 and were analyzed for 27 pesticides, with MDLs that averaged 7.02 ng(-1) L (range 0.39-25.1 ng(-1) L). We then simulated MDLs ranging from 25 to 1700 ng(-1) L, to determine the impact this would have on the reporting of pesticide concentrations and detections. The mean number of pesticides detected simultaneously declined with increasing, i.e. less sensitive MDLs, from 5.02 pesticides (native MDL) to 0.08 pesticides detected (MDL<1700 ng(-1) L). We compared the proportion of sites where pesticides were detected in surface waters under five MDL scenarios for 13 selected pesticides. The proportions decreased sharply with increasing MDLs. We calculated detection probabilities in an effort to compensate for higher MDLs using maximum likelihood; while adjusting for detection probabilities generally improved estimates of the presence of pesticides, as the MDLs increased the ability to compensate for detection probabilities deteriorated and became unviable at high MDLs. Depending on the method of substitution for observations below MDL (replacement with ½ × or 0 × MDL), the mean and median pesticide residues became increasingly over- and underestimated, respectively, at higher MDLs. Although monitoring programs that are focused on exceedences of water quality guidelines may not require low MDLs, the achievable goals of monitoring programs oriented towards other ecological and toxicological objectives may be limited by higher MDLs.

Bioremediation of tetrachloroethylene-contaminated groundwater in a model aquifer: effects on green frogs (Rana clamitans) and Xenopus laevis as potential wetland receptors.

Recent regulations require that the ecological effects of microorganisms introduced into the environment, such as for groundwater bioremediation, be assessed prior to their utilization. A native anuran (Rana clamitans) and a model anuran (Xenopus laevis) were used as potential wetland receptors of tetrachloroethylene (PCE)-contaminated groundwater, undergoing three bioremediation treatments: natural attenuation (NA), biostimulation (ST), and bioaugmentation (AU). Eggs of both species were exposed acutely (96 h) to remediated effluents. Xenopus tadpoles were chronically exposed to the effluents for 100 days and were screened for the presence of bacterial pathogens. There was no impact on the survivorship of the frogs exposed either acutely or chronically to the NA, ST, or AU effluents; nor was there any evidence of bacterial infection found, with the exception of control individuals. The results of these exposures suggest that bioremediation with KB-1trade mark culture poses a minimal threat to anuran development and survivorship.

Temporal and spatial trends in chlorinated hydrocarbon concentrations of mink in Canadian Lakes Erie and St. Clair.

Mink (Mustela vison) carcasses were collected from local commercial trappers from fall 1998 to spring 2003 from tributaries and marshes within 4.8 km from the shores of Lakes Erie and St. Clair, including the Wheatley Harbour and St. Clair River Areas of Concern (AOCs), as well as from inland sites (8 to 40 km from shore). Liver concentrations, on a lipid weight basis, of chlorinated hydrocarbons were measured and compared among sites and to tissue concentrations of mink from two previous collections from similar sites over the past 25 years. Mink from the western Lake Erie sites, which included the Wheatley Harbour AOC, had significantly higher concentrations of sum PCBs and PCB Aroclors than those from the St. Clair corridor or inland sites, with concentrations from the rest of Lake Erie being intermediate. Dieldrin concentrations were also significantly higher in western Lake Erie than many other sites, and those of oxychlordane and mirex also tended to be higher (0.05 < p < 0.1). There were no differences in contaminant concentrations between the St. Clair River AOC and the downstream non-AOC Lake St. Clair site, with the exception of slightly higher levels of octachlorostyrene (OCS). Concentrations of PCBs and other chlorinated hydrocarbons in mink showed a general decrease over the past two decades. In contrast, PCBs and some organochlorine pesticides tended to increase, significantly so with oxychlordane, in western Lake Erie mink over the same time period. DDE declined at all sites. Currently, mink liver PCB concentrations are within the range associated with reproductive impairment, as determined from captive mink studies, in 11.7% of all animals collected from the Lakes Erie and St. Clair basin overall, but in almost 40% of individuals from western Lake Erie.