Influence of wastewater effluents on the bioaccumulation of volatile methylsiloxanes in the St. Lawrence River.

The bioaccumulation of cyclic volatile methylsiloxanes (D3 to D6) as well as linear siloxanes (L3 to L5) was studied in a food web in the St. Lawrence River downstream of the effluent of the municipal wastewater treatment plant in Montreal, Canada. For most species, differences in δ15N in fish and prey showed a clear separation of individual fish feeding in food webs influenced by the wastewater plume from those feeding outside the plume. Cyclic siloxanes were detected in all biotic samples from the individuals identified as feeding in the effluent plume. Siloxane D5 accounted for more than 80% of the total siloxanes. Linear siloxane L5 was also abundant in walleye and gull eggs. Total siloxane concentrations in suspended sediments were 17.3 times higher than in surface sediments in the region of the river in the effluent plume. Caged freshwater mussels (Elliptio sp.), placed in the effluent plume, bioaccumulated 43 times more total siloxanes than PBDEs in 30 days, demonstrating how readily siloxanes are taken up in biota and what a significant component of the contaminant body burden they can account for. The sediment-biota accumulation factors (BSAF) for total siloxanes (∑ D3 to D6 and L3 to L5) showed values of 65.4, 27.8, 9.9 and 6.4 for walleye, northern pike, yellow perch and round goby respectively.

Isomer-Specific Hexabromocyclododecane (HBCDD) Levels in Top Predator Fish from Across Canada and 36-Year Temporal Trends in Lake Ontario.

Hexabromocyclododecane (HBCDD) is a high concern environmental pollutant due to its persistent, bioaccumulative, and toxic properties. The spatial distribution of HBCDD was investigated in top predator fish (lake trout, walleye, or brook trout) collected in 2013 ( n = 165) from 19 sampling sites and in 2015 ( n = 145) from 20 sites across Canada. HBCDD was measurable in at least one sample at each sampling site regardless of sampling year with the exception of walleye from the south basin of Lake Winnipeg (2013). Sampling sites in or near the Laurentian Great Lakes had greater ΣHBCDD concentrations compared to locations to the west or east. The greatest mean ΣHBCDD concentration was 72.6 ng/g lw in fish from Lake Huron-Goderich (2015). Regardless of the sampling sites, α-HBCDD was the dominant congener followed by γ-HBCDD, whereas ß-HBCDD was barely detectable. In fish from the same waterbody there were comparable α/γ isomer concentration ratios. The greatest ratio was 20.8 in fish from Lake Ontario, whereas the lowest ratio was 6.3 for fish from Lac Memphrémagog (Québec) likely related to more recent emissions of a technical HBCDD mixture. Temporal trends of HBCDD in lake trout from Lake Ontario showed a significant decreasing trend for γ-HBCDD with a half-life estimate of 10 years over a 36-year period (1979-2015), and for α-HBCDD with a half-life of 11 years over the years of 2008 to 2015. The proportion of α-HBCDD to ΣHBCDD increased significantly during 1979 to 2015. The present study provided novel information on the isomer-specific HBCDDs in Canada freshwater fish.

Organophosphate flame retardants and organosiloxanes in predatory freshwater fish from locations across Canada.

Whole body homogenates of Lake Trout (Salvelinus namaycush) or Walleye (Sander vitreus) collected from Canadian lakes were screened for organophosphate flame retardant (OPFR) and organosiloxane compounds. Six OPFR and five siloxane compounds were detected above quantitation limits in at least one individual fish from sampled lakes. The OPFRs, tris(2-chloroethyl) phosphate (TCEP) and tris(2-butoxyethyl) phosphate (TBOEP), were most frequently quantified with concentrations ranging from <0.07 to 9.8 ng/g (ww). Levels of TBOEP were highest in fish from the Great Lakes region while TCEP was detected only in fish from the northernmost lakes in our network. Concentrations of the cyclic siloxanes, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6), were above quantitation limits in all fish. D5 was the most abundant siloxane across all sampling locations with the highest concentrations (45-719 ng/g ww) observed in Lake Trout from the western end of Lake Ontario near the mouth of the Niagara River.

Concentrations and trophic magnification of cyclic siloxanes in aquatic biota from the Western Basin of Lake Erie, Canada.

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.

Spatial trends of polybrominated diphenyl ethers in Canadian fish and implications for long-term monitoring.

A nationwide study was conducted to examine concentrations of polybrominated diphenyl ethers (PBDEs) in top predatory fish, with a focus on lake trout (Salvelinus namaycush), across Canada, and to explore possible influences of food web processes. Concentrations of the three most abundant PBDE homolog groups (tetra-, penta-, and hexa-PBDEs) were, for the most part, higher in Great Lakes and Lake Champlain fish compared with fish from other systems. The Canadian Federal Environmental Quality Guideline for the penta-homolog was exceeded in 70% of the fish examined. However, virtually no guideline exceedances were found for other congeners. In general, PBDE-47 (a representative lower brominated congener) was significantly and positively correlated with fish length, weight, age, lipid content, and stable isotopes of nitrogen and carbon. Significant differences in the slopes of the PBDE-47/covariate relationships between sites prevented concentrations from being adjusted using an analysis of covariance (ANCOVA). However, plots showed that elevated concentrations of PBDE-47 in Great Lakes and Lake Champlain fish remained after accounting for the influence of covariates. In contrast, for PBDE-183 (a representative higher brominated congener), the relationships between fish concentrations and covariates were not consistent, which could be a result of biotransformation being more important in controlling its bioaccumulation. The data from the current study show an overall disconnect between fish PBDE concentrations and likely loadings, which may be caused by differences in food web processes between systems. Continued long-term fish contaminant monitoring is needed to evaluate potential risk to fish and their consumers. However, we also recommend sediment sampling and focused food web studies to provide information on PBDE inputs to the systems and mechanisms of biomagnification, respectively.