Organisms have long been treated as receptors in exposure studies of polychlorinated biphenyls (PCBs) and other persistent organic pollutants (POPs). The influences of environmental pollution on organisms are well recognized. However, the impact of biota on PCB transport in an environmental system has not been considered in sufficient detail. In this study, a population-based multi-compartment fugacity model is developed by reconfiguring the organisms as populated compartments and reconstructing all the exchange processes between the organism compartments and environmental compartments, especially the previously ignored feedback routes from biota to the environment. We evaluate the model performance by simulating the PCB concentration distribution in Lake Ontario using published loading records. The lake system is divided into three environment compartments (air, water, and sediment) and several organism groups according to the dominant local biotic species. The comparison indicates that the simulated results are well-matched by a list of published field measurements from different years. We identify a new process, called Facilitated Biotic Intermedia Transport (FBIT), to describe the enhanced pollution transport that occurs between environmental media and organisms. As the hydrophobicity of PCB congener increases, the organism population exerts greater influence on PCB mass flows. In a high biomass scenario, the model simulation indicates significant FBIT effects and biotic storage effects with hydrophobic PCB congeners, which also lead to significant shifts in systemic contaminant exchange rates between organisms and the environment.

Microplastics are a source of environmental pollution resulting from degradation of plastic products and spillage of resin pellets. We report the amounts of microplastics from various sites of Lake Ontario and evaluate their potential for preservation in the sediment record. A total of 4635 pellets were sampled from the Humber Bay shoreline on three sampling dates. Pellet colours were similar to those from the Humber River bank, suggesting that the river is a pathway for plastics transport into Lake Ontario. Once in the lake, high density microplastics, including mineral-polyethylene and mineral-polypropylene mixtures, sink to the bottom. The minerals may be fillers that were combined with plastics during production, or may have adsorbed to the surfaces of the polymers in the water column or on the lake bottom. Based on sediment depths and accumulation rates, microplastics have accumulated in the offshore region for less than 38 years. Their burial increases the chance of microplastics preservation. Shoreline pellets may not be preserved because they are mingled with organic debris that is reworked during storm events.

Seasonal variation in mercury (Hg) concentrations and food web structure was assessed for eastern Lake Ontario. Hg concentrations, measured in 6 species of invertebrates and 8 species of fishes, tended to be highest in the spring and lowest in the summer for most biota. Yellow perch (Perca flavescens) exhibited significant ontogenetic shifts in diet and Hg, although such patterns were not evident for other species. Food web structure, as indicated by stable isotope values (δ¹⁵N, δ¹³C) was not static. Log-transformed Hg data were strongly and consistently correlated with δ¹⁵N values for the whole food web in each of the three seasons (slopes, 0.17–0.24) and across the entire year (slope, 0.2). While significantly different between seasons, the regression slope values are still consistent with published global Hg biomagnification rates. Our results indicate that the assessment of Hg trends in Great Lakes must take into account seasonal patterns and time of sampling.

Mecoprop, dichlorprop and metolachlor concentrations and enantiomer signatures were determined in Ontario streams in 2006-2007 and compared to results from 2003 to 2004. Median concentrations of dichlorprop and metolachlor were not significantly different between the two campaigns, but mecoprop was higher in 2006-2007. Concentrations of mecoprop and dichlorprop in Lake Ontario surface water were 1-2 orders of magnitude lower than stream averages. Enantiomer fractions (EFs) > 0.5 of mecoprop in high-concentration stream water samples during 2006-2007 were related to replacement of racemic mecoprop by single (+) enantiomer mecoprop-P after 2004. EFs <0.5 in low-concentration samples suggested enantioselective degradation and/or interconversion. Metolachlor profiles were expressed as SF, the fraction of herbicidally active/(active + inactive) stereoisomers. Samples with higher concentrations of metolachlor had SFs similar to S-metolachlor which is enriched in the active stereoisomers. Low concentrations were associated with lower and more variable SFs, suggesting mixed input of racemic and S-metolachlor or stereoselective degradation.

This study determines spatial trends and congener patterns of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surficial sediments of Lakes Erie and Ontario. Sediments are enriched in 2378-PCDFs in Lake Ontario, and the PCDD/F concentrations increased from shallow near-shore sediments towards deep-water depositional zone sediments. In Lake Erie, sediments were dominated by octachlorodibenzo-p-dioxin, and the highest PCDD/F concentrations were observed in the western basin and the southern shoreline of the central basin with a decrease towards the eastern basin and the northern shoreline of the central basin. Principal components analysis revealed that chemical manufacture and disposal of chemical waste along the Niagara River has been a major PCDD/F source to Lake Ontario; while PCDD/Fs in Lake Erie are from multiple sources including industrial sources along the Detroit River, major tributaries along the southern shoreline of the lake, and atmospherically-derived material from the upper lakes and connecting channels. Lake-wide 2378-PCDD/F congener patterns are first reported in L. Erie and L. Ontario sediments.

Occurrence and fate of alkylphenols (APs), known endocrine disruptors, were investigated in a Great Lakes coastal wetland, Cootes Paradise, ON. The wetland, which receives discharges from a Wastewater Treatment Plant (WTP) and several Combined Sewer Overflows (CSOs), is an important spawning ground for fish and crucial habitat for other fauna. Elevated concentrations of nonylphenol ethoxylates (NPEs) and their degradation product nonylphenol (NP) were found in water and sediment samples near the sources. Since transfer of APs through the food chain is of concern, we compared their concentrations in invertebrates from clean and contaminated sites. The results reveal transfer of alkylphenolics from sediments to biota and their accumulation in the invertebrate tissue, particularly the highly hydrophobic 4-NP, whose concentrations ranged from 1.9 to 6.3 μg g-1. To our knowledge, this is the first study to evaluate AP concentrations in tissue of benthic invertebrates under real environmental conditions. Concentrations of alkylphenolic compounds in water, sediments and benthic invertebrates in a large coastal wetland and implications for trophic transfer.

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.

A recent data set for 22 poly- and per-fluorinated compounds (PFASs) in Ponar grab samples of surface sediments and cores from the Great Lakes of North America was examined for concentrations, loads, correlations with geographical coordinates and depth (time), and for sources. Correlations were determined by multivariate regression analyses. Source apportionment of PFASs was carried out by positive matrix factorization (PMF) for two cores from Lake Ontario. For the five lakes together, the total load of PFASs in sediments was estimated to be 245 ± 24 tonnes, which is about half the load for total PCBs. The recent annual loading was 1812 ± 320 kg/yr. Concentrations and inventories of PFASs were greatest in Lakes Erie and Ontario. Since 1947, concentrations of perfluorooctane sulfonic acid (PFOS) in ten cores have increased exponentially as a function of time with doubling times between 10 and 54 yr and have leveled off in three cores since 2000. PMF demonstrated an effective grouping of two particle-associated factors, characterized mainly by longer-chain PFASs (C ≥ 8) and two other factors of mainly shorter-chain compounds (C ≤ 6). Two factors feature only one dominant compound: factor 1, PFOS, and factor 3, perfluorobutane sulfonic acid (PFBS). Of all factors, factor 3 with PFBS has the largest contribution (47.8%). Significant scores for perfluorohexane sulfonic acid (PFHxS) and PFBS, along with flat or decreasing PFOS contributions since 2003, indicate that the replacement of PFOS with these compounds is beginning to take effect in the environment.

The HERMES model-predicted Hg concentrations and fluxes in Lake Ontario were based on twelve lake and drainage basin variables (i.e., water temperature, precipitation rate, air Hg, surface area, mean depth, water volume, water inflow rate, inflow water Hg, inflow and lake suspended particulate matter, air–water and water–air mass transfer coefficients, and sedimentation rate). The HERMES model-predicted Hg water and surface sediment concentrations were found to be significantly correlated (±20%) with measured values (r² = 0.94, p < 0.0001, n = 13) and mechanistic model predictions (LOTOX2-Hg, r² = 0.95, p < 0.0001, n = 10). The predictive capacity of HERMES was previously tested on smaller (≤1 km²) lakes in Nova Scotia and Ontario, Canada (i.e., water and sediment Hg concentrations were ±15% of measured data). Results suggest that HERMES could be applicable to a broad range of lake sizes. Uncertainty analyses on HERMES model input variables indicated a larger atmospheric Hg contribution for Lake Ontario when compared to previous predictions for smaller lakes.

Eggs from mature Chinook (Oncorhynchus tshawytscha) and Coho (Oncorhynchus kisutch) salmon were collected between 2004 and 2014 from the Salmon River fish hatchery in Altmar, New York. The egg samples were analyzed for seventeen polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), as well as four dioxin-like polychlorinated biphenyls (DL-PCBs) using USEPA methods 1613 and 1668. Salmonid eggs were chosen as a tissue of interest since salmon feed at all trophic levels of the food web as they grow, and spawn in a narrow range of ages providing consistent, representative, and temporal samples of contaminant exposure. First-order decay models indicate decreasing trends for all select contaminants in both species, expressed by a toxic equivalence (TEQ) half-life (t₁/₂) of 11 years in Chinook and Coho eggs. No significant statistical difference in contaminant elimination rates were noted between species. TEQ elimination rates for Coho and Chinook eggs were not significantly different (p > 0.05) when compared with published Lake Ontario whole-fish lake trout elimination rates. Our research demonstrates that salmonid eggs are an effective means to assess PCDD, PCDF, and DL-PCB exposures and long-term trends in the Great Lakes.