Search

BACKGROUND: Microplastics are a pervasive contaminant cycling through food webs—leading to concerns regarding exposure and risk to humans. OBJECTIVES: We aimed to quantify and characterize anthropogenic particle contamination (including microplastics) in fish caught for human consumption from the Humber Bay region of Lake Ontario. We related quantities of anthropogenic particles to other factors (e.g., fish size) that may help in understanding accumulation of microplastics in fish. METHODS: A total of 45 samples of six fish species collected from Humber Bay in Lake Ontario near Toronto, Ontario, Canada, were examined for anthropogenic particles in their gastrointestinal (GI) tracts and fillets. Using microscopy and spectroscopy, suspected anthropogenic particles were identified and characterized. RESULTS: We observed anthropogenic particles in the GI tracts and fillets of all species. Individual fish had a mean±standard deviation of 138±231 anthropogenic particles, with a single fish containing up to 1,508 particles. GI tracts had 93±226 particles/fish (9.8±32.6 particles/gram), and fillets had 56±61 particles/fish (0.5±0.8 particles/gram). Based on a consumption rate of 2 servings/week, the average yearly human exposure through the consumption of these fish fillets would be 12,800±18,300 particles. DISCUSSION: Our findings suggest that consumption of recreationally caught freshwater fish can be a pathway for human exposure to microplastics. The elevated number of particles observed in fish from Humber Bay highlights the need for large-scale geographic monitoring, especially near sources of microplastics. Currently, it is unclear what the effects of ingesting microplastics are for humans, but given that recreationally caught freshwater fish are one pathway for human exposure, these data can be incorporated into future human health risk assessment frameworks for microplastics. [ABSTRACT FROM AUTHOR] more...

Hexamethoxymethyl-melamine (HMMM) is used as a crosslinking agent in resins and plastics and in the manufacture of tires. In the present study, surface water samples were collected from two rivers adjacent to high traffic highways in the Greater Toronto Area in Ontario, Canada. Composite samples collected from the Don River and Highland Creek during rain events and a period of rapid snowmelt were preconcentrated using solid phase extraction and analyzed using liquid chromatography with high-resolution mass spectrometry. Elevated concentrations (> 1 µg/L) of HMMM were detected in surface waters during rain events in October of 2019 and during snow melt in early March of 2020. There were lower average concentrations of HMMM detected during rain events in the winter and spring of 2020. Temporal profiles of changes in the concentrations of HMMM in composite samples collected every 3 h during a rain event in October 2019 closely corresponded to the hydrograph profiles at the sampling sites, with the HMMM concentrations peaking > 6 h after the peak in water levels. This work contributes to the literature showing that HMMM is a ubiquitous contaminant of urban watersheds and that runoff from roads is a vector for the transport of this compound into urban surface waters. [ABSTRACT FROM AUTHOR] more...

Concentrations of polychlorinated naphthalenes (PCNs) were determined in archived lake trout (Salvelinus namaycush) from Lake Ontario, North America, collected between 1979 and 2004 to evaluate their temporal trends and the factors influencing their trends. Concentrations of PCNs, as well as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and non- and mono-ortho-substituted polychlorinated biphenyls (DL-PCBs), which were measured for comparative purposes, declined by eight-, seven-, and fivefold, respectively, between 1979 and 2004. Apparent elimination rate constants (κ2) were calculated as the slopes of the regression lines of concentration versus time for PCN, DL-PCB, and PCDD/F congeners to compare the rate of decrease among congeners within and between compound classes. The κ2 values for PCNs that had two pairs or three adjacent carbons unsubstituted with chlorine (congeners that can be biotransformed by vertebrates) were not significantly different from zero, indicating no decline in fish. For PCN congeners having no adjacent carbons unsubstituted with chlorine, the κ2 values generally increased with hydrophobicity and degree of chlorination. This pattern differed from that of PCDD/Fs and DL-PCBs and from previous findings for non-DL-PCBs, for which the rate of contaminant decline decreased with hydrophobicity, and the pattern also differed from expectations based on thermodynamics. Differences in the rate of decline of PCN congeners may be caused by changes in source or mixture formulations over time and/or metabolic dechlorination of the less stable, higher-chlorinated PCNs 73, 74, and 75 to lower-chlorinated congeners. Based on suggested dioxin toxic equivalency factors, PCN concentrations in these whole lake trout may be sufficient to trigger consumption restrictions in Ontario, Canada, and our results suggest that PCNs merit incorporation into monitoring and assessment programs. [ABSTRACT FROM AUTHOR] more...

Concentrations of non-polybrominated diphenyl ether (PBDE) brominated (hexabromocyclododecane [HBCD], 1,2- bis[2,4,6-tribromophenoxy]ethane [BTBPE], and pentabromoethylbenzene [PEB]) and chlorinated (Dechlorane Plus [DP] as well as short- and medium-chain chlorinated paraffins [SCCP and MCCP, respectively]) flame retardants were evaluated in archived Lake Ontario, Canada, lake trout (Salvelinus namaycush) samples collected between 1979 and 2004. Polybrominated diphenyl ethers also were analyzed to provide a point of reference for comparison to previous studies. Concentrations of the dominant PBDE congeners (BDEs 28, 47, 99, 100, 153, and 154) increased significantly from 1979 until the mid-1990s, then either leveled off or decreased significantly between 1998 and 2004, a result that corresponds to those of previous studies. In contrast, BDE 209 increased approximately fourfold between 1998 and 2004. The temporal trends of the non-PBDE flame retardants varied, with sum (Σ) HBCD and DP showing significant overall decreases; BTBPE, ΣSCCP, and ΣMCCP showing parabolic trends; and PEB showing no overall change during the study period. Because many of the non-PBDE chemicals may be used as replacements for penta- and octa-BDE mixtures, these results will provide a baseline to evaluate future usage patterns. Possible changes in food-web structure, evaluated through stable nitrogen isotopes (δ15N), may be influencing our interpretations of contaminant trends in lake trout and are hypothesized to be partially responsible for the observed decrease in concentrations of BDEs 28, 47, 99, 100, 153, and 154 between 1998 and 2004. Retrospective analyses evaluating temporal trends in stable isotope values at the base of the food web, however, are recommended to test this hypothesis further. [ABSTRACT FROM AUTHOR] more...

Concentrations and congener profile patterns of 2378-substituted PCDD/Fs and DLPCBs in offshore, nearshore and tributary sediments of Lakes Superior and Huron are reported, and spatial trends and source contributions assessed. PCDD/F concentrations ranged from 5 to 18 000 pg/g dw (Lake Superior) and 3 to 6100 pg/g dw (Lake Huron); DLPCBs ranged from 9 to 11 000 pg/g dw (Lake Superior) and 9 to 27 000 pg/g dw (Lake Huron). Our analysis indicated atmospheric deposition is a primary source to depositional areas of both lakes; however, greater PCDD/F and DLPCB concentrations were observed at several nearshore and tributary sites, and were attributed to corresponding land use in the watershed. Statistical analysis and pattern comparison suggested that industrial inputs mainly associated with wood treatment plants, pulp and paper mills, mining operations, and chlorine-based chemical manufacturing also contributed to contamination by PCDD/Fs and DLPCBs in certain nearshore and offshore areas of Lakes Superior and Huron. [Copyright &y& Elsevier] more...

The temporal trends of perfluoroalkyl compounds (PFCs), including C7-C15 perfluorocarboxylates (PFCAs), perfluorosul-fonates (PFSAs) and heptadecafluorooctane sulfonamide (PFOSA), were determined in lake trout collected between 1979 and 2004 from Lake Ontario. The average concentrations of total PFSAs (±standard error of the mean; range) increased from 20 ng g-1 wet weight (±4; 8-26) in 1979, peaked at 70 ng g-1 (±7; 58-91) in 1993, and were 46 ng g-1 (±10; 30-83) in 2004, with perfluorooctane sulfonate (PFOS) as the most abundant PFC. The PFCAs exhibited similar temporal variation, with concentrations increasing from 1.4 ng g-1 (±0.1; 0.9-1.9) in 1979 to 9.4 ng g¹ (±3.1; 3-17) in 1988, and were 6.8 ng g-1 (±1.0; 4.5-9.8) in 2004. Individual mean PFCA concentrations varied between 0.2 and 2 ng g-1 (wet weight). Perfluorodecane sulfortate (PFDS) and PFOSA were the only compounds showing a declining trend in the past decade, after reaching a peak value in 1993. Branched C11 and C13 PFCA isomers were detected in the lake trout and confirmed in Niagara River suspended sediments, with trends in both matrices suggesting that declining emissions or use of products containing these isomers in part account for the observed PFCA trends in the mid-1990s. However, the most recent samples, comprised almost exclusively of linear isomers, indicate that current PFCA sources to Lake Ontario result from the telomerization process of linear telogens. [ABSTRACT FROM AUTHOR] more...

Biota and surface sediments collected from Lake Ontario were analyzed for polychlorinated naphthalenes (PCNs) and non- and mono-ortho-substituted polychlorinated biphenyls (n/m-o-PCBs) to compare bioaccumulation behavior of these classes of dioxin-like chemicals in a food web from the Great Lakes. Mean ∑PCN concentrations (tri-octaCN) ranged from 14 ± 9 pg/g in plankton to 3500 ± 3200 pg/g (wet weight) in lake trout, while sediments contained from 21 to 38 ng/g (dry weight). Principal components analysis of PCN congener patterns indicated that chlorine substitution determined which congeners favored accumulation (e.g., CN-42, -52, -60, -66, -67, and -73), while others may be subject to metabolism. The bioaccumulative congeners exhibited similar trophic magnification factors (TMFs; 1.23-1.42) and biomagnification factors (BMFs; 5.5-8.6) to the n/m-o-PCBs for the trout/weighted diet relation, although BMFs for a benthic feeding relationship (slimy sculpin/Diporeia) indicated that the n/m-o-PCBs were more bioavailable through the benthic pathway. PCNs contribute significantly to the burden of dioxin-like compounds in Lake Ontario biota, contributing between 12 and 22% of total PCN + PCB TEQ in lake trout and up to 69% in benthic organisms. [ABSTRACT FROM AUTHOR] more...

Abstract: The distributions of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of Toronto, Canada and the surrounding suburban/rural area were examined. A series of temporally- and spatially-distributed air samples was collected over a 1-year period with a high-volume active air sampler at one downtown site and polyurethane foam passive air samplers at 19 sites. Passive sampler air concentrations of ΣPAHs ranged from 0.27 to 51ng/m3. Concentrations of ΣPCBs ranged from 6.0 to 1300pg/m3, and concentrations of ΣPBDEs ranged from 0.47 to 110pg/m3. All compounds exhibited the highest concentrations in the urban core, and lowest concentrations in the surrounding rural areas, however the exact ratio depended on location since concentrations varied considerably within the city. Results from the application of a radial dilution model highlighted the influence of the central business district (CBD) of the city as a source of contaminants to the surrounding environment, however the radial dilution comparison also demonstrated that sources outside the CBD have a significant influence on regional contaminant concentrations. A strong relationship between temperature and partial pressure of the gas-phase PCBs, low molecular weight PBDEs and less-reactive PAHs suggested that their dominant emissions originated from temperature-controlled processes such as volatilization from local sources of PCBs, PAHs and PBDEs at warm temperatures, condensation and deposition of emissions at cold temperatures, and ventilation of indoor air with elevated concentrations. The relationship between temperature and atmospheric PAH concentrations varied along the urban–rural gradient, which suggested that in highly urbanized areas, such as downtown Toronto, temperature-related processes have a significant impact on air concentrations, whereas winter emissions from domestic heating have a greater influence in areas with less impervious surface coverage. [Copyright &y& Elsevier] more...

Temporal trends and seasonal variation of Dechloranes (Dec) 602, 603, 604, and Chlordene Plus (CP) in Niagara River suspended sediment, a Lake Ontario sediment core, and Lake Ontario lake trout were investigated, with Mirex and Dechlorane Plus (DP) included for comparison. Temporal concentration trends were generally consistent in each of the media for all compounds with the lowest concentrations observed in or after the late 1990s. In Niagara River suspended sediments, all compounds showed seasonal variation over a year with distinct profiles observed. The relative concentration patterns observed were total DP > Mirex > Dec 602 and Dec 604 > Dec 603 > CP in suspended sediments and sediment cores, whereas Mirex was highest in lake trout, followed by Dec 602 and DP. Dec 602 concentrations were 50 to 380 times greater than those of DP in lake trout, indicating Dec 602 has a greater bioaccumulation potential. The estimated biota-sediment accumulation factor (BSAF) for Dec 602 was much greater than for DP in Lake Ontario, and was greater than those calculated for PBDEs, indicating that assessment of some dechlorane compounds is merited if use is ongoing or planned. [ABSTRACT FROM AUTHOR] more...

This work describes a single and fast approach using a filtering script as a means of prioritizing sample processing of data acquired by GCxGC-TOF MS for the identification of potentially novel persistent and bioaccumulative halogenated chemicals. The proposed script is based on the recognition of a generic halogenated isotope cluster pattern that allows for the simultaneous detection of chlorinated, brominated, or mixed halogensubstituted compounds in a single classification. Once developed, the script was applied to the identification of organohalogens in stream sediments collected across the southern region of Ontario (Canada). Classified peaks were first compared with available analytical standards and reference libraries to confirm the known chemicals. Unknown potential persistent organic pollutants (POPs) were evaluated for occurrence within the samples and high resolution mass spectrometry was used in order to identify some of the most prevalent compounds in the samples and resulting in the identification of three decachlorinated dechlorane analogs (C18H14Cl10), two undecachlorinated dechlorane species (C18H13C11), and a novel mixed chloro/bromo-carbazole (C12H5NCl2Br2) in a number of sediments analyzed. Relative peak abundances of these unknown halogenated compounds were in the same order of magnitude or slighdy higher than levels observed for conventional POPs detected in the samples. [ABSTRACT FROM AUTHOR] more...

Abstract: To investigate the significance of building sealants as a remaining source of PCBs to the environment a combined measurement campaign and GIS-based stock estimation were undertaken for Toronto, Canada. This showed that 14% of buildings measured had detectable quantities of PCBs present in sealants, with concentrations from 0.57mg/g to 82mg/g (n =95). We then constructed a GIS-based database of remaining PCB-containing sealants in Toronto. This showed that there is an estimated 13t still present in the city. Mass balance calculations showed that up to 9% had been lost via volatilization alone. This potentially has important implications for both human exposure and the continued presence of PCBs in the environment. [Copyright &y& Elsevier] more...

Dechlorane (Dec) 602, Dechlorane (Dec) 603, Dechlorane (Dec) 604, and Dechlorane Plus (DP) are flame retardant substitutes for mirex. Dec 602, 603, and 604 were detected in sediment and fish from the Laurentian Great Lakes. Lake Ontario surface sediments had the highest concentrations of Dec 602 and 604 at 6.0 and 4.0 ng/g dry weight, respectively. Temporal analysis of a Lake Ontario sediment core indicates that Dec 602 and 604 trends are similar to DP peaking in the early 1980s. Lake trout and whitefish from Lake Ontario also had the highest concentrations of Dec 602 and 604 at 34 and 1.2 ng/g lipid. Concentrations of Dec 602 were higher than those of DP in all fish samples, indicating that Dec 602 is likely more bioavailable and/or more readily bioaccumulates than DP. Spatial trends for Dec 602 and 604 in sediment and fish indicate that manufacturing plants along the Niagara River upstream of Lake Ontario were important sources of Dec 602 and 604 to the Great Lakes, while Dec 603 in the Great Lakes is likely from atmospheric deposition. The findings of this first report of Dec 602, 603, and 604 in the Laurentian Great Lakes basin suggests further investigation of halogenated norbornene flame retardants in the environment is merited. [ABSTRACT FROM AUTHOR] more...

The historical occurrence of Dechlorane Plus (DP) and detection of novel compounds structurally related to DP is described in a dated Lake Ontario sediment core. Our core was collected near the mouth of the Niagara River, which is known to be a major source of DP to the lake. Maximum DP concentrations (920 ng g-1, dry weight) were observed between 1976 and 1980, the highest reported to date. Following that time, we observed a dramatic decrease in DP concentration which coincided with the enactment of United States federal and state laws to mitigate free release of chemicals into the Niagara River and installation of an industrial wastewater treatment facility. During the course of our research, four new substances structurally related to DP were also identified. These compounds were thought to arise from the Diels—Alder reactions resulting from impurities present in 1,5-cyclooctadiene, a feedstock used in production of DP. To confirm our hypothesis, Diels—Alder reactions were performed on the individual impurities. Using different stationary-phase capillary gas chromatography columns and high-resolution mass spectrometry, we were able to positively identify some of these novel compounds in the core. Interestingly, we also were able to identify a monoadduct compound, formed by addition of 1 mol of hexachlorocyclopentadiene to 2 mol of 1,3-cyclooctadiene, in lake trout. The concentration of this monoadduct was approximately 2 orders of magnitude greater than that of DP, suggesting that it is more bioaccumulative. [ABSTRACT FROM AUTHOR] more...

A recently discovered chlorinated flame retardant, Dechlorane Plus (DP), was reported in air and a sediment core within the North American Great Lakes region. To further reveal the fate of DP in the Great Lakes, 40 surficial sediments from Lakes Erie and Ontario and two additional cores were analyzed using newly available analytical grade DP isomer solutions. The maximum total concentration in Lake Ontario was over 60-fold higher than Lake Erie, 586 ng/g and 8.62 ng/g, respectively. Additionally, analysis of archived suspended sediments collected from the Niagara River (1980-2002) showed a declining total DP concentration of 89 ng/g to 7.0 ng/g, suggesting a possible decrease in production orthe reduction of free DP released into the environment during manufacturing. The average syn-DP fractional abundance (fsyn) in our study was less than the commercial DP composition indicating a stereoselective enrichment of anti-DP in the environment Mean fsyn profiles were uniquely similar to both Lake Ontario and the Niagara River in comparison to Lake Erie. Ouring the course of our analysis we noticed an increasing fsyn value in the calibration standard which became exacerbated as the liner got dirtier and suggested the prospect of DP degradation. Follow- up studies indicated these compounds were dechlorinated DP species produced on the injection liner. Using a clean injection liner, these degradates were also detected in sediments from the Niagara River and Lake Ontario; tentatively identified as [-Cl+H] and [-2Cl+2H] by high resolution mass spectrometry. The observed similarity of fsyn profiles between Lake Ontario and Niagara River and the detection of the degradates only in their locations, suggest to us that the river is a major source to Lake Ontario's DP burden. To our knowledge, this is the first report of DP degradates in the environment [ABSTRACT FROM AUTHOR] more...

Coal tar-related products as a source of polycyclic aromatic compounds (PACs) are particularly concerning due to high PAC concentrations and inadequate source management. Benzo[b]carbazole, a benzocarbazole isomer exclusively found in coal tar-derived products, acts as an ideal marker to distinguish coal tar sources from others, enabling more robust quantification of coal tar contributions to PACs. To evaluate the historical and recent contributions of coal tar-related sources to the levels of PACs in Lake Ontario and associated ecological risk, we analyzed 31 PACs and 3 BCBz isomers in surface sediments and a sediment core. In the surface sediments, summed concentrations of the PACs ranged from 170 to 11,000 ng/g, dry weight, 63-90% of which were attributed to the 16 EPA polycyclic aromatic hydrocarbons (PAHs). Our results suggest the contribution by coal tar-related sources to PAC contamination has increased over the past decades and reached over 40% in Lake Ontario surface sediments. Employing the toxicological-priority-index scheme for the field data, high molecular weight EPA PAHs were identified as priority PACs. Cumulative PAC risk assessments indicate that with the exception of Mimico Creek, all other sampling sites exhibited elevated risk values. more...

Concentrations of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs) were analyzed and investigated in surficial sediment collected in 2018 from ten different nearshore sites in Lake Ontario and the St. Lawrence River influenced by inputs from varying urban and historical land uses. Sites were grouped into two categories of tributary and lake according to their location. Results show that tributary sites had higher concentrations of total chlorinated paraffin (CP) than lake sites. Humber Bay, a lake site, had the highest total CP concentration (55,000 ng/g TOC ) followed by Humber River, a tributary site (50,000 ng/g TOC ). The lowest concentrations were found in eastern Lake Ontario and Lake St. Francis in the St. Lawrence River (540 ng/g TOC ). Higher concentrations of chlorinated paraffins (CPs) were found where runoff and wastewater inputs from urban areas, current industrial activities, and population were the greatest. Levels of MCCPs were higher than SCCPs at all sites but one, Lake St. Francis. Among the SCCPs, C 13 and among the MCCPs C 14 were the dominant chain length alkanes, with C 14 being the highest among both groups. The SCCPs and MCCPs profiles suggest that they can be used to distinguish between sites impacted by local sources vs. sites impacted by short-/long-range transport of these chemicals., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.) more...

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. more...

The presence of microplastics within the gut of animals is well documented. Whether microplastics bioaccumulate in organisms and biomagnify in food webs remains unclear and relies on the ability of microplastics to translocate to other tissues. Here, we demonstrate the widespread presence of microplastics and other anthropogenic microparticles in the gastrointestinal tract, fillet, and livers of seven species of sportfish from Lake Simcoe, Ontario, Canada. Larger fish had a higher microplastic load compared to smaller fish, but the opposite trend was observed with translocated microplastics standardized by fish mass (i.e., smaller fish contained more translocated particles per gram wet weight than larger fish). Moreover, we observed no evidence of biomagnification as there was no significant relationship between the trophic level and total or translocated microplastics per individual. Overall, this suggests that microplastics are translocating, but that excretion of translocated particles or growth dilution may be occurring rather than bioaccumulation and biomagnification. Moreover, the assemblages of shapes and material types varied among tissues, suggesting that particle characteristics may predict biological fate. Our findings highlight the need for further work to understand the mechanisms of microplastic translocation and excretion and the implications for the dynamics of microplastics accumulation in food webs and human exposure. more...

Risk management measures (RMMs) are a broad set of tools used in global treaties and national regulations to manage, ban or restrict the use of toxic chemicals. Per- and polyfluoroalkyl substances (PFAS) are a group of chemicals that are persistent, bioaccumulate, biomagnify and are inherently toxic to the environment and human health. For these reasons global RMMs have been imposed on the manufacture and use of select PFAS. To evaluate the occurrence and potential current risk of PFAS in the Ontario environment, PFAS were quantitatively measured in source waters pre- (2005-2007) and post- (2012-2016, 2018-2019) implementation of RMMs. Source water samples were collected pre- (n = 105), and post-RMMs (n = 326) from lake, river and groundwater and analyzed for up to 14 PFAS. Pre-RMMs, the most frequently detected PFAS in source water were perfluorooctanoic acid (PFOA; 83%) and perfluorooctane sulfonate (PFOS; 76%) followed by perfluorohexane sulfonate (PFHxS; 47%) and the maximum ∑PFAS 10 was 42.1 ng/L. Post-RMMs, the maximum ∑PFAS 10 (which includes PFOS) was statistically significantly reduced to 15.5 ng/L, well below the Federal Environmental Quality Guidelines for PFOS. To evaluate post-RMMs risk to human health, 226 drinking water samples were collected from 25 drinking water systems with conventional and advanced treatment. All individual (or ∑PFAS) concentrations are well below current and proposed Health advisory levels or regulatory guidelines/standards for PFAS in drinking water with calculated Risk Quotients (RQ) <0.02. This survey indicates that the implementation of RMMs for select PFAS have made a significant difference to the concentrations detected in source waters in Ontario, Canada., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2020. Published by Elsevier B.V. All rights reserved.) more...

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2020. Published by Elsevier Ltd. All rights reserved.) more...

The sources of microplastics and other anthropogenic particles in freshwater are not well understood. The Greater Toronto Area, Canada's most populous urban area, offers a great study area for understanding the sources and pathways for microplastics to enter freshwater ecosystems. Here, we quantified and characterized microplastics and other anthropogenic particles from Lake Ontario surface waters and source waters (including stormwater runoff, agricultural runoff, and treated wastewater effluent) to better understand sources to the Great Lakes. Anthropogenic particle concentrations in lake samples were 0.8 particles L -1 . In source waters, average concentrations were relatively higher in stormwater and wastewater, with 15.4 particles L -1 and 13.3 particles L -1 , respectively, compared to 0.9 particles L -1 on average in agricultural runoff. Source waters revealed distinct signatures related to the morphologies of anthropogenic particles, e.g., fibers in wastewater. In addition, many upstream watershed characteristics were found to be significant predictors of anthropogenic particle concentration. Proximity to urban areas were positively correlated to anthropogenic particle concentrations. Future studies should focus on local source-apportionment to inform management and prevent further contamination of microplastics to freshwater ecosystems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.) more...

Organophosphate esters (OPEs), used as flame retardants and plasticizers, occur at relatively high concentrations in urban air and surface waters. We tested the hypothesis that some OPEs could be considered persistent and mobile organic compounds (PMOCs), using the poly parameter linear free energy relationship-modified Multimedia Urban Model (ppLFER-MUM) in Toronto, Canada, as a case study. Modeled air emissions of ∑ 6 OPEs of 3300 (190-190 000) kg yr -1 were 10-100 times higher than emissions of polychlorinated biphenyls (∑ 5 PCBs) and polybrominated diphenyl ethers (∑ 5 PBDEs). Model results suggested that measured ∑ 6 OPE stream concentrations of ∼2000 ng L -1 originate from emissions to urban air transferred to water mostly via precipitation. Water transport removed 7-28% of total air inputs compared to 0.1-10% for PCBs and 2-10% for PBDEs. Chlorinated OPEs were efficiently transported via surface water due to their persistence and high solubility. Loadings of ∑ 6 OPEs to Lake Ontario from wastewater treatment plants, streams, and atmospheric deposition were 70%, 18%, and 13%, respectively, of ∑ 6 OPE loadings of 3100 (1200-45 000) kg yr -1 . Our results support the hypothesis that three chlorinated OPEs, tris(2-chloroethyl)phosphate phosphate (TCEP), tris(chloroisopropyl)phosphate (TCiPP), and tris(1,3-dichloroisopropyl)phosphate (TDCiPP), fit the profile of PMOCs due to their mobility and persistence in surface waters. more...

The analytical conditions required to determine polybrominated diphenylethers (PBDEs) and a variety of other halogenated flame retardants (HFRs) by gas chromatography-high resolution mass spectrometry (HRMS) in environmental samples are reported. HRMS can be used to analyze brominated diphenylethers (BDEs), 2,2',4,4',5,5'-hexabromobiphenyl (BB-153) as well as for a number of other emerging HFRs like allyl 2,4,6-tribromophenyl ether (ATE), 2-bromoallyl 2,4,6-tribromophenyl ether (BATE), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE), octabromotrimethylphenylindane (OBIND), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenylethane (DBDPE), Dechlorane Plus (DP), hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO), tetrabromoethylcyclohexane (TBECH), 1,2,5,6-tetrabromocylcooctane (TBCO), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTeBB), and bis(2-ethly-1-hexyl)tetrabromophthalate (BEHTBP). The detection in environmental matrices and use of these non-BDE flame retardants is reviewed. A method for the analysis of PBDEs by isotope dilution HRMS and 16 other halogenated compounds primarily used as flame retardants is reported. A survey of selected environmental samples, which included Lake Ontario surface and tributary sediments, municipal wastewater effluent, sludge, and mussel tissues, detected PBDEs, DP, DBDPE, BTBPE, PBEB, BB-153, and HBB. more...

The extent of bioaccumulation of the syn- and anti-isomers of Dechlorane Plus (DP) is assessed in archived food web samples from Lake Winnipeg and Lake Ontario. Concentrations of the isomers were determined using purified analytical solutions of individual isomers as opposed to the technical mixture. The syn-isomer was consistently detected in all samples from both lakes; the anti-isomer was detected in all Lake Ontario samples, but only 45% of the samples from Lake Winnipeg. The pattern of bioaccumulation was different for the isomers in Lake Winnipeg. The anti-isomer was dominant in higher trophic level (TL) organisms like walleye [arithmetic mean +/- 1 x standard error: 730 +/- 120 pg/g, lipid weight (1w)] and goldeye (760 +/- 170 pg/g, Iw) while the syn-isomer dominated the lower TL organisms like zooplankton (550 +/- 40 pg/g, Iw) and mussels (430 +/- 140 pg/g, Iw). In Lake Ontario, the extent of bioaccumulation of the isomers and concentrations was greatest in the lower TL benthic organism, Diporeia (syn, 1307 +/- 554; and anti, 3108 +/- 898 pg/g Iw) and also high in zooplankton (syn, 719; and anti, 1332 pg/g Iw). This suggests that the isomers are bioavailable in sediment and that, despite their molecular size, diffusion from the water column into zooplankton can occur. Differences in the mean fractional abundance of the anti-isomer (mean fanti = mean concentration of the anti-isomer divided by sum of mean syn- and anti-concentrations) were pronounced in sediments between lakes (Lake Winnipeg mean fanti = 0.610, Lake Ontario mean fanti = 0.860) and the extent of enrichment (anti-) and depletion (syn-) of the isomers were more marked in Lake Winnipeg biota. There were also differences in the biomagnification potentials, as measured bythe trophic magnification factor (TMF), between the isomers in the Lake Winnipeg food web; no statistically significant TMFs for either isomer were found for the more...

Polychlorinated naphthalenes (PCNs) and mono- and non-ortho substituted PCBs were analyzed in air from two sites in Toronto, Ontario, Canada to determine whether current combustion-related sources contribute to the levels and profiles of PCNs found in urban air. High-volume air samples were collected periodically at the University of Toronto (UT, a downtown site) and in north Toronto at the Meteorological Service of Canada (MSC). SigmaPCN concentrations ranged from 31 to 78 pg m(-3) at UT and from 7 to 84 pg m(-3) at MSC with concentrations lower at MSC than UT for paired samples. Ambient air congener profiles contrasted between the two sites with MSC profiles indicating inputs from combustion-related sources when compared to combustion fly ash and technical PCN and PCB mixture profiles. Combustion markers, including CN-44, -29, and -54, the more toxic CN-66 and -67 congeners, and non-ortho PCBs, were enriched in air at MSC on a mass percent basis in several samples. As a result, CN-66/67 contributed proportionally more to dioxin toxic equivalents at MSC than at UT. Downtown air PCN profiles resembled those of technical PCN and PCB mixtures, reflecting evaporative emissions from past uses, while PCN levels and profiles at MSC, a more industrialized location, are also influenced by current combustion sources, contributing as much as an estimated 54% of sigmaPCN in samples collected. more...