Lake Superior Has Lost over 90% of Its Pesticide HCH Load since 1986.

The time trend of α- and γ-hexachlorocyclohexane (HCH) isomers in Lake Superior water was followed from 1986 to 2016, the longest record for any persistent organic pollutant (POP) in Great Lakes water. Dissipation of α-HCH and γ-HCHs was first order, with halving times (t1/2) of 5.7 and 8.5 y, respectively. Loss rates were not significantly different starting a decade later (1996-2016). Concentrations of ß-HCH were followed from 1996-2016 and dissipated more slowly (t1/2 = 16 y). In 1986, the lake contained an estimated 98.8 tonnes of α-HCH and 13.2 tonnes of γ-HCH; by 2016, only 2.7% and 7.9% of 1986 quantities remained. Halving times of both isomers in water were longer than those reported in air, and for γ-HCH, they were longer in water than those reported in lake trout. Microbial degradation was evident by enantioselective depletion of (+)α-HCH, which increased from 1996 to 2011. Volatilization was the main removal process for both isomers, followed by degradation (hydrolytic and microbial) and outflow through the St. Mary's River. Sedimentation was minor. Major uncertainties in quantifying removal processes were in the two-film model for predicting volatilization and in microbial degradation rates. The study highlights the value of long-term monitoring of chemicals in water to interpreting removal processes and trends in biota.

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.

Perfluoroalkyl Acids in Great Lakes Precipitation and Surface Water (2006-2018) Indicate Response to Phase-outs, Regulatory Action, and Variability in Fate and Transport Processes.

The concentrations of perfluoroalkyl acids (PFAAs) were determined in precipitation from three locations across the Great Lakes between 2006 and 2018 and compared to those in surface water. Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations generally decreased in precipitation, likely in response to phase-outs/regulatory actions. In comparison, concentrations of shorter-chained PFAA, which are not regulated in Canada did not decrease and those of perfluorohexanoate and perfluorobutanoate (PFBA) recently increased, which could be due to their use as replacements, as the longer-chained PFAAs are being phased-out by industry. PFOS and PFOA concentrations were greater in Lake Ontario precipitation than in precipitation from more remote locations. In comparison, PFBA concentrations were comparable across locations, suggesting greater atmospheric transport either through its more volatile precursors and/or directly in association with particles/aerosols. In Lake Ontario, the comparison of PFAAs in precipitation to those in surface water provides evidence of sources (e.g., street dust and wastewater effluent) in addition to wet deposition to surface water, whereas wet deposition appears to be dominant in Lakes Huron and Superior. Our results suggest that source control of shorter-chained PFAAs may be slow to be reflected in environmental concentrations due to emissions far from the location of detection and continued volatilization from existing in-use products and waste streams.

Bioaccumulation of Selected Halogenated Organic Flame Retardants in Lake Ontario.

The trophic magnification of polybrominated diphenyl ethers (PBDEs) and selected nonlegacy halogenated organic compounds (HOCs) was determined in the food web of Lake Ontario (ON, Canada). In all, 28 Br3 -Br8 -PBDEs and 24 HOCs (10 of which had not been targeted previously) were analyzed. Average concentrations of Σ28 PBDEs in fish ranged between 79.7 ± 54.2 ng/g lipid weight in alewife (Alosa pseudoharengus) and 815 ± 695 ng/g lipid weight in lake trout (Salvelinus namaycush). For invertebrates, concentrations were between 13.4 ng/g lipid weight (net plankton; >110 µm) and 41.9 ng/g lipid weight in Diaporeia (Diaporeia hoyi). Detection frequency (DF) for HOCs was highest for anti-Dechlorane Plus (anti-DDC-CO), 1,3-diiodobenzene (1,3-DiiB), tribromo-methoxy-methylbenzene (ME-TBP), allyl 2,4,6-tribromophenyl ether (TBP-AE), pentabromocyclododecene (PBCYD), α+ß-tetrabromocylcooctane (TBCO), 2-bromoallyl 2,4,6-tribromophenyl ether (BATE), and pentabromotoluene (PBT; DF for all = 100% in lake trout). Tetrabromoxylene (TBX), dibromopropyl 2,4,6-tribromophenyl ether (TBP-DBPE), and syn-DDC-CO were also frequently detected in trout (DF = 70-78%), whereas 2,3,4,5,6-pentabromoethyl benzene (PBEB) was detected only in plankton. Several HOCs were reported in aquatic biota in the Great Lakes (USA/Canada) for the first time in the present study, including PBCYD, 1,3DiiB, BATE, TBP-DBPE, PBT, α + ß-TBCO, and ME-TBP. The Br4-6 -BDEs (-47, -85, -99, -100, -153, and -154) all had prey-weighted biomagnification factors (BMFPW ) values >6, whereas BMFPW values for Br7-8 -BDEs were <1. The highest BMFPW values of non-PBDEs were for TBP-DBPE (10.6 ± 1.34) and ME-TBP (4.88 ± 0.60), whereas TBP-AE had a BMFPW value of <1. Significant (p ≤ 0.05) trophic magnification factors (TMFs), both positive and negative, were found for Br4-8- BDEs (BDE 196 = 0.4; BDE 154 = 9.5) and for bis(2,4,6-tribromophenoxy)ethane (BTBPE; 0.53), PBCYD (1.8), 1,3-DiiB (0.33), and pentabromobenzene (PBB; 0.25). Food chain length was found to have a significant influence on the TMF values. Environ Toxicol Chem 2019;38:1198-1210. © 2019 SETAC.

Investigation of Spatial Distributions and Temporal Trends of Triclosan in Canadian Surface Waters.

Triclosan is widely used in personal care products (skin creams, toothpastes, soaps, deodorants, body spray) and cleaning products (dishwashing detergent and all-purpose cleaners) (Halden in Environ Sci Technol 48:3603-3611, 2014). In 2001, it was selected for screening-level risk assessment under the Canadian Environmental Protection Act (HC and EC in Preliminary assessment. Triclosan. Chemical abstracts Service Number 3380-34-5, 2012. http://www.ec.gc.ca/ese-ees/default.asp?lang=En&n=6EF68BEC-1 ), and its physicochemical and toxicological characteristics indicate that there may be a risk to aquatic environments due to releases of the chemical in Canada. A surveillance initiative across Canada has included sampling at 44 sites from July 2012 to March 2018. Triclosan was detected in 226 of 918 samples; concentrations ranged from less than 6 to 874 ng L-1, and the detections averaged 54.23 ng L-1 (standard deviation; 97.6 ng L-1). However, using the entire dataset (including censored data estimated with the Kaplan-Meier model), the mean triclosan concentration was 17.95 ng L-1, and the standard deviation was 52.84 ng L-1. Three samples at Wascana Creek (downstream), Saskatchewan, had concentrations above the Federal Environmental Quality Guidelines of 470 ng L-1, indicating a potential risk to the aquatic ecosystem. In this study, triclosan in samples collected downstream from municipal wastewater treatment plant discharges usually demonstrated higher concentrations than upstream samples. Based on the results of this study, it is hypothesized that triclosan concentration have fluctuated between years of this study but not in an overall or significant increase or decreasing trend. Triclosan concentrations and detections also are more prevalent in urban than in rural or mixed development rivers. Performance evaluation of triclosan concentrations in the Canadian environment is scheduled to be reassessed by 2024. Therefore, a 3-year sampling program should be in place across Canada by 2021.

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.

Halogenated Flame Retardants in Predator and Prey Fish From the Laurentian Great Lakes: Age-Dependent Accumulation and Trophic Transfer.

The identification, persistence, accumulation and trophic transfer of 25 polybrominated diphenyl ether (PBDE) congeners, 23 non-PBDE halogenated flame retardants (NPHFRs), 4 polybrominated-diphenoxybenzenes (PB-DiPhOBzs) and 6 methoxylated (MeO-) PB-DiPhOBzs were investigated in predator and prey fish collected in 2010 from sites in the North American Great Lakes of Ontario (n = 26) and Erie (n = 39). Regardless of locations or species, 20 PBDEs and 12 NPHFRs were quantifiable in at least one of the 65 analyzed samples, and polybrominated-1,4-diphenoxybenzenes (PB-DiPhOBzs) and MeO-PB-DiPhOBzs were not detectable in any of analyzed samples. Among the FRs, the greatest concentrations were the ∑PBDE, ranging from 1.06 (Rainbow Smelt, Lake Erie) to 162 (Lake Trout, Lake Ontario) ng/g wet weight (ww), which was followed by mean HBCDD concentrations ranging ND to 17.3 (Lake Trout, Lake Ontario) ng/g ww. The remaining FRs were generally not detectable or at sub-ppb levels. In most of cases, FR concentrations in samples from Lake Ontario were greater than those from Lake Erie. Strong and significant positive linear relationships occurred between log-normalized FR concentrations (ww or lipid weight (lw)) and ages of the top predator Lake Trout (n = 16, from Lake Ontario), and the estimated FR doubling ages (T2) were 2.9-6.4 years. For Walleye from Lake Erie, significantly positive linear relationships were also observed for some FRs, but the linear relationships generally became negative after FR concentrations were normalized with lipid weight. This study provides novel information on FR accumulation in aquatic organisms, and for the first time, significant positive linear relationships are reported between log-normalized FR concentrations (lw or ww) and ages of Lake Trout from the Great Lakes.

Evidence for High Concentrations and Maternal Transfer of Substituted Diphenylamines in European Eels Analyzed by Two-Dimensional Gas Chromatography-Time-of-Flight Mass Spectrometry and Gas Chromatography-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Chemical pollution is hypothesized to be one of the factors driving the strong decline of the critically endangered European eel population. Specifically, the impact of contaminants on the quality of spawning eels and subsequent embryo survival and development has been discussed as crucial investigation point. However, so far, only very limited information on potential negative effects of contaminants on the reproduction of eels is available. Through the combination of nontargeted ultrahigh-resolution mass spectrometry and multidimensional gas chromatography, combined with more-conventional targeted analytical approaches and multimedia mass-balance modeling, compounds of particular relevance, and their maternal transfer in artificially matured European eels from the German river Ems have been identified. Substituted diphenylamines were, unexpectedly, found to be the primary organic contaminants in the eel samples, with concentrations in the µg g-1 wet weight range. Furthermore, it could be shown that these contaminants, as well as polychlorinated biphenyls (PCBs), organochlorine pesticides, and polyaromatic hydrocarbons (PAHs), are not merely stored in lipid rich tissue of eels but maternally transferred into gonads and eggs. The results of this study provide unique information on both the fate and behavior of substituted diphenylamines in the environment as well as their relevance as contaminants in European eels.

Retrospective analysis of organophosphate flame retardants in herring gull eggs and relation to the aquatic food web in the Laurentian Great Lakes of North America.

With the phase-out and regulation of some flame retardant chemicals, the production and usage of organophosphate triester flame retardants (OPFRs) has increased in recent years. In the present study, 14 OPFRs (either chlorinated, brominated or non-halogenated) were analyzed in egg pools of 10-13 individual herring gull eggs from five colonial nesting sites for 11 years spanning 1990-2010, (for a total of n=55 egg pools) in the Laurentian Great Lakes of North America (Chantry Island, Fighting Island, Agawa Rocks, Toronto Harbour and Gull Island). OPFR profiles varied slightly between colony sites and collection years. For all five sites tris(2-chloroisopropyl) phosphate (TCIPP), tris(2-chloroethyl) phosphate (TCEP) and tris(2-butoxyethyl) phosphate (TBOEP) were detected, while triphenyl phosphate (TPHP) was only quantifiable in eggs from Chantry Island and Gull Island collected in 2008 and 2010. For the 2010 egg pools, the ΣOPFR concentrations were generally low and ranged from 2.02 to 6.69 ng/g wet weight (ww). ΣOPFR concentrations in 2010 were significantly higher (p<0.05) than they were between 1990 and 2004 (4.06 vs. 1.55 ng/g ww, respectively). In a pilot examination of Great Lakes aquatic food webs, 2010-collected alewife and rainbow smelt (major herring gull fish prey) and lake trout from western Lake Erie and Ontario, only contained TBOEP at low to sub ng/g ww concentrations. These results demonstrate that low to sub-ppb concentrations of at least three OPFRs, TCIPP, TCEP and TBOEP, have been persistent in herring gull eggs from the Great Lakes for at least the past 20 years, probably bioaccumulate mainly via the fish diet, and are transferred to the eggs of exposed herring gulls.

Atmospheric concentrations and loadings of organochlorine pesticides and polychlorinated biphenyls in the Canadian Great Lakes Basin (GLB): Spatial and temporal analysis (1992-2012).

Long-term air monitoring data for POPs are required to determine the effectiveness of source reduction measures and factors controlling air concentrations. Air samples were collected between 1992 and 2012 at three sites with different geographical characteristics (Burnt Island, Egbert and Point Petre) in the Canadian Great Lakes Basin (GLB) using high-volume samplers and analyzed for organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). Spatial and temporal trends of gas-phase concentrations of OCPs, selected PCB congeners and Æ©PCBs (84 congeners) were assessed. Egbert had the highest concentrations of some OCPs due to historical [dichlorodiphenyltrichloroethanes (DDTs), dieldrin, γ-hexachlorocyclohexane (γ-HCH)] and current (endosulfan) applications of these pesticides in the surrounding agricultural cropland. This shows that agricultural areas are a source of OCPs to the GLB. High o,p'-/p,p'-DDT ratios were determined and an increasing trend was observed at Point Petre and Burnt Island up to 2004; indicating that the GLB is influenced by dicofol-type DDT sources, which have higher o,p'-/p,p'-DDT ratios than technical DDT. Atmospheric PCB concentrations at Egbert and Point Petre are higher than those measured at Burnt Island, likely due to urban influence and greater populations. Loadings calculations suggest that the atmosphere is a source of α-endosulfan and p,p'-DDT to the lakes and the opposite is true for p,p'-DDE. Long-term decreasing trends were observed for both OCPs and PCBs; consistent with control measures implemented in North America. Atmospheric PCB concentrations are decreasing relatively slowly, with halflives in the range of 9-39 years. Chlordane, α-endosulfan, ß-endosulfan, dieldrin, and DDT-related substances showed halflives in the range of 7-13 years. α-HCH and γ-HCH were decreasing rapidly in air, with halflives of 5 years. Long-term declining trends of PCBs and OCPs suggest that regulatory efforts to reduce emissions to the GLB environment have been effective, but emissions from primary and secondary sources might limit future declines.

A New Fluorinated Surfactant Contaminant in Biota: Perfluorobutane Sulfonamide in Several Fish Species.

Environmental contamination and regulation of longer-chain perfluoroalkyl substances (PFASs) such as perfluorooctanesulfonate (PFOS) has given rise to the increased use of shorter-chain PFASs as alternatives in new products, although confirmation of their presence in the environment remains limited. In this study, the PFAS alternative, perfluoro-1-butane-sulfonamide (FBSA), was identified for the first time in biota in homogenate samples of fish by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-ToF-MS) and quantified by ultra high performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-QQQ-MS/MS). In one flounder (Platichthys flesus) muscle sample from the Western Scheldt, The Netherlands, FBSA concentration was at 80.12 ng/g wet weight (w.w.) and was exceeded only by PFOS. FBSA was also detected in 32 out of 33 samples of freshwater fish collected (2009-2010) from water bodies across Canada. In lake trout (Salvelinus namaycush) from northern Canada (e.g., Lake Kusawa (Yukon Territory), Great Bear Lake (Northwest Territories and in the Arctic), and Lake Athabasca (northern Alberta)), the concentrations of FBSA ranged from below method detection limit (<0.01 ng/g w.w) to 0.44 ng/g w.w. and were much lower than those reported for lake trout from the more urbanized and industrialized Laurentian Great Lakes sites (3.17 ± 1.53 ng/g w.w.). In three species of fish purchased from a supermarket in Ottawa (ON, Canada), FBSA concentrations were the lowest of all fish and ranged from < MLOD to 0.29 ng/g w.w. and 0.03 to 0.76 ng/g w.w. in muscle and liver, respectively. FBSA is a bioaccumulative contaminant in fish in Canada and possibly in The Netherlands. It is likely sourced from new alternative perfluorobutane-based products, as well as other shorter chain perfluoroalkyl-based products.

Trends of persistent organic pollutants in American eel (Anguilla rostrata) from eastern Lake Ontario, Canada, and their potential effects on recruitment.

This study reports the history of contamination of American eels (Anguilla rostrata) from eastern Lake Ontario (LO) by persistent organic pollutants (POPs). Three groups of 10 large female eels captured in eastern LO in each of 1988, 1998, and 2008 were analysed for polychlorinated dibenzo-p-dioxins and furans, polychlorinated biphenyls, several organochlorine pesticides, and polybrominated diphenyl ethers. Mean concentrations were up to 3-fold lower in 2008 compared to previous years. When combined with the results of previous studies, these data show that concentrations of POPs in American eels have declined exponentially since the early 1980s by an average of 9.1±1.9% per year. Toxic equivalent (TEQ) concentrations of dioxin-like compounds (DLCs) were calculated from fish toxic equivalency factors. Assuming an efficient transfer of DLCs to their eggs, egg TEQs prior to 2000 exceeded the threshold for chronic toxicity to embryos of European eels (Anguilla anguilla) and lake trout (Salvelinus namaycush) (4-5 pg/g ww of TEQ). These results suggest that embryotoxicity of maternally-derived DLCs from LO eels, historically a major contributor to the spawning stock of American eels, could have impaired the reproductive and recruitment success of the species.

Current status of short- and medium chain polychlorinated n-alkanes in top predatory fish across Canada.

Short and medium chain polychlorinated n-alkanes (sPCAs and mPCAs) were measured in top predatory fish from nine freshwater bodies across Canada in 2010-2011. Maximum sPCA concentrations were measured in brook trout from Kejimikujik Lake in Nova Scotia (10±8 ng g(-1) wet weight) while the lowest concentrations were found in lake trout from Kusawa Lake in the Yukon (2±3 ng g(-1) wet weight). The presence of sPCAs in fish from these sites is strongly suggestive of long range atmospheric transport, given the absence of known point sources. The highest mPCA concentrations (11-12 ng g(-1) wet weight) were found in lake trout from Lakes Huron, Erie and Ontario. These results showed that fish from sites impacted mostly by atmospheric sources contained higher concentrations of sPCAs than mPCAs while the opposite was observed in sites impacted by industrialization. C12H20Cl6, C12H19Cl7, C14H24Cl6 and C14H23Cl7 were the most abundant homologue groups observed. Lake trout from Lake Huron showed a markedly different sPCA homologue profile, characterized by higher abundances of C11H15Cl9 and C12H17Cl9, indicating local sources. Principal components analysis of sPCA homologues abundances showed that C12H20Cl6, C12H19Cl7, C11H18Cl6, C11H17Cl7 were associated with lakes influenced by atmospheric sources while C11H16Cl8, C12H18Cl8, C11H15Cl9, C12H17Cl9 were associated with sites influenced by urban/industrial sources. Finally, concentrations of sPCAs in Lake Ontario lake trout collected in 2011 decreased 6.6-fold compared to 2001, however no significant differences were observed for mPCAs.

Identification and occurrence of analogues of dechlorane 604 in Lake Ontario sediment and their accumulation in fish.

The dechlorane family of flame retardants, which includes Mirex (also known as Dechlorane), Dechlorane Plus (DP), and Dechloranes (Dec) 602, 603, and 604, were manufactured at a facility along the Niagara River, upstream of Lake Ontario. Some of these compounds remain in use. In a previous study, we found Mirex and Dec602 to have greater bioaccumulation potentials than Dec604 and DP based on calculated biota-sediment accumulation factors (BSAFs). In this study, analogues of Dec604, containing fewer bromines and mixed substitutions of bromine and chlorine, were identified in Lake Ontario sediment and fish using high and ultrahigh resolution mass spectrometric techniques. The tribromo-Dec604 (Br3Dec604) analogue, known as Dechlorane 604 Component B (Dec604 CB), was present in lake trout and whitefish at concentrations of 10-60 ng/g lipid weight, approximately 50-200 times greater than concentrations measured for Dec604. In addition, BrDec604 and Br2Dec604 analogues, and mixed Br2Cl2Dec604, Br3ClDec604, Br2ClDec604, and BrCl2Dec604 analogues were also present. We have shown that solutions of Dec604 and Dec604 CB exposed to UV-light undergo photodebromination and give rise to the analogues found in sediment and fish. Dec604 CB and other lesser halogenated analogues of Dec604 show greater bioaccumulation potentials than Dec604, Dec602 and DP, based on BSAFs, which highlight the need to consider likely impurities and degradation products in the assessment of persistent, bioaccumulative, and toxic compounds.

Characterization of naphthenic acids by gas chromatography-Fourier transform ion cyclotron resonance mass spectrometry.

During the bitumen extraction from the oil sands of Alberta, large volumes of process water containing naphthenic acids are stored in tailing ponds. The naphthenic acids along with other components in the processed waters are known to be toxic in aquatic environments. In view of the complex matrix and the toxicity of the processed waters, there is a need for complementary analytical techniques for comprehensive characterization of the naphthenic acid mixtures. This study reports the online gas chromatographic separation of naphthenic acid mixtures prior to ultrahigh resolution mass spectrometry detection, using electron and chemical ionization. Two oil sands processed water samples and two groundwater samples were characterized to evaluate the performance of the instrumental technique. The high mass resolution of the system enabled visualization of the data using Kendrick mass defect plots. The addition of gas chromatographic separations enabled visualization of the data as unique compound class elution fingerprints. The technique is demonstrated to be a valuable tool for chemical fingerprinting of naphthenic acids.

Flame retardants and legacy chemicals in Great Lakes' water.

The Great Lakes have been the focus of extensive environmental research, but recent data on the aquatic concentrations of emerging compounds, such as flame retardants, are scarce. Water samples from 18 stations on the five Great Lakes were collected in 2011 and 2012 using XAD-2 resin adsorption and analyzed for PCBs, organochlorine pesticides, PAHs, polybrominated diphenyl ethers (PBDEs), and emerging flame retardants, including organophosphate flame retardants (OPEs). Total PCB concentrations ranged from 117 ± 18 pg/L in Lake Superior to 623 ± 113 pg/L in Lake Ontario. Among the organochlorine pesticides, the most abundant was dieldrin, with the highest average concentration of 99 ± 26 pg/L in Lake Erie, followed by p,p'-DDD with an average concentration of 37 ± 8 pg/L in Lake Ontario. Total PAH concentrations were higher in Lakes Erie and Ontario than in Lakes Michigan, Huron, and Superior. Total PBDE concentrations were highest in Lake Ontario (227 ± 75 pg/L), and the most abundant congeners were BDE-47, BDE-99, and BDE-209. Total OPE concentrations ranged between 7.3 ± 4.5 ng/L in Lake Huron to 96 ± 43 ng/L in Lake Erie.

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.

Qualitative analysis of halogenated organic contaminants in American eel by gas chromatography/time-of-flight mass spectrometry.

Target compound analysis with scanning mass spectrometers such as quadrupole or magnetic sector instruments is used extensively in environmental chemistry because of the selectivity, sensitivity, and robustness. Yet, target compound analysis selectively ignores the majority of compounds present in a sample, especially in complex matrices like fish. In this study, time-of-flight mass spectrometry was used to screen for and identify halogenated compounds in American eels (Anguilla rostrata). Individual and then pooled eel samples were analysed using electron ionization and electron capture negative ionization (ECNI) modes. Eels were differentiated by principal component analysis of chemical profiles and were grouped corresponding to their capture location, all with a single instrument injection per sample. Bromine containing compounds were further investigated by taking advantage of the selectivity of ECNI by utilizing the Br(-) ion m/z 79 and 81. A total of 51 brominated compounds were detected and their identities were attempted by authentic standards, library searching, and/or chemical formula prediction based on accurate mass measurements. Several PBDEs were identified in the samples, and the majority of the non-PBDEs identified were bromophenols, bromoanisoles, and bromobenzenes. These classes of compounds are synthesized for use in flame retardant production either as intermediates or as final products. However, their occurrence in eels was most likely the result of metabolism or break-down products of high production volume flame retardants like polybrominated diphenyl ethers and bromophenoxy compounds.

From the city to the Lake: loadings of PCBs, PBDEs, PAHs and PCMs from Toronto to Lake Ontario.

Loadings from Toronto, Canada to Lake Ontario were quantified and major sources and pathways were identified, with the goal of informing opportunities for loading reductions. The contaminants were polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs) and polycyclic musks (PCMs). Loadings were calculated from measured concentrations for three major pathways: atmospheric processes, tributary runoff, and wastewater treatment plant (WWTP) effluents. Although atmospheric deposition to the Great Lakes has received the greatest attention, this was the dominant loading pathway for PCBs only (17 ± 5.3 kg/y or 66% of total loadings). PCB loadings reflected elevated urban PCB air concentrations due to, predominantly, primary emissions. These loadings contribute to consumption advisories for nearshore fish. PBDE loadings to the lake, again from mainly primary emissions, were 48% (9.1 ± 1.3 kg/y) and 42% (8.0 ± 5.7 kg/y) via tributaries and WWTPs, respectively, consistent with emissions deposited and subsequently washed-off of urban surfaces and emissions to the sewage system. PAHs loadings of 1600 ± 280 kg/y (71%) from tributaries were strongly associated with vehicle transportation and impervious surfaces. PCM loadings were 83% (±140 kg/y) from WWTP final effluent, reflecting their use in personal care products. Opportunities for source reduction lie in reducing the current inventories of in-use PCBs and PBDE-containing products, reducing vehicle emissions of PAHs and use of PAHs in the transportation network (e.g., pavement sealants), and improving wastewater treatment technology.

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.