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.

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.

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.

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.

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.

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.

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.

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.

The use of mass defect plots for the identification of (novel) halogenated contaminants in the environment.

Mass defect is the difference between the nominal and exact mass of a chemical element or compound. An intrinsic property of polyhalogenated molecules is a uniquely negative mass defect, which readily distinguishes halogenated from non-halogenated compounds in a complex mass spectrum and can be visualized by constructing a mass defect plot. This study demonstrates the utility of the mass defect plot as a powerful tool to screen gas-chromatography (ultra)high-resolution mass spectrometry data for potentially toxic and bioaccumulative halogenated compounds in a Lake Ontario lake trout, an apex species in the Great Lakes environment. Our results indicate that the sample is contaminated with polychlorinated biphenyls, terphenyls, diphenylethers, as well as other chlorinated pesticides and flame retardants that are regulated and routinely analyzed by traditional target analyses. However, the mass defect plot also displays peaks which could be traced to the presence of as yet undiscovered contaminants. These include chlorinated polycyclic aromatic hydrocarbons as well as mixed halogenated analogues of the flame retardant Dechlorane 604. The identity of the latter class of compounds is supported by experiments with genuine standards.

Enantiospecific perfluorooctane sulfonate (PFOS) analysis reveals evidence for the source contribution of PFOS-precursors to the Lake Ontario foodweb.

Exposure to perfluorooctane sulfonate (PFOS) may arise directly, from emission and exposure to PFOS itself, or indirectly via the environmental release and degradation of PFOS-precursors. Human serum enantiomer fractions (EFs) of 1m-PFOS have been shown to be nonracemic, suggesting that PFOS-precursors are a significant source of PFOS in humans, but little is known about the importance of PFOS-precursors in ecosystems. In the current work, concentrations of PFOS, perfluorooctane sulfonamide (PFOSA), PFOS isomer profiles, and EFs of 1m-PFOS were determined in Lake Ontario water, sediment, fishes and invertebrates. Concentrations of PFOS and PFOSA were highest in slimy sculpin and Diporeia, and concentrations of the two compounds were often correlated. 1m-PFOS was racemic in sediment, water, sculpin and rainbow smelt, but nonracemic in the top predator, lake trout, and all invertebrate species. Furthermore, EFs were correlated with the relative concentrations of PFOS and PFOSA in invertebrates. Overall, these empirical observations with a new analytical tool confirm previous suggestions that PFOS-precursors contribute to PFOS in the food web, likely via sediment. Implications are that future PFOS exposures in this ecosystem will be influenced by an in situ source, and that the apparent environmental behavior of PFOS (e.g., bioaccumulation potential) can be confounded by precursors.

Perfluoroalkyl contaminants in Lake Ontario Lake Trout: detailed examination of current status and long-term trends.

Perfluoroalkyl contaminants (PFCs) were determined in Lake Ontario Lake Trout sampled annually between 1997 and 2008 in order to assess how current trends are responding to recent regulatory bans and voluntary phase-outs. We also combined our measurements with those of a previous study to provide an updated assessment of long-term trends. Concentrations of PFCs generally increased from the late 1970s until the mid-1980s to mid-1990s, after which concentrations either remained unchanged (perfluorooctane sulfonate (PFOS) and perfluorocarboxylates) or declined (perfluorodecanesulfonate (PFDS)). The temporal trends were assessed using three models, quadratic, exponential rise to maximum, and two-segment linear piecewise function, and then evaluated for best fit using Akaike Information Criteria. For PFOS and perfluorocarboxylates, the exponential rise to maximum function had the best fit. This is particularly interesting for PFOS as it suggests that although concentrations in Lake Ontario Lake Trout may have stopped increasing in response to voluntary phase-outs in 2000-2002, declines have yet to be observed. This may be due to continuing input of PFOS from products still in use and/or slow degradation of larger precursor molecules. A power analysis of PFOS suggested that 15 years of data with a within-year sample size of 10 is required to obtain sufficient power (80%) to detect a 5% decreasing trend. However, the length of the monitoring program had a greater influence on the ability to detect a trend compared to within-year sample size. This provides evidence that additional sampling years are required to detect a response to bans and phase-outs, given the variability in the fish data. The lack of observed declines of perfluorocarboxylate residues in fish may be expected as regulations for these compounds were only recently enacted. In contrast to the other compounds, the quadratic model had the best fit for PFDS. The results of this study emphasize the importance of long-term monitoring for assessing the effectiveness of bans and phase-outs on PFCs in the environment.

Identification and determination of the dechlorination products of Dechlorane 602 in Great Lakes fish and Arctic beluga whales by gas chromatography-high resolution mass spectrometry.

During the course of our studies of in-use chlorinated flame retardants, such as Dechlorane Plus(®) and Dechloranes 602 and 604, blubber of beluga whales from the Canadian Arctic and lake trout and whitefish from the North American Great Lakes were found to contain two novel dechlorination products of Dechlorane 602 (Dec602). The structures of these compounds were characterized by experiments performed using both gas chromatography-high resolution mass spectrometry and Fourier transform mass spectrometry with a prepared technical mixture of monohydro and dihydroDec602 derivatives. These Dec602 derivatives are analogous to the well-known monohydro and dihydro photochemical degradation products of Mirex. The ratio of the two monohydroDec602 diastereomers varied between Lake Ontario fish and those from the upper lakes, but only one isomer was found in Arctic beluga, indicating that one isomer is either more stable or more bioaccumulative. Dechlorane Plus(®), Dec603, and Dec 604 were not detected in Arctic beluga, but Dec602 and its monohydroDec602 derivative were measured in approximately equal concentrations, ranging from 25 to 300 pg/g lipid. In Great Lakes fish, concentrations of the monohydroDec602 derivatives were also close to those of Dec602, ranging from 2 to 67 ng/g lipid and were greatest in Lake Ontario. This study reports on the first measurements of dechlorane-related compounds in Arctic biota and the first detection of monohydroDec602 degradation products and their accumulation in biota.

Detection of the spatiotemporal trends of mercury in Lake Erie fish communities: a Bayesian approach.

The temporal trends of total mercury (THg) in four fish species in Lake Erie were evaluated based on 35 years of fish contaminant data. Our Bayesian statistical approach consists of three steps aiming to address different questions. First, we used the exponential and mixed-order decay models to assess the declining rates in four intensively sampled fish species, i.e., walleye (Stizostedion vitreum), yellow perch (Perca flavescens), smallmouth bass (Micropterus dolomieui), and white bass (Morone chrysops). Because the two models postulate monotonic decrease of the THg levels, we included first- and second-order random walk terms in our statistical formulations to accommodate nonmonotonic patterns in the data time series. Our analysis identified a recent increase in the THg concentrations, particularly after the mid-1990s. In the second step, we used double exponential models to quantify the relative magnitude of the THg trends depending on the type of data used (skinless-boneless fillet versus whole fish data) and the fish species examined. The observed THg concentrations were significantly higher in skinless boneless fillet than in whole fish portions, while the whole fish portions of walleye exhibited faster decline rates and slower rates of increase relative to the skinless boneless fillet data. Our analysis also shows lower decline rates and higher rates of increase in walleye relative to the other three fish species examined. The food web structural shifts induced by the invasive species (dreissenid mussels and round goby) may be associated with the recent THg trends in Lake Erie fish.

Detection of a cyclic perfluorinated acid, perfluoroethylcyclohexane sulfonate, in the Great Lakes of North America.

Perfluoroethylcyclohexanesulfonate (PFECHS) is a cyclic perfluorinated acid (PFA) mainly used as an erosion inhibitor in aircraft hydraulic fluids. It is expected to be as recalcitrant to environmental degradation as aliphatic PFAs including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). For the first time, PFECHS is reported in top predator fish (

Temporal PCB and mercury trends in Lake Erie fish communities: a dynamic linear modeling analysis.

We performed dynamic linear modeling analysis on fish contaminant data collected from the Ontario Ministry of the Environment and Environment Canada to examine long-term trends of total mercury (THg) and polychlorinated biphenyls (PCBs) in Lake Erie. Several sport fish species (walleye, smallmouth bass, rainbow trout) with differences in their diet habits, food competition strategies and foraging patterns are characterized by weakly increasing trends of their THg levels in Lake Erie after the mid- or late 1990s. Similarly, our analysis shows that the decline rates of the PCB body burdens in white bass, smallmouth bass, freshwater drum and whitefish have slowed down or have switched to weakly increasing rates over the last decade. Our analysis also provides evidence that the rainbow trout and coho salmon PCB concentrations have been decreasing steadily but the associated rates were fairly weak. The systematic shifts in energy trophodynamics along with the food web alterations induced from the introduction of non-native species, the new role of the sediments as a net contaminant source, and the potentially significant fluxes from the atmosphere stand out as some of the hypotheses proposed to explain the limited Lake Erie response in recent years to the various contamination mitigation strategies.

Spatiotemporal trends of mercury in walleye and largemouth bass from the Laurentian Great Lakes region.

The risk of mercury (Hg) exposure to humans and wildlife from fish consumption has driven extensive mercury analysis throughout the Great Lakes Region since the 1970s. This study compiled fish-Hg data from multiple sources in the region and assessed spatiotemporal trends of Hg concentrations in two representative top predator fish species. Walleye (Sander vitreus) and largemouth bass (Micropterus salmoides) were chosen for the trend analysis because they had more Hg records (63,872) than other fish species that had been sampled from waters throughout the region. Waterbody types were inland lakes (70%), the Great Lakes, impoundments, and rivers. The compiled datasets were analyzed with a mixed effects statistical model having random effects of station, year, and fish length; and fixed effects of year, tissue type, fish length, habitat, and season. The results showed a generally declining temporal trend in fish-Hg for the region (1970-2009), with spatial trends of increasing Hg concentration from south to north and from west to east across the region. Nonlinearity was evident in the general downward trends of Ontario walleye, with a shift to an upward trend beginning in the 1990s. Only ongoing monitoring can reveal if this upward shift is an oscillation in a long-term decline, a statistical anomaly, or a sustained declining temporal trend in regional fish-Hg concentrations.