Polycyclic aromatic compounds in the Canadian Environment: Aquatic and terrestrial environments.

Polycyclic aromatic compounds (PACs) are ubiquitous across environmental media in Canada, including surface water, soil, sediment and snowpack. Information is presented according to pan-Canadian sources, and key geographical areas including the Great Lakes, the Alberta Oil Sands Region (AOSR) and the Canadian Arctic. Significant PAC releases result from exploitation of fossil fuels containing naturally-derived PACs, with anthropogenic sources related to production, upgrading and transport which also release alkylated PACs. Continued expansion of the oil and gas industry indicates contamination by PACs may increase. Monitoring networks should be expanded, and include petrogenic PACs in their analytical schema, particularly near fuel transportation routes. National-scale roll-ups of emission budgets may not expose important details for localized areas, and on local scales emissions can be substantial without significantly contributing to total Canadian emissions. Burning organic matter produces mainly parent or pyrogenic PACs, with forest fires and coal combustion to produce iron and steel being major sources of pyrogenic PACs in Canada. Another major source is the use of carbon electrodes at aluminum smelters in British Columbia and Quebec. Temporal trends in PAC levels across the Great Lakes basin have remained relatively consistent over the past four decades. Management actions to reduce PAC loadings have been countered by increased urbanization, vehicular emissions and areas of impervious surfaces. Major cities within the Great Lakes watershed act as diffuse sources of PACs, and result in coronas of contamination emanating from urban centres, highlighting the need for non-point source controls to reduce loadings.

Deposition and Source Identification of Nitrogen Heterocyclic Polycyclic Aromatic Compounds in Snow, Sediment, and Air Samples from the Athabasca Oil Sands Region.

Polycyclic aromatic compounds (PACs) can have multiple sources in the Athabasca Oil Sands Region (AOSR). The current study was designed to identify and explore the potential of nitrogen heterocyclic PACs (NPACs) as source indicators in snowpack, lake sediment and passive air samples from the AOSR during 2014-2015. Source samples including petroleum coke (petcoke), haul road dust, and unprocessed oil sands were also analyzed. Samples were analyzed using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry, and liquid chromatography-high resolution Orbitrap mass spectrometry. Over 200 NPACs were identified and classified into at least 24 isomer groups, including alkylated carbazoles, benzocarbazoles, and indenoquinolines. Levels of NPACs in environmental samples decreased with distance from the main developments and with increasing depth in lake sediments but were detected within 50 km from the major developments. The composition profiles of several NPAC isomer classes, such as dimethylcarbazoles, showed that petcoke had a distinct distribution of NPACs compared to the haul road dust and unprocessed oil sands ores and was the most similar source material to near-field environmental samples. These results suggest that petcoke is a major contributing source for the identified NPACs and that these compounds have the potential to be used as source indicators for future research in the AOSR.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans associated with settling particles in Lake Ontario.

Sediment traps were deployed at seven sites in the western and central basins of Lake Ontario for calculation of concentrations and down fluxes for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) to assess ongoing loadings to Lake Ontario from the Niagara River watershed. Traps were deployed at multiple depths (beginning at 20 m) during two seasonal time periods at stations impacted by the outflow of the Niagara River, and stations reflecting deeper water offshore conditions. Settling particles were collected seasonally to assess the influence of physical characteristics of the water column, i.e., isothermal conditions vs. stratified conditions, on concentrations and fluxes of PCDD/Fs. At all stations and for all depth intervals, PCDD/F concentrations were higher in the winter sampling period (range of 3120-10,600 pg g-1), compared to the spring - summer - fall time period (range of 320-6900 pg g-1). These results indicated bottom sediments in central and western Lake Ontario were more highly-contaminated, compared to contemporary particulate material entering the lake via the Niagara River or resulting from shoreline erosion. However, assessment of PCDD/F congener profiles and ratios also indicated source areas within the Niagara River watershed continued to episodically contribute loadings to Lake Ontario. The results also indicated changes in discharges of PCDD/Fs from sources in the Niagara River result in changes in congener profiles in settling particles, which can be detected by continued monitoring.

Legacy of legacies: Chlorinated naphthalenes in Lake Trout, Walleye, Herring Gull eggs and sediments from the Laurentian Great Lakes indicate possible resuspension during contaminated sediment remediation.

Polychlorinated naphthalenes (PCNs) are legacy contaminants, produced primarily as flame retardants and dielectrics until phased-out in Europe and North America in the 1970s. Spatial and temporal trends (1979-2013) of PCN concentrations were studied in whole fish and herring gull eggs throughout the Great Lakes and St. Lawrence River, whereas sediments were analyzed for 2011-2013 only. For both fish and gull eggs, concentrations of PCNs were highest in western Lake Erie (7660 & 3020pg/gww respectively), and declined downstream to St. Lawrence River (range: 34-2370pg/gww). For sediments, concentrations were highest in suspended sediments from the Detroit River (264,000pg/g), and were lower in surficial sediments downstream to the St. Lawrence River (range=440-19,300pg/g). PCNs declined at all sites from ~1980 to 1995, but in Lake Erie concentrations of PCNs increased in gulls fish from 1995 until 2005. The resurgence in PCNs in biota corresponded to the timing of remedial dredging of sediment highly contaminated with PCNs in the Detroit River, whose effects appear to manifest themselves downstream to Lake Ontario. Congener profiles of PCNs differed between Lake Erie and Lake Ontario until post-dredging, where PCN profiles of fish in both lakes became increasingly more similar. PCNs in gull eggs were mostly hepta-PCNs, whereas fish had higher concentrations of lower chlorinated PCNs. Patterns of PCNs in gulls and fish appear to be influenced by differences in not only routes of exposure and differential metabolic ability, but also resuspension of PCN contaminated sediments.

Factors influencing the occurrence and distribution of neonicotinoid insecticides in surface waters of southern Ontario, Canada.

The widespread use of neonicotinoid insecticides and recent increased regulatory scrutiny requires the generation of monitoring data with sufficient scope and resolution to provide decision makers with a better understanding of occurrence and distribution in the environment. This study presents a wide-scale investigation of neonicotinoid insecticides used across the range of agricultural activities from fifteen surface water sites in southern Ontario. Using statistical analysis, the correlation of individual compounds with land use was investigated, and the relationship between neonicotinoid occurrence and hydrologic parameters in calibrated water courses was also assessed. Of the five neonicotinoids studied, imidacloprid, clothianidin and thiamethoxam exhibited detection rates above 90% at over half the sites sampled over a three year period (2012-2014). At two sites in southwestern Ontario, the Canadian Federal freshwater guideline value for imidacloprid (230 ng/L) was exceeded in roughly 75% of the samples collected. For some watersheds, there were correlations between the occurrence of neonicotinoids and precipitation and/or stream discharge. Some watersheds exhibited seasonal maxima in concentrations of neonicotinoids in spring and fall, particularly for those areas where row crop agriculture is predominant; these seasonal patterns were absent in some areas characterized by a broad range of agricultural activities.

Determination of substituted diphenylamines in environmental samples.

Owing to their stability at high temperature, low biodegradation, low water solubility, and low vapor pressure, substituted diphenylamines are used as antioxidants in rubber, foamed polymers, and as high-temperature functional fluids (e.g., lubricants, gear oils, and hydraulic fluids). There are few existing environmental measurements of these substances in any environmental medium. In this study, a method was developed for the determination of 10 substituted diphenylamines in wastewater, biosolids, and sediments using gas chromatography-tandem mass spectrometry (GC-MS/MS). The substituted diphenylamines that were measured were two styrenated diphenylamines isomers, three di-styrenated diphenylamine isomers, tert-butyl-diphenylamine, tert-octyl-diphenylamine, di-tert-butyl-diphenylamine, tert-butyl/tert-octyl-diphenylamine, and di-tert-octyl-diphenylamine. The instrument limits of detection (LODs) and limits of quantitation (LOQs) were 0.02-0.1 and 0.06-0.3 ng mL-1, respectively. Target compounds were spiked into sediment, effluent water, influent water, and biosolids at the 100- and 1000-ng levels (N = 6). Analyte recoveries ranged from 71.5 to 117 % with relative standard deviations (RSDs) of 2.12-12.4 %. The method was applied to the analysis of influent, effluent, and biosolid samples; the sum of substituted diphenylamines were 48.1-713, 1.04-28.5 ngL-1, and 85.3-1184 ngg-1dw (median: 71.0, 7.30 ngL-1, and 402 ngg-1dw), respectively. Nine sediment samples collected in Ontario, Canada contained concentrations of the sum of substituted diphenylamines ranging from 1.55 to 897 ngg-1dw.

Hexabromocyclododecane Flame Retardant Isomers in Sediments from Detroit River and Lake Erie of the Laurentian Great Lakes of North America.

Sediments collected in 2004 from along the Detroit River (n = 19) and across all of Lake Erie (n = 18) were analyzed for isomers of the flame retardant chemical, hexabromocyclododecane (HBCD), using liquid chromatography-tandem mass spectrometry. Sediment samples had ΣHBCD concentrations ranging from not detected to 1.6 ng/g d.w. γ-HBCD (56 %-100 % of ΣHBCDs) was the predominate isomer, observed in 7 of 19 samples from the Detroit River and 6 of 18 samples from Lake Erie (all within the western basin). α-HBCD was found in 4 Detroit River and 2 Lake Erie western basin sites, while ß-HBCD was only in two Detroit River samples. High ΣHBCD concentrations (>100 ng/g d.w.) were found in two sludge samples from two Windsor, ON, wastewater treatment plants that feed into the Detroit River upstream. HBCD contamination into the Detroit River is a major input vector into Lake Erie and with an apparent sediment dilution effect moving towards the eastern basin.

Hexabromocyclododecane: current understanding of chemistry, environmental fate and toxicology and implications for global management.

Hexabromocyclododecane (HBCD) is a globally produced brominated flame retardant (BFR) used primarily as an additive FR in polystyrene and textile products and has been the subject of intensified research, monitoring and regulatory interest over the past decade. HBCD is currently being evaluated under the Stockholm Convention on Persistent Organic Pollutants. HBCD is hydrophobic (i.e., has low water solubility) and thus partitions to organic phases in the aquatic environment (e.g., lipids, suspended solids). It is ubiquitous in the global environment with monitoring data generally exhibiting the expected relationship between proximity to known sources and levels; however, temporal trends are not consistent. Estimated degradation half-lives, together with data in abiotic compartments and long-range transport potential indicate HBCD may be sufficiently persistent and distributed to be of global concern. The detection of HBCD in biota in the Arctic and in source regions and available bioaccumulation data also support the case for regulatory scrutiny. Toxicity testing has detected reproductive, developmental and behavioral effects in animals where exposures are sufficient. Recent toxicological advances include a better mechanistic understanding of how HBCD can interfere with the hypothalamic-pituitary-thyroid axis, affect normal development, and impact the central nervous system; however, levels in biota in remote locations are below known effects thresholds. For many regulatory criteria, there are substantial uncertainties that reduce confidence in evaluations and thereby confound management decision-making based on currently available information.

Estimating sediment quality thresholds to prevent restrictions on fish consumption: Application to polychlorinated biphenyls and dioxins-furans in the Canadian Great Lakes.

Sediment quality thresholds (SQTs) are used by a variety of agencies to assess the potential for adverse impact of sediment-associated contaminants on aquatic biota, typically benthic invertebrates. However, sedimentary contaminants can also result in elevated fish contaminant levels, triggering consumption advisories that are protective of humans. As such, SQTs that would result in fish concentrations below consumption advisory levels should also be considered. To illustrate how this can be addressed, we first calculate biota sediment accumulation factors (BSAFs) for polychlorinated biphenyls (total PCB) and polychlorinated dioxins-furans (PCDD/Fs) in the Canadian Great Lakes using measured lake sediment and fish tissue concentrations in 4 fish species, namely, lake trout, whitefish, rainbow trout, and channel catfish. Using these BSAFs and tissue residue values for fish consumption advisories employed by the Ontario Ministry of the Environment (OMOE, Canada), we derive fish consumption advisory-based SQTs (fca-SQTs) that are likely to result in fish tissue residues that are safe to eat without restriction. The PCDD/Fs fca-SQTs ranged from 6 to 128 pg toxic equivalents (TEQ)/g dry weight (dw) and were above the Canadian Council of the Ministers of the Environment (CCME) threshold effect level (TEL) of 0.85 pg TEQ/g dw. In contrast, the total PCB fca-SQTs ranged from 1 to 60 ng/g dw and were generally below the CCME's TEL of 34.1 ng/g and OMOE's lowest effect level (LEL) of 70 ng/g; however, they were consistent with the OMOE's no effect level (NEL) of 10 ng/g. The fca-SQTs derived using the BSAF as well as food chain multiplier (FCM) approach for a smaller scale system (Hamilton Harbour in Lake Ontario) corresponded well with average lakewide Lake Ontario fca-SQTs. This analysis provides approximate sediment concentrations necessary for reducing fish consumption advisories for each of the Canadian Great Lakes and emphasizes the impacts of historical lake sediment contamination on fish advisories. We believe that this approach merits consideration in sediment guideline development.

Source apportionment of PAH in Hamilton Harbour suspended sediments: comparison of two factor analysis methods.

A total of 26 suspended sediment samples collected over a 5-year period in Hamilton Harbour, Ontario, Canada and surrounding creeks were analyzed for a suite of polycyclic aromatic hydrocarbons and sulfur heterocycles. Hamilton Harbour sediments contain relatively high levels of polycyclic aromatic compounds and heavy metals due to emissions from industrial and mobile sources. Two receptor modeling methods using factor analyses were compared to determine the profiles and relative contributions of pollution sources to the harbor; these methods are principal component analyses (PCA) with multiple linear regression analysis (MLR) and positive matrix factorization (PMF). Both methods identified four factors and gave excellent correlation coefficients between predicted and measured levels of 25 aromatic compounds; both methods predicted similar contributions from coal tar/coal combustion sources to the harbor (19 and 26%, respectively). One PCA factor was identified as contributions from vehicular emissions (61%); PMF was able to differentiate vehicular emissions into two factors, one attributed to gasoline emissions sources (28%) and the other to diesel emissions sources (24%). Overall, PMF afforded better source identification than PCA with MLR. This work constitutes one of the few examples of the application of PMF to the source apportionment of sediments; the addition of sulfur heterocycles to the analyte list greatly aided in the source identification process.

Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in dated sediment cores.

Enantiomer fractions (EFs) of seven chiral polychlorinated biphenyls (PCBs) were measured in dated sediment cores of Lake Hartwell (SC, USA) and Lake Ontario (USA) to detect, quantify, and gain insight regarding microbial reductive dechlorination of PCBs in lake sediments with high and low concentrations, respectively. Lake Hartwell sediments had high total PCBs (5-60 microg/g), with significantly nonracemic EFs that generally were consistent with those from previous laboratory microcosm reductive dechlorination experiments using sediments from these sites. Thus, stereoselective reductive dechlorination had occurred in situ, including at total PCB concentrations of less than the threshold of approximately 30 to 80 microg/g suggested as being necessary for reductive dechlorination. Enantiomer fractions of PCBs 91, 95, 132, and 136 in Lake Hartwell cores were significantly correlated both with concentrations of those individual congeners and with total PCB concentration for some sites. This result indicates that enantioselective microbial dechlorination activity increases with higher concentrations within sediments for these congeners. Enantiomer composition reversed with depth for PCBs 91, 132, and 176, suggesting that multiple microbial populations may be present within the same core that are enantioselectively dechlorinating PCBs. Such observations indicate that concentration and time are not the only factors affecting biotransformation, complicating prediction of enantioselectivity. Comparison of EFs with dates suggested biotransformation half-lives of approximately 30 years, which is on the same time scale as sequestration by burial. In contrast, Lake Ontario sediments (maximum total PCBs, 400 ng/g) had racemic or near-racemic amounts of most congeners throughout the core profile, which is consistent with achiral indicators suggesting no microbial biotransformation within Lake Ontario sediments. Thresholds for reductive dechlorination may exist, but they would be at concentrations of less than 30 to 80 microg/g.

Analytical methods in bioassay-directed investigations of mutagenicity of air particulate material.

The combination of short-term bioassays and analytical chemical techniques has been successfully used in the identification of a variety of mutagenic compounds in complex mixtures. Much of the early work in the field of bioassay-directed fractionation resulted from the development of a short-term bacterial assay employing Salmonella typhimurium; this assay is commonly known as the Ames assay. Ideally, analytical methods for assessment of mutagenicity of any environmental matrix should exhibit characteristics including high capacity, good selectivity, good analytical resolution, non-destructiveness, and reproducibility. A variety of extraction solvents have been employed in investigations of mutagenicity of air particulate; sequential combination of dichloromethane followed by methanol is most popular. Soxhlet extraction has been the most common extraction method, followed by sonication. Attempts at initial fractionation using different extraction solvents have met with limited success and highlight the need for fractionation schemes applicable to moderately polar and polar mutagenic compounds. Fractionation methods reported in the literature are reviewed according to three general schemas: (i) acid/base/neutral partitioning followed by fractionation using open-column chromatography and/or HPLC; (ii) fractionation based on normal-phase (NP) HPLC using a cyanopropyl or chemically similar stationary phase; and (iii) fractionation by open-column chromatography followed by NP-HPLC. The HPLC methods may be preparative, semi-preparative, or analytical scale. Variations based on acid/base/neutral partitioning followed by a chromatographic separation have also been employed. Other lesser-used approaches involve fractionation based on ion-exchange and thin-layer chromatographies. Although some of the methodologies used in contemporary studies of mutagenicity of air particulate do not represent significant advances in technology over the past 30 years, their simplicity, low cost, effectiveness, and robustness combine to result in their continued application in modern laboratories.

Refined tunable methodology for characterization of contaminant-particle relationships in surface water.

To understand contaminant transport in aquatic systems, it is essential to define the physical characteristics of the primary particulate carriers. The distribution of organic pollutants with particle-size class and particle morphology in a freshwater embayment (Hamilton Harbor, western Lake Ontario) was studied using a sequence of novel sample preparation and characterization techniques. Water samples (24 L) were fractionated according to particle-size distribution using differential cascade sedimentation and centrifugation methods. These size fractions were subsequently subjected to a physicochemical characterization using scanning transmission electron microscopy and energy-dispersive spectroscopy to identify flocs and individual colloidal particles in the size range of 1 nm to 1 mm in diameter. Analytical chemical analyses were performed to identify organic contaminants in extracts prepared from particle-size classes, including polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The contaminant distribution trends were very similar for all compound classes studied; contaminants were primarily associated with fractions containing particles less than 2 mum in diameter. Morphological characterization of these fractions showed the majority of the particulates to be humic fractals. The results of this study show that contaminants in aquatic systems can be preferentially associated with specific types of particle carriers, the characteristics of which can be clearly defined in terms of size and morphology.

Trends in spatial and temporal levels of persistent organic pollutants in Lake Erie sediments.

A Lake Erie sediment survey was conducted in 1997 to characterize spatial trends in contamination, and for comparison with a 1971 survey to assess any changes in environmental quality since the advent of measures to reduce contaminant sources. Contaminant data for some contaminant classes in 1971 was based on analysis of frozen archived samples, thereby allowing a direct comparison between surficial sediment contamination in 1971 and 1997 based on modern analytical methods. Lake-wide contaminant concentrations of polychlorinated biphenyls (PCBs) and organochlorine compounds including hexachlorobenzene and the DDT compounds in 1997 were substantially lower, compared to levels in samples collected in 1971. Lake-wide average sediment PCB levels were found to have decreased roughly 70% from 136 ng/g in 1971 to 43 ng/g in 1997. Similarly, reductions in other compound classes ranged from 40% to 80%. In 1997, some individual contaminants classes including PCBs exhibited a spatial trend toward increasing sediment contamination from the eastern basin to the western basin, and from the north-central basin to the south-central basin. Levels of organic contaminants in sediments in some areas of Lake Erie still exceeded the strictest Canadian Federal and Ontario Provincial guidelines. However, exceedances of guidelines describing contaminated environments in 1997 were predominantly restricted to the western basin and near-shore sites in the southern part of the central basin.

Polychlorinated dibenzo-p-dioxins and dibenzofurans and dioxinlike polychlorinated biphenyls in sediments and mussels at three sites in the lower Great Lakes, North America.

Levels of contaminants including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho-substituted and mono-ortho-substituted dioxinlike polychlorinated biphenyls (DLPCBs) were determined in sediments and freshwater mussels (Dreissena spp. and Elliptio complanata) at three sites in the lower Great Lakes (North America). Impacts of mussel colonization on sediment quality were investigated by comparing contaminant levels in colonized sediment with levels in sediment in the same area that was not colonized, but exposed to similar environmental conditions. Significant impacts on contaminant levels of colonized sediment, compared to noncolonized sediment, were observed at two sites exhibiting high mussel population densities (Fort Erie, eastern Lake Erie, ON, Canada, 2.2 kg/m2 dry wt biomass, and Port Dalhousie, western Lake Ontario, Ontario, Canada, 6.1 kg/m2 dry wt biomass); these differences were not observed at a site with lower mussel densities (Bay of Quinte, eastern Lake Ontario, Ontario, Canada, 0.7 kg/m2). Total organic carbon and contaminant concentrations were statistically significantly greater in colonized sediment, compared to noncolonized sediment, at the two impacted sites. Areal estimates of PCDD/PCDF and DLPCB toxicity equivalents (TEQs) in mussel biomass at the three sites averaged 0.16% and 3.3%, respectively, of the TEQs in the top 3 cm of sediment, indicating that the sediments were the primary sink for contaminants. The observed differences between colonized and noncolonized sediment suggest that Dreissena are capable of influencing the chemical properties of sediment they colonize.

Distribution of haloacetic acids in the water columns of the Laurentian Great Lakes and Lake Malawi.

Haloacetic acids (HAAs) are persistent and mildly phytotoxic compounds that have been detected in many aquatic environments, including the waters of the Great Lakes. Sources of HAAs, especially of trifluoroacetic acid (TFA), are not well understood. In this study we assessed the influence of urbanization on the concentrations and profiles of HAAs in the Laurentian Great Lakes and in Lake Malawi, an African Great Lake. Vertical depth profiles for these compounds were taken for each of the Great Lakes with additional profiles taken 2 years later for Lakes Erie and Ontario. The results showed that while TFA was relatively constant throughout the water column, the chloroacetic acids (CAAs) varied with depth. There was a trend of increasing TFA proceeding from Lake Superior to Lake Ontario (18-150 ng/L). Total CAA concentrations were relatively constant throughout the lakes (approximately 500 ng/L) with dichloroacetic acid being the most abundant. No bromoacetic acids were detected. In the Detroit River, a connecting channel between Lakes Huron and Erie, the TFA values were similar to those in Lake Huron, but the CAAs levels were higher than in the upstream lakes and dependent on location, indicating inputs from urban areas along the river. These results were compared to those from Lake Malawi, which has a high population density within the watershed but no heavy industry. CAAs were nondetectable, and TFA concentrations were just at the detection limit (1 ng/L). Total HAA in the water column of Lakes Superior and Huron was compared to annual precipitation inputs at a site situated near both lakes. For Lake Huron, precipitation was a minor contributor to the total HAA inventory of the lake, but for Lake Superior precipitation could be the major contributor to the mass of HAA in this lake. Generally, high HAA levels paralleled the degree of industrial activity in the adjacent waters.