Polycyclic aromatic compounds (PACs) in Canadian air and deposition were examined at the national scale for the first time in over twenty-five years. Air concentrations spanned four orders of magnitude, and were highest near industrial emitters and lowest in the Arctic. Declines in unsubstituted PAHs were observed at locations close to industrial facilities that had reduced emissions, but trends elsewhere were modest or negligible. Retene concentrations are increasing at several locations. Ambient concentrations of benzo[a]pyrene exceeded Ontario’s health-based guideline in many urban/industrial areas. The estimated toxicity of the ambient PAC mixture increased by up to a factor of six when including compounds beyond the US EPA PAHs. Knowledge of PAC deposition is limited to the Laurentian Great Lakes and Athabasca Oil Sands regions. The atmosphere remained a net source of PAHs to the Great Lakes, though atmospheric inputs were decreasing with halving times of 26–30 years. Chemical transport modelling substantially overestimated wet deposition, but model performance is unknown for dry deposition. Sources from Asia, Europe and North America contributed to Arctic and Sub-Arctic concentrations, whereas transboundary or long-range transport have not been assessed outside Canada’s north. Climate-related impacts from re-emission and forest fires were implicated in maintaining air concentrations in the high Arctic that were not consistent with global emissions reductions. Industrial emission decreases were substantial at the national scale, but their influence on the environment was limited to areas near relevant facilities. When examined through the lens of ambient levels at the local scale, evidence suggested that contributions from residential wood combustion and motor vehicles were smaller and larger, respectively, than those reported in national inventories. Future work aimed at characterizing PACs beyond the EPA PAHs, improving measurement coverage, elucidating deposition phenomena, and refining estimates of source contributions would assist in reducing remaining knowledge gaps about PACs in Canada.

Many types of contaminants of emerging concern (CECs), including per- and poly-fluoroalkyl substances (PFAS), have been found in leachate of operating municipal landfills. However, there is only limited information on CECs presence in leachate of historic landfills (≥3 decades since closure, often lacking engineered liners or leachate collection systems) at concentrations that may pose a risk to nearby wells and surface water ecosystems. In this study, 48 samples of leachate-impacted groundwater were collected from 20 historic landfills in Ontario, Canada. The CECs measured included artificial sweeteners (ASs), PFAS, organophosphate esters (OPE), pharmaceuticals, bisphenols, sulfamic acid, perchlorate, and substituted phenols. The common presence of the AS saccharin, a known indicator of old landfill leachate, combined with mostly negligible levels of the AS acesulfame, an indicator of modern wastewater, revealed that most samples were strongly influenced by leachate and not cross-contaminated by wastewater (which can contain these same CECs). Several landfills, including ones closed in the 1960s, had total PFAS concentrations similar to those previously measured at modern landfills, with a maximum observed here of 12.7 μg/L. Notably elevated concentrations of several OPE, sulfamic acid, cotinine, and bisphenols A and S were found at many 30-60 year-old landfills. There was little indication of declining concentrations with landfill age, suggesting historic landfills can be long-term sources of CECs to groundwater and that certain CECs may be useful tracers for historic landfill leachate. These findings provide guidance on which CECs may require monitoring at historic landfill sites and wastewater treatment plants receiving their effluent.

Mine tailings are found worldwide and can have significant impacts on ecosystem and human health. In this study, natural vegetation patterns on arsenical (As) gold (Au) mine tailings located in Sudbury, Ontario were assessed using transects located at the edge of the tailings and on the tailings. Vegetation communities were significantly different between the edge and open tailings areas of the site. Arsenic concentrations in both areas were extremely variable (from 285-17,567 mg/kg) but were not significantly correlated with vegetation diversity at the site. Nutrients (carbon (C), phosphorus (P)) and organic matter concentrations were associated with higher diversity and with the presence of climax vegetation on the tailings, but there were no significant relationships between tailings chemistry and vegetation indices on the edge. Encroachment onto the tailings from the edge occurred in conventional succession patterns, with a clear gradient from grasses (Agrostis gigantea) to trees such as Picea glauca. On the tailings, a nucleation pattern was visible, distinct from conventional succession. Trees and shrubs such as Betula papyrifera and Diervilla lonicera were associated with higher diversity and higher nutrient concentrations in the underlying tailings, whereas grasses such as A. gigantea were not. We concluded that at all areas of the site, vegetation - particularly trees - was facilitating amelioration of the underlying tailings. Despite high concentrations of As, nutrients appeared to have a greater influence than metals on vegetation diversity.

Organophosphate esters (OPEs) are high-production volume chemicals. Use of OPEs has largely increased since the phase-out/ban of polybrominated diphenyl ethers (PBDEs). The ubiquitous occurrence of OPEs, in higher concentrations in abiotic matrices than brominated flame retardants (BFRs), is a concern because several of the OPEs have been linked to adverse health effects. In this study, urinary metabolites of OPEs were measured in a subset of a population-based sample of women of child bearing age recruited in Ontario, and associations between serum lipid levels and urinary concentrations of OPE metabolites were evaluated. Urine samples (n = 120) were extracted using automated solid phase extraction and analysed by ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS). Diphenyl phosphate (DPHP), bis(2-chloropropyl) phosphate (BCIPP) and bis(1,3-dichloro-2 propyl) phosphate (BDCIPP) were detected with frequencies of 100%, 76% and 75% at median concentrations of 13.8 ng/mL, 0.5 ng/mL and 1.8 ng/mL, respectively. Bis(2-chloroethyl) hydrogen phosphate (BCEP) and di-cresyl phosphate (DCP; mixture of 3 isomers) were detected in 52% and 42% of the samples, respectively. Detected at lower frequencies were 1-hydroxy-2-propyl bis(1-chloro-2-propyl) phosphate (BCIPHIPP, 29%), bis-2(butoxyethyl) phosphate (BBOEP, 11%), and desbutyl-tris-(2-butoxy-ethyl) phosphate (desbutyl TBOEP, 9%). Using multiple regression model, a negative statistically significant correlation was observed between BCEP and cholesterol (p = 0.04), as well as BCEP and total lipid (p = 0.04). Whereas BCIPP was positively and significantly correlated with cholesterol (p = 0.003) and LDL (p = 0.001). Additional work to further explore these relationships and to evaluate more recently identified OPE metabolites is warranted.

Eating fish provides numerous health benefits, but it is also a dominant pathway for human exposure to contaminants. Many studies have examined mercury (Hg) accumulation in fish, but fewer have considered other elements, such as arsenic (As) and chromium (Cr). Recently, freshwater fish from several pristine boreal systems across northern Ontario, Canada, have been reported with elevated concentrations of As and Cr for reasons that are not well understood. Our goal was to investigate the ecological and environmental influences over concentrations of As, Cr, and other elements in these fish to better understand what affects metal uptake and the risk to consumers. We measured 10 elements (including As, Cr, Hg) as well as carbon (δ¹³C), nitrogen (δ¹⁵N), and sulfur (δ³⁴S) stable isotopes in 388 fish from 25 lake and river sites across this remote region. These data were used to determine the effect of: 1) trophic ecology; and 2) watershed geology on piscine elemental content. Overall, most element concentrations were low, often below provincial advisory benchmarks (ABs). However, traces of Hg, As, Cr, and selenium (Se) were detected in most fish. Based on their exceedance of their respective ABs, the most restrictive elements on fish consumption in these boreal systems were Hg > As > Cr. Arsenic and Se, but not Cr concentrations were related to fish size and trophic ecology (inferred from δ¹³C and δ¹⁵N), suggesting bioaccumulation of the former elements. Fish with enriched δ³⁴S values, suggestive of anadromous behaviour, had marginally lower Hg but higher Se concentrations. Modeling results suggested a strong effect of site-specific factors, though we found weak trends between piscine elemental content and geological features (e.g., mafic intrusions), potentially due to the broad spatial scale of this study. Results from this study address gaps in our understanding of As and Cr bioaccumulation and will help to inform fish consumption guidelines.

In temperate urbanized areas where road salting is used for winter road maintenance, the level of chloride in surface waters has been increasing. While a number of studies have shown that the early-life stages of freshwater mussels are particularly sensitive to salt; few studies have examined the toxicity of salt-impacted winter road runoff to the early-life stages of freshwater mussels to confirm that chloride is the driver of toxicity in this mixture. This study examines the acute toxicity of field-collected winter road runoff to the glochidia of wavy-rayed lampmussels (Lampsilis fasciola) (48 h exposure) and newly released juvenile fatmucket mussels (Lampsilis siliquoidea) (<1 week old; 96 h exposure) under different water hardness. The chronic toxicity (28 d) to older juvenile L. siliquoidea (7–12 months old) was also investigated. The 48-h EC50 and 96-h LC50 for L. fasciola glochidia and L. siliquoidea juveniles exposed to different dilutions of road run-off created with moderately hard synthetic water (∼80 mg CaCO3/L) were 1177 (95% confidence interval (CI): 1011–1344 mg Cl−/L) and 2276 mg Cl−/L (95% CI: 1698–2854 mg Cl−/L), respectively. These effect concentrations correspond with the toxicity of chloride reported in other studies, indicating that chloride is likely the driver of toxicity in salt-impacted road-runoff, with other contaminants (e.g., metals, polycyclic aromatic hydrocarbons) playing a de minimis role. Toxicity data from the current study and literature and concentrations of chloride in the surface waters of Ontario were used to conduct a probabilistic risk assessment of chloride to early-life stage freshwater mussels. The assessment indicated that chronic exposure to elevated chloride levels could pose a risk to freshwater mussels; further investigation is warranted to ensure that the most sensitive organisms are protected.

Yellow perch (Perca flavescens) collected from 11 lakes in the Canadian mining regions of Sudbury (Ontario) and Rouyn-Noranda (Quebec) display wide ranges in the concentrations of cadmium (Cd), nickel (Ni), selenium (Se), and thallium (Tl) in their livers. To determine if these trace elements, as well as copper (Cu) and zinc (Zn), are causing oxidative stress in these fish, we measured three biochemical indicators (glutathione (GSH), glutathione disulfide (GSSG) and thiobarbituric acid-reactive substances (TBARS)) in their livers. We observed that 44% of the yellow perch that we collected were at risk of cellular oxidative stress and lipid peroxidation. Considering all fish from all lakes, higher liver Se concentrations were coincident with both lower proportions of GSSG compared to GSH and lower concentrations of TBARS, suggesting that the essential trace-element Se acts as an antioxidant. Furthermore, fish suffering oxidative stress had higher proportions of Cd, Cu and Zn in potentially sensitive subcellular fractions (organelles and heat-denatured proteins) than did fish not suffering from stress. This result suggests that reactive oxygen species may oxidize metal-binding proteins and thereby reduce the capacity of fish to safely bind trace metals. High Cd concentrations in metal-sensitive subcellular fractions likely further exacerbate the negative effects of lower Se exposure.

Wetlands are prevalent in the Sudbury, Ontario region and often operate at the interface between terrestrial and aquatic ecosystems, modifying water chemistry and potentially affecting the recovery of impacted lakes. The deposition of metals and sulphur in Sudbury in 2010–2012 was far below that reported in the 1970's, but still higher than background values. Wetlands in the area have accumulated large quantities of metals, and high concentrations of these metals in streams occurred primarily in response to SO4-related acidification events or associated with high dissolved organic carbon production in early summer. Concentrations of most metals in streams exceeded provincial guidelines and fluxes of some metals from catchments exceeded deposition inputs to lakes by as much as 12 times. The release of metals long after emissions reductions have been achieved must be considered in ecosystem recovery studies, particularly as dry conditions may become more prevalent in boreal regions affected by mining.