Assessing Contributions of Synthetic Musk Compounds from Wastewater Treatment Plants to Atmospheric and Aquatic Environments.

The high environmental concentrations, persistence, and toxicity of synthetic musk compounds (SMCs) necessitate a better grasp of their fate in wastewater treatment plants (WWTPs). To investigate the importance of WWTPs as pathways of SMCs to the environment, air and wastewater samples were collected at four WWTPs in Ontario, Canada. Polycyclic musks (PCMs) were present at higher concentrations than nitro musks (NMs) and macrocyclic musks (MCMs). Three PCMs [galaxolide (HHCB), tonalide (AHTN), and iso-E super (OTNE)] were the most abundant compounds (0.30-680 ng/m3 in air, 0.40-15 µg/L in influent, and 0.007-6.0 µg/L in effluent). Analyses of multiyear data suggest that risk management measures put in place have been effective in reducing the release of many SMCs into the environment. The highest removal efficiency, up to almost 100% of some SMCs, was observed for the plant with the longest solid retention time. A fugacity-based model was established to simulate the transport and fate of SMCs in the WWTP, and good agreement was obtained between the measured and modeled values. These findings indicate that the levels of certain SMCs discharged into the atmospheric and aquatic environments were substantial, potentially resulting in exposure to both humans and wildlife.

Sources and environmental fate of halomethoxybenzenes.

Halomethoxybenzenes are pervasive in the atmosphere at concentration levels that exceed, often by an order of magnitude, those of the persistent organic pollutants with which they share the attributes of persistence and potential for long-range transport, bioaccumulation, and toxic effects. Long ignored by environmental chemists because of their predominantly natural origin-namely, synthesis by terrestrial wood-rotting fungi, marine algae, and invertebrates-knowledge of their environmental pathways remains limited. Through measuring the spatial and seasonal variability of four halomethoxybenzenes in air and precipitation and performing complementary environmental fate simulations, we present evidence that these compounds undergo continental-scale transport in the atmosphere, which they enter largely by evaporation from water. This also applies to halomethoxybenzenes originating in terrestrial environments, such as drosophilin A methyl ether, which reach aquatic environments with runoff, possibly in the form of their phenolic precursors. Our findings contribute substantially to the comprehension of sources and fate of halomethoxybenzenes, illuminating their widespread atmospheric dispersal.

Assessment of Alkylated and Unsubstituted Polycyclic Aromatic Hydrocarbons in Air in Urban and Semi-Urban Areas in Toronto, Canada.

22 alkylated polycyclic aromatic hydrocarbons (alk-PAHs) were characterized in ambient air individually for the first time in urban and semi-urban locations in Toronto, Canada. Five unsubstituted PAHs were included for comparison. Results from the measurements were used to estimate benzo[a]pyrene equivalent toxicity (BaPeq) of individual compounds in order to investigate the significance of a single compound in contributing to the overall toxic equivalency (TEQ) of air mixtures. To determine which compounds merit further investigation, BaPeq values of individual compounds were compared to the measured BaP toxicity. Our results showed that both unsubstituted and alkylated PAHs were more abundant in the urban area (38 and 30%, respectively). Benzo[a]pyrene levels at the urban location exceeded Ontario's 24 h guideline (40% of the events), and on average, it was 5 times higher than that at the semi-urban area. Gas-phase two- and three-ring compounds contributed up to 39% (urban) and 76% (semi-urban) of the TEQ of all compounds analyzed. Some alk-PAHs such as 7,12-dimethylbenzo[a]anthracene had a huge impact on the toxicity of urban air, and its BaPeq was on average 8 times higher than that of BaP. We emphasize that the toxic impact of alkylated and gaseous PAHs, which is not routinely included in many air monitoring programs, is significant and should not be neglected.

Multi-year Analyses Reveal Different Trends, Sources, and Implications for Source-Related Human Health Risks of Atmospheric Polycyclic Aromatic Hydrocarbons in the Canadian Great Lakes Basin.

Polycyclic aromatic hydrocarbons (PAHs) are of high concern to public health due to their carcinogenic and mutagenic properties. Here, we present the first comprehensive and quantitative analysis of sources, potential source regions according to source sectors and source-related human health risks of multi-year atmospheric measurements of PAHs in the Canadian Great Lakes Basin (GLB). The highest PAH concentrations were observed at a rural residential site (Egbert), followed by two regionally representative remote sites [Point Petre (PPT) and Burnt Island]. The levels of most PAHs in the GLB atmosphere significantly decreased between 1997 and 2017, broadly consistent with the decreasing trends of anthropogenic emissions. Coal, liquid fossil fuel, and biomass burning were the most common potential sources. The potential source regions for most source sectors were identified south or southwest of the sampling sites. Risk assessment suggests potential health risks associated with the inhalation of atmospheric PAHs. On a positive note, health risks from coal combustion, liquid fossil fuel combustion, and petrogenic sources at PPT significantly decreased, directly demonstrating the success of emission control in reducing health impacts. In contrast, the health risk from forest fire-related PAH emissions may play an increasing role in the future due to climate change.

Fugitive emissions of polycyclic aromatic compounds from an oil sands tailings pond based on fugacity and inverse dispersion flux calculations.

Alberta's oil sands tailings ponds are suspected to be a source of fugitive emissions of polycyclic aromatic compounds (PACs) to the atmosphere. Here we report, for the first time, fluxes of 6 parent and 21 alkylated PACs based on the measured co-located air and water concentrations using a two-film fugacity-based model (FUG), an inverse dispersion model (DISP) and a simple box model (BOX). Air samples were collected at the Suncor Tailings Pond 2/3 using a high volume air sampler from the "pond" and towards the pond ("non-pond") directions separately. Mean ∑27PACs in air from the "pond" direction was greater than the "non-pond" direction by a factor of 17. Water-air fugacity ratio of 20 PACs quantifiable in water indicated net volatilization from water. Dispersion and box model results also indicated upward fluxes of 22 PACs. Correlation between the estimated flux results of BOX and DISP model was statistically significant (r = 0.99 and p < 0.05), and correlation between FUG and DISP results ranged from 0.54 to 0.85. In this first-ever assessment of PAC fluxes from tailings pond, the three models confirmed volatilization fluxes of PACs indicating Suncor Tailings Pond 2/3 is a source of PAC emissions to the atmosphere. This study addressed a key data gap identified in the Joint Oil Sands Monitoring Emissions Inventory Compilation Report (Government of Alberta and Canada, 2016) which is the lack of consistent real-world tailings pond fugitive emission monitoring of organic chemicals. Our findings highlight the need for measurements from other tailings ponds to determine their overall contribution in releasing PACs to the atmosphere. This paper presents a practical method for estimating PAC emissions from other tailings ponds, which can provide a better understanding of these fugitive emissions, and thereby help to improve the overall characterization of emissions in the oil sands region.

Urban sources of synthetic musk compounds to the environment.

The occurrence and potential sources of synthetic musk compounds (SMCs) in the urban and surrounding environment were investigated. We analyzed air, soils and surface waters from a wide array of land-use types and urban densities including air from wastewater treatment plants (WWTPs), indoor, urban, rural, and remote Arctic sites; surface waters from urban and rural tributaries; and effluents of three WWTPs. In air, the median sum concentration of six selected polycyclic musks (Σ6PCMs) (i.e., galaxolide, tonalide, cashmeran, celestolide, phantolide, traseolide) were the highest from WWTP on-site > indoor > urban > WWTP off-site > rural. SMCs were not found in remote Arctic air indicating low potential for long-range atmospheric transport. SMCs were not found in soils, likely because of their high volatility and fast biodegradation rate. Galaxolide (HHCB) and tonalide (AHTN) were the two most abundant SMCs in air, tributaries and WWTP effluents. Σ6PCM concentrations in air taken along urban-rural transects and in tributary water were positively correlated with population density. In WWTP on-site air, trace levels of the toxic nitro-musks, namely musk xylene and musk ketone were detected and macrocyclic musks accounted for ∼10% of the total SMCs measured. In WWTP effluents, the concentrations of Σ6PCMs were proportional to the population served. We conclude that sources of SMCs to the outdoor urban environment and hence the surrounding region, originate from releases from indoor air, and temperature-dependent volatilization from WWTPs during treatment.

Temporal trends of halogenated flame retardants in the atmosphere of the Canadian Great Lakes Basin (2005-2014).

Organic pollutants have been monitored in the atmosphere of the Great Lake Basin (GLB) since the 1990s in support of the Canada-US Great Lakes Water Quality Agreement and to determine the effectiveness of source reduction measures and factors influencing air concentrations. Air samples were collected between 2005 and 2014 at three sites with different geographical characteristics (Burnt Island, Egbert and Point Petre) in the Canadian GLB using high-volume air samplers and the air samples were analyzed for polybrominated diphenyl ethers (PBDEs) and several other non-PBDE halogenated flame retardants (HFRs). Spatial and temporal trends of total concentrations of HFRs were examined. BDE-47, BDE-99, and BDE-209 were the dominant PBDE congeners found at the three sites. For the non-PBDE HFRs, allyl 2,4,6-tribromophenyl ether (TBP-AE), hexabromobenzene (HBBz), pentabromotoluene (PBT), anti-dechlorane plus (anti-DDC-CO) and syn-dechlorane plus (syn-DDC-CO) were frequently detected. High atmospheric concentrations of PBDEs were found at the Egbert site with a larger population, while lower levels of PBDEs were detected at Point Petre, which is close to urban centers where control measures are in place. The strong temperature dependence of air concentrations indicates that volatilization from local sources influences atmospheric concentrations of BDE-28 and BDE-47 at Point Petre and Burnt Island, while long-range atmospheric transport (LRAT) was important for BDE-99. However, a weaker correlation was observed between air concentrations and ambient temperature for non-PBDE HFRs such as TBP-AE and HBBz. Atmospheric PBDE concentrations are decreasing slowly, with half-lives in the range of 2-16 years. Faster declining trends of PBDEs were observed at Point Petre rather than at Burnt Island. As Point Petre is closer to urban centers, faster declining trends may reflect the phase out of technical BDE mixtures in urban centers while LRAT influences the air concentrations at Burnt Island. The levels of syn-DDC-CO and anti-DDC-CO are decreasing at Point Petre and the levels of other non-PBDE HFRs such as TBP-AE, PBT and HBBz are increasing. Long-term declining trends of PBDEs suggest that regulatory efforts to reduce emissions to the GLB environment have been effective but that continuous measurements are required to gain a better understanding of the trends of emerging chemicals in the atmosphere of the GLB.

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.

Multiyear Measurements of Flame Retardants and Organochlorine Pesticides in Air in Canada's Western Sub-Arctic.

Fourteen polybrominated diphenyl ethers (PBDEs), 14 non-BDE flame retardants (FRs), and 25 organochlorine pesticides (OCPs) were analyzed in air samples collected at Little Fox Lake (LFL) in Canada's Yukon Territory from August 2011 to December 2014. LFL is a long-term monitoring station operated under the Northern Contaminants Program (NCP) and one of only a few stations that contribute to the assessment of air pollution levels and pathways to the sub-Arctic region. BDE-47 was the most abundant congener among the 14 PBDEs, followed by BDE-99. Non-BDE FRs pentabromotoluene (PBT) and dechlorane plus (DP) were detected in all the samples. Dechlorane 602, 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), hexabromobenzene (HBB), and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) were also detected in >75% of all samples. PBDEs have shown a decreasing tendency as of 2013, which may reflect the phase-out of penta- and octa-BDE mixtures has led to significant decline in the atmosphere. The highest concentrations of OCPs were observed for hexachlorobenzene (HCB), with a median concentration of 61 pg/m(3), followed by α-hexachlorocyclohexane (α-HCH) and α-endosulfan. Potential source contribution function (PSCF) highlights Northern Canada, Pacific, and East Asia as potential sources in warm seasons; whereas in cold seasons, the chemicals mainly came from the Pacific Rim.

Atmospheric atrazine at Canadian IADN sites.

Atrazine is one of the most widely used herbicides in North America and has been primarily applied to corn production in the Great Lakes basin for over 30 years. During 1996-2002, atrazine concentrations in the atmospheric gas and particle phases were investigated at three Canadian Integrated Atmospheric Deposition Network (IADN) sites including two lakeside sites (Burnt Island and Point Petre) and a rural inland site (Egbert). Strong seasonality with peak concentrations occurring in late April-early July was observed. An atrazine usage map for Canada (sum: 870 t) and the United States (sum: 34 500 t) in 2002 was created. Local application and regional atmospheric transport both appear to contribute to its atmospheric occurrence, while the latter might episodically result in high concentrations events. No strong temperature dependence was observed for atrazine particle-gas partitioning. Recent measurement results of atrazine in precipitation samples collected at Egbert and another agricultural site, Vineland, through the Canadian Atmospheric Network for Currently Used Pesticides (CANCUP), are also presented, Dry, wet, and gas exchange deposition all contribute to atmospheric inputs of atrazine to the Great Lakes. For Lake Ontario, gas exchange is estimated to be of similar magnitude to dry and wet deposition.