NP, OP and Derivatives in Freshwater Sediment Downstream of Textile Associated Municipal Wastewater Discharges.

Alkylphenol ethoxylates comprise of many anthropogenic chemicals such as nonylphenol (NP), octylphenol (OP) and nonylphenol ethoxylates (NPEOs). The objectives of this study were to assess the frequency and magnitude of detections of 4-NP, OP and NPEOs in Canadian sediment downstream of textile associated municipal wastewater treatment plants (MWWTPs) to determine if regulatory actions have had a beneficial impact on the receiving environment. Surficial sediments were obtained in four locations in the province of Québec (Canada) and were analyzed for nonylphenol, nonylphenol monoethoxylates (NP1EO), nonylphenol diethoxylates (NP2EO) and octylphenol from 2015 to 2018. Individual concentrations of the compounds varied from non detect to 419 ng/g. Of the four compounds analyzed, NP was detected the most frequently with a 75% detection rate while OPs were not detected in any of the samples. Since the Canadian regulatory actions have drastically reduced NP/NPEOs usage in textile mill factories and manufactured products, the potential source of these compounds in sediment for this study could stem from the outfall from the MWWTPs but not related to textile mills as well as from the usage of these compounds as formulants in pesticide products. Lastly, there were no exceedances to the Canadian Sediment Quality guideline toxic equivalency approach (TEQ) of 1400 ng/g or the 1310 ng/g guideline for NP in freshwater sediment from the European Scientific Committee on Health, Environmental and Emerging Risks. We hypothesize that the significant concentrations of these compounds in sediment may be a relevant and continuous source of 4NP in surface waters due to resuspension of sediment in the water column.

Perfluoroalkyl Substances (PFASs) in the Canadian Freshwater Environment.

Per- and polyfluoroalkyl substances (PFASs) are anthropogenic substances that are very stable in the receiving environment. Legacy perfluoroalkane sulfonates (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) are especially persistent and resistant to typical environmental degradation processes and therefore are distributed across all trophic levels and environmental compartments (soil, air, water). Since most uses of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and LC-long-chain PFCAs are banned in Canada, alternative PFASs have been in use for a number of years. Twenty-nine sites across Canada were sampled for PFASs to determine concentrations and trends. Overall, 13 PFASs were measured in 566 Canadian freshwater samples from 2013 to 2020 with a range from below the detection limit (LOD range: 0.4-1.6 ng/L) of the laboratory to a maximum of 138 ng/L (for PFBS). While PFOS and PFOA concentrations are declining significantly over time, other compounds such as PFPeA and PFBA have increased significantly over 2013-2020. Overall, the range of concentrations found in this study was similar to that of other Canadian and international studies. However, this study also found a higher frequency of detections of the replacement PFASs than that of the other, older, Canadian studies.

Nonylphenol, Octylphenol, and Nonylphenol Ethoxylates Dissemination in the Canadian Freshwater Environment.

Nonylphenol, octylphenol, and nonylphenol ethoxylates are manmade compounds that are only discharged in the environment due to anthropogenic activities. The objectives of this study were to determine the current concentrations of these substances in the Canadian freshwater environment and to determine if past regulatory actions were beneficial to the environment. Freshwater samples (n = 241) were collected and analysed for 4-nonylphenols (NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), and octylphenols at 35 sites in Canada from 2014 to 2019 with individual compound concentrations ranging from 1.29 to 477.22 ng/L. In addition, 18-65% of the samples were reported to be under the laboratory detection limit, depending on the compound. Sampling sites were categorised into five groups based on the dominant activities present upstream in their watersheds: mixed use sites; municipal waste water treatment plant (MWWTP)-associated sites; textile mill-associated sites; urban; and reference sites. All four compounds in the study were detected more frequently in urban and MWWTP-associated sites than at other locations. Additionally, there is a statistically significant (p < 0.05) downward temporal trend in NP concentrations in Canadian surface waters from 2014 to 2019. There were no exceedances of the Canadian Water Quality Guideline of 1000 ng/L.

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.

Temporal and Spatial Analysis of Surface Water Pesticide Occurrences in the Maritime Region of Canada.

This study measured both nutrient and pesticide concentrations at up to 13 different freshwater stream sites in New Brunswick, Nova Scotia and Prince Edward Island between 2013 and 2018. Up to 62 different pesticides were analysed in 248 discreet samples. A large majority of pesticides were below the detection limit of the laboratory while seven pesticides had at least 20% or more detections throughout the years of this study. The four pesticides that had the highest frequency of detection were the insecticides chlorantraniliprole, clothianidin, imidacloprid, and thiamethoxam of which the last three are categorised as neonicotinoid insecticides.

Spatial and Temporal Distribution of BPA in the Canadian Freshwater Environment.

Bisphenol A (BPA) is a manmade chemical that is only found in the environment due to anthropogenic activities. A total of 1150 surface freshwater samples were collected and analysed for BPA at 44 sampling sites in Canada from 2012 to 2018. The resultant concentrations ranged from 3.05 to 1888.51 ng/L. In addition, 64% of the samples were reported to be under the detection limit of the laboratory. In comparison, the Federal Environmental Quality Guideline for the protection of aquatic life is 3500 ng/L. Sampling sites were categorised into four groups based on the dominant activities present upstream in their watersheds: reference sites, mixed use sites, urban sites, and municipal waste water treatment plants (MWWTP) associated sites. Based on the results of this study, detections of BPA in water samples were more frequent in urban and MWWTP-associated sites. Additionally, there does not seem to be a statistically significant temporal (upward or downward) or spatial trend in BPA concentrations in Canadian surface waters from 2012 to 2018 only. Overall, Canadian BPA results are of similar concentrations to that of other countries in Asia and Europe.

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.

Formaldehyde concentration in discharge from land based aquaculture facilities in Atlantic Canada.

Formaldehyde is used in freshwater aquaculture facilities in the Maritimes region of Canada to prevent external parasites and is discharged without treatment to freshwater receiving environments. In this study, formaldehyde was measured at effluent outfalls and 100 m downstream of four land based aquaculture facilities at various post-treatment time intervals. Concentrations of formaldehyde ranged from 0.2 to 7.1 mg/L. Based on Environment Canada's environmental no effect value, all of the samples show a potential risk to aquatic life. Furthermore, based on a chronic aquatic life water quality criterion of 1.61 mg/L all but two of the samples had concentrations considered to be toxic to aquatic life. An acute water quality criteria was only exceeded once in all of the environmental measurements of formaldehyde. These results lead us to hypothesize that the discharge of formaldehyde from land-based facilities may cause adverse chronic impacts.

Assessing the genotoxic potential of chlorothalonil drift from potato fields in Prince Edward Island, Canada.

Chlorothalonil, a broad-spectrum nonsystemic foliar fungicide, is one of the most extensively used pesticide active ingredients on Prince Edward Island, Canada, for blight control on potatoes. In ambient air-sampling programs conducted in 1998 and 1999 and from 2002 to 2004, chlorothalonil was measured in 97% of air samples collected. It is known to produce severe eye and skin irritation, is cytogenic and is considered a possible human carcinogen by the United States Environmental Protection Agency and the International Agency for Research on Cancer. Inhalation studies that quantify chlorothalonil subchronic effects (e.g., genotoxicity) are lacking. The purpose of this study was to assess the possible genotoxic potential of chlorothalonil under field conditions by using the alkaline comet assay to assess DNA damage in CD-1 mice. Mice were selected as a surrogate species for wild small mammals (e.g., meadow voles, deer mice) known to inhabit areas adjacent to potato fields. Mice were placed at three locations downwind of a chlorothalonil application (0, 30, and 100 m) and at one up-wind control location at least 30 m from the field. Downwind mice were exposed to drift throughout the spray period (approximately 30 min) and for an additional hour after spraying. Air samples were collected during the spray trials (before, during, and after spraying) using high-volume polyurethane foam and PM(2.5) air samplers. Pesticide deposits were measured using 20 × 25 cm glass-fibre filters. After exposure, blood was collected from each mouse, and DNA strand breaks in white blood cells measured using comet assay. Results suggest that metrics of DNA damage [tail length (TL), percent DNA in tail] were not significantly related to total air chlorothalonil concentration from the three spray trials (r (2) = 0.000, P = 0.907 for TL; r (2) = 0.001, P = 0.874 for percent DNA). In addition, no significant difference in DNA damage was observed between exposed (at 0 m) and control animals (P = 0.357 for TL; P = 0.958 for percent DNA). Based on these results it can be concluded that wild small mammals living beside fields sprayed with chlorothalonil are at no greater risk of exposure-related DNA damage than conspecifics from unexposed areas.

Concentrations and environmental risk of chlorothalonil in air near potato fields in Prince Edward Island, Canada.

BACKGROUND: Chlorothalonil is used extensively in Prince Edward Island for the control of blight on potatoes, and has been measured throughout summer months in ambient air monitoring studies. This study was designed to characterize near-field drift of chlorothalonil, and to evaluate how exposure to measured air concentrations might impact upon local wildlife species. RESULTS: Air samples were collected using high-volume samplers at three distances downwind of sprayed potato fields, and at four different time intervals. Chlorothalonil was detected in 73% of prespray samples (from < 0.013 to 0.440 µg m(-3)). The mean air concentration 0 m away from the field edge during spray was 5.8 µg m(-3), which was 7-41 times higher than concentrations measured in similar studies. Air concentrations were found to decline exponentially both with distance and time, although 0 m and 30 m concentrations at 2 h post-spray remained significantly (3 times) higher than prespray (P < 0.05). Wind speed was not found to be significantly correlated with air concentration; however, increases in temperature were found to be significantly correlated with increases in air concentrations at all sample times, at 0 m and 30 m distances. CONCLUSION: Frequent prespray detections and high post-spray concentrations suggest that both chronic and acute exposures to non-target species are occurring; however, risk calculations suggest a relatively low risk of effects to representative species. One measurement showed that a human-health-based short-term guideline had been exceeded, indicating that potential impacts to humans from chlorothalonil under current application conditions cannot be discounted.

Near-field air concentrations of pesticides in potato agriculture in Prince Edward Island.

BACKGROUND: Pesticides in air have become of increasing concern in recent years. This study examined downwind air concentrations of carbofuran, methamidophos, mancozeb and diquat dibromide resulting from spray drift within 24 h of application, within 100 m of potato fields. RESULTS: Concentrations ranged from less than 0.05 microg m(-3) in prespray samples to 6.37 microg m(-3) for methamidophos at 3 h post-spray. For most applications, air concentrations decreased with distance from the field and with time after application. Methamidophos concentrations in the air downwind continued to increase up to 3 h after spray. Air concentrations during spray were positively correlated with application rate (r = 0.904), and air concentrations at 1 h and 3 h post-spray were positively correlated with vapour pressure (r = 1.000 and r = 0.999 respectively). Carbofuran, methamidophos and diquat dibromide concentrations during spray were above some Canadian and international health protection guidelines. CONCLUSION: Although pesticide air concentrations measured in this study are generally consistent with other studies, maximum concentrations are greater than those that have been measured elsewhere, and some are above published air quality guidelines. An evaluation of the degree of risk posed by these and other pest control products to human and wildlife receptors is recommended.

Toxicity testing of sediment collected in the vicinity of effluent discharges from seafood processing plants in the maritimes.

There are over 1100 fish-processing plants in Canada and the majority of them discharge untreated effluents directly to marine or estuarine receiving environments. The purpose of this study was to evaluate chemical and toxicological characteristics of sediments near fish-processing plant effluent discharges to assess potential impacts of seafood-processing effluents on receiving environments. Eighteen sediment samples were collected near effluent discharges of six seafood-processing plant outfalls in New Brunswick, Canada in the winter of 2006. Ammonia levels ranged from <0.2 to 3480 microg/g, sulfide levels ranged from <0.4 to 6970 microg/g, and redox ranged from -255 to 443 mV. Only one sample had a Microtox Solid-Phase Test IC(50) value below 1000 mg/kg, whereas three samples caused greater than 30% reduction to amphipod survival. Redox, sulfide, and ammonia concentrations were all found to be significantly related to both Eohaustorius estuarius survival and Microto (Vibrio fischeri) IC(50). An increase in sulfide (R (2) = 0.584; 0.750) and ammonia (R (2) = 0.478; 0.552) and a decrease in redox (R (2) = 0.485; 0.651) were associated with an increase in toxicity to E. estuarius and Microtox, respectively. The highest toxicity to both test organisms, and the most contaminated sediments based on physical/chemical characteristics measured, was observed in samples from Blacks Harbour.

Ambient air concentrations of pesticides used in potato cultivation in Prince Edward Island, Canada.

Ambient air concentrations of nine selected pesticides used in potato cultivation were investigated on Prince Edward Island by collecting samples during the summer of 1998 at three potato farm sites and one non-agricultural site. In 1999, air samples were collected at a single potato farm site during local application of pesticides. The fungicide chlorothalonil was the only pesticide detected in every sample in both years, even in samples with a duration as little as 5 h. In 1998, maximum (45-458 ng m(-3)) and mean (22-193 ng m(-3)) concentrations of chlorothalonil from composite 42 h samples were one to two orders of magnitude greater at agricultural sites than at the non-agricultural site (3.9 and 2.5 ng m(-3), respectively). Maximum and mean concentrations of chlorothalonil from combined 24 h samples at the farm site in 1999 were higher than those measured in 1998 (636 and 284 ng m(-3), respectively). The ubiquitous presence in air of relatively high concentrations of chlorothalonil in agricultural areas on Prince Edward Island is likely related to its repeated use on potato farms where fungicides account for 80-90% of pesticides applied. Eight of nine pesticides were detected at farm sites in 1998 and they are ranked by mean concentration from highest to lowest as follows: chlorothalonil, methamidophos, azinphos-methyl, alpha-endosulfan, beta-endosulfan, pirimicarb, metobromuron, metribuzin, metalaxyl and fluazifop-P-butyl. Concentrations of metalaxyl, pirimicarb, metobromuron and fluazifop-P-butyl in air are among the first reported values for these pesticides. Five pesticides were detected at the Summerside farm in 1999, but only two fungicides (chlorothalonil and metalaxyl) were used locally, while the presence of metribuzin, alpha-endosulfan and methamidophos in air was not associated with local application. Evidence of pesticide drift was observed for chlorothalonil, alpha-endosulfan and methamidophos, and these pesticides were identified as being of high concern in terms of potential wildlife exposure on the Island.