[en] Haloacetic acids (HAAs) are contaminants of aquatic ecosystems with numerous sources, both anthropogenic and natural. The toxicity of HAAs to aquatic plants is generally uncharacterized. Laboratory tests were conducted with three macrophytes (Lemna gibba, Myriophyllum sibiricum and Myriophyllum spicatum) to assess the toxicity of five HAAs. Myriophyllum spp. has been proposed as required test species for pesticide registration in North America, but few studies have been conducted under standard test conditions. The HAAs in the present experiments were monochloroacetic acid (MCA), dichloroacetic acid (DCA), trichloroacetic acid (TCA), trifluoroacetic acid (TFA) and chlorodifluoroacetic acid (CDFA). MCA was the most toxic to Myriophyllum spp. with EC₅₀ values ranging from 8 to 12.4 mg/l depending on the endpoint, followed by DCA (EC₅₀ range 62-722.5 mg/l), TCA (EC₅₀ range 49.5-1702.6 mg/l), CDFA (EC₅₀ range 105.3 to >10,000 mg/l) and with TFA (EC₅₀ range 222.1 to 10,000 mg/l) the least toxic. Generally, L. gibba was less sensitive to HAA toxicity than Myriophyllum spp., with the difference in toxicity between them approximately threefold. The range of toxicity within Myriophyllum spp. was normally less than twofold. Statistically, plant length and node number were the most sensitive endpoints as they had the lowest observed coefficients of variation, but they were not the most sensitive to HAA toxicity. Toxicological sensitivity of endpoints varied depending on the measure of effect chosen and the HAA, with morphological endpoints usually an order of magnitude more sensitive than pigments for all plant species. Overall, mass and root measures tended to be the most sensitive indicators of HAA toxicity. The data from this paper were subsequently used in an ecological risk assessment for HAAs and aquatic plants. The assessment found HAAs to be of low risk to aquatic macrophytes and the results are described in the second manuscript of this series. - Monochloroacetic acid was the most toxic form to aquatic macrophytes

[en] Haloacetic acids (HAAs) are environmental contaminants found in aquatic ecosystems throughout the world as a result of both anthropogenic and natural production. The ecological risk posed by these compounds to organisms in freshwater environments, with a specific focus on aquatic macrophytes, was characterized. The plants evaluated were Lemna gibba, Myriophyllum spicatum and M. sibiricum and the HAAs screened were monochloroacetic acid (MCA), dichloroacetic acid (DCA), trichloroacetic acid (TCA), trifluoroacetic acid (TFA) and chlorodifluoroacetic acid (CDFA). Laboratory toxicity data formed the basis of the risk assessment, but field studies were also utilized. The estimated risk was calculated using hazard quotients (HQ), as well as effect measure distributions (EMD) in a modified probabilistic ecological risk assessment. EMDs were used to estimate HAA thresholds of toxicity for use in HQ assessments. This threshold was found to be a more sensitive measure of low toxicity than the no observed effect concentrations (NOEC) or the effective concentration (EC₁₀). Using both deterministic and probabilistic methods, it was found that HAAs do not pose a significant risk to freshwater macrophytes at current environmental concentrations in Canada, Europe or Africa for both single compound and mixture exposures. Still, HAAs are generally found as mixtures and their potential interactions are not fully understood, rendering this phase of the assessment uncertain and justifying further effects characterization. TCA in some environments poses a slight risk to phytoplankton and future concentrations of TFA and CDFA are likely to increase due to their recalcitrant nature, warranting continued environmental surveillance of HAAs. - Current environmental concentrations of haloacetic acids do not pose a risk to aquatic macrophytes, but could impact plankton

[en] Embryonic growth of the yellow-spotted salamander (Ambystoma maculatum) is enhanced by the presence of the green alga Oophila amblystomatis, in the egg capsule. To further assess potential impacts of herbicides on this relationship, A. maculatum egg masses were exposed to atrazine (0–338 μg/L) until hatching (up to 66 days). Exposure to atrazine reduced PSII yield of the symbiotic algae in a concentration-dependent manner, but did not significantly affect visible algal growth or any metrics associated with salamander development. Algal cells were also cultured in the laboratory for toxicity testing. In the 96-h growth inhibition test (0–680 μg/L), ECx values were generally greater than those reported for standard algal test species. Complete recovery of growth rates occurred within 96-h of transferring cells to untreated media. Overall, development of A. maculatum embryos was not affected by exposure to atrazine at concentrations and durations exceeding those found in the environment. - Highlights: • The yellow-spotted salamander produces eggs that are colonized by a symbiotic green alga. • We tested the sensitivity of this system to the herbicide atrazine. • Embryo development was not significantly affected by exposure at up to 300 μg/L. • The alga was isolated and 96-h growth tests were performed in the laboratory. • EC50s for Oophila sp. were >100 μg/L. - Development of Ambystoma maculatum embryos in egg masses was not impacted by exposure to atrazine at concentrations and durations exceeding those commonly found in the environment.

[en] Highlights: • Thiamethoxam is detected in the surface waters of agroecosystems. • A mesocosm study to understand freshwater aquatic organism responses was performed. • No indications of ecologically significant direct or indirect effects at environmental concentrations. Thiamethoxam is a neonicotinoid insecticide used widely in agriculture to control a broad spectrum of insect pests. To assess potential risks from this compound to non-target aquatic organisms, an outdoor mesocosm study was performed. Mesocosms (1300 L) were treated once with a formulated product with the active substance (a.s.) thiamethoxam at nominal concentrations of 1 (n = 3), 3 (n = 3), 10 (n = 4), 30 (n = 4), and 100 (n = 2) μg a.s./L, plus untreated controls (n = 4). Primary producers (phytoplankton), zooplankton, and macroinvertebrates were monitored for up to 93 days following treatment. Thiamethoxam was observed to have a water column dissipation half-life (DT50) of ≤1.6–5.2 days in the mesocosms. Community-based principal response curve analysis detected no treatment effects for phytoplankton, zooplankton, emergent insects, and macroinvertebrates, indicating a lack of direct and indirect effects. A number of statistically significant differences from controls were detected for individual phytoplankton and zooplankton species abundances, but these were not considered to be treatment-related due to their transient nature and lack of concentration-response. After application of 30 μg a.s./L, slight temporary effects on Asellus aquaticus could not be excluded. At 100 μg a.s./L, there was an effect with no clear recovery of Asellus observed, likely due to their inability to recolonize these isolated test systems. A statistically significant but transient reduction in the emergence of chironomids by day 23 at the 100 μg a.s./L treatment was observed and possibly related to direct toxicity from thiamethoxam on larval stages. Therefore, a conservative study specific No Observed Ecological Adverse Effect Concentration (NOEAEC) is proposed to be 30 μg a.s./L. Overall, based on current concentrations of thiamethoxam detected in North American surface waters (typically <0.4 μg/L), there is low likelihood of direct or indirect effects from a pulsed exposure on primary producers, zooplankton, and macroinvertebrates, including insects, as monitored in this study.

[en] Highlights: • The fate and effects of dilbit spills was monitored in large in-lake limnocorrals. • Total Petroleum Hydrocarbons in water increased in the first week, reaching a plateau. • Sediment Total Polycyclic Aromatic Compounds (PACs) increased over the study. • Water-column PACs increased to a maximum after the first week, decreasing afterward. • V, Mn, and Mo showed a treatment-dependent increase in the water column. Large-scale, in-lake enclosures (limnocorrals) were used to simulate spills of diluted bitumen (dilbit) in a boreal lake. In this study we use these simulated spills, which covered a range of sizes (oil:water ratio) representative of the upper 25% of onshore crude oil spills in North America (2008–2019), to assess the fate of dilbit-derived hydrocarbons and metals as well as the impacts of the spills on standard water quality parameters. The systems were monitored over 70 days following the application of dilbit amounts ranging between 1.5 and 179.8 L into 10-m diameter, ~100 m³ limnocorrals. The concentration of total petroleum hydrocarbons (TPH) in the water column increased rapidly over the first two weeks reaching a plateau that ranged between 200 μg/L and 2200 μg/L for the lowest and highest treatment respectively. The concentration of total polycyclic aromatic compounds (PACs) also increased over the first two weeks, prior to a slow decrease until day 70. The maximum measured concentrations in the highest treatment were 2858 ng/L for the sum of all 46 quantified PACs, 2716 ng/L for alkylated PACs and 154 ng/L for the 16 EPA priority PAHs. The concentrations of PACs in the sediment increased continuously over the study in the three highest treatments with maximum observed concentrations of 189 ng/g for ΣPAC₄₆, 169 ng/g for ΣPAC_alk. No significant treatment-related changes in the 16 EPA priority PAHs were observed in the sediment. Of the 25 metals quantified in the water column, only manganese, molybdenum, and vanadium displayed a significant treatment effect with increases of 280, 76 and 25% respectively in the total fraction. These results can help us understand and predict the fate of oil-derived contaminants following a spill and characterize the exposure of freshwater organisms living within them. These results should help inform the risk assessment of future dilbit transportation projects.

[en] Microplastics are an emerging contaminant of concern in aquatic ecosystems. To better understand microplastic contamination in North American surface waters, we report for the first time densities of microplastics in Lake Winnipeg, the 11th largest freshwater body in the world. Samples taken 2014 to 2016 revealed similar or significantly greater microplastic densities in Lake Winnipeg compared with those reported in the Laurentian Great Lakes. Plastics in the lake were largely of secondary origin, overwhelmingly identified as fibres. We detected significantly greater densities of microplastics in the north basin compared to the south basin of the lake in 2014, but not in 2015 or 2016. Mean lake-wide densities across all years were comparable and not statistically different. Scanning electron microscopy with energy dispersive X-ray spectroscopy indicated that 23% of isolated particles on average were not plastic. While the ecological impact of microplastics on aquatic ecosystems is still largely unknown, our study contributes to the growing evidence that microplastic contamination is widespread even around sparsely-populated freshwater ecosystems, and provides a baseline for future study and risk assessments. - Highlights: • Surface microplastic contamination in Lake Winnipeg comparable to Lake Erie. • Lake Winnipeg microplastic densities greater than Lake Huron, Superior. • More than 90% of all microplastic particles found were fibres. • Microplastic densities similar over three years of sampling (2014–2016). - Our 3-year survey demonstrates that microplastic contamination in Lake Winnipeg is comparable to or greater than currently reported densities in the Laurentian Great Lakes.

[en] The impact of a mixture of oxytetracycline, chlortetracycline, tetracycline and doxycycline on Myriophyllum sibiricum and Lemna gibba was investigated using fifteen 12,000-L microcosms (k = 5, n = 3). Significant concentration-response relationships were only found for M. sibiricum, where dry mass was 69, 47, 30, and 7% of controls at respective treatment concentrations of 0.080, 0.218, 0.668, and 2.289 μmol/L. Somatic endpoints were strongly and negatively correlated with percent light transmission, except plant length, which was positively correlated. Treated microcosms experienced a reduction in the percent of surface irradiance penetrating the water column as high as 99.8% at a depth of 70 cm, relative to controls. Position relative to the water column was likely responsible for the differential effects observed between floating (L. gibba) and submerged (M. sibiricum) species of macrophytes. A hazard quotient assessment of the lowest EC₁₀ value indicated significant risk, exceeding the critical HQ value, but not the lowest EC₂₅ value. - Mixtures of tetracycline antibiotics pose a risk to submerged but not floating aquatic plants

[en] Tylosin is a macrolide antibiotic commonly used for therapeutic treatment and prophylaxis in livestock. As part of a larger ecotoxicological study, the potential phytotoxic effects of tylosin on the rooted macrophyte Myriophyllum spicatum and the floating macrophyte Lemna gibba were assessed under semi-field conditions using 15 12000-L microcosms. Concentrations of 0, 10, 30, 300 μg/L (n = 3), and 600, 1000, and 3000 μg/L (n = 1) were evaluated as part of separate ANOVA and regression analyses over an exposure period of 35 days. Fate of tylosin was monitored over time in the highest three treatments, where dissipation followed pseudo-first order kinetics with associated half-lives ranging from 9 to 10 days. For both M. spicatum and L. gibba, tylosin was found to cause no biologically significant changes to any endpoint assessed compared to controls at a Type I error rate of 0.1. However, subsequent power analyses revealed that there was generally insufficient power to declare that there were no significant differences at a Type II error rate of 0.2. Conclusions concerning biologically significant impacts were therefore further assessed based on other statistical criteria including comparisons of percent differences between replicated treatments and controls, minimum significant and minimum detectable differences, and coefficients of variation. Based on these criteria, at an ecological effect size of >20% change, tylosin was concluded to elicit no biologically or ecologically significant toxicity to M. spicatum or L. gibba. A hazard quotient assessment indicated that tylosin poses little risk to either species of macrophyte, with an HQ value calculated to be nearly three orders of magnitude below 1 (0.002). - Tylosin is not expected to have ecologically significant effects on Ontario freshwater macrophytes

[en] The treatment of municipal wastewater in the Arctic is challenging due to a variety of financial, operational, climatic and technical issues. To better understand the efficacy of current wastewater treatment in this region and the hazard posed to receiving waters, we assessed the occurrence of nutrients and contaminants (i.e., pharmaceuticals, antibiotic resistance genes) as they moved through a lagoon-based treatment system in Cambridge Bay, Nunavut, Canada. Wastewater treatment in this community is performed by the use of a lagoon-tundra wetland system that is discharged into the marine environment and is representative of current common practices throughout the region. In 2014, samples were collected before and during lagoon discharge from two locations in the main lagoon, one location downstream from the lagoon effluent and three locations offshore. Grab samples were collected to measure nutrients (e.g., total nitrogen and phosphorus) and the presence of antibiotic resistance gene-bearing microbes, and Polar Organic Chemical Integrative Samplers (POCIS) were deployed to collect passively organic contaminants in all locations. A total of six pharmaceuticals were detected from a screen of twenty-eight analytes during the study: atenolol, carbamazepine, clarithromycin, metoprolol, sulfamethoxazole and trimethoprim. The greatest concentrations of nutrients, antibiotic resistance genes (ARGs), and pharmaceuticals were found in sampling locations within the treatment lagoon. Offshore of the release point, we observed limited to no detection of pharmaceuticals and ARGs, but no change in total nitrogen and phosphorus from pre-release. We conclude that the current concentrations of monitored pharmaceuticals do not pose a significant hazard at this time to aquatic organisms in Cambridge Bay. - Highlights: • First ecotoxicological assessment of wastewater micropollutants in Canadian Arctic. • The greatest concentrations of ARGs and pharmaceuticals were found in the lagoon. • Significant dilution of contaminants after discharge through wetland into bay. • Pharmaceuticals do not pose a significant hazard to aquatic fauna in Cambridge Bay. - Baseline exposure data for nutrients, antibiotic resistance genes and pharmaceuticals in surface and seawater at Cambridge Bay is introduced, alongside an ecotoxicological hazard assessment.

[en] Highlights: • Source apportionment and transboundary flux of contaminants in the Red River. • USA was the major source of atrazine into Canada, but not neonicotinoids. • Levels of atrazine and neonicotinoids pose minimal risk to aquatic organisms. • Pharmaceuticals found at elevated levels downstream of wastewater inputs. • PFAS and ARGs found throughout with no evidence of any significant point-sources. The Red River originates in the U.S., drains into Lake Winnipeg, and is a significant pathway for nutrients. We investigate its role as a source for pesticides, pharmaceuticals, per- and polyfluoroalkyl substances (PFASs), and microbes bearing antibiotic resistance genes (ARGs). We delineate agricultural, urban, and rural land-use for organic contaminants to determine the extent of chemical transboundary riverine fluxes, and characterize levels and trends of organic contaminants and ARGs between spring and fall 2014 and 2015. The herbicide atrazine peaked at over 500 ng/L (14-day time-weighted average) near the border, indicating that the U.S. represents the major source into Canada from the Red River. Neonicotinoid insecticides had relatively constant concentrations, suggesting more widespread agricultural use in both countries. Pesticide concentrations were greatest post-application in June and July. Mass loadings of pesticides over the sampling periods, from the river to Lake Winnipeg, ranged from approximately 800 kg of atrazine, to 120 kg of thiamethoxam and clothianidin, to 40 kg of imidacloprid. Exposure distributions for atrazine exceeded benchmark water quality guidelines for protection of aquatic life (0.2% probability of exceeding chronic benchmark) with no exceedances for neonicotinoids. Seven pharmaceuticals were detected, mostly at low ng/L levels downstream of the City of Winnipeg wastewater treatment plant. Carbamazepine, the only pharmaceutical detected consistently at all sites, contributed on average 20 kg each year into Lake Winnipeg. While minor inputs were observed all along the river, city inputs represented the greatest source of pharmaceuticals to the river. Both PFASs and ARGs were observed consistently and ubiquitously, indicative of an anthropogenically-influenced system with no indications of any single point-source signature. While transboundary flux from the U.S. was an important source of pesticides to the Red River, especially for atrazine, observed concentrations of all measured contaminants suggest that known aquatic toxicological risk is minimal.