Prioritization of Pesticides for Assessment of Risk to Aquatic Ecosystems in Canada and Identification of Knowledge Gaps.

Pesticides can enter aquatic environments via direct application, via overspray or drift during application, or by runoff or leaching from fields during rain events, where they can have unintended effects on non-target aquatic biota. As such, Fisheries and Oceans Canada identified a need to prioritize current-use pesticides based on potential risks towards fish, their prey species, and habitats in Canada. A literature review was conducted to: (1) Identify current-use pesticides of concern for Canadian marine and freshwater environments based on use and environmental presence in Canada, (2) Outline current knowledge on the biological effects of the pesticides of concern, and (3) Identify general data gaps specific to biological effects of pesticides on aquatic species. Prioritization was based upon recent sales data, measured concentrations in Canadian aquatic environments between 2000 and 2020, and inherent toxicity as represented by aquatic guideline values. Prioritization identified 55 pesticides for further research nationally. Based on rank, a sub-group of seven were chosen as the top-priority pesticides, including three herbicides (atrazine, diquat, and S-metolachlor), three insecticides (chlorpyrifos, clothianidin, and permethrin), and one fungicide (chlorothalonil). A number of knowledge gaps became apparent through this process, including gaps in our understanding of sub-lethal toxicity, environmental fate, species sensitivity distributions, and/or surface water concentrations for each of the active ingredients reviewed. More generally, we identified a need for more baseline fish and fish habitat data, ongoing environmental monitoring, development of marine and sediment-toxicity benchmarks, improved study design including sufficiently low method detection limits, and collaboration around accessible data reporting and management.

Chronic toxicity of technical atrazine to the fathead minnow (Pimephales promelas) during a full life-cycle exposure and an evaluation of the consistency of responses.

Fathead minnows (Pimephales promelas) were continuously exposed to the herbicide atrazine (0.15, 0.25, 0.46, 0.99, and 2.0 mg a.i./L, plus dilution water and solvent controls) for a complete life cycle (274 days). Concentrations of atrazine up to 2.0 mg a.i./L did not significantly reduce hatching success, larval survival at 30 or 60 days post-hatch, or reproduction (eggs/spawn, total eggs, spawns/female, or eggs/female) in the F0 generation. However, at 60 days of exposure, total length and total survival to study completion were significantly reduced in ≥0.46 mg a.i./L and ≥ 0.99 mg a.i./L treatments, respectively. In the F1 generation, hatchability of embryos at ≥0.25 mg a.i./L (range 74-82%) was significantly less than that of pooled control organisms (86%). Following 30 days' post-hatch exposure, F1 survival was not significantly different from pooled control for any treatment. Finally, tissues representing major life stages had bioconcentration factors ranging from 3.7× (F1 embryos, <24 h) to 8.5× (F0 adults), indicating little to no evidence of bioconcentration. We developed a series of questions to assess the consistency of observed responses in order to place the data in context with the wider available and relevant literature (e.g., Observed between studies? Observed between species? Observed at lower levels of biological organization?). The analysis for consistency supports the conclusion that atrazine does not pose a significant chronic risk to freshwater fish in terms of growth, reproduction, or survivorship at concentrations of up to at least 100 µg/L.

Anthropogenic factors affecting wildlife species status outcomes: why the fixation on pesticides?

Most Americans are at least three generations removed from the farm, thereby at least three generations removed from the reality of where their food comes from. Not surprisingly, there are many misconceptions about modern food production, including the potential collateral environmental damage attributed to agriculture, particularly the application of pesticides. However, the implication of conventional agriculture in the broader narrative of wildlife species status outcomes (SSOs) lacks context and relativity. Since the dawn of civilization, humans have had a profound impact on their environment. Originating as hunter-gatherer societies, our ancient ancestors initially exploited anything that could be consumed or brought to bear. With the advent of the "first proto-farmers," humans began manipulating their environments to maximize available resources. Urban centers propagated and flourished proximal to agricultural origins, where modern societies have been built primarily on an abundance of food. As societies "developed," and continue to develop, an inevitable economic transition occurs from agriculture to industry/service predominance, culminating in a corresponding shift in land use. Developed countries have typically experienced maximal expansion of the agricultural frontier, where farmland is now steadily eroding by a proverbial flood of urban development. In contrast, in developing countries, this shift in economic development has not yet fully manifested and the agricultural footprint continues to expand at the expense of native habitats. Thus, the relative influence of "agriculture" on SSOs, in terms of land use, is primarily dependent on economic developmental status, which can be, at least in part, ameliorated via technology by increasing yield from existing land. Moreover, in addition to the land use challenge, there are multiple other factors affecting wildlife SSOs, including a figurative plague of invasive species, a literal plague of disease, a barrage of buildings, bumpers, grilles, and windshields to collide with, light pollution to confuse cues with, poachers to contend with, and even more complicated factors such as climate change. Being an easy target does not mean pesticides are the right target, and this fixation can potentially detract from public awareness regarding the primary drivers affecting SSOs as well as the opportunity to proactively address them. So, relatively speaking, how do these other factors compare to "pesticides" in terms of driving SSOs? Moreover, why is the popular media so fixated on the pesticide narrative? Based on the available evidence, this manuscript attempts to address these questions from a holistic and relative perspective within the context of land use change, economic development, population growth, and associated implications of global connectivity and commerce.

Photodegradation of bitumen-derived organics in oil sands process-affected water.

The chemical composition of water-soluble organics in oil sands process-affected water (OSPW) is primarily composed of natural constituents of bitumen that are solubilized and concentrated during aqueous extraction of oil sands. OSPW organics are persistent and acutely toxic, and a leading remediation strategy is long-term ageing in end-pit lakes, despite limited data available on its photochemical fate. Here, direct photolysis of whole OSPW, or of its constituent fractions, was examined at environmentally relevant wavelengths (>290 nm) in bench-top studies. Changes in the chemical profiles of whole OSPW, acid- (AEO), and base-extractable organics (BEO) were characterized by liquid chromatography with ultra-high resolution mass spectrometry in negative (-) and positive (+) ionization modes. Following 18 d of irradiation, photolysis reduced the total ion intensity in all samples in both modes. The most photo-labile species included the O2-, O3-, O4-, O2S-, and O4S- chemical classes, which were depleted in whole OSPW by 93-100% after only 5 d. In positive mode, detected species were more recalcitrant than those detected in negative mode, with an average reduction across all heteroatomic classes of 75 ± 11.0% after 18 d. Estimated environmental half-lives for heteroatomic classes ranged from 57 d (O4S-) to 545 d (O3N+), with a greater recalcitrance for classes detected in positive mode compared to negative mode. Under field conditions in end-pit lakes, natural photolysis may be an important mechanism for effective OSPW remediation, and we suggest that future end-pit lakes be shallow to maximize light penetration and natural photolysis in ageing OSPW.

The agro-enabled urban revolution, pesticides, politics, and popular culture: a case study of land use, birds, and insecticides in the USA.

Urbanization is an inevitable process in human civilization. When populations expand, socio-economic and political dynamics typically shift from agricultural predominance to one of industry and services. Accordingly, agrarian societies transform from diffuse rural communities to dense urban centers. By 2050, the world's population is projected to reach 9.1 billion, with the urban population growing from 50 to 70%. Inevitably, this ever-expanding urban frontier encroaches along the human-ecological interface, creating a challenge for conservation and biodiversity. For the past 30 years, agricultural cropland area in the USA has remained fairly constant, despite significant population growth over the same time period. Thus, agricultural production in America has more than kept pace with rapid population growth and global export demand without increasing the farmland footprint at the expense of wildlife habitat. This is primarily due to considerable advances made in pesticide development, safety, and regulation, coupled with soil conservation and genetically modified crops. Still, the potential contribution of agriculture to ecosystem impairment remains contentious, particularly with regard to current use of pesticides. Recently, significant focus has been placed on the state of bird populations in the USA. Many species are considered imperiled, and this is often attributed in the popular media to pesticide use. However, focusing solely on the agricultural/chemical story as a significant driver of species viability and ecological risk within the broader biodiversity and conservation narrative lacks context and perspective. Moreover, the hypothesis that pesticides are indirectly affecting bird population status via reductions in food resources should be considered with caution and within the context of other likely causes. This work explores the dynamics between historical land use, human-controlled activity, and bird population trends from a holistic perspective within the USA. The aim is to provide context, developed from a relative comparison of potential contributing factors, in order to help inform discussion and foster dialogue between industry, academia, government, non-governmental organizations, and the public.

Extended fish short term reproduction assays with the fathead minnow and Japanese medaka: No evidence of impaired fecundity from exposure to atrazine.

Short-term reproduction assays were conducted with fathead minnow (Pimephales promelas) and Japanese medaka (Oryzias latipes) to evaluate responses from atrazine exposure at environmentally relevant concentrations and above. Breeding groups of fish with multiple males and females were exposed to atrazine under flow-through conditions. Fathead minnows were exposed to mean measured concentrations of 1.0, 10, 26, 52, and 105 µg atrazine/L for 28 days. Medaka were exposed to mean measured concentrations of 9.4, 48, 74, 97, and 244 µg atrazine/L for 28 or 29 days. Fish were evaluated for survival, fecundity, fertility, total length, wet weight, secondary sex characteristics, gonadosomatic index (GSI) (P. promelas only), plasma or hepatic vitellogenin (VTG), and histopathology of gonads. General observations of health and behaviour were also conducted. There were no statistically significant effects (i.e., p < 0.05) of atrazine on survival, size, reproduction, behaviour, GSI, VTG, or secondary sex characteristics in either species at any exposure level. In fathead minnows, there were no histopathological findings associated with atrazine exposure in male fish, but there was an increased proportion of Stage 4.0 ovaries accompanied by an increase in proportion of Grade 3 post-ovulatory follicles in females of the 105 µg/L treatment group. Without a concomitant increase in oocyte atresia, neither of these findings are considered adverse for the health of the fish. In medaka, there were no significant effects of atrazine exposure on histopathology in either sex. These data support current weight-of-evidence assessments that atrazine does not cause direct adverse effects on fish reproduction at environmentally realistic concentrations.

Fish short-term reproduction assay with atrazine and the Japanese medaka (Oryzias latipes).

Breeding groups of Japanese medaka (Oryzias latipes) were exposed to atrazine at measured concentrations of 0.6, 5.5, and 53 µg/L for 35 d. Evaluated endpoints included survival, fecundity, fertility, growth (weight and length), behavior, secondary sex characteristics (anal fin papillae), gonad histopathology, and hepatic vitellogenin. No statistically significant effects of atrazine exposure on survival and growth of medaka were noted during the test, and mean survival was ≥97.5% in all treatment groups on day 35. No significant effects of atrazine exposure on reproduction were observed. The number of mean cumulative eggs produced in the negative control and the 0.6, 5.5, and 53 µg/L treatment groups was 7158, 6691, 6883, and 6856, respectively. The mean number of eggs per female reproductive day was 40.9, 38.2, 40.2, and 39.2, respectively. There were also no dose-dependent effects on mean anal fin papillae counts among male fish or expression of vtg-II in males or females. In addition, atrazine exposure was not related to the developmental stage of test fish, with testes stages ranging from 2 to 3 in all groups and ovaries ranging from stage 2 to 2.5. Overall, exposure to atrazine up to 53 µg/L for 35 d did not result in significant, treatment-related effects on measured endpoints related to survival, growth, or reproduction in Japanese medaka. Environ Toxicol Chem 2017;36:2327-2334. © 2017 SETAC.

Microplastics in aquatic environments: Implications for Canadian ecosystems.

Microplastics have been increasingly detected and quantified in marine and freshwater environments, and there are growing concerns about potential effects in biota. A literature review was conducted to summarize the current state of knowledge of microplastics in Canadian aquatic environments; specifically, the sources, environmental fate, behaviour, abundance, and toxicological effects in aquatic organisms. While we found that research and publications on these topics have increased dramatically since 2010, relatively few studies have assessed the presence, fate, and effects of microplastics in Canadian water bodies. We suggest that efforts to determine aquatic receptors at greatest risk of detrimental effects due to microplastic exposure, and their associated contaminants, are particularly warranted. There is also a need to address the gaps identified, with a particular focus on the species and conditions found in Canadian aquatic systems. These gaps include characterization of the presence of microplastics in Canadian freshwater ecosystems, identifying key sources of microplastics to these systems, and evaluating the presence of microplastics in Arctic waters and biota.

Late season pharmaceutical fate in wetland mesocosms with and without phosphorous addition.

The fate of six human-use drugs was assessed and predicted in mesocosms designed to mimic shallow constructed wetlands during the onset of fall and senescence. Mesocosms were monitored for 28 days after the addition of carbamazepine, clofibric acid, fluoxetine and naproxen (nominal initial concentrations of 5 µg/L each), sulfamethoxazole, and sulfapyridine (nominal initial concentrations of 150 µg/L each), with and without phosphorous (P) addition at 1.6 mg/L. We hypothesized that addition of P would stimulate primary productivity and enhance removal of pharmaceuticals from the water column. Carbamazepine, clofibric acid, fluoxetine, and naproxen had half-lives of 8.7, 11, 1.5, and 2.5, and 8.6, 11.0, 1.4, and 2.5 days in treatments with and without P amendment, respectively. Sulfamethoxazole and sulfapyridine had half-lives of 17 and 4.9 days in mesocosms with P amendment and 17 and 4.7 days without amendment. A concurrent pulse of P with pharmaceuticals did not significantly enhance the removal of these compounds. Predicted half-lives from modeling efforts were consistent with observed values, with photolysis the greatest contributor to chemical attenuation.

Macrophytes may not contribute significantly to removal of nutrients, pharmaceuticals, and antibiotic resistance in model surface constructed wetlands.

Outdoor shallow wetland mesocosms, designed to simulate surface constructed wetlands to improve lagoon wastewater treatment, were used to assess the role of macrophytes in the dissipation of wastewater nutrients, selected pharmaceuticals, and antibiotic resistance genes (ARGs). Specifically, mesocosms were established with or without populations of Typha spp. (cattails), Myriophyllum sibiricum (northern water milfoil), and Utricularia vulgaris (bladderwort). Following macrophyte establishment, mesocosms were seeded with ARG-bearing organisms from a local wastewater lagoon, and treated with a single pulse of artificial municipal wastewater with or without carbamazepine, clofibric acid, fluoxetine, and naproxen (each at 7.6µg/L), as well as sulfamethoxazole and sulfapyridine (each at 150µg/L). Rates of pharmaceutical dissipation over 28d ranged from 0.073 to 3.0d(-1), corresponding to half-lives of 0.23 to 9.4d. Based on calculated rate constants, observed dissipation rates were consistent with photodegradation driving clofibric acid, naproxen, sulfamethoxazole, and sulfapyridine removal, and with sorption also contributing to carbamazepine and fluoxetine loss. Of the seven gene determinants assayed, only two genes for both beta-lactam resistance (blaCTX and blaTEM) and sulfonamide resistance (sulI and sulII) were found in sufficient quantity for monitoring. Genes disappeared relatively rapidly from the water column, with half-lives ranging from 2.1 to 99d. In contrast, detected gene levels did not change in the sediment, with the exception of sulI, which increased after 28d in pharmaceutical-treated systems. These shallow wetland mesocosms were able to dissipate wastewater contaminants rapidly. However, no significant enhancement in removal of nutrients or pharmaceuticals was observed in mesocosms with extensive aquatic plant communities. This was likely due to three factors: first, use of naïve systems with an unchallenged capacity for nutrient assimilation and contaminant removal; second, nutrient sequestration by ubiquitous filamentous algae; and third, dominance of photolytic processes in the removal of pharmaceuticals, which overshadowed putative plant-related processes.

Performance of a constructed wetland in Grand Marais, Manitoba, Canada: Removal of nutrients, pharmaceuticals, and antibiotic resistance genes from municipal wastewater.

BACKGROUND: The discharge of complex mixtures of nutrients, organic micropollutants, and antibiotic resistance genes from treated municipal wastewater into freshwater systems are global concerns for human health and aquatic organisms. Antibiotic resistance genes (ARGs) are genes that have the ability to impart resistance to antibiotics and reduce the efficacy of antibiotics in the systems in which they are found. In the rural community of Grand Marais, Manitoba, Canada, wastewater is treated passively in a sewage lagoon prior to passage through a treatment wetland and subsequent release into surface waters. Using this facility as a model system for the Canadian Prairies, the two aims of this study were to assess: (a) the presence of nutrients, micropollutants (i.e., pesticides, pharmaceuticals), and ARGs in lagoon outputs, and (b) their potential removal by the treatment wetland prior to release to surface waters in 2012. RESULTS: As expected, concentrations of nitrogen and phosphorus species were greatest in the lagoon and declined with movement through the wetland treatment system. Pharmaceutical and agricultural chemicals were detected at concentrations in the ng/L range. Concentrations of these compounds spiked downstream of the lagoon following discharge and attenuation was observed as the effluent migrated through the wetland system. Hazard quotients calculated for micropollutants of interest indicated minimal toxicological risk to aquatic biota, and results suggest that the wetland attenuated atrazine and carbamazepine significantly. There was no significant targeted removal of ARGs in the wetland and our data suggest that the bacterial population in this system may have genes imparting antibiotic resistance. CONCLUSIONS: The results of this study indicate that while the treatment wetland may effectively attenuate excess nutrients and remove some micropollutants and bacteria, it does not specifically target ARGs for removal. Additional studies would be beneficial to determine whether upgrades to extend retention time or alter plant community structure within the wetland would optimize removal of micropollutants and ARGs to fully characterize the utility of these systems on the Canadian Prairies.

Presence and hazards of nutrients and emerging organic micropollutants from sewage lagoon discharges into Dead Horse Creek, Manitoba, Canada.

Nutrient enrichment and loadings of pharmaceuticals and agrochemicals into freshwater systems are common concerns, especially for water bodies receiving wastewater inputs. In the rural communities of Morden and Winkler of Manitoba, Canada, sewage lagoons discharge their wastewater directly into Dead Horse Creek, a small tributary of the Red River that empties into Lake Winnipeg. This lagoon approach to managing rural wastewaters is common across the North American Prairies. Therefore, this study aimed to assess the hazards of lagoon treatment releases at this model site. This was done by characterizing the nutrients, organic micropollutants (i.e., pesticides, pharmaceuticals) and standard water quality parameters in the creek prior to and following lagoon discharge events over a number of years (2009-2011). Measured concentrations of nutrients were compared to regulatory expectations and micropollutants were assessed using hazard quotients. As expected, concentrations of nitrogen and phosphorus species were greatest in sites downstream of the sewage outfall immediately following discharge events. Pharmaceutical and agricultural chemicals were detected at concentrations between 0.5 and 90 ng/L. Detection frequencies and concentrations matched typical use patterns. Those compounds used predominately for human medicine were detected at downstream sites following discharge events, while those used in an agricultural setting were detected at relatively consistent levels over time at sites both upstream and downstream of the outfall location. Hazard quotients calculated for micropollutants of interest indicated minimal toxicological risk to aquatic biota in the creek, with only erythromycin and diazinon presenting a potential concern to aquatic algae and invertebrates. Concentrations of nutrients exceeded Canadian guideline thresholds during release, but returned to background levels once discharges ceased. Therefore, it is advisable that wastewater treatment and management strategies such as constructed wetlands and/or staggered releases be used in order to minimize the hazard posed by nutrient pulses in Dead Horse Creek and other similar systems.