Isotopic-based evidence for reduced benthic contributions to fish after a whole-lake addition of nanosilver.

Silver nanoparticles (AgNPs) are added as antibacterial and anti-odor agents to a wide range of textiles, with high potential for release into aquatic environments via domestic wastewater. Previous work demonstrating the negative impacts of AgNP exposure on periphyton production suggests benthic primary production could be reduced in aquatic ecosystems impacted by AgNP discharge. To evaluate the potential for AgNPs to alter benthic-pelagic coupling in aquatic ecosystems, tissue-stable isotope ratios of carbon and nitrogen from northern pike (Esox lucius) and yellow perch (Perca flavescens) were measured before, during, and after the addition of AgNPs to a whole-lake ecosystem, and compared to those collected from a nearby reference lake. A shift in carbon isotope ratios toward more negative values was observed in both P. flavescens and E. lucius collected from the lake where AgNPs were added, with no shift in similar magnitude observed in E. lucius from the reference lake. Consequently, Bayesian estimates of benthic energy consumed decreased by 32% for P. flavescens and by 40% for E. lucius collected after AgNP additions relative to pre-addition estimates, greater in magnitude or opposite in direction of trends observed in our reference lake. Analyses suggest no changes in fish nitrogen isotope ratios related to AgNP additions. We hypothesize that the observed reduction in littoral energy use of fish reported here is a response to AgNP settling in littoral benthic habitats-the main habitat in lakes supporting periphyton-as AgNP has been shown elsewhere to significantly reduce the rates of periphyton production. Further, our study highlights the need to broaden the scope of risk assessments for AgNPs and other emerging contaminants prone to settling to consider habitat-specific impacts on resource utilization by organisms after their release into aquatic ecosystems.

Compounds of wastewater origin in remote upland lakes in Ireland.

It is well established that persistent organic pollutants are transported long distances in the atmosphere and deposited into aquatic and terrestrial ecosystems in remote areas, including high altitude lakes. The objective of this research was to evaluate whether compounds of wastewater origin were present in four remote upland headwater lakes in Ireland that primarily receive loadings from atmospheric deposition. Using Polar Organic Chemical Integrative Samplers (POCIS) deployed in the lakes for 60 to 68 days, seven compounds were detected at levels that could be quantified but 25 of the target compounds were not detected. The detected compounds included the cannabinoid metabolite, tetrahydrocannabinol carboxylate (THC-COOH), codeine, acetaminophen (paracetamol), ibuprofen, and the artificial sweeteners, sucralose, and saccharin, which were all present at concentrations estimated to be < 125 ng/L. Caffeine was also present in the lakes at estimated concentrations between 213 and 1320 ng/L. Cocaine and tramadol were detected in POCIS deployed in some of the lakes, but at levels below the limits of quantitation. The highest concentrations of the target analytes were detected in two lakes located in the eastern part of Ireland. These data are consistent with regional atmospheric transport of these compounds originating from wastewater treatment plants in Ireland. However, contaminants from wastewater treatment plants in the United Kingdom may also be a source in these upland lakes that are located far from emissions of urban pollution.

The occurrence of tire wear compounds and their transformation products in municipal wastewater and drinking water treatment plants.

In the present study, 29 chemicals derived from tire wear were monitored by deploying Polar Organic Chemical Integrative Samplers (POCIS) in four WWTPs and two drinking water treatment plants (DWTPs) located in a municipality in southern Ontario, Canada. Target analytes included 1,3-diphenylguanidine (DPG), the oxidation byproduct of N-(1,3-dimethylbutyl)-N'-phenyl-1,4-benzenediamine called 6PPD-quinone, hexamethoxymethylmelamine (HMMM), and 26 of HMMM's known transformation products (TPs). This study is the first to monitor all these target compounds in DWTPs, as well as to report data for the presence of 6PPD-quinone in WWTPs. HMMM and selected TPs of this compound were detected in POCIS deployed in the WWTPs and in the DWTPs. The maximum estimated time-weighted average (TWA) concentration of HMMM of 83.2 ± 25.2 ng/L was observed in the effluent of one of the WWTPs. The TWA concentrations were not determined for any of the other target analytes, as POCIS sampling rates have not been determined for these chemicals. The total mass of HMMM and its TPs accumulated on POCIS frequently exceeded 4000 ng and the masses were generally lower in WWTP effluents relative to the influents. For other target analytes, the amounts accumulated on POCIS deployed in WWTP effluents frequently exceeded the amounts accumulated on POCIS deployed in the influents. DPG was detected in POCIS deployed in both the WWTPs and the DWTPs, and 6PPD-quinone was detected in POCIS deployed in both the influent and the effluent of WWTPs. We speculate that these tire wear compounds are entering WWTPs through stormwater overflows into the sewers or from commercial sources (e.g., car washes). This study highlights the need for an assessment of both WWTPs and DWTPs as sinks and sources of these tire wear compounds and the efficacy of treatment processes to remove them from both wastewater and drinking water.

Freshwater mussels in an impacted watershed: Influences of pollution from point and non-point sources.

The Grand River watershed in a densely populated region of Ontario supports one of the richest assemblages of freshwater mussels in Canada. However, water quality in this watershed is influenced by urban development, agriculture, and industry. Mussel populations and water chemistry in the lower Grand River and the Boston Creek tributary were evaluated to determine whether point sources of pollution such as discharges of domestic wastewater and industrial effluent, and non-point sources of pollution are affecting mussel distribution and population structure. Semi-quantitative population surveys conducted at 9 study sites identified 20 mussel species, including 3 Species at Risk. Mussel abundance (34-160 mussels/search hour) and species richness indicated that mussel populations in the lower Grand River watershed are continuing to recover from historical lows reported in the 1970s. However, changes in populations at some sites were consistent with altered water chemistry. Most notable was that the three most abundant mussel species in the Boston Creek tributary downstream of a gypsum plant discharge were significantly smaller in length than those upstream of this site. The water chemistry in this habitat was characterized by elevated conductivity (∼2000 µS/cm) and calcium (∼500 mg/L), as well as concentrations of sulfate (∼1000 mg/L) that can be toxic to freshwater mussels. In the Grand River downstream of the confluence with Boston Creek, there tended to be (p > 0.05) fewer mussels (mean 34 ± 20/search h) compared to upstream (mean 67 ± 15/search h) and this corresponded to altered water chemistry, including elevated sulfate (239 mg/L) downstream of the confluence relative to upstream (58 mg/L). These data indicate that chronic exposures to high levels of major ions is likely driving changes to mussel population structure. In addition, the discharges of wash water from a gypsum plant may be impacting sensitive biota in the main stem Grand River well beyond the immediate tributary receiving environment.

Calibration and field validation of POCIS passive samplers for tracking artificial sweeteners as indicators of municipal wastewater contamination in surface waters.

Polar organic chemical integrative samplers (POCIS) are widely used to track contaminants in surface waters. However, POCIS have not been used previously to monitor for artificial sweeteners as an indicator of wastewater pollution. In this study, we report for the first time the POCIS sampling rates (Rscal) for four artificial sweetener compounds, acesulfame (0.001 L/day), sucralose (0.114 L/day), cyclamate (0.001 L/day), and saccharin (0.002 L/day). We also prepared a modified POCIS with Strata X-AW anion exchange resin as a sorbent (i.e., ax-POCIS) and determined the sampling rates for sucralose (0.060 L/day) and acesulfame (0.128 L/day). Rscal values were adjusted according to the rate of loss of the performance reference compound, metoprolol-d6 from deployed POCIS to yield field sampling rates (i.e., Rsfield). Field validation of the monitoring method was conducted in Presqu'ile Bay on the north-central coast of Lake Ontario that is impacted by discharges from a sewage lagoon. POCIS were deployed at four sites within the bay and in the lagoon discharge. The four artificial sweeteners, as well as caffeine, ibuprofen, and other microcontaminants of sewage origin, were present throughout the bay at estimated concentrations in the ng/L range, and in the lagoon discharge at estimated concentrations higher by approximately one order of magnitude. Because acesulfame is present in ionic form over the pH range of natural waters, there are uncertainties related to the sampling rates using the standard POCIS. Sucralose is recommended as the best choice for source tracking using POCIS. There was good agreement between the concentrations of sucralose estimated from POCIS and the measured concentrations in grab samples of surface water in the bay. The present study provides key data for monitoring artificial sweeteners using POCIS.

Whole-lake nanosilver additions reduce northern pike (Esox lucius) growth.

Nanosilver (AgNP) is an anti-microbial agent widely used in consumer products, with significant potential for these nanoparticles to be released into aquatic environments. Laboratory studies involving short-term exposures of fish to AgNP show a range of toxicological effects, but these studies do not address potential responses in long-lived organisms resulting from chronic exposures. A collaborative study involving additions of AgNP to environmentally relevant concentrations over two field seasons took place at the IISD-Experimental Lakes Area, providing an opportunity to study the impacts of chronic exposures to long-lived fish species. In the present study, we evaluated the abundance and growth of an apex predator, Northern Pike (Esox lucius), collected from Lake 222 before, during and after the AgNP dosing period and compared results to those from a nearby unmanipulated lake (Lake 239). While the abundance of Northern Pike from Lake 222 during the study period was essentially stable, per capita availability of their primary prey species, Yellow Perch (Perca flavescens) declined by over 30%. Northern Pike fork length- and weight-at-age (indices of growth rate) declined following AgNP additions, most notably in age 4 and 5 fish. No similar changes in prey availability or growth were observed in Northern Pike from the reference lake. Body condition did not change in Northern Pike collected from either Lake 222 or Lake 239. Our results indicate that declines in the growth of Northern Pike chronically exposed to AgNP likely resulted from reduced prey availability but direct sublethal effects from AgNP exposure could also have been a factor. The persistence of reduced growth in Northern Pike two years after the cessation of AgNP additions highlight the potential legacy impacts of this contaminant once released into aquatic ecosystems.

Sources of microbial contamination in the watershed and coastal zone of Soufriere, St. Lucia.

The Sustainable Development Goal 6 calls for global progress by 2030 in treating domestic wastewater and providing access to adequate sanitation facilities. However, meeting these goals will be a challenge for most Small Island Developing States, including Caribbean island nations. In the nearshore zone of the Soufriere region on the Caribbean island of St. Lucia, there is a history of high levels of bacteria of fecal origin. Possible land-based sources of microbial contamination in the Soufriere Bay include discharges from the Soufriere River and transport of wastewater, including fecal material from the town of Soufriere. This area is an important tourist destination and supports a local fishery. To identify the sources of microbial contamination in Soufriere Bay, a range of monitoring methods were employed in this study. In grab samples of surface water collected from the Soufriere River, counts of total coliforms and Escherichia coli were elevated above water quality guidelines. However, the spikes in concentrations of these indicator organisms in the river did not necessarily coincide with the spikes in the levels of total coliforms and E. coli detected in samples collected on the same dates in Soufriere Bay, indicating that there are other sources of pollution in the Bay besides discharges from the river. Monitoring for chemical indicators of wastewater (i.e., caffeine, sucralose, fluconazole) in the Soufriere River indicated that there are inputs of sewage or human fecal material throughout the watershed. However, analysis of Bacteroidales 16S rRNA genetic markers for fecal bacteria originating from humans, bovine ruminants, or other warm-blooded animals indicated that the majority of microbial contamination in the river was not from humans. Monitoring for chemical indicators of wastewater using passive samplers deployed in Soufriere Bay indicated that there are two "hot spots" of contamination located offshore of economically depressed areas of the town of Soufriere. This study indicates that efforts to control contamination of Soufriere Bay by fecal microorganisms must include management of pollution originating from both sewage and domestic animals in the watershed.

Vitellogenin Induction in Mucus from Brook Trout (Salvelinus fontinalis).

Induction of vitellogenin (VTG) is widely used as a biomarker of exposure of male or immature fish to chemicals that are agonists of the estrogen receptor (i.e., xenoestrogens). Analysis of VTG in samples of epidermal mucosa collected from fish is a non-invasive method for evaluating whether wild fish are exposed to xenoestrogens. In this study, the mean levels of VTG in the mucus of immature brook trout (Salvelinus fontinalis) collected from the Credit River in Ontario, Canada downstream of aging residential septic systems and in an agricultural watershed were 0.67 ng per mg protein, which was significantly elevated relative to the mean VTG levels of 0.22 ng per mg protein in the mucus of immature brook trout collected from a less impacted site. To validate the mucus assay, immature brook trout were exposed in the laboratory to 17α-ethinylestradiol (EE2) at nominal concentrations of 10, 50 and 100 ng/L and VTG levels in mucus from these fish showed a concentration-dependent increase relative to fish from the control treatment. This study illustrates the utility of this non-lethal method for assessing whether wild fish have been exposed in situ to xenoestrogens. Exposures to xenoestrogens from non-point sources may be impacting brook trout populations in urban watersheds in southern Ontario.

Runoff of the Tire-Wear Compound, Hexamethoxymethyl-Melamine into Urban Watersheds.

Hexamethoxymethyl-melamine (HMMM) is used as a crosslinking agent in resins and plastics and in the manufacture of tires. In the present study, surface water samples were collected from two rivers adjacent to high traffic highways in the Greater Toronto Area in Ontario, Canada. Composite samples collected from the Don River and Highland Creek during rain events and a period of rapid snowmelt were preconcentrated using solid phase extraction and analyzed using liquid chromatography with high-resolution mass spectrometry. Elevated concentrations (> 1 µg/L) of HMMM were detected in surface waters during rain events in October of 2019 and during snow melt in early March of 2020. There were lower average concentrations of HMMM detected during rain events in the winter and spring of 2020. Temporal profiles of changes in the concentrations of HMMM in composite samples collected every 3 h during a rain event in October 2019 closely corresponded to the hydrograph profiles at the sampling sites, with the HMMM concentrations peaking > 6 h after the peak in water levels. This work contributes to the literature showing that HMMM is a ubiquitous contaminant of urban watersheds and that runoff from roads is a vector for the transport of this compound into urban surface waters.

The Tire Wear Compounds 6PPD-Quinone and 1,3-Diphenylguanidine in an Urban Watershed.

Prompted by a recent report that 6PPD-quinone (6PPD-q), a by-product of a common tire manufacturing additive that is present in road runoff, is toxic to coho salmon (Oncorhynchus kisutch), extracts of water samples collected from an urban river were re-analyzed to determine if this compound was present in stormwater-influenced flows. In addition, extracts were analyzed for 1,3-diphenylguanidine (DPG), which is also used in tire manufacturing. Samples were originally collected in the fall of 2019 and winter of 2020 in the Greater Toronto Area of Canada from the Don River, a highly urbanized watershed in close proximity to several major multi-lane highways. These target compounds were analyzed using ultra-high pressure liquid chromatography with high resolution mass spectrometric detection with parallel reaction monitoring. Both 6PPD-q and DPG were detected above limits of quantification (i.e., 0.0098 µg/L) in all extracts. Maximum concentrations for 6PPD-quinone of 2.30 ± 0.05 µg/L observed in the river during storm events exceeded the LC50 for this compound for coho salmon (i.e., > 0.8 µg/L). In composite samples collected at intervals throughout one rain event, both compounds reached peak concentrations a few hours after initiation of the event (i.e., 0.52 µg/L for DPG and 2.85 µg/L for 6PPD-q), but the concentrations of 6PPD-q remained elevated above 2 µg/L for over 10-h in the middle of the event. Estimates of cumulative loads of these compounds in composite samples indicated that kg amounts of these compounds entered the Don River during each hydrological event, and the loads were proportional to the amounts of precipitation. This study contributes to the growing literature indicating that potentially toxic tire-wear compounds are present at elevated levels and are transported via road runoff into urban surface waters during rain events.

Detection of selected tire wear compounds in urban receiving waters.

Road runoff is an important vector for the transport of chemicals originating from tire wear into receiving waters. In this study, samples of surface water were collected in the summer of 2020 from two rivers near high-traffic corridors in the Greater Toronto Area (GTA) in Canada. These samples were analyzed for two additives used in tire production, 1,3-diphenyl guanidine (DPG) and hexamethoxymethylmelamine (HMMM), as well 26 of the transformation compounds of HMMM. In addition, samples were analyzed for 6PPD-quinone (6PPD-q), an oxidation by-product of a tire additive that was recently identified as a candidate compound responsible for mass mortalities of Coho salmon (Oncorhynchus kisutch) in spawning streams in the USA. Grab and composite samples were collected during rain events (i.e., wet events) at both locations. Grab samples were collected from the Don River upstream, downstream and at the point of discharge from a municipal wastewater treatment plant (WWTP) during a period of dry weather. Of the target analytes, 6PPD-q, DPG and HMMM, as well as 15 of the transformation compounds of HMMM, were detected at concentrations above limits of quantitation. The concentrations of 6PPD-q in the receiving waters during wet events were within the range of the LC50 for adult Coho salmon. One of the transformation products (TPs) of HMMM, dimethoxymethylmelamine was detected in a composite sample from Highland Creek at an estimated concentration greater than 10 µg/L, indicating that more research is needed to evaluate the potential hazards to the aquatic environment from this compound. Sampling in the Don River during a dry period showed that discharges of wastewater from WWTPs are also continuous sources of the TPs of HMMM. This study contributes to the growing literature showing that chemicals derived from tire wear are ubiquitous in urban watersheds and may be a significant hazard to aquatic organisms.

Effects of opioids on reproduction in Japanese medaka, Oryzias latipes.

To study the effects of exposure of fish to opioid drugs, we exposed Japanese medaka (Oryzias latipes) over a full life cycle to codeine spiked into river water at nominal concentrations of 100, 1,000 and 25,000 ng/L and to fentanyl spiked into river water at nominal concentrations of 5, 25 and 1,000 ng/L. The measured concentrations during medaka exposures were consistent with the nominal concentrations. Treatments with codeine at all test concentrations reduced the number of eggs produced by female medaka, as well as the number of mature oocytes observed histologically in the ovaries. Exposures to codeine also resulted in altered concentrations of hormones within the hypothalamic-pituitary-gonadal axis, including reduced levels of 17ß-estradiol in female medaka. Fentanyl did not affect reproduction or the levels of hormones in medaka at the concentrations tested. Monitoring of surface waters in southern Ontario, Canada downstream of wastewater treatment plants showed that the test concentrations of fentanyl and codeine were environmentally relevant. The results of this work contribute to the literature on the impacts of opioids and other drugs of abuse released into surface waters.

Changes to levels of microcontaminants and biological responses in rainbow trout exposed to extracts from wastewater treated by catalytic ozonation.

Two separate pilot-scale studies were performed at two wastewater treatment plants comparing conventional ozonation and catalytic ozonation with an alumina-based catalyst supplied by BASF. The results of the first pilot study showed that catalytic ozonation achieved the same degree of disinfection as conventional ozonation with 30% lower applied ozone dose and enhanced the removal of several contaminants of emerging concern (CECs). The second pilot study conducted over 6 months of operation with the same batch of catalyst showed sustained enhanced removal of CECs relative to ozonation alone. The removals of CECs by catalytic ozonation was particularly effective for compounds with low reaction rates with ozone, indicating reactions with hydroxyl radicals formed in the presence of the catalyst. Analysis of plasma vitellogenin and total glutathione in liver tissues of juvenile rainbow trout (Oncorhynchus mykiss) injected with wastewater extracts indicated that catalytic ozonation removed the estrogenic activity and modulated oxidative stress caused by exposure to the organic compounds in wastewater extracts. Analysis of other biomarker responses indicated that no transformation products were formed that can cause lipid damage in the liver or affect levels of a brain neurotransmitter (i.e. serotonin). Catalytic ozonation is a promising technology to increase the efficiency of ozone treatment of municipal wastewater and to meet increasingly more stringent regulations for effluent quality.

Multi-Level Responses of Yellow Perch (Perca flavescens) to a Whole-Lake Nanosilver Addition Study.

Silver nanoparticles (AgNP) are widely used as antibacterial agents in both commercial products and for industrial applications. As such, AgNP has a high potential for release into freshwater environments. As part of a whole-lake ecosystem experiment to examine the impacts of AgNP exposure at low µg/L concentrations over multiple years, we evaluated biological responses in Yellow Perch (Perca flavescens) before, during, and after AgNP additions to a freshwater lake. Yellow Perch were monitored for responses to in situ AgNP additions at the cellular (suite of biomarkers), individual (growth, prey consumption, and metabolism), and population (abundance and gross prey consumption) scales. At the cellular level, several biomarkers of oxidative stress in liver tissues revealed down-regulation, including decreased mRNA levels of catalase and glutathione peroxidase in Yellow Perch collected during AgNP exposure, and elevated ratios of reduced to oxidized glutathione. At the individual level, Yellow Perch bioenergetic models revealed that prey consumption and total metabolism significantly declined during AgNP additions and remained depressed one year after AgNP addition. At the population level, Yellow Perch densities and gross prey consumption declined after AgNP was added to the lake. Together, these results reveal a holistic assessment of the negative impacts of chronic exposure to environmentally relevant AgNP concentrations (i.e., µg/L) on Yellow Perch at cellular, individual, and population levels.

Using Indigenous and Western knowledge systems for environmental risk assessment.

Indigenous rights, knowledge, and value systems are linked inextricably to the lands, waters, and non-human beings that form the environments of Indigenous Peoples. Across the globe, the rights of Indigenous peoples are being formally recognized and as a result, efforts are being made to include Indigenous Knowledge and value systems in environmental policy and decision making. Scientists and decision makers must not only recognize this reality, but also operationalize these efforts through meaningful changes to create space for the inclusion of Indigenous Knowledge, Indigenous values, and sovereignty within the current methods for scientific enquiry and the development of environmental policies. Professionals in the environmental field have a responsibility to ensure that their work has a positive impact on Indigenous Peoples and their environments. In this study, we explore the concept of consultation and informed consent through the lens of the development of environmental policy and decision making. We will discuss these concepts in the context of ecological risk assessment related to a case study focused on contaminated sediment in a harbor within the Great Lakes. We will demonstrate a process that deconstructs the current protocols for risk assessments at sites with localized pollutants in sediment and rebuilds them with elements that recognize both Western and Indigenous knowledge systems. This process includes collaborative fieldwork, relationship building, and informal and formal interviews with participants and community members. By utilizing such approaches, we were able to develop a risk assessment framework that recognizes the sovereignty of Indigenous peoples and promotes effective Nation-to-Nation decision making.

Pesticides in Surface Waters in Argentina Monitored Using Polar Organic Chemical Integrative Samplers.

Polar Organic Chemical Integrative Samplers (POCIS) were deployed in two watersheds in Córdoba province and one watershed in Buenos Aires province in Argentina. The fungicides, tebuconazole, carbendazim and azoxystrobin, and the herbicides, atrazine, dicamba and 2,4-D were detected in POCIS deployed in each of the three watersheds. Estimated time weighted average concentrations of atrazine were greater than 2 µg/L at the outflow of Brava Lake in Buenos Aires province, and this concentration exceeds the Canadian water quality guideline for protection of aquatic life. The concentrations of all other pesticides were less than 400 ng/L. The distribution of pesticides detected in surface waters indicated that the sources were runoff from agricultural and urban lands and discharges from wastewater treatment plants.

Micropollutants related to human activity in groundwater resources in Barbados, West Indies.

Several micropollutants, including caffeine, artificial sweeteners, pharmaceuticals, steroid hormones and a current-use pesticide were analyzed in water samples collected from five groundwater pumping stations in Barbados. The presence of caffeine and three artificial sweeteners (i.e. acesulfame, sucralose, saccharin) in groundwater samples indicated that groundwater was being contaminated by infiltration of wastewater into the karst aquifer. An estrogen (i.e. estrone), three pharmaceuticals (i.e. carbamazepine, trimethoprim, ibuprofen) and a transformation product of the fungicide, chlorothalonil (i.e. 4-hydroxychlorothalonil) were also detected at ng/L concentrations in groundwater collected from two or more pumping sites. The concentrations of carbamazepine and trimethoprim were correlated with the concentrations of caffeine (R2 values of 0.70 to 0.80), indicating pharmaceutical contamination of groundwater by infiltration from domestic wastewater. The concentrations of caffeine were generally higher in groundwater samples collected in June during the wet season relative to the concentrations in samples collected in February during the dry season, indicating that infiltration of contaminants is higher during periods of heavy rainfall. Rapid rates of degradation and relatively slow rates of infiltration may explain why several target analytes were not detected in groundwater. Elevated concentrations of 4-hydroxychlorothalonil > 0.1 µg/L in samples collected at two of the monitoring sites warrant further studies on the sources and the distribution of this compound and other pesticides used in agriculture and for turf-treatment (e.g. golf courses). Overall, more data are needed in order to implement mitigation strategies that are effective in reducing chemical contamination in groundwater in Barbados.

Pesticides related to land use in watersheds of the Great Lakes basin.

In this study, we evaluated the distribution and concentrations of a range of neonicotinoid insecticides (NNIs) and other insecticides, fungicides, biocides and selected herbicides in watersheds that drain into the lower Great Lakes in Ontario, Canada. Polar Organic Chemical Integrative Samplers (POCIS) were deployed in 18 watersheds during late May to late June of 2016. Grab samples were also collected in 7 of these watersheds. There was generally good agreement between the time-weighted average concentrations of pesticides estimated from the POCIS and the concentrations detected in grab samples. The NNIs, thiamethoxam, clothianidin and imidacloprid, were present in several watersheds at concentrations that exceeded the Canadian Water Quality Guideline for imidacloprid of 0.23 µg/L. The new generation insecticides, flonicamid and flupyradifurone were also detected in some watersheds, which is the first report of these pesticides in the peer-reviewed literature. Atrazine, 2,4-D, dicamba, carbendazim, thiophanate methyl and several azole-based fungicides were also widely detected. Discriminant Function Analysis (DFA) indicated that a high proportion (i.e. >80%) of the watersheds could be discriminated from each other on the basis of the pattern of pesticides detected in surface waters, and the proportion of field crops in the watershed.

Assessing the effects of environmentally relevant concentrations of antidepressant mixtures to fathead minnows exposed over a full life cycle.

Antidepressant drugs have been detected in municipal wastewater effluents (MWWEs) at ng/L to low µg/L concentrations. We exposed fathead minnow (Pimephales promelas) over a full lifecycle to a mixture of five antidepressants at concentrations similar to a MWWE (1× AntiD Mix); venlafaxine at 2400 ng/L, citalopram at 240 ng/L, fluoxetine at 90 ng/L, sertraline at 20 ng/L, and bupropion at 90 ng/L, and 10× these concentrations (i.e. 10× AntiD Mix). Mean measured concentrations of venlafaxine, citalopram, fluoxetine, sertraline, and bupropion were 2300, 160, 110, 7 ng/L, and below detection limits, respectively, for the 1× AntiD Mix, and 33,000, 2900, 1000, 210, and 100 ng/L, respectively for the 10× AntiD Mix. During the life-cycle exposure, no significant changes were observed in survival of fathead minnows. When male fish from the exposed treatments reached maturity, their weights were increased compared to control males. There were no significant differences in condition factor, gonadosomatic index, or liver-somatic index in the exposed fish. Exposed fathead minnows produced similar numbers of eggs as control fish, and there were no changes in nest-defense behaviours of male minnows. Egg quality, % fertilization, and % hatching in F1 fry were unaffected by exposure to the antidepressants. Eggs hatched 0.5 d earlier, deformities in fry were 50% lower, and there were transient decreases in length of F1 larvae at 8 days post-hatch in offspring from the treatment with the 10× AntiD Mix. Overall, exposure to the antidepressant mixture at environmentally relevant concentrations (i.e. 1× AntiD Mix) caused no adverse effects in fathead minnows. Exposure to the 10× AntiD Mix increased the weight of adult male minnows and caused subtle effects in F1 offspring. This study is the first to assess sublethal effects in fish exposed to mixtures of antidepressants over a full lifecycle. CAPSULE: No effects were observed in fathead minnow exposed for a lifecycle to antidepressant mixtures at environmentally-relevant concentrations.

Accumulation of Silver in Yellow Perch ( Perca flavescens) and Northern Pike ( Esox lucius) From a Lake Dosed with Nanosilver.

A total of 15 kg of silver nanoparticles (AgNPs) was added continuously over two ice-free field seasons to a boreal lake (i.e., Lake 222) at the IISD Experimental Lakes Area in Canada. We monitored the accumulation of silver (Ag) in the tissues of yellow perch ( Perca flavescens) and northern pike ( Esox lucius) exposed to the AgNPs under environmentally relevant conditions. The greatest accumulation was observed in the liver tissues of pike, and a single pike sampled in the second year of additions had the highest concentration observed in liver of 5.1 micrograms per gram of wet weight. However, the Ag concentrations in gill and muscle tissue of both pike and perch did not exceed 0.35 micrograms per gram of wet weight. Following additions of AgNP, the Ag residues in fish tissues declined, with a half-life of Ag in pike liver of 119 days. Monitoring using passive sampling devices and single-particle inductively coupled plasma mass spectrometry during the AgNP addition phase confirmed that Ag nanoparticles were present in the water column and that estimated mean concentrations of Ag increased over time to a maximum of 11.5 µg/L. These data indicate that both a forage fish and a piscivorous fish accumulated Ag in a natural lake ecosystem dosed with AgNPs, leading to Ag concentrations in some tissues of the piscivorous species that were 3 orders of magnitude greater than the concentrations in the water.