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Aquatic toxicity tests with benthic organisms are used to predict the toxicity of hydrophobic organic chemicals (HOCs) in sediments, assuming that the freely dissolved concentration (Cfree ) is a good surrogate of bioavailability in the exposure system. However, Cfree of HOCs is difficult to control in water-only setups. Moreover, the role of dissolved organic carbon (DOC) in the occurrence of toxicity needs clarification because DOC concentrations in sediment porewater can be substantially higher than in typical test water. We introduced biocompatible polyethylene meshes with high sorptive capacities and fast release kinetics as a novel passive dosing phase, which maintained Cfree and Cwater (i.e., free + DOC-bound) in Hyalella azteca water-only tests. Adding the supernatant fraction of peat to test water as a DOC source increased Cwater to an extent comparable to sediment porewater and significantly increased and decreased the observed toxicity of permethrin and benzo[a]pyrene, respectively, to H. azteca. This result indicates that DOC can both benefit and harm test species likely due to the increased health after ingestion of DOC and to the uptake of DOC-bound HOCs, respectively. Passive dosing in combination with the addition of sediment DOC surrogates may better reflect exposure and habitat conditions in sediment porewater than conventional aquatic tests. Environ Toxicol Chem 2022;00:1-10. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

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Aquatic communities can be exposed to pesticides transported from land. Characterizing this exposure is key to predicting potential toxic effects. In this study, samples of streamwater from 21 sites were used to characterize pesticide exposure to aquatic communities. Sites were in agricultural areas of southwestern Ontario, Canada and were sampled monthly from 2012 to 2019 from April to November. Samples were analyzed for a suite of hundreds of pesticides and pesticide degradation products and other water quality indicators (e.g., nutrients). Frequently detected pesticides included herbicides (2,4-D; bentazon; MCPP; metolachlor) and neonicotinoid insecticides (NNIs) (clothianidin; thiamethoxam) which were detected in >50% of samples collected between 2015 and 2019. Non-metric multidimensional scaling (NMDS) was used to explore connections between pesticide concentrations and upstream land use and crop type. Detectable concentrations of the NNI clothianidin and many herbicides were related to corn, soybean, and grain/cereal crops while concentrations of the NNI imidacloprid, insecticide flonicamid, and fungicide boscalid were related to greenhouse/nursery land use. Potential toxicity to aquatic communities was assessed by comparing pesticide concentrations to Pesticide Toxicity Index (PTI) values. Few samples exceeded levels where acute (1% of samples) or chronic toxicity (10.5%) would be expected. The diamide insecticide chlorantraniliprole was detected in several streamwater samples at levels that may cause toxicity to aquatic invertebrates, highlighting the need for continued toxicity research into this pesticide class. The number of pesticides detected was positively correlated with nutrient and total suspended solids levels, underscoring the multiple stressors aquatic communities are exposed to in these habitats.

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Pesticides occur in urban streams globally, but the relation of occurrence to urbanization can be obscured by regional differences. In studies of five regions of the United States, we investigated the effect of region and urbanization on the occurrence and potential toxicity of dissolved pesticide mixtures. We analyzed 225 pesticide compounds in weekly discrete water samples collected during 6-12 weeks from 271 wadable streams; development in these basins ranged from undeveloped to highly urbanized. Sixteen pesticides were consistently detected in 16 urban centers across the five regions-we propose that these pesticides comprise a suite of urban signature pesticides (USP) that are all common in small U.S. urban streams. These USPs accounted for the majority of summed maximum pesticide concentrations at urban sites within each urban center. USP concentrations, mixture complexity, and potential toxicity increased with the degree of urbanization in the basin. Basin urbanization explained the most variability in multivariate distance-based models of pesticide profiles, with region always secondary in importance. The USPs accounted for 83% of pesticides in the 20 most frequently occurring 2-compound unique mixtures at urban sites, with carbendazim+prometon the most common. Although USPs were consistently detected in all regions, detection frequencies and concentrations varied by region, conferring differences in potential aquatic toxicity. Potential toxicity was highest for invertebrates (benchmarks exceeded in 51% of urban streams), due most often to the neonicotinoid insecticide imidacloprid and secondarily to organophosphate insecticides and fipronil. Benchmarks were rarely exceeded in urban streams for plants (at 3% of sites) or fish (<1%). We propose that the USPs identified here would make logical core (nonexclusive) constituents for monitoring dissolved pesticides in U.S. urban streams, and that unique mixtures containing imidacloprid, fipronil, and carbendazim are priority candidates for mixtures toxicity testing.

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Water treatment and reuse initiatives are essential to combat declining water supplies in a changing climate, especially in arid and semi-arid regions. Pollution of water resources intensifies the search for strategies to provide water for potable and non-potable reuse that mitigates detrimental ecological and human health effects. Fipronil and synthetic pyrethroids are common urban-use insecticides that exert aquatic toxicity at trace levels and have been often found in urban surface streams. In this study, samples were collected from the 182 ha Prado Wetlands in Southern California for seven months to assess the occurrence of fipronil and its degradation products as well as pyrethroids (bifenthrin and cyfluthrin) in water, sediment, and plants in a 4.45 ha vegetated surface flow constructed wetland (CW). Concentration-based removal values and changes in mass flux were calculated to determine the efficacy of CW treatment. Observed water concentrations were further used to calculate toxic units for the invertebrates Hyalella azteca and Chironomus dilutus. Pesticide concentrations in water, sediment, and plant samples consistently decreased during passage through the CW at all time points. Removal values for fipronil desulfinyl, fipronil sulfide, fipronil, fipronil sulfone, bifenthrin, and cyfluthrin were 100%, 99.7-100%, 57.8-88.1%, 75.6-100%, 74.7-100%, and 36.6-82.2%, respectively, and there was a general net deposition of pesticides into CW compartments. Toxic unit values decreased in every instance for both aquatic invertebrates. Settling of contaminated particles, adsorption to sediment, plant uptake or adsorption, and subsequent degradation contributed to the effective removal of these urban-use insecticides, which highlights the potential of CWs for protecting urban water quality.

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This study assesses toxicity of groundwater from remediated fuel spill sites, as the final phase of an environmental risk assessment of contaminated sites at sub-Antarctic Macquarie Island, Tasmania, Australia. To complement previous terrestrial ecotoxicological research, we determine risk to marine environments from residual biodegraded hydrocarbon contaminants in groundwater discharges. Direct toxicity assessments were conducted on 7 composite groundwater test solutions, adjusted to ambient seawater salinity. Eleven native marine invertebrates (from varied taxa: gastropods, bivalves, flatworms, amphipods, copepods, isopods) were exposed and observed for up to 21 d. Lethal time estimates (LT10, LT50) showed sensitivity was time dependent (LT10s = 4-15 d) and variable between species. Three species showed no response to any test solution, and most species did not respond for up to 5 d. Data were interpreted using an expert judgment response matrix with multiple lines of evidence to predict risk. No consistent patterns in the relative toxicity of test solutions, based on polar or nonpolar hydrocarbon concentrations, were identified. Although toxicity was observed in some species, this was only under worst-case conditions of undiluted, continuous, extended exposure. Natural dynamics of the site, including low groundwater discharge rates, high rainfall, and a highly energetic receiving environment, ensure groundwater is rapidly diluted and dispersed. In this context, and based on site conditions at the time of testing, these toxicity assessments provide robust evidence that residual contamination in groundwater at remediated sites at Macquarie Island is unlikely to represent a risk to the adjacent marine communities tested. Integr Environ Assess Manag 2021;17:785-801. © 2020 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

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Aquatic organisms in streams are exposed to pesticide mixtures that vary in composition over time in response to changes in flow conditions, pesticide inputs to the stream, and pesticide fate and degradation within the stream. To characterize mixtures of dissolved-phase pesticides and degradates in Midwestern streams, a synoptic study was conducted at 100 streams during May-August 2013. In weekly water samples, 94 pesticides and 89 degradates were detected, with a median of 25 compounds detected per sample and 54 detected per site. In a screening-level assessment using aquatic-life benchmarks and the Pesticide Toxicity Index (PTI), potential effects on fish were unlikely in most streams. For invertebrates, potential chronic toxicity was predicted in 53% of streams, punctuated in 12% of streams by acutely toxic exposures. For aquatic plants, acute but likely reversible effects on biomass were predicted in 75% of streams, with potential longer-term effects on plant communities in 9% of streams. Relatively few pesticides in water-atrazine, acetochlor, metolachlor, imidacloprid, fipronil, organophosphate insecticides, and carbendazim-were predicted to be major contributors to potential toxicity. Agricultural streams had the highest potential for effects on plants, especially in May-June, corresponding to high spring-flush herbicide concentrations. Urban streams had higher detection frequencies and concentrations of insecticides and most fungicides than in agricultural streams, and higher potential for invertebrate toxicity, which peaked during July-August. Toxicity-screening predictions for invertebrates were supported by quantile regressions showing significant associations for the Benthic Invertebrate-PTI and imidacloprid concentrations with invertebrate community metrics for MSQA streams, and by mesocosm toxicity testing with imidacloprid showing effects on invertebrate communities at environmentally relevant concentrations. This study documents the most complex pesticide mixtures yet reported in discrete water samples in the U.S. and, using multiple lines of evidence, predicts that pesticides were potentially toxic to nontarget aquatic life in about half of the sampled streams.

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Despite increasing human activity and risk of fuel spills in Antarctica, little is known about the impact of fuel on Antarctic marine fauna. The authors performed both single- and multi-species (whole community) acute toxicity tests to assess the sensitivity of an Antarctic coastal zooplankton community to the water-accommodated fraction of Special Antarctic Blend diesel. Single-species tests using abundant copepods Oncaea curvata, Oithona similis, and Stephos longipes allowed comparisons of sensitivity of key taxa and of sensitivity estimates obtained from traditional single-species and more novel multi-species tests. Special Antarctic Blend diesel caused significant mortality and species compositional change in the zooplankton community within 4 d to 7 d. The sensitivity of the community also increased across the summer sampling period, with decreasing 7-d median lethal concentration (LC50) values for total petroleum hydrocarbons (TPH): 1091 µg TPH/L in early January 2011, 353 µg TPH/L in mid January 2011, and 186 µg TPH/L in early February 2011. Copepods showed similar sensitivities to Special Antarctic Blend diesel in single-species tests (7-d LC50s: O. curvata, 158 µg TPH/L; O. similis, 176 µg TPH/L; S. longipes, 188 µg TPH/L). The combined use of single- and multi-species toxicity tests is a holistic approach to assessing the sensitivity of key species and the interactions and interdependence between species, enabling a broader understanding of the effects of fuel exposure on the whole zooplankton community.

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