Multiple lines of evidence point to pesticides as stressors affecting invertebrate communities in small streams in five United States regions.

Multistressor studies were performed in five regions of the United States to assess the role of pesticides as stressors affecting invertebrate communities in wadable streams. Pesticides and other chemical and physical stressors were measured in 75 to 99 streams per region for 4 weeks, after which invertebrate communities were surveyed (435 total sites). Pesticides were sampled weekly in filtered water, and once in bed sediment. The role of pesticides as a stressor to invertebrate communities was assessed by evaluating multiple lines of evidence: toxicity predictions based on measured pesticide concentrations, multivariate models and other statistical analyses, and previously published mesocosm experiments. Toxicity predictions using benchmarks and species sensitivity distributions and statistical correlations suggested that pesticides were present at high enough concentrations to adversely affect invertebrate communities at the regional scale. Two undirected techniques-boosted regression tree models and distance-based linear models-identified which pesticides were predictors of (respectively) invertebrate metrics and community composition. To put insecticides in context with known, influential covariates of invertebrate response, generalized additive models were used to identify which individual pesticide(s) were important predictors of invertebrate community condition in each region, after accounting for natural covariates. Four insecticides were identified as stressors to invertebrate communities at the regional scale: bifenthrin, chlordane, fipronil and its degradates, and imidacloprid. Fipronil was particularly important in the Southeast region, and imidacloprid, bifenthrin, and chlordane were important in multiple regions. For imidacloprid, bifenthrin, and fipronil, toxicity predictions were supported by mesocosm experiments that demonstrated adverse effects on naïve aquatic communities when dosed under controlled conditions. These multiple lines of evidence do not prove causality-which is challenging in the field under multistressor conditions-but they make a strong case for the role of insecticides as stressors adversely affecting invertebrate communities in streams within the five sampled regions.

Contaminants in stream sediments from seven United States metropolitan areas: part I: distribution in relation to urbanization.

Organic contaminants and trace elements were measured in bed sediments collected from streams in seven metropolitan study areas across the United States to assess concentrations in relation to urbanization. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides, the pyrethroid insecticide bifenthrin, and several trace elements were significantly related to urbanization across study areas. Most contaminants (except bifenthrin, chromium, nickel) were significantly related to the total organic carbon (TOC) content of the sediments. Regression models explained 45-80 % of the variability in individual contaminant concentrations using degree of urbanization, sediment-TOC, and study-area indicator variables (which represent the combined influence of unknown factors, such as chemical use or release, that are not captured by available explanatory variables). The significance of one or more study-area indicator variables in all models indicates marked differences in contaminant levels among some study areas, even after accounting for the nationally modeled effects of urbanization and sediment-TOC. Mean probable effect concentration quotients (PECQs) were significantly related to urbanization. Trace elements were the major contributors to mean PECQs at undeveloped sites, whereas organic contaminants, especially bifenthrin, were the major contributors at highly urban sites. Pyrethroids, where detected, accounted for the largest share of the mean PECQ. Part 2 of this series (Kemble et al. 2012) evaluates sediment toxicity to amphipods and midge in relation to sediment chemistry.

Contaminants in stream sediments from seven United States metropolitan areas: part II--sediment toxicity to the amphipod Hyalella azteca and the midge Chironomus dilutus.

Relationships between sediment toxicity and sediment chemistry were evaluated for 98 samples collected from seven metropolitan study areas across the United States. Sediment-toxicity tests were conducted with the amphipod Hyalella azteca (28 day exposures) and with the midge Chironomus dilutus (10 day exposures). Overall, 33 % of the samples were toxic to amphipods and 12 % of the samples were toxic to midge based on comparisons with reference conditions within each study area. Significant correlations were observed between toxicity end points and sediment concentrations of trace elements, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), or organochlorine (OC) pesticides; however, these correlations were typically weak, and contaminant concentrations were usually below sediment-toxicity thresholds. Concentrations of the pyrethroid bifenthrin exceeded an estimated threshold of 0.49 ng/g (at 1 % total organic carbon) in 14 % of the samples. Of the samples that exceeded this bifenthrin toxicity threshold, 79 % were toxic to amphipods compared with 25 % toxicity for the samples below this threshold. Application of mean probable effect concentration quotients (PECQs) based on measures of groups of contaminants (trace elements, total PAHs, total PCBs, OC pesticides, and pyrethroid pesticides [bifenthrin in particular]) improved the correct classification of samples as toxic or not toxic to amphipods compared with measures of individual groups of contaminants.

Occurrence and potential sources of pyrethroid insecticides in stream sediments from seven U.S. metropolitan areas.

A nationally consistent approach was used to assess the occurrence and potential sources of pyrethroid insecticides in stream bed sediments from seven metropolitan areas across the United States. One or more pyrethroids were detected in almost half of the samples, with bifenthrin detected the most frequently (41%) and in each metropolitan area. Cyhalothrin, cypermethrin, permethrin, and resmethrin were detected much less frequently. Pyrethroid concentrations and Hyalella azteca mortality in 28-d tests were lower than in most urban stream studies. Log-transformed total pyrethroid toxic units (TUs) were significantly correlated with survival and bifenthrin was likely responsible for the majority of the observed toxicity. Sampling sites spanned a wide range of urbanization and log-transformed total pyrethroid concentrations were significantly correlated with urban land use. Dallas/Fort Worth had the highest pyrethroid detection frequency (89%), the greatest number of pyrethroids (4), and some of the highest concentrations. Salt Lake City had a similar percentage of detections but only bifenthrin was detected and at lower concentrations. The variation in pyrethroid concentrations among metropolitan areas suggests regional differences in pyrethroid use and transport processes. This study shows that pyrethroids commonly occur in urban stream sediments and may be contributing to sediment toxicity across the country.

The silence of the clams: Forestry registered pesticides as multiple stressors on soft-shell clams.

Contaminants are ubiquitous in the environment, often reaching aquatic systems. Combinations of forestry use pesticides have been detected in both water and aquatic organism tissue samples in coastal systems. Yet, most toxicological studies focus on the effects of these pesticides individually, at high doses, and over acute time periods, which, while key for establishing toxicity and safe limits, are rarely environmentally realistic. We examined chronic (90 days) exposure by the soft-shell clam, Mya arenaria, to environmentally relevant concentrations of four pesticides registered for use in forestry (atrazine, 5 µg/L; hexazinone, 0.3 µg/L; indaziflam, 5 µg/L; and bifenthrin, 1.5 µg/g organic carbon (OC)). Pesticides were tested individually and in combination, except bifenthrin, which was tested only in combination with the other three. We measured shell growth and condition index every 30 days, as well as feeding rates, mortality, and chemical concentrations in tissue from a subset of clams at the end of the experiment to measure contaminant uptake. Indaziflam caused a high mortality rate (max. 36%), followed by atrazine (max. 27%), both individually as well as in combination with other pesticides. Additionally, indaziflam concentrations in tissue (61.70-152.56 ng/g) were higher than those of atrazine (26.48-48.56 ng/g), despite equal dosing concentrations, indicating higher tissue accumulation. Furthermore, clams exposed to indaziflam and hexazinone experienced reduced condition index and clearance rates individually and in combination with other compounds; however, the two combined did not result in significant mortality. These two compounds, even at environmentally relevant concentrations, affected a non-target organism and, in the case of the herbicide indaziflam, accumulated in clam tissue and appeared more toxic than other tested pesticides. These findings underscore the need for more comprehensive studies combining multiple compounds at relevant concentrations to understand their impacts on aquatic ecosystems.

Ecological consequences of neonicotinoid mixtures in streams.

Neonicotinoid mixtures are common in streams worldwide, but corresponding ecological responses are poorly understood. We combined experimental and observational studies to narrow this knowledge gap. The mesocosm experiment determined that concentrations of the neonicotinoids imidacloprid and clothianidin (range of exposures, 0 to 11.9 µg/liter) above the hazard concentration for 5% of species (0.017 and 0.010 µg/liter, respectively) caused a loss in taxa abundance and richness, disrupted adult emergence, and altered trophodynamics, while mixtures of the two neonicotinoids caused dose-dependent synergistic effects. In 85 Coastal California streams, neonicotinoids were commonly detected [59% of samples (n = 340), 72% of streams], frequently occurred as mixtures (56% of streams), and potential toxicity was dominated by imidacloprid (maximum = 1.92 µg/liter) and clothianidin (maximum = 2.51 µg/liter). Ecological responses in the field were consistent with the synergistic effects observed in the mesocosm experiment, indicating that neonicotinoid mixtures pose greater than expected risks to stream health.

Response of algal metrics to nutrients and physical factors and identification of nutrient thresholds in agricultural streams.

Many streams within the United States are impaired due to nutrient enrichment, particularly in agricultural settings. The present study examines the response of benthic algal communities in agricultural and minimally disturbed sites from across the western United States to a suite of environmental factors, including nutrients, collected at multiple scales. The first objective was to identify the relative importance of nutrients, habitat and watershed features, and macroinvertebrate trophic structure to explain algal metrics derived from deposition and erosion habitats. The second objective was to determine if thresholds in total nitrogen (TN) and total phosphorus (TP) related to algal metrics could be identified and how these thresholds varied across metrics and habitats. Nutrient concentrations within the agricultural areas were elevated and greater than published threshold values. All algal metrics examined responded to nutrients as hypothesized. Although nutrients typically were the most important variables in explaining the variation in each of the algal metrics, environmental factors operating at multiple scales also were important. Calculated thresholds for TN or TP based on the algal metrics generated from samples collected from erosion and deposition habitats were not significantly different. Little variability in threshold values for each metric for TN and TP was observed. The consistency of the threshold values measured across multiple metrics and habitats suggest that the thresholds identified in this study are ecologically relevant. Additional work to characterize the relationship between algal metrics, physical and chemical features, and nuisance algal growth would be of benefit to the development of nutrient thresholds and criteria.

Is there an urban pesticide signature? Urban streams in five U.S. regions share common dissolved-phase pesticides but differ in predicted aquatic toxicity.

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.

Multiple in-stream stressors degrade biological assemblages in five U.S. regions.

Biological assemblages in streams are affected by a wide variety of physical and chemical stressors associated with land-use development, yet the importance of combinations of different types of stressors is not well known. From 2013 to 2017, the U.S. Geological Survey completed multi-stressor/multi-assemblage stream ecological assessments in five regions of the United States (434 streams total). Diatom, invertebrate, and fish communities were enumerated, and five types of potential stressors were quantified: habitat disturbance, excess nutrients, high flows, basic water quality, and contaminants in water and sediment. Boosted regression tree (BRT) models for each biological assemblage and region generally included variables from all five stressor types and multiple stressors types in each model was the norm. Classification and regression tree (CART) models then were used to determine thresholds for each BRT model variable above which there appeared to be adverse effects (multi-metric index (MMI) models only). In every region and assemblage there was a significant inverse relation between the MMI and the number of stressors exerting potentially adverse effects. The number of elevated instream stressors often varied substantially for a given level of land-use development and the number of elevated stressors was a better predictor of biological condition than was development. Using the adverse effects-levels that were developed based on the BRT model results, 68% of the streams had two or more stressors with potentially adverse effects and 35% had four or more. Our results indicate that relatively small increases in the number of stressors of different types can have a large effect on a stream ecosystem.

The relative influence of nutrients and habitat on stream metabolism in agricultural streams.

Stream metabolism was measured in 33 streams across a gradient of nutrient concentrations in four agricultural areas of the USA to determine the relative influence of nutrient concentrations and habitat on primary production (GPP) and respiration (CR-24). In conjunction with the stream metabolism estimates, water quality and algal biomass samples were collected, as was an assessment of habitat in the sampling reach. When data for all study areas were combined, there were no statistically significant relations between gross primary production or community respiration and any of the independent variables. However, significant regression models were developed for three study areas for GPP (r(2) = 0.79-0.91) and CR-24 (r(2) = 0.76-0.77). Various forms of nutrients (total phosphorus and area-weighted total nitrogen loading) were significant for predicting GPP in two study areas, with habitat variables important in seven significant models. Important physical variables included light availability, precipitation, basin area, and in-stream habitat cover. Both benthic and seston chlorophyll were not found to be important explanatory variables in any of the models; however, benthic ash-free dry weight was important in two models for GPP.

Legacy and Current-Use Contaminants in Sediments Alter Macroinvertebrate Communities in Southeastern US Streams.

Sediment contamination of freshwater streams in urban areas is a recognized and growing concern. As a part of a comprehensive regional stream-quality assessment, stream-bed sediment was sampled from streams spanning a gradient of urban intensity in the Piedmont ecoregion of the southeastern United States. We evaluated relations between a broad suite of sediment contaminants (metals, current-use pesticides, organochlorine pesticides, polychlorinated biphenyls, brominated diphenyl ethers, and polycyclic aromatic hydrocarbons), ambient sediment toxicity, and macroinvertebrate communities from 76 sites. Sediment toxicity was evaluated by conducting whole-sediment laboratory toxicity testing with the amphipod Hyalella azteca (for 28 d) and the midge Chironomus dilutus (for 10 d). Approximately one-third of the sediment samples were identified as toxic for at least one test species endpoint, although concentrations of contaminants infrequently exceeded toxicity benchmarks. Ratios of contaminant concentrations relative to their benchmarks, both individually and as summed benchmark quotients, were explored on a carbon-normalized and a dry-weight basis. Invertebrate taxa measures from ecological surveys tended to decline with increasing urbanization and with sediment contamination. Toxicity test endpoints were more strongly related to sediment contamination than invertebrate community measures were. Sediment chemistry and sediment toxicity provided moderate and weak, respectively, explanatory power for the similarity/dissimilarity of invertebrate communities. The results indicate that current single-chemical sediment benchmarks may underestimate the effects from mixtures of sediment contaminants experienced by lotic invertebrates. Environ Toxicol Chem 2020;39:1219-1232. Published 2020. This article is a U.S. Government work and is in the public domain in the USA.

Common insecticide disrupts aquatic communities: A mesocosm-to-field ecological risk assessment of fipronil and its degradates in U.S. streams.

Insecticides in streams are increasingly a global concern, yet information on safe concentrations for aquatic ecosystems is sparse. In a 30-day mesocosm experiment exposing native benthic aquatic invertebrates to the common insecticide fipronil and four degradates, fipronil compounds caused altered emergence and trophic cascades. Effect concentrations eliciting a 50% response (EC50) were developed for fipronil and its sulfide, sulfone, and desulfinyl degradates; taxa were insensitive to fipronil amide. Hazard concentrations for 5% of affected species derived from up to 15 mesocosm EC50 values were used to convert fipronil compound concentrations in field samples to the sum of toxic units (∑TUFipronils). Mean ∑TUFipronils exceeded 1 (indicating toxicity) in 16% of streams sampled from five regional studies. The Species at Risk invertebrate metric was negatively associated with ∑TUFipronils in four of five regions sampled. This ecological risk assessment indicates that low concentrations of fipronil compounds degrade stream communities in multiple regions of the United States.

Survey of bioaccessible pyrethroid insecticides and sediment toxicity in urban streams of the northeast United States.

Pyrethroids are a class of widely-used insecticides that can be transported from terrestrial applications to aquatic systems via runoff and tend to sorb to organic carbon in sediments. Pyrethroid occurrence is detrimental to stream ecosystems due to toxicity to sediment-dwelling invertebrates which are particularly at risk of pyrethroid exposure in urban streams. In this work, 49 streams located in watersheds in the northeastern United States were surveyed for nine current-use pyrethroids using two extraction methods. Total sediment concentrations were determined by exhaustive chemical extraction, while bioaccessible concentrations were determined by single-point Tenax extraction. Total and bioaccessible pyrethroid concentrations were detected in 76% and 67% of the sites, and the average sum of pyrethroids was 232 ng/g organic carbon (OC) for total and 43.8 ng/g OC for bioaccessible pyrethroids. Bifenthrin was the most commonly detected pyrethroid in streambed sediments. Sediment toxicity was assessed using 10-d Hyalella azteca bioassays, and 28% and 15% of sediments caused a decrease in H. azteca biomass and survival, respectively. A temperature-based focused toxicity identification evaluation was used to assess pyrethroids as the causal factor for toxicity. The concentrations of pyrethroids was only weakly correlated with the degree of urban land use. Sediment toxicity was predicted by total and bioaccessible pyrethroid concentrations expressed as toxic units. This work suggests that bioaccessibility-based methods, such as Tenax extraction, can be a valuable tool in assessing sediment toxicity.

Effects of urban multi-stressors on three stream biotic assemblages.

During 2014, the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) project assessed stream quality in 75 streams across an urban disturbance gradient within the Piedmont ecoregion of southeastern United States. Our objectives were to identify primary instream stressors affecting algal, macroinvertebrate and fish assemblages in wadeable streams. Biotic communities were surveyed once at each site, and various instream stressors were measured during a 4-week index period preceding the ecological sampling. The measured stressors included nutrients; contaminants in water, passive samplers, and sediment; instream habitat; and flow variability. All nine boosted regression tree models - three for each of algae, invertebrates, and fish - had cross-validation R2 (CV R2) values of 0.41 or above, and an invertebrate model had the highest CV R2 of 0.65. At least one contaminant metric was important in every model, and minimum daytime dissolved oxygen (DO), nutrients, and flow alteration were important explanatory variables in many of the models. Physical habitat metrics such as sediment substrate were only moderately important. Flow alteration metrics were useful factors in eight of the nine models. Total phosphorus, acetanilide herbicides and flow (time since last peak) were important in all three algal models, whereas insecticide metrics (especially those representing fipronil and imidacloprid) were dominant in the invertebrate models. DO values below approximately 7 mg/L corresponded to a strong decrease in sensitive taxa or an increase in tolerant taxa. DO also showed strong interactions with other variables, particularly contaminants and sediment, where the combined effect of low DO and elevated contaminants increased the impact on the biota more than each variable individually. Contaminants and flow alteration were strongly correlated to urbanization, indicating the importance of urbanization to ecological stream condition in the region.

Biological and chemical characterization of metal bioavailability in sediments from Lake Roosevelt, Columbia River, Washington, USA.

We studied the bioavailability and toxicity of copper, zinc, arsenic, cadmium, and lead in sediments from Lake Roosevelt (LR), a reservoir on the Columbia River in Washington, USA that receives inputs of metals from an upstream smelter facility. We characterized chronic sediment toxicity, metal bioaccumulation, and metal concentrations in sediment and pore water from eight study sites: one site upstream in the Columbia River, six sites in the reservoir, and a reference site in an uncontaminated tributary. Total recoverable metal concentrations in LR sediments generally decreased from upstream to downstream in the study area, but sediments from two sites in the reservoir had metal concentrations much lower than adjacent reservoir sites and similar to the reference site, apparently due to erosion of uncontaminated bank soils. Concentrations of acid-volatile sulfide in LR sediments were too low to provide strong controls on metal bioavailability, and selective sediment extractions indicated that metals in most LR sediments were primarily associated with iron and manganese oxides. Oligochaetes (Lumbriculus variegatus) accumulated greatest concentrations of copper from the river sediment, and greatest concentrations of arsenic, cadmium, and lead from reservoir sediments. Chronic toxic effects on amphipods (Hyalella azteca; reduced survival) and midge larvae (Chironomus dilutus; reduced growth) in whole-sediment exposures were generally consistent with predictions of metal toxicity based on empirical and equilibrium partitioning-based sediment quality guidelines. Elevated metal concentrations in pore waters of some LR sediments suggested that metals released from iron and manganese oxides under anoxic conditions contributed to metal bioaccumulation and toxicity. Results of both chemical and biological assays indicate that metals in sediments from both riverine and reservoir habitats of Lake Roosevelt are available to benthic invertebrates. These findings will be used as part of an ongoing ecological risk assessment to determine remedial actions for contaminated sediments in Lake Roosevelt.

Juvenile coho salmon growth and health in streams across an urbanization gradient.

Expanding human population and urbanization alters freshwater systems through structural changes to habitat, temperature effects from increased runoff and reduced canopy cover, altered flows, and increased toxicants. Current stream assessments stop short of measuring health or condition of species utilizing these freshwater habitats and fail to link specific stressors mechanistically to the health of organisms in the stream. Juvenile fish growth integrates both external and internal conditions providing a useful indicator of habitat quality and ecosystem health. Thus, there is a need to account for ecological and environmental influences on fish growth accurately. Bioenergetics models can simulate changes in growth and consumption in response to environmental conditions and food availability to account for interactions between an organism's environmental experience and utilization of available resources. The bioenergetics approach accounts for how thermal regime, food supply, and food quality affect fish growth. This study used a bioenergetics modeling approach to evaluate the environmental factors influencing juvenile coho salmon growth among ten Pacific Northwest streams spanning an urban gradient. Urban streams tended to be warmer, have earlier emergence dates and stronger early season growth. However, fish in urban streams experienced increased stress through lower growth efficiencies, especially later in the summer as temperatures warmed, with as much as a 16.6% reduction when compared to fish from other streams. Bioenergetics modeling successfully characterized salmonid growth in small perennial streams as part of a more extensive monitoring program and provides a powerful assessment tool for characterizing mixed life-stage specific responses in urban streams.

Effect of sample holding time on bioaccessibility and sediment ecotoxicological assessments.

The ecotoxicological effects of hydrophobic organic compound (HOC) contamination in sediment are often assessed using laboratory exposures of cultured invertebrates to field-collected sediment. The use of a sediment holding time (storage at 4 °C) between field sampling and the beginning of the bioassay is common practice, yet the effect of holding time on the reliability of bioassay results is largely unknown, especially for current-use HOCs, such as pyrethroid insecticides. Single-point Tenax extraction can be used to estimate HOC concentrations in the rapidly desorbing phase of the organic carbon fraction of sediment (i.e., bioaccessible concentrations), which relate to sediment toxicity and bioaccumulation in invertebrates. In this study, repeated measurements of bioaccessible concentrations (via Tenax), were made as a function of sediment holding time using pyrethroid-contaminated field sediment, and Hyalella azteca 10-d survival and growth was measured concurrently for comparison. Similarly, bioaccessible concentrations and 14-d bioaccumulation were measured in Lumbriculus variegatus as a comparison using the legacy HOCs, polychlorinated biphenyls (PCBs). While the bioaccessible and bioaccumulated PCB concentrations did not change significantly through 244 d of holding time, the bioaccessible pyrethroid concentrations were more varied. Depending on when pyrethroid-contaminated sediments were sampled, the bioaccessible pyrethroid concentrations showed first-order loss with half-lives ranging from 3 to 45 d of holding, or slower, linear decreases in concentrations up to 14% decrease over 180 d. These findings suggest that at least for some contaminants in sediments, holding the sediments prior to bioassays can bias toxicity estimates.

Complex mixtures of dissolved pesticides show potential aquatic toxicity in a synoptic study of Midwestern U.S. streams.

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.

Influence of sediment chemistry and sediment toxicity on macroinvertebrate communities across 99 wadable streams of the Midwestern USA.

Simultaneous assessment of sediment chemistry, sediment toxicity, and macroinvertebrate communities can provide multiple lines of evidence when investigating relations between sediment contaminants and ecological degradation. These three measures were evaluated at 99 wadable stream sites across 11 states in the Midwestern United States during the summer of 2013 to assess sediment pollution across a large agricultural landscape. This evaluation considers an extensive suite of sediment chemistry totaling 274 analytes (polycyclic aromatic hydrocarbons, organochlorine compounds, polychlorinated biphenyls, polybrominated diphenyl ethers, trace elements, and current-use pesticides) and a mixture assessment based on the ratios of detected compounds to available effects-based benchmarks. The sediments were tested for toxicity with the amphipod Hyalella azteca (28-d exposure), the midge Chironomus dilutus (10-d), and, at a few sites, with the freshwater mussel Lampsilis siliquoidea (28-d). Sediment concentrations, normalized to organic carbon content, infrequently exceeded benchmarks for aquatic health, which was generally consistent with low rates of observed toxicity. However, the benchmark-based mixture score and the pyrethroid insecticide bifenthrin were significantly related to observed sediment toxicity. The sediment mixture score and bifenthrin were also significant predictors of the upper limits of several univariate measures of the macroinvertebrate community (EPT percent, MMI (Macroinvertebrate Multimetric Index) Score, Ephemeroptera and Trichoptera richness) using quantile regression. Multivariate pattern matching (Mantel-like tests) of macroinvertebrate species per site to identified contaminant metrics and sediment toxicity also indicate that the sediment mixture score and bifenthrin have weak, albeit significant, influence on the observed invertebrate community composition. Together, these three lines of evidence (toxicity tests, univariate metrics, and multivariate community analysis) suggest that elevated contaminant concentrations in sediments, in particular bifenthrin, is limiting macroinvertebrate communities in several of these Midwest streams.

Development and application of freshwater sediment-toxicity benchmarks for currently used pesticides.

Sediment-toxicity benchmarks are needed to interpret the biological significance of currently used pesticides detected in whole sediments. Two types of freshwater sediment benchmarks for pesticides were developed using spiked-sediment bioassay (SSB) data from the literature. These benchmarks can be used to interpret sediment-toxicity data or to assess the potential toxicity of pesticides in whole sediment. The Likely Effect Benchmark (LEB) defines a pesticide concentration in whole sediment above which there is a high probability of adverse effects on benthic invertebrates, and the Threshold Effect Benchmark (TEB) defines a concentration below which adverse effects are unlikely. For compounds without available SSBs, benchmarks were estimated using equilibrium partitioning (EqP). When a sediment sample contains a pesticide mixture, benchmark quotients can be summed for all detected pesticides to produce an indicator of potential toxicity for that mixture. Benchmarks were developed for 48 pesticide compounds using SSB data and 81 compounds using the EqP approach. In an example application, data for pesticides measured in sediment from 197 streams across the United States were evaluated using these benchmarks, and compared to measured toxicity from whole-sediment toxicity tests conducted with the amphipod Hyalella azteca (28-d exposures) and the midge Chironomus dilutus (10-d exposures). Amphipod survival, weight, and biomass were significantly and inversely related to summed benchmark quotients, whereas midge survival, weight, and biomass showed no relationship to benchmarks. Samples with LEB exceedances were rare (n=3), but all were toxic to amphipods (i.e., significantly different from control). Significant toxicity to amphipods was observed for 72% of samples exceeding one or more TEBs, compared to 18% of samples below all TEBs. Factors affecting toxicity below TEBs may include the presence of contaminants other than pesticides, physical/chemical characteristics of sediment, and uncertainty in TEB values. Additional evaluations of benchmarks in relation to sediment chemistry and toxicity are ongoing.