Lisa H. Nowell

Pesticides in stream sediment and aquatic biota : distribution, trends, and governing factors

Introduction Purpose Previous Reviews Approach Characteristics of Studies Reviewed General Design Features Geographic Distribution Temporal Distribution Sampling Matrices Target Analytes Analytical Detection Limits National Distribution and Trends Pesticide Occurrence National Pesticide Use Geographic Distribution in Relation to Use Long-Term Trends Governing Processes Pesticide Sources Behavior and Fate of Pesticides in Bed Sediment Behavior and Fate of Pesticides in Aquatic Biota Analysis of Key Topics - Sources, Behavior, and Transport Effect of Land Use on Pesticide Contamination Pesticide Uptake and Accumulation by Aquatic Biota Seasonal Changes in Pesticide Residues Physical and Chemical Properties of Pesticides in Sediment and Aquatic Biota Composition of Total DDT as an Indicator of DDT Sources and Period of Use Analysis of Key Topics - Environmental Significance Effects of Pesticide Contaminants on Aquatic Organisms and Fish-Eating Wildlife Effects of Pesticide Contaminants in Aquatic Biota on Human Health Summary and Conclusion Appendix A: Table 2.1 Pesticides in bed sediment and aquatic biota from rivers and estuaries in the United States: National and multistate monitoring studies Appendix B: Table 2.2 Pesticides in bed sediment and aquatic biota from rivers in the United States: State and local monitoring studies Appendix C: Table 2.3 Pesticides in bed sediment and aquatic biota from rivers in the United States: Process and matrix distribution studies Appendix D: Common Names and Taxonomic Classifications of Aquatic Organisms Sampled in the Studies Reviewed Appendix E: Glossary of Common and Chemical Names of Pesticides References Index

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.

Pesticide Toxicity Index--a tool for assessing potential toxicity of pesticide mixtures to freshwater aquatic organisms.

Pesticide mixtures are common in streams with agricultural or urban influence in the watershed. The Pesticide Toxicity Index (PTI) is a screening tool to assess potential aquatic toxicity of complex pesticide mixtures by combining measures of pesticide exposure and acute toxicity in an additive toxic-unit model. The PTI is determined separately for fish, cladocerans, and benthic invertebrates. This study expands the number of pesticides and degradates included in previous editions of the PTI from 124 to 492 pesticides and degradates, and includes two types of PTI for use in different applications, depending on study objectives. The Median-PTI was calculated from median toxicity values for individual pesticides, so is robust to outliers and is appropriate for comparing relative potential toxicity among samples, sites, or pesticides. The Sensitive-PTI uses the 5th percentile of available toxicity values, so is a more sensitive screening-level indicator of potential toxicity. PTI predictions of toxicity in environmental samples were tested using data aggregated from published field studies that measured pesticide concentrations and toxicity to Ceriodaphnia dubia in ambient stream water. C. dubia survival was reduced to ≤50% of controls in 44% of samples with Median-PTI values of 0.1-1, and to 0% in 96% of samples with Median-PTI values >1. The PTI is a relative, but quantitative, indicator of potential toxicity that can be used to evaluate relationships between pesticide exposure and biological condition.

COMPARISON OF PESTICIDE CONCENTRATIONS IN STREAMS AT LOW FLOW IN SIX METROPOLITAN AREAS OF THE UNITED STATES

To examine the effect of urban development on pesticide concentrations in streams under low-flow conditions, water samples were collected at stream sites along an urban land use gradient in six environmentally heterogeneous metropolitan areas of the United States. In all six metropolitan areas, total insecticide concentrations generally increased significantly as urban land cover in the basin increased, regardless of whether the background land cover in the basins was agricultural, forested, or shrub land. In contrast, the response of total herbicide concentrations to urbanization varied with the environmental setting. In the three metropolitan areas with predominantly forested background land cover (Raleigh-Durham, NC, USA; Atlanta, GA, USA; Portland, OR, USA), total herbicide concentrations increased significantly with increasing urban land cover. In contrast, total herbicide concentrations were not significantly related to urban land cover in the three remaining metropolitan areas, where total herbicide concentrations appeared to be strongly influenced by agricultural as well as urban sources (Milwaukee-Green Bay, WI, USA; Dallas-Fort Worth, TX, USA), or by factors not measured in the present study, such as water management (Denver, CO, USA). Pesticide concentrations rarely exceeded benchmarks for protection of aquatic life, although these low-flow concentrations are likely to be lower than at other times, such as during peak pesticide-use periods, storm events, or irrigation discharge. Normalization of pesticide concentrations by the pesticide toxicity index -- an index of relative potential toxicity -- for fish and cladocerans indicated that the pesticides detected at the highest concentrations (herbicides in five of the six metropolitan areas) were not necessarily the pesticides with the greatest potential to adversely affect aquatic life (typically insecticides such as carbaryl, chlorpyrifos, diazinon, and fipronil).

Complex mixtures of Pesticides in Midwest U.S. streams indicated by POCIS time-integrating samplers

The Midwest United States is an intensely agricultural region where pesticides in streams pose risks to aquatic biota, but temporal variability in pesticide concentrations makes characterization of their exposure to organisms challenging. To compensate for the effects of temporal variability, we deployed polar organic chemical integrative samplers (POCIS) in 100 small streams across the Midwest for about 5 weeks during summer 2013 and analyzed the extracts for 227 pesticide compounds. Analysis of water samples collected weekly for pesticides during POCIS deployment allowed for comparison of POCIS results with periodic water-sampling results. The median number of pesticides detected in POCIS extracts was 62, and 141 compounds were detected at least once, indicating a high level of pesticide contamination of streams in the region. Sixty-five of the 141 compounds detected were pesticide degradates. Mean water concentrations estimated using published POCIS sampling rates strongly correlated with means of weekly water samples collected concurrently, however, the POCIS-estimated concentrations generally were lower than the measured water concentrations. Summed herbicide concentrations (units of ng/POCIS) were greater at agricultural sites than at urban sites but summed concentrations of insecticides and fungicides were greater at urban sites. Consistent with these differences, summed concentrations of herbicides correlate to percent cultivated crops in the watersheds and summed concentrations of insecticides and fungicides correlate to percent urban land use. With the exception of malathion concentrations at nine sites, POCIS-estimated water concentrations of pesticides were lower than aquatic-life benchmarks. The POCIS provide an alternative approach to traditional water sampling for characterizing chronic exposure to pesticides in streams across the Midwest region.

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.

Regression models for explaining and predicting concentrations of organochlorine pesticides in fish from streams in the United States

Empirical regression models were developed for estimating concentrations of dieldrin, total chlordane, and total DDT in whole fish from U.S. streams. Models were based on pesticide concentrations measured in whole fish at 648 stream sites nationwide (1992-2001) as part of the U.S. Geological Surveys National Water Quality Assessment Program. Explanatory variables included fish lipid content, estimates (or surrogates) representing historical agricultural and urban sources, watershed characteristics, and geographic location. Models were developed using Tobit regression methods appropriate for data with censoring. Typically, the models explain approximately 50 to 70% of the variability in pesticide concentrations measured in whole fish. The models were used to predict pesticide concentrations in whole fish for streams nationwide using the U.S. Environmental Protection Agencys River Reach File 1 and to estimate the probability that whole-fish concentrations exceed benchmarks for protection of fish-eating wildlife. Predicted concentrations were highest for dieldrin in the Corn Belt, Texas, and scattered urban areas; for total chlordane in the Corn Belt, Texas, the Southeast, and urbanized Northeast; and for total DDT in the Southeast, Texas, California, and urban areas nationwide. The probability of exceeding wildlife benchmarks for dieldrin and chlordane was predicted to be low for most U.S. streams. The probability of exceeding wildlife benchmarks for total DDT is higher but varies depending on the fish taxon and on the benchmark used. Because the models in the present study are based on fish data collected during the 1990s and organochlorine pesticide residues in the environment continue to decline decades after their uses were discontinued, these models may overestimate present-day pesticide concentrations in fish.

Similarities and differences in occurrence and temporal fluctuations in glyphosate and atrazine in small Midwestern streams (USA) during the 2013 growing season

Glyphosate and atrazine are the most intensively used herbicides in the United States. Although there is abundant spatial and temporal information on atrazine occurrence at regional scales, there are far fewer data for glyphosate, and studies that compare the two herbicides are rare. We investigated temporal patterns in glyphosate and atrazine concentrations measured weekly during the 2013 growing season in 100 small streams in the Midwestern United States. Glyphosate was detected in 44% of samples (method reporting level 0.2μg/L); atrazine was detected above a threshold of 0.2μg/L in 54% of samples. Glyphosate was detected more frequently in 12 urban streams than in 88 agricultural streams, and at concentrations similar to those in streams with high agricultural land use (>40% row crop) in the watershed. In contrast, atrazine was detected more frequently and at higher concentrations in agricultural streams than in urban streams. The maximum concentration of glyphosate measured at most urban sites exceeded the maximum atrazine concentration, whereas at agricultural sites the reverse was true. Measurement at a 2-day interval at 8 sites in northern Missouri revealed that transport of both herbicide compounds appeared to be controlled by spring flush, that peak concentration duration was brief, but that peaks in atrazine concentrations were of longer duration than those of glyphosate. The 2-day sampling also indicated that weekly sampling is unlikely to capture peak concentrations of glyphosate and atrazine.

Organic contaminants, trace and major elements, and nutrients in water and sediment sampled in response to the Deepwater Horizon oil spill

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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.