Sediment Sources and Sealed-Pavement Area Drive Polycyclic Aromatic Hydrocarbon and Metal Occurrence in Urban Streams.

Metals and polycyclic aromatic hydrocarbons (PAHs) are common pollutants in urban streambed sediment, yet their occurrence is highly variable and difficult to predict. To investigate sources of PAHs and metals to streambed sediment, we sampled pavement dust, soil, and streambed sediment in 10 urban watersheds in three regions of the United States and applied a fallout-radionuclide-based sediment-source analysis to quantify the pavement dust contribution to stream sediment (%dust). We also mapped the area of sealcoated pavement in each watershed (%sealed) to investigate the role of coal-tar pavement sealant (CTS) as a PAH source. Median total and carbon-normalized total PAH concentrations were significantly higher in streambed sediment in the Northeast (54.3 mg/kg and 2.71 mg/gOC) and Southeast (5.37 mg/kg and 1.36 mg/gOC), where CTS is commonly used, than in the Northwest (2.11 mg/kg and 0.071 mg/gOC), where CTS is rarely used. Generalized additive models indicated that %sealed and in some cases %dust significantly affected total PAH concentrations in streambed sediments. The %dust was a significant variable for common urban metals: Cu, Pb, and Zn. These findings advance our quantitative understanding of the role of pavement dust as a source and a vector of contaminants to urban streams.

Inclusion of Pesticide Transformation Products Is Key to Estimating Pesticide Exposures and Effects in Small U.S. Streams.

Improved analytical methods can quantify hundreds of pesticide transformation products (TPs), but understanding of TP occurrence and potential toxicity in aquatic ecosystems remains limited. We quantified 108 parent pesticides and 116 TPs in more than 3 700 samples from 442 small streams in mostly urban basins across five major regions of the United States. TPs were detected nearly as frequently as parents (90 and 95% of streams, respectively); 102 TPs were detected at least once and 28 were detected in >20% samples in at least one region-TPs of 9 herbicides, 2 fungicides (chlorothalonil and thiophanate-methyl), and 1 insecticide (fipronil) were the most frequently detected. TPs occurred commonly during baseflow conditions, indicating chronic environmental TP exposures to aquatic organisms and the likely importance of groundwater as a TP source. Hazard quotients based on acute aquatic-life benchmarks for invertebrates and nonvascular plants and vertebrate-centric molecular endpoints (sublethal effects) quantify the range of the potential contribution of TPs to environmental risk and highlight several TP exposure-response data gaps. A precautionary approach using equimolar substitution of parent benchmarks or endpoints for missing TP benchmarks indicates that potential aquatic effects of pesticide TPs could be underestimated by an order of magnitude or more.

Biofilms Provide New Insight into Pesticide Occurrence in Streams and Links to Aquatic Ecological Communities.

Streambed sediment is commonly analyzed to assess occurrence of hydrophobic pesticides and risks to aquatic communities. However, stream biofilms also have the potential to accumulate pesticides and may be consumed by aquatic organisms. To better characterize risks to aquatic life, the U.S. Geological Survey Regional Stream Quality Assessment measured 93 current-use and 3 legacy pesticides in bed sediment and biofilm from 54 small streams in California across a range of land-use settings. On average, 4 times as many current-use pesticides were detected in biofilm at a site (median of 2) as in sediment (median of 0.5). Of 31 current-use pesticides detected, 20 were detected more frequently in biofilm than in sediment and 10 with equal frequency. Pyrethroids as a class were the most potentially toxic to benthic invertebrates, and of the 9 pyrethroids detected, 7 occurred more frequently in biofilm than sediment. We constructed general additive models to investigate relations between pesticides and 6 metrics of benthic community structure. Pesticides in biofilm improved fit in 4 of the 6 models, and pesticides in sediment improved fit in 2. The results indicate that the sampling of stream biofilms can complement bed-sediment sampling by identification of more current-use pesticides present and better estimation of ecological risks.

Bifenthrin Causes Trophic Cascade and Altered Insect Emergence in Mesocosms: Implications for Small Streams.

Direct and indirect ecological effects of the widely used insecticide bifenthrin on stream ecosystems are largely unknown. To investigate such effects, a manipulative experiment was conducted in stream mesocosms that were colonized by aquatic insect communities and exposed to bifenthrin-contaminated sediment; implications for natural streams were interpreted through comparison of mesocosm results to a survey of 100 Midwestern streams, USA. In the mesocosm experiment, direct effects of bifenthrin exposure included reduced larval macroinvertebrate abundance, richness, and biomass at concentrations (EC50's ranged from 197.6 to 233.5 ng bifenthrin/g organic carbon) previously thought safe for aquatic life. Indirect effects included a trophic cascade in which periphyton abundance increased after macroinvertebrate scrapers decreased. Adult emergence dynamics and corresponding terrestrial subsidies were altered at all bifenthrin concentrations tested. Extrapolating these results to the Midwestern stream assessment suggests pervasive ecological effects, with altered emergence dynamics likely in 40% of streams and a trophic cascade in 7% of streams. This study provides new evidence that a common pyrethroid might alter aquatic and terrestrial ecosystem function at the regional scale.

High Nitrate Concentrations in Some Midwest United States Streams in 2013 after the 2012 Drought.

Nitrogen sources in the Mississippi River basin have been linked to degradation of stream ecology and to Gulf of Mexico hypoxia. In 2013, the USGS and the USEPA characterized water quality stressors and ecological conditions in 100 wadeable streams across the midwestern United States. Wet conditions in 2013 followed a severe drought in 2012, a weather pattern associated with elevated nitrogen concentrations and loads in streams. Nitrate concentrations during the May to August 2013 sampling period ranged from <0.04 to 41.8 mg L as N (mean, 5.31 mg L). Observed mean May to June nitrate concentrations at the 100 sites were compared with May to June concentrations predicted from a regression model developed using historical nitrate data. Observed concentrations for 17 sites, centered on Iowa and southern Minnesota, were outside the 95% confidence interval of the regression-predicted mean, indicating that they were anomalously high. The sites with a nitrate anomaly had significantly higher May to June nitrate concentrations than sites without an anomaly (means, 19.8 and 3.6 mg L, respectively) and had higher antecedent precipitation indices, a measure of the departure from normal precipitation, in 2012 and 2013. Correlations between nitrate concentrations and watershed characteristics and nitrogen and oxygen isotopes of nitrate indicated that fertilizer and manure used in crop production, principally corn, were the dominant sources of nitrate. The anomalously high nitrate levels in parts of the Midwest in 2013 coincide with reported higher-than-normal nitrate loads in the Mississippi River.

Declining Dioxin Concentrations in the Rhone River Basin, France, Attest to the Effectiveness of Emissions Controls.

Emission-control policies have been implemented in Europe and North America since the 1990s for polychlorodibenzodioxins (PCDDs) and furans (PCDFs). To assess the effect of these policies on temporal trends and spatial patterns for these compounds in a large European river system, sediment cores were collected in seven depositional areas along the Rhone River in France, dated, and analyzed for PCDDs and PCDFs. Results show concentrations increase in the downstream direction and have decreased temporally at all sites during the last two decades, with an average decrease of 83% from 1992 to 2010. The time for a 50% decrease in concentrations (t1/2) averaged 6.9±2.6 and 9.1±2.9 years for the sum of measured PCDDs and PCDFs, respectively. Congener patterns are similar among cores and indicate dominance of regional atmospheric deposition and possibly weathered local sources. Local sources are clearly indicated at the most downstream site, where concentrations of the most toxic dioxin, TCDD, are about 2 orders of magnitude higher than at the other six sites. The relatively steep downward trends attest to the effects of the dioxin emissions reduction policy in Europe and suggest that risks posed to aquatic life in the Rhone River basin from dioxins and furans have been greatly reduced.

Acute toxicity of runoff from sealcoated pavement to Ceriodaphnia dubia and Pimephales promelas.

Runoff from coal-tar-based (CT) sealcoated pavement is a source of polycyclic aromatic hydrocarbons (PAHs) and N-heterocycles to surface waters. We investigated acute toxicity of simulated runoff collected from 5 h to 111 days after application of CT sealcoat and from 4 h to 36 days after application of asphalt-based sealcoat containing about 7% CT sealcoat (AS/CT-blend). Ceriodaphnia dubia (cladocerans) and Pimephales promelas (fathead minnows) were exposed in the laboratory to undiluted and 1:10 diluted runoff for 48 h, then transferred to control water and exposed to 4 h of ultraviolet radiation (UVR). Mortality following exposure to undiluted runoff from unsealed asphalt pavement and UVR was ≤10% in all treatments. Test organisms exposed to undiluted CT runoff samples collected during the 3 days (C. dubia) or 36 days (P. promelas) following sealcoat application experienced 100% mortality prior to UVR exposure; with UVR exposure, mortality was 100% for runoff collected across the entire sampling period. Phototoxic-equivalent PAH concentrations and mortality demonstrated an exposure-response relation. The results indicate that runoff remains acutely toxic for weeks to months after CT sealcoat application.

PAH concentrations in lake sediment decline following ban on coal-tar-based pavement sealants in Austin, Texas.

Recent studies have concluded that coal-tar-based pavement sealants are a major source of polycyclic aromatic hydrocarbons (PAHs) in urban settings in large parts of the United States. In 2006, Austin, TX, became the first jurisdiction in the U.S. to ban the use of coal-tar sealants. We evaluated the effect of Austin's ban by analyzing PAHs in sediment cores and bottom-sediment samples collected in 1998, 2000, 2001, 2012, and 2014 from Lady Bird Lake, the principal receiving water body for Austin urban runoff. The sum concentration of the 16 EPA Priority Pollutant PAHs (∑PAH16) in dated core intervals and surficial bottom-sediment samples collected from sites in the lower lake declined about 44% from 1998-2005 to 2006-2014 (means of 7980 and 4500 µg kg(-1), respectively), and by 2012-2014, the decline was about 58% (mean of 3320 µg kg(-1)). Concentrations of ∑PAH16 in bottom sediment from two of three mid-lake sites decreased by about 71 and 35% from 2001 to 2014. Concentrations at a third site increased by about 14% from 2001 to 2014. The decreases since 2006 reverse a 40-year (1959-1998) upward trend. Despite declines in PAH concentrations, PAH profiles and source-receptor modeling results indicate that coal-tar sealants remain the largest PAH source to the lake, implying that PAH concentrations likely will continue to decline as stocks of previously applied sealant gradually become depleted.

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.

Cancer risk from incidental ingestion exposures to PAHs associated with coal-tar-sealed pavement.

Recent (2009-10) studies documented significantly higher concentrations of polycyclic aromatic hydrocarbons (PAHs) in settled house dust in living spaces and soil adjacent to parking lots sealed with coal-tar-based products. To date, no studies have examined the potential human health effects of PAHs from these products in dust and soil. Here we present the results of an analysis of potential cancer risk associated with incidental ingestion exposures to PAHs in settings near coal-tar-sealed pavement. Exposures to benzo[a]pyrene equivalents were characterized across five scenarios. The central tendency estimate of excess cancer risk resulting from lifetime exposures to soil and dust from nondietary ingestion in these settings exceeded 1 × 10(-4), as determined using deterministic and probabilistic methods. Soil was the primary driver of risk, but according to probabilistic calculations, reasonable maximum exposure to affected house dust in the first 6 years of life was sufficient to generate an estimated excess lifetime cancer risk of 6 × 10(-5). Our results indicate that the presence of coal-tar-based pavement sealants is associated with significant increases in estimated excess lifetime cancer risk for nearby residents. Much of this calculated excess risk arises from exposures to PAHs in early childhood (i.e., 0-6 years of age).

Coal-tar-based pavement sealcoat and PAHs: implications for the environment, human health, and stormwater management.

Coal-tar-based sealcoat products, widely used in the central and eastern U.S. on parking lots, driveways, and even playgrounds, are typically 20-35% coal-tar pitch, a known human carcinogen that contains about 200 polycyclic aromatic hydrocarbon (PAH) compounds. Research continues to identify environmental compartments-including stormwater runoff, lake sediment, soil, house dust, and most recently, air-contaminated by PAHs from coal-tar-based sealcoat and to demonstrate potential risks to biological communities and human health. In many cases, the levels of contamination associated with sealed pavement are striking relative to levels near unsealed pavement: PAH concentrations in air over pavement with freshly applied coal-tar-based sealcoat, for example, were hundreds to thousands of times higher than those in air over unsealed pavement. Even a small amount of sealcoated pavement can be the dominant source of PAHs to sediment in stormwater-retention ponds; proper disposal of such PAH-contaminated sediment can be extremely costly. Several local governments, the District of Columbia, and the State of Washington have banned use of these products, and several national and regional hardware and home-improvement retailers have voluntarily ceased selling them.

New-generation pesticides are prevalent in California's Central Coast streams.

Pesticides are widely recognized as important biological stressors in streams, especially in heavily developed urban and agricultural areas like the Central California Coast region. We assessed occurrence and potential toxicity of pesticides in small streams in the region using two analytical methods: a broad-spectrum (223 compounds) method in use since 2012 and a newly developed method for 30 additional new-generation fungicides and insecticides. At least one pesticide compound was identified in 83 of the 85 streams sampled. About one-half (48%) of the 253 pesticides measured were detected at least once and 27 were detected in 10% or more of samples. Three of the top 4, and 6 of the top 10 most frequently detected compounds (chlorantraniliprole, dinotefuran, boscalid, thiamethoxam, clothianidin and the fluopicolide degradate 2,6-dichlorobenzamide) were analyzed by the new method. Pesticide mixtures were common, with two or more pesticide compounds detected in 81% of samples and 10 or more in 32% of samples. The pesticide count at a site was relatively consistent over the 6-week study. Four sites with mixed land-use in the lower basin (<5 km from the sampling site) tended to have the highest pesticide counts and the highest concentrations. Potential toxicity (assessed by comparison to benchmarks) to invertebrates was much more common than potential toxicity to fish or plants and was associated with a wide array of insecticides. The common occurrence of new-generation pesticides highlights the need to continuously update analytical methods to keep pace with changing pesticide use for a fuller assessment of pesticide occurrence and effects on the environment.

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.

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.

Multi-region assessment of chemical mixture exposures and predicted cumulative effects in USA wadeable urban/agriculture-gradient streams.

Chemical-contaminant mixtures are widely reported in large stream reaches in urban/agriculture-developed watersheds, but mixture compositions and aggregate biological effects are less well understood in corresponding smaller headwaters, which comprise most of stream length, riparian connectivity, and spatial biodiversity. During 2014-2017, the U.S. Geological Survey (USGS) measured 389 unique organic analytes (pharmaceutical, pesticide, organic wastewater indicators) in 305 headwater streams within four contiguous United States (US) regions. Potential aquatic biological effects were evaluated for estimated maximum and median exposure conditions using multiple lines of evidence, including occurrence/concentrations of designed-bioactive pesticides and pharmaceuticals and cumulative risk screening based on vertebrate-centric ToxCast™ exposure-response data and on invertebrate and nonvascular plant aquatic life benchmarks. Mixed-contaminant exposures were ubiquitous and varied, with 78% (304) of analytes detected at least once and cumulative maximum concentrations up to more than 156,000 ng/L. Designed bioactives represented 83% of detected analytes. Contaminant summary metrics correlated strong-positive (rho (ρ): 0.569-0.719) to multiple watershed-development metrics, only weak-positive to point-source discharges (ρ: 0.225-353), and moderate- to strong-negative with multiple instream invertebrate metrics (ρ: -0.373 to -0.652). Risk screening indicated common exposures with high probability of vertebrate-centric molecular effects and of acute toxicity to invertebrates, respectively. The results confirm exposures to broad and diverse contaminant mixtures and provide convincing multiple lines of evidence that chemical contaminants contribute substantially to adverse multi-stressor effects in headwater-stream communities.

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.

Daily stream samples reveal highly complex pesticide occurrence and potential toxicity to aquatic life.

Transient, acutely toxic concentrations of pesticides in streams can go undetected by fixed-interval sampling programs. Here we compare temporal patterns in occurrence of current-use pesticides in daily composite samples to those in weekly composite and weekly discrete samples of surface water from 14 small stream sites. Samples were collected over 10-14 weeks at 7 stream sites in each of the Midwestern and Southeastern United States. Samples were analyzed for over 200 pesticides and degradates by direct aqueous injection liquid chromatography with tandem mass spectrometry. Nearly 2 and 3 times as many unique pesticides were detected in daily samples as in weekly composite and weekly discrete samples, respectively. Based on exceedances of acute-invertebrate benchmarks (AIB) and(or) a Pesticide Toxicity Index (PTI) >1, potential acute-invertebrate toxicity was predicted at 11 of 14 sites from the results for daily composite samples, but was predicted for only 3 sites from weekly composites and for no sites from weekly discrete samples. Insecticides were responsible for most of the potential invertebrate toxicity, occurred transiently, and frequently were missed by the weekly discrete and composite samples. The number of days with benthic-invertebrate PTI ≥0.1 in daily composite samples was inversely related to Ephemeroptera, Plecoptera, and Trichoptera (EPT) richness at the sites. The results of the study indicate that short-term, potentially toxic peaks in pesticides frequently are missed by weekly discrete sampling, and that such peaks may contribute to degradation of invertebrate community condition in small streams. Weekly composite samples underestimated maximum concentrations and potential acute-invertebrate toxicity, but to a lesser degree than weekly discrete samples, and provided a reasonable approximation of the 90th percentile total concentrations of herbicides, insecticides, and fungicides, suggesting that weekly composite sampling may be a compromise between assessment needs and cost.