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.

Prioritizing river basins for intensive monitoring and assessment by the US Geological Survey.

The US Geological Survey (USGS) is currently (2020) integrating its water science programs to better address the nation's greatest water resource challenges now and into the future. This integration will rely, in part, on data from 10 or more intensively monitored river basins from across the USA. A team of USGS scientists was convened to develop a systematic, quantitative approach to prioritize candidate basins for this monitoring investment to ensure that, as a group, the 10 basins will support the assessment and forecasting objectives of the major USGS water science programs. Candidate basins were the level-4 hydrologic units (HUC04) with some of the smaller HUC04s being combined; median candidate-basin area is 46,600 km2. Candidate basins for the contiguous United States (CONUS) were grouped into 18 hydrologic regions. Ten geospatial variables representing land use, climate change, water use, water-balance components, streamflow alteration, fire risk, and ecosystem sensitivity were selected to rank candidate basins within each of the 18 hydrologic regions. The two highest ranking candidate basins in each of the 18 regions were identified as finalists for selection as "Integrated Water Science Basins"; final selection will consider input from a variety of stakeholders. The regional framework, with only one basin selected per region, ensures that as a group, the basins represent the range in major drivers of the hydrologic cycle. Ranking within each region, primarily based on anthropogenic stressors of water resources, ensures that settings representing important water-resource challenges for the nation will be studied.

Linking the Agricultural Landscape of the Midwest to Stream Health with Structural Equation Modeling.

Multiple physical and chemical stressors can simultaneously affect the biological condition of streams. To better understand the complex interactions of land-use practices, water quality, and ecological integrity of streams, the U.S. Geological Survey National Water Quality Assessment Project is conducting regional-scale assessments of stream condition across the United States. In the summer of 2013, weekly water samples were collected from 100 streams in the Midwestern United States. Employing watershed theory, we used structural equation modeling (SEM) to represent a general hypothesis for how 16 variables (previously identified to be important to stream condition) might be inter-related. Again, using SEM, we evaluated the ability of this "stressor network" to explain variations in multimetrics of algal, invertebrate, and fish community health, trimming away any environmental variables not contributing to an explanation of the ecological responses. Seven environmental variables-agricultural and urban land use, sand content of soils, basin area, percent riparian area as forest, channel erosion, and relative bed stability-were found to be important for all three-community metrics. The algal and invertebrate models included water-chemistry variables not included in the fish model. Results suggest that ecological integrity of Midwest streams are affected by both agricultural and urban land uses and by the natural geologic setting, as indicated by the sand content of soils. Chemicals related to crops (pesticides and nutrients) and residential uses (pyrethroids) were found to be more strongly related to ecological integrity than were natural factors (riparian forest, watershed soil character).

Chemical and Physical Controls on Mercury Source Signatures in Stream Fish from the Northeastern United States.

Streams in the northeastern U.S. receive mercury (Hg) in varying proportions from atmospheric deposition and legacy point sources, making it difficult to attribute shifts in fish concentrations directly back to changes in Hg source management. Mercury stable isotope tracers were utilized to relate sources of Hg to co-located fish and bed sediments from 23 streams across a forested to urban-industrial land-use gradient within this region. Mass-dependent isotopes (δ202Hg) in prey and game fish at forested sites were depleted (medians -0.95 and -0.83 ‰, respectively) in comparison to fish from urban-industrial settings (medians -0.26 and -0.38 ‰, respectively); the forested site group also had higher prey fish Hg concentrations. The separation of Hg isotope signatures in fish was strongly related to in-stream and watershed land-use indicator variables. Fish isotopes were strongly correlated with bed sediment isotopes, but the isotopic offset between the two matrices was variable due to differing ecosystem-specific drivers controlling the extent of MeHg formation. The multivariable approach of analyzing watershed characteristics and stream chemistry reveals that the Hg isotope composition in fish is linked to current and historic Hg sources in the northeastern U.S. and can be used to trace bioaccumulated Hg.

Sources and ages of fine-grained sediment to streams using fallout radionuclides in the Midwestern United States.

Fallout radionuclides, 7Be and 210Pbex, sampled in bed sediment for 99 watersheds in the Midwestern region of the United States and in 15 samples of suspended sediment from 3 of these watersheds were used to partition upland from channel sources and to estimate the age or the time since the surface-derived portion of sediment was on the land surface (0-∼1 year). Channel sources dominate: 78 of the 99 bed material sites (79%) have >50% channel-derived sediment, and 9 of the 15 suspended-sediment samples (60%) have >50% channel-derived sediment. 7Be was detected in 82 bed sediment samples and all 15 suspended-sediment samples. The surface-derived portion of 54 of the 80 (68%) streams with detectable 7Be and 210Pbex were ≤ 100 days old and the surface-derived portion of all suspended-sediment samples were ≤ 100 days old, indicating that surface-derived fine-grained sediment moves rapidly though these systems. The concentrations of two hydrophobic pesticides-DDE and bifenthrin-are correlated with the proportion of surface-derived sediment, indicating a link between geomorphic processes and particle-associated contaminants in streams. Urban areas had the highest pesticide concentrations and the largest percentage of surface-derived sediment. Although the percentage of surface-derived sediment is less than channel sources at most of the study sites, the relatively young age of the surface-derived sediment might indicate that management actions to reduce sediment contamination where the land surface is an important source could have noticeable effects.

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.

Zinc isotopic signatures in eight lake sediment cores from across the United States.

Zinc is an important trace element pollutant in urban environments; however, the extent of Zn contamination and the sources of urban Zn pollution are often unclear. We measured Zn concentrations and isotopes in sediment cores collected from eight lakes or reservoirs across the United States. We paired these data with historical records of land use within each watershed to calculate a mean Zn concentration and δ(66)Zn for natural (less than 5% urban land use; 123 ± 21.7 mg/kg; +0.33 ± 0.08‰, n = 6 lakes) and urban (greater than 70% urban land use; 389 ± 200 mg/kg; +0.14 ± 0.07‰, n = 3 lakes) lake sediments. The relation between Zn concentration data and Zn isotope data allows us to create a mixing model between two end members: natural and urban. The δ(66)Zn of the urban end-member is consistent with Zn pollution from vehicle-related sources (tire wear and emissions). Application of this model to samples collected from lakes recording periods ranging from 5 to 70% urban land use in their surrounding watersheds indicates that the lakes and reservoirs were affected by large amounts of Zn from urban sources.

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).

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.

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.