Four decades of regional wet deposition, local bulk deposition, and stream-water chemistry show the influence of nearby land use on forested streams in Central Appalachia.

Hydrologic monitoring began on two headwater streams (<1 km2) on the University of Kentucky's Robinson Forest in 1971. We evaluated stream-water (1974-2013) and bulk-deposition (wet + dust) (1984-2013) chemistry in the context of regional wet-deposition patterns that showed decreases in both sulfate and nitrate concentrations as well as proximal surface-mine expansion. Decadal time steps (1974-83, 1984-93, 1994-2003, 2004-2013) were used to quantify change. Comparison of the first two decades showed similarly decreased sulfate (minimum flow-adjusted annual-mean concentration of ≈13.5 mg/L in 1982 to 8.8 mg/L in 1992) and increased pH (6.6-6.8) in both streams, reflecting contemporaneous changes in both bulk and wet deposition. In contrast, concentrations of nitrate (0.14 to >0.25 mg/L) and base cations increased between these two decades, coinciding with expansion of surface mining between 1985 and 1995. In 2004, stream-water pH (6.7 in 2004), sulfate (9.2 mg/L), and nitrate (>0.11 mg/L) were similar to 1982, despite wet-deposition concentrations being lower. Base-cation concentrations were higher in the stream adjacent to ongoing surface mining relative to the stream situated near the middle of the experimental forest. However, pH decreased to approximately 5.7 by 2013 for both streams, which, combined with a shift in dominant cations from calcium to magnesium and potassium, indicates that the soil-buffering capacity of this landscape has been exceeded. Ratios of bulk deposition and stream-water concentrations indicate enrichment of sulfate (1.7-25.2) and cations (0.5-64.8), but not nitrogen (0.1-5.6), indicating that the Forest is not nitrogen saturated and that ongoing changes in water-quality are sulfate driven. When concentrations were adjusted to account for changes in streamflow (climate) over the 4 decades, external influences (land management/regulation) explained most change. The amount and direction of change differed among constituents, both between consecutive decades and between the first and last decades, reflecting the influence of localized surface mining even as regional wet deposition continued to improve due to the Clean Air Act. The implication is that localized stressors have the potential to out-pace the benefits of national environmental policies for communities that depend on local water-resources in similar environments.

Pesticides in US Rivers: Regional differences in use, occurrence, and environmental toxicity, 2013 to 2017.

Pesticides pose a threat to the environment, but because of the substantial number of compounds, a comprehensive assessment of pesticides and an evaluation of the risk that they pose to human and aquatic life is challenging. In this study, improved analytical methods were used to quantify 221 pesticide concentrations in surface waters over the time period from 2013 to 2017. Samples were collected from 74 river sites in the conterminous US (CONUS). Potential toxicity was assessed by comparing surface water pesticide concentrations to standard concentrations that are considered to have adverse effects on human health or aquatic organisms. The majority of pesticide use is related to agriculture, and agricultural production varies across the CONUS. Therefore, our results were summarized by region (Northeast, South, Midwest, West and Pacific), with the expectation that crop production differences would drive variability in pesticide use, detection frequency, and benchmark exceedance patterns. Although agricultural pesticide use was at least 2.5 times higher in the Midwest (49 kg km-2) than in any of the other four regions (Northeast, South, West, and Pacific, 3 to 21 kg km-2) and the average number of pesticides detected in the Midwest was at least 1.5 higher (n = 25) than the other four regions (n = 8 to n = 16), the potential toxicity results were more evenly distributed. At least 50% of the sites within each of the 5 regions had at least 1 chronic benchmark exceedance. Imidacloprid posed the greatest potential threat to aquatic life with a total of 245 benchmark exceedances at 60 of the 74 sites. These results show that pesticides persist in the environment beyond the site of application and expected period of use. Continued monitoring and research are needed to improve our understanding of pesticide effects on aquatic and human life.

Pesticide mixtures show potential toxicity to aquatic life in U.S. streams, water years 2013-2017.

During water years (WY) 2013-2017, the U.S. Geological Survey, National Water-Quality Assessment (NAWQA) Project, sampled the National Water Quality Network - Rivers and Streams (NWQN) year-round and reported on 221 pesticides at 72 sites across the United States in agricultural, developed, and mixed land use watersheds. The Pesticide Toxicity Index (PTI) was used to estimate the potential chronic and acute toxicity to three taxonomic groups - fish, cladocerans, and benthic invertebrates. For invertebrates (either cladocerans, benthic invertebrates, or both), the maximum PTI score exceeded the predicted acute toxicity screening level at 18 of the 72 sites (25%) at some point during WY 2013-2017. The predicted toxicity of a single pesticide compound was found to overwhelm the toxicity of other pesticides in the mixtures after concentrations were toxicity weighted. For this study, about 71%, 72%, and 92% of the Fish-, Cladoceran-, and Benthic Invertebrate-PTI scores, respectively, had one pesticide compound primarily contributing to sample potential toxicity (>50%). There were 17 (13 insecticides, 2 herbicides, 1 fungicide, and 1 synergist) of the 221 pesticide compounds analyzed that were the primary drivers of potential toxicity in each water sample in which the PTI and TUmax (toxic unit score for the pesticide that makes the single largest contribution to the PTI) scores were above predicted chronic (>0.1) or acute (>1) toxicity levels for one of the three taxa. For cladocerans and benthic invertebrates, the drivers of predicted chronic (>0.1) and acute (>1) PTIs were mostly insecticides. For cladocerans, the pesticide compounds driving the PTI scores were bifenthrin, carbaryl, chlorpyrifos, diazinon, dichlorvos, dicrotophos, diflubenzuron, flubendiamide, and tebupirimfos. For benthic invertebrates, atrazine (an herbicide), as well as the insecticides - bifenthrin, carbaryl, carbofuran, chlorpyrifos, diazinon, dichlorvos, fipronil, imidacloprid, and methamidophos - were the drivers of predicted toxicity. For fish, there were three pesticide types that contributed the most to predicted chronic (>0.1) PTIs - acetochlor, an herbicide; carbendazim, a fungicide degradate; and piperonylbutoxide, a synergist.

Influence of land use and region on glyphosate and aminomethylphosphonic acid in streams in the USA.

Glyphosate is the most widely used herbicide in the United States for agricultural and non-agricultural weed control. Many studies demonstrate possible effects of glyphosate and its degradate AMPA on human and ecological health. Although glyphosate is thought to have limited mobility in soil, it is found year-round in many rivers and streams throughout the world in both agricultural and developed environments. It is vitally important to continue to increase the knowledge base of glyphosate use, distribution, transport, and impacts on human health and the environment. Here we show that glyphosate and AMPA are found in nearly all of 70 streams throughout the United States at concentrations far below human health or ecological benchmarks, with less occurrence in the Northeast and that undeveloped land, classified as such by land use near the sampling station, has lower concentrations compared to other types of land. Results also show that sites with large watersheds tend to have more AMPA than glyphosate and the opposite is true for small watersheds. Travel times and opportunity for glyphosate to degrade to AMPA and for reservoirs of AMPA to grow are greater in large watersheds. Factors that promoted quick movement of glyphosate to streams, such as subsurface tile or storm drains, sewers, overland flow from developed landscapes, and arid landscapes were associated with sites that had greater concentrations of glyphosate compared to AMPA. These results contribute contemporary information and generalized interpretations adding to the knowledge base of the fate of glyphosate on a national scale and provide a springboard for further exploration of technical processes controlling transport to streams.

Water-quality trends in U.S. rivers, 2002 to 2012: Relations to levels of concern.

Effective management and protection of water resources relies upon understanding how water-quality conditions are changing over time. Water-quality trends for ammonia, chloride, nitrate, sulfate, total dissolved solids (TDS), total nitrogen (TN) and total phosphorus (TP) were assessed at 762 sites located in the conterminous United States between 2002 and 2012. Annual mean concentrations at the start and end of the trend period were compared to an environmentally meaningful level of concern (LOC) to categorize patterns in water-quality changes. Trend direction, magnitude, and the proximity of concentrations to LOCs were investigated. Of the 1956 site-constituent combinations investigated, 30% were above the LOC in 2002, and only six (0.3%) crossed the LOC threshold, either from above or below, indicating that waterquality conditions are not substantially improving, nor are they degrading, in relation to the LOCs. The concentrations of ammonia, nitrate, sulfate, chloride, and TDS tended to be below the LOC, and in cases where the trend was increasing (concentrations approached the LOC from below), the increases were varied and small in magnitude. In contrast, concentrations of TN and TP tended to be above the LOC, and where the trend was decreasing (concentrations approached the LOC from above), the decreases were larger in magnitude and more consistent. These results indicate that if water-quality conditions continue to trend in the same direction, at the same rate, for all sites and constituents studied, elevated concentrations are more likely to drop below an LOC before low concentrations will exceed an LOC.

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.

Prediction of Pesticide Toxicity in Midwest Streams.

The occurrence of pesticide mixtures is common in stream waters of the United States, and the impact of multiple compounds on aquatic organisms is not well understood. Watershed Regressions for Pesticides (WARP) models were developed to predict Pesticide Toxicity Index (PTI) values in unmonitored streams in the Midwest and are referred to as WARP-PTI models. The PTI is a tool for assessing the relative toxicity of pesticide mixtures to fish, benthic invertebrates, and cladocera in stream water. One hundred stream sites in the Midwest were sampled weekly in May through August 2013, and the highest calculated PTI for each site was used as the WARP-PTI model response variable. Watershed characteristics that represent pesticide sources and transport were used as the WARP-PTI model explanatory variables. Three WARP-PTI models-fish, benthic invertebrates, and cladocera-were developed that include watershed characteristics describing toxicity-weighted agricultural use intensity, land use, agricultural management practices, soil properties, precipitation, and hydrologic properties. The models explained between 41 and 48% of the variability in the measured PTI values. WARP-PTI model evaluation with independent data showed reasonable performance with no clear bias. The models were applied to streams in the Midwest to demonstrate extrapolation for a regional assessment to indicate vulnerable streams and to guide more intensive monitoring.