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Conservation efforts have been implemented in agroecosystems to enhance pollinator diversity by creating grassland habitat, but little is known about the exposure of bees to pesticides while foraging in these grassland fields. Pesticide exposure was assessed in 24 conservation grassland fields along an agricultural gradient at two time points (July and August) using silicone band passive samplers (nonlethal) and bee tissues (lethal). Overall, 46 pesticides were detected including 9 herbicides, 19 insecticides, 17 fungicides, and a plant growth regulator. For the bands, there were more frequent/higher concentrations of herbicides in July (maximum: 1600 ng/band in July; 570 ng/band in August), while insecticides and fungicides had more frequent/higher concentrations in August (maximum: 110 and 65 ng/band in July; 1500 and 1700 ng/band in August). Pesticide concentrations in bands increased 16% with every 10% increase in cultivated crops. The bee tissues showed no difference in detection frequency, and concentrations were similar among months; maximum concentrations of herbicides, insecticides, and fungicides in July and August were 17, 27, and 180 and 19, 120, and 170 ng/g, respectively. Pesticide residues in bands and bee tissues did not always show the same patterns; of the 20 compounds observed in both media, six (primarily fungicides) showed a detection-concentration relationship between the two media. Together, the band and bee residue data can provide a more complete understanding of pesticide exposure and accumulation in conserved grasslands.

Continued improvements in drinking-water quality characterization and treatment/distribution infrastructure are required to address the expanding number of documented environmental contaminants. To better understand the variability in contaminant exposures from the drinking water resource (surface and groundwater), through the distribution process, to the point-of-use (tapwater), in 2019 a synoptic assessment of broad chemical exposures was conducted in system-specific source waters, finished drinking water and service-area tapwater from 10 drinking water treatment facilities in the greater Minneapolis/St. Paul area of Minnesota, United States. Source water, finished water (collected pre-distribution in the treatment facility), and tapwater samples were analyzed for 465 unique organic compounds, 34 inorganic constituents, and 3 field parameters as well as in vitroestrogen, androgen, and glucocorticoid bioactivities. Mixtures of organic and inorganic contaminants were prevalent in source water, finished water, and tapwater samples, indicating the continued need for broad assessments of mixed contaminant exposures to characterize potential drinking-water human health outcomes. Contaminant concentrations were similar among drinking water sources and no exceedances of Environmental Protection Agency maximum contaminant level(s) (MCL) were observed in any treated sample (finished water or tapwater) in this study. No treated sample contained estrogenic, androgenic, or glucocorticoid activity at concentrations that may cause adverse human health effects. However, there were multiple exceedances of non-enforceable MCL goal(s) (MCLG), and other health advisories combined with frequent exceedances of benchmark-based hazard indices in both finished water and tapwater samples. These results indicate that exposure to contaminant mixtures is a potential public health concern underscoring our continued efforts to assess contaminant mixture exposures at the drinking-water point of consumption using a broad analytical scope.

A multi-agency study of 438 organic and 62 inorganic chemicals measured in urban stormwater during 50 total runoff events at 21 sites across the United States demonstrated that stormwater discharges can generate localized, aquatic exposures to extensive contaminant mixtures, including organics suspected to cause adverse aquatic-health effects. The aggregated risks to multiple aquatic trophic levels (fish, invertebrates, plants) of the stormwater mixture exposures, which were documented in the national study, were explored herein by calculating cumulative ratios of organic-contaminant in vitroexposure–activity cutoffs (∑EAR) and health-benchmark-weighted cumulative toxicity quotients (∑TQ). Both risk assessment approaches indicated substantial (moderate to high) risk for acute adverse effects to aquatic organisms across multiple trophic levels (fish, macroinvertebrates, non-vascular/vascular plants) at or near stormwater discharge points across the United States. The results are interpreted as potential orders of magnitude underestimates of actual aquatic risk in stormwater control wetlands or in the immediate vicinity of such discharges to surface-water receptors, because the 438 organic-compound analytical space assessed in this study is orders of magnitude less than the 350 000 parent compounds estimated to be in current commercial use globally and the incalculable chemical-space of potential metabolites and degradates.

Widespread disposal of landfill leachate to municipal sewer infrastructure in the United States calls for an improved understanding of the relative organic-chemical contributions to the wastewater treatment plant (WWTP) waste stream and associated surface-water discharge to receptors in the environment. Landfill leachate, WWTP influent, and WWTP effluent samples were collected from three landfill-WWTP systems and compared with analogous influent and effluent samples from two WWTPs that did not receive leachate. Samples were analyzed for 73 per-/poly-fluoroalkyl substances (PFAS), 109 pharmaceuticals, and 21 hormones and related compounds. PFAS were detected more frequently in leachate (92%) than in influent (55%). Total PFAS concentrations in leachate (93 100 ng L−1) were more than 10 times higher than in influent (6950 ng L−1) and effluent samples (3730 ng L−1). Concentrations of bisphenol A; the nonprescription pharmaceuticals cotinine, lidocaine, nicotine; and the prescription pharmaceuticals amphetamine, carisoprodol, pentoxifylline, and thiabendazole were an order of magnitude higher in landfill leachate than WWTP influent. Leachate load contributions for PFAS (0.78 to 31 g d−1), bisphenol A (0.97 to 8.3 g d−1), and nonprescription (2.0 to 3.1 g d−1) and prescription (0.48 to 2.5 g d−1) pharmaceuticals to WWTP influent were generally low (<10 g d−1) for most compounds resulting from high influent-to-leachate volumetric ratios (0.983). No clear differences in concentrations were apparent between effluents from WWTPs receiving landfill leachate and those that did not receive landfill leachate.

AbstractHabitat disturbance is an important cause of global amphibian declines, with especially strong effects in areas of high agricultural use. Determining the influence of site characteristics on amphibian presence and success is vital to developing effective conservation strategies. We used occupancy analysis to estimate presence of four anuran species at wetlands in northern Iowa as a function of eight environmental covariates hypothesized to affect occupancy: fish and salamander abundance, invertebrate density, aquatic vegetative cover, wetland area, atrazine concentration in water, surrounding agricultural land use, and an overall wetland health score (wetland condition index WCI). We surveyed 27 wetlands multiple times in 2015 and 2016. Leopard Frogs (Lithobates pipiens) and American Toads (Anaxyrus americanus) were observed at 100 of the sites, Boreal Chorus Frogs (Pseudacris maculata) at 96, and Gray Treefrogs (Hylaspp.) at 81. Wetland site occupancy for all species in our study ranged from 0.23 (Hylaspp. tadpoles) to 0.95 (L. pipiensadults), indicating that agricultural wetlands can provide refuge or habitat for amphibians. Fish abundance, percentage of cropland cover within 500 m of the wetland, and salamander abundance were among the variables best supported by our models although their estimated effects were weak. Wetland area, atrazine concentration, vegetative cover, and WCI also influenced occupancy probability, but for only a small number of species and life stages. The direction of predicted effects varied by species and life stage. Despite only weak evidence that the environmental factors we measured influenced anuran occupancy, our results provide insights for managers seeking to understand how amphibians use landscapes modified by agriculture.

AbstractHabitat disturbance is an important cause of global amphibian declines, with especially strong effects in areas of high agricultural use. Determining the influence of site characteristics on amphibian presence and success is vital to developing effective conservation strategies. We used occupancy analysis to estimate presence of four anuran species at wetlands in northern Iowa as a function of eight environmental covariates hypothesized to affect occupancy: fish and salamander abundance, invertebrate density, aquatic vegetative cover, wetland area, atrazine concentration in water, surrounding agricultural land use, and an overall wetland health score (wetland condition index [WCI]). We surveyed 27 wetlands multiple times in 2015 and 2016. Leopard Frogs (Lithobates pipiens) and American Toads (Anaxyrus americanus) were observed at 100% of the sites, Boreal Chorus Frogs (Pseudacris maculata) at 96%, and Gray Treefrogs (Hylaspp.) at 81%. Wetland site occupancy for all species in our study ranged from 0.23 (Hylaspp. tadpoles) to 0.95 (L. pipiensadults), indicating that agricultural wetlands can provide refuge or habitat for amphibians. Fish abundance, percentage of cropland cover within 500 m of the wetland, and salamander abundance were among the variables best supported by our models although their estimated effects were weak. Wetland area, atrazine concentration, vegetative cover, and WCI also influenced occupancy probability, but for only a small number of species and life stages. The direction of predicted effects varied by species and life stage. Despite only weak evidence that the environmental factors we measured influenced anuran occupancy, our results provide insights for managers seeking to understand how amphibians use landscapes modified by agriculture.

Safe drinking water at the point-of-use (tapwater, TW) is a United States public health priority. Multiple lines of evidence were used to evaluate potential human health concerns of 482 organics and 19 inorganics in TW from 13 (7 public supply, 6 private well self-supply) home and 12 (public supply) workplace locations in 11 states. Only uranium (61.9 μg L–1, private well) exceeded a National Primary Drinking Water Regulation maximum contaminant level (MCL: 30 μg L–1). Lead was detected in 23 samples (MCL goal: zero). Seventy-five organics were detected at least once, with median detections of 5 and 17 compounds in self-supply and public supply samples, respectively (corresponding maxima: 12 and 29). Disinfection byproducts predominated in public supply samples, comprising 21% of all detected and 6 of the 10 most frequently detected. Chemicals designed to be bioactive (26 pesticides, 10 pharmaceuticals) comprised 48% of detected organics. Site-specific cumulative exposure–activity ratios (∑EAR) were calculated for the 36 detected organics with ToxCast data. Because these detections are fractional indicators of a largely uncharacterized contaminant space, ∑EARin excess of 0.001 and 0.01 in 74 and 26% of public supply samples, respectively, provide an argument for prioritized assessment of cumulative effects to vulnerable populations from trace-level TW exposures.

Evidence of disease and mortalities of young of the year (age‐0) Smallmouth Bass Micropterus dolomieuhas occurred during the late spring and summer in many parts of the Susquehanna River watershed since 2005. To better understand contributing factors, fish collected from multiple areas throughout the watershed as well as out‐of‐basin reference populations (Allegheny and Delaware River basins; experimental ponds, Kearneysville, West Virginia) were examined grossly and histologically for abnormalities. Tissue contaminant concentrations were determined from whole‐body homogenates, and water contaminant concentrations were estimated using time‐integrated passive samplers at selected sites. Observed or isolated pathogens included bacteria, predominantly motile Aeromonasspp. and Flavobacterium columnare; largemouth bass virus, and parasites, including trematode metacercariae, cestodes, and the myxozoan Myxobolus inornatus. Although these pathogens were found in age‐0 Smallmouth Bass from multiple sites, no one pathogen was consistently associated with mortality. Chemicals detected in tissue included polychlorinated biphenyl (PCB) congeners, organochlorine, and current‐use pesticides. Pyraclostrobin, PCB congeners 170 and 187, cis‐chlordane and trans‐nonachlor were detected in all Susquehanna watershed samples but rarely in samples from the reference site. The findings support the idea that there is no single cause for disease of age‐0 Smallmouth Bass; rather the cumulative effects of co‐infections and potential immunomodulation by environmental stressors during a sensitive developmental life stage may lead to mortality. Identifying the most important risk factors will be necessary for more in‐depth analyses of individual stressors and better management of the habitat and fish populations.

AbstractHistorically, wetland toxin exposure studies have relied on single time point samples from stationary sampling devices. Development of passive sampling devices (PSDs) that can be attached to individual animals within wetland habitats has greatly improved in recent years, presenting an innovative sampling technology that can potentially yield individual-specific, quantifiable data about chemical exposure. In this study, silicone based PSDs were attached to the ventral skin of 20 northern leopard frogs (Lithobates pipiens) with polypropylene sutures after radiotransmitters had been surgically implanted into the coleomic cavity. After a short recovery period, frogs were released back into the wetland habitat where they were acquired. The animals were located daily using radiotelemetry to assess how long PSDs would remain attached in the frogs' natural habitat. After one week, PSDs remained on 18 of the original 20 frogs. At two weeks, 17 frogs were recovered and no PSDs remained attached. Although valuable data can be obtained over a short time period, more research will be necessary to demonstrate the effectiveness of externally attaching silicone PSDs to northern leopard frogs for time periods longer than 1–2 weeks.

Mercury (Hg) is a toxic contaminant that has been mobilized and distributed worldwide and is a threat to many wildlife species. Amphibians are facing unprecedented global declines due to many threats including contaminants. While the biphasic life history of many amphibians creates a potential nexus for methylmercury (MeHg) exposure in aquatic habitats and subsequent health effects, the broad-scale distribution of MeHg exposure in amphibians remains unknown. We used nonlethal sampling to assess MeHg bioaccumulation in 3,241 juvenile and adult amphibians during 2017–2021. We sampled 26 populations (14 species) across 11 states in the United States, including several imperiled species that could not have been sampled by traditional lethal methods. We examined whether life history traits of species and whether the concentration of total mercury in sediment or dragonflies could be used as indicators of MeHg bioaccumulation in amphibians. Methylmercury contamination was widespread, with a 33-fold difference in concentrations across sites. Variation among years and clustered subsites was less than variation across sites. Life history characteristics such as size, sex, and whether the amphibian was a frog, toad, newt, or other salamander were the factors most strongly associated with bioaccumulation. Total Hg in dragonflies was a reliable indicator of bioaccumulation of MeHg in amphibians (R2≥ 0.67), whereas total Hg in sediment was not (R2≤ 0.04). Our study, the largest broad-scale assessment of MeHg bioaccumulation in amphibians, highlights methodological advances that allow for nonlethal sampling of rare species and reveals immense variation among species, life histories, and sites. Our findings can help identify sensitive populations and provide environmentally relevant concentrations for future studies to better quantify the potential threats of MeHg to amphibians.

Residues of toxaphene, a persistent organochlorine biocide, are difficult to characterize in the environment due to their complex composition, selective recalcitrance, and lack of a comprehensive standards set. No single gas chromatographic column stationary phase completely separates toxaphene on a congener specific basis. Using GC‐ECD and GC‐MS, the performance of a slightly polar stationary phase (DB‐XLB) was compared with that of a widely used nonpolar phase (DB‐5). Commercially available standard mixtures and tissue samples from a toxaphene‐contaminated coastal marsh were analyzed. Both DB‐5 and DB‐XLB fully resolved a similar number of target congeners (18 of 22). The XLB phase, however, better resolved congener pairs P31/32, P40/41, and several others (e.g. P26/‐1, Hx‐Sed, and Hp‐Sed). Compared with DB‐5 and several recently evaluated, slightly polar phases, DB‐XLB offers excellent overall performance for single column analysis of environmentally relevant toxaphene residues.

Process wastewaters from food, beverage, and feedstock facilities, although regulated, are an under-investigated environmental contaminant source. Food process wastewaters (FPWWs) from 23 facilities in 17 U.S. states were sampled and documented for a plethora of chemical and microbial contaminants. Of the 576 analyzed organics, 184 (32%) were detected at least once, with concentrations as large as 143 μg L–1(6:2 fluorotelomer sulfonic acid), and as many as 47 were detected in a single FPWW sample. Cumulative per/polyfluoroalkyl substance concentrations up to 185 μg L–1and large pesticide transformation product concentrations (e.g., methomyl oxime, 40 μg L–1; clothianidin TMG, 2.02 μg L–1) were observed. Despite 48% of FPWW undergoing disinfection treatment prior to discharge, bacteria resistant to third-generation antibiotics were found in each facility type, and multiple bacterial groups were detected in all samples, including total coliforms. The exposure–activity ratios and toxicity quotients exceeded 1.0 in 13 and 22% of samples, respectively, indicating potential biological effects and toxicity to vertebrates and invertebrates associated with the discharge of FPWW. Organic contaminant profiles of FPWW differed from previously reported contaminant profiles of municipal effluents and urban storm water, indicating that FPWW is another important source of chemical and microbial contaminant mixtures discharged into receiving surface waters.