To provide the first nationwide reconnaissance of the occurrence of pharmaceuticals, hormones, and other organic wastewater contaminants (OWCs) in water resources, the U.S. Geological Survey used five newly developed analytical methods to measure concentrations of 95 OWCs in water samples from a network of 139 streams across 30 states during 1999 and 2000. The selection of sampling sites was biased toward streams susceptible to contamination (i.e. downstream of intense urbanization and livestock production). OWCs were prevalent during this study, being found in 80% of the streams sampled. The compounds detected represent a wide range of residential, industrial, and agricultural origins and uses with 82 of the 95 OWCs being found during this study. The most frequently detected compounds were coprostanol (fecal steroid), cholesterol (plant and animal steroid), N,N-diethyltoluamide (insect repellant), caffeine (stimulant), triclosan (antimicrobial disinfectant), tri(2-chloroethyl)phosphate (fire retardant), and 4-nonylphenol (nonionic detergent metabolite). Measured concentrations for this study were generally low and rarely exceeded drinking-water guidelines, drinking-water health advisories, or aquatic-life criteria. Many compounds, however, do not have such guidelines established. The detection of multiple OWCs was common for this study, with a median of seven and as many as 38 OWCs being found in a given water sample. Little is known about the potential interactive effects (such as synergistic or antagonistic toxicity) that may occur from complex mixtures of OWCs in the environment. In addition, results of this study demonstrate the importance of obtaining data on metabolites to fully understand not only the fate and transport of OWCs in the hydrologic system but also their ultimate overall effect on human health and the environment.

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To assess the impact of an estrogenic wastewater treatment plant (WWTP) effluent on fish reproduction, white suckers (Catostomus commersoni) were collected from immediately upstream and downstream (effluent site) of the city of Boulder, CO, WWTP outfall. Gonadal intersex, altered sex ratios, reduced gonad size, disrupted ovarian and testicular histopathology, and vitellogenin induction consistent with exposure to estrogenic wastewater contaminants were identified in white suckers downstream from the WWTP outfall and not at the upstream site. The sex ratio was female-biased at the effluent site in both the fall of 2003 and the spring of 2004; the frequency of males at the effluent site (17-21%) was half that of the upstream site (36-46%). Intersex white suckers comprised 18-22% of the population at the effluent site. Intersex fish were not found at the upstream site. Chemical analyses determined that the WWTP effluent contained a complex mixture of endocrine-active chemicals, including 17beta-estradiol (E2) 17alpha-ethynylestradiol, alkylphenols, and bisphenol A resulting in an estimated total estrogen equivalence of up to 31 ng E2 L(-1). These results indicate that the reproductive potential of native fishes may be compromised in wastewater-dominated streams.

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Antidepressant pharmaceuticals are widely prescribed in the United States; release of municipal wastewater effluent is a primary route introducing them to aquatic environments, where little is known about their distribution and fate. Water, bed sediment, and brain tissue from native white suckers (Catostomus commersoni) were collected upstream and at points progressively downstream from outfalls discharging to two effluent-impacted streams, Boulder Creek (Colorado) and Fourmile Creek (Iowa). A liquid chromatography/tandem mass spectrometry method was used to quantify antidepressants, including fluoxetine, norfluoxetine (degradate), sertraline, norsertraline (degradate), paroxetine, citalopram, fluvoxamine, duloxetine, venlafaxine, and bupropion in all three sample matrices. Antidepressants were not present above the limit of quantitation in water samples upstream from the effluent outfalls but were present at points downstream at ng/L concentrations, even at the farthest downstream sampling site 8.4 km downstream from the outfall. The antidepressants with the highest measured concentrations in both streams were venlafaxine, bupropion, and citalopram and typically were observed at concentrations of at least an order of magnitude greater than the more commonly investigated antidepressants fluoxetine and sertraline. Concentrations of antidepressants in bed sediment were measured at ng/g levels; venlafaxine and fluoxetine were the predominant chemicals observed. Fluoxetine, sertraline, and their degradates were the principal antidepressants observed in fish brain tissue, typically at low ng/g concentrations. A qualitatively different antidepressant profile was observed in brain tissue compared to streamwater samples. This study documents that wastewater effluent can be a point source of antidepressants to stream ecosystems and that the qualitative composition of antidepressants in brain tissue from exposed fish differs substantially from the compositions observed in streamwater and sediment, suggesting selective uptake.

Surface water from 38 streams nationwide was assessed using 14 target-organic methods (719 compounds). Designed-bioactive anthropogenic contaminants (biocides, pharmaceuticals) comprised 57% of 406 organics detected at least once. The 10 most-frequently detected anthropogenic-organics included eight pesticides (desulfinylfipronil, AMPA, chlorpyrifos, dieldrin, metolachlor, atrazine, CIAT, glyphosate) and two pharmaceuticals (caffeine, metformin) with detection frequencies ranging 66-84% of all sites. Detected contaminant concentrations varied from less than 1 ng L to greater than 10 μg L, with 77 and 278 having median detected concentrations greater than 100 ng L and 10 ng L, respectively. Cumulative detections and concentrations ranged 4-161 compounds (median 70) and 8.5-102 847 ng L, respectively, and correlated significantly with wastewater discharge, watershed development, and toxic release inventory metrics. Log concentrations of widely monitored HHCB, triclosan, and carbamazepine explained 71-82% of the variability in the total number of compounds detected (linear regression; p-values: < 0.001-0.012), providing a statistical inference tool for unmonitored contaminants. Due to multiple modes of action, high bioactivity, biorecalcitrance, and direct environment application (pesticides), designed-bioactive organics (median 41 per site at μg L cumulative concentrations) in developed watersheds present aquatic health concerns, given their acknowledged potential for sublethal effects to sensitive species and lifecycle stages at low ng L.

Abstract-The effects of embryonic and larval exposure to environmentally relevant (ng/L) concentrations of common antidepressants, fluoxetine, sertraline, venlafaxine, and bupropion (singularly and in mixture) on C-start escape behavior were evaluated in fathead minnows (Pimephales promelas). Embryos (postfertilization until hatching) were exposed for 5 d and, after hatching, were allowed to grow in control well water until 12 d old. Similarly, posthatch fathead minnows were exposed for 12 d to these compounds. High-speed (1,000 frames/s) video recordings of escape behavior were collected and transferred to National Institutes of Health Image for frame-byframe analysis of latency periods, escape velocities, and total escape response (combination of latency period and escape velocity). When tested 12 d posthatch, fluoxetine and venlafaxine adversely affected C-start performance of larvae exposed as embryos. Conversely, larvae exposed for 12 d posthatch did not exhibit altered escape responses when exposed to fluoxetine but were affected by venlafaxine and bupropion exposure. Mixtures of these four antidepressant pharmaceuticals slowed predator avoidance behaviors in larval fathead minnows regardless of the exposure window. The direct impact of reduced C-start performance on survival and, ultimately, reproductive fitness provides an avenue to assess the ecological relevance of exposure in an assay of relatively short duration.

Growing evidence that certain poly- and perfluoroalkyl substances (PFASs) are associated with negative human health effects prompted the U.S. Environmental Protection Agency to issue lifetime drinking water health advisories for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in 2016. Given that groundwater is a major source of drinking water, the main objective of this work was to investigate geochemical and hydrological processes governing the subsurface transport of PFASs at a former fire training area (FTA) on Cape Cod, Massachusetts, where PFAS-containing aqueous film-forming foams were used historically. A total of 148 groundwater samples and 4 sediment cores were collected along a 1200-m-long downgradient transect originating near the FTA and analyzed for PFAS content. The results indicate that unsaturated zones at the FTA and at hydraulically downgradient former domestic wastewater effluent infiltration beds both act as continuous PFAS sources to the groundwater despite 18 and 20 years of inactivity, respectively. Historically different PFAS sources are evident from contrasting PFAS composition near the water table below the FTA and wastewater-infiltration beds. Results from total oxidizable precursor assays conducted using groundwater samples collected throughout the plume suggest that some perfluoroalkyl acid precursors at this site are transporting with perfluoroalkyl acids.