Per- and polyfluoroalkyl substances (PFAS) are contaminants that can lead to adverse health effects in aquatic organisms, including reproductive toxicity and developmental abnormalities. To assess the ecological health risk of PFAS in Pennsylvania stream surface water, we conducted a comprehensive analysis that included both measured and predicted estimates. The potential combined exposure effects of 14 individual PFAS to aquatic biota were estimated using the sum of exposure-activity ratios (ΣEARs) in 280 streams. Additionally, machine learning techniques were utilized to predict potential PFAS exposure effects in unmonitored stream reaches, considering factors such as land use, climate, and geology. Leveraging a tailored convolutional neural network (CNN), a validation accuracy of 78% was achieved, directly outperforming traditional methods that were also used, such as logistic regression and gradient boosting (accuracies of ~65%). Feature importance analysis highlighted key variables that contributed to the CNN’s predictive power. The most influential features highlighted the complex interplay of anthropogenic and environmental factors contributing to PFAS contamination in surface waters. Industrial and urban land cover, rainfall intensity, underlying geology, agricultural factors, and their interactions emerged as key determinants. These findings may help to inform biotic sampling strategies, water quality monitoring efforts, and policy decisions aimed to mitigate the ecological impacts of PFAS in surface waters.

Water is an increasingly precious resource in California as years of drought, climate change, pollution, as well as an expanding population have all stressed the state's drinking water supplies. Currently, there are increasing concerns about whether regulated and unregulated contaminants in drinking water are linked to a variety of human-health outcomes particularly in socially disadvantaged communities with a history of health risks. To begin to address this data gap by broadly assessing contaminant mixture exposures, the current study was designed to collect tapwater samples from communities in Gold Country, the San Francisco Bay Area, two regions of the Central Valley (Merced Fresno and Kern counties), and southeast Los Angeles for 251 organic chemicals and 32 inorganic constituents. Sampling prioritized low-income areas with suspected water quality challenges and elevated breast cancer rates. Results indicated that mixtures of regulated and unregulated contaminants were observed frequently in tapwater throughout the areas studied and the types and concentrations of detected contaminants varied by region, drinking-water source, and size of the public water system. Multiple exceedances of enforceable maximum contaminant level(s) (MCL), non-enforceable MCL goal(s) (MCLG), and other health advisories combined with frequent exceedances of benchmark-based hazard indices were also observed in samples collected in all five of the study regions. Given the current focus on improving water quality in socially disadvantaged communities, our study highlights the importance of assessing mixed-contaminant exposures in drinking water at the point of consumption to adequately address human-health concerns (e.g., breast cancer risk). Data from this pilot study provide a foundation for future studies across a greater number of communities in California to assess potential linkages between breast cancer rates and tapwater contaminants.

In the United States and globally, contaminant exposure in unregulated private-well point-of-use tapwater (TW) is a recognized public-health data gap and an obstacle to both risk-management and homeowner decision making. To help address the lack of data on broad contaminant exposures in private-well TW from hydrologically-vulnerable (al-luvial, karst) aquifers in agriculturally-intensive landscapes, samples were collected in 2018-2019 from 47 northeast Iowa farms and analyzed for 35 inorganics, 437 unique organics, 5 in vitro bioassays, and 11 microbial assays. Twenty- six inorganics and 51 organics, dominated by pesticides and related transformation products (35 herbicide-, 5 insecticide-, and 2 fungicide-related), were observed in TW. Heterotrophic bacteria detections were near ubiquitous (94 % of the samples), with detection of total coliform bacteria in 28 % of the samples and growth on at least one putative-pathogen selective media across all TW samples. Health-based hazard index screening levels were exceeded frequently in private-well TW and attributed primarily to inorganics (nitrate, uranium). Results support incorporation of residential treatment systems to protect against contaminant exposure and the need for increased monitoring of rural private-well homes. Continued assessment of unmonitored and unregulated private-supply TW is needed to model contaminant exposures and human-health risks.

First posted January 4, 2024 For additional information, contact: Director, New Jersey Water Science Center3450 Princeton Pike, Suite 110Lawrenceville, New Jersey 08648Contact Pubs Warehouse In response to previous reports of per- and polyfluoroalkyl substances (PFAS) contamination in French Island’s (located in the Mississippi River within the town of Campbell, Wisconsin) primary source of drinking water, 11 locations were sampled by the U.S. Geological Survey (USGS) in October 2021 to assess the potential presence of contaminant mixtures, including PFAS, in tapwater. Three locations were assessed seven times each over the course of three days. These samples were chosen to evaluate the water quality of the deeper Mount Simon bedrock aquifer and the water quality of the shallower sand and gravel (alluvial) aquifer at two locations. The other eight sample locations were spatially distributed within Campbell and were sampled once each. For each of these 11 sites, tapwater samples were analyzed for disinfection byproducts (DBP), pesticides, PFAS, pharmaceuticals, semi-volatile organic compounds (SVOC), volatile organic compounds (VOC), cations, anions, trace elements, alkalinity, microbial indicators, as well as measurements of water temperature, specific conductance, and pH. Of the 506 organic compounds analyzed in each water-quality sample, 74 (14 percent) were detected at least one time in any of the samples collected. Of the 14 percent, detected analytes included 27 pesticides (5 percent), 14 PFAS (3 percent), 6 pharmaceuticals (1 percent), 7 SVOC (1 percent), and 20 VOC (4 percent). No DBP were detected. The total number of organic compounds detected per sample ranged from 0–20 (median of 10), with the sum of concentrations ranging from not detected (nd)–2.53 micrograms per liter (μg/L; median of 0.333 μg/L). Of the inorganic constituents measured, eight were not detected above their reporting limit in any of the samples. The inorganic constituents that were not detected were antimony, arsenic, beryllium, cadmium, cobalt, molybdenum, selenium, and vanadium.Along with the 11 sites sampled throughout Campbell, Wisconsin, beginning in October 2021, four more wells were sampled on the Upper Midwest Environmental Sciences Center (UMESC) campus for PFAS. Three of these sites withdraw water from the shallow alluvial aquifer (the same source water for tapwater site 002) and one from the Mount Simon aquifer (the same source of water for tapwater site 001). This sampling is ongoing with results from samples through December 2022 summarized in this report. Of the 33 PFAS analyzed in samples from the four UMESC locations, 15 individual PFAS were detected at least one time in any of the samples analyzed with the sum of PFAS concentrations ranging from nd–1.49 μg/L (median of 0.309 μg/L).

Drinking-water quality is a rising concern in the United States (US), emphasizing the need to broadly assess exposures and potential health effects at the point-of-use. Drinking-water exposures to per- and poly-fluoroalkyl substances (PFAS) are a national concern, however, there is limited information on PFAS in residential tapwater at the point-of-use, especially from private-wells. We conducted a national reconnaissance to compare human PFAS exposures in unregulated private-well and regulated public-supply tapwater. Tapwater from 716 locations (269 private-wells; 447 public supply) across the US was collected during 2016-2021 including three locations where temporal sampling was conducted. Concentrations of PFAS were assessed by three laboratories and compared with land-use and potential-source metrics to explore drivers of contamination. The number of individual PFAS observed ranged from 1 to 9 (median: 2) with corresponding cumulative concentrations (sum of detected PFAS) ranging from 0.348 to 346 ng/L. Seventeen PFAS were observed at least once with PFBS, PFHxS and PFOA observed most frequently in approximately 15% of the samples. Across the US, PFAS profiles and estimated median cumulative concentrations were similar among private wells and public-supply tapwater. We estimate that at least one PFAS could be detected in about 45% of US drinking-water samples. These detection probabilities varied spatially with limited temporal variation in concentrations/numbers of PFAS detected. Benchmark screening approaches indicated potential human exposure risk was dominated by PFOA and PFOS, when detected. Potential source and land-use information was related to cumulative PFAS concentrations, and the number of PFAS detected; however, corresponding relations with specific PFAS were limited likely due to low detection frequencies and higher detection limits. Information generated supports the need for further assessments of cumulative health risks of PFAS as a class and in combination with other co-occurring contaminants, particularly in unmonitored private-wells where information is limited or not available.

Reservoirs in arid landscapes provide critical water storage and hydroelectric power but influence the transport and biogeochemical cycling of mercury (Hg). Improved management of reservoirs to mitigate the supply and uptake of bioavailable methylmercury (MeHg) in aquatic food webs will benefit from a mechanistic understanding of inorganic divalent Hg (Hg(ii)) and MeHg fate within and downstream of reservoirs. Here, we quantified Hg(ii), MeHg, and other pertinent biogeochemical constituents in water (filtered and associated with particles) at high temporal resolution from 2016-2020. This was done (1) at inflow and outflow locations of three successive hydroelectric reservoirs (Snake River, Idaho, Oregon) and (2) vertically and longitudinally within the first reservoir (Brownlee Reservoir). Under spring high flow, upstream inputs of particulate Hg (Hg(ii) and MeHg) and filter-passing Hg(ii) to Brownlee Reservoir were governed by total suspended solids and dissolved organic matter, respectively. Under redox stratified conditions in summer, net MeHg formation in the meta- and hypolimnion of Brownlee reservoir yielded elevated filter-passing and particulate MeHg concentrations, the latter exceeding 500 ng g(-1) on particles. Simultaneously, the organic matter content of particulates increased longitudinally in the reservoir (from 9-29%) and temporally with stratified duration. In late summer and fall, destratification mobilized MeHg from the upgradient metalimnion and the downgradient hypolimnion of Brownlee Reservoir, respectively, resulting in downstream export of elevated filter-passing MeHg and organic-rich particles enriched in MeHg (up to 43% MeHg). We document coupled biogeochemical and hydrologic processes that yield in-reservoir MeHg accumulation and MeHg export in water and particles, which impacts MeHg uptake in aquatic food webs within and downstream of reservoirs.

The objectives of this study are to identify per- and polyfluoroalkyl substances (PFAS) in Pennsylvania surface waters, corresponding associations with potential sources of PFAS contamination (PSOC) and other parameters, and compare raw surface water concentrations to human and ecological benchmarks. Surface water samples from 161 streams were collected in September 2019 and were analyzed for 33 target PFAS and water chemistry. Land use and physical attributes in upstream catchments and geospatial counts of PSOC in local catchments are summarized. The hydrologic yield of the sum of 33 PFAS (∑PFAS) for each stream was computed by normalizing each site's load by the drainage area of the upstream catchment. Utilizing conditional inference tree analysis, the percentage of development (>7.58 %) was identified as a primary driver of the ∑PFAS hydrologic yields. When percentage of development was removed from analysis, ∑PFAS yields were closely related to surface water chemistry associated with landscape alteration (e.g., development or agricultural cropland), such as concentrations of total nitrogen, chloride, and ammonia, but also to count of water pollution control facilities (agricultural, industrial, stormwater, and/or municipal waste pollution abatement facilities). In oil and gas development regions, ∑PFAS yields were associated with combined sewage outfalls. Sites surrounded by ≥2 electronic manufacturing facilities had elevated ∑PFAS yields (median = 241 ng/s/km2). Study results are critical to guide future research, regulatory policy, best practices that will mitigate PFAS contamination, and the communication of human health and ecological risks associated with PFAS exposure from surface waters.

Aquatic ecosystems convey complex contaminant mixtures from anthropogenic pollution on a global scale. Point (e.g., municipal wastewater) and nonpoint sources (e.g., stormwater runoff) are both drivers of contaminant mixtures in aquatic habitats. The objectives of this study were to identify the contaminant mixtures present in surface waters impacted by both point and nonpoint sources, to determine if aquatic biota (amphibian and fish) health effects (testicular oocytes and parasites) occurred at these sites, and to understand if differences in biological and chemical measures existed between point (on-stream) and nonpoint sources (off-stream). To accomplish this, water chemistry, fishes, and frogs were collected from 21 sites in the New Jersey Pinelands, United States. Off-stream sites consisted of 3 reference and 10 degraded wetlands. On-stream sites consisted of two reference lakes and six degraded streams/lakes (four sites above and two sites below wastewater outfalls). Surface water was collected four times at each site and analyzed for 133 organic and inorganic contaminants. One native and five non-native fish species were collected from streams/lakes and native green frogs from wetlands (ponds and stormwater basins). Limited differences in contaminant concentrations were observed in reference and degraded wetlands but for streams/lakes, results indicated that landscape alteration, (upland agricultural and developed land) was the primary driver of contaminant concentrations rather than municipal wastewater. Incidence of estrogenic endocrine disruption (intersex) was species dependent with the highest prevalence observed in largemouth bass and black crappie and the lowest prevalence observed in green frogs and tessellated darters. Parasite prevalence was site and species dependent. Prevalence of eye parasites increased with increasing concentrations of industrial, mycotoxin, and cumulative inorganic contaminants. These findings are critical to support the conservation, protection, and management of a wide range of aquatic species in the Pinelands and elsewhere as habitat loss, alteration, and fragmentation increase with increasing development.

In the United States (US), private-supply tapwater (TW) is rarely monitored. This data gap undermines individual/community risk-management decision-making, leading to an increased probability of unrecognized contaminant exposures in rural and remote locations that rely on private wells. We assessed point-of-use (POU) TW in three northern plains Tribal Nations, where ongoing TW arsenic (As) interventions include expansion of small community water systems and POU adsorptive-media treatment for Strong Heart Water Study participants. Samples from 34 private-well and 22 public-supply sites were analyzed for 476 organics, 34 inorganics, and 3 in vitro bioactivities. 63 organics and 30 inorganics were detected. Arsenic, uranium (U), and lead (Pb) were detected in 54%, 43%, and 20% of samples, respectively. Concentrations equivalent to public-supply maximum contaminant level(s) (MCL) were exceeded only in untreated private-well samples (As 47%, U 3%). Precautionary health-based screening levels were exceeded frequently, due to inorganics in private supplies and chlorine-based disinfection byproducts in public supplies. The results indicate that simultaneous exposures to co-occurring TW contaminants are common, warranting consideration of expanded source, point-of-entry, or POU treatment(s). This study illustrates the importance of increased monitoring of private-well TW, employing a broad, environmentally informative analytical scope, to reduce the risks of unrecognized contaminant exposures.

Chemical contamination of riverine ecosystems is largely a result of urbanization, industrialization, and agricultural activities occurring on adjacent terrestrial landscapes. Land management activities (e.g., Best Management Practices) are an important tool used to reduce point and non-point sources of pollution. However, the ability to confidently make inferences about the efficacy of land management activities on reducing in-stream chemical concentrations is poorly understood. We estimated regional temporal trends and components of variation for commonly used herbicides (atrazine and metolachlor), total estrogenicity, and riverine sediment concentrations of total PCBs for rivers in the Chesapeake Bay Watershed, USA. We then used the estimated variance components to perform a power analysis and evaluated the statistical power to detect regional temporal trends under different monitoring scenarios. Scenarios included varying the magnitude of the annual contaminant decline, the number of sites sampled each year, the number of years sampled, and sampling frequency. Monitoring for short time periods (e.g., 5 years) was inadequate for detecting regional temporal trends, regardless of the number of sites sampled or the magnitude of the annual declines. Even when monitoring over a 20-year period, sampling a relatively large number of sites each year was required (e.g., >50 sites) to achieve adequate statistical power for smaller trend magnitudes (declines of 5-7%/year). Annual sampling frequency had little impact on power for any monitoring scenario. All sampling scenarios were underpowered for sediment total PCBs. Power was greatest for total estrogenicity, suggesting that this aggregate measure of estrogenic activity may be a useful indicator. This study provides information that can be used to help (1) guide the development of monitoring programs aimed at detecting regional declines in riverine chemical contaminant concentrations in response to land management actions, and (2) set expectations for the ability to detect changes over time.

Human-use pharmaceuticals in urban streams link aquatic-ecosystem health to human health. Pharmaceutical mixtures have been widely reported in larger streams due to historical emphasis on wastewater-treatment plant (WWTP) sources, with limited investigation of pharmaceutical exposures and potential effects in smaller headwater streams. In 2014-2017, the United States Geological Survey measured 111 pharmaceutical compounds in 308 headwater streams (261 urban-gradient sites sampled 3-5 times, 47 putative lowimpact sites sampled once) in 4 regions across the US. Simultaneous exposures to multiple pharmaceutical compounds (pharmaceutical mixtures) were observed in 91% of streams (248 urban-gradient, 32 low-impact), with 88 analytes detected across all sites and cumulative maximum concentrations up to 36,142 ng/L per site. Cumulative detections and concentrations correlated to urban land use and presence/absence of permitted WWTP discharges, but pharmaceutical mixtures also were common in the 75% of sampled streams without WWTP. Cumulative exposure-activity ratios (EAR) indicated widespread transient exposures with high probability of molecular effects to vertebrates. Considering the potential individual and interactive effects of the detected pharmaceuticals and the recognized analytical underestimation of the pharmaceutical-contaminant (unassessed parent compounds, metabolites, degradates) space, these results demonstrate a nation-wide environmental concern and the need for watershed-scale mitigation of in-stream pharmaceutical contamination.

A pilot-scale expanded target assessment of mixtures of inorganic and organic contaminants in point-of-consumption drinking water (tapwater, TW) was conducted in Puerto Rico (PR) to continue to inform TW exposures and corresponding estimations of cumulative human-health risks across the US. In August 2018, a spatial synoptic pilot assessment of than 524 organic and 37 inorganic chemicals was conducted in 14 locations (7 home; 7 commercial) across PR. A follow-up 3-day temporal assessment of TW variability was conducted in December 2018 at two of the synoptic locations (1 home, 1 commercial) and included daily pre- and post-flush samples. Concentrations of regulated and unregulated TW contaminants were used to calculate cumulative in vitro bioactivity ratios and Hazard Indices (HI) based on existing human-health benchmarks. Synoptic results confirmed that human exposures to inorganic and organic contaminant mixtures, which are rarely monitored together in drinking water at the point of consumption, occurred across PR and consisted of elevated concentrations of inorganic contaminants (e.g., lead, copper), disinfection byproducts (DBP), and to a lesser extent per/polyfluoroalkyl substances (PFAS) and phthalates. Exceedances of human-health benchmarks in every synoptic TW sample support further investigation of the potential cumulative risk to vulnerable populations in PR and emphasize the importance of continued broad characterization of drinking-water exposures at the tap with analytical capabilities that better represent the complexity of both inorganic and organic contaminant mixtures known to occur in ambient source waters. Such health-based monitoring data are essential to support public engagement in source water sustainability and treatment and to inform consumer point-of-use treatment decision making in PR and throughout the US.

The United States (US) National Park Service (NPS) manages protected public lands to preserve biodiversity. Exposure to and effects of bioactive organic contaminants in NPS streams are challenges for resource managers. Recent assessment of pesticides and pharmaceuticals in protected-streams within the urbanized NPS Southeast Region (SER) indicated the importance of fluvial inflows from external sources as drivers of aquatic contaminant-mixture exposures. Great Smoky Mountains National Park (GRSM), lies within SER, has the highest biodiversity and annual visitation of NPS parks, but, in contrast to the previously studied systems, straddles a high-elevation hydrologic divide; this setting limits fluvial-inflows of contaminants but potentially increases visitation-driven contaminant deliveries. We leveraged the unique characteristics of GRSM to test further the importance of fluvial contaminant inflows as drivers of protected-stream exposures and to inform the relative importance of potential additional contaminant transport mechanisms, by comparing the estimated risks of 328 pesticides and pharmaceuticals in water at 16 GRSM stream locations to those estimated previously in SER streams. Extensive mixtures (31 compounds) were only observed in an atypical reach on the boundary of GRSM downstream of a wastewater discharge, while limited mixtures (2–5 compounds) were observed in one stream with elevated visitation pressure (recreational “tube floating”). The insecticide, imidacloprid, used to eradicate hemlock woolly adelgid, was detected in 8 (50%) streams. Infrequent exceedances of a cumulative ToxCast-based, exposure-activity ratio (ΣEAR) 0.001 screening-level of concern suggested limited risk to non-target, aquatic vertebrates, whereas exceedances of a cumulative benchmark-based, invertebrate toxicity quotient (ΣTQ) 0.1 screening level at 8 locations indicated generally high risk to invertebrates. The results are consistent with the importance of fluvial transport from extra-park sources as a driver of bioactive-contaminant mixture exposures in protected streams and illustrate the potential additional risks from visitation-driven and tactical-use-pesticides.

Most terrestrial allochthonous organic matter enters river networks through headwater streams during high flow events. In headwaters, allochthonous inputs are substantial and variable, but become less important in streams and rivers with larger watersheds. As allochthonous dissolved organic matter (DOM) moves downstream, the proportion of less aromatic organic matter with autochthonous characteristics increases. How environmental factors converge to control this transformation of DOM at a continental scale is less certain. We hypothesized that the amount of time water has spent travelling through surface waters of inland systems (streams, rivers, lakes, and reservoirs) is correlated to DOM composition. To test this hypothesis, we used established river network scaling relationships to predict relative river network flow-weighted travel time (FWTT) of water for 60 stream and river sites across the contiguous United States (3090 discrete samples over 10 water years). We estimated lentic contribution to travel times with upstream in-network lake and reservoir volume. DOM composition was quantified using ultraviolet and visible absorption and fluorescence spectroscopy. A combination of FWTT and lake and reservoir volume was the best overall predictor of DOM composition among models that also incorporated discharge, specific discharge, watershed area, and upstream channel length. DOM spectral slope ratio (R-2 = 0.77) and Freshness Index (R-2 = 0.78) increased and specific ultraviolet absorbance at 254 nm (R-2 = 0.68) and Humification Index (R-2 = 0.44) decreased across sites as a function of FWTT and upstream lake volume. This indicates autochthonous-like DOM becomes continually more dominant in waters with greater FWTT. We assert that river FWTT can be used as a metric of the continuum of DOM composition from headwaters to rivers. The nature of the changes to DOM composition detected suggest this continuum is driven by a combination of photo-oxidation, biological processes, hydrologically varying terrestrial subsidies, and aged groundwater inputs.

Wetlands provide ecological functionality by maintaining and promoting regional biodiversity supporting quality habitat for aquatic organisms. Globally, habitat loss, fragmentation and degradation due to increases in agricultural activities and urban development have reduced or altered geographically isolated wetlands, thus reducing biodiversity. The objective of this study was to assess the relative ecological function and integrity of natural ponds, excavated ponds and stormwater basins in the New Jersey Pinelands, located in the northeastern United States by comparing hydrologic conditions, water quality, pesticide concentrations (water, sediment and tissue) and wetland assemblages including amphibians. Twenty-four wetlands were selected based on surrounding land-use and sampled for a variety of abiotic and biotic variables. Abiotic and biotic wetland variables were similar between natural and excavated ponds, with notable differences between the ponds and stormwater basins. Natural and excavated ponds displayed characteristic Pinelands water quality (low pH, high organic carbon, and low pesticide concentrations), exhibited high ecological integrity and supported native ampbibians. Stormwater basins and degraded ponds surrounded by altered land-use exhibited degraded water quality (high pH, high pesticide concentrations) and were dominated by non-native and introduced plants and amphibians. Results from this study can broadly inform resource conservation strategies for amphibians and other communities with a diverse range of habitat requirements, particularly in areas where conservation and development are competing priorities. To conserve biodiversity in changing landscapes, wetlands with similar functionality and land-use characteristics need to be identified and managed to preserve water quality for species of conservation concern.