Validation of a vulnerability index of exposure to chemicals of emerging concern in surface water and sediment of Great Lakes tributaries of the United States.

Widespread occurrence of emerging contaminants in Great Lakes tributaries led to the development and publication of a vulnerability index (VI) to assess the potential exposure of aquatic communities to chemicals of emerging concern (CEC) in the Great Lakes basin. The robust nature of the VI was tested to evaluate the underlying statistical model and expand the spatial domain of the index. Data collected at 131 new sampling sites (Test 1) and published data from independent studies (Test 2) were used to test the model predictions. Test 1 water and sediment samples were analyzed for the same classes of CEC chemicals and compared to the predictions for the original VI. Concentrations and numbers of unique CECs detected in water and sediment samples were similar between the original data and the two test datasets, although CECs tended to have higher detection frequencies in the original dataset compared to the Test 1 and Test 2 datasets. For example, 69 CECs were detected in ≥30% of water samples in the original dataset compared with 17 CECs in the Test 1 data and 59 in the Test 2 data. Predicted vulnerability for test sites agreed with actual vulnerability 64% of the time for water and 71% of the time for sediment. Agreement percentage results were greater when individual sites were grouped by river, with 82% agreement between predictions and actual vulnerability for water and 78% agreement for sediment. For the entire dataset, the VI ranks correlated with an independent estimate of potential biological impact. Agreement percentage was the greatest for low or high vulnerability index values but highly variable for sites that are classified as having medium vulnerability. Despite the underlying variability, there is a significant correlation (R2 = 0.26; p < 0.01) between the VI ranking of tributaries and the independent ranking of potential negative biological impact.

A pilot study to assess the influence of infiltrated stormwater on groundwater: Hydrology and trace organic contaminants.

Underground infiltration basins (UIBs) mimic the natural hydrologic cycle by allowing stormwater to recharge local groundwater aquifers. However, little is known about the potential transport of organic contaminants to receiving groundwater. We conducted a pilot study in which we collected paired grab samples of stormwater runoff flowing into two UIBs (inflow) and shallow groundwater adjacent to the UIBs. Samples were collected coincident with three rain events and analyzed for volatile organic compounds, semi-volatile organic compounds, pharmaceuticals, and pesticides. Few contaminants were detected in groundwater, compared with inflow, and groundwater concentrations were typically an order of magnitude less. With one exception (trichloroethene), all groundwater concentrations were at least two orders of magnitude below available guidance or screening values. This short communication highlights information gaps in understanding the hydrologic connectivity between UIBs and receiving groundwater and potential consequent contaminant transport to the subsurface from varying climatic conditions. PRACTITIONER POINTS: Urban stormwater contains organic contaminants including pharmaceuticals, pesticides, and semi-volatile organic compounds that may be transported to groundwater via infiltration. In general, fewer contaminants were detected in groundwater and at lower concentrations, compared with urban stormwater runoff. Trace organic contaminant concentrations in groundwater were much lower than drinking water guidance/screening values.

Multiple lines of evidence for identifying potential hazards to fish from contaminants of emerging concern in Great Lakes tributaries.

Contaminants of emerging concern (CECs; e.g., pharmaceuticals, flame retardants, pesticides, and industrial chemicals) are omnipresent throughout tributaries to the Great Lakes. Furthermore, CECs are often present at concentrations that are potentially hazardous to aquatic species. Since 2010, we characterized the presence of CECs at 309 sites within 47 Great Lakes tributaries and characterized responses of fathead minnow (Pimephales promelas) exposed to river water at a subset of 26 sites within four tributaries. Our work resulted in three independent lines of evidence related to the potential hazards of CEC exposure to fish. First, vulnerability (where vulnerability refers to likelihood) of surface waters to CEC presence was predicted using select watershed characteristics. Second, hazard to fish (where hazard means the potential for adverse biological responses) was predicted using screening values for a subset of CECs. Third, biological responses of fathead minnow exposed to river water in streamside exposures were measured. We assessed the congruence of these three lines of evidence for identifying sites with elevated hazards to CEC exposure. Predicted vulnerability and hazards agreed at 66% of all sites. Where the two indices did not agree, vulnerability often underestimated predicted hazard. When compared with measured biological responses from streamside exposures, predicted hazards agreed for 42% of samples. Furthermore, when predicted hazards for specific effect categories were compared with similar measured biomarkers, 26% and 46% of samples agreed for reproductive and physiological effect categories, respectively. Overall, vulnerability and hazard predictions tended to overestimate the measured biological responses, providing a protective estimate of the potential hazards of CEC exposure to fish. When used together, these three approaches can help resource managers prioritize management activities in minimizing hazards of CEC exposure and can be used by researchers to prioritize studies focused on understanding the hazards of CEC exposure to fish. Integr Environ Assess Manag 2022;18:1246-1259. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC). This article has been contributed to by US Government employees and their work is in the public domain in the USA.

Machine-Learning Predictions of High Arsenic and High Manganese at Drinking Water Depths of the Glacial Aquifer System, Northern Continental United States.

Globally, over 200 million people are chronically exposed to arsenic (As) and/or manganese (Mn) from drinking water. We used machine-learning (ML) boosted regression tree (BRT) models to predict high As (>10 µg/L) and Mn (>300 µg/L) in groundwater from the glacial aquifer system (GLAC), which spans 25 states in the northern United States and provides drinking water to 30 million people. Our BRT models' predictor variables (PVs) included recently developed three-dimensional estimates of a suite of groundwater age metrics, redox condition, and pH. We also demonstrated a successful approach to significantly improve ML prediction sensitivity for imbalanced data sets (small percentage of high values). We present predictions of the probability of high As and high Mn concentrations in groundwater, and uncertainty, at two nonuniform depth surfaces that represent moving median depths of GLAC domestic and public supply wells within the three-dimensional model domain. Predicted high likelihood of anoxic condition (high iron or low dissolved oxygen), predicted pH, relative well depth, several modeled groundwater age metrics, and hydrologic position were all PVs retained in both models; however, PV importance and influence differed between the models. High-As and high-Mn groundwater was predicted with high likelihood over large portions of the central part of the GLAC.

Machine Learning Predictions of pH in the Glacial Aquifer System, Northern USA.

A boosted regression tree model was developed to predict pH conditions in three dimensions throughout the glacial aquifer system of the contiguous United States using pH measurements in samples from 18,386 wells and predictor variables that represent aspects of the hydrogeologic setting. Model results indicate that the carbonate content of soils and aquifer materials strongly controls pH and, when coupled with long flowpaths, results in the most alkaline conditions. Conversely, in areas where glacial sediments are thin and carbonate-poor, pH conditions remain acidic. At depths typical of drinking-water supplies, predicted pH >7.5-which is associated with arsenic mobilization-occurs more frequently than predicted pH <6-which is associated with water corrosivity and the mobilization of other trace elements. A novel aspect of this model was the inclusion of numerically based estimates of groundwater flow characteristics (age and flowpath length) as predictor variables. The sensitivity of pH predictions to these variables was consistent with hydrologic understanding of groundwater flow systems and the geochemical evolution of groundwater quality. The model was not developed to provide precise estimates of pH at any given location. Rather, it can be used to more generally identify areas where contaminants may be mobilized into groundwater and where corrosivity issues may be of concern to prioritize areas for future groundwater monitoring.

Contaminants in bald eagles of the upper Midwestern U.S.: A framework for prioritizing future research based on in-vitro bioassays.

Several organic contaminants (OCs) have been detected in bald eagle (Haliaeetus leucocephalus) nestling (eaglet) plasma in the upper Midwestern United States. Despite frequent and relatively high concentrations of OCs in eaglets, little is understood about potential biological effects associated with exposure. We screened an existing database of OC concentrations in eaglet plasma collected from the Midwestern United States against bioactivity information from the ToxCast database. ToxCast bioactivity information consists of concentrations expected to elicit responses across a range of biological space (e.g. cellular, developmental, etc.) obtained from a series of high throughput assays. We calculated exposure-activity ratios (EAR) by calculating the ratio of plasma concentrations to concentrations available in ToxCast. Bioactivity data were not available for all detected OCs. Therefore, our analysis provides estimates of potential bioactivity for 19 of the detected OCs in eaglet plasma. Perfluorooctanesulfonic acid (PFOS) EAR values were consistently the highest among all study areas. Maximum EAR values were ≥1 for PFOS, perfluorononanoic acid, and bisphenol A in 99.7, 0.53 and 0.26% of samples, indicating that some plasma concentrations were greater than what may be expected to elicit biological responses. About 125 gene targets, indicative of specific biological pathways, were identified as potentially being affected. Inhibition of several CYP genes, involved in xenobiotic metabolism, were most consistently identified. Other identified biological responses have potential implications for motor coordination, cardiac functions, behavior, and blood circulation. However, it is unclear what these results mean for bald eagles, given that ToxCast data are generated using mammalian-based endpoints. Despite uncertainties and limitations, this method of screening environmental data can be useful for informing future monitoring or research focused on understanding the occurrence and effects of OCs in bald eagles and other similarly-positioned trophic species.

Predicting the occurrence of chemicals of emerging concern in surface water and sediment across the U.S. portion of the Great Lakes Basin.

Chemicals of emerging concern (CECs) are introduced into the aquatic environment via various sources, posing a potential risk to aquatic organisms. Previous studies have identified relationships between the presence of CECs in water and broad-scale watershed characteristics. However, relationships between the presence of CECs and source-related watershed characteristics have not been explored across the Great Lakes basin. Boosted regression tree (BRT) analyses were used to develop predictive models of CEC occurrence in water and sediment throughout 24 U.S. tributaries to the Great Lakes. Models were based on the distribution of both broad-scale and source-related watershed characteristics. Twenty-one upstream watershed characteristics, including land cover, number of permitted point sources, and distance to point sources were used to develop models predicting the probability of CEC occurrence in surface water and bottom sediment. Total accuracy of BRT models ranged from 66% to 94% for both matrices. All 21 watershed characteristics were important predictor variables in at least one surface-water model; twenty were important in at least one bottom-sediment model. Among the model variables, developed land use and distance to point sources were important predictors of the presence of CEC classes in both water and sediment. Although limitations exist, BRT models are one tool available for assessing vulnerability of fisheries and aquatic resources to CEC occurrences.

Concentrations of pharmaceuticals and other micropollutants in groundwater downgradient from large on-site wastewater discharges.

Large subsurface treatment systems (LSTS) and rapid infiltration basins (RIB) are preferred onsite wastewater treatments compared to direct discharge of treated wastewater to streams and adjacent facilities. Discharge of these wastewater treatments may result in contaminant loading to aquifers that also serve as drinking water sources downgradient from the discharge site. Until recently, few studies have characterized the contribution of micropollutants (e.g. pharmaceuticals, fragrances, flame retardants, etc.) to receiving aquifers. We conducted a pilot project to characterize the occurrence of micropollutants in groundwater downgradient from 7 on-site treatment systems in Minnesota, USA: 5 community LSTS and 2 municipal RIB. One downgradient monitoring well was sampled three times at each facility over one year. Of 223 micropollutants analyzed, 35 were detected. Total sample concentrations ranged from 90 to 4,039 ng/L. Sulfamethoxazole (antibiotic) was detected in all samples at concentrations from 7 to 965 ng/L. Other pharmaceuticals (0.12-1,000 ng/L), organophosphorus flame retardants (10-500 ng/L), and other anthropogenic chemicals (4-775 ng/L) were also detected. The numbers and concentrations of micropollutants detected were inversely related to dissolved oxygen and depth to water. Ratios of pharmaceutical concentrations to human-health screening values were <0.10 for most samples. However, concentrations of carbamazepine and sulfamethoxazole exceeded screening values at two sites. Study results illustrate that large on-site wastewater systems designed to discharge to permeable soil or shallow groundwater effectively deliver pharmaceuticals and other micropollutants to groundwater aquifers and could contribute micropollutants to drinking water via water supply wells.

Contaminants of emerging concern in urban stormwater: Spatiotemporal patterns and removal by iron-enhanced sand filters (IESFs).

Numerous contaminants of emerging concern (CECs) typically occur in urban rivers. Wastewater effluents are a major source of many CECs. Urban runoff (stormwater) is a major urban water budget component and may constitute another major CEC pathway. Yet, stormwater-based CEC field studies are rare. This research investigated 384 CECs in 36 stormwater samples in Minneapolis-St. Paul, Minnesota, USA. Nine sampling sites included three large stormwater conveyances (pipes) and three paired iron-enhanced sand filters (IESFs; untreated inlets and treated outlets). The 123 detected compounds included commercial-consumer compounds, veterinary and human pharmaceuticals, lifestyle and personal care compounds, pesticides, and others. Thirty-one CECs were detected in ≥50% of samples. Individual samples contained a median of 35 targeted CECs (range: 18-54). Overall, median concentrations were ≥10 ng/L for 25 CECs and ≥100 ng/L for 9 CECs. Ranked, hierarchical linear modeling indicated significant seasonal- and site type-based concentration variability for 53 and 30 CECs, respectively, with observed patterns corresponding to CEC type, source, usage, and seasonal hydrology. A primarily warm-weather, diffuse, runoff-based profile included many herbicides. A second profile encompassed winter and/or late summer samples enriched with some recalcitrant, hydrophobic compounds (e.g., PAHs), especially at pipes, suggesting conservative, less runoff-dependent sources (e.g., sediments). A third profile, indicative of mixed conservative/non-runoff, runoff, and/or atmospheric sources and transport that collectively affect a variety of conditions, included various fungicides, lifestyle, non-prescription, and commercial-consumer CECs. Generally, pipe sites had large, diverse land-use catchments, and showed more frequent detections of diverse CECs, but often at lower concentrations; while untreated sites (with smaller, more residential-catchments) demonstrated greater detections of "pseudo-persistent" and other ubiquitous or residentially-associated CECs. Although untreated stormwater transports an array of CECs to receiving waters, IESF treatment significantly removed concentrations of 14 (29%) of the 48 most detected CECs; for these, median removal efficiencies were 26%-100%. Efficient removal of some hydrophobic (e.g., PAHs, bisphenol A) and polar-hydrophilic (e.g., caffeine, nicotine) compounds indicated particulate-bound contaminant filtration and for certain dissolved contaminants, sorption.

Effects of urban stormwater and iron-enhanced sand filtration on Daphnia magna and Pimephales promelas.

Urban stormwater is an important but incompletely characterized contributor to surface-water toxicity. The present study used 5 bioassays of 2 model organisms (Daphnia magna and fathead minnow, Pimephales promelas) to investigate stormwater toxicity and mitigation by full-scale iron-enhanced sand filters (IESFs). Stormwater samples were collected from major stormwater conveyances and full-scale IESFs during 4 seasonal events (winter snowmelt and spring, early summer, and late summer rainfalls) and analyzed for a diverse range of contaminants of emerging concern including pharmaceuticals, personal care products, industrial chemicals, and pesticides. Concurrently, stormwater samples were collected for toxicity testing. Seasonality appeared more influential and consistent than site type for most bioassays. Typically, biological consequences were least in early summer and greatest in late summer and winter. In contrast with the unimproved and occasionally reduced biological outcomes in IESF-treated and late summer samples, water chemistry indicated that numbers and total concentrations of detected organic chemicals, metals, and nutrients were reduced in late summer and in IESF-treated stormwater samples. Some potent toxicants showed more specific seasonality (e.g., high concentrations of polycyclic aromatic hydrocarbons and industrial compounds in winter, pesticides in early summer and spring, flame retardants in late summer), which may have influenced outcomes. Potential explanations for insignificant or unexpected stormwater treatment outcomes include confounding effects of complex stormwater matrices, IESF nutrient removal, and, less likely, unmonitored toxicants. Environ Toxicol Chem 2018;37:2645-2659. © 2018 SETAC.

Environmentally relevant chemical mixtures of concern in waters of United States tributaries to the Great Lakes.

The North American Great Lakes are a vital natural resource that provide fish and wildlife habitat, as well as drinking water and waste assimilation services for millions of people. Tributaries to the Great Lakes receive chemical inputs from various point and nonpoint sources, and thus are expected to have complex mixtures of chemicals. However, our understanding of the co-occurrence of specific chemicals in complex mixtures is limited. To better understand the occurrence of specific chemical mixtures in the US Great Lakes Basin, surface water from 24 US tributaries to the Laurentian Great Lakes was collected and analyzed for diverse suites of organic chemicals, primarily focused on chemicals of concern (e.g., pharmaceuticals, personal care products, fragrances). A total of 181 samples and 21 chemical classes were assessed for mixture compositions. Basin wide, 1664 mixtures occurred in at least 25% of sites. The most complex mixtures identified comprised 9 chemical classes and occurred in 58% of sampled tributaries. Pharmaceuticals typically occurred in complex mixtures, reflecting pharmaceutical-use patterns and wastewater facility outfall influences. Fewer mixtures were identified at lake or lake-influenced sites than at riverine sites. As mixture complexity increased, the probability of a specific mixture occurring more often than by chance greatly increased, highlighting the importance of understanding source contributions to the environment. This empirically based analysis of mixture composition and occurrence may be used to focus future sampling efforts or mixture toxicity assessments. Integr Environ Assess Manag 2018;14:509-518. © 2018 SETAC.

Contaminants of emerging concern presence and adverse effects in fish: A case study in the Laurentian Great Lakes.

The Laurentian Great Lakes are a valuable natural resource that is affected by contaminants of emerging concern (CECs), including sex steroid hormones, personal care products, pharmaceuticals, industrial chemicals, and new generation pesticides. However, little is known about the fate and biological effects of CECs in tributaries to the Great Lakes. In the current study, 16 sites on three rivers in the Great Lakes basin (Fox, Cuyahoga, and Raquette Rivers) were assessed for CEC presence using polar organic chemical integrative samplers (POCIS) and grab water samplers. Biological activity was assessed through a combination of in vitro bioassays (focused on estrogenic activity) and in vivo assays with larval fathead minnows. In addition, resident sunfish, largemouth bass, and white suckers were assessed for changes in biological endpoints associated with CEC exposure. CECs were present in all water samples and POCIS extracts. A total of 111 and 97 chemicals were detected in at least one water sample and POCIS extract, respectively. Known estrogenic chemicals were detected in water samples at all 16 sites and in POCIS extracts at 13 sites. Most sites elicited estrogenic activity in bioassays. Ranking sites and rivers based on water chemistry, POCIS chemistry, or total in vitro estrogenicity produced comparable patterns with the Cuyahoga River ranking as most and the Raquette River as least affected by CECs. Changes in biological responses grouped according to physiological processes, and differed between species but not sex. The Fox and Cuyahoga Rivers often had significantly different patterns in biological response Our study supports the need for multiple lines of evidence and provides a framework to assess CEC presence and effects in fish in the Laurentian Great Lakes basin.

Detecting sulfamethoxazole and carbamazepine in groundwater: Is ELISA a reliable screening tool?

In recent years, numerous studies have reported the prevalence of organic micropollutants in natural waters. There is an increasing interest in assessing the occurrence and transport of these contaminants in groundwater because a large number of people in the United States rely on groundwater for their drinking water. However, commonly used mass-spectrometry-based analytical methods are expensive and time-consuming. The enzyme-linked immunosorbent assay (ELISA) method offers an inexpensive analytical alternative that provides semi-quantitative results in a relatively quick timeframe. We investigated the use of ELISA for two commonly detected micropollutants, sulfamethoxazole (SMX) and carbamazepine (CBZ), in groundwater collected as part of two different studies, one in Minnesota and the other in Iowa. The ELISA results were compared with two mass-spectrometry-based methods: (1) direct aqueous injection-high performance liquid chromatography/tandem mass spectrometry (HPLC) and (2) online solid-phase extraction with liquid chromatography/electrospray ionization-mass spectrometry (SPE LC). Differences in SMX and CBZ observations between ELISA and both HPLC and SPE LC were analyzed using the Paired Prentice-Wilcoxon test. Estimates of bias and limits of agreement between paired observations also were calculated. The SMX determinations by ELISA yielded results that were 30 and 14% greater than HPLC and SPE LC, respectively. The CBZ determinations by ELISA yielded results that were 25 and 9% greater than HPLC and SPE LC, respectively. The ELISA determinations were in presence-absence agreement with HPLC for 83% of samples for SMX and CBZ; and with SPE LC for 76 and 80% of samples for SMX and CBZ, respectively. Results indicate that ELISA for SMX and CBZ is a reliable and cost effective screening-tool alternative to more commonly used mass spectrometry-based analytical methods.

Contaminants of emerging concern in tributaries to the Laurentian Great Lakes: I. Patterns of occurrence.

Human activities introduce a variety of chemicals to the Laurentian Great Lakes including pesticides, pharmaceuticals, flame retardants, plasticizers, and solvents (collectively referred to as contaminants of emerging concern or CECs) potentially threatening the vitality of these valuable ecosystems. We conducted a basin-wide study to identify the presence of CECs and other chemicals of interest in 12 U.S. tributaries to the Laurentian Great Lakes during 2013 and 2014. A total of 292 surface-water and 80 sediment samples were collected and analyzed for approximately 200 chemicals. A total of 32 and 28 chemicals were detected in at least 30% of water and sediment samples, respectively. Concentrations ranged from 0.0284 (indole) to 72.2 (cholesterol) µg/L in water and 1.75 (diphenhydramine) to 20,800 µg/kg (fluoranthene) in sediment. Cluster analyses revealed chemicals that frequently co-occurred such as pharmaceuticals and flame retardants at sites receiving similar inputs such as wastewater treatment plant effluent. Comparison of environmental concentrations to water and sediment-quality benchmarks revealed that polycyclic aromatic hydrocarbon concentrations often exceeded benchmarks in both water and sediment. Additionally, bis(2-ethylhexyl) phthalate and dichlorvos concentrations exceeded water-quality benchmarks in several rivers. Results from this study can be used to understand organism exposure, prioritize river basins for future management efforts, and guide detailed assessments of factors influencing transport and fate of CECs in the Great Lakes Basin.

A regional assessment of chemicals of concern in surface waters of four Midwestern United States national parks.

Anthropogenic chemicals and their potential for adverse biological effects raise concern for aquatic ecosystem health in protected areas. During 2013-15, surface waters of four Midwestern United States national parks were sampled and analyzed for wastewater indicators, pharmaceuticals, personal care products, and pesticides. More chemicals and higher concentrations were detected at the two parks with greater urban influences (Mississippi National River and Recreation Area and Indiana Dunes National Lakeshore) than at the two more remote parks (Apostle Islands National Lakeshore and Isle Royale National Park). Atrazine (10-15ng/L) and N,N-diethyl-meta-toluamide (16-120ng/L) were the only chemicals detected in inland lakes of a remote island national park (Isle Royale National Park). Bisphenol A and organophosphate flame retardants were commonly detected at the other sampled parks. Gabapentin and simazine had the highest observed concentrations (>1000ng/L) in three and two samples, respectively. At the two parks with urban influences, metolachlor and simazine concentrations were similar to those reported for other major urban rivers in the United States. Environmental concentrations of detected chemicals were often orders of magnitude less than standards or reference values with three exceptions: (1) hydrochlorothiazide exceeded a human health-based screening value in seven samples, (2) estrone exceeded a predicted critical environmental concentration for fish pharmacological effects in one sample, and (3) simazine was approaching the 4000ng/L Maximum Contaminant Level in one sample even though this concentration is not expected to reflect peak pesticide use. Although few environmental concentrations were approaching or exceeded standards or reference values, concentrations were often in ranges reported to elicit effects in aquatic biota. Data from this study will assist in establishing a baseline for chemicals of concern in Midwestern national parks and highlight the need to better understand the sources, pathways, and potential adverse effects to aquatic systems in national parks.