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.

Linking Trace Organic Contaminants in On-Site Wastewater-Treatment Discharge with Biological Effects.

Around the globe, on-site wastewater-treatment systems (OWTSs) are critical for rural communities without access to a municipal sewer system. However, their treatment efficiency does not match that of modern wastewater-treatment plants. The impact of OWTS discharge on nearby aquatic ecosystems and their resident fish species is poorly understood. In the present study, larval and adult fathead minnows (Pimephales promelas) and adult sunfish (Lepomis macrochirus) were exposed for 21 days to two trace organic contaminant (TOrC) mixtures replicating water chemistry derived from a previous environmental study. Larval fathead minnows were assessed for survival, growth, predator avoidance, and feeding efficiency. Adult fathead minnows and sunfish were assessed for a suite of physiological endpoints (condition indices, vitellogenin, glucose), histological changes, and fecundity. The only observed effect of TOrC mixture exposure on larval fathead minnows was a decrease in feeding efficiency. Effects were mixed in exposed adult fishes, except for male sunfish which realized a significant induction of vitellogenin (p < 0.05). The consequences of TOrC mixture exposure in the present controlled laboratory study match effects observed in wild-caught sunfish in a corresponding field study. The present study begins to bridge the gap by connecting nonpoint OWTS pollution with biological effects observed in resident lake fish species. Given the effects observed despite the brevity of the laboratory mixture exposure, longer-term studies are warranted to understand the full impacts of OWTS discharge to nearby aquatic ecosystems.  Environ Toxicol Chem 2021;40:3193-3204. © 2021 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.

Prioritizing potential endocrine active high resolution mass spectrometry (HRMS) features in Minnesota lakewater.

Liquid chromatography high-resolution mass spectrometry (LC-HRMS) shows great potential for expanding our understanding of relevant unknown chemical components present within complex environmental mixtures. This study identified potentially endocrine active components within Minnesota lakewater by prioritizing LC-HRMS features uniquely present at sunfish spawning habitats where male fish showed signs of estrogen agonism. Porewater samples from four locations within the same lake were analyzed using liquid chromatography quadrupole time of flight mass spectrometry (LC-QToF/MS) with positive (ESI+) and negative (ESI-) electrospray ionization. Plasma vitellogenin concentrations of captured male sunfish was used to designate sites as either endocrine active (ACT; 2 sites) or reference (REF; 2 sites). Assuming unique chemical presence at active sites contributed to endocrine activity, features at significantly higher intensities (p-value < 0.05, t-value > t-critical, log-fold change > 0.1; equal variance t-test of log2 transformed data) in ACT sites were then compiled into a suspect search list for feature identification. Adducts and isotopes of prioritized features were deprioritized using pattern recognizing algorithms using mass, retention time, and intensity. Feature identities were reported according to established confidence metrics using spectral libraries and elemental composition algorithms. This LC-HRMS approach identified a number of features omitted by targeted analysis with higher relative abundances in ACT sites, including plant essential oils, fatty acids, and mycotoxins. Multivariate analysis determined whether features were either present at both sites (AB) or unique to individual ACT sites (A or B). Detection frequency across datasets indicated bias in feature prioritization influenced by the chosen sampling method and sample acquisition mode. The majority of features prioritized by this workflow remain tentatively identified or unidentified masses of interest, reflective of current limitations in shared spectral libraries for soft ionization analyses. Strategies similar to this workflow have the potential to reduce bias in database-driven toxicological prioritization frameworks.

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.

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.

Trace organic contaminant (TOrC) mixtures in Minnesota littoral zones: Effects of on-site wastewater treatment system (OWTS) proximity and biological impact.

On-site wastewater treatment systems (OWTSs) are an international wastewater management strategy for rural and semi-rural communities without access to centralized sewage treatment. These systems are a suspected source of trace organic contaminants (TOrCs) that may be responsible for endocrine disrupting effects to resident fish species in Minnesota Lakes. This study assessed localized porewater concentrations of TOrCs in near-shore environments across five Minnesota Lakes. Sampling sites were designated as either likely (HOME) or unlikely (REF) to receive OWTS discharges based on their proximity to shoreline households. Sampling sites also served as sunfish spawning habitats concurrently studied for biological impacts to resident adult males. Two-group hypothesis tests demonstrated significantly (p = .02) higher total TOrC concentrations in HOME (Mean = 841 ng/L) versus REF (Mean = 222 ng/L) sites. HOME sites also contained a wider suite of TOrC detections relative to REF sites. The distance to the nearest household (most proximal distance; MPD) negatively correlated (r = -0.62) with total TOrC concentrations. However, 2,4-D and DEET were major contributors to these total concentrations, suggesting that anthropogenic influence from households may not be exclusively attributed to OWTS discharges. Further, TOrC presence and elevated nitrogen concentrations in REF site porewater suggest additional, non-household TOrC discharges to these lakes. Significantly higher blood concentrations of vitellogenin (p = .03) and 11-ketotestosterone (p = .01) were observed in adult male sunfish captured from HOME versus REF sites. Comparisons between chemical and biological data indicate enhanced bioactive effects of co-contaminants. The findings from this study demonstrate multiple diffuse transport pathways contribute to the presence of biologically active TOrC mixtures in Minnesota Lakes, and mitigation efforts should consider minimizing residential inputs of chemicals associated with both outdoor and OWTS activity.

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.

Identifying non-point sources of endocrine active compounds and their biological impacts in freshwater lakes.

Contaminants of emerging concern, particularly endocrine active compounds (EACs), have been identified as a threat to aquatic wildlife. However, little is known about the impact of EACs on lakes through groundwater from onsite wastewater treatment systems (OWTS). This study aims to identify specific contributions of OWTS to Sullivan Lake, Minnesota, USA. Lake hydrology, water chemistry, caged bluegill sunfish (Lepomis macrochirus), and larval fathead minnow (Pimephales promelas) exposures were used to assess whether EACs entered the lake through OWTS inflow and the resultant biological impact on fish. Study areas included two OWTS-influenced near-shore sites with native bluegill spawning habitats and two in-lake control sites without nearby EAC sources. Caged bluegill sunfish were analyzed for plasma vitellogenin concentrations, organosomatic indices, and histological pathologies. Surface and porewater was collected from each site and analyzed for EACs. Porewater was also collected for laboratory exposure of larval fathead minnow, before analysis of predator escape performance and gene expression profiles. Chemical analysis showed EACs present at low concentrations at each study site, whereas discrete variations were reported between sites and between summer and fall samplings. Body condition index and liver vacuolization of sunfish were found to differ among study sites as did gene expression in exposed larval fathead minnows. Interestingly, biological exposure data and water chemistry did not match. Therefore, although results highlight the potential impacts of seepage from OWTS, further investigation of mixture effects and life history factor as well as chemical fate is warranted.

Anthropogenic tracers, endocrine disrupting chemicals, and endocrine disruption in Minnesota lakes.

Concentrations of endocrine disrupting chemicals and endocrine disruption in fish were determined in 11 lakes across Minnesota that represent a range of trophic conditions and land uses (urban, agricultural, residential, and forested) and in which wastewater treatment plant discharges were absent. Water, sediment, and passive polar organic integrative samplers (POCIS) were analyzed for steroidal hormones, alkylphenols, bisphenol A, and other organic and inorganic molecular tracers to evaluate potential non-point source inputs into the lakes. Resident fish from the lakes were collected, and caged male fathead minnows were deployed to evaluate endocrine disruption, as indicated by the biological endpoints of plasma vitellogenin and gonadal histology. Endocrine disrupting chemicals, including bisphenol A, 17ß-estradiol, estrone, and 4-nonylphenol were detected in 90% of the lakes at part per trillion concentrations. Endocrine disruption was observed in caged fathead minnows and resident fish in 90% of the lakes. The widespread but variable occurrence of anthropogenic chemicals in the lakes and endocrine disruption in fish indicates that potential sources are diverse, not limited to wastewater treatment plant discharges, and not entirely predictable based on trophic status and land use.

Laboratory tests of ammonium and barley straw extract as agents to suppress abundance of the harmful alga Prymnesium parvum and its toxicity to fish.

Prymnesium parvum is a harmful alga whose blooms can cause fish kills in brackish waters. Two potential suppressants of this alga were tested, ammonium and barley straw extract (BSE), at temperatures of 10, 20 and 30 degrees C. Laboratory batch cultures were grown for 3 weeks at each temperature, with weekly doses of ammonium or BSE at either low or high levels, or a no-dose control treatment. The growth rate of P. parvum during exponential phase was highest at 20 degrees C and lowest at 10 degrees C, and was stimulated by the highest ammonium dose. Only cultures grown at 20 degrees C were toxic to fish. The highest ammonium dose abolished such toxicity and reduced the endpoint population density of P. parvum. BSE did not reduce the exponential growth rate, endpoint density, or toxicity to fish of P. parvum. The results support the use of ammonium additions, but not BSE, to suppress harmful blooms of P. parvum in those circumstances where the possible disadvantages can be managed.