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Heiko L. Schoenfuss

Publications and source records attributed to Heiko L. Schoenfuss.

At least 19 recordsLinked to original sources

A comprehensive assessment of membrane bioreactor contaminant removal efficacy through analytical chemistry, fish exposures, and microbiome characterization

Treated municipal wastewater effluent is an important pathway for Contaminants of Emerging Concern (CEC) to enter aquatic ecosystems. As the aging wastewater infrastructure in many industrialized countries requires upgrades or replacement, assessing new treatment technologies in the context of CEC effects may provide additional support for science-based resource management. Here, we used three lines of evidence, analytical chemistry, fish exposure experiments, and fish and water microbiome analysis, to assess the effectiveness of membrane bioreactor treatment (MBR) to replace traditional activated sludge treatment. To do this, we sampled a municipal wastewater treatment plant with a split wastewater stream, a portion of which was treated with an MBR and another via an oxidation ditch (OXI). The OXI and MBR treatments substantially reduced most measured CECs compared to the primary effluent (PRI). Only pesticides and some pharmaceuticals were recalcitrant to both secondary treatment methods. While ammonia toxicity of PRI prevented its inclusion in fish exposure experiments, exposure of fish with waters from the OXI or MBR treated wastewater produced only subtle biological differences with no adverse apical outcomes. These findings were consistent with low chemically derived exposure: activity ratios for OXI and MBR. Microbiome analysis of fish and wastewater highlighted the significant reduction of microbial abundance and diversity in the MBR treatment compared to all other treatments. The comparable removal efficacy of CECs in MBR makes it an attractive alternative to traditional OXI, especially when MBR may eliminate the need for tertiary treatment for wastewater disinfection.

Environmental Toxicology and Chemistry

Comparing contaminants of emerging concern and microbial signatures of wastewater treated by membrane bioreactor and oxidation ditch methods

Membrane bioreactors (MBRs) are an attractive option for upgrades to aging wastewater treatment infrastructure across the United States (U.S.) because they have a relatively small footprint and can handle various wastewater loading conditions. However, little is known regarding the efficiency with which MBRs can reduce contaminants of emerging concern (CECs) and microbial loads, or how they influence the microbiome of wastewater effluent. In 2022, we collected nine paired samples of primary treated effluent (PRI), secondary effluent treated by oxidation ditches (OXI), and secondary effluent treated by MBR from a facility in Minnesota, U.S. Samples were analyzed for CECs including 4 alkylphenol ethoxylates, 6 bisphenol analogues, 20 hormones, 110 pharmaceuticals, and 82 pesticides as well as heterotrophic bacteria counts (HPC) and microbiome communities. Except for pesticides, total sample concentrations of CEC classes in OXI and MBR effluents were similar and lower compared to PRI ( p < 0.01). Pesticide concentrations were similar among all treatments. HPC was lower in MBR, compared to OXI, in 67% of samples. Despite limited differences in CEC signatures, differences in the microbiome between the two secondary treatments were observed. OXI showed more distinct differences in bacterial operational taxonomic unit (OTU) presence from PRI, compared to MBR. Relations between some contaminant groups ( e.g. , pharmaceuticals, bisphenols) and effluent microbiomes were observed, though most correlated with PRI effluent. Results from our study indicate that MBR is as effective as OXI at producing high-quality effluent and offers a viable alternative to conventional secondary treatment methods. This full-scale study provides data that helps fill knowledge gaps related to MBR performance outside of lab or benchtop experiments and direct comparison to OXI treatment.

Environmental Science: Water Research & Technology

Assessing contaminants of emerging concern in the Great Lakes Ecosystem: A decade of method development and practical application

Assessing the ecological risk of contaminants in the field typically involves consideration of a complex mixture of compounds which may or may not be detected via instrumental analyses. Further, there are insufficient data to predict the potential biological effects of many detected compounds, leading to their being characterized as contaminants of emerging concern (CECs). Over the past several years, advances in chemistry, toxicology, and bioinformatics have resulted in a variety of concepts and tools that can enhance the pragmatic assessment of the ecological risk of CECs. The present Focus article describes a 10+- year multiagency effort supported through the U.S. Great Lakes Restoration Initiative to assess the occurrence and implications of CECs in the North American Great Lakes. State-of-the-science methods and models were used to evaluate more than 700 sites in about approximately 200 tributaries across lakes Ontario, Erie, Huron, Michigan, and Superior, sometimes on multiple occasions. Studies featured measurement of up to 500 different target analytes in different environmental matrices, coupled with evaluation of biological effects in resident species, animals from in situ and laboratory exposures, and in vitro systems. Experimental taxa included birds, fish, and a variety of invertebrates, and measured endpoints ranged from molecular to apical responses. Data were integrated and evaluated using a diversity of curated knowledgebases and models with the goal of producing actionable insights for risk assessors and managers charged with evaluating and mitigating the effects of CECs in the Great Lakes. This overview is based on research and data captured in approximately about 90 peer-reviewed journal articles and reports, including approximately about 30 appearing in a virtual issue comprised of highlighted papers published in Environmental Toxicology and Chemistry or Integrated Environmental Assessment and Management . Environ Toxicol Chem 2023;42:2506–2518. © 2023 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Environmental Toxicology and Chemistry

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.

Minnesota

Exposure and effects of bioaccumulative contaminants of emerging concern in tree swallows nesting across the Laurentian Great Lakes

Contaminants of emerging concern (CECs) are a loosely defined group of chemicals whose wide-spread usage or presence in the environment has occurred more recently or for which there has been relatively little research done until recently. Many of these CECs are not currently regulated. The National Toxicology Program within the U.S. Department of Health and Human Services estimates that about 2000 CECs are introduced each year (https://ntp.niehs.nih.gov/about/). An unknown number may pose a risk to human or animal health. The Phase 1 (2010 – 2014) CEC work in birds, which is the subject of this report, assessed exposure across the Great Lakes to polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFASs), and polycyclic aromatic hydrocarbons (PAHs), and put those exposures into context with data from biologically relevant endpoints such as reproductive success, as well as, physiological response indicators (bioindicators) to assess possible effects. The group of chemicals included in Phase 1 were mainly those chemicals that bioaccumulate in tissues. Phase 2 (2015 – 2019) CEC work with tree swallows was expanded to include CECs whose occurrence in the environment is more temporary or seasonal, and that do not necessarily bioaccumulate. These are often called pseudo-persistent, because, while they are not long-lived in the environment, there are often daily inputs via waste water treatment plants, and run-off from farm fields and storm drainages, thereby making them available to biota year-round. These include pharmaceuticals, personal care products, and newer pesticides including herbicides. Tree swallow work on these less persistent CECs will be reported in the future, however see other Appendices in this report for information on some of these types of CECs (Appendices A, B, D).

Laurentian Great Lakes

Contaminants of emerging concern in the Great Lakes: Science to inform management practices for protecting the health and integrity of wildlife populations from adverse effects: GLRI action plan I, focus area 1, goal 5

Executive Summary: Under Action Plan I (2010-2014) of the Great Lakes Restoration Initiative (GLRI), Federal and Academic partners began an investigation of the presence and distribution of contaminants of emerging concern (CECs) in the Great Lakes and potential impacts on fish and wildlife. The term CECs is applied to a broad range of chemicals that are currently in use but for which we currently lack good understanding of whether fish, wildlife, or humans are being exposed and/or whether negative health or environmental effects are expected if exposure occurs. Pharmaceuticals, personal care products, flame retardants, many current use pesticides, and poly- and perfluorinated chemicals are some well-known groups of CECs, but there is no definitive or comprehensive list that can be used to support the management of CECs to reduce impacts on the Great Lakes ecosystem. Four overarching goals were identified for this collaborative investigation: 1. Evaluate the sources, occurrence, and distribution of CECs across the Great Lakes Basin. 2. Examine associations between the distribution of CECs and land-use patterns. 3. Review both scientific literature and field-generated data to determine the potential for CECs to cause adverse effects on Great Lakes fish and wildlife populations. 4. Develop efficient strategies to survey and/or monitor for threats that CECs may pose in order to take effective management actions before those threats evolve into large scale impacts on Great Lakes ecosystems or the services they provide. Achievement of these goals ensures progress towards Focus Area 1: Toxic Substances and Areas of Concern from GLRI Action Plan I, Goal 5: “ The health and integrity of wildlife populations and habitat are protected from adverse chemical and biological effects associated with the presence of toxic substances in the Great Lakes Basin ”. This large-scale research effort was comprised of individual and collaborative projects from multiple federal agencies and academic institutions, involving over 85 investigators, and overseen by the U.S. Environmental Protection Agency (EPA) Region 5, Great Lakes National Program Office. Partners include the United States Geological Survey, the National Oceanic and Atmospheric Administration, U.S. Fish and Wildlife Service, Saint Cloud State University, the U.S. EPA Office of Research and Development, and the U.S. Army Corps of Engineers. Key findings: 1. Contaminants of emerging concern were found throughout the monitored Great Lakes tributaries, but types and concentrations vary in association with regional land use. CECs were detected in nearly all samples collected. The type and concentration of the specific contaminants detected varied considerably among field sites and in association with land use type, such as urban, agricultural, wetland, 2 or forest. Contaminants were detected in the water column, sediment, and tissues of all species surveyed in the current work (mussels, aquatic insects, fish, and insect-eating birds). 2. There were over 20 contaminants for which CEC concentrations approached or exceeded those reported to cause toxicity in laboratory experiments. This was based on detection in water, sediments and or biota at one or more field sites. These contaminants represent compounds that warrant further investigation and monitoring with respect to potential impacts in certain areas of the Great Lakes basin. Based on the present investigation, compounds of greatest concern include: polycyclic aromatic hydrocarbons, associated with oil-based products and combustion of organic matter; atrazine, an herbicide; dichlorvos, an insecticide; and ibuprofen and venlafaxine, both pharmaceuticals. 3. Results suggest that mixtures of CECs presently found in most Great Lakes tributary locations surveyed may elicit subtle biological effects, but likely are not, alone, causing obvious detriment to current communities of fish and wildlife. CECs detected in the Great Lakes were associated with subtle biological effects like changes in gene expression, altered circulating glucose, etc. in both wild-caught and laboratory-reared organisms. These effects were generally not indicative of reproductive failure or mortality. However, the effects may have more serious implications when combined with other sources of stress like habitat degradation, changing climate conditions, and competition with invasive species. Due to limited historical data, it is unknown whether severe CEC-related impacts have already affected aquatic communities in waterbodies that have received long-term inputs of these contaminants. Likewise, under Action Plan I, biological effects were not necessarily evaluated at the sites where CEC concentrations exceeding laboratory toxicity thresholds were detected. As a result, strategic, ongoing surveillance and monitoring of CECs is warranted. This collaborative investigation resulted in new tools, approaches, and data that can be used to inform and support the management of CECs to reduce their impacts on Great Lakes natural resources. The following products of this research effort are available through https://communities.geoplatform.gov/glri/ or by contacting the investigators (see technical chapters found in Appendices A-F): 1. Database of CEC occurrence and concentrations in US tributary streams. The database includes CEC detections in water, sediment, and fish and wildlife tissues, and represents the most comprehensive survey of CECs in the Great Lakes Region. 2. Synopses of results and key findings. Integrated summaries of results, conclusions, and management implications of the CEC research are available through reports, topical fact sheets, and presentations. 3. Technical publications: This collaborative research effort has resulted in over 50 peer-reviewed publications, agency reports, and data releases that can be of use to resource managers, the scientific community, and members of the public. 4. Innovative tools. Innovative monitoring devices, sampling equipment, conceptual frameworks, and software applications were developed over the course of this 3 research. These tools are transferable to stakeholders via internet accessibility or via specifications, instructions, and demonstration detailed in technical publications. Hypotheses to guide CECs research under Action Plan II. Findings from 2010-2014 were used to guide further research in 2015-2018 for basin-wide surveillance of CECs and for sites warranting further study of potential biological impacts of CECs. Additional surveillance included both evaluation of additional classes of contaminants and expanded lists for chemical classes shown to be of greatest concern. Mixtures of some of the most frequently detected contaminants were also tested in laboratory studies to understand whether long term exposures to multiple contaminants may result in effects not evident from uncontrolled, short-term field experiments.

Great Lakes

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.

Great Lakes

Identifying sources of contaminants in urban stormwater and evaluation of their removal efficacy across a continuum of urban best management practices

Precipitation events in urban areas often result in stormwater runoff containing a diverse array of chemical contaminants. Although many traditional contaminants, such as nutrients, heavy metals, and polycyclic aromatic hydrocarbons have been studied extensively, only recently has evidence emerged showing that trace organic compounds (TrOCs), including pharmaceuticals, personal care products and pesticides are frequently found in stormwater runoff. As there is little existing information about the sources of TrOCs in urban stormwater or their removal efficacy across a range of stormwater treatment options, we conducted a study to address these knowledge gaps and to characterize the potential contribution of TrOCs to groundwater resources from stormwater infiltration practices, based on several synoptic measurements. The current study allowed us to enhance an existing effort to assess TrOC presence and toxicity in stormwater runoff and treatment pond outflow by addressing questions related to TrOC sources to stormwater and TrOC transport to groundwaters. Analysis of eDNA confirms multiple sources of TrOCs to stormwater including human sewage, dog waste, and feces from waterfowl. It is likely that the presence of some TrOCs detected in stormwater are the result of direct, untreated sewage inputs to stormwater from either human (i.e., leaking sewer infrastructure) or pet waste (washed from sidewalks into storm drains). The seasonal detection of avian eDNA is noteworthy as it highlights seasonality and patterns of migration patterns as contributing factors to stormwater contamination. In contrast to human and pet waste, which likely enters stormwater ponds via the stormwater conveyance system, avian feces may enter ponds either through stormwater runoff or through direct inputs by waterfowl stopping-over temporarily at stormwater ponds. Stormwater ponds had little effect in reducing TrOCs as determined by comparative inflow and outflow analysis. Our results also indicate that overall few TrOCs were present in receiving groundwater adjacent to underground infiltration basins, compared to inflow. However, some contaminants were present at relatively high concentrations compared to stormwater flowing into the basins. This is particularly true for pesticides and their degradants. Fewer TrOCs were detected in interstitial water collected near stormwater ponds compared to inflow and outflow. The presence and concentrations of TrOCs in outflow from ponds was generally similar to or higher than what was observed in inflow. The data collected as part of this study can be used to guide future research or monitoring in an effort to better understand TrOC fate and transport in the environment via stormwater BMPs. Specifically, more work is needed to track parcels of water as they flow through BMPs to better quantify transport and degradation of TrOCs, monitor flow into and out of ponds for mass balance calculations, and conduct tracer tests to better quantify the amount of water that monitoring wells are intercepting from underground infiltration basins. These results have been shared in multiple presentations and in meetings with high school teachers to develop age-appropriate curriculum to highlight the role of individuals in reducing and preventing stormwater contamination. The ongoing pandemic hindered some of these efforts (cancelled conferences; suspended MN Water Roundtable meetings; pre-occupation with teachers moving materials online), however, as dissemination activities become more common in the near future, we will continue to educate stakeholders and educators about the root causes and effects of urban stormwater contamination.

Minnesota

Critical review: Grand challenges in assessing the adverse effects of contaminants of emerging concern on aquatic food webs

Much progress has been made in the past few decades in understanding the sources, transport, fate, and biological effects of contaminants of emerging concern (CECs) in aquatic ecosystems. Despite these advancements, significant obstacles still prevent comprehensive assessments of the environmental risks associated with the presence of CECs. Many of these obstacles center around the extrapolation of effects of single chemicals observed in the laboratory or effects found in individual organisms or species in the field to impacts of multiple stressors on aquatic food webs. In the present review, we identify 5 challenges that must be addressed to promote studies of CECs from singular exposure events to multispecies aquatic food web interactions. There needs to be: 1) more detailed information on the complexity of mixtures of CECs in the aquatic environment, 2) a greater understanding of the sublethal effects of CECs on a wide range of aquatic organisms, 3) an ascertaining of the biological consequences of variable duration CEC exposures within and across generations in aquatic species, 4) a linkage of multiple stressors with CEC exposure in aquatic systems, and 5) a documenting of the trophic consequences of CEC exposure across aquatic food webs. We examine the current literature to show how these challenges can be addressed to fill knowledge gaps.

Environmental Toxicology and Chemistry

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.

Environmental Toxicology and Chemistry

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.

Integrated Environmental Assessment and Management

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.

Environmental Pollution

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.

Minnesota

Contaminants of emerging concern in tributaries to the Laurentian Great Lakes: II. Biological consequences of exposure

The Laurentian Great Lakes contain one fifth of the world’s surface freshwater and have been impacted by human activity since the Industrial Revolution. In addition to legacy contaminants, nitrification and invasive species, this aquatic ecosystem is also the recipient of Contaminants of Emerging Concern (CECs) with poorly understood biological consequences. In the current study, we documented the presence, concentrations, and biological effects of CECs across 27 field sites in six Great Lakes tributaries by examining over 2250 resident and caged sunfish ( Lepomis ssp .) for a variety of morphological and physiological endpoints and related these results to CEC occurrence. CEC were ubiquitous across studies sites and their presence and concentrations in water and sediment were highest in effluent dominated rivers and downstream of municipal wastewater treatment plant discharges. However, even putative upstream reference sites were not free of CEC presence and fish at these sites exhibited biological effects consistent with CEC exposure. Only the Fox River exhibited consistent adverse biological effects, including increased relative liver size, greater prominence of hepatocyte vacuoles and increased plasma glucose concentrations. Canonical Redundancy Analysis revealed consistent patterns of biological consequences of CEC exposure across all six tributaries. Increasing plasma glucose concentrations, likely as a result of pollutant-induced metabolic stress, were associated with increased relative liver size and greater prominence of hepatocyte vacuoles. These indicators of pollutant exposure were inversely correlated with indicators of reproductive potential including smaller gonad size and less mature gametes. The current study highlights the need for greater integration of chemical and biological studies and suggests that CECs in the Laurentian Great Lakes Basin may adversely affect the reproductive potential of exposed fish populations.

PLoS ONE

Uptake and disposition of select pharmaceuticals by bluegill exposed at constant concentrations in a flow-through aquatic exposure system

The increasing use of pharmaceuticals has led to their subsequent input into and release from wastewater treatment plants, with corresponding discharge into surface waters that may subsequently exert adverse effects upon aquatic organisms. Although the distribution of pharmaceuticals in surface water has been extensively studied, the details of uptake, internal distribution, and kinetic processing of pharmaceuticals in exposed fish have received less attention. For this research, we investigated the uptake, disposition, and toxicokinetics of five pharmaceuticals (diclofenac, methocarbamol, rosuvastatin, sulfamethoxazole, and temazepam) in bluegill sunfish ( Lepomis macrochirus ) exposed to environmentally relevant concentrations (1000–4000 ng L –1 ) in a flow-through exposure system. Temazepam and methocarbamol were consistently detected in bluegill biological samples with the highest concentrations in bile of 4, 940, and 180 ng g –1 , respectively, while sulfamethoxazole, diclofenac, and rosuvastatin were only infrequently detected. Over 30-day exposures, the relative magnitude of mean concentrations of temazepam and methocarbamol in biological samples generally followed the order: bile ≫ gut > liver and brain > muscle, plasma, and gill. Ranges of bioconcentration factors (BCFs) in different biological samples were 0.71–3960 and 0.13–48.6 for temazepam and methocarbamol, respectively. Log BCFs were statistically positively correlated to pH adjusted log K ow (that is, log D ow ), with the strongest relations for liver and brain ( r 2 = 0.92 and 0.99, respectively), implying that bioconcentration patterns of ionizable pharmaceuticals depend on molecular status, that is, whether a pharmaceutical is un-ionized or ionized at ambient tissue pH. Methocarbamol and temazepam underwent rapid uptake and elimination in bluegill biological compartments with uptake rate constants ( K u ) and elimination rate constants ( K e ) at 0.0066–0.0330 h –1 and 0.0075–0.0384 h –1 , respectively, and half-lives at 18.1–92.4 h. Exposure to mixtures of diclofenac, methocarbamol, sulfamethoxazole, and temazepam had little or no influence on the uptake and elimination rates, suggesting independent multiple uptake and disposition behaviors of pharmaceuticals by fish would occur when exposed to effluent-influenced surface waters.

Environmental Science & Technology

Prior knowledge-based approach for associating contaminants with biological effects: A case study in the St. Croix River basin, MN, WI, USA

Evaluating potential adverse effects of complex chemical mixtures in the environment is challenging. One way to address that challenge is through more integrated analysis of chemical monitoring and biological effects data. In the present study, water samples from five locations near two municipal wastewater treatment plants in the St. Croix River basin, on the border of MN and WI, USA, were analyzed for 127 organic contaminants. Known chemical-gene interactions were used to develop site-specific knowledge assembly models (KAMs) and formulate hypotheses concerning possible biological effects associated with chemicals detected in water samples from each location. Additionally, hepatic gene expression data were collected for fathead minnows ( Pimephales promelas ) exposed in situ , for 12 d, at each location. Expression data from oligonucleotide microarrays were analyzed to identify functional annotation terms enriched among the differentially-expressed probes. The general nature of many of the terms made hypothesis formulation on the basis of the transcriptome-level response alone difficult. However, integrated analysis of the transcriptome data in the context of the site-specific KAMs allowed for evaluation of the likelihood of specific chemicals contributing to observed biological responses. Thirteen chemicals (atrazine, carbamazepine, metformin, thiabendazole, diazepam, cholesterol, p-cresol, phenytoin, omeprazole, ethyromycin, 17β-estradiol, cimetidine, and estrone), for which there was statistically significant concordance between occurrence at a site and expected biological response as represented in the KAM, were identified. While not definitive, the approach provides a line of evidence for evaluating potential cause-effect relationships between components of a complex mixture of contaminants and biological effects data, which can inform subsequent monitoring and investigation.

Minnesota, Wisconsin

Complex mixtures, complex responses: Assessing pharmaceutical mixtures using field and laboratory approaches

Pharmaceuticals are present in low concentrations (<100&thinsp;ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows ( Pimephales promelas ) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning levels of biological organization and life stages when assessing contaminant interactions.

Environmental Toxicology and Chemistry

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.

Minnesota