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Biological implications for contaminants of emerging concern in the Great Lakes–Upper St Lawrence River drainage: An effect-based ecological hazard assessment in fish

Contaminants of emerging concern (CECs) are released widely and continuously into the Great Lakes Basin–Upper St Lawrence River study area, with many detected in surface water at concentrations known to adversely affect fish. We applied a recent ecological hazard assessment methodology to identify the biological significance of a database of 21,441 surface water CEC concentrations compiled from 7,162 surface water samples collected at 1,021 sampling sites in 387 individual waterbodies throughout the Great Lakes Basin. We assessed hazard to fish in 12 effect categories (e.g., mortality, developmental, reproductive) from aqueous exposure to 16 emerging contaminants. Our hazard assessment used pairs of screening values to generate contaminant- and effect-specific ordinal hazard scores. Using this novel methodology, we generated a database of 93,864 hazard scores. We found the highest level of hazard to fish, indicating probable adverse impacts, was broadly distributed and often associated with municipalities. Mortality, reproductive, and developmental effect categories combined accounted for 17.5% of high hazard observations. Low hazard, indicating possible adverse effects, was prevalent for numerous effect categories and occurred throughout the period 1991–2021. For mortality, reproductive, and developmental effect categories, the incidence of elevated hazard (low or high hazard) among assessed water samples was 20.4%, 39.5%, and 20.3%, respectively. On a local scale, effect-based assessment is an efficient and conceptually simple tool for natural resource managers to obtain effect- and site-specific hazard information concerning CEC effects in fish that can be used in project planning and results interpretation for natural resource monitoring, restoration, and protection.

Great Lakes–Upper St Lawrence River study area↗

Agricultural sources of contaminants of emerging concern and adverse health effects on freshwater fish

Agricultural contaminants of emerging concern (CECs) are generally thought of as certain classes of chemicals associated with animal feeding and production facilities. Veterinary pharmaceuticals used in animal food production systems represent one of the largest groups of CECs. In our review, we discuss the extensive increase in use of antibiotics in animal feeding operations (AFOs) around the world. AFOs are a major consumer of antibiotics and other veterinary pharmaceuticals and over the past decade there has been growing information on the occurrence, release, and fate of CECs from animal food production operations, including the application of pharmaceutical-containing manure to agricultural fields and releases from waste lagoons. Concentrations of CECs in surface and ground water in proximity to AFOs correspond to their presence in the AFO wastes. In many cases, the environmental concentrations of agriculturally-derived CECs are below toxicity thresholds. Hormones and hormone replacement compounds are a notable exception, where chemical concentrations near AFOs can exceed concentrations known to cause adverse effects on endocrine-related functions in fish. In addition, some agricultural pesticides, once thought to be safe to non-target organisms, have demonstrated endocrine-related effects that may pose threats to fish populations in agricultural regions. That is, we have pesticides with emerging concerns, thus, the concern is emerging and not necessarily the chemical. In this light, one must consider certain agricultural pesticides to be included in the list of CECs. Even though agricultural pesticides are routinely evaluated in regulatory testing schemes which have been used for decades, the potential hazards of some pesticides have only recently been emerging. Emerging concerns of pesticides in fish include interference with hormone signaling pathways; additive (or more than additive) effects from pesticide mixtures; and adverse population-level effects at concentrations below predicted toxicity thresholds. Consequently, there is a need to evaluate the environmental concerns related to pesticide exposures to fish populations based on current biological and toxicological techniques. This presentation reviews some of the agricultural chemicals that have emerged as contaminants of concern and potentially threaten fish populations in agricultural watersheds.

Conference Paper↗

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↗

Partitioning of chemicals in aquatic organisms

Human populations have utilized heavy metals and persistent organic pollutants for their physiochemical properties in industrial, agricultural, and consumer goods for decades. Limited knowledge on their persistence and toxicological effects has resulted in organisms being exposed to some of the most problematic compounds ever generated by humans. Although overlap in exposure paradigms exists for historical and emerging contaminants, the different physiochemical properties, sources into the environment, and bioactivity of contaminants of emerging concern (CECs) have highlighted the importance of characterizing their risk to aquatic wildlife under chronic low-dose exposure scenarios. This chapter defines the fundamental terminology associated with characterizing the exposure paradigm in ecological risk assessment. The different sources and fate, routes of exposure, and biotransformation of common contaminants are covered using model chemicals to emphasize important factors that affect their partitioning among different environmental matrices. Finally, this chapter concludes with a discussion about bioaccumulation models and an example of how two similar CECs demonstrate different clearance rates and bioaccumulation potentials in fish.

Book chapter↗

Microbial pathogens and contaminants of emerging concern in groundwater at an urban subsurface stormwater infiltration site

Urban stormwater may contain a variety of pollutants, including viruses and other pathogens, and contaminants of emerging concern (pharmaceuticals, artificial sweeteners, and personal care products). In vulnerable geologic settings, the potential exists for these contaminants to reach underlying aquifers and contaminate drinking water wells. Viruses and other pathogens, as well as other contaminants of emerging concern, were measured in stormwater and groundwater at an urban site containing a stormwater cistern and related subsurface infiltration gallery, three shallow lysimeter wells, and a monitoring well. Five of 12 microbial targets were detected more than once across the eight rounds of sampling and at multiple sampling points, with human-specific Bacteroides detected most frequently. The microbial and chemical contaminants present in urban stormwater were much lower in the water table monitoring well than the vadose zone lysimeters. There may be numerous causes for these reductions, but they are most likely related to transit across fine-grained sediments that separate the water table from the vadose zone at this location. Precipitation amount prior to sample collection was significantly associated with microbial load. A significant relation between microbial load and chloride-bromide ratio was also observed. The reduction in number and concentrations of contaminants found in the monitoring well indicates that although geologically sensitive aquifers receiving urban stormwater effluent in the subsurface may be prone to contamination, those with a protective cap of fine-grained sediments are less vulnerable. These results can inform stormwater infiltration guidance relative to drinking water wells, with an emphasis on restricting infiltration near water supply wells finished in geologically sensitive aquifers to reduce public health risks.

Minnesota↗

Assessment of general health of fishes collected at selected sites in the Great Lakes Basin In 2012

During the past decade, there has been a substantive increase in the detection of “emerging contaminants”, defined as a new substance, chemical, or metabolite in the environment; or a legacy substance with a newly expanded distribution, altered release, or a newly recognized effect (such as endocrine disruption). Emerging contaminants include substances such as biogenic hormones (human and animal), brominated flame retardants, pharmaceuticals, personal care products, plasticizers, current use pesticides, detergents, and nanoparticles. These contaminants are frequently not regulated or inadequately regulated by state or Federal water quality programs. Information about the toxicity of these substances to fish and wildlife resources is generally limited, compared to more highly regulated contaminants, and some classes have been shown to cause affects (for example feminization of male fish, immunomodulation) that are not evaluated via traditional toxicity testing protocols. As a result, these compounds may pose a substantial, but currently poorly documented threat to aquatic ecosystems. Failure to identify and understand the impacts of these emerging contaminants on fish and wildlife resources may result in deleterious impacts to Great Lakes resources that can result in adverse ecological, economic and recreational consequences. The U. S. Fish and Wildlife Service received funding through the Great Lakes Restoration Initiative (GLRI) for an Early Warning Program to detect and identify emerging contaminants and to evaluate the effects of these contaminants on fish and wildlife. The U.S. Geological Survey (WV Cooperative Fish and Wildlife Research Unit and National Fish Health Research Laboratory, Leetown Science Center) developed and implemented a biological effects monitoring protocol to assist in this program. Fish collections and measurements of biomarkers of exposure in Fall 2010 and Spring 2011 occurred at individual sites within select Areas of Concern (AOCs). They provided an assessment of the utility of the suite of biomarkers and also identified sites for more in-depth analyses. Selected areas are characterized as areas with known emerging contaminants, sensitive or listed species, areas downstream from municipal wastewater discharges or receiving waters for industrial facilities, and/or areas susceptible to agricultural or urban contamination, or harbors or ports. The results of the 2010- 2011 studies were summarized in Blazer et al. 2014 a, b, c; Braham et al. in review and Blazer et al. in review.

Great Lakes↗

RNA-seq reveals potential gene biomarkers in fathead minnows (Pimephales promelas) for exposure to treated wastewater effluent

Discharged wastewater treatment plant (WWTP) effluent greatly contributes to the generation of complex mixtures of contaminants of emerging concern (CECs) in aquatic environments which often contain neuropharmaceuticals and other emerging contaminants that may impact neurological function. However, there is a paucity of knowledge on the neurological impacts of these exposures to aquatic organisms. In this study, caged fathead minnows ( Pimephales promelas ) were exposed in situ in a temperate-region effluent-dominated stream ( i.e. , Muddy Creek) in Coralville, Iowa, USA upstream and downstream of a WWTP effluent outfall. The pharmaceutical composition of Muddy Creek was recently characterized by our team and revealed many compounds there were at a low microgram to high nanogram per liter concentration. Total RNA sequencing analysis on brain tissues revealed 280 gene isoforms that were significantly differentially expressed in male fish and 293 gene isoforms in female fish between the upstream and downstream site. Only 66 (13%) of such gene isoforms overlapped amongst male and female fish, demonstrating sex-dependent impacts on neuronal gene expression. By using a systems biology approach paired with functional enrichment analyses, we identified several potential novel gene biomarkers for treated effluent exposure that could be used to expand monitoring of environmental effects with respect to complex CEC mixtures. Lastly, when comparing the results of this study to those that relied on a single-compound approach, there was relatively little overlap in terms of gene-specific effects. This discovery brings into question the application of single-compound exposures in accurately characterizing environmental risks of complex mixtures and for gene biomarker identification.

Iowa↗

Reconnaissance of pharmaceuticals and wastewater indicators in streambed sediments of the lower Columbia River basin, Oregon and Washington

One by-product of advances in modern chemistry is the accumulation of synthetic chemicals in the natural environment. These compounds include contaminants of emerging concern (CECs), some of which are endocrine disrupting compounds (EDCs) that can have detrimental reproductive effects. The role of sediments in accumulating these types of chemicals and acting as a source of exposure for aquatic organisms is not well understood. Here we present a small-scale reconnaissance of CECs in bed sediments of the lower Columbia River and several tributaries and urban streams. Surficial bed sediment samples were collected from the Columbia River, the Willamette River, the Tualatin River, and several small urban creeks in Oregon. Thirty-nine compounds were detected at concentrations ranging from <1 to >1,000 ng [g sediment] -1 dry weight basis. Columbia River mainstem, suggesting a higher risk of exposure to aquatic life in lower order streams. Ten known or suspected EDCs were detected during the study. At least one EDC was detected at 21 of 23 sites sampled; several EDCs were detected in sediment from most sites. This study is the first to document the occurrence of a large suite of CECs in the sediments of the Columbia River basin. A better understanding of the role of sediment in the fate and effects of emerging contaminants is needed.

Oregon;Washington↗

Screening for contaminants of emerging concern in Northern Colorado Plateau Network waters: 2015 surface-water data

In 2015, as part of an on-going screening program for contaminants of emerging concern (CECs) in conjunction with the Environmental Protection Agency (EPA) Region 8, surface waters at 18 locations in or near seven national park units within the Northern Colorado Plateau Network (NCPN) were sampled for pesticides and pesticide degradation products, pharmaceuticals and personal care products, hormones, organic-wastewater-indictor chemicals, and nutrients. Most sites were sampled in spring (May or June) and fall (September). The Colorado River at the Potash boat ramp site, just upstream of Canyonlands National Park, continued to show chronic contamination by caffeine, the pesticide 2,4-D, and prescription drugs (gabapentin, lamotrigine, metformin, and sulfamethoxazole). Samples at the Moab wastewater treatment plant effluent outflow pipe showed a high number and concentration of contaminants entering the river about 14 miles upstream of the long-term sampling location and are the nearest point source for contaminants of emerging concern. Samples from 400 m downstream of the effluent pipe in the Colorado River had decreased numbers and concentrations of contaminants, indicating relatively quick dilution by the river. However, some contaminants persisted at the long-term sampling site downstream. Patterns of detections at other sampling locations will be explored in future reports. This is an interim report. Limited sampling will continue in 2016 at selected sites in coordination with the USGS. A final report is expected upon completion of the USGS project in 2017.

Arizona, Colorado, Idaho, Utah, Wyoming↗

The importance of quality control in validating concentrationsof contaminants of emerging concern in source and treateddrinking water samples

A national-scale survey of 247 contaminants of emerging concern (CECs), including organic and inorganic chemical compounds, andmicrobial contaminants, was conducted in source and treated drinkingwater samples from 25 treatment plants across the United States.Multiplemethodswere used to determine these CECs, including six analytical methods tomeasure 174 pharmaceuticals, personal care products, and pesticides. A three-component quality assurance/quality control (QA/QC) programwas designed for the subset of 174 CECswhich allowed us to assess and compare performances of themethods used. The three components included: 1) a common field QA/ QC protocol and sample design, 2) individual investigator-developed method-specific QA/QC protocols, and 3) a suite of 46method comparison analytes thatwere determined in two or more analytical methods. Overallmethod performance for the 174 organic chemical CECs was assessed by comparing spiked recoveries in reagent, source, and treated water over a two-year period. In addition to the 247 CECs reported in the larger drinking water study, another 48 pharmaceutical compoundsmeasured did not consistentlymeet predetermined quality standards. Methodologies that did not seem suitable for these analytes are overviewed. The need to exclude analytes based on method performance demonstrates the importance of additional QA/QC protocols.

Science of the Total Environment↗

Contaminants of emerging concern in ambient groundwater in urbanized areas of Minnesota, 2009-12

A study of contaminants of emerging concern (CECs) in ambient groundwater in urbanized areas of Minnesota was completed by the U.S. Geological Survey in cooperation with the Minnesota Pollution Control Agency. For this study, water samples were collected from November 2009 through June 2012 from 118 wells located in different land-use settings. The sampled wells primarily were screened in vulnerable sand and gravel aquifers (surficial and buried glacial aquifers) or vulnerable bedrock aquifers such as the Prairie du Chien-Jordan aquifer. Sampled well depths ranged from 9 to 285 feet below land surface. Water samples were collected by Minnesota Pollution Control Agency staff. The water samples were analyzed at U.S. Geological Survey laboratories for steroidal hormones, human-use pharmaceutical compounds, human- and animal-use antibiotics, and a broad suite of organic chemicals associated with wastewater. Reported detections were censored and not counted as detections in the data analyses if the chemical was detected in a laboratory or field blank at a similar concentration. During this study, 38 out of 127 CECs analyzed were detected among all water samples collected. Three of the detected CECs, however, were analyzed using two different analytical methods, so 35 distinct chemicals were detected. The number of detections of CECs in individual water samples ranged from 0 to 10. The three wells in proximity to landfills had the most CEC detections. One or more CECs were detected in a total of 43 samples (35 percent); no CECs were detected in 80 samples. Of the 127 CECs included for analysis in this study, 28 have established enforceable or non-enforceable health-based water-quality standards or benchmarks. Fourteen of the 35 chemicals detected in this study have established water-quality standards, whereas 21 of the chemicals detected have no established standard or benchmark. All detections in this study were less than established health-based water-quality standards, although p-cresol was detected at a concentration nearing a health-based water quality standard. Four of the six most frequently detected chemicals&mdash;azithromycin, diphenhydramine, tributyl phosphate, and lincomycin&mdash;have no health-based water-quality standards or benchmarks. The antibiotic sulfamethoxazole was the most frequently detected CEC, detected in a total of 14 of 123 samples (11.4 percent) by one or both analytical methods that include sulfamethoxazole as an analyte. Most (11 of 14, or 79 percent) of the detections of sulfamethoxazole were in samples from domestic wells or monitoring wells located in areas where septic systems or potentially leaking centralized sewers are prevalent. The chemical N,N-Diethyl-meta-toluamide (DEET) was detected at the highest concentration of any CEC, at 7.9 micrograms per liter. Bisphenol A was detected second most frequently of all chemicals. DEET and Bisphenol A were detected most frequently in wells in proximity to closed landfills. Samples from bedrock wells, most of which are drinking water wells that are deeper than glacial wells, had a higher percentage of wells with CEC detections compared to samples from wells completed in glacial aquifers. The higher dissolved oxygen concentrations and lower specific conductance for the bedrock wells sampled indicate shorter duration flow paths from the land surface to these wells than for wells completed in glacial aquifers.

Minnesota↗

Nationwide reconnaissance of contaminants of emerging concern in source and treated drinking waters of the United States

When chemical or microbial contaminants are assessed for potential effect or possible regulation in ambient and drinking waters, a critical first step is determining if the contaminants occur and if they are at concentrations that may cause human or ecological health concerns. To this end, source and treated drinking water samples from 29 drinking water treatment plants (DWTPs) were analyzed as part of a two-phase study to determine whether chemical and microbial constituents, many of which are considered contaminants of emerging concern, were detectable in the waters. Of the 84 chemicals monitored in the 9 Phase I DWTPs, 27 were detected at least once in the source water, and 21 were detected at least once in treated drinking water. In Phase II, which was a broader and more comprehensive assessment, 247 chemical and microbial analytes were measured in 25 DWTPs, with 148 detected at least once in the source water, and 121 detected at least once in the treated drinking water. The frequency of detection was often related to the analyte's contaminant class, as pharmaceuticals and anthropogenic waste indicators tended to be infrequently detected and more easily removed during treatment, while per and polyfluoroalkyl substances and inorganic constituents were both more frequently detected and, overall, more resistant to treatment. The data collected as part of this project will be used to help inform evaluation of unregulated contaminants in surface water, groundwater, and drinking water.

Science of the Total Environment↗

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 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↗

Contaminants of emerging concern in fresh leachate from landfills in the conterminous United States

To better understand the composition of contaminants of emerging concern (CECs) in landfill leachate, fresh leachate from 19 landfills was sampled across the United States during 2011. The sampled network included 12 municipal and 7 private landfills with varying landfill waste compositions, geographic and climatic settings, ages of waste, waste loads, and leachate production. A total of 129 out of 202 CECs were detected during this study, including 62 prescription pharmaceuticals, 23 industrial chemicals, 18 nonprescription pharmaceuticals, 16 household chemicals, 6 steroid hormones, and 4 plant/animal sterols. CECs were detected in every leachate sample, with the total number of detected CECs in samples ranging from 6 to 82 (median = 31). Bisphenol A (BPA), cotinine, and N , N -diethyltoluamide (DEET) were the most frequently detected CECs, being found in 95% of the leachate samples, followed by lidocaine (89%) and camphor (84%). Other frequently detected CECs included benzophenone, naphthalene, and amphetamine, each detected in 79% of the leachate samples. CEC concentrations spanned six orders of magnitude, ranging from ng L &minus;1 to mg L &minus;1 . Industrial and household chemicals were measured in the greatest concentrations, composing more than 82% of the total measured CEC concentrations. Maximum concentrations for three household and industrial chemicals, para -cresol (7 020 000 ng L &minus;1 ), BPA (6 380 000 ng L &minus;1 ), and phenol (1 550 000 ng L &minus;1 ), were the largest measured, with these CECs composing 70% of the total measured CEC concentrations. Nonprescription pharmaceuticals represented 12%, plant/animal sterols 4%, prescription pharmaceuticals 1%, and steroid hormones <1% of the total measured CEC concentrations. Leachate from landfills in areas receiving greater amounts of precipitation had greater frequencies of CEC detections and concentrations in leachate than landfills receiving less precipitation.

Environmental Science: Processes and Impacts↗

Legacy and contaminants of emerging concern (CECs) in tree swallows along an agricultural to industrial gradient: Maumee River, OH

Exposure to multiple classes of contaminants, both legacy and contaminants of emerging concern (CECs), were assessed in tree swallow ( Tachycineta bicolor ) tissue and diet samples from 6 sites along the Maumee River, Ohio, USA, to understand both exposure and possible effects of exposure to those CECs for which there are little avian data. The 6 sites represented a gradient from intensive agriculture upstream to highly urbanized and industrial landscapes downstream; 1 or 2 remote Wisconsin lakes were assessed for comparative purposes. Cytochrome P450 induction, DNA damage, and thyroid function were also assessed relative to contaminant exposure. Bioaccumulative CECs, such as polybrominated diphenyl ethers (PBDEs) and perfluorinated substances, did not follow any upstream to downstream gradient; but both had significantly greater concentrations along the Maumee River than at the remote lake sites. Greater exposure to PBDEs was apparent in swallows at or near wastewater‐treatment facilities than at other sites. Total polychlorinated biphenyl and total polycyclic aromatic hydrocarbon concentrations were greater in swallows at downstream locations compared to upstream sites and were associated with higher ethoxyresorufin‐ O ‐dealkylase activity. Few herbicides or nonorganochlorine insecticides were detected in swallow tissues or their food, except for atrazine and its metabolite desethylatrazine. Few pharmaceuticals and personal care products were detected except for DEET and iopamidol. Both were detected in most liver samples but not in eggs, as well as detected at the remote lake sites. This is one of the most comprehensive assessments to date of exposure and effects of a wide variety of CECs in birds.

Ohio↗

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↗

Bioactive contaminants of emerging concern in National Park waters of the northern Colorado Plateau, USA

Pharmaceuticals and personal care products (PPCPs), wastewater indicators (WWIs), and pesticides (herein, Contaminants of Emerging Concern [CECs]) have been documented in surface waters throughout the world and have associated risks to aquatic life. While much research has focused on temperate and urbanized watersheds, less is known about CEC presence in semi-arid landscapes, where water availability is limited and populations are low. CEC presence in water and sediment is reported for 21 sites in eight U.S. national parks in the northern Colorado Plateau region. From 2012 to 2016, at least one PPCP and/or WWI was detected at most sites on over half of sampling visits, indicating that CECs are not uncommon even in isolated areas. CEC detections were generally fewer and at lower concentrations than in urbanized or agricultural watersheds. Consistent with studies from other U.S. regions, the most frequently detected CECs in this study include DEET, caffeine, organophosphorus flame retardants, and bisphenol A in water and fecal indicators and polycyclic aromatic hydrocarbons in sediment. Maximum concentrations in this study were generally below available water quality benchmarks, sediment quality guidelines, and risk assessment thresholds associated with vertebrates. Additional work is needed to assess the potential activity of hormones, which had high reporting limits in our study, and potential bioactivity of environmental concentrations for invertebrates, microbial communities, and algae. Potential sources of CEC contamination include upstream wastewater effluent discharges and National Park Service invasive-plant-control herbicide applications. CEC occurrence patterns and similarities between continuous and isolated flow locations suggest that direct contamination from individual visitors may also occur. While our data indicate there is little aquatic health risk associated with CECs at our sites, our results demonstrate the ubiquity of CECs on the landscape and a continued need for public outreach concerning resource-use ethics and the potential effects of upstream development.

Colorado Plateau↗