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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

2013 Survey of Iowa groundwater and evaluation of public well vulnerability classifications for contaminants of emerging concern

Studies in Iowa have long documented the vulnerability of wells with less than 50 feet (15 meters) of confining materials above the source aquifer to contamination from nitrate and various pesticides. Recent studies in Wisconsin have documented the occurrence of viruses in untreated groundwater, even in wells considered to have little vulnerability to contamination from near-surface activities. In addition, sensitive methods have become available for analyses of pharmaceuticals and pesticides. This study represents the first comprehensive examination of contaminants of emerging concern in Iowa’s groundwater conducted to date, and one of the first conducted in the United States. Raw groundwater samples were collected from 66 public supply wells during the spring of 2013, when the state was recovering from drought conditions. Samples were analyzed for 206 chemical and biological parameters; including 20 general water-quality parameters and major ions, 19 metals, 5 nutrients, 10 virus groups, 3 species of pathogenic bacteria, 5 microbial indicators, 108 pharmaceuticals, 35 pesticides and pesticide degradates, and tritium. The wells chosen for this study represent a diverse range of ages, depths, confining material thicknesses, pumping rates, and land use settings. The most commonly detected contaminant group was pesticide compounds, which were present in 41% of the samples. As many as 6 pesticide compounds were found together in a sample, most of which were chloroacetanilide degradates. While none of the measured concentrations of pesticide compounds exceeded current benchmark levels, several of these compounds are listed on the U.S. Environmental Protection Agency’s Contaminant Candidate List and could be subject to drinking water standards in the future. Despite heavy use in the past decade, glyphosate was not detected, and its metabolite, aminomethylphosphonic acid, was only detected in two of 60 wells tested (3%) at the detection limit of 0.02 μg/L. Pharmaceutical compounds were detected in 35% of 63 samples. Of the 14 pharmaceuticals detected, six had reported concentrations above the method reporting limit, with the maximum reported concentration of 826 ng/L for acetaminophen. Diphenhydramine was the only pharmaceutical to have two detections above the reporting limit, at 24.5 and 145 ng/L. Eight pharmaceuticals had confirmed detections at concentrations below the method reporting limit. Caffeine was the most frequently detected pharmaceutical compound (25%), followed by the caffeine metabolite, 1,7- dimethylxanthine (16%). Microorganisms were detected in 21% of the wells using quantitative polymerase chain reaction methodologies. The most frequently detected microorganism was the pepper mild mottle virus (PMMV), a plant pathogen found in human waste. PMMV was detected in 17% of samples at concentrations ranging from 0.4 to 6.38 gene copies per liter. GII norovirus, human polyomavirus, bovine polyomavirus, and Campylobacter were also detected, while adenovirus, enterovirus, GI norovirus, swine hepatitis E, Salmonella, and enterohemmorhagic E. coli were not detected. No correlations were found between viruses or pathogenic bacteria and microbial indicators. Wells with less than 50 feet (15 meters) of confining material were shown to have greater incidence of surface-related contaminants; however, significant relationships (p<0.05) between confining layer thickness and contaminants were only found for nitrate and herbicides.

Iowa

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

The Mussel Watch California pilot study on contaminants of emerging concern (CECs): synthesis and next steps

A multiagency pilot study on mussels ( Mytilus spp.) collected at 68 stations in California revealed that 98% of targeted contaminants of emerging concern (CECs) were infrequently detectable at concentrations ⩽1 ng/g. Selected chemicals found in commercial and consumer products were more frequently detected at mean concentrations up to 470 ng/g dry wt. The number of CECs detected and their concentrations were greatest for stations categorized as urban or influenced by storm water discharge. Exposure to a broader suite of CECs was also characterized by passive sampling devices (PSDs), with estimated water concentrations of hydrophobic compounds correlated with Mytilus concentrations. The results underscore the need for focused CEC monitoring in coastal ecosystems and suggest that PSDs are complementary to bivalves in assessing water quality. Moreover, the partnership established among participating agencies led to increased spatial coverage, an expanded list of analytes and a more efficient use of available resources.

California

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