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Emerging contaminants in groundwater, karst, and the Edwards Aquifer

Karst aquifers have hydrogeologic characteristics that render them uniquely vulnerable to contamination from emerging contaminants (ECs). ECs comprise numerous chemical groups, including pharmaceuticals, personal-care products, flame retardants, perfluorinated and polyfluorinated compounds, nanoparticles and microplastics. Many ECs have sources, transport pathways, and chemical characteristics that facilitate their infiltration into groundwater, either indirectly from surface water or directly from sources such as landfill leachate and septic systems. What little is known about the occurrence, fate, and transport of ECs in the Edwards aquifer indicates that the aquifer might be increasingly vulnerable to this type of contamination. The natural physical characteristics of this karst aquifer and anthropogenic sources of ECs associated with increased urbanization in central Texas contribute to this vulnerability. In this chapter, we review groups of ECs and their sources, occurrence of ECs in groundwater and karst, and what is known about occurrence of ECs in the Edwards aquifer. We conclude by discussing specific factors, such as rapid flow and contaminant sources, that contribute to the vulnerability of the Edwards aquifer to contamination by ECs.

Texas

Exposure to and biomarker responses from legacy and emerging contaminants along three drainages in the Milwaukee Estuary, Wisconsin, USA

Legacy contaminants and contaminants of emerging concern (CECs) were assessed in tree swallow ( Tachycineta bicolor ) tissue and diet samples from three drainages in the Milwaukee estuary, Wisconsin, USA, to understand exposures and possible biomarker responses. Two remote Wisconsin lakes were assessed for comparative purposes. Bioaccumulative classes of contaminants, such as polybrominated diphenyl ethers and per- and polyfluoroalkyl substances, while at higher concentrations than the reference lakes, did not vary significantly among sites or among the three drainages. Polycyclic aromatic hydrocarbons were assessed in diet and sediment and were from primarily pyrogenic sources. Ten biomarkers were assessed relative to contaminant exposure. Polychlorinated biphenyls (PCBs) were elevated above reference conditions at all Milwaukee sites but did not correlate with any measured biomarker responses. Only one site, Cedarburg, just downstream from a Superfund site, had elevated PCBs compared to other sites in the Milwaukee estuary. Few non-organochlorine insecticides or herbicides were detected in tree swallow liver tissue, except for the atrazine metabolite desethylatrazine. Few pharmaceuticals and personal care products were detected in liver tissue except for N,N -diethyl-meta-toluamide, iopamidol, and two antibiotics. The present study is one of the most comprehensive assessments to date, along with the previously published Maumee River data, on the exposure and effects of a wide variety of CECs in birds. Environ Toxicol Chem 2024;00:1–22. © 2024 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Wisconsin

Occurrence of emerging contaminants in water and bed material in the Missouri River, North Dakota, 2007

The U.S. Geological Survey (USGS), in cooperation with the Standing Rock Sioux Tribe, conducted a reconnaissance study to determine the occurrence of emerging contaminants in water and bed sediment within the Missouri River upstream and downstream from the cities of Bismarck and Mandan, North Dakota, and upstream from the city of Fort Yates, North Dakota, during September-October 2007. At each site, water samples were collected twice and bed-sediment samples were collected once. Samples were analyzed for more than 200 emerging contaminants grouped into four compound classes - wastewater compounds, human-health pharmaceutical compounds, hormones, and antibiotics. Only sulfamethoxazole, an antibiotic, was present at a concentration higher than minimum detection limits. It was detected in a water sample collected downstream from the cities of Bismarck and Mandan, and in bed-sediment samples collected at the two sites downstream from the cities of Bismarck and Mandan and upstream from Fort Yates. Sulfamethoxazole is an antibiotic commonly used for treating bacterial infections in humans and animals.

North Dakota

A Reconnaissance for Emerging Contaminants in the South Branch Potomac River, Cacapon River, and Williams River Basins, West Virginia, April-October 2004

In 2003 a team of scientists from West Virginia Division of Natural Resources and the U. S. Geological Survey found a high incidence of an intersex condition, oocytes in the testes, among smallmouth bass (Micropterus dolomieu) in the South Branch Potomac River and the Cacapon River of West Virginia, indicating the possible presence of endocrine-disrupting compounds (EDCs). Possible sources of EDCs include municipal and domestic wastewater, and agricultural and industrial activities. Several sampling strategies were used to identify emerging contaminants, including potential EDCs, and their possible sources in these river basins and at an out-of-basin reference site. Passive water-sampling devices, which accumulate in-stream organic chemical compounds, were deployed for 40-41 days at 8 sampling sites. Sampler extracts were analyzed for a broad range of polar and non-polar organic compounds including pesticides, flame retardants, pharmaceuticals, and personal-care products. Analysis of passive-sampler extracts found 4 compounds; hexachloro-benzene; pentachloroanisole; 2,2',4,4',5-penta-bromo-diphenyl ether (BDE 47); and 2,2',4,4',6-penta-bromo-diphenyl ether (BDE 99) to be present at every sampled site, including the reference site, and several sites had detectable quantities of other compounds. No detectable quantity of any antibiotics was found in any passive-sampler extract. Effluent samples were analyzed for 39 antibiotics as tracers of human and agricultural waste. Additionally, poultry-processing plant effluent was sampled for roxarsone, an organoarsenic compound used as a poultry-feed additive, and other arsenic species as tracers of poultry waste. Antibiotics were detected in municipal wastewater, aquaculture, and poultry-processing effluent, with the highest number of antibiotics and the greatest concentrations found in municipal effluent. Arsenate was the only arsenic species detected in the poultry-processing plant effluent, at a concentration of 1.0 ?g/L. Water samples were collected from 7 stream sites and analyzed for arsenic species, including roxarsone. Arsenate was detected in samples from 6 of the 7 stream samples, in concentrations ranging from 0.3 to 0.5 ?g/L. Additionally, the analysis of smallmouth bass blood plasma for potential EDCs indicated the presence of several compounds including some found in the passive sampler extracts, specifically BDE 47 and BDE 99. Data from this reconnaissance will help to focus efforts for further studies of the occurrence of emerging contaminants, EDCs, and intersex in smallmouth bass in these Potomac River tributaries.

Open-File Report

Point sources of emerging contaminants along the Colorado River Basin: Source water for the arid Southwestern United States

Emerging contaminants (ECs) (e.g., pharmaceuticals, illicit drugs, personal care products) have been detected in waters across the United States. The objective of this study was to evaluate point sources of ECs along the Colorado River, from the headwaters in Colorado to the Gulf of California. At selected locations in the Colorado River Basin (sites in Colorado, Utah, Nevada, Arizona, and California), waste stream tributaries and receiving surface waters were sampled using either grab sampling or polar organic chemical integrative samplers (POCIS). The grab samples were extracted using solid-phase cartridge extraction (SPE), and the POCIS sorbents were transferred into empty SPEs and eluted with methanol. All extracts were prepared for, and analyzed by, liquid chromatography–electrospray-ion trap mass spectrometry (LC–ESI-ITMS). Log D OW values were calculated for all ECs in the study and compared to the empirical data collected. POCIS extracts were screened for the presence of estrogenic chemicals using the yeast estrogen screen (YES) assay. Extracts from the 2008 POCIS deployment in the Las Vegas Wash showed the second highest estrogenicity response. In the grab samples, azithromycin (an antibiotic) was detected in all but one urban waste stream, with concentrations ranging from 30 ng/L to 2800 ng/L. Concentration levels of azithromycin, methamphetamine and pseudoephedrine showed temporal variation from the Tucson WWTP. Those ECs that were detected in the main surface water channels (those that are diverted for urban use and irrigation along the Colorado River) were in the region of the limit-of-detection (e.g., 10 ng/L), but most were below detection limits.

Arizona;California;Colorado;Nevada;New Mexico;Utah

Research plan and preliminary results: A field research site for emerging contaminants in Iowa

Research has recently documented the prevalence of a wide variety of pharmaceuticals and other emerging contaminants (ECs) in streams across the United States. Wastewater treatment plants (WWTPs) have been found to be an important source and collection point of ECs to streams as many ECs are incompletely removed during treatment. To investigate the complex in-stream processes (e.g., dilution, sorption, degradation, dispersion, etc.) that can affect ECs following their input from a WWTP and determining if such input is having an effect on the aquatic ecosystem requires the integration of multi-disciplinary efforts at a carefully selected field site. Preliminary work has identified an 8-km reach of Fourmile Creek in central Iowa as an ideal research site to investigate such important research questions pertaining to ECs. Unique aspects of Fourmile Creek included: (1) it single source effluent-dominated stream, (2) background data document the input of a wide variety of ECs from WWTP discharge, (3) small basin size, (4) relatively simple flow system, (5) background data suggest that undefined processes are taking place decreasing the level of select ECs during stream transport, (6) the WWTP uses a treatment technology (activated sludge) typical of many towns in Iowa and the United States (7) a hydrogeologic setting of a low-gradient, small stream (average discharge less than 1.41 m³/s) in glacial drift is typical of many areas in Iowa and across the Midwest, and (8) the existence of a low-head clam approximately 2 km upstream of the WWTP outfall allowing more accurate "above WWTP" and "below WWTP" comparisons in aquatic ecosystems. Furthermore, the WWTP is scheduled to close by 2011 providing a unique opportunity to determine how stream hydrology, water chemistry and aquatic biota react to the removal of the primary source of flow and ECs in this system. This will allow a novel "before" and "after" assessment not previously available in EC research. Research to date at the site has included installation of a streamflow gauging station, dye-tracing tests (to determine water travel times), Lagrangian water-quality sampling at two flow/water temperature regimes, and sampling for ECs in bed sediment. Selected fish have been collected for analysis and identification. In addition, basic fish community and fish health assessment for different seasons and spawning conditions are being analyzed. The research "framework" is unique at Fourmile Creek for investigating the important question of how ECs are transported through the environment and if the presence of such compounds is having a deleterious effect on aquatic ecosystems.

Iowa

A multi-disciplinary approach to the removal of emerging contaminants in municipal wastewater treatment plans in New York State, 2003-2004

Across the United States, there is a rapidly growing awareness of the occurrence and the toxicological impacts of natural and synthetic trace compounds in the environment. These trace compounds, referred to as emerging contaminants (ECs), are reported to cause a range of negative impacts in the environment, such as adverse effects on biota in receiving streams and interference with the normal functions of the endocrine system, which controls growth and development in living organisms. Wastewater treatment plants (WWTPs) have been identified as a key collection point for ECs in the water cycle and potentially an ideal location at which to treat to remove them, thereby mitigating their release into the environment ( Figure 1 ). This presents wastewater industry professionals with both a significant opportunity and a tremendous challenge: to identify cost effective treatment processes that can remove or reduce these contaminants before they are released into the environment. Although WWTPs have been identified as strategic focal points and potential treatment locations for the removal of ECs from the environment, little is known about the nature, variability, transport and fate of this class of compounds in typical wastewaters and treatment facilities in the United States. Furthermore few studies have been performed to monitor or understand the capability of conventional or innovative wastewater treatment processes to remove or reduce the concentrations of a wide variety of ECs at wastewater facilities. This study was designed to provide baseline information on this topic. While other studies have examined the occurrence of a limited number of representative contaminants in the environment (generally five to 10 compounds), this study is unique in that it provides information on a comprehensive list of ECs (63 ECs in total, Contaminant List in Appendix A, not included here) in the wastewater collection and treatment systems for four diverse communities over a two-year period. (It should be noted that the study is ongoing and additional data are pending but only 18 months of data are presented in this paper). The study was conducted in two phases. Phase 1 was designed to provide information concerning the general character and concentration of ECs commonly detected in wastewaters, the variability over a prolonged period of time, the transport and fate of ECs through typical wastewater treatment plants operating with a range of conventional technologies and the impact of WWTP discharges on receiving streams. It also provided guidance in understanding the capability of distinct wastewater treatment processes or technologies to reduce or remove ECs. The second phase of the study focused on one of the most common wastewater treatment processes operated in the United States, the Activated Sludge process. Using four controlled parallel activated sludge pilots, a more detailed assessment of the impact of Sludge Retention Time (SRT) on the reduction or removal of ECs was performed.

New York

A multi-disciplinary approach to the removal of emerging contaminants in municipal wastewater treatment plants in New York state (2003-2004)

Across the United States, there is a rapidly growing awareness of the occurrence and the toxicological impacts of natural and synthetic trace compounds in the environment. These trace compounds, referred to as emerging contaminants (ECs), are reported to cause a range of negative impacts in the environment, such as adverse effects on biota in receiving streams and interference with the normal functions of the endocrine system, which controls growth and development in living organisms.

New York

1.13 – Emerging contaminants

Since the Industrial Revolution, a diversity of large-scale chemical innovations has impacted aquatic systems in urban environments. Beginning in the 1990s, there has been a growing scientific interest and public awareness of the effects of the chemicals used in domestic, commercial, industrial, and agricultural applications, referred to in this article as ‘emerging contaminants’ (ECs), on ecosystem and human health. The growing global population and its increasing demands on water supplies in conjunction with climate-induced changes in hydrologic regimes place stress on freshwater resources, resulting in a greater reliance on reuse of reclaimed municipal wastewater treatment plant (WWTP) effluents to meet human and environmental needs. WWTP effluents are a major source of ECs, and it is important to have an understanding of the chemical composition of the reclaimed water, because many ECs are biologically active and the effects of chronic exposure to low concentration complex mixtures are unknown. Several classes of ECs that have been shown to be widespread in the aquatic environment are discussed in this chapter, including surfactants, complexing agents, fragrances, antimicrobials, industrial chemicals, pharmaceuticals, natural and synthetic estrogens, and disinfection byproducts. All of these compounds are biologically active via a variety of modes of action, and can occur in aquatic systems at concentrations ranging from <0.001 to >100 μg l −1 .

Book chapter

Emerging contaminants at a closed and an operating landfill in Oklahoma

Landfills are the final depositories for a wide range of solid waste from both residential and commercial sources, and therefore have the potential to produce leachate containing many organic compounds found in consumer products such as pharmaceuticals, plasticizers, disinfectants, cleaning agents, fire retardants, flavorings, and preservatives, known as emerging contaminants (ECs). Landfill leachate was sampled from landfill cells of three different age ranges from two landfills in Central Oklahoma. Samples were collected from an old cell containing solid waste greater than 25 years old, an intermediate age cell with solid waste between 16 and 3 years old, and operating cell with solid waste less than 5 years old to investigate the chemical variability and persistence of selected ECs in landfill leachate of differing age sources. Twenty-eight of 69 analyzed ECs were detected in one or more samples from the three leachate sources. Detected ECs ranged in concentration from 0.11 to 114 μg/L and included 4 fecal and plant sterols, 13 household\industrial, 7 hydrocarbon, and 4 pesticide compounds. Four ECs were solely detected in the oldest leachate sample, two ECs were solely detected in the intermediate leachate sample, and no ECs were solely detected in the youngest leachate sample. Eleven ECs were commonly detected in all three leachate samples and are an indication of the contents of solid waste deposited over several decades and the relative resistance of some ECs to natural attenuation processes in and near landfills.

Oklahoma

Evaluation of emerging contaminants of concern at the South District Wastewater Treatment Plant based on seasonal sampling events, Miami-Dade County, Florida, 2004

The Comprehensive Everglades Restoration Plan has identified highly treated wastewater as a possible water source for the restoration of natural water flows and hydroperiods in selected coastal areas, including the Biscayne Bay coastal wetlands. One potential source of reclaimed wastewater for the Biscayne Bay coastal wetlands is the effluent from the South District Wastewater Treatment Plant in southern Miami-Dade County. The U.S. Geological Survey, in cooperation with the Comprehensive Everglades Restoration Plan Wastewater Reuse Technology Pilot Project Delivery Team, initiated a study to assess the presence of emerging contaminants of concern in the South District Wastewater Treatment Plant influent and effluent using current wastewater-treatment methods. As part of the study, 24-hour composite and discrete samples were collected at six locations (influent at plants 1 and 2, effluent pump, reuse train, chlorine dioxide unit, and ultraviolet pilot unit) at the plant during: (1) a dry-season, low-flow event on March 2-3, 2004, with an average inflow rate of 83.7 million gallons per day; (2) a wet-season, average-flow event on July 20-21, 2004, with an average inflow rate of 89.7 million gallons per day; and (3) high-rate disinfection tests on October 5 and 20, 2004, with average flow rates of 84.1 and 119.6 million gallons per day, respectively. During these four sampling events, 26, 27, 29, and 35 constituents were detected, respectively. The following transformations in concentration were determined in the waste stream: -100 to 180 percent at the effluent pump and -100 to 85 percent at the reuse train on March 2-3, 2004, and -100 to 1,609 percent at the effluent pump and -100 to 832 percent at the reuse train on July 20-21, 2004; -100 to -37 percent at the effluent pump, -100 to -62 percent at the reuse train, -100 to -56 percent at the chlorine dioxide unit, and -100 to -40 percent at the ultraviolet pilot unit on October 5, 2004; and -100 to -4 percent at the effluent pump, -100 to 17 percent at the reuse train, -100 to -40 percent at the chlorine dioxide unit, and -100 to -14 percent at the ultraviolet pilot unit on October 20, 2004. Samples were tested for detection of household and industrial (organic) wastewater compounds, pharmaceutical compounds, antibiotic compounds, and hormones in influent. Two 'known' endocrine disrupting compounds?17 beta-estradiol (E2) and diethoxynonylphenol? and four 'suspected' endocrine-disrupting compounds?1,4-dichlorobenzene, benzophenone, tris(2-chloroethyl) phosphate, and tris(dichloroisopropyl) phosphate?were detected during these sampling events. Phenanthrene and indole showed the greatest concentration ranges and highest concentrations for the organic wastewater compounds. Acetaminophen showed the greatest concentration range and highest concentration, and warfarin showed the smallest concentration range for the pharmaceutical compounds. Sulfamethoxazole (a sulfonamide) showed the greatest concentration range and highest concentration, and sulfathiozole (also a sulfonamide) showed the smallest concentration range for the antibiotic compounds. Two hormones, 17 beta-estradiol (E2) and estrone (E1), were detected in influent. Samples were also tested for detection of organic wastewater compounds, pharmaceutical compounds, antibiotic compounds, and hormones in effluent. Indole showed the greatest concentration range and highest concentration, and triphenyl phosphate showed the smallest concentration range for the organic wastewater compounds. Dehydronifedipine showed the greatest concentration range and highest concentration, and warfarin had the smallest concentration range for the pharmaceutical compounds. Anhydro-erythromycin (a macrolide degradation product) showed the greatest concentration range, and sulfadiazine (a sulfonamide) and tetracycline showed the lowest concentration ranges for the antibiotic compounds. One hormone, 17 beta-estradiol (E2), was det

Florida

The emerging contaminant 3,3’-dichlorobiphenyl (PCB-11) impedes Ahr activation and Cyp1a activity to modify embryotoxicity of Ahr ligands in the zebrafish embryo model (Danio rerio)

Background: 3,3’-Dichlorobiphenyl (PCB-11) is a non-legacy PCB congener widely detected in environmental samples and has been detected in human serum, but its toxicity potential is poorly understood. Objectives: We measured PCB-11 in wild caught fish and assessed its embryotoxicity and interactions with the aryl hydrocarbon receptor (Ahr) pathway in developing zebrafish (Danio rerio). Methods: PCB-11 was measured in wild freshwater fish from a river in Western Massachusetts. In the laboratory, zebrafish embryos were exposed to 45 µg/L, 450 µg/L, or 4,500 µg/L PCB-11 from 24-96 hours post fertilization (hpf), when they were assessed for gross morphology and Cyp1a activity using the in vivo EROD bioassay. Ahr pathway interactions were probed by co-exposing zebrafish to the Ahr agonists PCB-126 and the model PAH beta-naphthoflavone (BNF). Liver development was assessed using the Tg(gut:GFP) zebrafish line. Zebrafish exposed to 4,500 µg/L PCB-11 were also collected at 96 hpf for qRT-PCR, RNAseq, and histology. Results: Environmental concentrations of PCB-11 ranged from 103.0-136.0 ng/kg wet weight in wild fish tissue. Exposure to PCB-11 alone mildly affected EROD activity but did not affect gross morphology. However, 4,500 µg/L PCB-11 alone altered the expression of xenobiotic metabolism and liver development genes, impeded liver development, and increased vacuole formation in histology sections. In co-exposures, 4,500 µg/L PCB-11 prevented deformities caused by PCB-126 but exacerbated deformities in co-exposures with BNF. Discussion: PCB-11 is present in wild fish caught near a paper recycling facility in Western Massachusetts. Higher concentrations that may be present elsewhere such as the 4,500 µg/L PCB-11 concentration tested in zebrafish, can affect liver development, act as both a partial agonist/antagonist of the Ahr pathway, and act as an antagonist of Cyp1a activity to modify the toxicity of compounds that interact with the Ahr pathway.

Environmental Pollution

Reconnaissance of persistent and emerging contaminants in the Shenandoah and James River Basins, Virginia, during Spring of 2007

Fish exhibiting external lesions, incidences of intersex, and death have recently been observed in the Shenandoah and James River Basins. These basins are characterized by widespread agriculture (intensive in some areas), several major industrial discharges, numerous sewage treatment plant discharges, and urban, transportation, and residential growth that has increased rapidly in recent years. Nine locations in the Shenandoah River Basin, Virginia, and two in the James River Basin, Virginia, were selected for study in an attempt to identify chemicals that may have contributed to the declining fish health. Two passive sampling devices, semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCIS), were deployed during the spring and early summer of 2007 to measure select organic contaminants to which fish may have been exposed. This study determined that concentrations of persistent hydrophobic contaminants, such as polycyclic aromatic hydrocarbons (<17,000 picograms per liter), legacy pesticides (<510 picograms per liter), and polychlorinated biphenyls (<1,600 picograms per liter) were generally low and indicative of a largely agricultural area. Chlorpyrifos, endosulfan, and lindane were the most commonly detected chlorinated pesticides. Atrazine, which was detected at concentrations much greater than other pesticides associated with agricultural use, ranged from <0.18 to 430 nanograms per liter during the deployment period. Few chemicals characteristic of wastewater treatment plant effluent or septic tank discharges were detected. The fragrance components, galaxolide, indole, and tonalide, were the predominant waste indicator chemicals detected. Caffeine, the caffeine metabolite 1,7-dimethylxanthine, the nicotine metabolite cotinine, and the prescription pharmaceuticals carbamazepine, venlafaxine, and trimethoprim were detected at several sites. Natural and synthetic hormones were detected at a few sites with 17α-ethynylestradiol concentrations esimated up to 8.1 nanograms per liter. Screening of the POCIS extracts for estrogenic chemicals by using the yeast estrogen screen revealed estrogenicity similar to levels reported for rural areas with minor effect from wastewater effluents.

Virginia

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

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