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Contaminant fluxes across ecosystems mediated by aquatic insects

Metals and organic contaminants in aquatic systems affect the coupling of aquatic and terrestrial ecosystems through two pathways: contaminant-induced effects on insect emergence and emergence-induced contaminant transfer. Consequently, the impact of aquatic contaminants on terrestrial ecosystems can be driven by modifications in the quantity and quality of adult aquatic insects serving as prey or contaminants entering terrestrial food webs as part of the diet of terrestrial predators. Here, we provide an overview of recent advances in the field, separating metals from organic contaminants due to their differential propensity to bioaccumulate and thus their potential contribution to either of the two pathways. Finally, this review highlights the knowledge gap in the relative impact of these pathways on terrestrial insectivores.

Current Opinion in Insect Science

Pharmaceutical compounds in shallow groundwater in non-agricultural areas of Minnesota: study design, methods, and data, 2013

The U.S. Geological Survey, in cooperation with the Minnesota Pollution Control Agency, completed a study on the occurrence of pharmaceutical compounds and other contaminants of emerging concern in shallow groundwater in non-agricultural areas of Minnesota during 2013. This report describes the study design and methods for the study on the occurrence of pharmaceuticals and other contaminants of emerging concern, and presents the data collected on pharmaceutical compounds. Samples were analyzed by the U.S. Geological Survey National Water Quality Laboratory for 110 pharmaceutical compounds using research method 9017. Samples from 21 of 45 wells had detectable concentrations of at least one of the 110 compounds analyzed. One sample contained detectable concentrations of nine compounds, which was the most detected in a single sample. Fewer than five compounds were detected in most samples. Among all samples, 27 of the 110 compounds were detected in groundwater from at least one well. Desmethyldiltiazem and nicotine were the most frequently detected compounds, each detected in 5 of 46 environmental samples (one well was sampled twice so a total of 46 environmental samples were collected from 45 wells). Caffeine had the highest detectable concentration of all the compounds at 2,060 nanograms per liter.

Minnesota

Contaminants of legacy and emerging concern in largescale suckers (Catostomus macrocheilus) and the foodweb in the lower Columbia River, Oregon and Washington, USA

We investigated occurrence, transport pathways, and effects of polybrominated diphenyl ether (PBDE) flame retardants and other endocrine disrupting chemicals (EDCs) in aquatic media and the foodweb in the lower Columbia River. In 2009 and 2010, foodweb sampling at three sites along a gradient of contaminant exposure near Skamania (Washington), Columbia City (Oregon) and Longview (Washington) included water (via passive samplers), bed sediment, invertebrate biomass residing in sediment, a resident fish species (largescale suckers [ Catostomus macrocheilus ]), and eggs from osprey ( Pandion haliaetus ). This paper primarily reports fish tissue concentrations. In 2009, composites of fish brain, fillet, liver, stomach, and gonad tissues revealed that overall contaminant concentrations were highest in livers, followed by brain, stomach, gonad, and fillet. Concentrations of halogenated compounds in tissue samples from all three sites ranged from < 1 to 400 nanograms per gram of wet tissue. Several chemical classes, including PBDEs, organochlorine pesticides, and polychlorinated biphenyls (PCBs), were detected at all sites and in nearly all fish tissues sampled. In 2010, only fish livers were sampled and inter-site concentration differences were not as pronounced as in 2009. Chemical concentrations in sediments, fish tissues, and osprey eggs increased moving downstream from Skamania to the urbanized sites near Columbia City and Longview. Numerous organochlorine (OC) pesticides, both banned and currently used, and PBDEs, were present at each site in multiple media and concentrations exceeded environmental quality benchmarks in some cases. Frequently detected OC compounds included hexachlorobenzene, pentachloroanisole, dichlorodiphenyltrichloroethane (DDT) and its degradates, chlorpyrifos, and oxyfluorofen. Biomagnification of BDE47, 100, 153, and 154 occurred in largescale suckers and osprey eggs. Results support the hypothesis that contaminants in the environment lead to bioaccumulation and potential negative effects in multiple levels of the foodweb.

Oregon, Washington

Contaminants in linked aquatic–terrestrial ecosystems: Predicting effects of aquatic pollution on adult aquatic insects and terrestrial insectivores

Organisms that move across ecosystem boundaries connect food webs in apparently disparate locations. As part of their life cycle, aquatic insects transition from aquatic larvae to terrestrial adults, thereby linking freshwater ecosystem processes and terrestrial insectivore dynamics. These linkages are strongly affected by contamination of freshwater ecosystems, which can reduce production of adult aquatic insects (i.e., emergence), increase contaminant concentrations in adult insect tissues, and alter contaminant flux to terrestrial ecosystems. Despite the potential impact of contaminants on adult aquatic insects, little is known about predicting these effects. Here, I develop a heuristic model based on contaminant properties and ecotoxicological principles to predict the effects of various classes of aquatic contaminants on adult aquatic insects and discuss implications for terrestrial insectivores living near contaminated freshwaters. The main finding is that contaminant classes vary greatly in how their biologically-mediated effects on aquatic insects affect terrestrial insectivores. Highly bioaccumulative contaminants that are well retained during metamorphosis, like polychlorinated biphenyls (PCBs), are often non-toxic to aquatic insect larvae at concentrations commonly found in the environment. Such contaminants flux from aquatic ecosystems in large quantities in the bodies of emerging adult aquatic insects and expose terrestrial insectivores to toxic levels of pollution. On the other hand, contaminants that are less bioaccumulative, excreted during metamorphosis, and more toxic to insects, like trace metals, tend to affect terrestrial insectivores by reducing production of adult aquatic insects on which they prey. Management applications of this model illustrate type and severity of risk of aquatic contaminants to consumers of adult aquatic insects.

Freshwater Science

De facto water reuse: Investigating the fate and transport of chemicals of emerging concern from wastewater discharge through drinking water treatment using non-targeted analysis and suspect screening

Wastewater is a source for many contaminants of emerging concern (CECs), and surface waters receiving wastewater discharge often serve as source water for downstream drinking water treatment plants. Nontargeted analysis and suspect screening methods were used to characterize chemicals in residence-time-weighted grab samples and companion polar organic chemical integrative samplers (POCIS) collected on three separate hydrologic sampling events along a surface water flow path representative of de facto water reuse. The goal of this work was to examine the fate of CECs along the study flow path as water is transported from wastewater effluent through drinking water treatment. Grab and POCIS samples provided a comparison between residence-time-weighted single-point and integrative sample results. This unique and rigorous study design, coupled with advanced analytical chemistry tools, provided important insights into chemicals found in drinking water and their potential sources, which can be used to help prioritize chemicals for further study. K -means clustering analysis was used to identify patterns in chemical occurrences across both sampling sites and sampling events. Chemical features that occurred frequently or survived drinking water treatment were prioritized for identification, resulting in the probable identification of over 100 CECs in the watershed and 28 CECs in treated drinking water.

Environmental Science & Technology

Treatment of trace organic compounds in common onsite wastewater systems

Onsite wastewater systems (OWS) have historically been relied on to treat conventional pollutants and pathogens in a fashion similar to that expected from centralized wastewater systems. However, based on the occurrence of, and potential effects from, contaminants of emerging concern in wastewaters, OWS as well as centralized systems need to account for these compounds in system design and use. One group of contaminants involves organic compounds such as those associated with consumer product chemicals and pharmaceuticals, which are collectively referred to as trace organic compounds (TOrCs) due to their very low levels (e.g., ng/L to ug/L) relative to other pollutants. The question being confronted today is how best to account for TOrCs in onsite system design and use while also achieving other goals such as system simplicity, limited operation and maintenance requirements, low cost, and sustainability. In contrast to conventional pollutants such as nutrients and pathogens which have specific and achievable treatment goals, there are currently no enforceable treatment standards for TOrCs, which often have non-traditional toxicological endpoints (i.e. endocrine disruption). As highlighted in this paper, there are a large number of TOrCs that can be present in OWS and they have different properties, can be present at different frequencies of occurrence and concentrations, and have different susceptibilities to treatment in OWS. In general, based on the studies summarized in this paper, TOrCs normally should not require additional considerations beyond those for conventional pollutants and pathogens (e.g., nitrogen or bacteria and virus) during design and use of OWS. That said, there are situations where TOrCs could be a serious concern warranting special consideration in system design and use. In this paper, the frequency of occurrence of TOrCs and the range of concentrations encountered are highlighted. An evolving approach is outlined that could help assess the likelihood of occurrence and levels of TOrCs along with the treatment anticipated in different OWS and assimilation conditions.

Conference Paper

Fish health altered by contaminants and low water temperatures compounded by prolonged regional drought in the Lower Colorado River Basin, USA

The goal of this study was to assess health of male Common Carp (carp, Cyprinus carpio ) at four sites with a wide range in environmental organic contaminant (EOC) concentrations and water temperatures in Lake Mead National Recreation Area NV/AZ, US, and the potential influence of regional drought. Histological and reproductive biomarkers were measured in 17–30 carp at four sites and 130 EOCs in water per site were analyzed using passive samplers in 2010. Wide ranges among sites were noted in total EOC concentrations (>10Xs) and water temperature/degree days (10Xs). In 2007/08, total polychlorinated biphenyls (tPCBs) in fish whole bodies from Willow Beach (WB) in the free-flowing Colorado River below Hoover Dam were clearly higher than at the other sites. This was most likely due to longer exposures in colder water (12–14 °C) and fish there having the longest lifespan (up to 54 years) for carp reported in the Colorado River Basin. Calculated estrogenicity in water exceeded long-term, environmentally safe criteria of 0.1–0.4 ng/L by one to three orders of magnitude at all sites except the reference site. Low ecological screening values for four contaminants of emerging concern (CEC) in water were exceeded for one CEC in the reference site, two in WB and Las Vegas Bay and three in the most contaminated site LVW. Fish health biomarkers in WB carp had 25% lower liver glycogen, 10Xs higher testicular pigmented cell aggregates and higher sperm abnormalities than the reference site. Sperm from LVW fish also had significantly higher fragmentation of DNA, lower motility and testis had lower percent of spermatozoa, all of which can impair reproduction. Projections from a 3D water quality model performed for WB showed that EOC concentrations due to prolonged regional drought and reduced water levels could increase as high as 135%. Water temperatures by late 21st century are predicted to rise between 0.7 and 2.1 °C that could increase eutrophication, algal blooms, spread disease and decrease dissolved oxygen over 5%.

Arizona, Nevada

Towards identifying the next generation of superfund and hazardous waste site contaminants

Background This commentary evolved from a workshop sponsored by the National Institute of Environmental Health Sciences titled "Superfund Contaminants: The Next Generation" held in Tucson, Arizona, in August 2009. All the authors were workshop participants. Objectives Our aim was to initiate a dynamic, adaptable process for identifying contaminants of emerging concern (CECs) that are likely to be found in future hazardous waste sites, and to identify the gaps in primary research that cause uncertainty in determining future hazardous waste site contaminants. Discussion Superfund-relevant CECs can be characterized by specific attributes: They are persistent, bioaccumulative, toxic, occur in large quantities, and have localized accumulation with a likelihood of exposure. Although still under development and incompletely applied, methods to quantify these attributes can assist in winnowing down the list of candidates from the universe of potential CECs. Unfortunately, significant research gaps exist in detection and quantification, environmental fate and transport, health and risk assessment, and site exploration and remediation for CECs. Addressing these gaps is prerequisite to a preventive approach to generating and managing hazardous waste sites. Conclusions A need exists for a carefully considered and orchestrated expansion of programmatic and research efforts to identify, evaluate, and manage CECs of hazardous waste site relevance, including developing an evolving list of priority CECs, intensifying the identification and monitoring of likely sites of present or future accumulation of CECs, and implementing efforts that focus on a holistic approach to prevention.

Environmental Health Perspectives

Prioritizing chemicals of emerging concern in the Great Lakes Basin using covariance of chemical concentrations and diverse biological responses from a variety of species

The Great Lakes Restoration Initiative aims to protect and restore the nation’s largest freshwater resource, in part, by furthering our understanding of the effects of contaminants of emerging concern (CECs) and chemical mixtures on aquatic and terrestrial organisms. To address this goal, an interagency team conducted field studies at sites along the Maumee River in Ohio, USA, in 2016–2017, monitoring CEC levels along with diverse in vitro and in vivo biological effects in ecologically relevant species (fathead minnows, tree swallows, and golden clams). The objective of the present work was to prioritize the CECs in these studies for further monitoring and assessment by determining if there are patterns in chemical–bioeffect relations across data sets, species, and response types that indicate relatively high or low hazard to aquatic life from CEC exposure. Of the 748 monitored chemicals, 425 were detected and were analyzed for covariance with bioeffects. All 748 chemicals were placed into 10 bins based on their frequencies of monitoring, detection, and covariance with bioeffects across studies and species. We describe how chemicals can be prioritized across bins to aid monitoring and assessment efforts. Our approach using effects-based monitoring data is especially useful for prioritizing chemicals with little or no traditional toxicity testing data. Similar evidence-based prioritizations will allow agencies to more efficiently allocate limited resources to improve the ability to protect aquatic and terrestrial organisms from adverse impacts due to contaminant exposure.

Ohio

Framework for the development of the Columbia River mainstem fish tissue and water quality monitoring program - Bonneville Dam to Canadian border

The Columbia River provides important cultural, economic, and ecological services to a significant portion of the United States. Anadromous and resident fish species and other wildlife are integrated into the cultural traditions of all Tribes in the Columbia River Basin. Salmon, lamprey, sturgeon, and resident fish are an integral part of Tribal religion, culture, and physical sustenance. Despite concerns about the effect of contaminants on the aquatic ecosystem, the disproportionate effects of contaminants on members of Tribal sovereignties, and the known effects of contaminants on species protected under the Endangered Species Act, efforts to address toxic chemical pollution in the Columbia River have been limited. The lack of a dedicated contaminant monitoring program impedes evaluation and decision making regarding the health of the Columbia River ecosystem, as well as human health for Tribal members and others that consume fish and other biota from the Columbia River. The purpose of this framework is to provide guidance for the development of a long-term program (Program) that provides the basis for assessing the status and trends of contaminants in fish, sediment, water, and invertebrates along the 962-kilometer length of the Columbia River from the Bonneville Dam upriver to the Canadian Border (Figure ES1). This framework will focus on four persistent and bioaccumulative classes of toxic contaminants: • Mercury • Polychlorinated biphenyls (PCBs) • Dichlorodiphenyltrichloroethane (DDT) • Polybrominated diphenyl ethers (PBDEs) Media of interest in this framework include anadromous and resident fish, sediment, invertebrates, biofilm, and surface water. Future consideration of additional contaminants could include pesticides, per or poly-fluoroalkyl substances, 6PPD-quinone, and contaminants of emerging concern (CECs), which comprises a diverse group of anthropogenic chemicals that include thousands of pharmaceuticals, hormones, illicit drugs, new pesticides, personal care products, flame retardants, artificial sweeteners, perfluorinated compounds, disinfection byproducts, ultraviolet filters, and other industrial chemicals. This framework includes the vision, goals, and objectives for the Program. The vision for the Program is that it will provide the basis for assessing the status and trends of contaminants in the Columbia River to guide ecosystem recovery resulting in clean, healthy fish for current and future generations . The goals of the Program are to 1) conduct long-term monitoring to assess the spatial and temporal status and trends of toxics in fish, water, sediment, and other potential media in the Columbia River mainstem, from Bonneville Dam to the Canadian Border in perpetuity, 2) stimulate conversion of science into action by providing information to facilitate future decision making that improves ecosystem function and reduces contaminants in all levels of the food chain, and 3) adaptively manage the Program to address new key questions, incorporate new and emerging science advancements, and respond to community information needs. To facilitate achieving these goals, this framework provides details on technical planning; community outreach and engagement; and adaptive management to promote understanding and improve future decision making over the long-term, including updating the Program with new and emerging science and community needs. Additionally, data associated with the Program will be made available to the public through the EPA Water Quality Exchange (https://www.epa.gov/waterdata/water-quality-data). Documents and other materials associated with the Program can be accessed via a website hosted by Yakama Nation Fisheries (https://yakamafish-nsn.gov/restore/projects/columbia-river-mainstem- water-quality-monitoring-program). Although the Program is limited to the Columbia River upstream of the Bonneville Dam, collaboration with other entities that monitor contaminants in the Columbia River Basin, including the Columbia River estuary below Bonneville Dam, are also an important component of outreach. Our goal is to encourage efforts to ensure data comparability across programs and recognize that the growth and adaptive management of the Program considers basin-wide monitoring developments.

Oregon, Washington

Cell-Based metabolomics for untargeted screening and prioritization of vertebrate-active stressors in streams across the United States

The U.S. Geological Survey and the U.S. Environmental Protection Agency have assessed contaminants in 38 streams across the U.S., using an extensive suite of target-chemical analysis methods along with a variety of biological effects tools. Here we report zebrafish liver (ZFL) cell-culture based NMR metabolomic analysis of these split stream samples. We used this untargeted approach to evaluate the sites according to overall impact on the ZFL metabolome and found that neither the total number of organics detected at the sites, nor their cumulative concentrations, were good predictors of these impacts. Further, we used partial-least squares regression to compare ZFL endogenous metabolite profiles to values for 455 potential stressors (organics, inorganics, and physical properties) measured in these waters and found that the profiles covaried with at most 280 of the stressors, which were subsequently ranked into quartiles based on the strength of their covariance. While contaminants of emerging concern (CECs) were well represented in the top, most strongly, covarying quartile – suggesting considerable potential for eliciting biological responses at these sites – there was even higher representation of various well-characterized legacy contaminants (e.g., PCBs). These results emphasize the importance of complementing chemical analysis with untargeted bioassays to help focus regulatory efforts on the most significant ecosystem threats.

Environmental Science & Technology

Effects-based monitoring of bioactive compounds associated with municipal wastewater treatment plant effluent discharge to the South Platte River, Colorado, USA

Previous studies have detected numerous organic contaminants and in vitro bioactivities in surface water from the South Platte River near Denver, Colorado, USA. To evaluate the temporal and spatial distribution of selected contaminants of emerging concern, water samples were collected throughout 2018 and 2019 at 11 sites within the S. Platte River and surrounding tributaries with varying proximities to a major wastewater treatment plant (WWTP). Water samples were analyzed for pharmaceuticals, pesticides, steroid hormones, and wastewater indicators and screened for in vitro biological activities. Multiplexed, in vitro assays that simultaneously screen for agonistic activity against 24 human nuclear receptors detected estrogen receptor (ER), peroxisome proliferator activated receptor-gamma (PPARγ), and glucocorticoid receptor (GR) bioactivities in water samples near the WWTP outflow. Targeted in vitro bioassays assessing ER, GR, and PPARγ agonism corroborated bioactivities for ER (up to 55 ± 9.7 ng/L 17β-estradiol equivalents) and GR (up to 156 ± 28 ng/L dexamethasone equivalents), while PPARγ activity was not confirmed. To evaluate the potential in vivo significance of the bioactive contaminants, sexually-mature fathead minnows were caged at six locations upstream and downstream of the WWTP for 5 days after which targeted gene expression analyses were performed. Significant up-regulation of male hepatic vitellogenin was observed at sites with corresponding in vitro ER activity. No site-related differences in GR-related transcript abundance were detected in female adipose or male livers, suggesting observed environmental concentrations of GR-active contaminants do not induce a detectable in vivo response. In line with the lack of detectable targeted in vitro PPARɣ activity, there were no significant effects on PPARɣ-related gene expression. Although the chemicals responsible for GR and PPAR-mediated bioactivities are unknown, results from the present study provide insights into the significance (or lack thereof) of these bioactivities relative to short-term in situ fish exposures.

Environmental Pollution

Selected anthropogenic contaminants in groundwater, Papio-Missouri River Natural Resources District, eastern Nebraska, 1992–2020

A study in cooperation with the Papio-Missouri River Natural Resources District was completed in 2019 to determine the concentration of contaminants of emerging concern (CEC) in groundwater in the Papio-Missouri River Natural Resources District, eastern Nebraska. Each well was sampled twice (in June and October or November) in 2019, totaling 34 samples. Samples were analyzed for 132 CECs, which include pharmaceutical, steroid hormone, and other organic chemicals. Seven of the 132 CEC analytes were detected in samples collected during this study. The most commonly detected CEC in this study was the antibiotic sulfamethoxazole. Other CECs detected in this study were nicotine, methyl-1 H -benzotiazole (industrial product), acetaminophen (analgesic), caffeine, and metformin (diabetes medicine). None of the detected CECs have health-based water-quality standards. The agricultural herbicide atrazine was also sampled for and was detected in 15 of 26 samples from 8 wells, but all samples were below the established water-quality standard. Nitrate, dissolved oxygen, and iron sampling results for 2010–19 and 1992–2020 were also assessed to determine the extent and trend of anthropogenic contamination in the Papio-Missouri River Natural Resources District. Nitrate as nitrogen was detected at a concentration greater than 4 milligrams per liter in 92 samples (19 percent), and detections in 36 samples (7.6 percent) exceeded 10 milligrams per liter, which is the U.S. Environmental Protection Agency’s maximum contaminant level for drinking water and Nebraska’s Title 118 maximum contaminant level for groundwater. Time series analysis showed that nitrate concentrations are not increasing or decreasing in any of the aquifers except for in three specific well nests, which are in phase 2 management areas. Dissolved oxygen results indicate potential denitrification throughout the Elkhorn alluvial aquifer; iron concentrations indicate potential denitrification in parts of the Missouri River alluvial aquifer.

Nebraska

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

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

Minnesota

Effects of urban stormwater and iron‐enhanced sand filtration on Daphnia magna and Pimephales promelas

Urban stormwater is an important but incompletely characterized contributor to surface‐water toxicity. The present study used 5 bioassays of 2 model organisms ( Daphnia magna and fathead minnow, Pimephales promelas ) to investigate stormwater toxicity and mitigation by full‐scale iron‐enhanced sand filters (IESFs). Stormwater samples were collected from major stormwater conveyances and full‐scale IESFs during 4 seasonal events (winter snowmelt and spring, early summer, and late summer rainfalls) and analyzed for a diverse range of contaminants of emerging concern including pharmaceuticals, personal care products, industrial chemicals, and pesticides. Concurrently, stormwater samples were collected for toxicity testing. Seasonality appeared more influential and consistent than site type for most bioassays. Typically, biological consequences were least in early summer and greatest in late summer and winter. In contrast with the unimproved and occasionally reduced biological outcomes in IESF‐treated and late summer samples, water chemistry indicated that numbers and total concentrations of detected organic chemicals, metals, and nutrients were reduced in late summer and in IESF‐treated stormwater samples. Some potent toxicants showed more specific seasonality (e.g., high concentrations of polycyclic aromatic hydrocarbons and industrial compounds in winter, pesticides in early summer and spring, flame retardants in late summer), which may have influenced outcomes. Potential explanations for insignificant or unexpected stormwater treatment outcomes include confounding effects of complex stormwater matrices, IESF nutrient removal, and, less likely, unmonitored toxicants.

Environmental Toxicology and Chemistry

Laboratory-derived bioaccumulation kinetic parameters for four per- and polyfluoroalkyl substances in freshwater mussels

Although freshwater mussels are imperiled and identified as key conservation priorities, limited bioaccumulation information is available on these organisms for contaminants of emerging concern. In the present study we investigated the bioaccumulation of per- and polyfluoroalkyl substances (PFAS) in the model freshwater pond mussel Sagittunio subrostratus because mussels provide important ecosystem services and are important components of aquatic systems where PFAS occur. In the present study we selected four representative perfluorinated carboxylic acids and sulfonic acids, then determined the bioaccumulation kinetics of freshwater mussels in a controlled laboratory study. Because uptake ( k u ) and elimination ( k e ) rate constants and time to steady state are important parameters for food web bioaccumulation models, we derived bioaccumulation kinetic parameters following exposure to perfluorohexane sulfonic acid (PFHxS), perfluorooctane sulfonic acid (PFOS), and perfluorodecanoic acid (PFDA) at 10 µg/L and perfluoroundecanoic acid (PFUnDA) at 1 µg/L during a 14-day uptake period followed by a 7-day elimination period. Kinetic and ratio-based bioaccumulation factors (BAFs) were subsequently calculated, for example ratio-based BAFs for mussel at day 7 were determined for PFHxS (0.24 ± 0.08 L/kg), PFOS (7.73 ± 1.23 L/kg), PFDA (4.80 ± 1.21 L/kg), and PFUnDA (84.0 ± 14.4 L/kg). We generally observed that, for these four model PFAS, freshwater mussels have relatively low BAF values compared with other aquatic invertebrates and fish.

Environmental Toxicology and Chemistry

Temporal variability and sources of PFAS in the Rio Grande, New Mexico through an arid urban area using multiple tracers and high-frequency sampling

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in the environment but sources are not well defined for temporal and spatial aspects within an urban environment, and especially for an arid urban environment subject to seasonal short term high-intensity precipitation events. A focused diel sampling was conducted in the summer of 2021 to assess the temporal and spatial variability of PFAS in the Rio Grande near Albuquerque, New Mexico and showed an order of magnitude increase of PFAS as it flows through the Albuquerque urban area. Discrete samples were collected at two different locations on the Rio Grande in addition to wastewater treatment plant (WWTP) effluent that discharges directly to the Rio Grande between the sampling locations. Short-term high-intensity precipitation events occurred during the study period and mobilized PFAS from urban runoff. Dissolved organic matter composed of tryptophan-like organic substances and refined fuel and fuel byproducts, characteristic of an urban signature, were also related to the precipitation events. The PFAS in discharge from the WWTP was consistent over a 24-h period with slight differences in some compounds. Wastewater presence on the Rio Grande downstream of the WWTP was evidenced by a gadolinium anomaly as well as increases in several other trace elements, total dissolved nitrogen, and fluorescence indicators, in addition to PFAS. PFAS varied depending on source contribution, where urban runoff was associated with PFOA, PFOS, and PFBA, whereas PFHxA and PFPeA were associated with wastewater effluent. In addition, passive polar organic chemical integrative samplers (POCIS) using hydrophilic-lipid balance (HLB) sorption media were deployed for a month at two locations on the Rio Grande to assess longer term PFAS concentrations. The POCIS results show some compounds (PFPeA and PFHpA) were greater than the average concentration from discrete samples, whereas other compounds (PFHxA, PFOA, PFDA, and PFNA) were lower in the POCIS, and PFOS was very similar between the two. The POCIS did not detect PFBA, which may be related to the HLB media not performing well for short chain PFAS compounds. The results show promise for integrative samplers utilizing sorbent media. More detailed investigation of the spatial and temporal variability of water chemistry on the Rio Grande as it flows through Albuquerque could provide information applicable to urban areas worldwide.

New Mexico