Meta‐Analysis Comparing Nominal and Measured Concentrations of Perfluorooctanoic Acid and Perfluorooctane Sulfonate in Aquatic Toxicity Studies Across Various Experimental Conditions

Abstract

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are among the most frequently detected chemicals among the per- and polyfluoroalkyl substances in aquatic environments. Because of their high detection frequency, persistence, and potential toxicity, interest in both PFOA and PFOS has increased in recent years. However, a substantial number of PFOA and PFOS toxicity tests only report nominal, or unmeasured, treatment concentrations, which may complicate the determination of protective values. In addition, previous literature has indicated that differences between nominal and measured concentrations of both PFOA and PFOS could be linked to experimental conditions (e.g., feeding regimes for test organisms, test vessel material [glass or plastic], use of solvent, and the presence of substrate). Therefore, this critical review examined whether nominal and measured concentrations were in close agreement with each other among the current PFOA and PFOS aquatic toxicity literature and if experimental conditions were associated with any observed differences. Nominal and measured concentrations in the current PFOA and PFOS aquatic toxicity literature generally displayed a high degree of linear correlation and relatively low median percent differences. Correlations between measured and nominal concentrations were >0.98 for PFOA and >0.95 for PFOS in freshwater tests across experimental conditions. For saltwater tests, correlations of >0.84 were observed for PFOA and PFOS (separate and combined) across experimental conditions. While measured PFOA and PFOS toxicity tests are generally preferred, the present meta-analysis demonstrated that experimental conditions had little influence on observed discrepancies between nominal and measured concentrations, with the exception of PFOS saltwater tests and PFOA and PFOS freshwater studies that contained substrate. Unmeasured tests with these conditions should be considered carefully based on project needs, with the caveat that the data sets for these two experimental conditions were limited. Environ Toxicol Chem 2023;00:1–13. Published 2023. This article is a U.S. Government work and is in the public domain in the USA.

Spatiotemporal Changes in Trace Metal Bioavailability in The Sediment Porewater of a Constructed Wetland Using Passive Porewater Samplers

ABSTRACT

Sediments in aquatic systems often act as a major sink for contaminants. Diffusive gradient in thin films (DGTs) and in situ equilibrium dialysis samplers (peepers) are two major in situ porewater sampling devices that overcome the problems associated with conventional porewater sampling methods. In this study, DGTs and peepers were used to study the spatial and seasonal effects (cool months: October-February, warm months: May-September) on metal bioavailability in the H-02 constructed wetland, and the sink vs. source role of the sediments by calculating the metal resupply capacity (R). Data showed similar seasonal trends in metal concentrations using both passive samplers, peepers and DGTs. Pooled Cu and Zn concentrations measured using DGTs were lower in warm months (1.67 ± 1.50 and 2.62 ± 0.68 μg.L-1, respectively, p < 0.001) vs. (2.12 ± 0.65 and 5.58 ± 1.33 μg.L-1, respectively, p < 0.001) in cool months (mean ± 95% Confidence Intervals). Sulfate (SO4 2-) concentrations were significantly (p = 0.0139) lower in warm months (averaged at 0.22 ± 0.05 mg.L-1) compared to (0.16 ± 0.05 mg.L-1) in cool months. The increase in SO4 2- concentration is an indicator of the lower activity of sulfate reducing bacteria (SRB) which need SO4 2- during the anaerobic respiration, in which SO4 2- is reduced to sulfide (S2-) which forms insoluble salts with Cu and Zn, which could partially explain higher bioavailability of these metals in the cool season. Metal resupply capacity of the sediments was mostly < 0.2 for Cu and Zn. Taken together, the H0-2 wetland sediments mostly acted as a sink to both Cu and Zn over the course of this study.

Microplastic Pollution in the Gastrointestinal Tract and Gills of Some Teleost and Sturgeon Fish from the Caspian Sea, Northern Iran

Microplastic Pollution in the Gastrointestinal Tract and Gills of Some Teleost and Sturgeon Fish from the Caspian Sea, Northern Iran

Microplastic pollution was found in the gastrointestinal tract and gills of some commercially important fish species, particularly sturgeon from the Caspian Sea.


Abstract

The increasing microplastic pollution in the marine environment has raised global concern. The main risk of microplastics in aquatic ecosystem is their bioaccumulation in aquatic organisms. A few studies have reported microplastic pollution in the digestive system of Caspian Sea fish species, but there is no research on sturgeon species, nor on fish gills. We investigated the occurrence of microplastics in the gastrointestinal tract (GIT) and gills of 62 specimens belonging to four species including three teleosts (Cyprinus carpio, Rutilus kutum, and Chelon aurata) and one sturgeon (Acipenser persicus, a valuable endangered species) from the Caspian Sea between January and March 2022. Fish tissues were removed, exposed for 24 h to 10% KOH, and then dried on filter paper. Particles were observed under a stereomicroscope and analyzed by Raman microspectrometry, scanning electron microscopy, and energy-dispersive spectroscopy. A total of 91 microplastics were detected in the GIT (average of 1.46 ± 1.17 items/individual) and 63 microplastics in the gills (average of 1.01 ± 0.62 items/individual). A significant correlation was not found between the number of microplastics found in both tissues and fish body length, body weight, GIT weight, and gill weight (p > 0.05), except between microplastics isolated from gills and gill weight in C. carpio (r s = 0.707, p = 0.022). The abundance of microplastics in fish followed the order of A. persicus > C. aurata > R. kutum > C. carpio. The microplastics were in the size range of 45 to 5000 µm, with particles of 300 to 1000 µm being the most prevalent; 74.68% of the particles were shaped like fibers, 30.53% were red, and 70.6% were composed of nylon polymer. Environ Toxicol Chem 2023;00:1–13. © 2023 SETAC

Assessing Contaminants of Emerging Concern in the Great Lakes Ecosystem: A Decade of Methods Development and Practical Application

ABSTRACT

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. This paper 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 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 paper is based on research and data captured in about 90 peer-reviewed journal articles and reports, including about 30 appearing in a Virtual Issue comprised of highlighted papers published in Environmental Toxicology and Chemistry or Integrated Environmental Assessment and Management.

Acute Toxicity of Copper to Three Species of Pacific Salmon Fry in Water with Low Hardness and Low Dissolved Organic Carbon

Abstract

Proposed development of a mine within Alaska's Bristol Bay watershed (USA) has raised concerns about the potential impact of copper (Cu) on Pacific salmon (Oncorhynchus spp.). We conducted 96-h flow-through bioassays using low-hardness and low dissolved organic carbon water to determine the acute lethal toxicity of Cu to sockeye (Oncorhynchus nerka), Chinook (Oncorhynchus tshawytscha), and coho salmon (Oncorhynchus kisutch) fry. We aimed to determine Cu toxicity under field-relevant water quality conditions and to assess three methods of calculating ambient Cu criteria: the biotic ligand model (BLM), a multiple linear regression model endorsed by the US Environmental Protection Agency, and the hardness-based model currently used by the State of Alaska. The criteria generated by all models were below 20% lethal Cu concentrations by factors ranging from 2.2 to 54.3, indicating that all criteria would be protective against mortality. The multiple linear regression-based criteria were the most conservative and were comparable to BLM-based criteria. The median lethal concentrations (LC50s) for sockeye, Chinook, and coho were 35.2, 23.9, and 6.3 µg Cu/L, respectively. We also used the BLM to predict LC50s for each species. Model predictions differed from empirical LC50s by factors of 0.7 for sockeye and Chinook salmon, and 1.1 for coho salmon. These differences fell within the acceptable range of ±2, indicating the model's accuracy. We calculated critical lethal Cu accumulation values for each species to account for differing water chemistry in each bioassay; the present study revealed that coho salmon were most sensitive to Cu, followed by sockeye and Chinook salmon. Our findings underscore the importance of considering site- and species-specific factors when modeling Cu toxicity. The empirical data we present may enhance Cu risk assessments for Pacific salmon. Environ Toxicol Chem 2023;00:1–13. © 2023 SETAC

Agricultural Use of Insecticides Alters Homeostatic Behaviors and Cognitive Ability in Lymnaea stagnalis

Abstract

Lymnaea stagnalis is an ecologically important, stress-sensitive, freshwater mollusk that is at risk for exposure to insecticides via agricultural practices. We provide insight into the impact insecticides have on L. stagnalis by comparing specific behaviors including feeding, locomotion, shell regeneration, and cognition between snails collected at two different sites: one contaminated by insecticides and one not. We hypothesized that each of the behaviors would be altered in the insecticide-exposed snails and that similar alterations would be induced when control snails were exposed to the contaminated environment. We found no significant differences in locomotion, feeding, and shell regeneration of insecticide-exposed L. stagnalis compared with nonexposed individuals. Significant changes in feeding and shell repair were observed in nonexposed snails inhabiting insecticide-contaminated pond water. Most importantly, snails maintained and trained in insecticide-contaminated pond water did not form configural learning, but this cognitive deficit was reversed when these snails were maintained in insecticide-free pond water. Our findings conclude that insecticides have a primarily negative impact on this higher form of cognition in L. stagnalis. Environ Toxicol Chem 2023;00:1–12. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Application of Ion Mobility Spectrometry–Mass Spectrometry for Compositional Characterization and Fingerprinting of a Library of Diverse Crude Oil Samples

Abstract

Exposure characterization of crude oils, especially in time-sensitive circumstances such as spills and disasters, is a well-known analytical chemistry challenge. Gas chromatography–mass spectrometry is commonly used for “fingerprinting” and origin tracing in oil spills; however, this method is both time-consuming and lacks the resolving power to separate co-eluting compounds. Recent advances in methodologies to analyze petroleum substances using high-resolution analytical techniques have demonstrated both improved resolving power and higher throughput. One such method, ion mobility spectrometry–mass spectrometry (IMS–MS), is especially promising because it is both rapid and high-throughput, with the ability to discern among highly homologous hydrocarbon molecules. Previous applications of IMS–MS to crude oil analyses included a limited number of samples and did not provide detailed characterization of chemical constituents. We analyzed a diverse library of 195 crude oil samples using IMS–MS and applied a computational workflow to assign molecular formulas to individual features. The oils were from 12 groups based on geographical and geological origins: non-US (1 group), US onshore (3), and US Gulf of Mexico offshore (8). We hypothesized that information acquired through IMS–MS data would provide a more confident grouping and yield additional fingerprint information. Chemical composition data from IMS–MS was used for unsupervised hierarchical clustering, as well as machine learning–based supervised analysis to predict geographic and source rock categories for each sample; the latter also yielded several novel prospective biomarkers for fingerprinting of crude oils. We found that IMS–MS data have complementary advantages for fingerprinting and characterization of diverse crude oils and that proposed polycyclic aromatic hydrocarbon biomarkers can be used for rapid exposure characterization. Environ Toxicol Chem 2023;00:1–14. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Exposure of Lemna minor (Common Duckweed) to Mixtures of Uranium and Perfluorooctanoic Acid (PFOA)

Abstract

A variety of processes, both natural and anthropogenic, can have a negative impact on surface waters, which in turn can be detrimental to human and environmental health. Few studies have considered the ecotoxicological impacts of concurrently occurring contaminants, and that is particularly true for mixtures that include contaminants of emerging concern (CEC). Motivated by this knowledge gap, the present study considers the potential ecotoxicity of environmentally relevant contaminants in the representative aquatic plant Lemna minor (common duckweed), a model organism. More specifically, biological effects associated with exposure of L. minor to a ubiquitous radionuclide (uranium [U]) and a fluorinated organic compound (perfluorooctanoic acid [PFOA], considered a CEC), alone and in combination, were monitored under controlled laboratory conditions. Lemna minor was grown for 5 days in small, aerated containers. Each treatment consisted of four replicates with seven plants each. Treatments were 0, 0.3, and 3 ppb PFOA; 0, 0.5, and 5 ppb U; and combinations of these. Plants were observed daily for frond number and signs of chlorosis and necrosis. Other biological endpoints examined at the conclusion of the experiment were chlorophyll content and antioxidant capacity. In single-exposure experiments, a slight stimulatory effect was observed on frond number at 0.3 ppb PFOA, whereas both concentrations of U had a detrimental effect on frond number. In the dual-exposure experiment, the combinations with 5 ppb U also had a detrimental effect on frond number. Results for chlorophyll content and antioxidant capacity were less meaningful, suggesting that environmentally relevant concentrations of PFOA and U have only subtle effects on L. minor growth and health status. Environ Toxicol Chem 2023;00:1–10. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

The Use of Multiple Biomarkers to Assess the Health of Anuran Amphibians in the Brazilian Cerrado Savanna: An Ecotoxicological Approach

The Use of Multiple Biomarkers to Assess the Health of Anuran Amphibians in the Brazilian Cerrado Savanna: An Ecotoxicological Approach

A worrisome look into aquatic life: Anuran egg masses in Goiás State reveal toxic and DNA damage.


Abstract

Changes in the natural landscape and the indiscriminate use of pesticides can have a major impact on aquatic environments and have contributed to the worldwide decline of amphibian populations. In the present study, we sampled tadpoles of three anuran amphibians (Boana albopunctata, Physalaemus cuvieri, and Dendropsophus minutus) from ponds in six different agricultural landscapes of the Brazilian Cerrado savanna and evaluated whether and to what extent genotoxic and mutagenic damage was related to land use (the amount of forest and agricultural remnants, and related physicochemical factors) and the presence of pesticides in the water of the study ponds. We also evaluated the hepatotoxicity in P. cuvieri, which was the most abundant species at five of the six sampling points. Clomazone and atrazine were the most common pesticides found in the ponds. The B. albopunctata and P. cuvieri tadpoles presented similar patterns of DNA damage among the sampling points. The least DNA damage was found in the D. minutus tadpoles, although this species was present in only one of the study ponds. More binucleated and anucleated cells were observed in B. albopunctata, but there was no significant variation among species in terms of the number of micronuclei or other erythrocytic nuclear abnormalities. Land use and physicochemical factors did not explain the variation in the DNA damage observed in the three anurans. The hepatotoxicity analyses of P. cuvieri revealed the presence of a series of alterations, including the enlargement of the sinusoids, vacuolization of the hepatocytes, the infiltration of inflammatory cells, hepatic steatosis, and dilation of the blood vessels. The interaction between physicochemical factors and the biomarkers analyzed in the present study is complex. In particular, it will be important to better elucidate which factors are contributing, either directly or indirectly, to the decline of anuran amphibian populations, especially in threatened biomes, such as the Brazilian Cerrado. In this case, we would encourage further in situ studies that assess the ecotoxicology of the landscape, together with the systematic monitoring of aquatic environments, to guarantee the long-term integrity of amphibian populations, and those of other organisms that play an essential functional role in the ecosystem. Environ Toxicol Chem 2023;00:1–18. © 2023 SETAC

Maternal Transfer and Effects of Selenium on Early Life Stage Development of Redside Shiner (Richardsonius balteatus)

Abstract

Maternal transfer of selenium (Se) to developing fish eggs during vitellogenesis can cause larval deformity and mortality. Previous studies have shown wide variation among fish species in both the magnitude of maternal transfer (exposure) and the egg Se concentration causing effects (sensitivity). We studied maternal transfer and effects of Se on early life stage development, survival, and growth of redside shiner (Richardsonius balteatus), a small-bodied cyprinid that has been reported to have relatively high ovary:muscle Se concentration ratios. Gametes were collected from lentic areas in southeast British Columbia (Canada) with a range of dietary Se concentrations related to weathering of waste rock from coal mining. Eggs were fertilized and reared in the laboratory from hatch to the onset of exogenous feeding. Larvae were assessed for survival, length, weight, Se-characteristic deformities, and edema. Eggs from a total of 56 females were collected, with egg Se concentrations from 0.7 to 28 mg/kg dry weight. Maternal transfer varied among sites, with egg:muscle Se concentration ratios ranging from <1 to >4. We also found that sampling residual ovaries can overestimate Se concentrations in ripe eggs by up to a factor of 5.7. A correlation between larval weight and egg Se concentration was identified, although the relationship was weak (r 2 < 0.1) and appeared to be a site effect. No other relationships were observed between larval endpoints and egg Se concentrations up to the highest concentration tested, indicating that the effects threshold for this species may be >28 mg/kg dry weight in eggs. These data indicate that redside shiner is less sensitive to maternally transferred Se than most other tested fish species. Environ Toxicol Chem 2023;00:1–8. © 2023 SETAC