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Perfluorodecanoic acid (PFDA) disrupts immune regulation via the toll-like receptor signaling pathway in zebrafish

As there are a growing number of per- and polyfluoroalkyl substances (PFAS) alternative substitutes applied globally, it remains paramount to characterize their potential health risks. Perfluorodecanoic acid (PFDA) is the most common alternative PFAS detected in the environment; however, its toxic effects and underlying mechanism of action to aquatic biota remains unclear. In this study, we present in vitro evidence of PFDA-induced immunotoxicity and gain insight into underlying molecular mechanisms. PFDA induced immune dysfunction in zebrafish primarily through immunosuppression, apoptosis, and inflammatory response which further cascaded to suppress innate and adaptive immunities, ultimately weaking the ability of larvae to defend against pathogenic infection. PFDA-induced immunotoxicity was driven by a dysregulation in the toll-like receptor (TLR) signaling pathway, which was validated through a cotreatment of PFDA with either a morpholino knockdown or inhibitor of myeloid differentiation factor 88. Comparative toxicity studies were carried out with a subset of other alternative PFAS (PFBA, PFOA, PFNA) and it was found that PFDA posed a greater immunotoxic response than other commonly identified PFAS in the environment. This work identified a major target of PFDA, disrupting immune function through the TLR signaling pathway, while inducing a greater toxic response among other tested PFAS, which provides novel insights into understanding the potential environmental risks of PFAS substitutes.

Environmental Science & Technology

Bioaccumulation and transfer of per- and polyfluoroalkyl substances (PFAS) in a stream and riparian food web contaminated by food processing wastewater

We evaluated the bioaccumulation and transfer of per- and polyfluoroalkyl substances (PFAS) in a stream food web contaminated by a food processing facility. Abiotic (i.e., water, sediment, and foam) and biotic (i.e., algae, aquatic insect larvae and adults, fish, and riparian spiders) matrices were sampled upstream and downstream of the facility’s wastewater outfall. Compared with upstream, PFAS concentrations were 600-fold higher in downstream water (mean ∑ 40 PFAS 3.67 ng mL –1 ± 0.48 (standard error)) and reflected inputs from the outfall, with 6:2 fluorotelomer sulfonate (6:2 FTS) dominating the PFAS profile. Within the aquatic food web, perfluorooctanesulfonate (PFOS) was the most biomagnified, and 6:2 FTS was the most biodiluted. In contrast, insect-mediated transfer of PFAS to riparian spiders showed trophic enrichment of 6:2 FTS and dilution of PFOS. We observed significant positive associations between phospholipid membrane-water partition coefficient (log K MW ) and perfluoroalkyl carboxylate (PFCA) chain length on bioaccumulation across most biological matrices, demonstrating that these chemical parameters are predictive of PFAS bioaccumulation potential in the field. Our research reveals important differences in aquatic versus terrestrial exposure for certain PFAS and that biological processes (e.g., trophic interactions and metamorphosis) and chemical properties (e.g., chain length, log K MW , and concentration) control PFAS uptake, bioaccumulation, and transfer in linked freshwater and terrestrial ecosystems.

Environmental Science & Technology

Revealing organofluorine contamination in effluents and surface waters with complementary analytical approaches: Fluorine-19 nuclear magnetic resonance spectroscopy (19F-NMR) and liquid chromatography-tandem mass spectrometry (LC-MS/MS)

Fluorinated organic contaminants, including per- and polyfluoroalkyl substances (PFASs) and fluorinated pesticides and pharmaceuticals (FPPs), pose a persistent threat to environmental health. Widely used liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods fail to capture large fractions of total organofluorine in environmental samples, confounding the assessment of fluorinated contamination. Fluorine-19 nuclear magnetic resonance spectroscopy ( 19 F-NMR) is an inclusive method for total and class-based organofluorine analysis. Here, we apply 19 F-NMR to 31 effluent, surface water, and foam samples collected at 13 potential organofluorine point sources or source regions and compare the results to targeted LC-MS/MS for 34 or 64 PFASs. LC-MS/MS detected a median of 11.4% of total organofluorine detected by 19 F-NMR (range: nondetect to 8190 nM F 19 F-NMR; nondetect to 8010 nM F LC-MS/MS). The highest 19 F-NMR total organofluorine concentrations, detected in wastewater treatment plant (WWTP)-associated foam and at a soy oil production facility, arose from resonances characteristic of per- and polyfluorinated alkyl chains. 19 F-NMR resonances from aryl CF 3 moieties were abundant in the WWTP-associated samples, consistent with prior reports of substantial contributions from pharmaceuticals to WWTP effluents. 19 F-NMR enables the quantitative assessment of total organofluorine and qualitative insight into fluorinated structures, providing complementary analysis of organofluorine compounds missed by targeted mass spectrometry-based protocols.

Environmental Science & Technology

Imidacloprid in United States rivers, 2013–2022: Persistent presence and emerging chronic hazard

Imidacloprid, a neonicotinoid insecticide, is used for agricultural and nonagricultural purposes and is toxic to nontarget organisms at low concentrations in aquatic ecosystems. A total of 12,547 water samples were collected from 2013 to 2022 from 77 rivers across the United States (U.S.) and were analyzed to evaluate detections and temporal trends in imidacloprid concentrations. Imidacloprid was detected in 44% of all samples, and the mean concentration, adjusted for nondetect samples, of 24.9 ng/L (median = 11.9 ng/L) was more than twice the chronic benchmark for freshwater invertebrates (10 ng/L). This potential hazard to aquatic life was persistent, with 44% of the sites having a median concentration exceeding the chronic benchmark. Half of the sites ( n = 38) had increasing trends, including large river sites along the Mississippi River. The mean increase was 10.6 ng/L over the past decade, while only six sites indicated decreasing trends. The estimated total loading of imidacloprid delivered to the Gulf of America from 2013 to 2022 was 129,489 kg (142.7 U.S. ton). The extensive presence of imidacloprid in U.S. waterways, the high percentage of sites with trends of increasing concentrations, and the prevalence of concentrations exceeding chronic benchmarks suggest widespread persistent risks to ecosystem health.

Environmental Science & Technology

Tetrabromobisphenol S (TBBPS) causes non-negligible and multigenerational reproductive toxicity in zebrafish

Tetrabromobisphenol S (TBBPS) is one of the most extensively used brominated flame retardants detected in the environment. Despite its widespread presence, the effects of persistent environmental exposure to TBBPS on the reproductive system remain unclear, raising significant health concerns. Here, using the zebrafish ( Danio rerio ) model, we identified significant intergenerational endocrine disruption and reproductive toxicity induced by TBBPS after a life-cycle (150 days) of parental exposure to environmentally relevant concentrations of TBBPS (0.01, 0.1, 1, 10, and 100 μg/L). TBBPS interfered with hormone levels and the expression of genes within the hypothalamic–pituitary–gonadal (HPG) axis in both F0 males and females, leading to reduced embryo quality. The parental transmission of TBBPS also impacted the endocrine and reproductive systems of the F1 fish, including the increase of gonadotropin-releasing hormone 3 neuron numbers, changes in hormone levels, and a decrease in embryo numbers. F2 fish also displayed endocrine disruption, even in the absence of detectable TBBPS residues, evidenced by altered fertilization rates and vitellogenin levels. Together, our findings show that exposure to environmentally relevant concentrations of TBBPS can induce reproductive toxicity that persists across generations, weakening the endocrine system and early growth in offspring by disrupting the HPG axis. These data provide critical insight into the persistent health risks posed by TBBPS.

Environmental Science & Technology

Roadway runoff induced acute mortality in juvenile coho salmon during spring storm events

Extensive mortalities of adult coho salmon ( Oncorhynchus kisutch ), often called “Urban Runoff Mortality Syndrome” (URMS), have been documented during the fall in creeks where water quality has been degraded by roadway runoff. The primary cause of mortality is 6PPD-quinone (6PPDQ; N -(1,3-dimethylbutyl)- N ′-phenyl- p -phenylenediamine quinone)–an ozone transformation product that forms on all vehicle tires. Laboratory studies have shown that juvenile coho salmon are highly sensitive to 6PPDQ exposure. Unlike adults, juveniles reside in impacted watersheds year-round, including during the spring when 6PPDQ concentrations can frequently exceed lethal thresholds during storms. To assess the potential incidence of URMS in springtime rearing habitats for juvenile coho salmon, we conducted a paired water quality and toxicology study at Miller Creek, a runoff-impacted watershed in Normandy Park, WA, USA. Using a small field facility, three naïve groups of juvenile coho salmon ( N = 720) were exposed to either creek water or groundwater ( N = 120 per treatment per storm), across three spring storms while comparing water quality and mortality end points. In creek water during exposures, peak 6PPDQ concentrations reached 73–110 ng/L, exceeding reported median lethal concentrations (LC 50 ) for coho salmon. Over each 24–73 h storm exposure period, ∼80% of Miller Creek-exposed juvenile salmon died. No mortality occurred among control fish exposed to groundwater. These results indicate previously unidentified mortality risks for juvenile life stages of coho salmon during spring storms, suggesting substantial and year-round water quality impediments to coho salmon health and recovery across roadway runoff-impacted spawning, rearing, and migratory habitats.

Washington

Predictions of anthropogenic background PFAS concentrations in soil and relation to bedrock lithology and groundwater quality

Detectable concentrations of per- and polyfluoroalkyl substances (PFAS) have been observed in soils in remote areas and presumably originate from atmospheric deposition. These anthropogenic background concentrations may enable some PFAS to leach to groundwater at levels that exceed regulatory criteria for drinking water. However, anthropogenic background soil concentrations and their connection to groundwater are not well characterized. We developed a boosted regression tree model to predict perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) concentrations in shallow soils across northern New England. Low soil pH was the most important predictor of elevated anthropogenic PFOS and PFOA concentrations in background soils, rather than potential PFAS sources, land use, or population density. Total organic carbon (TOC) was also an important predictor for PFOS soil concentrations. Model predictions indicate that 73% of the shallow soils within Maine, Vermont, and New Hampshire exceed New Hampshire’s Soil Remediation Standard for PFOS (0.5 ng/g) and 41% exceed the PFOA standard (0.4 ng/g). Analysis of soil model results and groundwater data suggests that areas with high soil pH are associated with higher groundwater detection frequencies, illustrating how areas with less retention in soil are, conversely, also areas with potentially greater groundwater vulnerability. Further analysis indicates that groundwater may be more vulnerable in calcareous lithologies.

Maine, New Hampshire, Vermont

Trophic magnification of organic chemicals: A global synthesis

Production of organic chemicals (OCs) is increasing exponentially, and some OCs biomagnify through food webs to potentially toxic levels. Biomagnification under field conditions is best described by trophic magnification factors (TMFs; per trophic level change in log-concentration of a chemical) which have been measured for more than two decades. Syntheses of TMF behavior relative to chemical traits and ecosystem properties are lacking. We analyzed >1500 TMFs to identify OCs predisposed to biomagnify and to assess ecosystem vulnerability. The highest TMFs were for OCs that are slowly metabolized by animals (metabolic rate k M < 0.01 day &ndash;1 ) and are moderately hydrophobic (log K OW 6&ndash;8). TMFs were more variable in marine than freshwaters, unrelated to latitude, and highest in food webs containing endotherms. We modeled the probability that any OC would biomagnify as a combined function of K OW and k M . Probability is greatest (&sim;100%) for slowly metabolized compounds, regardless of K OW , and lowest for chemicals with rapid transformation rates ( k M > 0.2 day &ndash;1 ). This probabilistic model provides a new global tool for screening existing and new OCs for their biomagnification potential.

Environmental Science & Technology

Wastewater disposal from unconventional oil and gas development degrades stream quality at a West Virginia injection facility

The development of unconventional oil and gas (UOG) resources has rapidly increased in recent years; however, the environmental impacts and risks are poorly understood. A single well can generate millions of liters of wastewater, representing a mixture of formation brine and injected hydraulic fracturing fluids. One of the most common methods for wastewater disposal is underground injection; we are assessing potential risks of this method through an intensive, interdisciplinary study at an injection disposal facility in West Virginia. In June 2014, waters collected downstream from the site had elevated specific conductance (416 &mu;S/cm) and Na, Cl, Ba, Br, Sr, and Li concentrations, compared to upstream, background waters (conductivity, 74 &mu;S/cm). Elevated TDS, a marker of UOG wastewater, provided an early indication of impacts in the stream. Wastewater inputs are also evident by changes in 87Sr/86Sr in streamwater adjacent to the disposal facility. Sediments downstream from the facility were enriched in Ra and had high bioavailable Fe(III) concentrations relative to upstream sediments. Microbial communities in downstream sediments had lower diversity and shifts in composition. Although the hydrologic pathways were not able to be assessed, these data provide evidence demonstrating that activities at the disposal facility are impacting a nearby stream and altering the biogeochemistry of nearby ecosystems.

Environmental Science & Technology

Exposure to the contraceptive progestin, gestodene, alters reproductive behavior, arrests egg deposition, and masculinizes development in the fathead minnow ( Pimephales promelas )

Endogenous progestogens and pharmaceutical progestins enter the environment through wastewater treatment plant effluent and agricultural field runoff. Lab studies demonstrate strong, negative exposure effects of these chemicals on aquatic vertebrate reproduction. Behavior can be a sensitive, early indicator of exposure to environmental contaminants associated with altered reproduction yet is rarely examined in ecotoxicology studies. Gestodene is a human contraceptive progestin and a potent activator of fish androgen receptors. Our objective was to test the effects of gestodene on reproductive behavior and associated egg deposition in the fathead minnow. After only 1 day, males exposed to ng/L of gestodene were more aggressive and less interested in courtship and mating, and exposed females displayed less female courtship behavior. Interestingly, 25% of the gestodene tanks contained a female that drove the male out of the breeding tile and displayed male-typical courtship behaviors toward the other female. Gestodene decreased or arrested egg deposition with no observed gonadal histopathology. Together, these results suggest that effects on egg deposition are primarily due to altered reproductive behavior. The mechanisms by which gestodene disrupts behavior are unknown. Nonetheless, the rapid and profound alterations of the reproductive biology of gestodene-exposed fish suggest that wild populations could be similarly affected.

Environmental Science & Technology

Predicting arsenic in drinking water wells of the Central Valley, California

Probabilities of arsenic in groundwater at depths used for domestic and public supply in the Central Valley of California are predicted using weak-learner ensemble models (boosted regression trees, BRT) and more traditional linear models (logistic regression, LR). Both methods captured major processes that affect arsenic concentrations, such as the chemical evolution of groundwater, redox differences, and the influence of aquifer geochemistry. Inferred flow-path length was the most important variable but near-surface-aquifer geochemical data also were significant. A unique feature of this study was that previously predicted nitrate concentrations in three dimensions were themselves predictive of arsenic and indicated an important redox effect at >10 μg/L, indicating low arsenic where nitrate was high. Additionally, a variable representing three-dimensional aquifer texture from the Central Valley Hydrologic Model was an important predictor, indicating high arsenic associated with fine-grained aquifer sediment. BRT outperformed LR at the 5 μg/L threshold in all five predictive performance measures and at 10 μg/L in four out of five measures. BRT yielded higher prediction sensitivity (39%) than LR (18%) at the 10 μg/L threshold–a useful outcome because a major objective of the modeling was to improve our ability to predict high arsenic areas.

California

A gas-tracer injection for evaluating the fate of methane in a coastal plain stream: Degassing versus in-stream oxidation

Methane emissions from streams and rivers have recently been recognized as an important component of global greenhouse budgets. Stream methane is lost as evasion to the atmosphere or in-stream methane oxidation. Previous studies have quantified evasion and oxidation with point-scale measurements. In this study, dissolved gases (methane, krypton) were injected into a coastal plain stream in North Carolina to quantify stream CH 4 losses at the watershed scale. Stream-reach modeling yielded gas transfer and oxidation rate constants of 3.2 ± 0.5 and 0.5 ± 1.5 d –1 , respectively, indicating a ratio of about 6:1. The resulting evasion and oxidation rates of 2.9 mmol m –2 d –1 and 1,140 nmol L –1 d –1 , respectively, lie within ranges of published values. Similarly, the gas transfer velocity ( K 600 ) of 2.1 m d –1 is consistent with other gas tracer studies. This study illustrates the utility of dissolved-gas tracers for evaluating stream methane fluxes. In contrast to point measurements, this approach provides a larger watershed-scale perspective. Further work is needed to quantify the magnitude of these fluxes under varying conditions (e.g., stream temperature, nutrient load, gradient, flow rate) at regional and global scales before reliable bottom-up estimates of methane evasion can be determined at global scales.

Environmental Science & Technology

Biogeochemical controls of uranium bioavailability from the dissolved phase in natural freshwaters

To gain insights into the risks associated with uranium (U) mining and processing, we investigated the biogeochemical controls of U bioavailability in the model freshwater species Lymnaea stagnalis (Gastropoda). Bioavailability of dissolved U(VI) was characterized in controlled laboratory experiments over a range of water hardness, pH, and in the presence of complexing ligands in the form of dissolved natural organic matter (DOM). Results show that dissolved U is bioavailable under all the geochemical conditions tested. Uranium uptake rates follow first order kinetics over a range encompassing most environmental concentrations. Uranium uptake rates in L. stagnalis ultimately demonstrate saturation uptake kinetics when exposure concentrations exceed 100 nM, suggesting uptake via a finite number of carriers or ion channels. The lack of a relationship between U uptake rate constants and Ca uptake rates suggest that U does not exclusively use Ca membrane transporters. In general, U bioavailability decreases with increasing pH, increasing Ca and Mg concentrations, and when DOM is present. Competing ions did not affect U uptake rates. Speciation modeling that includes formation constants for U ternary complexes reveals that the aqueous concentration of dicarbonato U species (UO 2 (CO 3 ) 2 –2 ) best predicts U bioavailability to L. stagnalis , challenging the free-ion activity model postulate.

Environmental Science & Technology

Direct photolysis rates and transformation pathways of the lampricides TFM and niclosamide in simulated sunlight

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2′,5-dichloro-4′-nitrosalicylanilide (niclosamide) are directly added to many tributaries of the Great Lakes that harbor the invasive parasitic sea lamprey. Despite their long history of use, the fate of lampricides is not well understood. This study evaluates the rate and pathway of direct photodegradation of both lampricides under simulated sunlight. The estimated half-lives of TFM range from 16.6 ± 0.2 h (pH 9) to 32.9 ± 1.0 h (pH 6), while the half-lives of niclosamide range from 8.88 ± 0.52 days (pH 6) to 382 ± 83 days (pH 9) assuming continuous irradiation over a water depth of 55 cm. Both compounds degrade to form a series of aromatic intermediates, simple organic acids, ring cleavage products, and inorganic ions. Experimental data were used to construct a kinetic model which demonstrates that the aromatic products of TFM undergo rapid photolysis and emphasizes that niclosamide degradation is the rate-limiting step to dehalogenation and mineralization of the lampricide. This study demonstrates that TFM photodegradation is likely to occur on the time scale of lampricide applications (2–5 days), while niclosamide, the less selective lampricide, will undergo minimal direct photodegradation during its passage to the Great Lakes.

Environmental Science & Technology

Bifenthrin causes trophic cascades and alters insect emergence in mesocosms: implication for small streams

Direct and indirect ecological effects of the widely used insecticide bifenthrin on stream ecosystems are largely unknown. To investigate such effects, a manipulative experiment was conducted in stream mesocosms that were colonized by aquatic insect communities and exposed to bifenthrin-contaminated sediment; implications for natural streams were interpreted through comparison of mesocosm results to a survey of 100 Midwestern streams, USA. In the mesocosm experiment, direct effects of bifenthrin exposure included reduced larval macroinvertebrate abundance, richness, and biomass at concentrations (EC50s ranged 197.6 – 233.5 ng bifenthrin/ g organic carbon) previously thought safe for aquatic life. Indirect effects included a trophic cascade in which periphyton abundance increased after macroinvertebrate scrapers decreased. Adult emergence dynamics and corresponding terrestrial subsidies were altered at all bifenthrin concentrations tested. Extrapolating these results to the Midwestern stream assessment suggests pervasive ecological effects, with altered emergence dynamics likely in 40% of streams and a trophic cascade in 7% of streams. This study provides new evidence that a common pyrethroid might alter aquatic and terrestrial ecosystem function at the regional scale.

Environmental Science & Technology

Plastic debris in 29 Great Lakes tributaries: Relations to watershed attributes and hydrology

Plastic debris is a growing contaminant of concern in freshwater environments, yet sources, transport, and fate remain unclear. This study characterized the quantity and morphology of floating micro- and macroplastics in 29 Great Lakes tributaries in six states under different land covers, wastewater effluent contributions, population densities, and hydrologic conditions. Tributaries were sampled three or four times each using a 333 μm mesh neuston net. Plastic particles were sorted by size, counted, and categorized as fibers/lines, pellets/beads, foams, films, and fragments. Plastics were found in all 107 samples, with a maximum concentration of 32 particles/m 3 and a median of 1.9 particles/m 3 . Ninety-eight percent of sampled plastic particles were less than 4.75 mm in diameter and therefore considered microplastics. Fragments, films, foams, and pellets/beads were positively correlated with urban-related watershed attributes and were found at greater concentrations during runoff-event conditions. Fibers, the most frequently detected particle type, were not associated with urban-related watershed attributes, wastewater effluent contribution, or hydrologic condition. Results from this study add to the body of information currently available on microplastics in different environmental compartments, including unique contributions to quantify their occurrence and variability in rivers with a wide variety of different land-use characteristics while highlighting differences between surface samples from rivers compared with lakes.

Environmental Science & Technology

Effects of flow regime on metal concentrations and the attainment of water quality standards in a remediated stream reach, Butte, Montana

Low-flow synoptic sampling campaigns are often used as the primary tool to characterize watersheds affected by mining. Although such campaigns are an invaluable part of site characterization, investigations which focus solely on low-flow conditions may yield misleading results. The objective of this paper is to demonstrate this point and elucidate the mechanisms responsible for the release of metals during rainfall runoff. This objective is addressed using data from diel and synoptic sampling campaigns conducted over a two-day period. Low-flow synoptic sampling results indicate that concentrations of most constituents meet aquatic standards. This finding is in contrast to findings from a diel sampling campaign that captured dramatic increases in concentrations during rainfall runoff. Concentrations during the rising limb of the hydrograph were 2–23 times concentrations observed during synoptic sampling (most increases were >10-fold), remaining elevated during the receding limb of the hydrograph to produce a clockwise hysteresis loop. Hydrologic mechanisms responsible for the release of metals include increased transport due to resuspension of streambed solids, erosion of alluvial tailings, and overland flow. Rainfall also elevated the alluvial groundwater table and increased infiltration through the vadose zone, likely resulting in dissolution from alluvial tailings that were dry prior to the event.

Montana

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Florida