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Evaluating per- and polyfluoroalkyl substance (PFAS) prevalence and potential for biological effects in Lake Superior tributaries

Several per- and polyfluoroalkyl substances (PFAS) are Great Lakes binational chemicals of mutual concern. Although known to be persistent, data gaps regarding PFAS prevalence and biological effects exist, especially within Lake Superior’s watershed. In this 2022 study of 27 United States tributaries to Lake Superior, water samples were collected during spring runoff, summer baseflow, and fall baseflow, and stream bed-sediment samples were collected during fall. PFAS were detected in 97% of water samples and 59% of sediment samples. Summed PFAS water sample concentrations (33 analytes) were generally low relative to other environmental studies (median = 6.5 ng/L), except at Newton, Miller, and Sargent Creeks (up to 391 ng/L). Maximum water concentrations were from perfluorooctane sulfonic acid (PFOS) and perfluorohexane sulfonate (PFHxS); perfluorobutanoic acid (PFBA) had the greatest median concentration. PFBA and perfluorooctanoic acid (PFOA) were most frequently detected in water samples (>90%). Summed PFAS sediment sample concentrations (33 analytes) were also generally low (median = 19 ng/kg), except at Newton and Muggun Creeks (up to 797 ng/kg). In sediment, PFOS occurred most frequently and had the greatest concentrations. The most contaminated samples came from sites with documented aqueous film forming foam or wastewater contamination; summer baseflow samples exhibited elevated PFAS concentrations. Comparison of observed water concentrations to published and derived water-quality guidelines indicated PFOS and PFHxS pose the greatest potential ecological risks. Observed PFAS mixtures may affect lipid metabolism, growth, thyroid hormones, and survival of aquatic organisms. The observed concentrations and predicted biological effects are likely underestimates of the environmental impact of PFAS. Despite low anthropogenic influence in Lake Superior’s watershed, PFAS were ubiquitous and occurred at potentially harmful concentrations.

Michigan, Minnesota, Wisconsin↗

Per- and polyfluoroalkyl substances in surface water and sediment in Great Lakes tributaries and relations with watershed attributes

Per- and polyfluoroalkyl substances (PFAS) are chemicals of emerging concern that potentially pose risks to human and environmental health. In May–Oct 2018, sediment and passively collected surface water samples were collected from 62 tributary sites of the Laurentian Great Lakes with site catchments spanning various land cover types. Discrete samples of sediment collected manually and time-integrated surface water samples collected with polar organic chemical integrative samplers (POCIS) were analyzed for 23 and 34 PFAS, respectively. Concentrations of individual PFAS in sediment and surface water varied immensely among sites from below detection to 20,800 ng kg −1 and 247 ng L −1 , respectively. Of all target compounds, PFOS was the most frequently detected in sediment (56 of 62 sites) and had the highest median concentration (132 ng kg −1 ). PFOA, PFHxS, PFOS, PFHpA, and PFNA (full chemical names are listed in online supplementary material Table S2) were detected in all 60 surface water sites, with median estimated concentrations of 5.9, 5.2, 4.6, 3.7, and 1.3 ng L −1 , respectively. Compounds with 8–13 fluorinated carbons comprised a larger proportion of sediment PFAS than compounds with 4–7 fluorinated carbons, whereas compounds with 4–7 fluorinated carbons comprised a greater proportion of PFAS in surface waters. Watershed attributes, including urban land cover, airports per catchment area, and wastewater treatment plants flow percentage were significantly ( p < 0.05) and positively related with PFAS sum concentrations in sediment and (or) surface water. Collectively, these results, albeit with some uncertainty in the estimated concentrations, highlight the relation PFAS occurrence has with human activities and documents widespread low-level PFAS contamination across the Great Lakes basin.

Great Lakes↗

Mercury trophic transfer to a freshwater biosentinel: Quantifying controlled bioaccumulation in larval dragonflies

Mercury bioavailability and biomagnification in freshwater systems can be highly variable; thus, tissue data from biosentinel taxa can be useful to assess risk. Dragonfly larvae have emerged as biological indicators of mercury impairment, yet their mercury biodynamics over time and across exposure levels are not well understood. Evaluating these attributes using controlled experimental approaches is an important step to validate larval dragonflies as biosentinels for spatial and temporal trends in mercury risk. We conducted an experimental series quantifying methylmercury trophic transfer from dosed prey to predatory dragonfly larvae at environmentally relevant concentrations. Dragonfly total mercury concentrations increased proportionally by factors of 2.7 to 4.2 with each doubling of prey methylmercury concentration, responding to dietary treatments in 7–28 days and reaching equilibrium in as little as 40 days, supporting their utility to indicate changing mercury exposure regimes. Dosed dragonflies biomagnified methylmercury by factors of 1.0 ± 0.1 to 3.4 ± 0.2 relative to their prey, and biomagnification efficiency decreased by over 40% for each doubling of prey methylmercury concentration. Dragonfly development had dose-dependent effects on bioaccumulation: mercury concentrations increased with growth and decreased with age in higher exposure treatments, whereas they decreased with growth and increased with age in lower exposure treatments. Bioaccumulation also varied taxonomically; within treatments, mean mercury concentrations for each genus varied up to 10% from family-level means. Dragonfly sex, size, and body condition did not significantly affect mercury concentrations. These results help validate and expand the utility of dragonfly larvae as biosentinels to monitor mercury risk and better protect wildlife and human health.

Oregon↗

Occurrence of pesticides in Oregon coastal waters

Pesticides are used globally for a wide range of applications including agricultural, forestry, roadsides, freshwater systems, and personal use. While pesticides have ensured efficient crop production, they are frequently transported away from application sites and are found in almost all terrestrial and aquatic environments. Pesticides are frequently detected in watersheds and rivers, but there is limited research on pesticide presence in United States (U.S.) marine environments. To address these data gaps, this study documents pesticide occurrence in U.S. coastal waters, providing new understanding of pesticide contamination in offshore environments. Polar organic chemical integrative samples (POCIS) were deployed at five sites along the Oregon, U.S. coast to examine the occurrence of pesticides. Between two and seven different pesticides were detected at every site, with herbicides diuron, and atrazine, and fungicides carbendazim, propiconazole, and tebuconazole being the most frequently detected at three sites. The prevalence of herbicides and fungicides in coastal waters indicates a connection between terrestrial pesticide practices and marine contamination. These findings provide new insights into the presence of pesticides in coastal nearshore and offshore waters and suggest that a comprehensive monitoring effort could enhance our understanding of sources, transport, and pesticide risks for marine species both nearshore and offshore.

Oregon↗

Fate and effects to the benthic community of a copper treatment to eradicate invasive mussels in a large western river, USA

Copper-based chemical treatments are commonly used to eradicate invasive mussels in small ponds and lakes, but their use in large rivers has been limited. In 2023, in response to a detection of invasive quagga mussels, a 10-km reach of the Snake River (Idaho, USA), was treated with an unprecedented 19,300 kg of chelated copper molluscicide to a target concentration of 1,000 µg/L for 10 days. We assessed the transport and fate of the copper and its exposure and effects on the nontarget benthic community downstream. Water samples were collected at seven locations throughout the treatment period, and sediment, periphyton, and benthic macroinvertebrates were collected pre- and posttreatment. Nearly half of the original mass of copper was removed from the water column via sedimentation, sorption to algae, or biological uptake within the 10-km treatment reach and the first 15 km downstream. Even so, dissolved copper concentrations exceeded the acute toxicity threshold at least as far as 28 km downstream for more than 2 weeks. Sediment copper increased by up to 8.3-fold, exceeding the consensus-based sediment quality threshold effect concentration at several sites. Effects on benthic macroinvertebrates varied by taxa. From 0–28 km downstream, invertebrate abundances decreased 52%–94%, with gastropods among the most affected. Of the unique taxa present at these sites pretreatment, 52%–64% were not found posttreatment but were replaced by other taxa, indicating a reorganization of the base of the food web. Additionally, from 0–15 km downstream, the percentage of individuals from tolerant taxa increased two to15-fold. Findings from this study can help watershed managers plan future invasive mussel responses while protecting culturally, economically, and ecologically important nontarget species in large rivers.

Idaho↗

Pesticide concentrations in multiple physical and biological stream matrices are impacted by a bioenergy production facility receiving pesticide coated corn seeds

Insecticide and fungicide seed coatings have become prevalent in conventional agriculture in recent decades. From 2015 to 2021, the AltEn bioenergy plant (Mead, Nebraska, USA) generated ethanol from almost 100% unused/expired treated corn seeds. This use of these seeds for ethanol production resulted in the accumulation of large amounts of contaminated wastewater and solid residue, a portion of which was applied to surrounding farmland. To better understand the potential long-term environmental effects from the processing of treated seeds at this facility, five nearby stream sites were sampled in 2022 after the closure of the plant; these included two sites directly impacted by AltEn, one upstream, and two downstream of the impacted sites. Water and sediment were collected in March through July, and algae and fish samples were collected in July for chemical analysis. Overall, 60 pesticide compounds (parents and transformation products) were detected in one or more matrices, including 23 fungicides, 20 insecticides, 16 herbicides, and 1 bacterial growth inhibitor. Pesticide results (maximum detection frequency, maximum concentration) varied substantially by environmental compartment: water (100% multiple pesticides; 4,600 ng L −1 thiamethoxam transformation product (NOA-407475)), algae (100% multiple pesticides, 190 ng g −1 atrazine), sediment (60% dithiopyr, 2.3 ng g −1 acetochlor) and fish (20% pyraclostrobin, 2.2 ng g −1 atrazine). Pesticides associated with treated corn seeds (e.g., insecticides clothianidin, thiamethoxam; fungicides fluoxastrobin, thiabendazole) were detected at significantly higher concentrations ( p < 0.05) in stream water from sites impacted by the AltEn facility compared to non-impacted sites. Study results indicate that pesticides associated with the AltEn facility continue to be a source of contaminants to aquatic systems after the plant’s closure in 2021.

Environmental Toxicology and Chemistry↗

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↗

Bioaccumulation and trophic transfer of selenium in a large oligotrophic river

In flowing waters with elevated selenium concentrations, fish are often considered to be at risk from selenium toxicity owing to dietary exposure and accumulation in ovary tissues and subsequent deformities in developing larvae. We studied selenium throughout components of the aquatic food webs at geomorphically distinct locations along the oligotrophic Kootenai River (Montana and Idaho, USA), a river with moderately elevated dissolved selenium concentrations (~ 1 µg/L). Components included water, sediment, freshly accrued biofilms, in-situ periphyton, sestonic detritus, aquatic invertebrates, and fish, with spring and fall sampling. Selenium concentrations were similar among the sediment, biofilm, periphyton, and detritus samples with most concentrations ranging between 0.5 to 2.0 (mg/kg dry weight (dw)). Among the aquatic invertebrates, the highest selenium concentrations were observed in Paraleptophlebia sp. mayflies (>15 mg/kg dw) and oligochaetes (>30 mg/kg dw). Selenium in chironomids was higher in the spring than fall, but otherwise, no consistent concentration patterns with season or feeding traits were observed. Fish tissue selenium concentrations were highly variable among species and tissue type. Selenium in fish tissues tended to be highest in livers of rainbow trout and mountain whitefish relative to egg/ovary, muscle, and carcass tissue. With northern pikeminnow, redside shiner, and slimy sculpin, selenium concentrations tended to be highest in ovary tissues. For example, selenium in rainbow trout livers ranged from an average (range) of 37 (4.5 to 151) compared to 8.7 (2.7 to 12.3) in northern pikeminnow livers. Egg/ovary concentrations ranged from a high of 26 (10.7 to 64) in redside shiner in contrast to 12.2 (6.9 to 17) mg/kg dw in slimy sculpin. A drawback of the fish-tissue approach to monitoring and managing selenium risks in freshwaters is the need to kill multiple fish per site and event. Potential alternative monitoring approaches are illustrated using aquatic invertebrates or using the food web monitoring results to derive monitoring targets for selenium in water or invertebrate tissue that could avoid the need to kill fish to assess whether fish protection guidelines are met.

Idaho, Montana↗

Targeted quantitation of 6ppd-quinone in fish tissue samples with liquid chromatography-tandem mass spectrometry

The tire additive transformation product N -(1,3-dimethylbutyl)- N’ -phenyl- p -phenylenediamine-quinone (6PPD-quinone) has recently garnered global attention due to its acute toxicity to some salmonids, such as coho salmon ( Oncorhynchus kisutch ), and its ubiquitous presence in urban stormwater systems. In the present study, we developed and compared the extraction efficiency of two sample preparation methodologies for quantification of 6PPD-quinone among two fish tissue sample types that included fillet of smallmouth bass ( Micropterus dolomieu ) and whole-body samples of O. kisutch fry subjected to in vivo exposure tests with 6PPD-quinone. The two sample preparation methods tested included an accelerated solvent extraction (ASE) approach and a sonication extraction approach. Both sample preparation methods included identical purification steps for the crude sample extracts with enhanced matrix removal cartridges. The purified sample extracts were subjected to targeted analysis of 6PPD-quinone using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The results showed that extractions made with the reported ASE method demonstrated significantly higher absolute recovery (80–96%) of the extracted internal standard, [ 13 C 6 ]-6PPD-quinone, than sonication-based extractions (74–80%) in both fish tissue sample types. The proposed ASE method shows acceptable limits of quantification (0.37–0.67 ng g −1 ), linearity (R 2 > 0.996), and repeatability (RSD ≤ 9%). This work advances research capabilities for investigations on the toxicokinetic processes of 6PPD-quinone in biological samples.

Environmental Toxicology and Chemistry↗

Pyrethroid insecticides implicated in mass mortality of monarch butterflies at an overwintering site in California

Since the 1980s, monarch butterfly ( Danaus plexippus plexippus ) populations across North America have declined by 80–95%. Although several studies have implicated pesticides as a contributing factor to their population declines, our understanding of monarch exposure levels in nature remains limited. In January 2024, a mass mortality event near an overwintering site in Pacific Grove, California, USA, provided an opportunity to analyze dead overwintering monarch butterflies for pesticide residues. Ten recently deceased butterflies were collected and analyzed using liquid and gas chromatography with tandem mass spectrometry (LC-MS/MS and GC-MS/MS). We identified a total of 15 pesticides and associated metabolites in the butterflies, including 8 insecticides (plus 1 associated metabolite), 2 herbicides (plus 2 associated metabolites), and 2 fungicides. On average, each monarch butterfly contained 7 pesticides, excluding transformation products if the parent compound was also detected. Notably, three pyrethroid insecticides—bifenthrin, cypermethrin, and permethrin—were consistently detected at or near each chemical’s lethal dose (LD 50 ). Bifenthrin and cypermethrin were found in every sample, while permethrin was present in all but two samples. The average concentrations of these insecticides were 451.9 ng/g dry weight (dw) for bifenthrin, 646.9 ng/g dw for cypermethrin, and 337.1 ng/g dw for permethrin. These findings demonstrate pesticide contamination in monarch butterflies, including within urban areas, and highlight the risks pesticides, especially insecticides, pose to monarch populations. Additional measures may be required to safeguard this species from pesticide exposure, particularly near aggregation locations, such as overwintering sites in coastal California.

California↗

Ecotoxicological effects of crude oil to early life stage Danio rerio: A molecular, morphological and behavioral approach focused on swim bladder development

Proper development and inflation of the swim bladder is essential for swimming and foraging behavior in fish. To characterize the effects of the Brazilian oil spill that occurred between 2019 and 2020 to early life stage fish, the expression of genes involved in swim bladder development were targeted, with biochemical assays, morphology, and behavior assessed. The swim bladder was focused on due to recent findings of being a target of polycyclic aromatic hydrocarbons (PAHs) present in oil. Zebrafish ( Danio rerio ) were exposed to oil water accommodated fractions at concentrations measured following the spill, 1.12–71.8 total PAHs (μg-ΣPAHt L −1 ). Larvae exposed to 4.49 and 17.9 μg-ΣPAHt L −1 had a downregulation in swim bladder development genes hb9 , sox2 , has2 , and elovl1a at 48 hr postfertilization (hpf). Downregulation in these genes was associated with a high frequency of uninflated swim bladders at 96 and 168 hpf, with uninflated swim bladders detected in 100% of 96 to 168 hpf larvae exposed to 35.9 and 71.8 μg-ΣPAHt L −1 . Superoxide dismutase and catalase levels were inhibited in larvae exposed to 1.12 and 2.24 μg-ΣPAHt L −1 , respectively. There was an increase in glutathione-S-transferase and glutathione levels in exposed larvae. Average swimming speed and distance were reduced in larvae exposed to 1.12 μg-ΣPAHt L −1 . This suggests that complex mixtures of PAHs from crude oil can inhibit the transcription of genes involved in swim bladder tissue development and proper swim-up behavior, which may have implications for the viability and success of developing larvae, affecting recruitment.

Environmental Toxicology and Chemistry↗

Evaluation of the effects of sediments contaminated by industrial discharges to a unionid mussel (Fatmucket, Lampsilis siliquoidea) and a common test benthic organism (Amphipod, Hyalella azteca)

Freshwater mussels are among the most sensitive species to a variety of chemicals in water exposures. However, few studies have been conducted to evaluate the effect of toxicants in sediments on mussels. Industrial discharges containing polyaromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), and metals entered the Kanawha River surrounding Blaine Island, South Charleston, West Virginia, USA; a river which supports eight federally endangered mussel species. We collected sediment samples from a highly contaminated site, a nearby upstream site, and a further upstream reference site to assess the effects of contaminated sediment on the survival and growth of a unionid mussel (fatmucket, Lampsilis siliquoidea ) and a commonly tested benthic organism (amphipod, Hyalella azteca ) using standard 28-d sediment toxicity tests. We also determined mussel toxicity in a serial dilution of the highly contaminated sediment. Results showed that concentrations of PAHs, VOCs, and metals in the contaminated sediment were consistently greater than the other two sites. The mean survival of mussels and amphipods in the reference sediment was 100% and 95%, respectively, whereas the mean survival of both test species in the contaminated sediment was 0%. In the sediment dilution study, mean survival and biomass of mussels in the ≥6.25% treatment were significantly reduced relative to the control, with a 25% inhibition concentration of 4.1% for survival and 3.6% for biomass. We used sediment screening values and equilibrium partitioning sediment benchmarks to determine that nickel, mercury, and PAH mixture were likely responsible for the toxicity observed to mussels and amphipods and will provide critical data to identify and mitigate the sources of the mixture in contaminated sediment.

West Virginia↗

Tree swallows as indicators of per- and polyfluoroalkyl substance exposure and effects at select Department of Defense sites along the East Coast and at sites with different sources in the Upper Midwest, United States

Questions remain about the distribution of per- and polyfluoroalkyl substances (PFAS) in the environment, the sources and movement within and between ecosystems, and whether there are effects from such exposure. Information from the Upper Midwest and the mid-Atlantic regions of the United States, which have different PFAS sources, were investigated. Concentrations of Total 40 (sum of 40 PFAS), perfluorooctane sulfonate, perfluorohexane sulfonate, and Total 13 (sum of 13 PFAS) were consistently higher, by as much as a factor of 40, in tree swallow ( Tachycineta bicolor ) tissue samples (eggs, nestlings, and diet) at sites along the East Coast, where aqueous film-forming foams (AFFF) were extensively used when compared with East Coast reference sites. Sites in the Upper Midwest, with other PFAS sources, had qualitatively lower concentrations of PFAS than AFFF source sites. Perfluorooctane sulfonate was the only PFAS detected in all samples. Concentrations of most other PFAS, such as the carboxylates and fluorotelomers, did not differ between AFFF and reference sites. Perfluorohexane sulfonate, the second-most common constituent of some legacy AFFF formulations, was <1% of Total 40 at the reference sites in eggs and nestlings, but perfluorohexane sulfonate represented up to 9.7% (eggs) and 9.0% (nestlings) at AFFF-influenced sites. Despite differences in PFAS exposure, the daily probability of egg and nestling survival, as well as haptoglobin-like activity (PIT54) and total immunoglobulin Y, was similar across all sites. There were also no significant associations between these end points and concentrations of Total 40 or individual PFAS in eggs or nestlings.

East Coast, Upper Midwest↗

Effects of dietary selenium on the amphipod Hyalella azteca and the midge Chironomus dilutus

Chronic selenium (Se) water quality criteria are based primarily on dietary organoselenium exposure and subsequent reproductive effects in fish. Available chronic Se toxicity data suggests that invertebrates are less sensitive than fish, but chronic invertebrate studies are limited. We evaluated yeast-based diets for chronic toxicity studies with Hyalella azteca and Chironomus dilutus. Growth and survival were similar among C. dilutus fed a yeast-only diet, a mixture of yeast and fish flake food, and a mixture of yeast and diatoms. Survival and growth of H. azteca were best in the yeast + diatom diet, so this diet was used for subsequent tests. In rangefinder tests, H. azteca 28-day survival, growth, and biomass, and C. dilutus 11-day survival were all significantly reduced at a dietary Se concentration of 49 µg/g dry weight, whereas C. dilutus growth and biomass were only affected at 200 µg/g dry weight Se. H. azteca had similar sensitivity to dietary Se in a 28–42-day chronic test—survival, growth, and biomass were significantly reduced at 44.5 µg/g dry weight Se. Dietary selenium reduced H. azteca reproduction by 75%–100% relative to Controls, but differences were not significant. Tissue Se EC10s were lower for H. azteca (9.0–23 µg/g dry weight) than for C. dilutus (11–56 µg/g dry weight). However, model evaluations suggest that the C. dilutus 11-day survival and H. azteca 42-day EC10s were less reliable than other endpoints. When tissue EC10s were converted to equivalent Se concentrations in fish tissue with a food web model, H. azteca (18 µg/g dry weight) and C . dilutus (68 µg/g dry weight) ranked 6th and 12th of 13 freshwater genera, respectively. Overall, these results suggest that the current U.S. Environmental Protection Agency tissue-based Se water quality criteria would be protective for fish and invertebrates and could be used for management of fishless waters.

Environmental Toxicology and Chemistry↗

Predictors of mercury and pesticide fluxes by emerging adult aquatic insects from prairie pothole wetlands

Aquatic and terrestrial food webs are linked by movements of aquatic insects during their development from larvae to adults. Contaminants can affect these linkages by reducing insect survival and increasing tissue contaminant concentrations through adult metamorphosis, thus changing contaminant flux from water to land. Most anthropogenically influenced freshwater ecosystems are exposed to multiple contaminants. To better understand the combined effects of contaminants on aquatic–terrestrial linkages, we investigated how adult aquatic insect emergence and tissue contaminant concentrations affect insect-mediated contaminant flux of mercury and pesticides from wetlands. In a field survey of 15 wetlands in the Prairie Pothole Region, an important agricultural region of North America, we found that insect-mediated mercury flux was 3.5 times more strongly predicted by emergence biomass than tissue mercury concentration. Thus, factors that were previously found to influence aquatic insect emergence biomass in this system—including insecticide tissue concentrations in adult insects, open water surface area, and agricultural land use—were the most likely to drive insect-mediated mercury flux. Pesticide flux, however, was 3.3 times more strongly predicted by the tissue pesticide concentration than by emergence. Thus, factors that influence pesticide exposure and, to a smaller extent, emergence biomass were the most likely to drive pesticide flux. Our results show how factors driving contaminant fluxes by adult aquatic insects differ by contaminant class, and they suggest one mechanism by which toxic effects of one contaminant (pesticides) could influence the flux of another (mercury). Predicting contaminant fluxes in areas where different mixtures of contaminants are present can aid in identifying risk to insectivores.

Prairie Pothole Region↗

Accumulation of per- and polyfluoroalkyl substances (PFAS) and their association with immune parameters in nestling ospreys (Pandion haliaetus) from Chesapeake and Delaware Bays, USA

Per- and polyfluoroalkyl substances (PFAS) are a class of widespread, environmentally persistent compounds that pose a potential threat to wildlife and human health. Despite recent efforts to reduce the use of long-chain PFAS in industrial practices and commercial/consumer products, the persistence and solubility of PFAS have led to their detection in wildlife on a global scale. Osprey ( Pandion haliaetus ) have long been used as a sentinel species with an extensive history of serving as an effective bioindicator of contamination. Here we report on a large-scale evaluation of PFAS and potential health effects in osprey from the Chesapeake and Delaware Bays, USA. In 2011 and 2015, we collected plasma samples from osprey nestlings throughout the Chesapeake and Delaware Bay watersheds. We quantified 40 PFAS congeners in osprey plasma via liquid chromatography-mass spectrometry and analyzed plasma for indicators of immune and thyroid function, and plasma biochemistry. In all birds, perfluorooctanesulfonic acid (PFOS) was the most commonly detected PFAS, followed by perfluoroundecanoic acid, (PFUnA) and perfluorodecanoic acid (PFDA). In nestling plasma from Chesapeake Bay, PFOS tended to be a higher average contributor to PFAS profiles compared to samples from Delaware Bay. In contrast, long-chain perfluoroalkyl carboxylic acids (PFCAs) such as PFUnA and PFDA comprised larger percentages of total PFAS in osprey plasma from Delaware Bay relative to Chesapeake Bay. While some PFAS concentrations were associated with plasma health indicators, the proportion of variation explained was low. Overall, our study provides a more thorough understanding of PFAS presence in the Chesapeake and Delaware Bays and is one of the first to examine whether PFAS exposure is associated with adverse health effects in wildlife.

Chesapeake and Delaware Bays↗

Using organic compounds and salt mixtures to investigate potential mechanisms of major ion toxicity to the mayfly Neocloeon triangulifer

Field assessments and laboratory studies have demonstrated that mayflies (Ephemeroptera) are relatively sensitive to increased concentrations of major geochemical ions (Na + , Ca 2+ , Mg 2+ , K + , Cl − , SO 4 2− , HCO 3 − /CO 3 2- ), but much remains to be learned about potential mechanisms of toxicity. In the present study, we sought to determine whether solution osmolarity is sufficient to predict the toxic effects of major ions to a mayfly, Neocloeon triangulifer . We further investigated whether binary mixtures of major ion salts with common cations or common anions provide evidence of concentration addition or independent action, potentially illuminating toxicity drivers for this species. Finally, we sought to determine if there are mechanisms for major ion toxicity to mayflies that are comparable to those for other species. The toxicity of single salts showed a Ca-dependent correlation with the total component concentration (the sum of individual ion concentrations, a close correlate of osmolarity), but the effect concentrations were well below those causing toxicity from mannitol (presumed to have only an osmotic effect), suggesting that a general osmotic effect is not responsible for major ion toxicity in this species. The mixture experiments consistently indicated additive toxicity and consistency with the relationship to total component concentration, which supports a single toxic mechanism and thus no evidence for ion-specific mechanisms, as reported for other species. Given the lack of evidence of ion-specific toxicity, the total component metric is likely useful for a broad range of ionic compositions.

Environmental Toxicology and Chemistry↗

Temperature influences on water permeability and chlorpyrifos uptake in aquatic insects with differing respiratory strategies

Aquatic insects have evolved diverse respiratory strategies that range from breathing atmospheric air to breathing dissolved oxygen. These strategies result in vast morphological differences among taxa in terms of exchange epithelial surface areas that are in direct contact with the surrounding water that, in turn, affect physiological processes. This paper examines the effects of acute temperature shifts on water permeability and chlorpyrifos uptake in aquatic insects with different respiratory strategies. While considerable differences existed in water permeability among the species tested, acute temperature shifts raised water influx rates similarly in air-breathing and gill-bearing taxa. This contrasts significantly with temperature-shift effects on chlorpyrifos uptake. Temperature shifts of 4.5??C increased 14C-chlorpyrifos accumulation rates in the gill-bearing mayfly Cinygma sp. and in the air-breathing hemipteran Sigara washingtonensis. However, the temperature-induced increase in 14C-chlorpyrifos uptake after 8 h of exposure was 2.75-fold higher in Cinygma than in Sigara. Uptake of 14C-chlorpyrifos was uniformly higher in Cinygma than in Sigara in all experiments. These findings suggest that organisms with relatively large exchange epithelial surface areas are potentially more vulnerable to both osmoregulatory distress as well as contaminant accumulation. Temperature increases appear more likely to impact organisms that have relatively large exchange epithelial surface areas, both as an individual stressor and in combination with additional stressors such as contaminants.

Environmental Toxicology and Chemistry↗