Chronic Engineered Nanoparticle Additions Alter Insect Emergence and Result in Metal Flux from Aquatic Ecosystems into Riparian Food Webs.

Freshwater ecosystems are exposed to engineered nanoparticles (NPs) through discharge from wastewater and agricultural runoff. We conducted a 9-month mesocosm experiment to examine the combined effects of chronic NP additions on insect emergence and insect-mediated contaminant flux to riparian spiders. Two NPs (copper, gold, plus controls) were crossed by two levels of nutrients in 18 outdoor mesocosms open to natural insect and spider colonization. We collected adult insects and two riparian spider genera, Tetragnatha and Dolomedes, for 1 week on a monthly basis. We estimated a significant decrease in cumulative insect emergence of 19% and 24% after exposure to copper and gold NPs, irrespective of nutrient level. NP treatments led to elevated copper and gold tissue concentrations in adult insects, which resulted in terrestrial fluxes of metals. These metal fluxes were associated with increased gold and copper tissue concentrations for both spider genera. We also observed about 25% fewer spiders in the NP mesocosms, likely due to reduced insect emergence and/or NP toxicity. These results demonstrate the transfer of NPs from aquatic to terrestrial ecosystems via emergence of aquatic insects and predation by riparian spiders, as well as significant reductions in insect and spider abundance in response to NP additions.

Copper and Gold Nanoparticles Increase Nutrient Excretion Rates of Primary Consumers.

Freshwater ecosystems are exposed to engineered nanoparticles through municipal and industrial wastewater-effluent discharges and agricultural nonpoint source runoff. Because previous work has shown that engineered nanoparticles from these sources can accumulate in freshwater algal assemblages, we hypothesized that nanoparticles may affect the biology of primary consumers by altering the processing of two critical nutrients associated with growth and survivorship, nitrogen and phosphorus. We tested this hypothesis by measuring the excretion rates of nitrogen and phosphorus of Physella acuta, a ubiquitous pulmonate snail that grazes heavily on periphyton, exposed to either copper or gold engineered nanoparticles for 6 months in an outdoor wetland mesocosm experiment. Chronic nanoparticle exposure doubled nutrient excretion when compared to the control. Gold nanoparticles increased nitrogen and phosphorus excretion rates more than copper nanoparticles, but overall, both nanoparticles led to higher consumer excretion, despite contrasting particle stability and physiochemical properties. Snails in mesocosms enriched with nitrogen and phosphorus had overall higher excretion rates than ones in ambient (no nutrients added) mesocosms. Stimulation patterns were different between nitrogen and phosphorus excretion, which could have implications for the resulting nutrient ratio in the water column. These results suggest that low concentrations of engineered nanoparticles could alter the metabolism of consumers and increase consumer-mediated nutrient recycling rates, potentially intensifying eutrophication in aquatic systems, for example, the increased persistence of algal blooms as observed in our mesocosm experiment.

Differential Reactivity of Copper- and Gold-Based Nanomaterials Controls Their Seasonal Biogeochemical Cycling and Fate in a Freshwater Wetland Mesocosm.

Reliable predictions of the environmental fate and risk of engineered nanomaterials (ENMs) require a better understanding of ENM reactivity in complex, biologically active systems for chronic low-concentration exposure scenarios. Here, simulated freshwater wetland mesocosms were dosed with ENMs to assess how their reactivity and seasonal changes in environmental parameters influence ENM fate in aquatic systems. Copper-based ENMs (Kocide), known to dissolve in water, and gold nanoparticles (AuNPs), stable against dissolution in the absence of specific ligands, were added weekly to mesocosm waters for 9 months. Metal accumulation and speciation changes in the different environmental compartments were assessed over time. Copper from Kocide rapidly dissolved likely associating with organic matter in the water column, transported to terrestrial soils and deeper sediment where it became associated with organic or sulfide phases. In contrast, Au accumulated on/in the macrophytes where it oxidized and transferred over time to surficial sediment. A dynamic seasonal accumulation and metal redox cycling were found between the macrophyte and the surficial sediment for AuNPs. These results demonstrate the need for experimental quantification of how the biological and chemical complexity of the environment, combined with their seasonal variations, drive the fate of metastable ENMs.

Oxidative Potential of Chemical Mixtures Extracted from Contaminated Galveston Bay, TX Seafood Using a Human Cell Co-culture Model.

Increasing levels of pollution in Galveston Bay, TX, are of significant concern for populations that directly depend on fishing activities. Efforts to evaluate contaminant levels in commercial fish have been largely limited to the quantification of chemical mixtures in fish tissue, but little information exists about the toxicological potential of these chemicals on consumption of contaminated seafood. The present study makes use of a human cell co-culture model, mimicking the digestive system, to address the oxidative potential of chemical mixtures in seafood. Chemical extractions were performed on fillets from three fish species and oysters collected from different areas in Galveston Bay. The resulting extracts were used to expose intestinal and liver cells before the measurement of cytotoxicity and activity of antioxidant enzymes. The pesticide 4,4'-DDE was found in nearly all samples from all sites in concentrations ranging from 0.23-9.4 µg/kg. Similarly, total PCBs found in fish and oyster tissue ranged from 0.68-65.65 µg/kg, with PCB-118 being the most common congener measured. In terms of cytotoxicity, oyster extracts led to significant cell mortality, contrary to observations for fish extracts. Antioxidant enzymes, while not directly related to the presence of chemical mixtures in tissue, presented evidence of potential increases in activity from spotted trout extracts. Observations from this study suggest the need to evaluate toxicological aspects of contaminated seafood and support the use of in vitro models for the screening of accumulated chemicals.

Dosing, Not the Dose: Comparing Chronic and Pulsed Silver Nanoparticle Exposures.

The environmental impacts of manufactured nanoparticles are often studied using high-concentration pulse-additions of freshly synthesized nanoparticles, while predicted releases are characterized by chronic low-concentration additions of weathered particles. To test the effects in wetlands of addition rate and nanoparticle speciation on water column silver concentrations, ecosystem impacts, and silver accumulation by biota, we conducted a year-long mesocosm experiment. We compared a pulse addition of Ag0-NPs to chronic weekly additions of either Ag0-NPs or sulfidized silver nanoparticles. The initially high water column silver concentrations in the pulse treatment declined such that after 4 weeks it was lower on average than in the two chronic treatments. While the pulse caused a marked increase in dissolved methane in the first week of the experiment, the chronic treatments had smaller increases in methane concentration that were more prolonged between weeks 28-45. Much like water column silver, most organisms in chronic treatments had comparable silver concentrations to the pulse treatment after only 4 weeks, and all but one organism had similar or higher concentrations than the pulse treatment after one year. Pulse exposures thus both overestimate the intensity of short-term exposures and effects and underestimate the more realistic long-term exposure, ecosystem effects, and accumulation seen in chronic exposures.

Size-Based Differential Transport, Uptake, and Mass Distribution of Ceria (CeO2) Nanoparticles in Wetland Mesocosms.

Trace metals associated with nanoparticles are known to possess reactivities that are different from their larger-size counterparts. However, the relative importance of small relative to large particles for the overall distribution and biouptake of these metals is not as well studied in complex environmental systems. Here, we have examined differences in the long term fate and transport of ceria (CeO2) nanoparticles of two different sizes (3.8 vs 185 nm), dosed weekly to freshwater wetland mesocosms over 9 months. While the majority of CeO2 particles were detected in soils and sediments at the end of nine months, there were significant differences observed in fate, distribution, and transport mechanisms between the two materials. Small nanoparticles were removed from the water column primarily through heteroaggregation with suspended solids and plants, while large nanoparticles were removed primarily by sedimentation. A greater fraction of small particles remained in the upper floc layers of sediment relative to the large particles (31% vs 7%). Cerium from the small particles were also significantly more bioavailable to aquatic plants (2% vs 0.5%), snails (44 vs 2.6 ng), and insects (8 vs 0.07 µg). Small CeO2 particles were also significantly reduced from Ce(IV) to Ce(III), while aquatic sediments were a sink for untransformed large nanoparticles. These results demonstrate that trace metals originating from nanoscale materials have much greater potential than their larger counterparts to distribute throughout multiple compartments of a complex aquatic ecosystem and contribute to the overall bioavailable pool of the metal for biouptake and trophic transfer.

Validation of a Sulfuric Acid Digestion Method for Inductively Coupled Plasma Mass Spectrometry Quantification of TiO2 Nanoparticles.

A consistent analytical method incorporating sulfuric acid (H2SO4) digestion and ICP-MS quantification has been developed for TiO2 quantification in biotic and abiotic environmentally relevant matrices. Sample digestion in H2SO4 at 110°C provided consistent results without using hydrofluoric acid or microwave digestion. Analysis of seven replicate samples for four matrices on each of 3 days produced Ti recoveries of 97% ± 2.5%, 91 % ± 4.0%, 94% ± 1.8%, and 73 % ± 2.6% (mean ± standard deviation) from water, fish tissue, periphyton, and sediment, respectively. The method demonstrated consistent performance in analysis of water collected over a 1 month.

Relative Contributions of Copper Oxide Nanoparticles and Dissolved Copper to Cu Uptake Kinetics of Gulf Killifish (Fundulus grandis) Embryos.

The toxicity of soluble metal-based nanomaterials may be due to the uptake of metals in both dissolved and nanoparticulate forms, but the relative contributions of these different forms to overall metal uptake rates under environmental conditions are not quantitatively defined. Here, we investigated the linkage between the dissolution rates of copper(II) oxide (CuO) nanoparticles (NPs) and their bioavailability to Gulf killifish (Fundulus grandis) embryos, with the aim of quantitatively delineating the relative contributions of nanoparticulate and dissolved species for Cu uptake. Gulf killifish embryos were exposed to dissolved Cu and CuO NP mixtures comprising a range of pH values (6.3-7.5) and three types of natural organic matter (NOM) isolates at various concentrations (0.1-10 mg-C L-1), resulting in a wide range of CuO NP dissolution rates that subsequently influenced Cu uptake. First-order dissolution rate constants of CuO NPs increased with increasing NOM concentration and for NOM isolates with higher aromaticity, as indicated by specific ultraviolet absorbance (SUVA), while Cu uptake rate constants of both dissolved Cu and CuO NP decreased with NOM concentration and aromaticity. As a result, the relative contribution of dissolved Cu and nanoparticulate CuO species for the overall Cu uptake rate was insensitive to NOM type or concentration but largely determined by the percentage of CuO that dissolved. These findings highlight SUVA and aromaticity as key NOM properties affecting the dissolution kinetics and bioavailability of soluble metal-based nanomaterials in organic-rich waters. These properties could be used in the incorporation of dissolution kinetics into predictive models for environmental risks of nanomaterials.

A non-destructive BFCOD assay for in vivo measurement of cytochrome P450 3A (CYP3A) enzyme activity in fish embryos and larvae.

There is increasing interest in quantifying the exposure and effects of anthropogenic contaminants in fish. Determination of exposures in wild fish is routinely performed, but methods to investigate potential effects are less established. One of the most relevant approaches would be the use of in vivo assays, but existing assays are often limited to in vitro determination of enzyme activity. Many pharmaceuticals and some persistent pollutants activate, and are metabolized by cytochrome P4503A (CYP3A), which make it a relevant and desirable target for biomarker research. We altered the established 7-benzyloxy-4-trifluoromethylcoumarin-O-debenzylation (BFCOD) in vitro protocol for CYP3A activity determination, developing a rapid and inexpensive method to measure in vivo (and in ovo) CYP3A activity in two fish systems: Gulf killifish (Fundulus grandis) and zebrafish (Danio rerio) early life stages. Even with very low concentrations of 7-benzyloxy-4-trifluoromethyl coumarin (BFC, 0.06 µM or 20 µg/L), we were able to detect significant induction in CYP3A activity in embryos of F. grandis, as well as in larvae of D. rerio in response to benzo[a]pyrene (BaP) and fluoranthene (FL) exposures. Because of concerns regarding the possible contribution of CYP1A to BFCOD activity from previous research, we have used a CYP1A post-translational inhibitor (FL) in order to calculate the contribution of CYP1A to the BFCOD assay. We also dosed with benzo[k]fluoranthene (BkF) and showed significant induction of CYP1A activity, with no concurrent increase in CYP3A activity. In this paper, we have taken an established in vitro CYP3A activity assay, and utilized the reaction in a novel way to allow for the non-destructive determination of CYP3A. In summary, we describe a sensitive, cheap, fast and easy modified BFCOD assay for in ovo and in vivo determination of CYP3A activity for use in moderate throughput early-life-stage fish experiments.

EROD activity, chromosomal damage, and oxidative stress in response to contaminants exposure in tree swallow (Tachycineta bicolor) nestlings from Great Lakes Areas of Concern.

Tree swallow, Tachycineta bicolor, nestlings were collected from 60 sites in the Great Lakes, which included multiple sites within 27 Areas of Concern (AOCs) and six sites not listed as AOCs from 2010 to 2014. Nestlings, approximately 12 days-of-age, were evaluated for ethoxyresorufin-O-dealkylase (EROD) activity, chromosomal damage, and six measures of oxidative stress. Data on each of these biomarkers were divided into four equal numbered groups from the highest to lowest values and the groups were compared to contaminant concentrations using multivariate analysis. Contaminant concentrations, from the same nestlings, included polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), and 17 elements. Alkylated polycyclic aromatic hydrocarbons (aPAHs) and parent PAHs (pPAHs) were measured in pooled nestling dietary samples. Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and pesticides were measured in sibling eggs. Concentrations of aPAHs, pPAHs, chlordane, dieldrin, heptachlor, and PCBs, in that order, were the major contributors to the significant differences between the lowest and highest EROD activities; PFCs, PBDEs, the remaining pesticides, and all elements were of secondary importance. The four categories of chromosomal damage did not separate out well based on the contaminants measured. Concentrations of aPAHs, pPAHs, heptachlor, PCBs, chlordane, and dieldrin were the major contributors to the significant differences between the lowest and highest activities of two oxidative stress measures, total sulfhydryl (TSH) activity and protein bound sulfhydryl (PBSH) activity. The four categories of thiobarbituric acid reacting substances (TBARS), oxidized glutathione (GSSG), reduced glutathione (GSH), and the ratio of GSSG/GSH did not separate well based on the contaminants measured.

Evolutionary toxicology: Meta-analysis of evolutionary events in response to chemical stressors.

The regulatory decision-making process regarding chemical safety is most often informed by evidence based on ecotoxicity tests that consider growth, reproduction and survival as end-points, which can be quantitatively linked to short-term population outcomes. Changes in these end-points resulting from chemical exposure can cause alterations in micro-evolutionary forces (mutation, drift, selection and gene flow) that control the genetic composition of populations. With multi-generation exposures, anthropogenic contamination can lead to a population with an altered genetic composition, which may respond differently to future stressors. These evolutionary changes are rarely discussed in regulatory or risk assessment frameworks, but the growing body of literature that documents their existence suggests that these important population-level impacts should be considered. In this meta-analysis we have compared existing contamination levels of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) that have been documented to be associated with evolutionary changes in resident aquatic organisms to regulatory benchmarks for these contaminants. The original intent of this project was to perform a meta-analysis on evolutionary events associated with PCB and PAH contamination. However, this effort was hindered by a lack of consistency in congener selection for "total" PCB or PAH measurements. We expanded this manuscript to include a discussion of methods used to determine PCB and PAH total contamination in addition to comparing regulatory guidelines and contamination that has caused evolutionary effects. Micro-evolutionary responses often lead populations onto unique and unpredictable trajectories. Therefore, to better understand the risk of population-wide alterations occurring, we need to improve comparisons of chemical contamination between affected locations. In this manuscript we offer several possibilities to unify chemical comparisons for PCBs and PAHs that would improve comparability among evolutionary toxicology investigations, and with regulatory guidelines. In addition, we identify studies documenting evolutionary change in the presence of PCB and PAH contamination levels below applicable regulatory benchmarks.

Silver toxicity across salinity gradients: the role of dissolved silver chloride species (AgCl x ) in Atlantic killifish (Fundulus heteroclitus) and medaka (Oryzias latipes) early life-stage toxicity.

The influence of salinity on Ag toxicity was investigated in Atlantic killifish (Fundulus heteroclitus) early life-stages. Embryo mortality was significantly reduced as salinity increased and Ag(+) was converted to AgCl(solid). However, as salinity continued to rise (>5 ‰), toxicity increased to a level at least as high as observed for Ag(+) in deionized water. Rather than correlating with Ag(+), Fundulus embryo toxicity was better explained (R(2) = 0.96) by total dissolved Ag (Ag(+), AgCl2 (-), AgCl3 (2-), AgCl4 (3-)). Complementary experiments were conducted with medaka (Oryzias latipes) embryos to determine if this pattern was consistent among evolutionarily divergent euryhaline species. Contrary to Fundulus data, medaka toxicity data were best explained by Ag(+) concentrations (R(2) = 0.94), suggesting that differing ionoregulatory physiology may drive observed differences. Fundulus larvae were also tested, and toxicity did increase at higher salinities, but did not track predicted silver speciation. Alternatively, toxicity began to increase only at salinities above the isosmotic point, suggesting that shifts in osmoregulatory strategy at higher salinities might be an important factor. Na(+) dysregulation was confirmed as the mechanism of toxicity in Ag-exposed Fundulus larvae at both low and high salinities. While Ag uptake was highest at low salinities for both Fundulus embryos and larvae, uptake was not predictive of toxicity.

In situ effects of pesticides on amphibians in the Sierra Nevada.

For more than 20 years, conservationists have agreed that amphibian populations around the world are declining. Results obtained through laboratory or mesocosm studies and measurement of contaminant concentrations in areas experiencing declines have supported a role of contaminants in these declines. The current study examines the effects of contaminant exposure to amphibians in situ in areas actually experiencing declines. Early larval Pseudacris regilla were translocated among Lassen Volcanic, Yosemite and Sequoia National Parks, California, USA and caged in wetlands in 2001 and 2002 until metamorphosis. Twenty contaminants were identified in tadpoles with an average of 1.3-5.9 (maximum = 10) contaminants per animal. Sequoia National Park, which had the greatest variety and concentrations of contaminants in 2001, also had tadpoles that experienced the greatest mortality, slowest developmental rates and lowest cholinesterase activities. Yosemite and Sequoia tadpoles and metamorphs had greater genotoxicity than those in Lassen during 2001, as determined by flow cytometry. In 2001 tadpoles at Yosemite had a significantly higher rate of malformations, characterized as hemimelia (shortened femurs), than those at the other two parks but no significant differences were observed in 2002. Fewer differences in contaminant types and concentrations existed among parks during 2002 compared to 2001. In 2002 Sequoia tadpoles had higher mortality and slower developmental rates but there was no difference among parks in cholinesterase activities. Although concentrations of most contaminants were below known lethal concentrations, simultaneous exposure to multiple chemicals and other stressors may have resulted in lethal and sublethal effects.

Chromosomal damage and EROD induction in tree swallows (Tachycineta bicolor) along the Upper Mississippi River, Minnesota, USA.

The health of tree swallows, Tachycineta bicolor, on the Upper Mississippi River (UMR) was assessed in 2010 and 2011 using biomarkers at six sites downriver of Minneapolis/St. Paul, MN metropolitan area, a tributary into the UMR, and a nearby lake. Chromosomal damage was evaluated in nestling blood by measuring the coefficient of variation of DNA content (DNA CV) using flow cytometry. Cytochrome P450 1A activity in nestling liver was measured using the ethoxyresorufin-O-dealkylase (EROD) assay, and oxidative stress was estimated in nestling livers via determination of thiobarbituric acid reacting substances (TBARS), reduced glutathione (GSH), oxidized glutathione (GSSG), the ratio GSSG/GSH, total sulfhydryl, and protein bound sulfhydryl (PBSH). A multilevel regression model (DNA CV) and simple regressions (EROD and oxidative stress) were used to evaluate biomarker responses for each location. Chromosomal damage was significantly elevated at two sites on the UMR (Pigs Eye and Pool 2) relative to the Green Mountain Lake reference site, while the induction of EROD activity was only observed at Pigs Eye. No measures of oxidative stress differed among sites. Multivariate analysis confirmed an increased DNA CV at Pigs Eye and Pool 2, and elevated EROD activity at Pigs Eye. These results suggest that the health of tree swallows has been altered at the DNA level at Pigs Eye and Pool 2 sites, and at the physiological level at Pigs Eye site only.

Emerging contaminant or an old toxin in disguise? Silver nanoparticle impacts on ecosystems.

The use of antimicrobial silver nanoparticles (AgNPs) in consumer-products is rising. Much of these AgNPs are expected to enter the wastewater stream, with up to 10% of that eventually released as effluent into aquatic ecosystems with unknown ecological consequences. We examined AgNP impacts on aquatic ecosystems by comparing the effects of two AgNP sizes (12 and 49 nm) to ionic silver (Ag(+); added as AgNO3), a historically problematic contaminant with known impacts. Using 19 wetland mesocosms, we added Ag to the 360 L aquatic compartment to reach 2.5 mg Ag L(-1). Silver treatments and two coating controls were done in triplicate, and compared to four replicate controls. All three silver treatments were toxic to aquatic plants, leading to a significant release of dissolved organic carbon and chloride following exposure. Simultaneously, dissolved methane concentrations increased forty-fold relative to controls in all three Ag treatments. Despite dramatic toxicity differences observed in lab studies for these three forms of Ag, our results show surprising convergence in the direction, magnitude, and duration of ecosystem-scale impacts for all Ag treatments. Our results suggest that all forms of Ag changed solute chemistry driving transformations of Ag which then altered Ag impacts.

The Tissue-Specific Eco-Exposome: Differential Pharmaceutical Bioaccumulation and Disposition in Fish among Trophic Positions.

Though bioaccumulation of pharmaceuticals by aquatic organisms continues to receive scientific attention, the internal disposition of these contaminants among different tissue compartments of fish species has been infrequently investigated, particularly among fish at different trophic positions. We tested a human to fish biological read-across hypothesis for contaminant disposition by examining tissue-specific accumulation in three understudied species, longnose gar (Lepisosteus osseus; piscivore), gizzard shad (Dorosoma cepedianum; planktivore/detritivore), and smallmouth buffalo (Ictiobus bubalus; benthivore), from a river influenced by municipal effluent discharge. In addition to surface water, fish plasma, and brain, gill, gonad, liver, and lateral muscle fillet tissues were analyzed via isotope dilution liquid chromatography tandem mass spectrometry. Caffeine and sucralose, two common effluent tracers, were quantitated at low micrograms per liter levels in surface water, while an anticonvulsant, carbamazepine, was observed at levels up to 37 ng/L. The selective serotonin reuptake inhibitors (SSRIs) fluoxetine and sertraline and primary metabolites were detected in at least one tissue of all three species at low micrograms per kilogram concentrations. Within each species, brain and liver of select fish contained the highest levels of SSRIs compared to plasma and other tissues, which is generally consistent with human tissue disposition patterns. However, we observed differential accumulation among specific tissue types and species. For example, mean levels of sertraline in brain and liver tissues were 13.4 µg/kg and 1.5 µg/kg in gizzard shad and 1.3 µg/kg and 7.3 µg/kg in longnose gar, respectively. In contrast, smallmouth buffalo did not consistently accumulate SSRIs to detectable levels. Tissue-specific eco-exposome efforts are necessary to understand mechanisms associated with such marked bioaccumulation and internal dispositional differences among freshwater fish species occupying different trophic positions. Environ Toxicol Chem 2024;43:1894-1902. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Differentiating between point and non-point source nutrient loadings of wastewater in an agriculturally impacted area using a hybrid statistical model.

Nutrient contamination from point and non-point sources can lead to harmful consequences, such as algal blooms. Point and non-point nutrient loading estimation is determined using modeling approaches and often require an abundance of variables and observations for calibration. Small rural streams that lack water use designations often lack available data to utilize current modeling strategies. This study proposes the use of a 3-phase hybrid stepwise statistical modeling approach using generalized linear mixed models (GLMM) and a reference stream. Two streams in Central Texas were sampled for 13 months between February 2020 and February 2021, one being impacted by a wastewater treatment plant (WWTP). Dissolved phosphorus (PO4-P), ammonia (NH3-N), nitrite/nitrate (NO2 + NO3-N), total nitrogen (TN), and total phosphorus (TP) were sampled in both streams for each month. Non-point sources of contamination, such as land use/land cover and geomorphology composition, were quantified for both sub-basin drainage areas. Phase I models predicted nutrient concentrations in the reference stream using non-point source variables along with discharge and temporal variables. Best fit models were carried forward to phase II and leveraged a point-source variable, which is a naïve estimate of effluent nutrient concentration in the absence of assimilation. Phase II model coefficients highlight the significance of point-source contamination in predicting nutrient concentration, but overall lacked the ability to make future predictions under new hydrologic regimes from WWTP intensification. Phase III models included deterministically calculating an uptake variable using the relationship between discharge and wetted widths, predicting background non-point concentrations by leveraging phase I models, and calculating future nutrient loadings from WWTP intensification. This approach predicted significant increases in nutrient concentrations under planned WWTP intensification scenarios and decreased uptake efficiencies under the new hydrologic regimes.

Exposure to and Biomarker Responses From Legacy and Emerging Contaminants Along Three Drainages in the Milwaukee Estuary, Wisconsin, USA.

Legacy contaminants and contaminants of emerging concern (CECs) were assessed in tree swallow (Tachycineta bicolor) tissue and diet samples from three drainages in the Milwaukee estuary, Wisconsin, USA, to understand exposures and possible biomarker responses. Two remote Wisconsin lakes were assessed for comparative purposes. Bioaccumulative classes of contaminants, such as polybrominated diphenyl ethers and per- and polyfluoroalkyl substances, while at higher concentrations than the reference lakes, did not vary significantly among sites or among the three drainages. Polycyclic aromatic hydrocarbons were assessed in diet and sediment and were from primarily pyrogenic sources. Ten biomarkers were assessed relative to contaminant exposure. Polychlorinated biphenyls (PCBs) were elevated above reference conditions at all Milwaukee sites but did not correlate with any measured biomarker responses. Only one site, Cedarburg, just downstream from a Superfund site, had elevated PCBs compared to other sites in the Milwaukee estuary. Few non-organochlorine insecticides or herbicides were detected in tree swallow liver tissue, except for the atrazine metabolite desethylatrazine. Few pharmaceuticals and personal care products were detected in liver tissue except for N,N-diethyl-meta-toluamide, iopamidol, and two antibiotics. The present study is one of the most comprehensive assessments to date, along with the previously published Maumee River data, on the exposure and effects of a wide variety of CECs in birds. Environ Toxicol Chem 2024;43:856-877. © 2024 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Multi-omics responses in tree swallow (Tachycineta bicolor) nestlings from the Maumee Area of Concern, Maumee River, Ohio.

A multi-omics approach was utilized to identify altered biological responses and functions, and to prioritize contaminants to assess the risks of chemical mixtures in the Maumee Area of Concern (AOC), Maumee River, OH, USA. The Maumee AOC is designated by the United States Environmental Protection Agency as having significant beneficial use impairments, including degradation of fish and wildlife populations, bird or animal deformities or reproduction problems, and loss of fish and wildlife habitat. Tree swallow (Tachycineta bicolor) nestlings were collected at five sites along the Maumee River, which included wastewater treatment plants (WWTPs) and industrial land-use sites. Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo p dioxins and furans (PCDD/Fs), and chlorinated pesticide concentrations were elevated in Maumee tree swallows, relative to a remote reference site, Star Lake, WI, USA. Liver tissue was utilized for non-targeted transcriptome and targeted metabolome evaluation. A significantly differentially expressed gene cluster related to a downregulation in cell growth and cell cycle regulation was identified when comparing all Maumee River sites with the reference site. There was an upregulation of lipogenesis genes, such as PPAR signaling (HMGCS2, SLC22A5), biosynthesis of unsaturated fatty acids (FASN, SCD, ELOVL2, and FADS2), and higher lipogenesis related metabolites, such as docosapentaenoic acid (DPA), docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and arachidonic acid (AA) at two industrial land-use sites, Ironhead and Maumee, relative to WWTP sites (Perrysburg and SideCut), and the reference site. Toledo Water, in the vicinity of the other two industrial sites and also adjacent to a WWTP, showed a mix of signals between industrial land-use and WWTP land-use. PAHs, oxychlordane, and PBDEs were determined to be the most likely causes of the differentiation in biological responses, including de novo lipogenesis and biosynthesis of unsaturated fatty acids.

Biotic and abiotic interactions in aquatic microcosms determine fate and toxicity of Ag nanoparticles. Part 1. Aggregation and dissolution.

To better understand their fate and toxicity in aquatic environments, we compared the aggregation and dissolution behavior of gum arabic (GA) and polyvinylpyrrolidone (PVP) coated Ag nanoparticles (NPs) in aquatic microcosms. There were four microcosm types: surface water; water and sediment; water and aquatic plants; or water, sediment, and aquatic plants. Dissolution and aggregation behavior of AgNPs were examined using ultracentrifugation, ultrafiltration, and asymmetrical flow field flow fractionation coupled to ultraviolet-visible spectroscopy, dynamic and static laser light scattering, and inductively coupled plasma mass spectrometry. Plants released dissolved organic matter (DOM) into the water column either through active or passive processes in response to Ag exposure. This organic matter fraction readily bound Ag ions. The plant-derived DOM had the effect of stabilizing PVP-AgNPs as primary particles, but caused GA-AgNPs to be removed from the water column, likely by dissolution and binding of released Ag ions on sediment and plant surfaces. The destabilization of the GA-AgNPs also corresponded with X-ray absorption near edge spectroscopy results which suggest that 22-28% of the particulate Ag was associated with thiols and 5-14% was present as oxides. The results highlight the potential complexities of nanomaterial behavior in response to biotic and abiotic modifications in ecosystems, and may help to explain differences in toxicity of Ag observed in realistic exposure media compared to simplified laboratory exposures.