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Isotopic composition of inorganic mercury and methylmercury downstream of a historical gold mining region

We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ 202 Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ 202 Hg = −0.38 ± 0.17‰ and Δ 199 Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ 202 Hg of MMHg prior to photodegradation (−1.29 to −1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to −0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments.

California

Dietary uptake of Cu sorbed to hydrous iron oxide is linked to cellular toxicity and feeding inhibition in a benthic grazer

Whereas feeding inhibition caused by exposure to contaminants has been extensively documented, the underlying mechanism(s) are less well understood. For this study, the behavior of several key feeding processes, including ingestion rate and assimilation efficiency, that affect the dietary uptake of Cu were evaluated in the benthic grazer Lymnaea stagnalis following 4–5 h exposures to Cu adsorbed to synthetic hydrous ferric oxide (Cu–HFO). The particles were mixed with a cultured alga to create algal mats with Cu exposures spanning nearly 3 orders of magnitude at variable or constant Fe concentrations, thereby allowing first order and interactive effects of Cu and Fe to be evaluated. Results showed that Cu influx rates and ingestion rates decreased as Cu exposures of the algal mat mixture exceeded 10 4 nmol/g. Ingestion rate appeared to exert primary control on the Cu influx rate. Lysosomal destabilization rates increased directly with Cu influx rates. At the highest Cu exposure where the incidence of lysosomal membrane damage was greatest (51%), the ingestion rate was suppressed 80%. The findings suggested that feeding inhibition was a stress response emanating from excessive uptake of dietary Cu and cellular toxicity.

Environmental Science & Technology

High-throughput screening identifies bisphenol P as a potent cardiotoxin, inducing cardiotoxicity through apoptosis and NF-κB Pathway

The increasing use of plastic additives, particularly bisphenols (BPs), has raised significant concerns about their potential risks to human health, especially during critical developmental stages. In this study, we developed a novel high-throughput toxicity screening platform using zebrafish ( Danio rerio ) to identify and prioritize chemicals with cardiotoxic potential, which is based on multidimensional exposure pathways ranging from environmental to human levels. The platform quantitatively assesses heart rate changes based on multilevel exposure pathways (environmental, ecological, and human), effectively prioritizing the most relevant cardiotoxic compounds with potential health risks. Using this platform, we identified bisphenol P (BPP), a widely used substitute for bisphenol A, as a potent cardiotoxic compound. BPP exposure significantly inhibited heart development and function in zebrafish, inducing abnormal heart morphology, reduced heart rate, cardiac output, and hemodynamic disturbances. Additionally, NF-κB signaling pathway analysis, including morpholino knock-down and inhibitor experiments, confirmed that BPP mediates cardiac toxicity by inducing cardiomyocyte apoptosis. Our findings underscore the toxicity that BP substitutes can have, while highlighting the potential of this multidimensional screening platform in evaluating cardiovascular toxicity and guiding future toxicological assessments during critical developmental windows.

Environmental Science & Technology

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

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

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

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

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

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

Amino acid specific stable nitrogen isotope values in avian tissues: Insights from captive American kestrels and wild herring gulls

Through laboratory and field studies, the utility of amino acid compound-specific nitrogen isotope analysis (AA-CSIA) in avian studies is investigated. Captive American kestrels ( Falco sparverius ) were fed an isotopically characterized diet and patterns in δ 15 N values of amino acids (AAs) were compared to those in their tissues (muscle and red blood cells) and food. Based upon nitrogen isotope discrimination between diet and kestrel tissues, AAs could mostly be categorized as source AAs (retaining baseline δ 15 N values) and trophic AAs (showing 15 N enrichment). Trophic discrimination factors based upon the source (phenylalanine, Phe) and trophic (glutamic acid, Glu) AAs were 4.1 (muscle) and 5.4 (red blood cells), lower than those reported for metazoan invertebrates. In a field study involving omnivorous herring gulls ( Larus argentatus smithsonianus ), egg AA isotopic patterns largely retained those observed in the laying female’s tissues (muscle, red blood cells, and liver). Realistic estimates of gull trophic position were obtained using bird Glu and Phe δ 15 N values combined with β values (difference in Glu and Phe δ 15 N in primary producers) for aquatic and terrestrial food webs. Egg fatty acids were used to weight β values for proportions of aquatic and terrestrial food in gull diets. This novel approach can be applied to generalist species that feed across ecosystem boundaries.

Environmental Science & Technology

Mercury bioaccumulation in estuarine fishes: Novel insights from sulfur stable isotopes

Estuaries are transitional habitats characterized by complex biogeochemical and ecological gradients that result in substantial variation in fish total mercury concentrations (THg). We leveraged these gradients and used carbon (δ 13 C), nitrogen (δ 15 N), and sulfur (δ 34 S) stable isotopes to examine the ecological and biogeochemical processes underlying THg bioaccumulation in fishes from the San Francisco Bay Estuary. We employed a tiered approach that first examined processes influencing variation in fish THg among wetlands, and subsequently examined the roles of habitat and within-wetland processes in generating larger-scale patterns in fish THg. We found that δ 34 S, an indicator of sulfate reduction and habitat specific-foraging, was correlated with fish THg at all three spatial scales. Over the observed ranges of δ 34 S, THg concentrations in fish increased by up to 860% within wetlands, 560% among wetlands, and 291% within specific impounded wetland habitats. In contrast, δ 13 C and δ 15 N were not correlated with THg among wetlands and were only important in low salinity impounded wetlands, possibly reflecting more diverse food webs in this habitat. Together, our results highlight the key roles of sulfur biogeochemistry and ecology in influencing estuarine fish THg, as well as the importance of fish ecology and habitat in modulating the relationships between biogeochemical processes and Hg bioaccumulation.

California

Metamorphosis affects metal concentrations and isotopic signatures in a mayfly ( Baetis tricaudatus ): Implications for the aquatic-terrestrial transfer of metals

Insect metamorphosis often results in substantial chemical changes that can alter contaminant concentrations and fractionate isotopes. We exposed larval mayflies ( Baetis tricaudatus ) and their food (periphyton) to an aqueous zinc gradient (3-340 µg Zn/l) and measured zinc concentrations at different stages of metamorphosis: larval, subimago, and imago. We also measured changes in stable isotopes (δ 15 N and δ 13 C) in unexposed mayflies. Larval zinc concentrations were positively related to aqueous zinc, increasing 9-fold across the exposure gradient. Adult zinc concentrations were also positively related to aqueous zinc, but were 7-fold lower than larvae. This relationship varied according to adult substage and sex. Tissue concentrations in female imagoes were not related to exposure concentrations, but the converse was true for all other stage-by-sex combinations. Metamorphosis also increased δ 15 N by ~0.8‰, but not δ 13 C. Thus, the main effects of metamorphosis on insect chemistry were large declines in zinc concentrations coupled with increased δ 15 N signatures. For zinc, this change was largely consistent across the aqueous exposure gradient. However, differences among sexes and stages suggest that caution is warranted when using nitrogen isotopes or metal concentrations measured in one insect stage (e.g. larvae) to assess risk to wildlife that feed on subsequent life stages (e.g. adults).

Environmental Science & Technology

Neutron scattering measurements of carbon dioxide adsorption in pores within the Marcellus Shale: Implications for sequestration

Shale is an increasingly viable source of natural gas and a potential candidate for geologic CO 2 sequestration. Understanding the gas adsorption behavior on shale is necessary for the design of optimal gas recovery and sequestration projects. In the present study neutron diffraction and small-angle neutron scattering measurements of adsorbed CO 2 in Marcellus Shale samples were conducted on the Near and InterMediate Range Order Diffractometer (NIMROD) at the ISIS Pulsed Neutron and Muon Source, STFC Rutherford Appleton Laboratory along an adsorption isotherm of 22 °C and pressures of 25 and 40 bar. Additional measurements were conducted at approximately 22 and 60 °C at the same pressures on the General-Purpose Small-Angle Neutron Scattering (GP-SANS) instrument at Oak Ridge National Laboratory. The structures investigated (pores) for CO 2 adsorption range in size from Å level to ∼50 nm. The results indicate that, using the conditions investigated densification or condensation effects occurred in all accessible pores. The data suggest that at 22 °C the CO 2 has liquid-like properties when confined in pores of around 1 nm radius at pressures as low as 25 bar. Many of the 2.5 nm pores, 70% of 2 nm pores, most of the <1 nm pores, and all pores <0.25 nm, are inaccessible or closed to CO 2 , suggesting that despite the vast numbers of micropores in shale, the micropores will be unavailable for storage for geologic CO 2 sequestration.

Environmental Science & Technology

Unconventional oil and gas spills: Risks, mitigation priorities, and state reporting requirements

Rapid growth in unconventional oil and gas (UOG) has produced jobs, revenue, and energy, but also concerns over spills and environmental risks. We assessed spill data from 2005 to 2014 at 31 481 UOG wells in Colorado, New Mexico, North Dakota, and Pennsylvania. We found 2–16% of wells reported a spill each year. Median spill volumes ranged from 0.5 m 3 in Pennsylvania to 4.9 m 3 in New Mexico; the largest spills exceeded 100 m 3 . Seventy-five to 94% of spills occurred within the first three years of well life when wells were drilled, completed, and had their largest production volumes. Across all four states, 50% of spills were related to storage and moving fluids via flowlines. Reporting rates varied by state, affecting spill rates and requiring extensive time and effort getting data into a usable format. Enhanced and standardized regulatory requirements for reporting spills could improve the accuracy and speed of analyses to identify and prevent spill risks and mitigate potential environmental damage. Transparency for data sharing and analysis will be increasingly important as UOG development expands. We designed an interactive spills data visualization tool ( http://snappartnership.net/groups/hydraulic-fracturing/webapp/spills.html ) to illustrate the value of having standardized, public data.

Environmental Science & Technology

Acetylene fuels TCE reductive dechlorination by defined Dehalococcoides / Pelobacter consortia

Acetylene (C 2 H 2 ) can be generated in contaminated groundwater sites as a consequence of chemical degradation of trichloroethene (TCE) by in situ minerals, and C 2 H 2 is known to inhibit bacterial dechlorination. In this study, we show that while high C 2 H 2 (1.3 mM) concentrations reversibly inhibit reductive dechlorination of TCE by Dehalococcoides mccartyi isolates as well as enrichment cultures containing D. mccartyi sp., low C 2 H 2 (0.4 mM) concentrations do not inhibit growth or metabolism of D. mccartyi . Cocultures of Pelobacter SFB93, a C 2 H 2 -fermenting bacterium, with D. mccartyi strain 195 or with D. mccartyi strain BAV1 were actively sustained by providing acetylene as the electron donor and carbon source while TCE or cis -DCE served as the electron acceptor. Inhibition by acetylene of reductive dechlorination and methanogenesis in the enrichment culture ANAS was observed, and the inhibition was removed by adding Pelobacter SFB93 into the consortium. Transcriptomic analysis of D. mccartyi strain 195 showed genes encoding for reductive dehalogenases (e.g., tceA ) were not affected during the C 2 H 2 -inhibition, while genes encoding for ATP synthase, biosynthesis, and Hym hydrogenase were down-regulated during C 2 H 2 inhibition, consistent with the physiological observation of lower cell yields and reduced dechlorination rates in strain 195. These results will help facilitate the optimization of TCE-bioremediation at contaminated sites containing both TCE and C 2 H 2 .

Environmental Science & Technology

Assessing the dietary bioavailability of metals associated with natural particles: Extending the use of the reverse labeling approach to zinc

We extend the use of a novel tracing technique to quantify the bioavailability of zinc (Zn) associated with natural particles using snails enriched with a less common Zn stable isotope. Lymnaea stagnalis is a model species that has relatively fast Zn uptake rates from the dissolved phase, enabling their rapid enrichment in 67 Zn during the initial phase of labeling. Isotopically enriched snails were subsequently exposed to algae mixed with increasing amounts of metal-rich particles collected from two acid mine drainage impacted rivers. Zinc bioavailability from the natural particles was inferred from calculations of 66 Zn assimilation into the snail’s soft tissues. Zinc assimilation efficiency (AE) varied from 28% for the Animas River particles to 45% for the Snake River particles, indicating that particle-bound, or sorbed Zn, was bioavailable from acid mine drainage wastes. The relative binding strength of Zn sorption to the natural particles was inversely related to Zn bioavailability; a finding that would not have been possible without using the reverse labeling approach. Differences in the chemical composition of the particles suggest that their geochemical properties may influence the extent of Zn bioavailability.

Environmental Science & Technology

PFAS mixture composition and internal exposure profiles shape biological responses under field-realistic exposure

Per- and polyfluoroalkyl substances (PFAS) occur as complex mixtures, yet mixture-dependent biological effects under environmentally realistic exposure conditions remain poorly understood. We conducted multiyear (2018, 2019, 2021) continuous-flow, field-based exposures of male fathead minnows ( Pimephales promelas ) using a low-PFAS reference well (REF; sum of measured PFAS (∑PFAS) 0.1–0.2 μg L –1 ) and PFAS-contaminated groundwater from a fire-training area (FTA) at Joint Base Cape Cod, Massachusetts. Dilution treatments enabled separation of concentration and mixture effects. Groundwater from well FTA1 was perfluorooctanesulfonate (PFOS) dominated (∑PFAS 10–31 μg L –1 ), whereas groundwater from well FTA2 had higher concentrations and was enriched in perfluorooctanoate (PFOA) and diverse precursors (∑PFAS ∼ 80 μg L –1 ). Despite comparable plasma ∑PFAS and PFOS in FTA1–100% and FTA2–50% on day-7, cumulative mortality reached approximately 35% in FTA2–50% and 17% in FTA2–100%, and secondary sex trait expression was reduced by approximately 65–80% relative to REF, whereas sperm motility effects were mixture- and time-dependent. Plasma PFAS profiles were dominated by perfluorohexanesulfonate (PFHxS), PFOS, and sulfonamide precursors. Liver transcriptomics from REF-acclimated fish revealed robust disruption of metabolic, mitochondrial, and endocrine pathways that link PFAS mixture chemistry and internal exposure profiles to organismal outcomes, and testis transcriptomics provided complementary insight into reproductive impairment. These results indicate that PFAS mixture composition and internal exposure profiles, including precursor-associated differences, are important determinants of ecotoxicological outcomes under field-realistic conditions.

Massachusetts