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Declining Dioxin concentrations in the Rhone River, France, attest to the effectiveness of emissions controls

Emission-control policies have been implemented in Europe and North America since the 1990s for polychlorodibenzodioxins (PCDDs) and furans (PCDFs). To assess the effect of these policies on temporal trends and spatial patterns for these compounds in a large European river system, sediment cores were collected in seven depositional areas along the Rhone River in France, dated, and analyzed for PCDDs and PCDFs. Results show concentrations increase in the downstream direction and have decreased temporally at all sites during the last two decades, with an average decrease of 83% from 1992 to 2010. The time for a 50% decrease in concentrations (t1/2) averaged 6.9 ± 2.6 and 9.1 ± 2.9 years for the sum of measured PCDDs and PCDFs, respectively. Congener patterns are similar among cores and indicate dominance of regional atmospheric deposition and possibly weathered local sources. Local sources are clearly indicated at the most downstream site, where concentrations of the most toxic dioxin, TCDD, are about 2 orders of magnitude higher than at the other six sites. The relatively steep downward trends attest to the effects of the dioxin emissions reduction policy in Europe and suggest that risks posed to aquatic life in the Rhone River basin from dioxins and furans have been greatly reduced.

Environmental Science & Technology↗

Identification of groundwater nitrate contamination from explosives used in road construction: Isotopic, chemical, and hydrologic evidence

Explosives used in construction have been implicated as sources of NO 3 – contamination in groundwater, but direct forensic evidence is limited. Identification of blasting-related NO 3 – can be complicated by other NO 3 – sources, including agriculture and wastewater disposal, and by hydrogeologic factors affecting NO 3 – transport and stability. Here we describe a study that used hydrogeology, chemistry, stable isotopes, and mass balance calculations to evaluate groundwater NO 3 – sources and transport in areas surrounding a highway construction site with documented blasting in New Hampshire. Results indicate various groundwater responses to contamination: (1) rapid breakthrough and flushing of synthetic NO 3 – (low δ 15 N, high δ 18 O) from dissolution of unexploded NH 4 NO 3 blasting agents in oxic groundwater; (2) delayed and reduced breakthrough of synthetic NO 3 – subjected to partial denitrification (high δ 15 N, high δ 18 O); (3) relatively persistent concentrations of blasting-related biogenic NO 3 – derived from nitrification of NH 4 + (low δ 15 N, low δ 18 O); and (4) stable but spatially variable biogenic NO 3 – concentrations, consistent with recharge from septic systems (high δ 15 N, low δ 18 O), variably affected by denitrification. Source characteristics of denitrified samples were reconstructed from dissolved-gas data (Ar, N 2 ) and isotopic fractionation trends associated with denitrification (Δδ 15 N/Δδ 18 O ≈ 1.31). Methods and data from this study are expected to be applicable in studies of other aquifers affected by explosives used in construction.

Environmental Science & Technology↗

Long-term changes in sediment and nutrient delivery from Conowingo Dam to Chesapeake Bay: Effects of reservoir sedimentation

Reduction of suspended sediment (SS), total phosphorus (TP), and total nitrogen is an important focus for Chesapeake Bay watershed management. The Susquehanna River, the bay’s largest tributary, has drawn attention because SS loads from behind Conowingo Dam (near the river’s mouth) have been rising dramatically. To better understand these changes, we evaluated histories of concentration and loading (1986–2013) using data from sites above and below Conowingo Reservoir. First, observed concentration-discharge relationships show that SS and TP concentrations at the reservoir inlet have declined under most discharges in recent decades, but without corresponding declines at the outlet, implying recently diminished reservoir trapping. Second, best estimates of mass balance suggest decreasing net deposition of SS and TP in recent decades over a wide range of discharges, with cumulative mass generally dominated by the 75∼99.5th percentile of daily Conowingo discharges. Finally, stationary models that better accommodate effects of riverflow variability also support the conclusion of diminished trapping of SS and TP under a range of discharges that includes those well below the literature-reported scour threshold. Overall, these findings suggest that decreased net deposition of SS and TP has occurred at subscour levels of discharge, which has significant implications for the Chesapeake Bay ecosystem.

Maryland↗

Copper speciation in variably toxic sediments at the Ely Copper Mine, Vermont, United States

At the Ely Copper Mine Superfund site, Cu concentrations exceed background values in both streamwater (160–1200 times) and sediments (15–79 times). Previously, these sediment samples were incubated with laboratory test organisms, and they exhibited variable toxicity for different stream sites. In this study we combined bulk- and microscale techniques to determine Cu speciation and distribution in these contaminated sediments on the basis of evidence from previous work that Cu was the most important stressor in this environment and that variable observed toxicity could have resulted from differences in Cu speciation. Copper speciation results were similar at microscopic and bulk scales. The major Cu species in the more toxic samples were sorbed or coprecipitated with secondary Mn (birnessite) and Fe minerals (jarosite and goethite), which together accounted for nearly 80% of the total Cu. The major Cu species in the less toxic samples were Cu sulfides (chalcopyrite and a covellite-like phase), making up about 80–95% of the total Cu, with minor amounts of Cu associated with jarosite or goethite. These Cu speciation results are consistent with the toxicity results, considering that Cu sorbed or coprecipitated with secondary phases at near-neutral pH is relatively less stable than Cu bound to sulfide at lower pH. The more toxic stream sediment sites were those that contained fewer detrital sulfides and were upstream of the major mine waste pile, suggesting that removal and consolidation of sulfide-bearing waste piles on site may not eliminate all sources of bioaccessible Cu.

Vermont↗

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↗

Polyoxyethylene tallow amine, a glyphosate formulation adjuvant: Soil adsorption characteristics, degradation profile, and occurrence on selected soils from agricultural fields in Iowa, Illinois, Indiana, Kansas, Mississippi, and Missouri

Polyoxyethylene tallow amine (POEA) is an inert ingredient added to formulations of glyphosate, the most widely applied agricultural herbicide. POEA has been shown to have toxic effects to some aquatic organisms making the potential transport of POEA from the application site into the environment an important concern. This study characterized the adsorption of POEA to soils and assessed its occurrence and homologue distribution in agricultural soils from six states. Adsorption experiments of POEA to selected soils showed that POEA adsorbed much stronger than glyphosate; calcium chloride increased the binding of POEA; and the binding of POEA was stronger in low pH conditions. POEA was detected on a soil sample from an agricultural field near Lawrence, Kansas, but with a loss of homologues that contain alkenes. POEA was also detected on soil samples collected between February and early March from corn and soybean fields from ten different sites in five other states (Iowa, Illinois, Indiana, Missouri, Mississippi). This is the first study to characterize the adsorption of POEA to soil, the potential widespread occurrence of POEA on agricultural soils, and the persistence of the POEA homologues on agricultural soils into the following growing season.

Iowa, Illinois, Indiana, Kansas, Mississippi, Miss↗

Occurrence of triclocarban and triclosan in an agro-ecosystem following application of biosolids

Triclocarban (TCC) and triclosan (TCS), two of the most commonly used antimicrobial compounds, can be introduced into ecosystems by applying wastewater treatment plant biosolids to agricultural fields. Concentrations of TCC and TCS were measured in different trophic levels within a terrestrial food web encompassing land-applied biosolids, soil, earthworms ( Lumbricus ), deer mice ( Peromyscus maniculatus ), and eggs of European starlings ( Sturnus vulgaris ) and American kestrels ( Falco sparverius ) at an experimental site amended with biosolids for the previous 7 years. The samples from this site were compared to the same types of samples from a reference (biosolids-free) agricultural site. Inter-site comparisons showed that concentrations of both antimicrobials were higher on the experimental site in the soil, earthworms, mice (livers), and European starling eggs, but not American kestrel eggs, compared to the control site. Inter-species comparisons on the experimental site indicated significantly higher TCC concentrations in mice (TCC: 12.6–33.3 ng/g) and in starling eggs (TCC: 15.4–31.4 ng/g) than in kestrel eggs (TCC: 3.6 ng/g). Nesting success of kestrels only was significantly lower on the experimental site compared to the reference site due to nest abandonment. This study demonstrates that biosolids-derived TCC and TCS are present throughout the terrestrial food web, including secondary (e.g., starlings) and tertiary (i.e., kestrels) consumers, after repeated, long-term biosolids application.

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↗