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Ubiquitous tar balls with a California-source signature on the shorelines of Prince William Sound, Alaska

Although the shorelines of Prince William Sound still bear traces of the 1989 Exxon Valdez oil spill, most of the flattened tar balls that can be found today on these shorelines are not residues of Exxon Valdez oil. Instead, the carbon-isotopic and hydrocarbonbiomarker signatures of 61 tar ball samples, collected from shorelines throughout the northern and western parts of the sound, are all remarkably similar and have characteristics consistent with those of oil products that originated from the Monterey Formation source rocks of California. The carbonisotopic compositions of the tar balls are all closely grouped (<513Cpdb = -23.7 ± 0.2%o), within the range found in crude oils from those rocks, but are distinct from isotopic compositions of 28 samples of residues from the Exxon ValdezoW spill (<513Cpdb = -29.4 ± 0.1%o). Likewise, values for selected biomarker ratios in the tar balls are all similar but distinct from values of residues from the 1989 oil spill. Carbon-isotopic and biomarker signatures generally relate the tar balls to oil products used in Alaska before ~1970 for construction and pavements. How these tar balls with such similar geochemical characteristics became so widely dispersed throughout the northern and western parts of the sound is not known with certainty, but the great 1964 Alaska earthquake was undoubtedly an important trigger, causing spills from ruptured storage facilities of California-sourced asphalt and fuel oil into Prince William Sound.

Alaska

Toxicogenomics in regulatory ecotoxicology

Recently, we have witnessed an explosion of different genomic approaches that, through a combination of advanced biological, instrumental, and bioinformatic techniques, can yield a previously unparalleled amount of data concerning the molecular and biochemical status of organisms. Fueled partially by large, well-publicized efforts such as the Human Genome Project, genomic research has become a rapidly growing topical area in multiple biological disciplines. Since 1999, when the term “toxicogenomics” was coined to describe the application of genomics to toxicology (1), a rapid increase in publications on the topic has occurred (Figure 1). The potential utility of toxicogenomics in toxicological research and regulatory activities has been the subject of scientific discussions and, as with any new technology, has evoked a wide range of opinion (2–6).

Environmental Science & Technology

Bioenergy potential of the United States constrained by satellite observations of existing productivity

United States (U.S.) energy policy includes an expectation that bioenergy will be a substantial future energy source. In particular, the Energy Independence and Security Act of 2007 (EISA) aims to increase annual U.S. biofuel (secondary bioenergy) production by more than 3-fold, from 40 to 136 billion liters ethanol, which implies an even larger increase in biomass demand (primary energy), from roughly 2.9 to 7.4 EJ yr –1 . However, our understanding of many of the factors used to establish such energy targets is far from complete, introducing significgant uncertainty into the feasibility of current estimates of bioenergy potential. Here, we utilized satellite-derived net primary productivity (NPP) data—measured for every 1 km 2 of the 7.2 million km 2 of vegetated land in the conterminous U.S.—to estimate primary bioenergy potential (PBP). Our results indicate that PBP of the conterminous U.S. ranges from roughly 5.9 to 22.2 EJ yr –1 , depending on land use. The low end of this range represents the potential when harvesting residues only, while the high end would require an annual biomass harvest over an area more than three times current U.S. agricultural extent. While EISA energy targets are theoretically achievable, we show that meeting these targets utilizing current technology would require either an 80% displacement of current crop harvest or the conversion of 60% of rangeland productivity. Accordingly, realistically constrained estimates of bioenergy potential are critical for effective incorporation of bioenergy into the national energy portfolio.

Environmental Science & Technology

The role of behavioral ecotoxicology in environmental protection

For decades, we have known that chemicals affect human and wildlife behavior. Moreover, due to recent technological and computational advances, scientists are now increasingly aware that a wide variety of contaminants and other environmental stressors adversely affect organismal behavior and subsequent ecological outcomes in terrestrial and aquatic ecosystems. There is also a groundswell of concern that regulatory ecotoxicology does not adequately consider behavior, primarily due to a lack of standardized toxicity methods. This has, in turn, led to the exclusion of many behavioral ecotoxicology studies from chemical risk assessments. To improve understanding of the challenges and opportunities for behavioral ecotoxicology within regulatory toxicology/risk assessment, a unique workshop with international representatives from the fields of behavioral ecology, ecotoxicology, regulatory (eco)toxicology, neurotoxicology, test standardization, and risk assessment resulted in the formation of consensus perspectives and recommendations, which promise to serve as a roadmap to advance interfaces among the basic and translational sciences, and regulatory practices.

Environmental Science & Technology

A high efficiency method for the extraction and quantitative analysis of 45 PFAS in whole fish

This study describes and validates a new method for extracting perfluoroalkyl and polyfluoroalkyl substances (PFAS) from whole-body fish tissue, demonstrates that freeze-dry preservation of tissue conserves bioaccumulative PFAS, and details a method demonstration on Lake Michigan fish. While fish filets are more commonly analyzed for their significance to human health, whole fish are useful to determine ecological impacts, but published methods such as EPA 1633 do not produce reliable results for this more challenging matrix. Here we show that lipid removal technology produces clean extracts without the need for solid-phase extraction or evaporative concentration, which often lead to loss of some PFAS. This method achieves an accuracy of 96 ± 9% for the detection of 45 PFAS while also offering benefits of a simple procedure, reduced processing time, and decreased waste generation compared to multistep cleanup and concentration methods. A test of freeze-drying demonstrated that compounds detected in Great Lakes fish were retained, but volatile compounds including sulfonamide precursors and ethanols were lost. To demonstrate field performance, the entire method was applied to whole-fish composites from Lake Michigan. Results from these samples reveal that the PFAS concentration was driven by collection location, while the distribution of PFAS was dictated by fish species.

Environmental Science & Technology

Investigating the potential role of persistent organic pollutants in Hawaiian green sea turtle fibropapillomatosis

It has been hypothesized for decades that environmental pollutants may contribute to green sea turtle fibropapillomatosis (FP), possibly through immunosuppression leading to greater susceptibility to the herpesvirus, the putative causative agent of this tumor-forming disease. To address this question, we measured concentrations of 164 persistent organic pollutants (POPs) and halogenated phenols in 53 Hawaiian green turtle ( Chelonia mydas ) plasma samples archived by the Biological and Environmental Monitoring and Archival of Sea Turtle Tissues (BEMAST) project at the National Institute of Standards and Technology Marine Environmental Specimen Bank. Four groups of turtles were examined: free-ranging turtles from Kiholo Bay (0% FP, Hawaii), Kailua Bay (low FP, 8%, Oahu), and Kapoho Bay (moderate FP, 38%, Hawaii) and severely tumored stranded turtles that required euthanasia (high FP, 100%, Main Hawaiian Islands). Four classes of POPs and seven halogenated phenols were detected in at least one of the turtles, and concentrations were low (often <200 pg/g wet mass). The presence of halogenated phenols in sea turtles is a novel discovery; their concentrations were higher than most man-made POPs, suggesting that the source of most of these compounds was likely natural (produced by the algal turtle diet) rather than metabolites of man-made POPs. None of the compounds measured increased in concentration with increasing prevalence of FP across the four groups of turtles, suggesting that these 164 compounds are not likely primary triggers for the onset of FP. However, the stranded, severely tumored, emaciated turtle group ( n = 14) had the highest concentrations of POPs, which might suggest that mobilization of contaminants with lipids into the blood during late-stage weight loss could contribute to the progression of the disease. Taken together, these data suggest that POPs are not a major cofactor in causing the onset of FP.

Hawai'i

Ecological risks of shale oil and gas development to wildlife, aquatic resources and their habitats

Technological advances in hydraulic fracturing and horizontal drilling have led to the exploration and exploitation of shale oil and gas both nationally and internationally. Extensive development of shale resources has occurred within the United States over the past decade, yet full build out is not expected to occur for years. Moreover, countries across the globe have large shale resources and are beginning to explore extraction of these resources. Extraction of shale resources is a multistep process that includes site identification, well pad and infrastructure development, well drilling, high-volume hydraulic fracturing and production; each with its own propensity to affect associated ecosystems. Some potential effects, for example from well pad, road and pipeline development, will likely be similar to other anthropogenic activities like conventional gas drilling, land clearing, exurban and agricultural development and surface mining (e.g., habitat fragmentation and sedimentation). Therefore, we can use the large body of literature available on the ecological effects of these activities to estimate potential effects from shale development on nearby ecosystems. However, other effects, such as accidental release of wastewaters, are novel to the shale gas extraction process making it harder to predict potential outcomes. Here, we review current knowledge of the effects of high-volume hydraulic fracturing coupled with horizontal drilling on terrestrial and aquatic ecosystems in the contiguous United States, an area that includes 20 shale plays many of which have experienced extensive development over the past decade. We conclude that species and habitats most at risk are ones where there is an extensive overlap between a species range or habitat type and one of the shale plays (leading to high vulnerability) coupled with intrinsic characteristics such as limited range, small population size, specialized habitat requirements, and high sensitivity to disturbance. Examples include core forest habitat and forest specialists, sagebrush habitat and specialists, vernal pond inhabitants and stream biota. We suggest five general areas of research and monitoring that could aid in development of effective guidelines and policies to minimize negative impacts and protect vulnerable species and ecosystems: (1) spatial analyses, (2) species-based modeling, (3) vulnerability assessments, (4) ecoregional assessments, and (5) threshold and toxicity evaluations.

Environmental Science & Technology

Comparative effects of energy-related saline wastewaters and sodium chloride on hatching, survival, and fitness-associated traits of two amphibian species

Salinity (sodium chloride [NaCl]) is a prevalent and persistent contaminant that negatively affects freshwater ecosystems. Although most studies focus on effects of salinity from road salts (primarily NaCl), high-salinity wastewaters from energy extraction (wastewaters) could be more harmful because they contain NaCl and other toxic components. Many amphibians are sensitive to salinity, and their eggs are thought to be the most sensitive life-history stage. However, there are few investigations with salinity that include eggs and larvae sequentially in long-term exposures. We investigated the relative effects of wastewaters from a large energy reserve, the Williston Basin (USA), and NaCl on northern leopard ( Rana pipiens ) and boreal chorus ( Pseudacris maculata ) frogs. We exposed eggs and tracked responses through larval stages (for 24 days). Wastewaters and NaCl caused similar reductions in hatching and larval survival, growth, development, and activity, while also increasing deformities. Chorus frog eggs and larvae were more sensitive to salinity than leopard frogs, suggesting species-specific responses. Contrary to previous studies, eggs of both species were less sensitive to salinity than larvae. Our ecologically relevant exposures suggest that accumulating effects can reduce survival relative to starting experiments with unexposed larvae. Alternatively, egg casings of some species may provide some protection against salinity. Notably, effects of wastewaters on amphibians were predominantly due to NaCl rather than other components. Therefore, findings from studies with other sources of increased salinity (e.g., road salts) could guide management of wastewater-contaminated ecosystems, and vice versa, to mitigate effects of salinization.

Montana, Wyoming

Occurrence and spatiotemporal dynamics of pharmaceuticals in a temperate-region wastewater effluent-dominated stream: Variable inputs and differential attenuation yield evolving complex exposure mixtures

Effluent-dominated streams are becoming increasingly common in temperate regions and generate complex pharmaceutical mixture exposure conditions that may impact aquatic organisms via drug–drug interactions. Here, we quantified spatiotemporal pharmaceutical exposure concentrations and composition mixture dynamics during baseflow conditions at four sites in a temperate-region effluent-dominated stream (upstream, at, and progressively downstream from effluent discharge). Samples were analyzed monthly for 1 year for 109 pharmaceuticals/degradates using a comprehensive U.S. Geological Survey analytical method and biweekly for 2 years focused on 14 most common pharmaceuticals/degradates. We observed a strong chemical gradient with pharmaceuticals only sporadically detected upstream from the effluent. Seventy-four individual pharmaceuticals/degradates were detected, spanning 5 orders of magnitude from 0.28 to 13 500 ng/L, with 38 compounds detected in >50% of samples. “Biweekly” compounds represented 77 ± 8% of the overall pharmaceutical concentration. The antidiabetic drug metformin consistently had the highest concentration with limited in-stream attenuation. The antihistamine drug fexofenadine inputs were greater during warm- than cool-season conditions but also attenuated faster. Differential attenuation of individual pharmaceuticals (i.e., high = citalopram; low = metformin) contributed to complex mixture evolution along the stream reach. This research demonstrates that variable inputs over multiple years and differential in-stream attenuation of individual compounds generate evolving complex mixture exposure conditions for biota, with implications for interactive effects.

Environmental Science & Technology

Demethylation of methylmercury in bird, fish, and earthworm

Toxicity of methylmercury (MeHg) to wildlife and humans results from its binding to cysteine residues of proteins, forming MeHg-cysteinate (MeHgCys) complexes that hinder biological functions. MeHgCys complexes can be detoxified in vivo, yet how this occurs is unknown. We report that MeHgCys complexes are transformed into selenocysteinate (Hg(Sec)4) complexes in multiple animals from two phyla (a waterbird, freshwater fish, and earthworms) sampled in different geographical areas and contaminated by different Hg sources. In addition, high energy-resolution X-ray absorption spectroscopy and chromatography-ICP mass spectrometry of the waterbird liver support the binding of Hg(Sec)4 to selenoprotein P and biomineralization of Hg(Sec)4 to chemically inert nanoparticulate mercury selenide (HgSe). The results provide a foundation for understanding mercury detoxification in higher organisms, and suggest that the identified MeHgCys to Hg(Sec)4 demethylation pathway is common in nature.

Environmental Science & Technology

Pesticides and pesticide degradates in groundwater used for public supply across the United States: Occurrence and human-health context

This is the first assessment of groundwater from public-supply wells across the United States to analyze for >100 pesticide degradates and to provide human-health context for degradates without benchmarks. Samples from 1204 wells in aquifers representing 70% of the volume pumped for drinking supply were analyzed for 109 pesticides (active ingredients) and 116 degradates. Among the 41% of wells where pesticide compounds were detected, nearly two-thirds contained compound mixtures and three-quarters contained degradates. Atrazine, hexazinone, prometon, tebuthiuron, four atrazine degradates, and one metolachlor degradate were each detected in >5% of wells. Detection frequencies were largest for aquifers with more shallow, unconfined wells producing modern-age groundwater. To screen for potential human-health concerns, benchmark quotients (BQs) were calculated by dividing concentrations by the human-health benchmark, when available. For degradates without benchmarks, estimated values (estimated benchmark quotients (BQE)) were first calculated by assuming equimolar toxicity to the most toxic parent; final analysis excluded degradates with likely overestimated toxicity. Six pesticide compounds and 1.6% of wells had concentrations approaching levels of potential concern (individual or summed BQ or BQE values >0.1), and none exceeded these levels (values >1). Therefore, although pesticide compounds occurred frequently, concentrations were low, even accounting for mixtures and degradates without benchmarks.

Continental United States

Spatial distribution of microplastics in surficial benthic sediment of Lake Michigan and Lake Erie

The spatial distribution, concentration, particle size, and polymer compositions of microplastics in Lake Michigan and Lake Erie sediment were investigated. Fibers/lines were the most abundant of the five particle types characterized. Microplastic particles were observed in all samples with mean concentrations for particles greater than 0.355 mm of 65.2 p kg –1 in Lake Michigan samples ( n = 20) and 431 p kg –1 in Lake Erie samples ( n = 12). Additional analysis of particles with size 0.1250–0.3549 mm in Lake Erie resulted in a mean concentration of 631 p kg –1 . The majority of polymers in Lake Michigan samples were poly(ethylene terephthalate) (PET), high-density polyethylene (HDPE), and semisynthetic cellulose (S.S. Cellulose), and in Lake Erie samples were S.S. Cellulose, polypropylene (PP), and poly(vinyl chloride) (PVC). Polymer density estimates indicated that 85 and 74% of observed microplastic particles have a density greater than 1.1 g cm –3 for Lake Michigan and Lake Erie, respectively. The current study provided a multidimensional dataset on the spatial distribution of microplastics in benthic sediment from Lake Michigan and Lake Erie and valuable information for assessment of the fate of microplastics in the Great Lakes.

Lake Ontario, Lake Erie

Discrete sample introduction module for quantitative and isotopic analysis of methane and other gases by cavity ring-down spectroscopy

Carbon dioxide (CO 2 ) and methane (CH 4 ) are natural and anthropogenic products that play a central role in the global carbon cycle and regulating Earth’s climate. Applications utilizing laser absorption spectroscopy, which continuously measure concentrations and stable isotope ratios of these greenhouse gases, are routinely employed to measure the source and magnitude of atmospheric inputs. We developed a discrete sample introduction module (DSIM) to enable measurements of methane and CO 2 concentrations and δ 13 C values from limited volume (5–100 mL) gas samples when interfaced with a commercially available cavity ring-down spectroscopy (CRDS) analyzer. The analysis has a dynamic range that spans six orders of magnitude from 100% analyte to the lower limit of instrument detection (2 ppm). We demonstrate system performance for methane by comparing concentrations and δ 13 C results from the DSIM-CRDS system and traditional methods for a variety of sample types, including low concentration (nanomolar CH 4 ) seawater and high concentration (>90% CH 4 ) natural gas. The expansive concentration range of the field-portable DSIM-CRDS system can measure enhances analytical performance for investigating methane and CO 2 dynamics and, potentially, other gases measured by laser absorption spectroscopy.

Environmental Science & Technology

Characterization of halogenated organic compounds in pelagic sharks and sea turtles using a nontargeted approach

Halogenated organic compounds (HOCs) in marine species collected from the Atlantic Ocean [3 shortfin mako ( Isurus oxyrinchus ) and 1 porbeagle ( Lamna nasus )], and 12 sea turtles collected from the Pacific Ocean [3 loggerhead ( Caretta caretta ), 3 green ( Chelonia mydas ), 3 olive ridley ( Lepidochelys olivacea ), and 3 hawksbill ( Eretmochelys imbricata )] were analyzed with a nontargeted analytical method using two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry. Sharks and sea turtles had distinct HOC profiles. Halogenated methoxyphenols (halo-MeOPs) were the most abundant compound class identified in sea turtle livers, while polychlorinated biphenyls (PCBs) were the most abundant in shark livers. In addition to legacy contaminants and halo-MeOPs, a total of 110 nontargeted/novel HOCs (NHOCs) were observed in the shark livers. Shortfin mako collected from the northern Gulf of Mexico contained the largest number (89) and most diverse structural classes of NHOCs. Among all NHOCs, a group of compounds with the elemental composition C 14 H 12– n Cl n ( n = 5–8) exhibited the highest concentrations, followed by chlorocarbazoles and tris(chlorophenyl) methanes (TCPMs). Using nontargeted workflows, a variety of known and unknown HOCs were observed, which demonstrate the need to develop more complete chemical profiles in the marine environment.

Environmental Science & Technology

Rock-to-metal ratio: A foundational metric for understanding mine wastes

The quantity of ore mined and waste rock (i.e., overburden or barren rock) removed to produce a refined unit of a mineral commodity, its rock-to-metal ratio (RMR), is an important metric for understanding mine wastes and environmental burdens. In this analysis, we provide a comprehensive examination of RMRs for 25 commodities for 2018. The results indicate significant variability across commodities. Precious metals like gold have RMRs in the range of 10 5 –10 6 , while iron ore and aluminum are on the order of 10 1 . The results also indicate significant variability across operations for a single commodity. The interquartile range of RMRs for individual cobalt operations, for example, varies from 465 to 2157, with a global RMR of 859. RMR variability is mainly driven by ore grades and revenue contribution. The total attributable ore mined and waste rock removed in the production of these 25 commodities sums to 37.6 billion metric tons, 83% of which is attributable to iron ore, copper, and gold. RMRs provide an additional dimension for evaluating the impact of materials and material choice trade-offs. The results can enhance life cycle inventories and be extended to evaluate areas of surface disturbances, mine tailings, energy requirements, and associated greenhouse gas emissions.

Environmental Science & Technology

Complex life histories alter patterns of mercury exposure and accumulation in a pond-breeding amphibian

Quantifying how contaminants change across life cycles of species that undergo metamorphosis is critical to assessing organismal risk, particularly for consumers. Pond-breeding amphibians can dominate aquatic animal biomass as larvae and are terrestrial prey as juveniles and adults. Thus, amphibians can be vectors of mercury exposure in both aquatic and terrestrial food webs. However, it is still unclear how mercury concentrations are affected by exogenous (e.g., habitat or diet) vs endogenous factors (e.g., catabolism during hibernation) as amphibians undergo large diet shifts and periods of fasting during ontogeny. We measured total mercury (THg), methylmercury (MeHg), and isotopic compositions (δ 13 C, δ 15 N) in boreal chorus frogs ( Pseudacris maculata ) across five life stages in two Colorado (USA) metapopulations. We found large differences in concentrations and percent MeHg (of THg) among life stages. Frog MeHg concentrations peaked during metamorphosis and hibernation coinciding with the most energetically demanding life cycle stages. Indeed, life history transitions involving periods of fasting coupled with high metabolic demands led to large increases in mercury concentrations. The endogenous processes of metamorphosis and hibernation resulted in MeHg bioamplification, thus decoupling it from the light isotopic proxies of diet and trophic position. These step changes are not often considered in conventional expectations of how MeHg concentrations within organisms are assessed.

Environmental Science & Technology

Mercury bioaccumulation and cortisol interact to influence endocrine and immune biomarkers in a free-ranging marine mammal

Mercury bioaccumulation from deep-ocean prey and the extreme life history strategies of adult female northern elephant seals ( Mirounga angustirostris ) provide a unique system to assess the interactive effects of mercury and stress on animal health by quantifying blood biomarkers in relation to mercury (skeletal muscle and blood mercury) and cortisol concentrations. The thyroid hormone thyroxine (tT4) and the antibody immunoglobulin E (IgE) were associated with mercury and cortisol concentrations interactively, where the magnitude and direction of the association of each biomarker with mercury or cortisol changed depending on the concentration of the other factor. For example, when cortisol concentrations were lowest, tT4 was positively related to muscle mercury, whereas tT4 had a negative relationship with muscle mercury in seals that had the highest cortisol concentrations. Additionally, we observed that two thyroid hormones, triiodothyronine (tT3) and reverse triiodothyronine (rT3), were negatively (tT3) and positively (rT3) associated with mercury concentrations and cortisol in an additive manner. As an example, tT3 concentrations in late breeding seals at the median cortisol concentration decreased by 14% across the range of observed muscle mercury concentrations. We also observed that immunoglobulin M (IgM), the pro-inflammatory cytokine IL-6 (IL-6), and a reproductive hormone, estradiol, were negatively related to muscle mercury concentrations but were not related to cortisol. Specifically, estradiol concentrations in late molting seals decreased by 50% across the range of muscle mercury concentrations. These results indicate important physiological effects of mercury on free-ranging apex marine predators and interactions between mercury bioaccumulation and extrinsic stressors. Deleterious effects on animals’ abilities to maintain homeostasis (thyroid hormones), fight off pathogens and disease (innate and adaptive immune system), and successfully reproduce (endocrine system) can have significant individual- and population-level consequences.

Environmental Science & Technology

Tire-derived transformation product 6PPD-quinone induces mortality and transcriptionally disrupts vascular permeability pathways in developing coho salmon

Urban stormwater runoff frequently contains the car tire transformation product 6PPD-quinone, which is highly toxic to juvenile and adult coho salmon ( Onchorychus kisutch ). However, it is currently unclear if embryonic stages are impacted. We addressed this by exposing developing coho salmon embryos starting at the eyed stage to three concentrations of 6PPD-quinone twice weekly until hatch. Impacts on survival and growth were assessed. Further, whole-transcriptome sequencing was performed on recently hatched alevin to address the potential mechanism of 6PPD-quinone-induced toxicity. Acute mortality was not elicited in developing coho salmon embryos at environmentally measured concentrations lethal to juveniles and adults, however, growth was inhibited. Immediately after hatching, coho salmon were sensitive to 6PPD-quinone mortality, implicating a large window of juvenile vulnerability prior to smoltification. Molecularly, 6PPD-quinone induced dose-dependent effects that implicated broad dysregulation of genomic pathways governing cell–cell contacts and endothelial permeability. These pathways are consistent with previous observations of macromolecule accumulation in the brains of coho salmon exposed to 6PPD-quinone, implicating blood–brain barrier disruption as a potential pathway for toxicity. Overall, our data suggests that developing coho salmon exposed to 6PPD-quinone are at risk for adverse health events upon hatching while indicating potential mechanism(s) of action for this highly toxic chemical.

Environmental Science & Technology