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An amendment to this paper has been published and can be accessed via a link at the top of the paper.
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Thermosets-polymeric materials that adopt a permanent shape upon curing-have a key role in the modern plastics and rubber industries, comprising about 20 per cent of polymeric materials manufactured today, with a worldwide annual production of about 65 million tons1,2. The high density of crosslinks that gives thermosets their useful properties (for example, chemical and thermal resistance and tensile strength) comes at the expense of degradability and recyclability. Here, using the industrial thermoset polydicyclopentadiene as a model system, we show that when a small number of cleavable bonds are selectively installed within the strands of thermosets using a comonomer additive in otherwise traditional curing workflows, the resulting materials can display the same mechanical properties as the native material, but they can undergo triggered, mild degradation to yield soluble, recyclable products of controlled size and functionality. By contrast, installation of cleavable crosslinks, even at much higher loadings, does not produce degradable materials. These findings reveal that optimization of the cleavable bond location can be used as a design principle to achieve controlled thermoset degradation. Moreover, we introduce a class of recyclable thermosets poised for rapid deployment.
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Chemical degradation testing often involves monitoring the loss of a chemical or the evolution of a single diagnostic product through time. Here, we demonstrate a novel approach to tracing complex degradation networks using mass-spectrometry-based methods and open cheminformatics tools. Ester- and ether-based thermoplastic polyurethane (TPU_Ester and TPU_Ether) microplastics (350 µm) and microplastics-derived dissolved organic carbon (MP-DOC) were photoweathered in a simulated marine environment and subsequently analyzed by liquid chromatography coupled to high-resolution mass spectrometry. We formula-annotated 1342 and 2344 unique features in the MP-DOC of TPU_Ester and TPU_Ether, respectively. From these, we extracted 199 and 568 plausible parent-transformation product pairs via matching of features (a) with complementary increasing and decreasing trends (Spearman's correlation coefficient between normalized intensity and time), (b) spectral similarities of at least three accurate mass MS2 fragments, and (c) at least 3 ppm agreement between the theoretical and measured change in m/z between the parent-transformation product formula. Molecular network analysis revealed that both chain scission and cross-linking reactions occur dynamically rather than degradation proceeding in a monotonic progression to smaller or more oxygenated structures. Network nodes with the highest degree of centrality were tentatively identified using in silico fragmentation and can be prioritized for toxicity screening or other physicochemical properties of interest. This work has important implications for chemical transformation tracking in complex mixtures and may someday enable improved elucidation of environmental transformation rules (i.e., structure-reactivity relationships) and fate modeling.
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Microplásticos , Plásticos , Matéria Orgânica Dissolvida , Espectrometria de Massas/métodos , Éteres , Ésteres , CarbonoRESUMO
The production of fossil fuels, including oil, gas, and coal, retains a dominant share in US energy production and serves as a major anthropogenic source of methane, a greenhouse gas with a high warming potential. In addition to directly emitting methane into the air, fossil fuel production can release methane into groundwater, and that methane may eventually reach the atmosphere. In this study, we collected 311 water samples from an unconventional oil and gas (UOG) production region in Pennsylvania and an oil and gas (O&G) and coal production region across Ohio and West Virginia. Methane concentration was negatively correlated to distance to the nearest O&G well in the second region, but such a correlation was shown to be driven by topography as a confounding variable. Furthermore, sulfate concentration was negatively correlated with methane concentration and with distance to coal mining in the second region, and these correlations were robust even when considering topography. We hypothesized that coal mining enriched sulfate in groundwater, which in turn inhibited methanogenesis and enhanced microbial methane oxidation. Thus, this study highlights the complex interplay of multiple factors in shaping groundwater methane concentrations, including biogeochemical conversion, topography, and conventional fossil extraction.
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Combustíveis Fósseis , Água Subterrânea , Campos de Petróleo e Gás , Metano , Região dos Apalaches , Carvão Mineral , SulfatosRESUMO
BACKGROUND: Chemicals used or emitted by unconventional oil and gas development (UOGD) include reproductive/developmental toxicants. Associations between UOGD and certain birth defects were reported in a few studies, with none conducted in Ohio, which experienced a thirty-fold increase in natural gas production between 2010 and 2020. METHODS: We conducted a registry-based cohort study of 965,236 live births in Ohio from 2010 to 2017. Birth defects were identified in 4653 individuals using state birth records and a state surveillance system. We assigned UOGD exposure based on maternal residential proximity at birth to active UOG wells and a metric specific to the drinking-water exposure pathway that identified UOG wells hydrologically connected to a residence ("upgradient UOG wells"). We estimated odds ratios (ORs) and 95% confidence intervals (CIs) for all structural birth defects combined and specific birth defect types using binary exposure metrics (presence/absence of any UOG well and presence/absence of an upgradient UOG well within 10 km), adjusting for confounders. Additionally, we conducted analyses stratified by urbanicity, infant sex, and social vulnerability. RESULTS: The odds of any structural defect were 1.13 times higher in children born to mothers living within 10 km of UOGD than those born to unexposed mothers (95%CI: 0.98-1.30). Odds were elevated for neural tube defects (OR: 1.57, 95%CI: 1.12-2.19), limb reduction defects (OR: 1.99, 95%CI: 1.18-3.35), and spina bifida (OR 1.93; 95%CI 1.25-2.98). Hypospadias (males only) was inversely related to UOGD exposure (OR: 0.62, 95%CI: 0.43-0.91). Odds of any structural defect were greater in magnitude but less precise in analyses using the hydrological-specific metric (OR: 1.30; 95%CI: 0.85-1.90), in areas with high social vulnerability (OR: 1.27, 95%CI: 0.99-1.60), and among female offspring (OR: 1.28, 95%CI: 1.06-1.53). CONCLUSIONS: Our results suggest a positive association between UOGD and certain birth defects, and findings for neural tube defects corroborate results from prior studies.
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Gás Natural , Defeitos do Tubo Neural , Masculino , Gravidez , Recém-Nascido , Criança , Humanos , Feminino , Ohio/epidemiologia , Estudos de Coortes , PartoRESUMO
Health studies report associations between metrics of residential proximity to unconventional oil and gas (UOG) development and adverse health endpoints. We investigated whether exposure through household groundwater is captured by existing metrics and a newly developed metric incorporating groundwater flow paths. We compared metrics with detection frequencies/concentrations of 64 organic and inorganic UOG-related chemicals/groups in residential groundwater from 255 homes (Pennsylvania n = 94 and Ohio n = 161). Twenty-seven chemicals were detected in ≥20% of water samples at concentrations generally below U.S. Environmental Protection Agency standards. In Pennsylvania, two organic chemicals/groups had reduced odds of detection with increasing distance to the nearest well: 1,2-dichloroethene and benzene (Odds Ratio [OR]: 0.46, 95% confidence interval [CI]: 0.23-0.93) and m- and p-xylene (OR: 0.28, 95% CI: 0.10-0.80); results were consistent across metrics. In Ohio, the odds of detecting toluene increased with increasing distance to the nearest well (OR: 1.48, 95% CI: 1.12-1.95), also consistent across metrics. Correlations between inorganic chemicals and metrics were limited (all |ρ| ≤ 0.28). Limited associations between metrics and chemicals may indicate that UOG-related water contamination occurs rarely/episodically, more complex metrics may be needed to capture drinking water exposure, and/or spatial metrics in health studies may better reflect exposure to other stressors.
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Água Potável , Água Subterrânea , Poluentes Químicos da Água , Região dos Apalaches , Monitoramento Ambiental/métodos , Campos de Petróleo e Gás , Poluentes Químicos da Água/análiseRESUMO
Worldwide heavy oil and bitumen deposits amount to 9 trillion barrels of oil distributed in over 280 basins around the world, with Canada home to oil sands deposits of 1.7 trillion barrels. The global development of this resource and the increase in oil production from oil sands has caused environmental concerns over the presence of toxic compounds in nearby ecosystems and acid deposition. The contribution of oil sands exploration to secondary organic aerosol formation, an important component of atmospheric particulate matter that affects air quality and climate, remains poorly understood. Here we use data from airborne measurements over the Canadian oil sands, laboratory experiments and a box-model study to provide a quantitative assessment of the magnitude of secondary organic aerosol production from oil sands emissions. We find that the evaporation and atmospheric oxidation of low-volatility organic vapours from the mined oil sands material is directly responsible for the majority of the observed secondary organic aerosol mass. The resultant production rates of 45-84 tonnes per day make the oil sands one of the largest sources of anthropogenic secondary organic aerosols in North America. Heavy oil and bitumen account for over ten per cent of global oil production today, and this figure continues to grow. Our findings suggest that the production of the more viscous crude oils could be a large source of secondary organic aerosols in many production and refining regions worldwide, and that such production should be considered when assessing the environmental impacts of current and planned bitumen and heavy oil extraction projects globally.
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Aerossóis/análise , Aerossóis/química , Atmosfera/química , Campos de Petróleo e Gás , Indústria de Petróleo e Gás , Alberta , Clima , Atividades Humanas , Hidrocarbonetos/análise , Hidrocarbonetos/química , Material Particulado/análise , Material Particulado/química , Petróleo , VolatilizaçãoRESUMO
Conflicting evidence exists as to whether or not unconventional oil and gas (UOG) development has enhanced methane transport into groundwater aquifers over the past 15 years. In this study, recent groundwater samples were collected from 90 domestic wells and 4 springs in Northeastern Pennsylvania located above the Marcellus Shale after more than a decade of UOG development. No statistically significant correlations were observed between the groundwater methane level and various UOG geospatial metrics, including proximity to UOG wells and well violations, as well as the number of UOG wells and violations within particular radii. The δ13C and methane-to-higher chain hydrocarbon signatures suggested that the elevated methane levels were not attributable to UOG development nor could they be explained by using simple biogenic-thermogenic end-member mixing models. Instead, groundwater methane levels were significantly correlated with geochemical water type and topographical location. Comparing a subset of contemporary methane measurements to their co-located pre-drilling records (n = 64 at 49 distinct locations) did not indicate systematic increases in methane concentration but did reveal several cases of elevated concentration (n = 12) across a spectrum of topographies. Multiple lines of evidence suggested that the high-concentration groundwater methane could have originated from shallow thermogenic methane that migrated upward into groundwater aquifers with Appalachian Basin brine.
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Água Subterrânea , Poluentes Químicos da Água , Monitoramento Ambiental , Metano/análise , Gás Natural , Campos de Petróleo e Gás , Pennsylvania , Poluentes Químicos da Água/análiseRESUMO
The surface mining and bitumen extraction of oil sands (OS) generates over one million barrels of heavy oil each day in the Alberta Oil Sands Region of Canada. Recent observations suggest that emissions from OS development contribute to secondary organic aerosol (SOA) formation, but the chemical composition, mass fluxes, and sources of those emissions are poorly delineated. Here, we simulated OS extraction and used comprehensive two-dimensional gas chromatography to quantify and characterize direct air emissions, bitumen froth, residual wastewater, and tailings components, ultimately enabling fate modeling of over 1500 chromatographic features simultaneously. During the non-ice cover season, tailings ponds emissions contributed 15â¯000-72â¯000 metric tonnes of hydrocarbon SOA precursors, translating to 3000-13â¯000 tonnes of SOA, whereas direct emissions during the extraction process itself were notably smaller (960 ± 500 tonnes SOA yr-1). These results suggest that tailings pond waste management practices should be targeted to reduce environmental emissions.
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Campos de Petróleo e Gás , Lagoas , Aerossóis , Alberta , MineraçãoRESUMO
Artisanal and small-scale gold mining (ASGM) is a significant contributor of mercury (Hg) contamination and deforestation across the globe. In the Colorado River watershed in Madre de Dios, Peru, mining and deforestation have increased exponentially since the 1980s, resulting in major socioeconomic shifts in the region and two national state of emergency (2016 and 2019) in response to concerns for wide-scale mercury poisoning by these activities. This research employed a watershed-scale soil particle detachment model and environmental field sampling to estimate the role of land cover change and soil erosion on river transport of Hg in a heavily ASGM-impacted watershed. The model estimated that observed decreases in forest cover increased soil mobilization by a factor of two in the Colorado River watershed during the 18 year period and by 4-fold in the Puquiri subwatershed (the area of most concentrated ASGM activity). If deforestation continues to increase at its current exponential rate through 2030, the annual mobilization of soil and Hg may increase by an additional 20-25% relative to 2014 levels. While, the estimated total mass of Hg transported by rivers is substantially less than the estimated tons of Hg used with ASGM in Peru, this research shows that deforestation associated with ASGM is an additional mechanism for mobilizing naturally occurring and anthropogenic Hg from terrestrial landscapes to aquatic environments in the region, potentially leading to bioaccumulation in fish and exposure to communities downstream.
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Mercúrio , Poluentes Químicos da Água , Animais , Conservação dos Recursos Naturais , Monitoramento Ambiental , Ouro , Mineração , Peru , SoloRESUMO
A number of flowback samples derived from horizontally drilled hydraulic fracturing (HDHF) operations reveal consistent detections of halogenated organic species , yet the source of these compounds remains uncertain. Studies simulating subsurface conditions have found that oxidative "breakers" can halogenate certain additives, but these pathways are unverified in the presence of cross-linked-gels, common features of HDHF operations. Using a high-throughput custom reactor system, we implemented a reaction matrix to test the capacity for halogenation of two frequently disclosed compounds with demonstrated halogenation pathways (cinnamaldehyde and citric acid) across guar gels with varied types and concentrations of cross-linkers and oxidative breakers. Cinnamaldehyde halogenation proceeded most readily in borate cross-linked gels at high ammonium persulfate dosages. Citric acid formed trihalomethanes (THMs) broadly across the matrix, generating brominated THMs at higher levels of hypochlorite breaker. Isolated removals of cross-linker or guar enhanced or diminished certain product formations, highlighting additional capacities for relevant ingredients to influence halogenation. Finally, we analyzed flowback samples from the Denver-Julesberg Basin, finding that additions of oxidant enhanced halogenation. As a more realistic subsurface simulation, this work demonstrates strict criteria for the subsurface halogenation of cinnamaldehyde and the broad capacity for THM formation due to systematic oxidant usage as gel breakers in HDHF operations.
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Cyamopsis , Fraturamento Hidráulico , Poluentes Químicos da Água , Purificação da Água , Halogenação , Estresse Oxidativo , TrialometanosRESUMO
The equimolar C2 H2 -CO2 reaction has shown promise for carbon nanotube (CNT) production at low temperatures and on diverse functional substrate materials; however, the electron-pushing mechanism of this reaction is not well demonstrated. Here, the role of CO2 is explored experimentally and theoretically. In particular, 13 C labeling of CO2 demonstrates that CO2 is not an important C source in CNT growth by thermal catalytic chemical vapor deposition. Consistent with this experimental finding, the adsorption behaviors of C2 H2 and CO2 on a graphene-like lattice via density functional theory calculations reveal that the binding energies of C2 H2 are markedly higher than that of CO2 , suggesting the former is more likely to incorporate into CNT structure. Further, H-abstraction by CO2 from the active CNT growth edge would be favored, ultimately forming CO and H2 O. These results support that the commonly observed, promoting role of CO2 in CNT growth is due to a CO2 -assisted dehydrogenation mechanism.
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Unconventional natural gas extraction via hydraulic fracturing coupled with horizontal drilling (HDHF) has generated disruptive growth in the domestic energy sector. Field analyses of residual HDHF fluids have detected halogenated species, potentially the product of unexplored reactions between authigenic halides and HDHF additives. Utilizing a custom high-pressure reactor system, we simultaneously screened 12 frequently disclosed, functionally diverse HDHF additives to uncover transformation chemistry. One emergent pathway, the halogenation of cinnamaldehyde in the presence of ammonium persulfate, demonstrated the potential for oxidative breakers to react with halides to yield reactive halogen species. Halogenated product formation, product distribution, and kinetics were evaluated with respect to shale well subsurface condition, linking transformation risk to measurable well-dependent characteristics (e.g., halide compositions, well temperatures, and pH). In a representative flowback brine, the brominated product dominated on a molar percent basis (6 ± 2%, as normalized by initial cinnamaldehyde loading) over chlorinated (1.4 ± 0.4%) and iodinated forms (2.5 ± 0.9%), reflecting relative halide abundance and propensity for oxidation. This work demonstrates that relevant subsurface reactions between natural brines and hydraulic fracturing additives can result in the unintended formation of halogenated products.
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Fraturamento Hidráulico , Halogenação , Minerais , Gás Natural , Águas ResiduáriasRESUMO
Over 4 million Americans live within 1.6â¯km of an unconventional oil and gas (UO&G) well, potentially placing them in the path of toxic releases. We evaluated relationships between residential proximity to UO&G wells and (1) water contamination and (2) health symptoms in an exploratory study. We analyzed drinking water samples from 66 Ohio households for 13 UO&G-related volatile organic compounds (VOCs) (e.g., benzene, disinfection byproducts [DBPs]), gasoline-range organics (GRO), and diesel-range organics. We interviewed participants about health symptoms and calculated metrics capturing proximity to UO&G wells. Based on multivariable logistic regression, odds of detection of bromoform and dibromochloromethane in surface water decreased significantly as distance to nearest UO&G well increased (odds ratios [OR]: 0.28-0.29 per km). Similarly, distance to nearest well was significantly negatively correlated with concentrations of GRO and toluene in ground water (rSpearman: -0.40 to -0.44) and with concentrations of bromoform and dibromochloromethane in surface water (rSpearman: -0.48 to -0.50). In our study population, those with higher inverse-distance-squared-weighted UO&G well counts within 5â¯km around the home were more likely to report experiencing general health symptoms (e.g. stress, fatigue) (OR: 1.52, 95%CI: 1.02-2.26). This exploratory study, though limited by small sample size and self-reported health symptoms, suggests that those in closer proximity to multiple UO&G wells may be more likely to experience environmental health impacts. Further, presence of brominated DBPs (linked to UO&G wastewater) raises the question of whether UO&G activities are impacting drinking water sources in the region. The findings from this study support expanded studies to advance knowledge of the potential for water quality and human health impacts; such studies could include a greater number of sampling sites, more detailed chemical analyses to examine source attribution, and objective health assessments.
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Água Potável/análise , Monitoramento Ambiental , Água Subterrânea/análise , Nível de Saúde , Campos de Petróleo e Gás , Poluentes Químicos da Água/análise , Qualidade da Água , Humanos , Ohio , Compostos Orgânicos Voláteis/análiseRESUMO
Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency's maximum contaminant levels, and low levels of both gasoline range (0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.
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Gasolina/análise , Água Subterrânea/química , Indústria de Petróleo e Gás , Compostos Orgânicos/análise , Poluentes Químicos da Água/análise , Cromatografia Gasosa-Espectrometria de MassasRESUMO
Carbon nanotubes (CNTs) have numerous exciting potential applications and some that have reached commercialization. As such, quantitative measurements of CNTs in key environmental matrices (water, soil, sediment, and biological tissues) are needed to address concerns about their potential environmental and human health risks and to inform application development. However, standard methods for CNT quantification are not yet available. We systematically and critically review each component of the current methods for CNT quantification including CNT extraction approaches, potential biases, limits of detection, and potential for standardization. This review reveals that many of the techniques with the lowest detection limits require uncommon equipment or expertise, and thus, they are not frequently accessible. Additionally, changes to the CNTs (e.g., agglomeration) after environmental release and matrix effects can cause biases for many of the techniques, and biasing factors vary among the techniques. Five case studies are provided to illustrate how to use this information to inform responses to real-world scenarios such as monitoring potential CNT discharge into a river or ecotoxicity testing by a testing laboratory. Overall, substantial progress has been made in improving CNT quantification during the past ten years, but additional work is needed for standardization, development of extraction techniques from complex matrices, and multimethod comparisons of standard samples to reveal the comparability of techniques.
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Meio Ambiente , Nanotubos de Carbono/toxicidade , Humanos , Limite de DetecçãoRESUMO
Unconventional natural gas development (UNGD) generates large volumes of wastewater, the detailed composition of which must be known for adequate risk assessment and treatment. In particular, transformation products of geogenic compounds and disclosed additives have not been described. This study investigated six Fayetteville Shale wastewater samples for organic composition using a suite of one- and two-dimensional gas chromatographic techniques to capture a broad distribution of chemical structures. Following the application of strict compound-identification-confidence criteria, we classified compounds according to their putative origin. Samples displayed distinct chemical distributions composed of typical geogenic substances (hydrocarbons and hopane biomarkers), disclosed UNGD additives (e.g., hydrocarbons, phthalates such as diisobutyl phthalate, and radical initiators such as azobis(isobutyronitrile)), and undisclosed compounds (e.g., halogenated hydrocarbons, such as 2-bromohexane or 4-bromoheptane). Undisclosed chloromethyl alkanoates (chloromethyl propanoate, pentanoate, and octanoate) were identified as potential delayed acids (i.e., those that release acidic moieties only after hydrolytic cleavage, the rate of which could be potentially controlled), suggesting they were deliberately introduced to react in the subsurface. In contrast, the identification of halogenated methanes and acetones suggested that those compounds were formed as unintended byproducts. Our study highlights the possibility that UNGD operations generate transformation products and underscores the value of disclosing additives injected into the subsurface.
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Fraturamento Hidráulico , Gás Natural , Águas Residuárias/químicaRESUMO
The Twelve Principles of Green Chemistry were first published in 1998 and provide a framework that has been adopted not only by chemists, but also by design practitioners and decision-makers (e.g., materials scientists and regulators). The development of the Principles was initially motivated by the need to address decades of unintended environmental pollution and human health impacts from the production and use of hazardous chemicals. Yet, for over a decade now, the Principles have been applied to the synthesis and production of engineered nanomaterials (ENMs) and the products they enable. While the combined efforts of the global scientific community have led to promising advances in the field of nanotechnology, there remain significant research gaps and the opportunity to leverage the potential global economic, societal and environmental benefits of ENMs safely and sustainably. As such, this tutorial review benchmarks the successes to date and identifies critical research gaps to be considered as future opportunities for the community to address. A sustainable material design framework is proposed that emphasizes the importance of establishing structure-property-function (SPF) and structure-property-hazard (SPH) relationships to guide the rational design of ENMs. The goal is to achieve or exceed the functional performance of current materials and the technologies they enable, while minimizing inherent hazard to avoid risk to human health and the environment at all stages of the life cycle.
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Volumes of natural gas extraction-derived wastewaters have increased sharply over the past decade, but the ultimate fate of those waste streams is poorly characterized. Here, we sought to (a) quantify natural gas residual fluid sources and endpoints to bound the scope of potential waste stream impacts and (b) describe the organic pollutants discharged to surface waters following treatment, a route of likely ecological exposure. Our findings indicate that centralized waste treatment facilities (CWTF) received 9.5% (8.5 × 10(8) L) of natural gas residual fluids in 2013, with some facilities discharging all effluent to surface waters. In dry months, discharged water volumes were on the order of the receiving body flows for some plants, indicating that surface waters can become waste-dominated in summer. As disclosed organic compounds used in high volume hydraulic fracturing (HVHF) vary greatly in physicochemical properties, we deployed a suite of analytical techniques to characterize CWTF effluents, covering 90.5% of disclosed compounds. Results revealed that, of nearly 1000 disclosed organic compounds used in HVHF, only petroleum distillates and alcohol polyethoxylates were present. Few analytes targeted by regulatory agencies (e.g., benzene or toluene) were observed, highlighting the need for expanded and improved monitoring efforts at CWTFs.
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Fraturamento Hidráulico/métodos , Gás Natural , Águas Residuárias/química , Poluentes Químicos da Água/análise , Meio Ambiente , Resíduos Industriais , Compostos Orgânicos/análise , Pennsylvania , Petróleo , Estações do Ano , Águas Residuárias/análiseRESUMO
Little is known of the attenuation of chemical mixtures created for hydraulic fracturing within the natural environment. A synthetic hydraulic fracturing fluid was developed from disclosed industry formulas and produced for laboratory experiments using commercial additives in use by Marcellus shale field crews. The experiments employed an internationally accepted standard method (OECD 301A) to evaluate aerobic biodegradation potential of the fluid mixture by monitoring the removal of dissolved organic carbon (DOC) from an aqueous solution by activated sludge and lake water microbial consortia for two substrate concentrations and four salinities. Microbial degradation removed from 57 % to more than 90 % of added DOC within 6.5 days, with higher removal efficiency at more dilute concentrations and little difference in overall removal extent between sludge and lake microbe treatments. The alcohols isopropanol and octanol were degraded to levels below detection limits while the solvent acetone accumulated in biological treatments through time. Salinity concentrations of 40 g/L or more completely inhibited degradation during the first 6.5 days of incubation with the synthetic hydraulic fracturing fluid even though communities were pre-acclimated to salt. Initially diverse microbial communities became dominated by 16S rRNA sequences affiliated with Pseudomonas and other Pseudomonadaceae after incubation with the synthetic fracturing fluid, taxa which may be involved in acetone production. These data expand our understanding of constraints on the biodegradation potential of organic compounds in hydraulic fracturing fluids under aerobic conditions in the event that they are accidentally released to surface waters and shallow soils.