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.natural gas extraction | high-volume hydraulic fracturing | groundwater | hydrophobic organic contaminants | transport mechanisms
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.
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.
More than 30 years separate the two largest oil spills in North American history (the Ixtoc I and Macondo well blowouts), yet the responses to both disasters were nearly identical in spite of advanced material innovation during the same time period. Novel, mechanically durable sorbents could enable (a) sorbent use in the open ocean, (b) automated deployment to minimize workforce exposure to toxic chemicals, and (c) mechanical recovery of spilled oils. Here, we explore the use of two mechanically durable, low-density (0.1-0.2 g cm(-3)), highly porous (85-99% porosity), hydrophobic (water contact angles >120°), flexible aerogel composite blankets as sorbent materials for automated oil capture and recovery: Cabot Thermal Wrap (TW) and Aspen Aerogels Spaceloft (SL). Uptake of crude oils (Iraq and Sweet Bryan Mound oils) was 8.0 ± 0.1 and 6.5 ± 0.3 g g(-1) for SL and 14.0 ± 0.1 and 12.2 ± 0.1 g g(-1) for TW, respectively, nearly twice as high as similar polyurethane- and polypropylene-based devices. Compound-specific uptake experiments and discrimination against water uptake suggested an adsorption-influenced sorption mechanism. Consistent with that mechanism, chemical extraction oil recoveries were 95 ± 2 (SL) and 90 ± 2% (TW), but this is an undesirable extraction route in decentralized oil cleanup efforts. In contrast, mechanical extraction routes are favorable, and a modest compression force (38 N) yielded 44.7 ± 0.5% initially to 42.0 ± 0.4% over 10 reuse cycles for SL and initially 55.0 ± 0.1% for TW, degrading to 30.0 ± 0.2% by the end of 10 cycles. The mechanical integrity of SL deteriorated substantially (800 ± 200 to 80 ± 30 kPa), whereas TW was more robust (380 ± 80 to 700 ± 100 kPa) over 10 uptake-and-compression extraction cycles.
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