Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities

Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of American 112 (2015): 13184-13189, doi: 10.1073/pnas.1511474112 .Hundreds of organic chemicals are utilized during natural gas extraction via high volume hydraulic fracturing (HVHF). However, it is unclear if these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and impact local water quality, either from deep underground 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 (GRO; 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 1) inorganic chemical fingerprinting of deep saline groundwater, 2) characteristic noble gas isotopes, and 3) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety (EHS) violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and a 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.The authors thank Duke University’s Pratt School of Engineering and the National Science Foundation’s CBET Grant Number 1336702 and NSF EAGER (EAR-1249255) for financial support.2016-04-1

Waste Containment Ponds Are a Major Source of Secondary Organic Aerosol Precursors from Oil Sands Operations

Copyright © 2020 American Chemical Society. 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 15000-72000 metric tonnes of hydrocarbon SOA precursors, translating to 3000-13000 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

Small aromatic hydrocarbons control the onset of soot nucleation

The gas-to-particle transition is a critical and hitherto poorly understood aspect in carbonaceous soot particle formation. Polycyclic Aromatic Hydrocarbons (PAHs) are key precursors of the solid phase, but their role has not been assessed quantitatively probably because, even if analytical techniques to quantify them are well developed, the challenge to adapt them to flame environments are longstanding. Here, we present simultaneous measurements of forty-eight gaseous species through gas capillary-sampling followed by chemical analysis and of particle properties by optical techniques. Taken together, they enabled us to follow quantitatively the transition from parent fuel molecule to PAHs and, eventually, soot. Importantly, the approach resolved spatially the structure of flames even in the presence of steep gradients and, in turn, allowed us to follow the molecular growth process in unprecedented detail. Noteworthy is the adaptation to a flame environment of a novel technique based on trapping semi-volatile compounds in a filter, followed by off-line extraction and preconcentration for quantitative chemical analyses of species at mole fractions as low as parts per billion. The technique allowed for the quantitation of PAHs containing up to 6 aromatic rings. The principal finding is that only one- and two-ring aromatic compounds can account for soot nucleation, and thus provide the rate-limiting step in the reactions leading to soot. This finding impacts the fundamental understanding of soot formation and eases the modeling of soot nucleation by narrowing the precursors that must be predicted accurately

Waste Containment Ponds Are a Major Source of Secondary Organic Aerosol Precursors from Oil Sands Operations

Copyright © 2020 American Chemical Society. 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 15000-72000 metric tonnes of hydrocarbon SOA precursors, translating to 3000-13000 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

Natural Gas Residual Fluids: Sources, Endpoints, and Organic Chemical Composition after Centralized Waste Treatment in Pennsylvania

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 × 10⁸ 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

Indications of Transformation Products from Hydraulic Fracturing Additives in Shale-Gas Wastewater

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