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

Advanced Aerogel Composites for Oil Remediation and Recovery

<p>Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents. </p><p>The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space. </p><p>Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices. </p><p>To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE). </p><p>The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel. </p><p>Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.</p>Dissertatio

Treatment of Low Concentrations of Volatile Organic Compounds by Non-thermal Plasma

<p>Non-thermal plasma (NTP) technology is an emerging method to degrade otherwise recalcitrant volatile organic compounds (VOCs) in air. Here, a dielectric barrier discharge (DBD) NTP was used to evaluate the degradation efficiency of several VOCs (toluene, benzene, ethylbenzene, MEK (methyl ethyl ketone), MTBE (methyl-tert-butyl ether) 3-pentanone and n-hexane) under constant experimental conditions (6.6 L/min, 95 and 100 ppm average inlet concentrations). The efficiency with which toluene, ethylbenzene, benzene, MEK, MTBE, 3-pentanone, and n-hexane were removed was 74.03 ± 0.30%, 80.94 ± 0.07%, 57.82 ± 0.06%, 50.00 ± 0.20%, 80.00 ± 1.40%, 76.00 ± 1.4%, and 90.00 ± 0.30 %, respectively, at an inlet concentration 95 ppm, gas flow rate 6.6 L/min, and a specific input energy (SIE) of 350 J/L. The effects of various operating conditions on pollutant removal were investigated. Interestingly, the highest removal efficiencies were observed for compounds that have the highest percentage of hydrogen in the molecular structure. </p><p>During treatment of toluene and ethylbenzene, a deposit was formed inside the plasma reactor. This deposit was dark brown in color and gave off an oil-like odor, suggesting the formation of higher-order hydrocarbon compounds. The deposit mass was quantified and the impact of the deposit on the DBD reactor performance was discussed. It was noted that the time required for the deposit to clog the reactor depended on the experimental conditions. The clogging time when treating toluene in dry air conditions was more than 1.5 times greater than under humidified conditions (30% RH), suggesting that attention to the treated air relative humidity is critical. The quantity and structure of the deposits depended on both input VOC molecular structure as well as the experimental conditions. Thus, this study provides recommendations for the current applications of this technology.</p>Thesi

Natural Aerogels with Interesting Environmental Features: C-Sequestration and Pesticides Trapping

International audienceThis chapter discusses the emerging and promising field of environmental applications of aerogels. Due to their large pore volume, specific surface area, and diverse range of tailorable solid-phase and surface chemistries, aerogel materials are interesting candidates for addressing many challenging environmental remediation objectives. Herein we review the use of silicate, nonsilicate, and allophane-clay-based aerogels in several challenging environmental remediation applications including the removal of air pollutants, water remediation, oil spill reclamation, heavy metal capture, CO2 sequestration, trapping of pesticides, immobilization of nuclear waste, and capture of orbital space debris

Flexible, Mechanically Durable Aerogel Composites for Oil Capture and Recovery

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

Deforestation Due to Artisanal and Small-Scale Gold Mining Exacerbates Soil and Mercury Mobilization in Madre de Dios, Peru

© 2019 American Chemical Society. 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

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