Repository for Oil and Gas Energy Research (ROGER)

Abstract:
Membrane distillation (MD) has great potentials to treat produced water in energy industries. However, volatile organic compounds (VOCs) existing in the produced water added in the fracking process can hinder the treatment process regarding two aspects: permeate quality and MD flux performance. To address this challenge, this study aims to systematically study the effects of the VOCs on the MD permeation performance and permeate quality, and the mechanism of its penetration. Acetic acid, ethylene glycol, isopropyl alcohol (IPA), and 2-Butoxyethanol (2-BE), which are commonly found in the produced water, were extensively investigated and their impacts were reviewed and compared. Among all the VOCs, 2-BE had the highest mass transfer despite its low vapour pressure and large molecule weight. Some of the VOCs had surfactant properties, which meant they could penetrate the membrane pores easily during MD process. In long-term operation, pore wetting started to appear as the salt rejection was dropping in the MD process, and flux was also decreasing. Based on the results, this study suggested that the strength of surfactant properties and intra-molecular hydrogen bonds between water molecules and VOCs are as significant as vapour pressure for the VOCs in terms of mass transfer efficiency in MD system.

Abstract:
Sustainable wastewater management strategies are required to further minimize impacts of high-volume hydraulic fracturing (HVHF) as current practices such as reuse or direct disposal have long term limitations. Membranes can provide superior effluent quality in HVHF wastewater treatment, but the application of these systems is severely limited by membrane fouling. However, the key fouling components in HVHF wastewater have not yet been clearly identified and characterized. Here we demonstrate that fouling of microfiltration membranes by synthetic flowback water is mostly due to polyacrylamide (PAM), a major additive in slickwater fracturing fluids. A synthetic fracturing fluid was incubated with Marcellus Shale under HVHF conditions (80 degrees C, 83 bar, 24 h) to generate synthetic flowback water. Different HVHF conditions and fracturing fluid compositions generated a fouling index for flowback water ranging from 0.1 to 2000 m(-1), with these values well correlated with the peakmolecular weight (MW) (ranging from 10 to 1.5 x 10(4) kDa) and the concentration of high MW components in the water. The lowest fouling index was observed when PAM was further degraded by ammonium persulfate under HVHF conditions, although this is infrequently used with PAM in current fracturing operations. These results highlight the importance of PAM and its degradation products in fouling of subsequent membrane systems, providing insights that can help in the development of effective treatment processes for HVHF wastewater.

Abstract:
The extensive application of hydraulic fracturing technology has significantly promoted the large-scale development of shale gas. However, it is a great challenge for shale gas extraction to effectively manage large-volume flowback water (FW) with high salinity and complex organic substances. Here, we report an aerobic granular sludge (AGS) tolerable to high salinity, and suited to the treatment of FW. The performance of a sequencing batch reactor (SBR) with the AGS for the treatment of the synthetic FW and the microbial community structure at different salinity levels were investigated. The AGS fed with synthetic FW possessed a larger average particle size and a higher settling rate (50 m h−1). When NaCl concentration increased to 50.0 g L−1, the removal efficiency of total organic carbon (TOC) increased to 79 ± 1%, and the removal rate of polyacrylamide (PAM) raised up to 42.7 ± 0.7 g m−3 d−1. Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Sphingobacteriia dominated in the microbial community of AGS. Cellvibrionaceae, Rhodocyclaceae, Enterobacteriaceae, Moraxellaceae, Pseudomonadaceae, and Halomonadaceae belonging to Betaproteobacteria and Gammaproteobacteria played important role in degrading PAM, polycyclic aromatic hydrocarbons (PAH), and some other organics in FW at high salinity. These results suggest that an AGS-based SBR is a promising technology for the treatment of FW.

Abstract:
Radium in hydraulic fracturing wastewaters derives from two isotopically distinct end-members in the shale, labile 228Ra hosted by mineral surfaces (226Ra/228Ra atom ratio ~250) and exchangeable 226Ra hosted by organic surfaces (226Ra/228Ra ~10,000). Here we use mass balance and isotope mixing models to reconcile extraction of Ra from these phases with mechanisms of Marcellus wastewater production. Radium isotopic mass balance requires that the characteristic water-rock ratio between wastewater and shale is exceedingly low, on the order of 0.04, and that this ratio decreases with time during wastewater production. An evolving water-rock interaction drives increasing Ra concentrations (=[Ra]) and 226Ra/228Ra ratios during wastewater production, all mediated by increasing [Ca2+] that favors desorption of 226Ra from organics. Our observations and models of Ra isotope geochemistry are best reconciled with observations of water and salinity mass balance, δ18O, Na-Br-Cl, and 87Sr/86Sr if wastewater is produced by mixing of injected fluids with a limited volume of pore brine (on the order of 13% by volume), accompanied by contemporaneous extraction of excess alkaline earth elements by water-rock exchange. Validated using Ra isotope data, this model attributes the extreme salinity and [Ra] in wastewaters to the progressive, hydrologic enrichment of injected fluids during hydraulic fracturing.

Abstract:
The recent increase in unconventional oil and gas exploration and production has prompted a large amount of research on hydraulic fracturing, but the majority of chemical reactions between shale minerals and organic matter with fracturing fluids are not well understood. Organic matter, primarily in the form of kerogen, dominates the transport pathways for oil and gas; thus any alteration of kerogen (both physical and chemical properties) upon exposure to fracturing fluid may impact hydrocarbon extraction. In addition, kerogen is enriched in metals, making it a potential source of heavy metal contaminants to produced waters. In this study, we reacted two different kerogen isolates of contrasting type and maturity (derived from Green River and Marcellus shales) with a synthetic hydraulic fracturing fluid for two weeks in order to determine the effect of fracturing fluids on both shale organic matter and closely associated minerals. ATR-FTIR results show that the functional group compositions of the kerogen isolates were in fact altered, although by apparently different mechanisms. In particular, hydrophobic functional groups decreased in the Marcellus kerogen, which suggests the wettability of shale organic matter may be susceptible to alteration during hydraulic fracturing operations. About 1% of organic carbon in the more immature and Type I Green River kerogen isolate was solubilized when it was exposed to fracturing fluid, and the released organic compounds significantly impacted Fe oxidation. Based on the alteration observed in both kerogen isolates, it should not be assumed that kerogenic pores are chemically inert over the timeframe of hydraulic fracturing operations. Shifts in functional group composition and loss of hydrophobicity have the potential to degrade transport and storage parameters such as wettability, which could alter hydrocarbon and fracturing fluid transport through shale. Additionally, reaction of Green River and Marcellus kerogen isolates with low pH solutions (full fracturing fluid, which contains hydrochloric acid, or pH 2 water) mobilized potential trace metal(loid) contaminants, primarily S, Fe, Co, Ni, Zn, and Pb. The source of trace metal(loid)s varied between the two kerogen isolates, with metals in the Marcellus shale largely sourced from pyrite impurities, whereas metals in the Green River shale were sourced from a combination of accessory minerals and kerogen.

Abstract:
The global energy landscape has significantly changed in the past several years because horizontal drilling and hydraulic fracturing enable unconventional oil and gas extraction from previously inaccessible shale formations. However, opportunities and challenges coexist. Large volumes of freshwater consumed and wastewater discharge increasingly affect the environment and ecosystem. Much freshwater is pumped into deep formations during hydraulic fracturing process, and flowback with high-salinity brines, producing large volumes of wastewater. Such wastewater contains not only many toxic chemicals and high levels of total dissolved solids, but also abundant stratigraphic minerals and radioactive substances, which may pose a serious risk to the surrounding environment and public health. One of the greatest challenges for current oil and gas extraction is handling those wastewaters in a reasonable and efficient way. This paper described the current methods for dealing with these challenges and put forward some suggestions and expectations for future management of water resources in hydraulic fracturing. Open image in new window Graphical Abstract

Abstract:
High-quality water is essential for most industrial processes, and many of these processes generate large volumes of contaminated wastewater. Nanotechnology has the potential to make industrial water treatment more efficient and less expensive, though promising technologies must be demonstrated at higher scales to make a real impact.

Abstract:
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.

Abstract:
Water scarcity severely affects drylands threatening their food security, whereas, the oil and gas industry produces significant and increasing volumes of produced water that could be partly reused for agricultural irrigation in these regions. In this review, we summarise recent research and provide a broad overview of the potential for oil and gas produced water to irrigate food crops in drylands. The quality of produced water is often a limiting factor for the reuse in irrigation as it can lead to soil salinisation and sodification. Although the inappropriate use of produced water in irrigation could be damaging for the soil, the agricultural sector in dry areas is often prone to challenges in soil salinity. There is a lack of knowledge about the main environmental and economic conditions that could encourage or limit the development of irrigation with oil and gas effluents at the scale of drylands in the world. Cheaper treatment technologies in combination with farm-based salinity management techniques could make the reuse of produced water relevant to irrigate high value-crops in hyper-arid areas. This review paper approaches an aspect of the energy-water-food nexus: the opportunities and challenges behind the reuse of abundant oil and gas effluents for irrigation in hydrocarbon-rich but water-scarce and food-unsecured drylands.

Abstract:
The rapid rise of shale gas development has triggered environmental and human health concerns due to its impacts on water resources, especially on disinfection byproduct (DBP) formation upon chlorination. Despite the recently reported results on bromide, the effects of non-bromide ions in production wastewater at extremely high levels are vaguely defined. In this study, we investigated the effects of production wastewater, with bromide and non-bromide species, on the formation of DBPs when production wastewater was spiked into surface waters at various percentages. Results showed that the introduction of debrominated production wastewater led to increased formation of some chlorinated DBP species in selected surface water and wastewater. As the spiking percentage of debrominated production wastewater increased, the chlorinated DBP species increased. The contributions of individual cations to DBP formation followed a sequence of magnesium > calcium > barium at 0.10% spiking percentage due to the different catalytic effects of their chelates with organic precursors. The study of anions suggested that the discharge of treated production wastewater containing elevated sulfate may further enhance DBP formation. The significance of this study lies in the fact that in addition to bromide concerns from production wastewater, non-bromide species also contributed to DBP formation. The gas production wastewater management decision should consider the negative impacts from both bromide and non-bromide species to better protect the receiving water resources.

Abstract:
Surface spills of water produced from hydraulic fracturing can expose soil and groundwater to organics such as BTEX and naphthalene (BTEX&N) as well as high concentrations of salt. As an alternative to soil excavation, we evaluated the effectiveness of BTEX&N soil remediation using 2 grasses present in Colorado. Perennial ryegrass and foxtail barley were grown separately in pots in the greenhouse and exposed to salt or a synthesized produced-water slurry containing relevant levels of salt and BTEX&N. Plant biomass was measured 14 days post-spill, and levels of BTEX&N were quantified using GC/MS for soil, roots, and shoots at day 7 and 14 post-spill. Foxtail barley shoot growth was limited by BTEX&N, whereas perennial ryegrass shoot growth was enhanced by salt but not BTEX&N. While BTEX&N in soil associated with foxtail barley mainly decreased over time, the soil associated with perennial ryegrass mainly saw an increase in BTEX&N with time. However, further research is needed to determine the fate of BTEX&N within grasses and soil.

Abstract:
BACKGROUND: Hydraulically fractured wells produce 2–14 million liters of wastewater, which may contain toxic and radioactive compounds. The wastewater is predominantly disposed of using Class II injection wells. OBJECTIVE: Our objective was to evaluate the relationship between sociodemographic characteristics and injection well locations in Ohio. METHODS: Using state and federal data sources, we classified Ohio census block groups by presence of injection wells, number of hydraulically fractured wells, sociodemographic factors (median household income, % white, population density, % ≥high school education, median age, voter turnout), and geographic information (land area, water area, situated over shale). We modeled the odds of having at least one injection well within a block group with respect to all covariates using three multivariable models incorporating different spatial components to account for similarities in neighboring block groups. RESULTS: In bivariate analyses, block groups with injection wells (n=156) compared with those without (n=9,049) had lower population density (71 vs. 2,210 people/mi2 or 27 vs. 854 people/km2), larger median area (43.5 vs. 1.35 km2), higher median age (42.8 vs. 40.2 y), and higher % white (98.1% vs. 92.1%). After adjustment using a spatial logistic regression model, the odds of a block group containing an injection well were 16% lower per $10,000 increase in median income [odds ratio(OR)=0.837; 95% credible interval (CI): 0.719, 0.961] and 97% lower per 1,000 people/mi2 (or per 386 people/km2) increase (OR=0.030; 95% CI=0.008, 0.072). Block groups on shale and those containing fewer hydraulically fractured wells were more likely to include an injection well. Percentage white, median age, % ≥high school education, and % voter turnout were not significant predictors of injection well presence. CONCLUSION: In Ohio, injection wells were inversely associated with block groups’ median incomes after adjusting for other sociodemographic and geographic variables. Research is needed to determine whether residents in census blocks with injection wells face increased risk of chemical exposures or adverse health outcomes.

Abstract:
A fuzzy-based indexing approach was developed for the management of hydraulic fracturing chemical additives. The environmental and human health hazards of an additive are converted to hazard indices using an indexing system. To account for uncertainties, a fuzzy-based approach is adopted based on fuzzy inference and fuzzy clustering analysis to assess the risk potential of different additives for informed chemical management decision making. The assessment of the randomly selected additives showed that this fuzzy-based indexing approach gave different chemical hazard assessment results for about 30% of the assessed additives. This shows that accounting for uncertainties using this methodology can lead to better informed chemical management decision making. The hazard assessment results also indicate that based on current indexing methodology more than half of the additives permitted for use in hydraulic fracturing operations are considered moderate environmental and human health hazards. However, based on the new fuzzy-based approach the majority (80%) of the additives were identified as low and very low risk potential due to their low use frequencies. (C) 2018 Elsevier Ltd. All rights reserved.

Abstract:
Hydraulic fracturing is one of the industrial processes behind the surging natural gas output in the United States. This technology inadvertently creates an engineered microbial ecosystem thousands of meters below Earth’s surface. Here, we used laboratory reactors to perform manipulations of persisting shale microbial communities that are currently not feasible in field scenarios. Metaproteomic and metabolite findings from the laboratory were then corroborated using regression-based modeling performed on metagenomic and metabolite data from more than 40 produced fluids from five hydraulically fractured shale wells. Collectively, our findings show that Halanaerobium, Geotoga, and Methanohalophilus strain abundances predict a significant fraction of nitrogen and carbon metabolites in the field. Our laboratory findings also exposed cryptic predatory, cooperative, and competitive interactions that impact microorganisms across fractured shales. Scaling these results from the laboratory to the field identified mechanisms underpinning biogeochemical reactions, yielding knowledge that can be harnessed to potentially increase energy yields and inform management practices in hydraulically fractured shales.

Abstract:
Biological treatment is effective but infrequently used for oil and gas produced water. To date, physical–chemical treatment methods have been favored due to the smaller space requirements and operational simplicity. Changing regulatory requirements and increased interest in recycling and beneficial reuse have led to increased interest in biological treatment. To elucidate its potential role, we reviewed and summarized 59 studies on the biological treatment of produced water. Oilfield produced water was predominantly studied (> 50%). More studies using real produced water were from China than from any other country (37%). Real produced water was used in most studies (73%). Studies were predominantly bench-scale experiments (69%). Fixed-film reactors were most prevalent (27%). Water quality of produced waters treated was variable; median total dissolved solids (TDS) was 28,000 mg L−1 and median chemical oxygen demand (COD) was 1125 mg L−1. Inhibition by salinity was variable according to the treatment system and study design, but efficacy generally decreased when TDS was above 50,000 mg L−1. For studies treating real samples, average COD removal was 73% when TDS was less than 50,000 mg L−1, and 54% when TDS was greater than 50,000 mg L−1. Key issues were microbial acclimation, toxicity, biological fouling, and mineral scaling. Finding an inoculum was not problematic as microorganisms capable of degrading hydrocarbons were isolated from various environments. Treatment performance was better where synthetic produced water was used in lieu of real samples. Biological treatment is promising for producing effluents suitable for reuse, particularly where it functions as part of a larger treatment train.

Abstract:
The chemistry of hydraulic fracturing fluids and wastewaters is complex and is known to vary by operator, geologic formation, and fluid age. A time series of hydraulic fracturing fluids, flowback fluids, and produced waters was collected from two adjacent Marcellus Shale gas wells for organic chemical composition analyses using ultrahigh resolution mass spectrometry. Hierarchical clustering was used to compare and extract ions related to different fluid ages and many halogenated organic molecular ions were identified in flowback fluids and early produced waters based on exact mass. Iodinated organic compounds were the dominant halogen class in these clusters and were nearly undetectable in hydraulic fracturing fluid prior to injection. The iodinated ions increased in flowback and remained elevated after ten months of well production. We suggest that these trends are mainly driven by dissolved organic matter reacting with reactive halogen species formed abiotically through oxidizing chemical additives applied to the well and biotically via iodide-oxidizing bacteria. Understanding the implications of these identified halogenated organic compounds will require future investigation in to their structures and environmental fate.

Abstract:
Horizontal drilling and hydraulic fracturing are technologies designed to increase natural gas flow and to improve productivity in low permeability formations. During this drilling operation, tons of flowback and produced water, which contain several organic compounds, return to the surface with a potential risk of influencing the surrounding environment and human health. In order to conduct predictive risk assessments a mathematical model is needed to evaluate organic compound behaviour along the water transportation process as well as concentration changes over time throughout the operational life cycle. A comprehensive model, which fits the experimental data, combining an Organic Matter Transport Dynamic Model with a Two-Compartment First-order Rate Constant (MC) Model has been established to quantify the organic compounds concentrations. This algorithm model incorporates two transportation rates, fast and slow. The results show that the higher the value of the organic carbon partition coefficient (k(oc)) in chemicals, the later the maximum concentration in water will be reached. The maximum concentration percentage would reach up to 90% of the available concentration of each compound in shale formation (whose origin may be associated to drilling fluid, connate water and/or rock matrix) over a sufficiently long period of time. This model could serve as a contribution to enhance monitoring strategy, increase benefits out of optimizing health risk assessment for local residents and provide initial baseline data to further operations. (C) 2018 Elsevier B.V. All rights reserved.

Abstract:
Thirteen states in the United States allow the spreading of O&G wastewaters on roads for deicing or dust suppression. In this study, the potential environmental and human health impacts of this practice are evaluated. Analyses of O&G wastewaters spread on roads in the northeastern, U.S. show that these wastewaters have salt, radioactivity, and organic contaminant concentrations often many times above drinking water standards. Bioassays also indicated that these wastewaters contain organic micropollutants that affected signaling pathways consistent with xenobiotic metabolism and caused toxicity to aquatic organisms like Daphnia magna. The potential toxicity of these wastewaters is a concern as lab experiments demonstrated that nearly all of the metals from these wastewaters leach from roads after rain events, likely reaching ground and surface water. Release of a known carcinogen (e.g., radium) from roads treated with O&G wastewaters has been largely ignored. In Pennsylvania from 2008 to 2014, spreading O&G wastewater on roads released over 4 times more radium to the environment (320 millicuries) than O&G wastewater treatment facilities and 200 times more radium than spill events. Currently, state-by-state regulations do not require radium analyses prior to treating roads with O&G wastewaters. Methods for reducing the potential impacts of spreading O&G wastewaters on roads are discussed.

Abstract:
This research aimed to elucidate the effect of brine salinity and guar gum on the sorption and transport of Ba in dolomite rocks collected from the Arbuckle formation in Oklahoma, USA. Guar gum represents the most important organic additive used in viscosified fracturing fluids, and Ba constitutes the most common and abundant heavy metal found in unconventional oil and gas (UOG) wastewater. Batch experiments conducted using powdered dolomite rocks (500–600 μm particle size) revealed that at brine salinities of UOG wastewater, chloro-complexation reactions between Ba and Cl ions and pH changes that results from dolomite dissolution are the controlling factors of Ba sorption on dolomite. Competition of Ba with common cations (Ca and Mg) for hydration sites of dolomite, plays a secondary role. Core-flooding experiments conducted to analyze the transport of Ba through natural and synthetic dolomite core plugs are in agreement with the batch sorption experimental results. The transport of Ba through dolomite rocks, increases with increasing brine salinity (0–180,000 mg-NaCl/L). The presence guar gum (50–500 mg/L) does not affect the transport of Ba through dolomite rocks of high flow properties (25–29.6% porosity, 9.6–13.7 mD permeability). However, core-flooding experiments conducted using tight dolomite rocks (6.5–8.6% porosity, 0.06–0.3 mD permeability), revealed that guar gum can retard the transport of Ba by clogging high permeability/porosity regions of tight dolomite rocks. The mechanism of Ba sorption on dolomite can be represented by a sorption model that accounts for both surface complexation reactions on three distinct hydration sites (>CaOHo, >MgOHo, and >CO3Ho), and the kinetic dissolution of dolomite. These results are important in understanding and predicting the fate of Ba present in UOG wastewater disposed into deep dolomite saline aquifers.

Abstract:
Despite a declining trend, California remains a significant oil-producing state. For every barrel of crude oil, an average of 15 barrels of oilfield produced water (OPW) is generated, some of which is used to boost freshwater sources for crop irrigation in the agriculturally important Central Valley. OPW is known to contain salts, metals, hydrocarbons, alkylphenols, naturally radioactive materials, biocides, and other compounds from drilling and production processes. Less is known about the potential uptake and accumulation of these compounds in crops and soil irrigated with OPW. In this study, 23 potted mandarin orange plants were irrigated two to three times weekly (depending on season) with water containing three different concentrations of the known OPW heavy metals barium, chromium, lead, and silver. Seven sets of samples of soil and leaves and 11 fruits were collected and processed using microwave-assisted digestion (EPA Method 3051A). Processed samples were analyzed using inductively coupled plasma-optical emission spectroscopy (ICP-OES). Analysis of variance (ANOVA) and covariance (ANCOVA) coupled with Tukey’s honest significant difference test were used to examine the effects of metal concentrations in the irrigation water and number of watering days, respectively, on the metal concentrations in the soil, leaf, and fruit samples. Accumulation of barium in soil and leaves was strongly positively associated with sample and number of watering days, increasing nearly 2000-fold. Lead also showed an upward trend, increasing up to 560-fold over the baseline level. Total chromium showed an increase in the soil that tapered off, but less consistent results in the leaves and fruit. The silver results were more volatile, but also indicated at least some level of accumulation in the tested media. The smallest absolute accumulation was observed for chromium. Concentrations in the fruit were highest in the peel, followed by pith and juice. Accumulation of all heavy metals was generally highest in the soil and plants that received the highest irrigation water concentration. Considering the potential for adverse human health effects associated with ingesting soluble barium contained in food and drinking water, and to a lesser extent chromium and lead, the study signals that it is important to conduct further research into the accessibility and bioavailability of the tested heavy metals in the soil and whether they pose risks to consumers.

Abstract:
Abstract: The production of gas from unconventional resources became an important position in the world energy economics. In 2012, the European...

Abstract:
We measured fluxes of methane, a suite of non-methane hydrocarbons (C2–C11), light alcohols, and carbon dioxide from oil and gas produced water storage and disposal ponds in Utah (Uinta Basin) and Wyoming (Upper Green River Basin) United States during 2013–2016. In this paper, we discuss the characteristics of produced water composition and air-water fluxes, with a focus on flux chamber measurements. In companion papers, we will (1) report on inverse modeling methods used to estimate emissions from produced water ponds, including comparisons with flux chamber measurements, and (2) discuss the development of mass transfer coefficients to estimate emissions and place emissions from produced water ponds in the context of all regional oil and gas-related emissions. Alcohols (made up mostly of methanol) were the most abundant organic compound group in produced water (91% of total volatile organic concentration, with upper and lower 95% confidence levels of 89 and 93%) but accounted for only 34% (28 to 41%) of total organic compound fluxes from produced water ponds. Non-methane hydrocarbons, which are much less water-soluble than methanol and less abundant in produced water, accounted for the majority of emitted organics. C6–C9 alkanes and aromatics dominated hydrocarbon fluxes, perhaps because lighter hydrocarbons had already volatilized from produced water prior to its arrival in storage or disposal ponds, while heavier hydrocarbons are less water soluble and less volatile. Fluxes of formaldehyde and other carbonyls were low (1% (1 to 2%) of total organic compound flux). The speciation and magnitude of fluxes varied strongly across the facilities measured and with the amount of time water had been exposed to the atmosphere. The presence or absence of ice also impacted fluxes.

Abstract:
The rapid expansion of unconventional natural gas production has triggered considerable public concerns, particularly regarding environmental and human health (EHH) risks posed by various chemical additives used in hydraulic fracturing (HF) operations. There is a need to assess the potential EHH hazards of additives used in real-world HF operations. In this study, HF additive and fracturing fluid data was acquired, and EHH hazards were assessed using an indexing approach. The indexing system analyzed chemical toxicological data of different ingredients contained within additives and produced an aggregated EHH safety index for each additive, along with an indicator describing the completeness of the chemical toxicological data. The results show that commonly used additives are generally associated with medium-level EHH hazards. In each additive category, ingredients of high EHH concern were identified, and the high hazard designation was primarily attributed to ingredients' high aquatic toxicity and carcinogenic effects. Among all assessed additive categories, iron control agents were identified as the greatest EHH hazards. Lack of information, such as undisclosed ingredients and chemical toxicological data gaps, has resulted in different levels of assessment uncertainties. In particular, friction reducers show the highest data incompleteness with regards to EHH hazards. This study reveals the potential EHH hazards associated with chemicals used in current HF field operations and can provide decision makers with valuable information to facilitate sustainable and responsible unconventional gas production. (c) 2017 Elsevier B.V. All rights reserved.

Abstract:
A bounding risk assessment is presented that evaluates possible human health risk from a hypothetical scenario involving a 10,000-gallon release of flowback water from horizontal fracturing of Marcellus Shale. The water is assumed to be spilled on the ground, infiltrates into groundwater that is a source of drinking water, and an adult and child located downgradient drink the groundwater. Key uncertainties in estimating risk are given explicit quantitative treatment using Monte Carlo analysis. Chemicals that contribute significantly to estimated health risks are identified, as are key uncertainties and variables to which risk estimates are sensitive. The results show that hypothetical exposure via drinking water impacted by chemicals in Marcellus Shale flowback water, assumed to be spilled onto the ground surface, results in predicted bounds between 10(-10) and 10(-6) (for both adult and child receptors) for excess lifetime cancer risk. Cumulative hazard indices (HICUMULATIVE) resulting from these hypothetical exposures have predicted bounds (5th to 95th percentile) between 0.02 and 35 for assumed adult receptors and 0.1 and 146 for assumed child receptors. Predicted health risks are dominated by noncancer endpoints related to ingestion of barium and lithium in impacted groundwater. Hazard indices above unity are largely related to exposure to lithium. Salinity taste thresholds are likely to be exceeded before drinking water exposures result in adverse health effects. The findings provide focus for policy discussions concerning flowback water risk management. They also indicate ways to improve the ability to estimate health risks from drinking water impacted by a flowback water spill (i.e., reducing uncertainty).

Abstract:
The use of hydraulic fracturing for production of petroleum and natural gas has increased dramatically in the last decade, but the environmental impacts of this technology remain unclear. Experiments were conducted to quantify airborne emissions from twelve samples of hydraulic fracturing flowback wastewater collected in the Permian Basin, as well as the photochemical processing of these emissions leading to the formation of particulate matter. The concentration of total volatile carbon (TVC, hydrocarbons evaporating at room temperature) averaged 29 mg of carbon (C) L-1. After photochemical oxidation under high NOx conditions the amount of organic particulate matter (PM) formed per milliliter of wastewater evaporated averaged 24 µg; the amount of ammonium nitrate formed averaged 262 µg. Based on the mean PM formation observed in these experiments, the estimated formation of PM from evaporated flowback wastewater in the state of Texas is in the range of estimated PM emissions from diesel engines used in oil rigs. Evaporation of flowback wastewater, a hitherto unrecognized source of secondary pollutants, could significantly contribute to ambient PM concentrations.

Abstract:
Hydraulic fracturing is an increasingly common technique for the extraction of natural gas entrapped in shale formations. This technique has been highly criticized due to the possibility of environmental contamination, underscoring the need for method development to identify chemical factors that could be utilized in point-source identification of environmental contamination events. Here, we utilize comprehensive two-dimensional gas chromatography (GC × GC) coupled to high-resolution time-of-flight (HRT) mass spectrometry, which offers a unique instrumental combination allowing for petroleomics hydrocarbon fingerprinting. Four flowback fluids from Marcellus shale gas wells in geographic proximity were analyzed for differentiating factors that could be exploited in environmental forensics investigations of shale gas impacts. Kendrick mass defect (KMD) plots of these flowback fluids illustrated well-to-well differences in heteroatomic substituted hydrocarbons, while GC × GC separations showed variance in cyclic hydrocarbons and polyaromatic hydrocarbons among the four wells. Additionally, generating plots that combine GC × GC separation with KMD established a novel data-rich visualization technique that further differentiated the samples.

Abstract:
Due to stricter environmental regulations and lack of other alternatives, saline effluents reuse is becoming necessary in arid regions. Produced water generated in oil and gas exploration is a promising stream for this purpose, since remarkable quantities are available. In order to turn desalination routes into economically attractive options, it is mandatory to choose and to optimize technologies aiming to minimize capital and operational costs. Therefore, several combinations of technologies, involving forward osmosis (FO), reverse osmosis (RO), assisted reverse osmosis (ARO), microfiltration (MF), mechanical vapor compression (MVC), and membrane distillation (MD) were simulated and optimized for different reuse destinations. Results indicated MF-RO as the cheapest route for salinities lower than 90 g/L, while FO-RO had the highest cost and could be unfeasible depending on salinity. For higher salt content, MF-ARO-RO was the cheapest alternative, followed by thermal processes (MF-MVC and FO-MVC, respectively). However, applicability of MVC depends on final water quality due to possible volatiles constraints. MF-ARO-RO process, which is a novel technology, was submitted to a retro-techno-economic analysis (RTEA) to investigate its potentialities. Although membrane parameters had minor influence, external parameters as ARO membrane cost, energy cost and interest rate play important roles on process cost.

Abstract:
Skip to Next Section The production of hydraulic fracturing fluids (HFFs) in natural gas extraction and their subsequent management results in waste streams highly variable in total dissolved solids (TDS). Because TDS measurement is time-consuming, it is often estimated from electrical conductivity (EC) assuming dissolved solids are predominantly ionic species of low enough concentration to yield a linear TDS-EC relationship: TDS (mg/L) = ke × EC (μS cm−1) where ke is a constant of proportionality. HHFs can have TDS levels from 20,000 to over 300,000 mg L−1 wherein ion-pair formation and un-ionized solutes invalidate a simple TDS/EC relationship. Therefore, the composition and TDS-EC relationship of several fluids from Marcellus gas wells in Pennsylvania was assessed. Below EC of 75,000 μS cm−1, TDS (mg L−1) can be estimated with little error assuming ke = 0.7. For more concentrated HFFs, a curvilinear relationship (R2 = 0.99) is needed: TDS = 27,078e1.05E−05*EC. For hypersaline HFFs, the use of an EC/TDS meter underestimates TDS by as much as 50%. A single linear relationship is unreliable as a predictor of brine strength and, in turn, potential water quality and soil impacts from accidental releases or the suitability of HFFs for industrial wastewater treatment.

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A non-targeted study of hydraulic fracturing fluids and corresponding flowback fluids allows for the understanding of the origin of wastewater constituents and provides insight into chemical signatures that may inform wastewater management practices for unconventional gas development. The source water for the hydraulic fracturing fluids, the actual hydraulic fracturing fluids used in four stimulation stages, and four flowback samples were obtained from a single unconventional gas well located in northeastern, PA. The chemical complexity of these fluids required high-resolution non-targeted methodologies. Analyses were therefore performed by GC  ×  GC-TOFMS with the use of mass spectral scripting algorithms to expedite data analysis while maintaining a discovery approach. Our results indicate that during the flowback period hydrocarbon concentrations increase with time. The relative chemical composition remains nearly constant, which is hypothesized to be representative of the hydrocarbons present in the native shale that were extracted during the hydraulic fracturing process. Additionally, a comparison of fracturing fluids and flowback with high-resolution time-of-flight mass spectrometry inferred the fate of three common organic modifiers: ethylene glycol, glutaraldehyde, and cinnamaldehyde. It was determined that ethylene glycol is removed from the well within the first four days of flowback, while polymerization reactions are primary mechanisms of glutaraldehyde and cinnamaldehyde transformation.

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There are significant recoverable oil and gas resources stored in shale reservoirs throughout the world. Horizontal well with multistage hydraulic fracturing is an enabling technology for economic production of these shale resources. Recovery factors of liquid rich shale reservoirs is typically less than 10%, hence, there is an incentive for implementing enhanced oil recovery (EOR) technologies to improve oil production from these very tight reservoirs. Brine, chemical (surfactant), gas, or combination of these fluids imbibition or injection in huff-n-puff scenario could improve oil recovery of liquid rich shale reservoirs. In this study, low-salinity water and low-salinity water + surfactant imbibition are assessed as both hydraulic fracturing and EOR fluids in liquid rich shale reservoirs. Osmosis, capillary pressure, wettability alteration, and other effects are among the mechanisms by which these fluids can improve oil recovery from shale reservoirs. These favorable effects were investigated through imbibition experiments. Experiments show: (a) low-salinity water huff-n-puff in tight formations can improve oil production from tight formations. This is because wettability alteration, capillary, and osmotic forces; (b) surfactant + low-salinity-water huff-n-puff can further improve oil production due to additional IFT decrease and wettability alteration by surfactants; hence, improve oil production from stimulated ultra-tight formations. Based on experimental observations and literature reviewed, low-salinity water huff-n-puff (until economical), followed by low-salinity water + surfactant huff-n-puff EOR process is recommended to optimize production from liquid rich shale reservoirs, while minimizing cost. These fluids can be used to reduce matrix-fracture skin damage. The effectiveness of these hydraulic fracturing and EOR fluids in shales is highly dependent on the existence and extent of natural fractures or laminations within the stimulated reservoir volume; this is because osmosis and diffusion are very slow processes.

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Hydraulic fracking is used to enhance the production of tight gas reservoirs. Because shale reservoirs can contain toxic elements (metals and radionuclides), the release rates of these elements must be quantified in order to determine the possible environmental impact of fracking. This paper is devoted to the complete and precise determination of the mineralogy of the Alum Shale in Denmark, which is known for its high content of gaseous hydrocarbons. Its metal-bearing phases are identified and quantified using complementary analytical techniques (i.e., X-ray diffraction, electron microscopy and electron probe analysis, and X-ray tomography). A detailed quantitative mineralogical composition is calculated using three different approaches (i.e., matrix inversion, quantitative X-ray diffraction, and the MQ program), which is then used to determine the quantity of polluting elements in each phase. Pyrite (FeS2) is the major metal-bearing phase (e.g., As, Cu, Co, Ni, Pb, Zn, V, U). Elements such as V, Ra, Cs, Be, Cr, Ba are trapped in clay minerals, whereas U, Cd, Mo, and Hg are present in organic matter. It is essential to better identify toxic element-bearing phases to formulate fracking fluids with the lowest possible chemical reactivity in order to avoid the release of pollution by flowback waters.

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The development of unconventional oil and gas (UOG) resources results in production of large volumes of wastewater containing a complex mixture of hydraulic fracturing chemical additives and components from the formation. Release of these wastewaters into the environment poses potential risks that are poorly understood. Microbial communities in stream sediments form the base of the food chain, and may serve as sentinels for changes in stream health. Iron reducing organisms have been shown to play a role in the biodegradation of a wide range of organic compounds, and to evaluate their response to UOG wastewater, we enriched anaerobic microbial communities from sediments collected upstream (background) and downstream (impacted) of an UOG wastewater injection disposal facility in the presence of hydraulic fracturing fluid (HFF) additives: guar gum, ethylene glycol, and two biocides, DBNPA and Bronopol. Iron reduction was significantly inhibited early in the incubations with the addition of biocides, whereas amendment with guar gum and ethylene glycol stimulated iron reduction relative to unamended controls. Changes in the microbial community structure were observed across all treatments, indicating the potential for even small amounts of UOG wastewater components to influence natural microbial processes. Microbial community structure differed between enrichments with background and impacted sediments, suggesting that impacted sediments may have been pre-conditioned by exposure to wastewater. These experiments demonstrated the potential for biocides to significantly decrease iron reduction rates immediately following a spill, and demonstrated how microbial communities previously exposed to UOG wastewater may be more resilient to additional spills. Importance: Organic components of UOG wastewater can alter microbial communities and biogeochemical processes, which could alter the rates of essential natural attenuation processes. These findings provide new insights into microbial responses following a release of UOG wastewaters, and are critical for identifying strategies for remediation and natural attenuation of impacted environments.

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In this study, alginate and polyvinyl alcohol (PVA)-alginate entrapped nanoscale zero-valent iron (nZVI) was tested for structural evolution, chemical transformation, and metals/metalloids removal (Cu(II), Cr(VI), Zn(II), and As(V)) after 1-2 month passivation in model saline wastewaters from hydraulic fracturing. X-ray diffraction analysis confirmed successful prevention of Fe-0 corrosion by polymeric entrapment. Increasing ionic strength (I) from 0 to 4.10 M (deionized water to Day-90 fracturing wastewater (FWW)) with prolonged aging time induced chemical instability of alginate due to dissociation of carboxyl groups and competition for hydrogen bonding with nZVI, which caused high Na (7.17%) and total organic carbon (24.6%) dissolution from PVA-alginate entrapped nZVI after 2-month immersion in Day-90 FWW. Compared to freshly-made beads, 2-month aging of PVA-alginate entrapped nZVI in Day-90 FWW promoted Cu(II) and Cr(VI) uptake in terms of the highest removal efficiency (84.2% and 70.8%), pseudo-second-order surface area-normalized rate coefficient k(sa) (2.09 x 10(-1) L m(-2) h(-1) and 1.84 x 10(-1) L m(-2) h(-1)), and Fe dissolution after 8-h reaction (13.9% and 8.45%). However, the same conditions inhibited Zn(II) and As(V) sequestration in terms of the lowest removal efficiency (31.2% and 39.8%) by PVA-alginate nZVI and ksa (4.74 x 10(-2) Lm(-2) h(-1) and 6.15 x 10(-2) Lm(-2) h(-1)) by alginate nZVI. The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in metals/metalloids removal by entrapped nZVI after aging was attributed to distinctive removal mechanisms: (i) enhanced Cu(II) and Cr(VI) removal by nZVI reduction with accelerated electron transfer after pronounced dissolution of non-conductive polymeric immobilization matrix; (ii) suppressed Zn(II) and As(V) removal by nZVI adsorption due to restrained mass transfer after blockage of surface-active micropores. Entrapped nZVI was chemically fragile and should be properly stored and regularly replaced for good performance. (C) 2017 Elsevier B.V. All rights reserved.

Abstract:
In this study, alginate and polyvinyl alcohol (PVA)-alginate entrapped nanoscale zero-valent iron (nZVI) was tested for structural evolution, chemical transformation, and metals/metalloids removal (Cu(II), Cr(VI), Zn(II), and As(V)) after 1-2 month passivation in model saline wastewaters from hydraulic fracturing. X-ray diffraction analysis confirmed successful prevention of Fe-0 corrosion by polymeric entrapment. Increasing ionic strength (I) from 0 to 4.10 M (deionized water to Day-90 fracturing wastewater (FWW)) with prolonged aging time induced chemical instability of alginate due to dissociation of carboxyl groups and competition for hydrogen bonding with nZVI, which caused high Na (7.17%) and total organic carbon (24.6%) dissolution from PVA-alginate entrapped nZVI after 2-month immersion in Day-90 FWW. Compared to freshly-made beads, 2-month aging of PVA-alginate entrapped nZVI in Day-90 FWW promoted Cu(II) and Cr(VI) uptake in terms of the highest removal efficiency (84.2% and 70.8%), pseudo-second-order surface area-normalized rate coefficient k(sa) (2.09 x 10(-1) L m(-2) h(-1) and 1.84 x 10(-1) L m(-2) h(-1)), and Fe dissolution after 8-h reaction (13.9% and 8.45%). However, the same conditions inhibited Zn(II) and As(V) sequestration in terms of the lowest removal efficiency (31.2% and 39.8%) by PVA-alginate nZVI and ksa (4.74 x 10(-2) Lm(-2) h(-1) and 6.15 x 10(-2) Lm(-2) h(-1)) by alginate nZVI. The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in metals/metalloids removal by entrapped nZVI after aging was attributed to distinctive removal mechanisms: (i) enhanced Cu(II) and Cr(VI) removal by nZVI reduction with accelerated electron transfer after pronounced dissolution of non-conductive polymeric immobilization matrix; (ii) suppressed Zn(II) and As(V) removal by nZVI adsorption due to restrained mass transfer after blockage of surface-active micropores. Entrapped nZVI was chemically fragile and should be properly stored and regularly replaced for good performance. (C) 2017 Elsevier B.V. All rights reserved.

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Forward osmosis is an emerging membrane based separation technology that could find niche applications in the treatment of oil and gas produced water. Here, the feasibility of treating hydraulic fracturing produced waters using a combined electrocoagulation (EC) and forward osmosis (FO) process has been investigated. EC is shown to be effective in removing suspended solids and organic compounds which foul the membrane during FO. The amount of suspended solids and organic compounds that are removed depends on the EC reaction time. By accounting for internal and external concentration polarization as well as fouling due to deposition on the feed side barrier surface of the FO membrane, the expected flux may be determined. The effectiveness of removal of suspended solids and organic compounds may be modeled as changes in the permeability of the foulant layer that develops on the feed side of the membrane. The results obtained for real produced waters from Southwestern Energy operations in the Fayetteville Shale indicate that combined EC and FO could be an effective method for water recovery from hydraulic fracturing produced waters.

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The state of Oklahoma has experienced a dramatic increase in the amount of measurable seismic activities over the last decade. The needs of a petroleum-driven world have led to increased production utilizing various technologies to reach energy reserves locked in tight formations and stimulate end-of-life wells, creating significant amounts of undesirable wastewater ultimately injected underground for disposal. Using Phased Array L-band Synthetic Aperture Radar (PALSAR) data, we performed a differential Synthetic Aperture Radar Interferometry (InSAR) technique referred to as the Small BAseline Subset (SBAS)-based analysis over east central Oklahoma to identify ground surface deformation with respect to the location of wastewater injection wells for the period of December 2006 to January 2011. Our results show broad spatial correlation between SBAS-derived deformation and the locations of injection wells. We also observed significant uplift over Cushing, Oklahoma, the largest above ground crude oil storage facility in the world, and a key hub of the Keystone Pipeline. This finding has significant implications for the oil and gas industry due to its close proximity to the zones of increased seismicity attributed to wastewater injection. Results southeast of Drumright, Oklahoma represent an excellent example of the potential of InSAR, identifying a fault bordered by an area of subduction to the west and uplift to the east. This differentiated movement along the fault may help explain the lack of any seismic activity in this area, despite the large number of wells and high volume of fluid injected.

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Abstract, Radioactive materials for the medical, technological, and industrial sectors have been effectively regulated in the United States since as early as 1962. The steady increase in the exploration and production of shale gas in recent years has led to concerns about exposures to Naturally Occurring Radioactive Materials (NORM) and Technologically Enhanced Naturally Occurring Radioactive Materials (TENORM) in oil and gas waste streams. This study applied policy surveillance methods to conduct a cross-sectional fifty-state survey of law and regulations of NORM and TENORM waste from oil and gas operations. Results indicated that seventeen states drafted express regulations to reduce exposure to oil and gas NORM and TENORM waste. States with active oil and gas drilling that lack regulations controlling exposure to NORM and TENORM may leave the public and workers susceptible to adverse health effects from radiation. The study concludes with recommendations in regard to regulating oil and gas NORM and TENORM waste.

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Dissolved organic matter (DOM) present in oil and gas (O&G) produced water and fracturing flowback was characterized and quantified by multiple analytical techniques throughout a hybrid biological-physical treatment process. Quantitative and qualitative analysis of DOM by liquid chromatography – organic carbon detection (LC-OCD), liquid chromatography–high-resolution mass spectrometry (LC-HRMS), gas chromatography–mass spectrometry (GC–MS), and 3D fluorescence spectroscopy, demonstrated increasing removal of all groups of DOM throughout the treatment train, with most removal occurring during biological pretreatment and some subsequent removal achieved during membrane treatment. Parallel factor analysis (PARAFAC) further validated these results and identified five fluorescent components, including DOM described as humic acids, fulvic acids, proteins, and aromatics. Tryptophan-like compounds bound by complexation to humics/fulvics were most difficult to remove biologically, while aromatics (particularly low molecular weight neutrals) were more challenging to remove with membranes. Strong correlation among PARAFAC, LC-OCD, LC-HRMS, and GC–MS suggests that PARAFAC can be a quick, affordable, and accurate tool for evaluating the presence or removal of specific DOM groups in O&G wastewater.

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The safe and effective management of wastewaters from unconventional hydrocarbon production using the hydraulic fracturing (fracking) process poses a major challenge. Exploitation of unconventional hydrocarbons, such as shale gas, remains controversial in the UK primarily due to concerns surrounding the hydraulic fracturing process required to extract the resource. The key issue of how waste fluids produced by hydraulic fracturing in the UK will be safely managed has yet to be adequately addressed, and the capacity for the specialist treatment required is currently uncertain. To address this critical knowledge gap we review, for the first time, the available management options for these waste fluids in the UK. We find that these are limited in comparison to the options available in the U.S., due to uncertainty surrounding whether wastewater injection wells will be permitted in the UK. Consequently, it is highly probable that these fluids will need to be treated and safely disposed of at the surface. In order to constrain the composition of wastewater which will require treatment in the UK, we analyse the only existing data set of returned waters from hydraulic fracturing (n = 31). We supplement this with measurements of wastewater from UK conventional onshore hydrocarbon (n = 3), and offshore hydrocarbon (n = 14), operations which produce water from similar formations as those currently targeted for shale gas exploration. Comparison of this limited UK data to the more extensive unconventional production dataset from the United States (n = 3092) provides confidence in our projected UK wastewater compositions. We find that the high level of salinity and concentration of naturally occurring radioactive material (NORM) in UK wastewaters will be problematic to treat for disposal into a freshwater environment. We use our data compilation to estimate costs of treating such wastewaters in a number of relevant scenarios. We find that the projected salinity in FP waters from UK hydraulic fracturing operations can be treated at a cost of between $2701 (similar to 2000) pound and $1376093 (similar to 1047000) pound per well, requiring between 2 and 26% of expected revenue. Additional costs, specific to the UK of up to 163 pound 450 per well, will be incurred due to the legislative requirement for disposal of NORM concentrated sludge in permitted landfill sites. We find that existing capacity to receive NORM waste at currently permitted UK treatment facilities is limited, and that this will pose management problems if wastewaters are generated from multiple unconventional wells simultaneously.

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Hydraulic fracturing (HF) has emerged as a major recovery method of unconventional oil and gas reservoirs and concerns have been raised regarding the environmental impact of releases of Flowback and Produced Water (FPW) to aquatic ecosystems. To investigate potential effects of HF-FPW on fish embryo development, HF-FPW samples were collected from two different wells and the organic fractions were isolated from both aqueous and particle phases to eliminate the confounding effects of high salinity. Each organic extract was characterized by non-target analysis with HPLC-Orbitrap-MS, with targeted analysis for polycyclic aromatic hydrocarbons provided as markers of petroleum-affected water. The organic profiles differed between samples, including PAHs and alkyl PAHs, and major substances identified by non-target analysis included polyethylene glycols, alkyl ethoxylates, octylphenol ethoxylates and other high molecular weight (C49-79) ethylene oxide polymeric material. Zebrafish embryos were exposed to various concentrations of FPW organic extracts to investigate acute (7-day) and developmental toxicity in early life stages. The acute toxicity (LD50) of the extracted FPW fractions ranged from 2.8× to 26× the original organic content. Each extracted FPW fraction significantly increased spinal malformation, pericardial edema, and delayed hatch in exposed embryos and altered the expression of a suite of target genes related to biotransformation, oxidative stress and endocrine-mediation in developing zebrafish embryos. These results provide novel information on the variation of organic profiles and developmental toxicity among different sources and fractions of HF-FPWs.

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This study evaluates and compares the performance of microbial fuel cells (MFCs) and microbial capacitive deionization cells (MCDCs) fed with wastewater produced from the Bakken shale. The produced water was characterized by high levels of dissolved solids and chemical oxygen demand (COD). Two-compartment MFCs and three-compartment MCDCs were evaluated under batch-fed mode using mixed microbial consortia in the anode, ferricyanide in the cathode, and produced water as the electrolyte in the anode and capacitive deionization units. COD removal in the MFCs was 88%, while that in the MCDCs was limited to 76%. The lower performance of the MCDCs was due to the large impedance (6600 Ω cm2) compared with the MFCs (870 Ω cm2). However, the MCDCs achieved two-fold higher removal of dissolved solids. Both the MFCs and MCDCs suffered from a higher impedance induced by fouling in the latter stages of the operation.

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Hydraulic fracturing, or fracking, is a process of introducing liquid at high pressure to create fractures in shale rock formations, thus releasing natural gas. Flowback and produced water from fracking operations is typically stored in temporary open-air earthen impoundments, or frack ponds. Unfortunately, in the United States there is no public record of the location of impoundments, or the dates that impoundments are created or removed. In this study we use a dataset of drilling-related impoundments in Pennsylvania identified through the FrackFinder project led by SkyTruth, an environmental non-profit. For each impoundment location, we compiled all low cloud Landsat imagery from 2000 to 2016 and created a monthly time series for three bands: red, near-infrared (NIR), and the Normalized Difference Vegetation Index (NDVI). We identified the approximate date of creation and removal of impoundments from sudden breaks in the time series. To verify our method, we compared the results to date ranges derived from photointerpretation of all available historical imagery on Google Earth for a subset of impoundments. Based on our analysis, we found that the number of impoundments built annually increased rapidly from 2006 to 2010, and then slowed from 2010 to 2013. Since newer impoundments tend to be larger, however, the total impoundment area has continued to increase. The methods described in this study would be appropriate for finding the creation and removal date of a variety of industrial land use changes at known locations.

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In Pennsylvania, Appalachian oil and gas wastewaters (OGW) are permitted for release to surface waters after some treatment by centralized waste treatment (CWT) facilities. While this practice was largely discontinued in 2011 for unconventional Marcellus OGW, it continues for conventional OGW. This study aimed to evaluate the environmental implications of the policy allowing the disposal of conventional OGW. We collected stream sediments from three discharge sites receiving treated OGW between 2014-2017 and measured 228Ra, 226Ra, and their decay products, 228Th and 210Pb, respectively. We consistently found elevated activities of 228Ra and 226Ra in stream sediments in the vicinity of the outfall (total Ra = 90-25,000 Bq/kg) compared to upstream sediments (20-80 Bq/kg). In 2015 and 2017, 228Th/228Ra activity ratios in sediments from two disposal sites were relatively low (0.2-0.7), indicating that a portion of the Ra has accumulated in the sediments in recent (<3) years, when no unconventional Marcellus OGW was reportedly discharged. 228Ra/226Ra activity ratios were also higher than what would be expected solely from disposal of low 228Ra/226Ra Marcellus OGW. Based on these variations, we concluded that recent disposal of treated conventional OGW is the source of high Ra in stream sediments at CWT facility disposal sites. Consequently, policies pertaining to the disposal of only unconventional fluids are not adequate in preventing radioactive contamination in sediments at disposal sites, and the permission to release of treated Ra-rich conventional OGW through CWT facilities should be reconsidered.

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Polyacrylamide (PAM) based friction reducers are a primary ingredient of slickwater hydraulic fracturing fluids. Little is known regarding the fate of these polymers under downhole conditions, which could have important environmental impacts including decisions on strategies for reuse or treatment of flowback water. The objective of this study was to evaluate the chemical degradation of high molecular weight PAM, including the effects of shale, oxygen, temperature, pressure, and salinity. Data were obtained with a slickwater fracturing fluid exposed to both a shale sample collected from a Marcellus outcrop and to Marcellus core samples at high pressures/temperatures (HPT) simulating downhole conditions. Based on size exclusion chromatography analyses, the peak molecular weight of the PAM was reduced by 2 orders of magnitude, from roughly 10 MDa to 200 kDa under typical HPT fracturing conditions. The rate of degradation was independent of pressure and salinity but increased significantly at high temperatures and in the presence of oxygen dissolved in fracturing fluids. Results were consistent with a free radical chain scission mechanism, supported by measurements of sub-μM hydroxyl radical concentrations. The shale sample adsorbed some PAM (∼30%), but importantly it catalyzed the chemical degradation of PAM, likely due to dissolution of Fe2+ at low pH. These results provide the first evidence of radical-induced degradation of PAM under HPT hydraulic fracturing conditions without additional oxidative breaker.

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Abstract: Unconventional oil production in North Dakota (ND) and other states in the United States uses large amounts of water for hydraulic fracturing to...

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Petrochemical and oil & gas industries are crucial for global economy while great attention is needed for the related contamination and its impact on the environment. Papers reviewed herein represent the recent research and development on petrochemical wastewater and produced water from oil & gas industry, published in 2017 and beginning of 2018 globally. In the petrochemical wastewater, progresses were made in characterization, physicochemical treatment and biological treatment. In the oil & gas produced water, efforts were made on the characterization, the environmental impact and treatment options.

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Pollutants and microbiota present in the residual sludge of hydraulic fracturing were determined and characterized physicochemically. Analyses included determination of pH, electric conductivity, organic matter percentage, as well as total carbonates, inorganic nitrogen and extractable phosphorous. In addition, presence of hydrocarbons by gas chromatography, potentially toxic elements (PTEs) by atomic absorption and presence of radioactive isotopes by gamma spectrometry were determined. Moreover, fungi and bacteria present in the residual sludge were classified taxonomically to the level of genus. Medium and heavy hydrocarbon fractions were found in concentrations above the maximum limits permitted (MLP) by Mexican environmental norms. Cu, Pb, Zn, Fe and Mg, however, were below the MLP. Likewise, gamma spectrometry analysis revealed naturally occurring Ac-228, Ra-226 and K-40. The microbiological analysis found presence of the bacteria Bacillus spp., Micrococcus sp., Diplococcus sp. and Staphylococcus sp. and the fungi Trichoderma sp., Aspergillus sp. and Penicillium spp.

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Abstract:
Hydraulic fracturing technologies have facilitated the rapid development of shale gas and other unconventional hydrocarbon resources throughout the world. Following hydraulic fracturing operations, a large quantity of water flows back to the surface. Understanding the provenance and composition of this returned water is therefore of paramount importance in order to optimize the recycling and reuse of the millions of litres of wastewater generated by hydraulic fracturing and to reduce freshwater consumption. Here we report flowback and produced fluids data obtained from a horizontal well in a low permeability reservoir within the Montney formation in Alberta, Canada. The reservoir was fractured with a mixture of nitrogen and water and the returned water was sampled 24 times during the first week of flowback and once after more than one year of production. The samples were analyzed for concentrations of major ions and for the stable isotope composition of water. The TDS (total dissolved solids) of the samples increased rapidly from 395 mg/L for the injected water to 50,000 mg/L after two days and 96,000 mg/L at the end of the first week of flowback. At the same time, δ 2 H values increased from −142 to −113 and δ 18 O values increased from −18.3 to −9.8. After more than one year, TDS reached 204,000 mg/L while δ 2 H and δ 18 O values further increased to −68 and + 2.7. The salinity of the returned water is shown to be the result of the mixing between the highly saline formation water initially present in the reservoir before hydraulic fracturing, with the fresh water used for hydraulic fracturing. The presented mathematical model allows the calculation of the amount of fracturing fluid recovered as well as the quantity of saline formation water produced and reveals that most of the injected water is imbibed in the host rock of the producing formation. After a week of flowback, only 18% of the injected water had been recovered, while the recovery of fracturing fluids after 14.5 months is estimated at 36% of the total volume injected.

Abstract:
Forward osmosis (FO) has proven to be a robust, low-pressure membrane separation process capable of rejecting a broad range of contaminants; thus, providing a high quality diluted brine suitable for further desalination by reverse osmosis (RO). In this study, a pilot-scale FO-RO system treated >10,000 L of raw produced water from the Denver-Julesburg basin (Colorado) over a four-week period using commercially available FO and RO membranes. Overall, the FO-RO pilot system maintained >99% rejection of nearly all measured ions and >95% rejection of hydrocarbons such as semi-volatile linear aliphatic hydrocarbons and polycyclic aromatic hydrocarbons. Although the FO-RO system was able to treat raw produced water, high concentrations of organic compounds severely fouled the FO membrane and substantially reduced water flux by 68% within 21 days. Membrane degradation due to interaction between organic constituents such as aliphatic and aromatic hydrocarbons and the membrane polymer may have compromised the FO membranes, resulting in substantial increase (×15) in reverse salt flux within 21 days. Further investigations of membrane cleaning and pretreatment will be required in order to better understand the overall economic feasibility of treating raw produced water using FO.