Repository for Oil and Gas Energy Research (ROGER)

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Production of high volumes of flowback and produced water (FPW) from hydraulic fracturing (HF) is among the environmental concerns associated with hydrocarbon recovery from unconventional low-permeability formations. FPW management costs are a key factor for oil and gas companies in deciding the fate of FPW (treatment, disposal, recycling, and reuse). In this study, a comprehensive library of more than 20,000 oil and gas wells in the Montney Formation, Canada, is created to compare the FPW management costs from conventional and hydraulically fractured wells. The results indicate that for oil wells, both conventional and HF wells have similar volumetric oil–water ratios during the first two years of production. Since HF wells in the study region produce higher volumes of oil, on average, than conventional wells, the gross revenue from a typical HF oil well is higher than a typical conventional oil well. However, over the course of two years of production, conventional gas wells have higher volumetric gas–water ratios than HF gas wells. Estimation of the gross revenue for gas wells is sensitive to the average natural gas price and FPW management costs as HF wells typically generate more natural gas and FPW than conventional wells. Due to the fluctuating nature of oil and gas prices, we have created master curves for revenue (i.e., produced hydrocarbon value) and FPW management costs. The master curves cover oil and gas price ranges of $10–100/bbl and $0.5–5/MMBtu, respectively. Furthermore, since the FPW management costs may vary depending on the implemented technology or local labor costs, the master curves encompass a FPW management cost range of $5–100/m3. The provided master curves introduce a basis for the rapid analysis of FPW management costs of oil and gas wells, and can be incorporated with other well operational costs (such as drilling and completions, water withdraw permit, and well maintenance) for detailed evaluation of the profitability of hydrocarbon recovery processes.

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This study focuses on rock-fluid interaction during hydraulic fracturing in shale gas reservoir. Hydraulic fracturing is a well stimulation technique used to create fracture network in reservoirs by connecting the main planar hydraulic fracture with the pre-existing natural fracture. Hydraulic fracturing fluid additives such as surfactants are added into the hydraulic fracturing fluid system to enhance oil and gas productivity by assisting fluid recovery after fracturing. The main objective of this study is to evaluate the effectiveness and formation damage parameters of the proposed novel green surfactant as hydraulic fracturing fluid additive where commercial-chemical based surfactant was studied for comparison purpose. The green surfactant used was D-limonene whereas Sodium Alpha Olefin Sulfonate (AOS) was used as commercial-chemical based surfactant. Thermogravimetric analysis (TGA) was done to ensure the D-limonene can withstand the high reservoir temperature in which the D-limonene had inflection point and onset temperature of 410 °C and 380 °C respectively. Soaking test was then conducted where the shale samples were soaked in hydraulic fracturing fluid for seven days. The outcome of the soaking test was then studied in Scanning Electron Microscopy (SEM) and wettability analysis. The SEM test showed that the average pore size of the soaked shale samples were similar to the original shale sample which indicated minimal to no formation damage caused by the hydraulic fracturing fluid. Besides that, the contact angle test resulted in the distilled water and D-limonene forming a contact angle of 90° and 0° respectively on the shale samples. The AOS formed contact angles between 65° and 75° for the tested concentrations. From the results, the shale sample was found to be oil wet and showed a high affinity towards the D-limonene followed by AOS and distilled water. Higher affinity of the surfactants promoted the desorption of the hydraulic fracturing fluid from the shale surface.

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Hydraulic fracturing (HF) of shale and other permeable rock formations to extract gas and oil is a water-intensive process that returns a significant amount of flowback and produced water (FPW). Due to the complex chemical composition of HF fluids and FPW, this process has led to public concern on the impacts of FPW disposal, spillage and spreading to regional freshwater resources, in particular to shallow groundwater aquifers. To address this, a better understanding of the chemical composition of HF fluid and FPW is needed, as well as the environmental fate properties of the chemical constituents, such as their persistence, mobility and toxicity (PMT) properties. Such research would support risk-based management strategies for the protection of regional water quality, including both the phase-out of problematic chemicals and better hydraulic safeguards against FPW contamination. This article presents recent strategies to advance the assessment and analysis of HF and FPW associated organic chemicals.

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Produced water (PW) is a hypersaline waste stream generated from the shale oil and gas industry, consisting of numerous anthropogenic and geogenic compounds. Despite prior geochemical characterization, the comprehensive toxicity assessment is lacking for evaluating treatment technologies and the beneficial use of PW. In this study, a suite of in vitro toxicity assays using various aquatic organisms (luminescent bacterium Vibrio fischeri, fish gill cell line RTgill-W1, and microalgae Scenedesmus obliquus) were developed to investigate the toxicological characterizations of PW from the Permian Basin. The exposure to PW, PW inorganic fraction (PW-IF), and PW salt control (PW-SC) at 30– 50% dilutions caused significant toxicological effects in all model species, revealing the high salinity was the foremost toxicological driver in PW. In addition, the toxicity level of PW was usually higher than that of PW-IF, suggesting that organic contaminants might also play a critical role in PW toxicity. When comparing the observed toxicity with associated chemical characterizations in different PW samples, strong correlations were found between them since higher concentrations of contaminants could generally result in higher toxicity towards exposed organisms. Furthermore, the toxicity results from the pretreated PW indicated that those in vitro toxicity assays had different sensitives to the chemical components present in PW. As expected, the combination of multiple pretreatments could lead to a more significant decrease in toxicity compared to the single pretreatment since the mixture of contaminants in PW might exhibit synergistic toxicity. Overall, the current work is expected to enhance our understanding of the potential toxicological impacts of PW to aquatic ecosystems and the relationships between the chemical profiles and observed toxicity in PW, which might be conducive to the establishment of monitoring, remediation, treatment, and reuse protocols for PW.

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Hydraulic fracturing (HF) remains a current global energy policy issue, and understanding risks to drinking water resources from HF chemicals is an important aspect of this topic. The quantity and quality of disclosed HF chemical information are significant barriers for stakeholders attempting to perform systemic environmental and public health research. A repeatable approach for processing HF chemical disclosure data is provided using United States FracFocus data as a case study. We fill research gaps by examining HF chemical trends between 2014 and 2020 and comparing HF chemicals with a list of reference chemicals known or suspected to be in contact (unrelated to HF) with drinking water, food, or cosmetics. In total, 1,244 unique HF chemicals were identified. Compared with EPA's 2016 HF chemical disclosure research, 480 new chemicals are identified, and 318 previously reported chemicals were not observed. The annual unique chemical counts have dropped from 878 to 594 (32.3%) over the research period, while data quality and transparency have increased. Approximately 69.7% of the identified HF ingredients were found in a list of reference chemicals known or suspected to be in contact (unrelated to HF) with drinking water, food, or cosmetics. Chemical differences between production types (gas and oil) and states are also reviewed. Our research reveals that the sociotechnical system surrounding HF is dynamic and moving toward fewer and, in general, safer chemicals, for those that are disclosed. This study highlights opportunities for new and updated systemic research regarding HF chemical hazard dynamics and associated risk to drinking water resources.

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Advances in water treatment technologies paired with potential restrictions on oil and gas (O the sole major breakthrough has been in the development of salt-tolerant fracturing chemicals that allow for reuse of produced water for fracking operations. Guided research should assist in the development of fit-for-purpose solutions to maximize the reuse of treated produced water. This is exemplified by the case studies presented here that detail currently operating treatment facilities for reclamation and reuse of produced water.

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Biocides are applied as chemical additives in hydraulic fracturing fluids to control subsurface microbial activity. When biocides are released into the subsurface, their fate is controlled by sorption to solids and heterogeneous electron transfer (redox) reactions at the mineral–fluid interface. The ability to predict whether produced water may contain unreacted biocides, or biocide–mineral transformation products, is relevant for defining optimal produced water treatment and beneficial use approaches. This article reviews major minerals that may impact biocide sorption and reactivity in the Marcellus Shale, with a specific focus on biocide–mineral interactions. The chemical and physical properties of quartz, illite, chlorite, pyrite, calcite and dolomite are presented and their reactions with organic compounds structurally similar to biocides are identified. Oxygen-containing functional groups are common among organic biocides, where the carbonyl (–C=O) substructure is integrated into many biocides. Cationic surfactant biocides are expected to sorb to every mineral. Clays, because of their negative surface charge and comparatively high surface area, make excellent sorbents of positively charged biocides. Sorption to organic matter is expected to be limited due to the very polar groups found in biocides. Pyrite is most likely to cause transformation of biocides due to its ability to reduce halogenated organic compounds and initiate Fenton-like reactions, which generate non-specific hydroxyl radicals that react with biocides. Carbonate minerals may act as potential chemisorption sites for biocides possessing a carbonyl group adjacent to another electronegative group. However, the rapid dissolution of this mineral limits its persistence at the mineral–fluid interface. These potential sorption versus transformation reactions can be applied to predict biocide fate in unconventional oil and gas reservoirs and, where appropriate, other subsurface reservoirs used for energy resource extraction or storage.

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There is public and scientific concern about air, soil and water contamination and possible adverse environmental and human health effects as a result of hydraulic fracturing activities. The use of greener chemicals in fracturing fluid aims to mitigate these effects. This study compares fracturing fluids marketed as either ‘conventional’ or ‘green’, as assessed by their chemical composition and their toxicity in bioassays. Chemical composition was analysed via non-target screening using liquid chromatography - high resolution mass spectrometry, while toxicity was evaluated by the Ames fluctuation test to assess mutagenicity and CALUX reporter gene assays to determine specific toxicity. Overall, the results do not indicate that the ‘green’ fluids are less harmful than the ‘conventional’ ones. First, there is no clear indication that the selected green fluids contain chemicals present at lower concentrations than the selected conventional fluids. Second, the predicted environmental fate of the identified compounds does not seem to be clearly distinct between the ‘green’ and ‘conventional’ fluids, based on the available data for the top five chemicals based on signal intensity that were tentatively identified. Furthermore, Ames fluctuation test results indicate that the green fluids have a similar genotoxic potential than the conventional fluids. Results of the CALUX reporter gene assays add to the evidence that there is no clear difference between the green and conventional fluids. These results do not support the claim that currently available and tested green-labeled fracturing fluids are environmentally more friendly alternatives to conventional fracturing fluids.

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The chemical characteristic of flowback fluid from hydraulic fracturing for shale gas exploration/production in various localizations is presented. The results of statistical analysis have shown that variability in the chemical composition of these fluids is statistically significant and depends on the time difference between fracturing process and flowback sampling as well as sampling spot within the installation for flowback collection. Parameters which depend on sampling schedule (time and spot of sampling) are as follows: electrical conductivity and concentration of ammonia, boron, barium, calcium, lithium, sodium, magnesium, manganese, sodium, strontium, silicate, bromide, and chloride. Independent parameters are pH, total organic carbon (TOC), concentration of potassium, and iron. The ranges of the values of the characteristic parameters were determined, taking into account the representativeness of the samples, supported by statistical tests. The methods for the reuse of flowback fluids in terms of chemical composition are presented.

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Tracing produced water origins from wells hydraulically fractured with freshwater-based fluids is sometimes predicated on assumptions that (1) each geological formation contains compositionally unique brine and (2) produced water from recently hydraulically fractured wells resembles fresher meteoric water more so than produced water from older wells. These assumptions are not valid in Williston Basin oil wells sampled in this study. Although distinct average 228Ra/226Ra ratios were found in water produced from the Bakken and Three Forks Formations, average δ2H, δ18O, specific gravity, and conductivity were similar but exhibited significant variability across five oil fields within each formation. Furthermore, initial produced water (“flowback”) was operationally defined based on the presence of glycol ether compounds and water from wells that had produced <56% of the amount of fluids injected and sampled within 160 days of fracturing. Flowback unexpectedly exhibited higher temperature, specific gravity, conductivity, δ2H, and δ18O, but lower oxidation–reduction potential and δ11B, relative to the wells thought to be producing formation brines (from wells with a produced-to-injected water ratio [PIWR] > 0.84 and sampled more than 316 days after fracturing). As such, establishing an overall geochemical and isotopic signature of produced water compositions based solely on chemical similarity to meteoric water and formation without the consideration of well treatments, well completion depth, or lateral location across the basin could be misleading if these signatures are assumed to be applicable across the entire basin. These findings have implications for using produced water compositions to understand the interbasin fluid flow and trace sources of hydraulic fracturing fluids.

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The large-scale extraction of unconventional resources from shale reservoirs utilizing horizontal hydraulic fracturing has significantly improved economic development in U.S. However, the increased well production has been accompanied by rising concerns about potential impact resulting from excessive freshwater usage and wastewater generation. Currently, water issues have become increasingly challenging with the development of shale reservoirs. In this paper, technical, economic, and environmental challenges encountered during energy production are reviewed with a focus on water issues due to hydraulic fracturing in the U.S. Moreover, the detailed discussion of characteristics and contaminant sources of wastewater indicates the wastewater composition is complicated and varies over time and location. Understanding these factors contributed to high contaminant levels of wastewaters is important to grow awareness of the impacts of hydraulic fracturing on water quality for both operators and the public. Furthermore, pertinent wastewater management strategies for different purposes are highlighted. Although there is no one-size-fits-all solution, understanding the advantages and limitations of different treatment methods is critical for decision-makers to develop appropriate management system. The aim behind this review is to provide a reference for selecting better and practical solutions for current wastewater issues and identifying key issues for future research.

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Formulated products used in hydraulic fracturing are designed to address specific subsurface challenges during oil and gas well completion and are intended for the treatment of a myriad of issues in a wellbore; however, there are public concerns regarding the use of certain chemical ingredients in hydraulic fracturing. Public perception of hydraulic fracturing and concerns regarding water and chemical usage provide the industry with a unique opportunity to review current chemistries and water management practices with the aim being to identify more environmentally acceptable alternatives or replacements. Herein we describe what the industry considers to be the greatest challenges, what is currently being done, and potential opportunities to provide alternatives that lead to a more sustainable industry.

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Hydraulic fracturing (HF) technology is increasingly utilized for oil and gas extraction operations. The widespread use of HF has led to concerns of negative impacts on both the environment and human health. Indeed, the potential endocrine disrupting impacts of HF chemicals is one such knowledge gap. Herein, we used structure-based molecular docking to assess the binding affinities of 60 HF chemicals to the human androgen receptor (AR). Five HF chemicals had relatively high predicted AR binding affinity, suggesting the potential for endocrine disruption. We next assessed androgenic and antiandrogenic activities of these chemicals in vitro. Of the five candidate AR ligands, only Genapol®X–100 significantly modified AR transactivation. To better understand the structural effect of Genapol®X–100 on the potency of AR inhibition, we compared the antiandrogenic activity of Genapol®X–100 with that of its structurally similar chemical, Genapol®X–080. Interestingly, both Genapol®X–100 and Genapol®X–080 elicited an antagonistic effect at AR with 20% relative inhibitory concentrations of 0.43 and 0.89 μM, respectively. Furthermore, we investigated the mechanism of AR inhibition of these two chemicals in vitro, and found that both Genapol®X–100 and Genapol®X–080 inhibited AR through a noncompetitive mechanism. The effect of these two chemicals on the expression of AR responsive genes, e.g. PSA, KLK2, and AR, was also investigated. Genapol®X–100 and Genapol®X–080 altered the expression of these genes. Our findings heighten awareness of endocrine disruption by HF chemicals and provide evidence that noncompetitive antiandrogenic Genapol®X–100 could cause adverse endocrine health effects.

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Large amounts of fracturing flowback and wastewater with complex compositions are produced during hydraulic fracturing. Characterization of hydraulic fracturing flowback and produced water (HF-FPW) is an important initial step in efforts to determine a suitable treatment method for this type of wastewater. In the present study, fracturing flowback and produced water samples were obtained from well CN-F and well CN-E in the prophase and anaphase stages of the Changning shale gas mining area. Chemical characterization of inorganic and organic substances was then conducted. Metal contents were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES), and all inorganic anions involved were determined by ion chromatography. The organic pollutant components were analyzed in detail by combining Fourier transform infrared spectrometer (FTIR) and gas chromatography-mass spectrometer (GC-MS). Results showed that samples contained salt (TDS = 30,000–50,000 mg/L), metals (e.g., 650 ± 50 mg/L calcium), and total organic carbon (TOC = 32–178 mg/L). The organic substances detected in all samples could be divided into six categories, alkanes, aromatics, halogenated hydrocarbons, alcohols, esters, and ketones. C6–C21 straight-chain alkanes and C7–C13 naphthenes had the highest amount of organic matter, reaching more than 48%. The organic matter contained fracturing fluid additives, such as surfactants (e.g., ethylene glycol), and nitrotrichloromethane, which is a chlorinated product of some additives. These results provide information on the chemical composition of HF-FPW in Sichuan, China, as well as a basis for subsequent processing.

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Background Hydraulic fracturing often involves the injection of millions of gallons of fracturing fluids into underground shales to extract oil and natural gas, raising health concerns over potential water contamination. Many state and federal governmental agencies rely on the third-party FracFocus online registry for disclosure of chemical ingredients in fracturing fluids, but withholding chemicals as trade secrets is common. In 2016, a new format, known as the systems approach was widely encouraged as a method of reducing withholding by decoupling disclosed chemicals from their functions, protecting against reverse-engineering of fracture fluid formulas by competitors. In this study, we assess the extent to which elevated use of the systems approach in FracFocus version 3.0 translated into greater chemical disclosure. Methods We analysed 108 137 disclosure forms submitted to FracFocus between Jan 1, 2011, and Dec 31, 2018, to estimate the effect of expanded use of the systems approach on chemical withholding. We compared the proportion of forms withholding at least one chemical ingredient across time, between approaches, and by state and drilling operator. Findings Since the 2016 expansion of the systems approach, 15 677 (82%) of systems approach forms have withheld an ingredient. 13 462 (89%) of 15 062 traditional FracFocus version 3.0 forms withheld an ingredient. In the quarter following the transition (July, to September, 2016), 1211 (93%) of 1304 traditional forms withheld an ingredient, compared with only 958 (76%) of 1262 systems approach forms. However, withholding rates increased throughout 2017 and, by 2018, 6949 (87%) of 8016 systems approach forms were withholding ingredients. At the end of our analysis period in the fourth quarter of 2018, systems approach forms had even greater withholding (903 [88%] of 1025 forms) than did traditional forms (855 [85%] of 1004 forms). We did not find that states or operators that submitted more systems approach forms had lower withholding. Interpretation The systems approach has not reduced FracFocus chemical withholding, which continues to occur in around 87% of well fracture disclosures. FracFocus might not be an appropriate substitute for regulatory action, and measures are urgently needed for environmental and public safety. Funding University of Chicago Argonne National Laboratory Seed Grant.

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While development of the Utica/Point Pleasant Shale (UPP) is extensive in Ohio (U.S.) and increasing in Pennsylvania and West Virginia, few studies report the chemistry of produced waters from UPP wells. These data have important implications for developing best management practices for handling and waste disposal, or identifying the fluid in the event of accidental spill events. Here, we evaluated the elemental and isotope chemistry of UPP produced waters from 26 wells throughout Ohio, Pennsylvania, and West Virginia to determine any unique fluid chemistries that could be used for forensic studies. Compared to the Marcellus, UPP produced waters contain higher activities of total radium (226Ra + 228Ra) and higher 228Ra/226Ra ratios. As with the Marcellus Shale, elemental ratios (Sr/Ca) and isotope ratios (87Sr/86Sr) can distinguish UPP produced waters from many conventional oil and gas formations. Sr/Ca and 87Sr/86Sr ratios can fingerprint small fractions (∼0.1%) of UPP produced water in freshwater. However, because Marcellus and UPP produced waters display similar major elemental chemistry (i.e., Na, Ca, and Cl) and overlapping ratios of Sr/Ca and 87Sr/86Sr, 228Ra/226Ra ratios may be the best tracer to distinguish these waters.

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Produced water is a byproduct of oil and gas production. The chemistry of produced water may provide information about the source of the fluid and its evolution, leading to an improved understanding of the hydrology of petroleum systems. In this study, samples from 19 wells from the Tuscaloosa Marine Shale (TMS) in Mississippi and Louisiana, USA were analyzed for their major and trace element compositions. Data obtained from produced waters from the TMS were compared to existing chemical data from produced waters collected from nearby hydrocarbon reservoir rocks within the Gulf Coast Basin. The results show that produced waters from the TMS are highly saline, with a mean concentration of 15.9 g/L of total dissolved solids. Comparison of the chemistry of produced water from the TMS to early flowback waters demonstrated a rapid shift from the more dilute fracturing fluid to the formation water endmember composition. Most of the trace metals showed a moderate to strong correlation with the overall salinity of the waters. Concentrations of Cu and V showed a moderate correlation with the amount of oil produced from the TMS wells, suggesting that these elements are strongly affiliated with the kerogen and subsequent dissolved (<0.45 μm) organic phases. Analysis of the volume of produced water compared to the volume of water used during hydraulic fracturing indicates that 15%–110% of the water volume used for fracking had been returned to the surface over the 2–5 year production period of the sampled wells. Chloride to bromide ratios suggest that the formation water in the TMS was derived from evaporated seawater. Comparison to historical data for produced waters in other formations in and around the Mississippi Salt Basin showed that waters in all the formations had a consistent origin (bitterns likely derived from the formation of the Louann salt). This implies that over geologic time periods fluids migrated through the TMS despite its low permeability present-day. The TMS also exhibited lower concentrations of dissolved transition metals such as Zn and Pb relative to those described in adjacent formations. This observation may suggest the presence of larger amounts of H2S, limiting the solubility of sulfide phases, in the shale unit relative to adjacent reservoir units.

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Unconventional oil and natural gas extraction (UOG) combines directional drilling and hydraulic fracturing and produces billions of liters of wastewater per year. Herein, we review experimental studies that evaluated the potential endocrine-mediated health impacts of exposure to a mixture of 23 UOG chemicals commonly found in wastewater. The purpose of this manuscript is to synthesize and summarize a body of work using the same UOG-mix but with different model systems and physiological endpoints in multiple experiments. The studies reviewed were conducted in laboratory animals (mice or tadpoles) and human tissue culture cells. A key feature of the in vivo studies was the use of four environmentally relevant doses spanning three orders of magnitude ranging from concentrations found in surface and ground water in UOG dense areas to concentrations found in UOG wastewater. This UOG-mix exhibited potent antagonist activity for the estrogen, androgen, glucocorticoid, progesterone, and thyroid receptors in human tissue culture cells. Subsequently, pregnant mice were administered the UOG-mix in drinking water and offspring were examined in adulthood or to tadpoles. Developmental exposure profoundly impacted pituitary hormone concentrations, reduced sperm counts, altered folliculogenesis, and increased mammary gland ductal density and preneoplastic lesions in mice. It also altered energy expenditure, exploratory and risk-taking behavior, the immune system in three immune models in mice, and affected basal and antiviral immunity in frogs. These findings highlight the diverse systems affected by developmental EDC exposure and the need to examine human and animal health in UOG regions.

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The worldwide expansion of shale gas production and increased use of hydraulic fracturing have raised public concerns about safety and risks of groundwater resources in shale gas extraction areas. China has the largest shale gas resources in the world, most of which are located in the Sichuan Basin. Shale gas extraction in the Sichuan Basin has been increasing rapidly in recent years. However, the potential impact on shallow groundwater quality has not yet been systematically investigated. In order to evaluate the possible impact of shale gas extraction on groundwater quality, we present, for the first time, the hydrochemistry and Sr isotopic data of shallow groundwater, as well as flowback and produced water (FP water) in the Changning shale gas field in Sichuan Basin, one of the major shale gas fields in China. The Changning FP water is characterized by high salinity (TDS of 13,100–53,500 mg/L), Br/Cl (2.76 × 10−3) and 87Sr/86Sr (0.71849), which are distinguished from the produced waters from nearby conventional gas fields with higher Br/Cl (4.5 × 10−3) and lower 87Sr/86Sr (0.70830–0.71235). The shallow groundwater samples were collected from a Triassic karst aquifer in both active and nonactive shale gas extraction areas. They are dominated by low salinity (TDS of 145–1100 mg/L), Ca-HCO3 and Ca-Mg-HCO3 types water, which are common in carbonate karst aquifers. No statistical difference of the groundwater quality was observed between samples collected in active versus nonactive shale gas extraction areas. Out of 66 analyzed groundwater, three groundwater samples showed relatively higher salinity above the background level, with low 87Sr/86Sr (0.70824–0.7110) and Br/Cl (0.5–1.8 × 10−3) ratios relatively to FP water, excluding the possibility of contamination from FP water. None of the groundwater samples had detected volatile organic compounds (VOCs). The integration of geochemical and statistical analysis shows no direct evidence of groundwater contamination caused by shale gas development.

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Regulatory monitoring of oil and gas development requires the accurate multi-elemental analysis of wellbore samples on a regular basis. In this study, an unconventional method, comparative neutron activation analysis (comparative NAA), was applied for the multi-elemental characterization of solid and liquid hydraulic fracturing samples at the ppm level. The obtained values from three wastewater samples were compared with the most probable values determined via an inter-laboratory study, which involved 15 different laboratories from the United States, Canada, and Germany. The comparison showed that 15 out of 19 comparative NAA trace element concentration values were considered acceptable, providing a new technique to determine elemental concentrations in high salinity hydraulic fracturing samples.

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Limited understanding of wastewater streams produced from shale oil and gas wells impedes best practices of wastewater treatment and reuse. This study provides a comprehensive and comparative analysis of flowback and produced water from three major and newly developed shale plays (the Bakken shale, North Dakota; the Barnett shale, Texas; and the Denver-Julesburg (DJ) basin, Colorado) in central and western United States. Geochemical features that included more than 10 water quality parameters, dissolved organic matter, as well as microbial community structures were characterized and compared. Results showed that wastewater from Bakken and Barnett shales has extremely high salinity (∼295 g/L total dissolved solids (TDS)) and low organic concentration (80–252 mg/L dissolved organic carbon (DOC)). In contrast, DJ basin showed an opposite trend with low TDS (∼30 g/L) and high organic content (644 mg/L DOC). Excitation-emission matrix (EEM) fluorescence spectra demonstrated that more humic acid and fluvic acid-like organics with higher aromaticity existed in Bakken wastewater than that in Barnett and DJ basin. Microbial communities of Bakken samples were dominated by Fe (III)-reducing bacteria Geobacter, lactic acid bacteria Lactococcus and Enterococcus, and Bradyrhizobium, while DJ basin water showed higher abundance of Rhodococcus, Thermovirga, and sulfate reducing bacteria Thermotoga and Petrotoga. All these bacteria are capable of hydrocarbon degradation. Hydrogenotrophic methanogens dominated the archaeal communities in all samples.

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Various chemicals used in hydraulic fracturing have raised environmental and human health (EHH) concerns regarding water resources contamination, leading to the transition towards the use of chemicals with minimum EHH hazards. Chemical hazard screening and indexing approaches have been used to measure the chemical hazard of hydraulic fracturing, and each approach is associated with inherent advantages and limitations. In this study, the two chemical hazard assessment approaches were discussed, and an integrated chemical hazard screening and indexing system was developed to combine the strengths of the two approaches. The integrated system was applied to assess the EHH hazards of representative hydraulic fracturing chemicals used in British Columbia, Canada. The hazard screening results showed that more than half of the ingredients and additives were classified into high hazard groups. Moreover, the integrated system generated more critical hazard assessment results than two hazard indexing systems, revealing that using the individual hazard indexing approach could result in underestimated EHH hazards for chemicals. The integrated system can significantly improve the data confidence levels of hazard assessment results compared to a previously developed indexing system. The integrated system can also help formulate fracturing fluids with low EHH hazards by identifying ingredients of high hazard concerns.

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Hydraulic fracturing (HF) flowback and produced water (FPW) can be toxic to aquatic life but its chemical content is largely unknown, variable and complex. Seven FPW samples were collected from a HF operation in the Duvernay Formation (Alberta, Canada) over 30 days of flowback and characterized by a nontarget workflow based on high performance liquid chromatography - high resolution mass spectrometry (HRMS). A modified Kendrick mass defect plot and MS/MS spectral interpretation revealed seven series of homologues composed of ethylene oxide (i.e. -CH2CH2O-), among which a series of aldehydes was proposed as degradation products of polyethylene glycols, and two series of alkyl ethoxylate carboxylates could be proprietary HF additives. Many other ions were confidently assigned a formula by accurate mass measurement and were subsequently prioritized for identification by matching to records in ChemSpider and the US EPA's CompTox Chemistry Dashboard. Quaternary ammonium compounds, amine oxides, organophosphorous compounds, phthalate diesters and hydroxyquinoline were identified with high confidence by MS/MS spectra (Level 3), matching to reference spectra in MassBank (Level 2) or to authentic standards (Level 1). Temporal trends showed that most of the compounds declined in abundance over the first nine days of flowback, except for phthalate diesters and hydroxyquinoline that were still observed on Day 30 and had disappearance half-lives of 61 and 91 days, respectively. All the compounds followed first-order disappearance kinetics in flowback, except for polyoxygenated acids which followed second-order kinetics. This analysis and the workflow, based largely on public on-line databases, enabled profiling of complex organic compounds in HF-FPW, and will likely be useful for further understanding the toxicity and chemical fate of HF-FPW.

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The fracking industry faces various challenges although technologies have been advanced in the hydraulic fracturing and horizontal drilling. Treatment for the water used after the fracking process is one of the key issues preventing hydraulic fracturing from being widely implemented. Especially the chemicals that are used for various purposes during fracking remain in the water that flows back to the surface. Reports have been seen that the problematic chemicals used in the fracking process cause HSE (Health, Safety and Environment) issues. Before any chemical used in the fracking is eliminated or replaced with alternatives, its greenness should be evaluated. A tool called Greenness Index was used in this study to evaluate several typical chemicals used in the current fracking process. SDS (Safety Data Sheet) information was used by Greenness Index to assess the chemicals. It was found that with similar amount of SDS information available, citric acid is relatively greener than ammonium persulfate. SDS information of guar gum is less than that of citric acid and ammonium persulfate, but the evaluation for guar gum still indicates that it is a green chemical based on the limited data from its SDS. When more information with respect to how they behave during the fracking process is available, Greenness Index can provide more comprehensive evaluations.

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Biocides used in unconventional oil and gas (UOG) practices, such as hydraulic fracturing, control microbial growth. Unwanted microbial growth can cause gas souring, pipeline clogging, and microbial-induced corrosion of equipment and transportation pipes. However, optimizing biocide use has not been a priority. Moreover, biocide efficacy has been questioned because microbial surveys show an active microbial community in hydraulic fracturing produced and flowback water. Hydraulic fracturing produced and flowback water increases risks to surface aquifers and rivers/lakes near the UOG operations compared with conventional oil and gas operations. While some biocides and biocide degradation products have been highlighted as chemicals of concern because of their toxicity to humans and the environment, the selective antimicrobial pressure they cause has not been considered seriously. This perspective article aims to promote research to determine if antimicrobial pressure in these systems is cause for concern. UOG practices could potentially create antimicrobial resistance hotspots under-appreciated in the literature, practice, and regulation arena, hotspots that should not be ignored. The article is distinctive in discussing antimicrobial resistance risks associated with UOG biocides from a biological risk, not a chemical toxicology, perspective. We outline potential risks and highlight important knowledge gaps that need to be addressed to properly incorporate antimicrobial resistance emergence and selection into UOG environmental and health risk assessments.

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Potential effects of horizontal drilling combined with high-volume hydraulic fracturing (HF) have drawn significant public concern, especially on the handling, treatment, and disposal of HF flowback and produced water (HF-FPW). Previous studies indicated HF-FPW could significantly disrupt biotransformation and expressions of genes related to the endocrine system. This study focused on effects of organic extracts of HF-FPW on receptor binding activity using several transactivation assays. Six HF-FPW samples were collected from 2 wells (Well A and Well B, 3 time points at each well). These were separated by filtration into aqueous (W) and particulate (S) phases, and organics were extracted from all 12 subsamples. Of all the tested fractions, sample B1-S had the greatest Σ13PAH (11,000 ng/L) and B3-S has the greatest Σ4alkyl-PAHs (16,000 ng/L). Nuclear receptor binding activity of all the extracts on aryl hydrocarbon receptor (AhR), estrogen receptor (ER), and androgen receptor (AR) were screened using H4IIE-luc, MVLN-luc, and MDA-kb2 cells, respectively. FPWs from various HF wells exhibited distinct nuclear receptor binding effects. The strongest AhR agonist activity was detected in B3-S, with 450 ± 20 μg BaP/L equivalency at 5 × exposure. The greatest ER agonist activity was detected in A1-W, with 5.3 ± 0.9 nM E2 equivalency at 10× exposures. There is a decreasing trend in ER agonist activity from A1 to A3 in both aqueous and particulate fractions from Well A, while there is an increasing trend in ER agonist activity from B1 to B3 in aqueous fractions from Well B. This study provides novel information on the sources of endocrine disruptive potentials in various HF-FPW considering both temporal and spatial variability. Results suggest that reclamation or remediation and risk assessment of HF-FPW spills likely requires multiple strategies including understanding the properties of each spill with respect to fractured geological formation and physiochemical properties of the injected fluid.

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Recent advances in hydraulic fracturing, in conjunction with horizontal drilling, have enabled large-scale extraction of natural gas and oil from shale formations. Despite its advances and enormous economic benefits, opportunities remain to increase hydraulic fracturing efficiency and minimize potential environmental impacts. This review specifically examines three key themes associated with development and utilization of hydraulic fracturing fluids: 1) characteristics and behavior of fracturing fluids, 2) understanding and predicting migration and fate of fracturing fluids, 3) technologies to reduce environmental impact of fracturing fluids. The paper discusses key and new techniques and findings on rheology of hydrogel-based fluids, high fidelity simulation of propagation transport, potential environmental impacts, geosynthetics in mitigating contamination, and greener fracturing fluids. It is indicated that future development relies on advances in understanding of physical processes, modeling capabilities, and monitoring techniques.

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Polyethylene glycols (PEG) and polypropylene glycols (PPG) are frequently used in hydraulic fracturing fluids and have been detected in water returning to the surface from hydraulically-fractured oil and gas wells in multiple basins. We identified degradation pathways and kinetics for PEGs and PPGs under conditions simulating a spill of produced water to shallow groundwater. Sediment-groundwater microcosm experiments were conducted using four produced water samples from two Denver Julesburg Basin wells at early and late production. High resolution mass spectrometry was used to identify the formation of mono- and di-carboxylated PEGs and mono-carboxylated PPGs, which are products of PEG and PPG biodegradation, respectively. Under oxic conditions, first-order half lives were more rapid for PEG (<0.4-1.1 d) compared to PPG (2.5-14 d). PEG and PPG degradation corresponded to increased relative abundance of primary alcohol dehydrogenase genes predicted from metagenome analysis of the 16S rRNA gene. Further degradation was not observed under anoxic conditions. Our results provide insight to the differences between degradation rates and pathways of PEGs and PPGs, which may be utilized to better characterize shallow groundwater contamination following a release of produced water.

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The overall mass of sodium chloride salt used to treat icy roads can be significantly reduced by pretreating roads or prewetting dry rock salt with concentrated brine solutions. Brine solutions can be made from rock salt; however, an alternative source of brine for some communities is brine that is a waste product of oil and gas extraction. This study compares contaminant chemistry of brine made from rock salt with literature data on oil and gas well brine from conventional and unconventional wells. In addition to reviewing existing literature, this paper analyzes four rock salt samples for a suite of chemical constituents. Maximum reported levels of some harmful contaminants are higher for well brines than for rock salt brines and are higher for unconventional than for conventional well brines. Because the regulatory structure for using well brines varies among states, the authors recommend a consistent approval process for permitting the use of waste brines that includes specific maximum allowable limits for potentially harmful contaminants, and that each batch of solution be tested before use. Although the use of brine, including waste brine, can reduce the overall amount of salt needed for snow and ice control, adequate steps should be taken to ensure the safety of the brine solutions before they are used.

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This work describes the discovery of amino-polyethylene-glycols, amino-polyethylene-glycol-carboxylates, and amino-polyethylene-glycol-amines in 20 produced water-samples from hydraulic fracturing in the western United States. These compounds, with masses in the range of m/z 120–986, were identified using solid phase extraction and liquid chromatography/quadrupole-time-of-flight mass spectrometry. The polymeric sorbent, Oasis HLB, gave the best recovery for all three ethoxylated surfactants and desalted the samples, which significantly reduced suppression of the mass spectral signal allowing detection and identification. The Kendrick mass defect, mass spectra, fragmentation pathways, and pure standards were used for confirmation. Finally, because these compounds are not explicitly listed in FracFocus reports, rather they are categorized as a proprietary surfactant blend; their identification is an important step in understanding the chemistry, treatment, and possible toxicity of hydraulic fracturing wastewater.

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.

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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.

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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:
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 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.

Abstract:
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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As high-volume hydraulic fracturing (HF) has grown substantially in the United States over the past decade, so has the volume of produced water (PW), i.e., briny water brought to the surface as a byproduct of oil and gas production. According to a recent study (Groundwater Protection Council, 2015), more than 21 billion barrels of PW were generated in 2012. In addition to being high in TDS, PW may contain hydrocarbons, PAH, alkylphenols, naturally occurring radioactive material (NORM), metals, and other organic and inorganic substances. PW from hydraulically fractured wells includes flowback water, i.e., injection fluids containing chemicals and additives used in the fracturing process such as friction reducers, scale inhibitors, and biocides – many of which are known to cause serious health effects. It is hence important to gain a better understanding of the chemical composition of PW and how it is managed. This case study of PW from hydraulically fractured wells in California provides a first aggregate chemical analysis since data collection began in accordance with California's 2013 oil and gas well stimulation law (SB4, Pavley). The results of analyzing one-time wastewater analyses of 630 wells hydraulically stimulated between April 1, 2014 and June 30, 2015 show that 95% of wells contained measurable and in some cases elevated concentrations of BTEX and PAH compounds. PW from nearly 500 wells contained lead, uranium, and/or other metals. The majority of hazardous chemicals known to be used in HF operations, including formaldehyde and acetone, are not reported in the published reports. The prevalent methods for dealing with PW in California – underground injection and open evaporation ponds – are inadequate for this waste stream due to risks from induced seismicity, well integrity failure, well upsets, accidents and spills. Beneficial reuse of PW, such as for crop irrigation, is as of yet insufficiently safety tested for consumers and agricultural workers as well as plant health. Technological advances in onsite direct PW reuse and recycling look promising but need to control energy requirements, productivity and costs. The case study concludes that (i) reporting of PW chemical composition should be expanded in frequency and cover a wider range of chemicals used in hydraulic fracturing fluids, and (ii) PW management practices should be oriented towards safer and more sustainable options such as reuse and recycling, but with adequate controls in place to ensure their safety and reliability.

Abstract:
Hydraulic fracturing fluids are injected into shales" to extend fracture networks that enhance oil and natural gas production from unconventional reservoirs. Here we evaluated the biodegradability of three widely used nonionic polyglycol ether surfactants (alkyl ethoxylates (AEOs), nonylphenol ethoxylates (NPEOs), and polypropylene glycols (PPGs)) that function as weatherizers, emulsifiers, wetting agents, and corrosion inhibitors in injected fluids. Under anaerobic conditions, we observed complete removal of AEOs and NPEOs from solution within 3 weeks regardless of whether surfactants were part of a chemical mixture or amended as individual additives. Microbial enzymatic chain shortening was responsible for a shift in ethoxymer molecular weight distributions and the accumulation of the metabolite acetate. PPGs bioattenuated the slowest, producing sizable concentrations of acetone, an isomer of propionaldehyde. Surfactant chain shortening was coupled to an increased abundance of the diol dehydratase gene cluster (pduCDE) in Firmicutes metagenomes predicted from :the 16S rRNA gene. The pduCDE enzymes are responsible for cleaving ethoxylate chain units into aldehydes before their fermentation into alcohols and carboxylic acids. These data provide new mechanistic insight into the environmental fate of hydraulic fracturing surfactants after accidental release through chain shortening and biotransformation, emphasizing the importance of compound structure disclosure for predicting biodegradation products.

Abstract:
Hydraulic fracturing (HF) has allowed for the utilization of previously unattainable shale oil and gas (O&G) resources. After HF is complete, the waters used to increase the facies' permeability return uphole as wastewaters. When these waters return to the surface, they are characterized by complex organic and inorganic chemistry, and can pose a health risk if not handled correctly. Therefore, these waters must be treated or disposed of properly. However, the variability of these waters' chemical composition over time is poorly understood and likely limits the applicability of their reuse. This study examines the water chemistry of a hydraulically fractured site in the Niobrara formation throughout the flowback period. Samples were collected every other day for the first 18days, then on a regular basis for three months. We identified HF fluid additives, including benzalkonium chlorides (BACs), alkyl ethoxylates (AEOs), and polyethylene glycols (PEGs), as well as geogenic components present in flowback and produced waters, their overall temporal pattern, and variables affecting the reuse of these waters. Observations indicate that alkalinity and iron may limit the reuse of these waters in HF, while chloride and alkalinity may limit the use of these waters for well-casing cement. The presence of numerous surfactant homologs, including biocides, was also observed, with the highest levels at the beginning of the flowback period. Principal component analysis identified three unique groupings in the chemical data that correspond to different stages in the flowback period: (1) the flowback stage (days 1-2); (2) the transition stage (days 6-21); and (3) the produced water stage (days 21-87). Results from this study will be important when designing decision frameworks for assessing water treatment options, particularly if onsite treatment is attempted. Successful reclamation of these waters may alleviate stress on water resources that continues to negatively impact the U. S.

Abstract:
A long-term field study (405 days) of a hydraulically fractured well from the Niobrara Formation in the Denver-Julesburg Basin was completed. Characterization of organic chemicals used in hydraulic fracturing and their changes through time, from the preinjected fracturing fluid to the produced water, was conducted. The characterization consisted of a mass balance by dissolved organic carbon (DOC), volatile organic analysis by gas chromatography/mass spectrometry, and nonvolatile organic analysis by liquid chromatography/mass spectrometry. DOC decreased from 1500 mg/L in initial flowback to 200 mg/L in the final produced water. Only ∼11% of the injected DOC returned by the end of the study, with this 11% representing a maximum fraction returned since the formation itself contributes DOC. Furthermore, the majority of returning DOC was of the hydrophilic fraction (60–85%). Volatile organic compound analysis revealed substantial concentrations of individual BTEX compounds (0.1–11 mg/L) over the 405-day study. Nonvolatile organic compounds identified were polyethylene glycols (PEGs), polypropylene glycols (PPG), linear alkyl-ethoxylates, and triisopropanolamine (TIPA). The distribution of PEGs, PPGs, and TIPA and their ubiquitous presence in our samples and the literature illustrate their potential as organic tracers for treatment operations or in the event of an environmental spill.

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.

Abstract:
High volume hydraulic fracturing (HVHF) of shale to stimulate the release of natural gas produces a large quantity of wastewater in the form of flowback fluids and produced water. These wastewaters are highly variable in their composition and contain a mixture of fracturing fluid additives, geogenic inorganic and organic substances, and transformation products. The qualitative and quantitative analyses of organic compounds identified in HVHF fluids, flowback fluids, and produced waters are reviewed here to communicate knowledge gaps that exist in the composition of HVHF wastewaters. In general, analyses of organic compounds have focused on those amenable to gas chromatography, focusing on volatile and semi-volatile oil and gas compounds. Studies of more polar and non-volatile organic compounds have been limited by a lack of knowledge of what compounds may be present as well as quantitative methods and standards available for analyzing these complex mixtures. Liquid chromatography paired with high-resolution mass spectrometry has been used to investigate a number of additives and will be a key tool to further research on transformation products that are increasingly solubilized through physical, chemical, and biological processes in situ and during environmental contamination events. Diverse treatments have been tested and applied to HVHF wastewaters but limited information has been published on the quantitative removal of individual organic compounds. This review focuses on recently published information on organic compounds identified in flowback fluids and produced waters from HVHF.

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Hydraulic fracturing, coupled with the advances in horizontal drilling, has been used for recovering oil and natural gas from shale formations and has aided in increasing the production of these energy resources. The large volumes of hydraulic fracturing fluids used in this technology contain chemical additives, which may be toxic organics or produce toxic degradation byproducts. This paper investigated the chemicals introduced into the hydraulic fracturing fluids for completed wells located in Pennsylvania and West Virginia from data provided by the well operators. The results showed a total of 5071 wells, with average water volumes of 5,383,743 ± 2,789,077 gal (mean ± standard deviation). A total of 517 chemicals was introduced into the formulated hydraulic fracturing fluids. Of the 517 chemicals listed by the operators, 96 were inorganic compounds, 358 chemicals were organic species, and the remaining 63 cannot be identified. Many toxic organics were used in the hydraulic fracturing fluids. Some of them are carcinogenic, including formaldehyde, naphthalene, and acrylamide. The degradation of alkylphenol ethoxylates would produce more toxic, persistent, and estrogenic intermediates. Acrylamide monomer as a primary degradation intermediate of polyacrylamides is carcinogenic. Most of the chemicals appearing in the hydraulic fracturing fluids can be removed when adopting the appropriate treatments.

Abstract:
The large volumes and unknown composition of flowback and produced waters cause public concerns about the environmental and social compatibility of hydraulic fracturing and the exploitation of unconventional gas. Flowback and produced waters contain not only residues of fracking additives but also chemical species that are dissolved from the shales. Interactions of different shales with an artificial fracturing fluid were studied in lab experiments under ambient and elevated temperature and pressure conditions. Fluid-rock interactions change the chemical composition of the fracturing fluid and this indicates that geochemistry of the fractured shale needs to be considered to understand flowback water composition.

Abstract:
With the economic establishment of the shale gas exploitation, horizontal drilling and hydraulic fracturing have become nowadays common procedures, but not without any controversy. In parallel, the emergent case of deep geothermal energy systems is claimed to not have much to do with the fracking process. Through an intensive review of the available literature and data, we aim to lift the veil on the differences and similarities between shale gas and deep geothermal energy regarding the chemical substances used during the stimulation phase, as far as possible. Such a comparison appears finally not so obvious. In a general way, the effective used quantity of each chemical should not be neglected, even if advertised as being an extremely small percentage of the total stimulation fluids composition. Although some of these substances are considered purely environment/human health friendly, the diversity of potential risks associated with the hazardous chemicals can lead to severe consequences. However, the multitude of possible pathways for these risks tends to show that the main hazards are not especially or exclusively linked to the fluids injection process itself.