Repository for Oil and Gas Energy Research (ROGER)

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.

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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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Demand for high-volume, short duration water withdrawals could create water stress to aquatic organisms in Fayetteville Shale streams sourced for hydraulic fracturing fluids. We estimated potential water stress using permitted water withdrawal volumes and actual water withdrawals compared to monthly median, low, and high streamflows. Risk for biological stress was considered at 20% of long-term median and 10% of high- and low-flow thresholds. Future well build-out projections estimated potential for continued stress. Most water was permitted from small, free-flowing streams and “frack” ponds (dammed streams). Permitted 12-h pumping volumes exceeded median streamflow at 50% of withdrawal sites in June, when flows were low. Daily water usage, from operator disclosures, compared to median streamflow showed possible water stress in 7–51% of catchments from June–November, respectively. If 100% of produced water was recycled, per-well water use declined by 25%, reducing threshold exceedance by 10%. Future water stress was predicted to occur in fewer catchments important for drinking water and species of conservation concern due to the decline in new well installations and increased use of recycled water. Accessible and precise withdrawal and streamflow data are critical moving forward to assess and mitigate water stress in streams that experience high-volume withdrawals.

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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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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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Sutton’s Law urges the medical practitioner to utilize the test that goes directly to the problem. When applied to exposure science, Sutton’s Law would argue that the major emphasis should be on techniques that directly measure exposure in or close to the human, animal or ecosystem receptors of concern. Exposure science largely and appropriately violates Sutton’s Law by estimating exposure based on information on emissions or measurements obtained at a distance from the receptors of concern. I suggest four criteria to help determine whether Sutton’s law should be violated for an innovative technology, and explore these criteria in relation to potential human exposure resulting from unconventional gas drilling (UGD): (1) The technological processes possibly leading to release of the chemical or physical agents of concern are reasonably understood; (2) the agents of concern are known; (3) the source and geographical location of the releases can be reasonably identified; and (4) there is information about the likely temporal pattern of the releases and resulting pollutant levels in relation to the temporal patterns of receptor susceptibility. For UGD, the complexity of the technology including many possible release points at different time periods; the existence of three variable mixtures of chemical and physical agents as well as possible unknown reactants; the demonstrated large variation in releases from site to site; and deficiencies in transparency and regulatory oversight, all suggest that studies of the potential health impact of UGD should follow Sutton’s Law. This includes the use of techniques that more directly measure exposure close to or within the receptors of concern, such as biological markers or through community-based citizen science. Understanding the implications of Sutton’s Law could help focus scientific and regulatory efforts on effective approaches to evaluate the potential health and ecosystem implications of new and evolving technologies.

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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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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.

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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.

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Ozonation, sorption to granular activated carbon and aerobic degradation were compared as potential treatment methods for removal of dissolved organic carbon (DOC) fractions and selected organic compounds from shale gas flowback water after pre-treatment in dissolved air flotation unit. Flowback water was characterised by high chemical oxygen demand and DOC. Low molecular weight (LMW) acids and neutral compounds were the most abundant organic fractions, corresponding to 47% and 35% of DOC respectively. Ozonation did not change distribution of organic carbon fractions and concentrations of detected individual organic compounds significantly. Sorption to activated carbon targeted removal of individual organic compounds with molecular weight >115 Da, whereas LMW compounds remained largely unaffected. Aerobic degradation was responsible for removal of LMW compounds and partial ammonium removal, whereas formation of intermediates with molecular weight of 200–350 Da was observed. Combination of aerobic degradation for LMW organics removal with adsorption to activated carbon for removal of non-biodegradable organics is proposed to be implemented between pre-treatment (dissolved air floatation) and desalination (thermal or membrane desalination) steps.

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This study investigates the flowback water impacts on the corrosion of mild steel pipelines used to transport the saline wastewater generated during fracturing of the Bakken shale. The uniform corrosion rates were high under acidic conditions compared to those under neutral and alkaline conditions. The pitting attack on the flowback water pipelines was 100-fold and 10-fold higher for acidic and alkaline conditions, respectively, than those for the neutral conditions. The corrosion deposits on the mild steel were characterized by a large specific surface area and high reactivity. These results suggest that the flowback water pipelines become a potential source of contaminants that threaten agricultural land and water resources.

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Produced water originated from oil and gas production wells was treated by a pilot-scale system including pre-treatment (chemical precipitation), pre-filtration, and post-filtration units. Pre-filtration unit consisted of sand filter, granulated activated carbon (GAC) filter, and ultrafiltration (UF) membrane. Post-filtration unit included reverse osmosis (RO) membrane unit. In this study, two different RO membranes including sea water (SW) and brackish water (BW) membranes were comparatively evaluated in terms of treatment and filtration performance. Besides, a cost analysis was conducted for a real scale RO membrane unit by using the data obtained from the pilot plant study. Average fluxes of 12.7 and 9.4 L/m2 h were obtained by SW and BW membrane units, respectively. Higher COD and conductivity removal efficiencies were obtained by SW membrane in comparison to BW membrane. Total cost of 0.88 €/m3 was estimated for a RO plant treating produced water with a flowrate capacity of 300 m3/d.

Abstract:
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 (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.

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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.

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The widespread use of unconventional drilling involving hydraulic fracturing (“fracking”) has allowed for increased oil-and-gas extraction, produced water generation, and subsequent spills of produced water in Colorado and elsewhere. Produced water contains BTEX (benzene, toluene, ethylbenzene, xylene) and naphthalene, all of which are known to induce varying levels of toxicity upon exposure. When spilled, these contaminants can migrate through the soil and contaminant groundwater. This research modeled the solute transport of BTEX and naphthalene for a range of spill sizes on contrasting soils overlying groundwater at different depths. The results showed that benzene and toluene were expected to reach human health relevant concentration in groundwater because of their high concentrations in produced water, relatively low solid/liquid partition coefficient and low EPA drinking water limits for these contaminants. Peak groundwater concentrations were higher and were reached more rapidly in coarser textured soil. Risk categories of “low,” “medium,” and “high” were established by dividing the EPA drinking water limit for each contaminant into sequential thirds and modeled scenarios were classified into such categories. A quick reference guide was created that allows the user to input specific variables about an area of interest to evaluate that site’s risk of groundwater contamination in the event of a produced water spill. A large fraction of produced water spills occur at hydraulic-fracturing well pads; thus, the results of this research suggest that the surface area selected for a hydraulic-fracturing site should exclude or require extra precaution when considering areas with shallow aquifers and coarsely textured soils.

Abstract:
Hydraulic fracturing flowback and produced water (FPW) is a wastewater produced during fracturing activities in an operating well which is hyper saline and chemically heterogeneous in nature, containing both anthropogenic and petrogenic chemicals. Determination of FPW associated toxicity to embryonic fish is limited, while investigation into how embryonic exposures may affect later life stages is not yet studied. Juvenile zebrafish embryos (24hrs post fertilization) were acutely exposed to 2.5% and 5% FPW fractions for either 24 or 48hrs and returned to freshwater. After either 24 or 48h exposures, embryos were examined for expression of 3 hypoxia related genes. Erythropoietin (epoa) but not hypoxia inducible factor (hif1aa) nor hemoglobin −ß chain (hbbe1.1) was up-regulated after either 24 or 48h FPW exposure. Surviving embryos were placed in freshwater and grown to a juvenile stage (60days post fertilization). Previously exposed zebrafish were analyzed for both swim performance (Ucrit and Umax) and aerobic capacity. Fish exposed to both sediment containing (FPW-S) or sediment free (FPW-SF) FPW displayed significantly reduced aerobic scope and Ucrit/Umax values compared to control conditions. Our results collectively suggest that organics present in our FPW sample may be responsible for sub-lethal fitness and metabolic responses. We provide evidence supporting the theory that the cardio-respiratory system is impacted by FPW exposure. This is the first known research associating embryonic FPW exposures to sub-lethal performance related responses in later life fish stages.

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One promising water management strategy during hydraulic fracturing is treatment and reuse of flowback/produced water. In particular, the saline flowback water contains many of the chemicals employed for fracking, which need to be removed before possible reuse as “frac water.” This manuscript targets one of the additives; borate-based cross-linkers used to adjust the rheological characteristics of the frac-fluid and turbidity. Alum and ferric chloride were evaluated as coagulants for clarification and boron removal from saline flowback water obtained from a well in the Eagle Ford shale. Extremely high dosages (>9000 mg/L or 333 mM Al and 160 mM Fe) corresponding to Al/B and Fe/B mass ratios of ∼70 and molar ratios of ∼28 and 13 respectively were necessary to remove ∼80% boron. Hence, coagulation does not appear to be feasible for boron removal from high-strength waste streams. X-ray photoelectron spectroscopy revealed BO bonding on surfaces of freshly precipitated Al(OH)3(am) and Fe(OH)3(am) suggesting boron uptake was predominantly via ligand exchange. Attenuated total reflection-Fourier transform infrared spectroscopy provided direct evidence of inner-sphere boron complexation with surface hydroxyl groups on both amorphous aluminum and iron hydroxides. Only trigonal boron was detected on aluminum flocs since possible presence of tetrahedral boron was masked by severe AlO interferences. Both trigonal and tetrahedral conformation of boron complexes were identified on Fe(OH)3 surfaces.

Abstract:
Hydraulic fracturing to extract oil and natural gas reserves is an increasing practice in many international energy sectors. Hydraulic fracturing flowback and produced water (FPW) is a hyper saline wastewater returned to the surface from a fractured well containing chemical species present in the initial fracturing fluid, geogenic contaminants, and potentially newly synthesized chemicals formed in the fracturing well environment. However, information on FPW toxicological mechanisms of action remain largely unknown. Both cardiotoxic and respirometric responses were explored in zebrafish (Danio rerio) embryos after either an acute sediment-free (FPW-SF) or raw/sediment containing (FPW-S) fraction exposure of 24 and 48 h at 2.5% and 5% dilutions. A 48 h exposure to either FPW fraction in 24–72 h post fertilization zebrafish embryos significantly increased occurrences of pericardial edema, yolk-sac edema, and tail/spine curvature. In contrast, larval heart rates significantly decreased after FPW fraction exposures. FPW-S, but not FPW-SF, at 2.5% doses significantly reduced embryonic respiration/metabolic rates (MO2), while for 5% FPW, both fractions reduced MO2. Expression of select cardiac genes were also significantly altered in each FPW exposure group, implicating a cardiovascular system compromise as the potential cause for reduced embryonic MO2. Collectively, these results support our hypothesis that organics are major contributors to cardiac and respiratory responses to FPW exposure in zebrafish embryos. Our study is the first to investigate cardiac and respiratory sub-lethal effects of FPW exposure, demonstrating that FPW effects extend beyond initial osmotic stressors and verifies the use of respirometry as a potential marker for FPW exposure.

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The Permian Basin is being transformed by the “shale revolution” from a major conventional play to the world’s largest unconventional play, but water management is critical in this semiarid region. Here we explore evolving issues associated with produced water (PW) management and hydraulic fracturing water demands based on detailed well-by-well analyses. Our results show that although conventional wells produce ∼13 times more water than oil (PW to oil ratio, PWOR = 13), this produced water has been mostly injected back into pressure-depleted oil-producing reservoirs for enhanced oil recovery. Unconventional horizontal wells use large volumes of water for hydraulic fracturing that increased by a factor of ∼10–16 per well and ∼7–10 if normalized by lateral well length (2008–2015). Although unconventional wells have a much lower PWOR of 3 versus 13 from conventional wells, this PW cannot be reinjected into the shale reservoirs but is disposed into nonproducing geologic intervals that could result in overpressuring and induced seismicity. The potential for PW reuse from unconventional wells is high because PW volumes can support hydraulic fracturing water demand based on 2014 data. Reuse of PW with minimal treatment (clean brine) can partially mitigate PW injection concerns while reducing water demand for hydraulic fracturing.

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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.

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In the present study, the K-40, U-238, Ra-226, Pb-210, Ra-228 and Th-228 activity concentrations were measured in 64 samples of wastes generated from shale gas exploration in North-Eastern Poland. The measured samples consist of drill cuttings, solid phase of waste drilling muds, fracking fluids, return fracking fluids and waste proppants. The measured activity concentrations in solid samples vary in a wide range from 116 to around 1100 Bq/kg for K-40, from 14 to 393 Bq/kg for U-238, from 15 to 415 Bq/kg for Ra-226, from 12 to 391 Bq/kg for Pb-210, from a few Bq/kg to 516 Bq/kg for Ra-228 and from a few Bq/kg to 515 Bq/kg for Th-228. Excluding the waste proppants, the measured activity concentrations in solid samples oscillate around their worldwide average values in soil. In the case of the waste proppants, the activity concentrations of radionuclides from uranium and thorium decay series are significantly elevated and equal to several hundreds of Bq/kg but it is connected with the mineralogical composition of proppants. The significant enhancement of Ra-226 and Ra-228 activity concentrations after fracking process was observed in the case of return fracking fluids, but the radium isotopes content in these fluids is comparable with that in waste waters from copper and coal mines in Poland.

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Unconventional oil and gas development using hydraulic fracturing has caused conflict and controversy across the globe including the U.S. where some States banned the practice. Nevertheless, North Dakota (ND) has supported the practice because the State perceives the risks to be acceptable and because it has brought growth and opportunities to small communities. However, social acceptance of new technology is based on a number of factors and not contingent on economic benefits. To date, no research has been conducted to understand public risk perception of hazards associated with produced water from hydraulic fracturing in ND. This study focuses on understanding the risk perception of select ND stakeholder groups regarding produced water management and naturally occurring radioactive material. The software Qualtrics was used to create an online survey, collect data, and perform statistical analysis. The most important variables that seem to influence risk perception are the images and thoughts associated with produced water, level of knowledge about produced water handling and content, and knowing how to proceed in case of a spill of produced water. Overall, social risk perception could be in alignment with actual technical risk if availability of objective information is improved.

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Hydraulic fracturing (HF) has emerged as a major method of unconventional oil and gas recovery. The toxicity of hydraulic fracturing flowback and produced water (HF-FPW) has not been previously reported and is complicated by the combined complexity of organic and inorganic constituents in HF fluids and deep formation water. In this study, we characterized the solids, salts, and organic signatures in an HF-FPW sample from the Duvernay Formation, Alberta, Canada. Untargeted HPLC-Orbitrap revealed numerous unknown dissolved polar organics. Among the most prominent peaks, a substituted tri-phenyl phosphate was identified which is likely an oxidation product of a common polymer antioxidant. Acute toxicity of zebrafish embryo was attributable to high salinity and organic contaminants in HF-FPW with LC50 values ranging from 0.6% to 3.9%, depending on the HF-FPW fractions and embryo developmental stages. Induction of ethoxyresorufin-O-deethylase (EROD) activity was detected, due in part to polycyclic aromatic hydrocarbons (PAHs), and suspended solids might have a synergistic effect on EROD induction. This study demonstrates that toxicological profiling of real HF-FPW sample presents great challenges for assessing the potential risks and impacts posed by HF-FPW spills.

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This study examined water quality, naturally-occurring radioactive materials (NORM), major ions, trace metals, and well flow data for water used and produced from start-up to operation of an oil and gas producing hydraulically-fractured well (horizontal) in the Denver-Julesburg (DJ) Basin in northeastern Colorado. Analysis was conducted on the groundwater used to make the fracturing fluid, the fracturing fluid itself, and nine flowback/produced water samples over 220days of operation. The chemical oxygen demand of the wastewater produced during operation decreased from 8200 to 2500mg/L, while the total dissolved solids (TDS) increased in this same period from 14,200 to roughly 19,000mg/L. NORM, trace metals, and major ion levels were generally correlated with TDS, and were lower than other shale basins (e.g. Marcellus and Bakken). Although at lower levels, the salinity and its origin appear to be the result of a similar mechanism to that of other shale basins when comparing Cl/Br, Na/Br, and Mg/Br ratios. Volumes of returned wastewater were low, with only 3% of the volume injected (11millionliters) returning as flowback by day 15 and 30% returning by day 220. Low levels of TDS indicate a potentially treatment-amenable wastewater, but low volumes of flowback could limit onsite reuse in the DJ Basin. These results offer insight into the temporal water quality changes in the days and months following flowback, along with considerations and implications for water reuse in future hydraulic fracturing or for environmental discharge.

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Large volumes of water return to the surface following hydraulic fracturing of deep shale formations to retrieve oil and natural gas. Current understanding of the specific organic constituents in these hydraulic fracturing wastewaters is limited to hydrocarbons and a fraction of known chemical additives. In this study, we analyzed hydraulic fracturing wastewater samples using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) as a non-targeted technique to assign unambiguous molecular formulas to singly charged molecular ions. Halogenated molecular formulas were identified and confirmed using isotopic simulation and MS-MS fragmentation spectra. The abundance of halogenated organic compounds in flowback fluids rather than older wastewaters suggested that the observed molecular ions might have been related to hydraulic fracturing additives and related subsurface reactions, such as through the reaction of shale-extracted chloride, bromide, and iodide with strong oxidant additives (e.g., hypochlorite, persulfate, hydrogen peroxide) and subsequently with diverse dissolved organic matter. Some molecular ions matched the exact masses of known disinfection by-products including diiodoacetic acid, dibromobenzoic acid, and diiodobenzoic acid. The identified halogenated organic compounds, particularly iodinated organic molecules, are absent from inland natural systems and these compounds could therefore play an important role as environmental tracers.

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Organic contaminants in shale gas flowback and produced water (FPW) are traditionally expressed as total organic carbon (TOC) or chemical oxygen demand (COD), though these parameters do not provide information on the toxicity and environmental fate of individual components. This review addresses identification of individual organic contaminants in FPW, and stresses the gaps in the knowledge on FPW composition that exist so far. Furthermore, the risk quotient approach was applied to predict the toxicity of the quantified organic compounds for fresh water organisms in recipient surface waters. This resulted in an identification of a number of FPW related organic compounds that are potentially harmful namely those compounds originating from shale formations (e.g. polycyclic aromatic hydrocarbons, phthalates), fracturing fluids (e.g. quaternary ammonium biocides, 2-butoxyethanol) and downhole transformations of organic compounds (e.g. carbon disulphide, halogenated organic compounds). Removal of these compounds by FPW treatment processes is reviewed and potential and efficient abatement strategies are defined.

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The purpose of the study was to separate and identify the unknown surfactants present in flowback and produced water from oil and gas wells in the Denver-Julesburg Basin (Niobrara Formation) in Weld County, Colorado, USA. Weld County has been drilled extensively during the last five years for oil and gas between 7000–8000 feet below land-surface. Polypropylene glycols (PPGs) and polyethylene glycols carboxylates (PEG-Cs) were found for the first time in these flowback and produced water samples. These ethoxylated surfactants may be used as friction reducers, clay stabilizers, and surfactants. Ultrahigh-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry (UHPLC/QTOF-MS) was used to separate and identify the different classes of PPGs, PEG-Cs, and their isomers. The Kendrick mass scale was applied along with mass spectrometry/mass spectrometry (MS-MS) with accurate mass for rapid and unequivocal identification. The PPGs and their isomers occur at the ppm concentration range and may be useful as “fingerprints” of hydraulic-fracturing. Comparing these detections to the compounds used in the fracturing process from FracFocus 3.0 (https://fracfocus.org), it appears that both PPGs and polyethylene glycols (PEGs) are commonly named as additives, but the PEG-Cs have not been reported. The PEG-Cs may be trace impurities or degradation products of PEGs.

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Microbial activity in the produced water from hydraulically fractured oil and gas wells may potentially interfere with hydrocarbon production and cause damage to the well and surface infrastructure via corrosion, sulfide release, and fouling. In this study, we surveyed the microbial abundance and community structure of produced water sampled from 42 Marcellus Shale wells in southwestern Pennsylvania (well age ranged from 150 to 1846 days) to better understand the microbial diversity of produced water. We sequenced the V4 region of the 16S rRNA gene to assess taxonomy and utilized qPCR to evaluate the microbial abundance across all 42 produced water samples. Bacteria of the order Halanaerobiales were found to be the most abundant organisms in the majority of the produced water samples, emphasizing their previously suggested role in hydraulic fracturing related microbial activity. Statistical analyses identified correlations between well age and biocide formulation and the microbial community, in particular the relative abundance of Halanaerobiales. We further investigated the role of the order Halanaerobiales in produced water by reconstructing and annotating a Halanaerobium draft genome (named MDAL1), using shotgun metagenomic sequencing and metagenomic binning. The recovered draft genome was found to be closely related to the species H. congolense, an oil-field isolate, and Halanaerobium sp. T82-1, also recovered from hydraulic fracturing produced water. Reconstruction of metabolic pathways revealed Halanaerobium sp. MDAL1 to have the potential for acid production, thiosulfate reduction, and biofilm formation, suggesting it have the capability to contribute to corrosion, souring, and biofouling events in the hydraulic fracturing infrastructure. Importance There are an estimated 15,000 unconventional gas wells in the Marcellus Shale region, each generating up to 8000 liters of hypersaline produced water per day throughout their lifetime (1-3). Microbial activity in produced waters could lead to issues with corrosion, fouling, and souring, potentially interfering with hydraulic fracturing operations. Previous studies have found microorganisms contributing to corrosion, fouling, and souring to be abundant across produced water samples from hydraulically fractured wells (4-12); however, these findings were based on a limited number of samples and six total well sites. In the current paper we investigate the microbial community structure in produced water samples from 42 unconventional Marcellus Shale wells, confirming the dominance of the genus Halanaerobium in produced water and its metabolic potential for acid and sulfide production and biofilm formation.

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Hydraulic fracturing is an industrial process allowing for the extraction of gas or oil. To fracture the rocks, a proprietary mix of chemicals is injected under high pressure, which later returns to the surface as flowback and produced water (FPW). FPW is a complex chemical mixture consisting of trace metals, organic compounds, and often, high levels of salts. FPW toxicity to the model freshwater crustacean, Daphnia magna, was characterized utilizing acute (48 h median lethal concentrations; LC50) and chronic (21 d) exposures. A decrease in reproduction was observed, with a mean value of 18.5 neonates produced per replicate over a 21-d chronic exposure to 0.04% FPW, significantly decreased from the average of 64 neonates produced in controls. The time to first brood was delayed in the highest FPW (0.04%) treatment. Neonates exhibited an LC50 of 0.19% of full-strength FPW, making them more sensitive than adults, which displayed an LC50 value of 0.75%. Quantitative PCR highlighted significant changes in expression of genes encoding xenobiotic metabolism (cyp4) and moulting (cut). This study is the first to characterize chronic FPW toxicity and will help development of environmental monitoring and risk assessment of FPW spills.

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The effects of hydraulic fracturing (HF) flowback and produced water (HF-FPW), a complex saline mixture of injected HF fluids and deep formation water that return to the surface, was examined in rainbow trout (Oncorhynchus mykiss). Exposure to HF-FPWs resulted in significant induction of ethoxyresorufin-O-deethylase (EROD) activity in both liver and gill tissues. Increased lipid peroxidation via oxidative stress was also detected by thiobarbituric acid reactive substances (TBARS) assay. The mRNA expressions of a battery of genes related to biotransformation, oxidative stress, and endocrine disruption were also measured using quantitative real-time polymerase chain reaction (Q-RT-PCR). The increased expression of cyp1a (2.49 ± 0.28-fold), udpgt (2.01 ± 0.31-fold), sod (1.67 ± 0.09-fold), and gpx (1.58 ± 0.10-fold) in raw sample exposure group (7.5%) indicated elevated metabolic enzyme activity, likely through the aryl hydrocarbon receptor pathway, and generation of reactive oxygen species. In addition, the elevated vtg and era2 expression demonstrated endocrine disrupting potential exerted by HF-FPW in rainbow trout. The overall results suggested HF-FPW could cause significant adverse effects on fish, and the organic contents might play the major role in its toxicity. Future studies are needed to help fully determine the toxic mechanism(s) of HF-FPW on freshwater fish, and aid in establishing monitoring, treatment, and remediation protocols for HF-FPW.

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Microorganisms present in production facilities of shale gas can cause substantial increases in production costs and complicate water management. Here, an uncommon microbial distribution was observed at six gas-gathering stations of deep shale wells (average depth: 4162 m) in Sichuan Basin, China. Employing Illumina MiSeq 16S rRNA gene sequencing and quantitative polymerase chain reaction (qPCR), the majority of bacterial communities in gas-water separators and water storage tanks sampled belonged to the genus Shewanella (accounting for 60.67% of total bacterial sequences detected) as well as Marinobacter, Marinobacterium, Arcobacter, Acetobacterium, Alkalibacter that were encountered in previously reported shale produced water. Archaea were mainly methylotrophic and halotolerant methanogenic genera, including Methanolobus, Methanohalophilus, and Methanocalculus. For the first time, fungi (primarily Ascomycota and Basidiomycota) were detected in the produced water from production facilities, and some genera, such as Cladosporium, may be associated with corrosion. Apart from Shewanella, other sulfidogenic taxa mainly belonging to Dethiosulfovibrio, Dethiosulfatibacter and acid producers belonging to Acetobacterium were also encountered. Microbial communities in storage tanks were more abundant and diverse than that in separators. Notably, detection of biocorrosive sulfate-reducing bacteria (SRB), increased from separators (0.39%) to storage tanks (2.37%). This study expands our knowledge about microbial diversity in production facilities of shale gas and the findings may have implications in guiding wastewater management during shale gas production.

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Fluids injected into shale formations during hydraulic fracturing of black shale return with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium (Ba) and radium (Ra). Barite, BaSO4, has been implicated as a possible source of Ba as well as a problematic mineral scale that forms on internal well surfaces, often in close association with radiobarite, (Ba,Ra)SO4. The dissolution of barite by abiotic processes is well quantified. However, the identification of microbial communities in flowback and produced water necessitates the need to understand barite dissolution in the presence of bacteria. Therefore, we evaluated the rates and mechanisms of abiotic and microbially-mediated barite dissolution under anoxic and hypersaline conditions in the laboratory. Barite dissolution experiments were conducted with bacterial enrichment cultures established from produced water from Marcellus Shale wells located in northcentral Pennsylvania. These cultures were dominated by anaerobic halophilic bacteria from the genus Halanaerobium. Dissolved Ba was determined by ICP-OES and barite surfaces were investigated by SEM and AFM. Our results reveal that: 1) higher amounts of barium (up to ∼5 × ) are released from barite in the presence of Halanaerobium cultures compared to brine controls after 30 days of reaction, 2) etch pits that develop on the barite (001) surface in the presence of Halanaerobium exhibit a morphology that is distinct from those that form during control experiments without bacteria, 3) etch pits that develop in the presence of Halanaerobium exhibit a morphology that is similar to the morphology of etch pits formed in the presence of strong organic chelators, EDTA and DTPA, and 4) experiments using dialysis membranes to separate barite from bacteria suggest that direct contact between the two is not required in order to promote dissolution. These results suggest that Halanaerobium increase the rate of barite dissolution in anoxic and high ionic strength solutions. Additionally, the increase in rate occurs without direct microbe-mineral contact suggesting that metabolites secreted by the bacteria may be responsible for promotion of dissolution. The findings of this study have implications for understanding barium cycling in marine/hypersaline environments, release of barium (and associated radium) from waste solids generated from energy and mining industries, as well as potential for developing new anti-scaling chemicals.

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The inorganic geochemistry of hydraulic fracturing fluids is reviewed with new insights on the role of entrapped formation waters in unconventional shale gas and tight sand formations on the quality of flowback and produced waters that are extracted with hydrocarbons. The rapid increase of the salinity of flowback fluids during production, combined with geochemical and isotopic changes, indicate mixing of the highly saline formation water with the injected water. The salinity increase suggests that the volume of the injected water that is returned to the surface with the flowback water is much smaller than previous estimates, and thus the majority of the injected water is retained within the shale formations. The high salinity of the flowback and produced water is associated with high concentrations of halides, ammonium, metals, metalloids, and radium nuclides that pose environmental and human health risks upon the release of the hydraulic fracturing fluids to the environment.

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The management and disposal of flowback and produced waters (FP water) is one of the greatest challenges associated with unconventional oil and gas development. The development and production of unconventional natural gas and oil is projected to increase in the coming years, and a better understanding of the volume and quality of FP water is crucial for the safe management of the associated wastewater. We analyzed production data using multiple statistical methods to estimate the total FP water generated per well from six of the major unconventional oil and gas formations in the United States. The estimated median volume ranges from 1.7 to 14.3millionL (0.5 to 3.8milliongal) of FP per well over the first 5-10years of production. Using temporal volume production and water quality data, we show a rapid increase of the salinity associated with a decrease of FP production rates during the first months of unconventional oil and gas production. Based on mass-balance calculations, we estimate that only 4-8% of FP water is composed of returned hydraulic fracturing fluids, while the remaining 92-96% of FP water is derived from naturally occurring formation brines that is extracted together with oil and gas. The salinity and chemical composition of the formation brines are therefore the main limiting factors for beneficial reuse of unconventional oil and gas wastewater.

Abstract:
A dramatic increase in unconventional drilling that utilizes hydraulic fracturing to extract oil/gas over the past decade has led to concern over handling and management of produced/ flowback water (PFW; hydraulic-fracturing wastewater) because the potential exists for its accidental release into the environment. This PFW contains high amounts of total dissolved solids acquired from interaction with the reservoir formation. Development and testing of geochemical methods, such as strontium (Sr) isotope ratio (87Sr/86Sr) analysis, to determine the origin of dissolved solids in an environment would be valuable. Samples acquired from different sources in Texas overlying and within the Barnett Shale, such as surface/ground water and PFW, contain unique Sr concentrations and 87Sr/86Sr values, with the potential to be used as a geochemical fingerprint. This study shows that because of the very high concentration of Sr in PFW and its high 87Sr/86Sr value, when as little as 1% of a sample is PFW, the sample experiences a measurable change in 87Sr/86Sr. To determine which phase within the reservoir rock imparts its 87Sr/86Sr to the PFW, sequential extractions were performed on powdered Barnett Shale core samples. Results of the extractions show varying geochemical affinities and distinct 87Sr/86Sr values by leaching solution. However, a direct link to the PFW sample was not conclusive, likely because of the unknown location of the PFW sample and the spatially variable 87Sr/86Sr of the Barnett Shale. Future work requires further cooperation with industry or federal agencies that could provide a more complete set of samples.

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The environmental impact of shale oil and gas production by hydraulic fracturing (fracking) is of increasing concern. The biggest potential source of environmental contamination is flowback and produced water, which is highly contaminated with hydrocarbons, bacteria and particulates, meaning that traditional membranes are readily fouled. We show the chemical functionalisation of alumina ceramic microfiltration membranes (0.22 μm pore size) with cysteic acid creates a superhydrophilic surface, allowing for separation of hydrocarbons from frac and produced waters without fouling. The single pass rejection coefficients was >90% for all samples. The separation of hydrocarbons from water when the former have hydrodynamic diameters smaller than the pore size of the membrane is due to the zwitter ionically charged superhydrophilic pore surface. Membrane fouling is essentially eliminated, while a specific flux is obtained at a lower pressure (<2 bar) than that required achieving the same flux for the untreated membrane (4–8 bar).

Abstract:
Produced water is a type of wastewater generated from hydraulic fracturing, which may pose a risk to the environment and humans due to its high ionic strength and the presence of elevated concentrations of metals/metalloids that exceed maximum contamination levels. The mobilization of As(V) and Se(VI) in produced water and selected soils from Qingshankou Formation in the Songliao Basin in China were investigated using column experiments and synthetic produced water whose quality was representative of waters arising at different times after well creation. Temporal effects of produced water on metal/metalloid transport and sorption/desorption were investigated by using HYDRUS-1D transport modelling. Rapid breakthrough and long tailings of As(V) and Se(VI) transport were observed in Day 1 and Day 14 solutions, but were reduced in Day 90 solution probably due to the elevated ionic strength. The influence of produced water on the hydrogeological conditions (i.e., change between equilibrium and non-equilibrium transport) was evidenced by the change of tracer breakthrough curves before and after the leaching of produced water. This possibly resulted from the sorption of polyacrylamide (PAM (-CH2CHCONH2-)n) onto soil surfaces, through its use as a friction reducer in fracturing solutions. The sorption was found to be reversible in this study. Minimal amounts of sorbed As(V) were desorbed whereas the majority of sorbed Se(VI) was readily leached out, to an extent which varied with the composition of the produced water. These results showed that the mobilization of As(V) and Se(VI) in soil largely depended on the solution pH and ionic strength. Understanding the differences in metal/metalloid transport in produced water is important for proper risk management.

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After the completion of hydraulic fracturing, some part of injected fluids mixed with the formation brines - so called flowback brine, migrate back through the well to the surface. Our autoclave experiments were aimed to reproduce and evaluate the chemical composition of the flowback brine derived from CO2-energized fluid fracturing of shale gas of the Baltic province (Poland).Results show the flowback composition is controlled mainly by the interactions between fracturing fluids and original pore water, and to a lesser extent with the reservoir rock.

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To find out the impact of chemical potential difference between the low salinity fracturing fluid and the high salinity formation water on fracturing fluid flowback, a chemical potential difference expression of fracturing fluid and formation water was deduced, on this basis, a mathematical model which considers viscous force, capillary force and osmosis pressure driven gas-water flow in matrix-fracture system was built, the flow back performance of fracturing fluid driven by chemical potential difference was simulated, and the formation water saturation and salt concentration profile with flow back time were analyzed. The results show that in the process of flow back, the water molecules in the matrix driven by the chemical potential difference continually migrated to the deeper reservoirs, while salt ions in the matrix constantly spread to the fractures. After 168 h of fracturing-fluid flow back, the migration distance of water was up to 40 cm, and the salt concentration near the fracture surface increased by 0.841%, and the cumulative flowback ratio of the gas well was only 22.1%. The cumulative flowback ratio would be 23.5%, 32.4% and 41.1% respectively, without taking into account the effect of gas absorption, chemical osmosis or capillary imbibition. The capillary imbibition and chemical osmosis seriously hindered the fracturing-fluid flow back, therefore, the two factors should be fully considered in the post-fracturing evaluation of shale gas wells.

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Determination of in situ formation water chemistry is an essential component of reservoir management. This paper details the use of thermodynamic computer models to calculate reservoir pH and restore produced water analyses for prediction of scale formation. Bakken produced water samples were restored to formation conditions and calculations of scale formation performed. In situ pH is controlled by feldspar-clay equilibria. Calcite scale is readily formed due to changes in pH during pressure drop from in situ to surface conditions. The formation of anhydrite and halite scale, which has been observed, was predicted only for the most saline samples. In addition, the formation of anhydrite and/or halite may be related to the localized conditions of increased salinity as water is partitioned into the gas phase during production.

Abstract:
Shale with high clay content has caused instability from hydration during the hydraulic fracturing process. Macro-level migration phenomenon of water molecules is induced by the chemical potential difference between low-salinity fracturing fluid and high-salinity formation brine. This study aims to establish the equation for the chemical potential difference between fracturing fluid and formation brine by theoretical deduction in order to investigate the effect of the aforementioned phenomenon on fracturing flowback. Accordingly, a mathematical model was established for the gas–water two-phase flow which driven by the chemical potential difference. Viscous force, capillarity and chemiosmosis were considered as the driving forces. A numerical simulation of fracturing fluid flowback with or without considering of the effect of chemiosmosis was performed. A simulation analysis of the water saturation and salinity profiles was also conducted. Results show that capillarity and chemiosmosis hinder fracturing fluid flowback in different degrees. As the condition worsens, they inhibit more than 80% of water to flow back out of the formation, forming a permanent water lock. This study contributes to improvement of the theory on shale gas–water two-phase flow, establishment of a flowback model that suitable for shale gas wells, and accurate evaluation of the fracturing treatment.

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Flowback/produced water reuse cannot be optimized without a thorough understanding of the quality of the water that needs to be treated for reuse, including the temporal variability. Samples for flowback/produced water were collected over a 200-day period (day 0 refers to when flowback began) from two wells. One of the frac fluids had an initial pH greater than 10 and used a guar-based gel and the second fluid contained a non-guar polysaccharide based polymer with an initial pH of less than 6. Total dissolved solids (TDS) and total organic carbon (TOC) were used as macro-indicators and key ions (barium, calcium, chloride, magnesium, sodium, strontium, boron and iron) were compared to TDS with the different frac fluids and there were significant positive correlations observed between the key ions and TDS with relatively high values of the coefficient of determinant (over 0.85). The concentrations of calcium, chloride, sodium and strontium are statistically equivalent between the two fluids. A mass balance approach was applied to evaluate the quantity of mass of injected additives that was recovered over the 200-day period. Recoveries of zirconium, potassium and aluminum ranged from 3% to 33% after 200 days, and notable differences were observed between frac fluids.

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Summary Fracture fluid is composed of fresh water, proppant, and a small percentage of other additives, which support the hydraulic-fracturing process. Excluding situations in which flowback water is recycled and reused, the total dissolved solids (

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Hydraulic fracturing fluid (HFF) additives are used to enhance oil and gas extraction from unconventional shale formations. Several kilometers downhole, these organic chemicals are exposed to temperatures up to 200 °C, pressures above 10 MPa, high salinities, and a pH range from 5 - 8. Despite this, very little is known about the fate of HFF additives under these extreme conditions. Here, stainless steel reactors are used to simulate the downhole chemistry of the commonly used HFF biocide glutaraldehyde (GA). The results show that GA rapidly (t1/2 < 1 hr) autopolymerizes, forming water-soluble dimers and trimers, and eventually precipitates out at high temperatures (~140 ºC) and/or alkaline pH. Interestingly, salinity was found to significantly inhibit GA transformation. Pressure and shale did not affect GA transformation and/or removal from the bulk fluid. Based on experimental second-order rate constants, a kinetic model for GA downhole half-life predictions for any combination of these conditions within the limits tested was developed. These findings illustrate that the biocidal GA monomer has limited time to control microbial activity in hot and/or alkaline shales, and may return along with its aqueous transformation products to the surface via flowback and produced water in cooler, more acidic, and saline shales.

Abstract:
Wastewater from shale oil and gas wells contains high levels of organic and inorganic compounds, and the beneficial reuse of produced water requires some level of treatment to remove emulsified oil and grease, suspended solids, and multivalent ions. It is important to identify the quantity and makeup of solids in produced water, so that an optimized reuse or treatment approach can be achieved. This study provides a qualitative and quantitative characterization of solids in frac flowback and produced water from five horizontal wells at two separate sites in the Wattenberg field of Northern Colorado. Difference in solids from wells fractured with fresh water and recycled water is compared in this study, and their distribution and characterization are identified by particle size distribution measurement and X-ray photoelectron spectroscopy (XPS). Results show that particle sizes were smaller and more uniform in produced water samples collected during the first week of production from the wells fractured with recycled water, suggesting that the recycled water was more compatible with the shale formation and wells fractured with recycled water tend to clean out faster.