Repository for Oil and Gas Energy Research (ROGER)

Abstract:
The significant development of oil and gas from the Marcellus Shale and other geological formations in Pennsylvania over the last decade has generated large volumes of liquid and solid waste. In this paper we use data reported to the Pennsylvania Department of Environmental Protection (PADEP) to examine temporal and spatial trends in generation and management of liquid and solid waste from both conventional and unconventional oil and gas activities in Pennsylvania between 1991 and 2017. While previous assessments have examined this waste inventory in part, no complete assessment of waste quantity, waste types, waste handling practices, and spatial waste tracking has been undertaken using all currently available full years of Pennsylvania oil and gas waste data. In 2017 more than half of oil and gas wastewater by volume was reused at well pads to facilitate more hydrocarbon production while the majority of solid waste by volume was disposed of at in-state landfills. The spatial resolution of reporting of wastewater generation and handling from unconventional operations has improved substantially with recent regulations and reporting requirements; however, conventional oil and gas development was exempt from the more stringent reporting requirements and thus spatially-explicit data on wastewater generation and handling from conventional oil and gas development is still lacking. In addition, a third of the liquid waste across all years in the database lack a reported final destination. Spatially explicit cradle-to-grave reporting for waste handling from both conventional and unconventional oil and gas development is important to assess a number of environmental and human health hazards and risks of oil and gas development and associated operations and practices.

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Recovery of natural gas and oil from unconventional (shale) reservoirs relies on horizontal drilling and hydraulic fracturing to make it economical. Hydraulic fracturing generates vast quantities of flowback and produced water (FPW) and its composition exhibits huge spatial and temporal variations among shale plays. This review focuses on the characteristics and management of wastewaters originating for oil and gas extraction. Wastewater characteristics, including the quantity and chemical composition of the FPW, are discussed. The future of unconventional oil and gas industry hinges on effective management of FPW. Membrane technologies have the potential to offer solutions to sustainable reuse of this water resource. The performance of a range of membrane processes is evaluated and compared. Emerging membrane-based technologies employed in similar fields are also discussed. The results in peer-reviewed publications could offer a guide for the selection of appropriate technologies based on the desired application. Membrane fouling, lack of pilot- and full-scale experience and high energy consumption are primary challenges for membrane applications in FPW. Then challenges and future research needs are addressed, advances in membrane materials, systematic analyses of organics and electric generation from salinity gradient are promising approaches to address the issues.

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We developed an integrated treatment train that enables effective treatment of shale oil and gas produced water generated from the Wattenberg field in northeast Colorado. Membrane distillation (MD) was performed in tandem with simple and inexpensive pretreatment steps, namely precipitative softening (PS) and walnut shell filtration (WSF). PS removed various particulate, organic, and inorganic foulants, thereby mitigating fouling and scaling potential of the produced water. WSF displayed exceptional efficiencies (≥95%) in eliminating volatile toxic compounds including benzene, ethylbenzene, toluene, and xylenes (BTEX) along with additional gasoline and diesel range organic compounds. With pretreatment, the water vapor flux of MD decreased by only 10% at a total water recovery of 82.5%, with boron and total BTEX concentrations in the MD distillate meeting the regulatory requirements for irrigation and typical discharge limits, respectively. The use of pretreatment also led to robust membrane reusability within three consecutive treatment cycles, with MD water flux fully restored after physical membrane cleaning. Our results highlight the necessity of pretreatment prior to MD treatment of produced water and demonstrate the potential of our treatment train to achieve a cost-effective and on-site wastewater treatment system that improves the sustainability of the shale oil and gas industry.

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Forward osmosis (FO) and membrane distillation (MD) are emerging technologies of interest for the treatment of high salinity brines. In this study, we aim to demonstrate the feasibility of an integrated FO-MD system for water recovery from high salinity produced waters obtained from shale gas extraction facilities. In the proposed hybrid system, FO draws water from high salinity feed, while MD regenerates the diluted FO draw solution. We show that this process integration can combine the advantages of both processes; low fouling tendency, possibility of using low-grade waste heat as the main energy source and high quality permeate. We further integrate the FO-MD system with an electrocoagulation (EC) system as pretreatment and show stable performance with minimal fouling. EC removed total organic carbon and total suspended solids by up to 78% and 96%, respectively. We studied the impact of experimental conditions (temperature, flow velocity and draw solution concentration) on performance of the integrated system in short-term experiments. In addition, we conducted long-term experiments using two different produced waters. We show that to achieve continuous high recovery with maximized water flux, a combination of two MD membranes can provide a viable solution.

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Colloids and organics in shale gas fracturing flowback water (SGFFW) during shale gas extraction are of primary concerns. Coagulation combined with oxidation might be a promising process for SGFFW treatment. In this study, a novel electrocoagulation-peroxone (ECP) process was developed for SGFFW treatment by simultaneous coagulation and oxidation process with a Al plate as the anode and a carbon-PTFE gas diffusion electrode as the cathode, realizing the simultaneous processes of coagulation, H2O2 generation and activation by O3 at the cathode. Compared with electrocoagulation (EC) and peroxi-electrocoagulation (PEC), COD removal efficiency mainly followed the declining order of ECP, PEC and EC under the optimal current density of 50 mA cm−2. The appearance of medium MW fraction (1919 Da) during ozonation and PEC but disappearance in ECP indicated that these intermediate products couldn't be degraded by ozonation and PEC but could be further oxidized and mineralized by the hydroxyl radical produced by the cathode in ECP, demonstrating the hydroxyl radical might be responsible for the significant enhancement of COD removal. The pseudo-first order kinetic model can well fit ozonation and EC process but not the PEC and ECP process due to the synthetic effect of coagulation and oxidation. However, the proposed mechanism based model can generally fit ECP satisfactorily. The average current efficiency for PEC was 35.4% and 12% higher than that of ozonation and EC, respectively. This study demonstrated the feasibility of establishing a high efficiency and space-saving electrochemical system with integrated anodic coagulation and cathodic electro-peroxone for SGFFW treatment.

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Shale gas exploitation is booming in China. Unlike the traditional oil extraction industry, shale gas extraction will generate more solid waste. Water-based drill cuttings (WBDC) as one of them is currently under regulatory vacuum. This article studied the status of heavy metal pollution and evaluated the ecological risk of WBDC. Cd, Cr, Cu, Hg, Mn, Ni, Pb and Zn were selected for the study. The results showed that except for Ni, other heavy metals showed different degrees of pollution, but the leaching toxicity was rather limited. Meanwhile, the ecological risks of all samples were significant, which posed a huge threat to environment. Though its limitation, this article can provide theoretical foundation for regulatory decisions of WBDC.

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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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The selection of an appropriate draw solution is crucial to the successful implementation of desalination for the treatment of highly saline fracking wastewaters via the forward osmosis (FO) process. In this report, four organic compounds (potassium acetate, potassium formate, sodium glycolate, and sodium propionate) were identified as candidate draw solutes for the first time for desalination of fracking wastewater by FO. Higher average FO water fluxes were achieved for the identified organic draw solutions (10.50–13.26 LMH for synthetic fracking wastewater and 19.05–24.05 LMH for real fracking wastewater) compared to commonly used draw solution, NaCl (average FO water flux: 8.25 LMH for synthetic fracking wastewater and 14.44 LMH for real fracking wastewater). Higher average FO water fluxes were obtained due to likely lower reverse salt fluxes for the organic draw solutions compared to NaCl. Higher FO water fluxes were achieved for the real fracking wastewater, as compared to the synthetic wastewater, due to higher osmotic pressure differences between feed and draw solutions. Membrane distillation could be used as a downstream separation technique in the FO process for recycling of the identified draw solutes.

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Water generated by hydraulic fracturing for the production of oil and gas, commonly termed ‘produced water’, may contain residual organic compounds from the fracturing process or the subsurface formation. Biological treatment is a potential technology to remove residual organic compounds in produced water. Biocides are often added to both fracturing fluids and produced water to limit undesirable microbiological activity, and glutaraldehyde is the most commonly used biocide in hydraulic fracturing. Residual biocides in produced water can limit biological treatment efficiency. We evaluated the effect of glutaraldehyde on the biodegradation of five of the most commonly reported organic compounds in hydraulic fracturing fluids in an engineered biofilm treatment. Our results demonstrated that glutaraldehyde delays biological organic compound removal by introducing a biodegradation lag phase. In addition, the effects of glutaraldehyde were more pronounced for more rapidly degraded compounds. Finally, the presence of glutaraldehyde did not decrease microbial abundance nor drive microbial community structure, suggesting that observed effects were due to altered microbial activity. These results highlight the necessity to consider co-contaminant interactions during treatment of complex waste streams where residual biocide may be present.

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Two traditional pretreatment methods were adopted for the pretreatment of shale gas produced water in view of facilitation for subsequent treatment processes. The research was focused on alkali precipitation due to its better performance on shale gas produced water pretreatment compared with flocculation. Agitating time, settling time, stirring speed, dosage of coagulant aids were determined by optimal configuration. The results showed that adding together with 1.0 g/L NaOH and 2.0 g/L Na2CO3 under 200 rpm stirring for 5 min and after 30 min settling, suspended solids (SS) in the effluent could drop below 20 mg/L and concentration of hardness ion could be less than 150 mg/L, which was well met the water quality to facilitate the following single or multiple-effect evaporation. The optimized alkaline pretreatment method towards produced water had excellent adaptability and practicability with economic cost and easy operation. It had significant potential and could be widely used in the shale gas produced water pretreatment process.

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Accidental spills and surface discharges of shale gas produced water could contaminate water resources and generate health concerns. The study explored the formation and speciation of disinfection by-products (DBPs) during chlorination of natural waters under the influence of shale gas produced water. Results showed the presence of produced water as low as 0.005% changed the DBP profile measurably. A shift to a more bromine substitution direction for the formation of trihalomethanes, dihaloacetic acids, trihaloacetic acids, and dihaloacetonitriles was illustrated by exploring the individual DBP species levels, bromine substitution factors, and DBP species fractions, and the effect was attributable to the introduction of bromide from produced water. The ratio of dichloroacetic and trichloroacetic acids also increased, which was likely affected by different bromination degrees at elevated bromide concentrations. Increasing blend ratios of produced water enhanced the formation of DBPs, especially the brominated species, while such negative effects could be alleviated by pre-treating the produced water with ozone/air stripping to remove bromide. The study advances understandings about the impacts of produced water spills or surface discharges regarding potential violation of Stage 2 DBP rules at drinking water treatment facilities.

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Wastewater recovered from hydraulic fracturing is referred to as flowback and produced water (FPW), and is often saline, contains numerous organic and inorganic constituents, and may pose threats to groundwater resources. Hundreds of spills of FPW have been reported to the Alberta Energy Regulator each year. Recently, samples of FPW derived from hydraulic fracturing of the Duvernay Formation, AB, were found to contain a previously unidentified class of aryl phosphates, including diphenyl phosphate (DPP), triphenyl phosphate (TPP), and others. Aryl phosphates are also used in a variety of other industries and their constituents can be found in flame retardants, plasticizers, lubricants, hydraulic fluids, and oxidizers. Many of these aryl phosphates break down into DPP. Therefore, it is important to determine the environmental fate and potential impact of DPP if spilled in the near-surface, as DPP is an emerging contaminant in soil and groundwater systems. This study was aimed at determining 1) the sorption behavior of DPP onto various surficial sediments collected within the Fox Creek, AB region, and 2) the toxicity of DPP toward aquatic ecosystems. We report that the sorption of DPP onto both clay-rich soils and sandy sediment was low compared to that of other aryl phosphates, with an average log KOC value of 2.30 ± 0.42 (1σ). Therefore, the transport of DPP in groundwater would be rapid due to its low degree of sorption on surficial materials. We also determined the acute 96 h-LC50 of DPP on zebrafish embryos to be 50.0 ± 7.1 mg/L. Su et al. (2014) studied the toxic effects of DPP and TPP on chicken embryonic hepatocytes and found that DPP had less cytotoxic effects than TPP but altered more gene transcripts. From the results our study, we infer that DPP may pose an environmental risk to aquatic ecosystems if released into the environment.

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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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Previous studies conducted in our laboratory have found altered adult health outcomes in animals with prenatal exposure to environmentally relevant levels of unconventional oil and gas (UOG) chemicals with endocrine-disrupting activity. This study aimed to examine potential metabolic health outcomes following a preconception, prenatal and postnatal exposure to a mixture of 23 UOG chemicals. Prior to mating and from gestation day 1 to postnatal day 21, C57BL/6J mice were developmentally exposed to a laboratory-created mixture of 23 UOG chemicals in maternal drinking water. Body composition, spontaneous activity, energy expenditure, and glucose tolerance were evaluated in 7-month-old female offspring. Neither body weight nor body composition differed in 7-month female mice. However, females exposed to 1.5 and 150 µg/kg/day UOG mix had lower total and resting energy expenditure within the dark cycle. In the light cycle, the 1500 µg//kg/day group had lower total energy expenditure and the 1.5 µg/kg/day group had lower resting energy expenditure. Females exposed to the 150 µg/kg/day group had lower spontaneous activity in the dark cycle, and females exposed to the 1500 µg/kg/day group had lower activity in the light cycle. This study reports for the first time that developmental exposure to a mixture of 23 UOG chemicals alters energy expenditure and spontaneous activity in adult female mice.

Abstract:
Hydraulic fracturing is a prominent method of natural gas production that uses injected, high-pressure fluids to fracture low permeability, hydrocarbon rich strata such as shale. Upon completion of a well, the fluid returns to the surface (produced water) and contains natural gas, subsurface constituents, and microorganisms (Barbot et al., 2013, Daley et al., 2016). While the microbial community of the produced fluids has been studied in multiple gas wells, the activity of these microorganisms and their relation to biogeochemical activity is not well understood. In this experiment, we supplemented produced fluid with 13C-labeled carbon sources (glucose, acetate, bicarbonate, methanol, or methane), and 15N-labeled ammonium chloride in order to isotopically trace microbial activity over multiple day in anoxic incubations. Nanoscale secondary ion mass spectrometry (NanoSIMS) was used to generate isotopic images of 13C and 15N incorporation in individual cells, while isotope ratio monitoring – gas chromatography – mass spectrometry (IRM-GC-MS) was used to measure 13CO2, and 13CH4 as metabolic byproducts. Glucose, acetate, and methanol were all assimilated by microorganisms under anoxic conditions. 13CO2 production was only observed with glucose as a substrate indicating that catabolic activity was limited to this condition. The microbial communities observed at 0, 19, and 32 days of incubation did not vary between different carbon sources, were low in diversity, and composed primarily of the class Clostridia. The primary genera detected in the incubations, Halanaerobium and Fusibacter, are known to be adapted to harsh physical and chemical conditions consistent with those that occur in the hydrofracturing environment. This study provides evidence that microorganisms in produced fluid are revivable in laboratory incubations and retained the ability to metabolize added carbon and nitrogen substrates.

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High-volume, hydraulic fracturing (HVHF) is widely applied for natural gas and oil production from shales, coals or tight sandstone formations in the United States, Canada, and Australia, and is being widely considered by other countries with similar unconventional energy resources. Secure retention of fluids (natural gas, saline formation waters, oil, HVHF fluids) during and after well stimulation is important to prevent unintended environmental contamination, and release of greenhouse gases to the atmosphere. Here, we critically review state-of-the-art techniques and promising new approaches for identifying oil and gas production from unconventional reservoirs to resolve whether they are the source of fugitive methane and associated contaminants into shallow aquifers. We highlight future research needs and propose a phased program, from generic baseline to highly specific analyses, to inform HVHF and unconventional oil and gas production and impact assessment studies. These approaches may also be applied to broader subsurface exploration and development issues (e.g., groundwater resources), or new frontiers of low-carbon energy alternatives (e.g., subsurface H2 storage, nuclear waste isolation, geologic CO2 sequestration).

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Hydraulic fracturing in shale/tight gas reservoirs creates fracture network systems that can intersect pre-existing subsurface flow pathways, e.g. fractures, faults or abandoned wells. This way, hydraulic fracturing operations could possibly pose environmental risks to shallow groundwater systems. This paper explores the long-term (>30 years) flow and transport of fracturing fluids into overburden layers and groundwater aquifers through a leaky abandoned well, using the geological setting of North German Basin as a case study. A three-dimensional model consisting of 15 sedimentary layers with three hydrostratigraphic units representing the hydrocarbon reservoir, overburden, and the aquifer is built. The model considers one perforation location at the first section of the horizontal part of the well, and a discrete hydraulic fracture intersecting an abandoned well. A sensitivity analysis is carried out to quantify and understand the influence of a broad spectrum of field possibilities (reservoir properties, overburden properties, salinity, abandoned well properties and its proximity to hydraulic fractures) on the flow of fracturing fluid to shallower permeable strata. The model results suggest the spatial properties of the abandoned well as well as its distance from the hydraulic fracture are the most important factors influencing the vertical flow of fracturing fluid. It is observed that even for various field settings, only a limited amount fracturing fluid can reach the aquifer in a long-term period.

Abstract:
Hydraulic fracturing wastewaters (HFWWs) contain synthetic organic components and metal ions derived from the formation waters. The risk of spills of HFWW that could impact soil quality and water resources is of great concern. The ability of synthetic components, such as surfactants, in HFWW to be transported through soil and to mobilize metals in soil was examined using column experiments. A spill of HFWW was simulated in bench scale soil column experiments that used an agricultural soil and simulated seven 10-year rain events representing a total of one year's worth of precipitation for Weld County, Colorado. Although no surfactants or their transformation products were found in leachate samples, copper, lead, and iron were mobilized at environmentally relevant concentrations. In general, after the initial spill event, metal concentrations increased until the fourth rain event before decreasing. Results from this study suggest that transport of metals was caused by the high concentrations of salts present in HFWW. This is the first study utilizing authentic HFWWs to investigate the transport of surfactants and their effect on metal mobilization. Importantly, a significant decrease in the water infiltration rate of the soil was observed, leading to the point where water was unable to percolate through due to increasing salinity, potentially having a severe impact on crop production.

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Hydraulic fracturing flowback and produced water (FPW) samples were analyzed for toxicity and microbiome characterization over 220 days for a horizontally drilled well in the Denver-Julesberg (DJ) Basin in Colorado. Cytotoxicity, mutagenicity, and estrogenicity of FPW were measured via the BioLuminescence Inhibition Assay (BLIA), Ames II mutagenicity assay (AMES), and Yeast Estrogen Screen (YES). Raw FPW stimulated bacteria in BLIA, but were cytotoxic to yeast in YES. Filtered FPW stimulated cell growth in both BLIA and YES. Concentrating 25× by solid phase extraction (SPE) revealed significant toxicity throughout well production by BLIA, toxicity during the first 55 days of flowback by YES, and mutagenicity by AMES. The selective pressures of fracturing conditions (including toxicity) affected bacterial and archaeal communities, which were characterized by 16S rRNA gene V4V5 region sequencing. Conditions selected for thermophilic, anaerobic, halophilic bacteria and methanogenic archaea from the groundwater used for fracturing fluid, and from the native shale community. Trends in toxicity echoed the microbial community, which indicated distinct stages of early flowback water, a transition stage, and produced water. Biota in another sampled DJ Basin horizontal well resembled similarly aged samples from this well. However, microbial signatures were unique compared to samples from DJ Basin vertical wells, and wells from other basins. These data can inform treatability, reuse, and management decisions specific to the DJ Basin to minimize adverse environmental health and well production outcomes.

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Public concern is heightened around flowback and produced water (FPW) generated by the hydraulic fracturing process. FPW is a complex mix of organic and inorganic solutes derived from both the injected hydraulic fracturing fluid and interactions with the subsurface lithology. Few studies to date have systematically investigated the composition of FPW or its individual components. Here, we provide the first systematic characterization of the composition of the solids associated with FPW by analyzing samples from three wells drilled into the Duvernay Formation in Alberta, Canada. The FPW initially returned to the surface with high total dissolved solids (greater than 170 000 mg L−1) and enriched with Fe(II), silica, sulfate, barium, and strontium. The solids form two distinct phases once the FPW reached the surface: (1) silica-enriched Fe(III) oxyhydroxides, and (2) a barite–celestine solid solution. We hypothesize that the precipitation of the amorphous silica-enriched Fe(III) oxyhydroxide is a two-step process, where first the silica precipitates as a function of the cooling of the FPW from elevated subsurface temperatures to ambient surface temperatures. Next, the silica acts as a template for the precipitation of Fe(III) oxyhydroxide as the diffusion of oxygen into the subsurface causes oxidation of aqueous Fe(II). The barite–celestine solid solution precipitates solely as a function of cooling. Elevated dissolved Fe concentrations in FPW and modeled saturation indices from five North American shale plays (Marcellus, Fayetteville, Barnett, Bakken, and Denver-Julesburg) indicate that solids similar to those found in Duvernay FPW, specifically Fe(III) oxyhydroxides, barite and quartz, are likely to occur. With the solids known to carry a significant portion of FPW's toxicity and organic contaminant load, the development of new treatment technologies, such as the oxidation of the Fe(II) in FPW, may increase FPW reuse and reduce the environmental risk posed by FPW.

Abstract:
Hydraulic fracturing has become a well-established and widespread technology for the extraction of oil and natural gas. Hydraulic fracturing fluids (HFFs) are widely varied and contain many chemicals that are toxic to human and ecological health. HFFs are often spilled on surface soils where their fate and transport is uncertain. In this study, six representative mixtures of HFFs were incubated with a surface soil in bench-scale microcosms, and the microbial community was analyzed over 78 days. The chemical oxygen demand decreased over time, although a significant recalcitrant fraction was found for four of the six amended fluids. With Illumina MiSeq sequencing of a 16S ribosomal RNA (rRNA) gene amplification and follow-through quantitative polymerase chain reaction (qPCR) assays, 24 bacterial taxa closely related to known species were identified to be enriched by at least one of the representative HFFs. These taxa are mostly closely related to well-known xenobiotic degraders, however, the composition of the enrichment was highly unique for each representative HFF. The results indicate that the complex mixtures of biocides and other components elicit unique bacterial community responses in the same soil, thus suggesting that the bioremediation pathways of HFF constituents in soils may differ based on exact HFF composition.

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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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Unconventional oil and gas development is achieved through a series of sub-processes, which utilize large amounts of water, proppant, and chemical additives to retrieve sequestered hydrocarbons from low permeability petroliferous strata. As a result, a large amount of wastewater is produced, which is traditionally disposed of via subsurface injection into non-productive stratum throughout the country. However, this method of waste management has been linked to the induction of seismic events in a number of regions across North America, calling into question the environmental stewardship and sustainability of subsurface waste disposal. Advancements in water treatment technologies have improved the efficacy and financial viability of produced water recycling for beneficial reuse in the oil and gas sector. This review will cover the various treatment options that are currently being utilized in shale energy basins to remove organic, inorganic, and biological constituents, as well as some emerging technologies that are designed to remove pertinent contaminants that would otherwise preclude the reuse of produced water for production well stimulation.

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Shale gas development has been heralded as a game changer that has had, and will continue to have, repercussions for energy scenarios around the world, and natural gas has been hailed as the transition fuel to a low carbon future. Shale gas production-made feasible and economical by advances in hydraulic fracturing-offers a solution in the face of increased demand, instability in key producing regions, and societal aversion to the risks of nuclear energy. This "golden future," however, has come into conflict with increasing concerns over water. This paper examines policy and regulatory frameworks around hydraulic fracturing in Texas and Spain in order to consider the trade-offs-particularly at the expense of water security-that may occur as decision-makers pursue improvements in energy security. We compare regulatory, institutional, and cultural contexts in order to understand and evaluate the robustness of these frameworks to prevent the reduction in water security as a consequence of the pursuit of energy security. Paucity of data is discussed. We also consider questions such as disclosure of information to the public about water use or the chemical composition of frac fluids and public opinion about hydraulic fracturing. Lessons are drawn that may assist policymakers who seek to guarantee water security while pursuing energy security.

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In the western U.S., produced water from oil and gas wells discharged to surface water augments downstream supplies used for irrigation and livestock watering. Here we investigate six permitted discharges on three neighboring tributary systems in Wyoming. During 2013–16, we evaluated radium activities of the permitted discharges and the potential for radium accumulation in associated stream sediments. Radium activities of the sediments at the points of discharge ranged from approximately 200–3600 Bq kg−1 with elevated activities above the background of 74 Bq kg−1 over 30 km downstream of one permitted discharge. Sediment as deep as 30 cm near the point of discharge had radium activities elevated above background. X-ray diffraction and targeted sequential extraction of radium in sediments indicate that radium is likely coprecipitated with carbonate and, to a lesser extent, sulfate minerals. PHREEQC modeling predicts radium coprecipitation with aragonite and barite, but over-estimates the latter compared to observations of downstream sediment, where carbonate predominates. Mass-balance calculations indicate over 3 billion Bq of radium activity (226Ra + 228Ra) is discharged each year from five of the discharges, combined, with only 5 percent of the annual load retained in stream sediments within 100 m of the effluent discharges; the remaining 95 percent of the radium is transported farther downstream as sediment-associated and aqueous species.

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Shale gas extraction through hydraulic fracturing and horizontal drilling is increasing in China, particularly in Sichuan Basin. Production of unconventional shale gas with minimal environmental effects requires adequate management of wastewater from flowback and produced water (FP water) that is coextracted with natural gas. Here we present, for the first time, inorganic chemistry and multiple isotope (oxygen, hydrogen, boron, strontium, radium) data for FP water from 13 shale gas wells from the Lower Silurian Longmaxi Formation in the Weiyuan gas field, as well as produced waters from 35 conventional gas wells from underlying (Sinian, Cambrian) and overlying (Permian, Triassic) formations in Sichuan Basin. The chemical and isotope data indicate that the formation waters in Sichuan Basin originated from relics of different stages of evaporated seawater modified by water-rock interactions. The FP water from shale gas wells derives from blending of injected hydraulic fracturing water and entrapped saline (Cl ∼ 50,000 mg/L) formation water. Variations in the chemistry, δ18O, δ11B, and 87Sr/86Sr of FP water over time indicate that the mixing between the two sources varies with time, with a contribution of 75% (first 6 months) to 20% (>year) of the injected hydraulic fracturing water in the blend that compose the FP water. Mass-balance calculation suggests that the returned hydraulic fracturing water consisted of 28-49% of the volume of the injected hydraulic fracturing water, about a year after the initial hydraulic fracturing. We show differential mobilization of Na, B, Sr, and Li from the shale rocks during early stages of operation, which resulted in higher Na/Cl, B/Cl, Li/Cl, and 87Sr/86Sr and lower δ11B of the FP water during early stages of FP water formation relative to the original saline formation water recorded in late stages FP water. This study provides a geochemical framework for characterization of formation waters from different geological strata, and thus the ability to distinguish between different sources of oil and gas wastewater in Sichuan Basin.

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Hydraulic fracturing generates large volumes of produced water, and treatment of produced water may be necessary for disposal or reuse. Biological treatment of produced water is a potential approach to remove organic constituents and reduce fouling, in conjunction with other treatment processes. This study investigates the biological treatability of produced water samples from the Utica and Bakken Shales using engineered biofilms. Observed total dissolved organic carbon (DOC) removal varied between 1-87% at normalized total dissolved solids concentrations, suggesting that the composition of produced water, including organic constituents and trace elements such as nutrients and metals, is an important driver of biological treatment performance. Mass spectrometric analyses of the DOC composition revealed various alkanes in all samples, but differences in non-ionic surfactant, halogenated, and acidic compound content. Statistical data reduction approaches suggest that the latter two groups are correlated with reduced biodegradation kinetics. These results demonstrate that the combination of biodegradation performance and organic speciation can guide the assessment of the biological treatment of produced water.

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Unconventional oil and gas extraction (UOG) has expanded rapidly across the United States, as it has become an established technique for oil and gas extraction from low permeability shales. There are more than 900,000 active oil and gas wells in the United States, and more than 130,000 have been drilled since 2010.1 The U.S. Energy Information Administration (EIA) estimates that in 2017, about 16.76 trillion cubic feet (Tcf) of dry natural gas was produced from shale resources in the United States, including the Bakken (North Dakota and Montana), Niobrara (Colorado), Marcellus and Utica (Pennsylvania, Ohio, and West Virginia), Haynesville (Louisiana and East Texas), Eagle Ford (South Texas), and Permian Basin (West Texas and Southeast New Mexico) shale plays.

Abstract:
The Colorado Water Plan estimates as much as 0.8 million irrigated acres may dry up statewide from agricultural to municipal and industrial transfers. To help mitigate this loss, new sources of water are being explored in Colorado. One such source may be produced water. Oil and gas production in 2016 alone produced over 300 million barrels of produced water. Currently, the most common method of disposal of produced water is deep well injection, which is costly and has been shown to cause induced seismicity. Treating this water to agricultural standards eliminates the need to dispose of this water and provides a new source of water. This research explores which counties in Colorado may be best suited to reusing produced water for agriculture based on a combined index of need, quality of produced water, and quantity of produced water. The volumetric impact of using produced water for agricultural needs is determined for the top six counties. Irrigation demand is obtained using evapotranspiration estimates from a range of methods, including remote sensing products and ground-based observations. The economic feasibility of treating produced water to irrigation standards is also determined using an integrated decision selection tool (iDST). We find that produced water can make a substantial volumetric impact on irrigation demand in some counties. Results from the iDST indicate that while costs of treating produced water are higher than the cost of injection into private disposal wells, the costs are much less than disposal into commercial wells. The results of this research may aid in the transition between viewing produced water as a waste product and using it as a tool to help secure water for the arid west.

Abstract:
Unconventional oil and gas residual solid wastes are generally disposed in municipal waste landfills (RCRA Subtitle D), but they contain valuable raw materials such as proppant sands. A novel process for recovering raw materials from hydraulic fracturing residual waste is presented. Specifically, a novel hydroacoustic cavitation system, combined with physical separation devices, can create a distinct stream of highly concentrated sand, and another distinct stream of clay from the residual solid waste by the dispersive energy of cavitation conjoined with ultrasonics, ozone and hydrogen peroxide. This combination cleaned the sand grains, by removing previously aggregated clays and residues from the sand surfaces. When these unit operations were followed by a hydrocyclone and spiral, the solids could be separated by particle size, yielding primarily cleaned sand in one flow stream; clays and fine particles in another; and silts in yet a third stream. Consequently, the separation of particle sizes also affected radium distribution – the sand grains had low radium activities, as lows as 0.207 Bq g−1 (5.6 pCi g−1). In contrast, the clays had elevated radium activities, as high as 1.85–3.7 Bq g−1 (50–100 pCi g−1) – and much of this radium was affiliated with organics and salts that could be separated from the clays. We propose that the reclaimed sand could be reused as hydraulic fracturing proppant. The separation of sand from silt and clay could reduce the volume and radium masses of wastes that are disposed in landfills. This could represent a significant savings to facilities handling oil and gas waste, as much as $100 000–300 000 per year. Disposing the radium-enriched salts and organics downhole will mitigate radium release to the surface. Additionally, the reclaimed sand could have market value, and this could represent as much as a third of the cost savings. Tests that employed the toxicity characteristic leaching protocol (TCLP) on these separated solids streams determined that this novel treatment diminished the risk of radium mobility for the reclaimed sand, clays or disposed material, rendering them better suited for landfilling.

Abstract:
Unconventional oil and gas operations are on the rise and an integral component to meeting the nation's energy needs. Produced water is the primary by-product of oil and gas operations, and it has proven challenging to treat to date. The aim of this study was to evaluate the feasibility of using forward osmosis with thin-film composite hollow fiber membranes as a remediation option for produced water with high total dissolved solids levels from the Permian Basin. Trials consisted of a series of 5 experiments in order to evaluate the performance of the membrane. Three PW samples, each from different locations, were used to conduct the series of experiments and compare the performance of the membranes with TDS levels ranging from 16,000 to 210,000 mg/L. It can be concluded that forward osmosis can be used to extract water from high salinity oil field brines and PW. Flux decreased over the course of the trials due to a combination of membrane fouling, concentration polarization, and temperature fluctuations. The flux of the PW was similar to the flux measured for the PW mimic with small difference due to the influence of activity on the osmotic pressure. The flux was also influenced by temperature and the linear velocity of the feed solution and draw solution.

Abstract:
The high volume of flowback water (FW) generated during shale gas exploitation is highly saline, and contains complex organics, iron, heavy metals, and sulfate, thereby posing a significant challenge for the environmental management of the unconventional natural gas industry. Herein, the treatment of FW in a sulfur-cycle-mediated microbial fuel cell (MFC) is reported. Simultaneous removal efficiency for chemical oxygen demand (COD) and total iron from a synthetic FW was achieved, at 72±7% and 90.6±8.7%, respectively, with power generation of 2667±529 mW/m3 in a closed-circuit MFC (CC-MFC). However, much lower iron removal (38.5±4.5%) occurred in the open-circuit MFC (OC-MFC), where the generated FeS fine did not precipitate because of sulfide supersaturation. Enrichment of both sulfur-oxidizing bacteria (SOB), namely Helicobacteraceae in the anolyte and the electricity-producing bacteria, namely Desulfuromonadales on the anode likely accelerated the sulfur cycle through the biological and bioelectrochemical oxidation of sulfide in the anodic chamber, and effectively increased the molar ratio of total iron to sulfide, thus alleviating sulfide supersaturation in the closed circuitry. Enrichment of SOB in the anolyte might be attributed to the formation of FeS electricity wire and likely contributed to the stable high power generation. Bacteroidetes, Firmicutes, Proteobacteria, and Chloroflexi enriched in the anodic chamber were responsible for degrading complex organics in the FW. The treatment of real FW in the sulfur-cycle-mediated MFC also achieved high efficiency. This research provides a promising approach for the treatment of wastewater containing organic matters, heavy metals, and sulfate by using a sulfur-cycle-mediated MFC.

Abstract:
Development of unconventional gas resources is currently one of the most rapidly growing trends in the oil and natural gas industry. Exploration of shale gas requires significant quantities of water for hydraulic fracturing. Meanwhile, large volumes of produced water are generated during gas production. Treatment and beneficial use of hydraulic fracturing flowback and produced water provides opportunities for sustainable unconventional gas operations while minimizing impacts to environment, local water resources, and public health. Considering the broad variety of treatment technologies and the wide spectrum of flowback and produced water qualities, selecting appropriate treatment and management options involves a complex decision-making process that requires understanding of treatment technologies, water quality, reuse requirements, and consideration of multiple criteria, constraints, and objectives. This study presents an integrated decision support tool (iDST) to assist in selection of treatment technologies and evaluation of the feasibility of potential water reuse options. The Marcellus Shale in Pennsylvania and the Barnett Shale in Texas were selected as case studies to demonstrate produced water treatment technologies and beneficial reuse options considering realistic site-specific conditions, assumptions, and future projections such as well numbers and locations, water demands, flowback and produced water quality and quantity, disposal availability, and costs. The iDST provides an interactive user interface to select suitable technologies for produced water treatment and reuse based on user preference, target water quality, and current disposal options.

Abstract:
Hydraulic fracturing of the Marcellus Shale produces wastewaters that are hypersaline and highly enriched in isotopes of radium. Radium is understood to derive from the Marcellus Shale itself, but its source phases and their contributions to wastewater production have not been described. Using sequential extractions and experimental leachates, we characterize two distinct end-members that could contribute Ra to wastewaters, (1) a mineral phase, which hosts labile228Ra and has 226Ra/228Ra atom ratios ~250, and (2) an organic phase, which hosts exchangeable226Ra and has 226Ra/228Ra ~10,000. In leaching experiments we observed rapid extraction of Ra from these phases, with high ionic strength solutions leaching up to 14% of Ra from the shale in just hours. Radium concentrations and 226Ra/228Ra ratios increase with [Ca2+] of the leaching solution, and solutions approaching 1 M Ca2+ produce 226Ra/228Ra ratios compatible with Marcellus wastewaters. In contrast, pure water removes <0.5% of Ra from the shale with low 226Ra/228Ra ratios incompatible with wastewaters. Experimental results and wastewater data together provide a coherent picture, that the distinctive Ra isotopic signature of Marcellus wastewaters results from contemporaneous water-rock interactions that promote desorption of 226Ra from organics during hydraulic fracturing.

Abstract:
Effective and affordable treatment of hydraulic fracturing flowback and produced water (FPW) is a major challenge for the sustainability of unconventional shale-gas exploration and development. We investigated the effectiveness of different combinations of activated sludge (AS), three microbial preparations, and ten plants (ryegrass, water dropwort, typha, reed, iris, canna, water caltrop, rape, water spinach, and Alternanthera philoxeroides) on the treatment performance of FPW. Water quality parameters (NH4-N, NO3-N, NO2-N, CODcr, and BOD) and the algal toxicity of the treated FPW were used as metrics to assess the treatment efficiency. The results showed that AS had higher treatment efficiency than the prepared microorganisms, and water dropwort was the best plant candidate for boosting performance of AS treatment of FPW. The treated FPW showed improved water quality and microbial diversity. The Shannon-Wiener index increased from 4.76 to 7.98 with FPW treatment. The relative abundance of microbes with a greater resistance to high salt conditions, such as Bacteroidetes, Firmicutes, Chloroflexi, increased substantially in the treated FPW. The combination of water dropwort and AS showed the greatest improvement in water quality, the highest algal density and microbial diversity, thus indicating good potential for this candidate in the treatment of FPW.

Abstract:
This work proposes an optimization approach for designing efficient water networks for the shale gas production through the recycle and reuse of wastewater streams reducing the freshwater consumption and effluents considering economic and environmental goals. The economic objective function aims to minimize the total annual cost for the water network including the costs associated with storage, treatment and disposal (capital cost) as well as freshwater cost, treatment cost and transportation costs. The environmental objective is addressed to deal with the minimization of the environmental impact associated with the discharged concentration of total dissolved solids in the wastewater streams and the freshwater consumption through an environmental function that represents the benefit for removing pollutants using the eco-indicator 99 methodology. The methodology requires a given scheduling for the completion phases of the target wells to be properly implemented by the available hydraulic fracturing crews during a time horizon. The model formulation is configured to determine the optimal sizes for the equipment involved by the project, particularly the sizes for storage and treatment units are quantified by the optimization process. A case study is solved to evaluate the effectiveness of the proposed optimization approach.Graphical abstract Open image in new window

Abstract:
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.

Abstract:
Extensive efforts have been made to tailor membrane surface wettability in order to mitigate fouling and wetting in membrane distillation (MD), but the developed membranes have rarely been challenged with real industrial wastewater. This study compared three membranes − a hydrophobic PVDF membrane, a superhydrophobic PVDF membrane, and a composite PVDF membrane with hydrophilic coating − in MD desalination of shale oil and gas produced water from the Wattenberg field in northeast Colorado. Two produced water samples with varied chemical compositions were collected and used as the feedwater. In a single treatment cycle, the composite membrane showed the best fouling resistance for the first sample, while all the tested membranes experienced similar flux decline with the second sample. Thus, the relationship between membrane surface wettability and fouling propensity in MD treatment of real produced water was influenced by feedwater composition. This effect was reflected by distinct features of fouling layers resulting from the two produced water samples, revealed by detailed microscopic and spectroscopic characterization. In three treatment cycles with physical membrane cleaning, the hydrophobic and composite membranes suffered from accelerated membrane fouling after each cycle, whereas a decelerated flux decline was observed for the superhydrophobic membrane. The better reusability of the superhydrophobic membrane, however, was achieved at the expense of initial water vapor flux. Our study suggests that one should comprehensively consider fouling/wetting resistance, water productivity, and reusability in the design and selection of appropriate membranes for MD treatment, and that long-term testing with multiple treatment cycles should be performed to assess MD membrane performance more accurately.

Abstract:
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.

Abstract:
Oil- and gas-produced water (PW) which contains various pollutants is an enormous threat to the environment. In this study, a novel low-cost bio-adsorbent was prepared from shrimp shell and acid-activated montmorillonite. The results of FT-IR spectroscopy, energy dispersive X-ray (EDX) analysis, and SEM-EDX technique indicated that the chitosan-activated montmorillonite (CTS-A-MMT) was prepared successfully. The synthesized CTS-A-MMT was applied to remove simultaneously five cationic and anionic metal species and crude oil from synthetic and real oilfield PW. The adsorption data indicated that crude oil and all studied metals (except As) were adsorbed to CTS-A-MMT in a monolayer model (best fitted by Langmuir model), while As adsorption fits well with Freundlich model. Kinetic models’ evaluation demonstrated that the adsorption kinetics of metals on CTS-A-MMT are initially controlled by the chemical reaction (film diffusion) followed by intra-particle diffusion. Application of the prepared CTS-A-MMT in real oilfield PW indicated removal efficiency of 65 to 93% for metals and 87% for crude oil in simultaneous removal experiments. Presence of additional ions in PW decreased the removal of studied metals and crude oil considerably; however, the concentration of the investigated pollutants in treated PW is less than the ocean discharge criteria. It is concluded that the prepared CTS-A-MMT composite is a low-cost and effective adsorbent for treating wastewater contaminated with crude oil and heavy metals (i.e., PW).

Abstract:
For several decades, high-salinity water brought to the surface during oil and gas (O&G) production has been treated and discharged to waterways under National Pollutant Discharge Elimination System (NPDES) permits. In Pennsylvania, USA, a portion of the treated O&G wastewater discharged to streams from 2008 to 2011 originated from unconventional (Marcellus) wells. We collected freshwater mussels, Elliptio dilatata and Elliptio complanata, both upstream and downstream of a NPDES-permitted facility, and for comparison, we also collected mussels from the Juniata and Delaware Rivers that have no reported O&G discharge. We observed changes in both the Sr/Cashell and 87Sr/86Srshell in shell samples collected downstream of the facility that corresponded to the time period of greatest Marcellus wastewater disposal (2009–2011). Importantly, the changes in Sr/Cashell and 87Sr/86Srshell shifted toward values characteristic of O&G wastewater produced from the Marcellus Formation. Conversely, shells collected upstream of the discharge and from waterways without treatment facilities showed lower variability and no trend in either Sr/Cashell or 87Sr/86Srshell with time (2008–2015). These findings suggest that (1) freshwater mussels may be used to monitor changes in water chemistry through time and help identify specific pollutant sources and (2) O&G contaminants likely bioaccumulated in areas of surface water disposal.

Abstract:
At the forefront of the discussions about climate change and energy independence has been the process of hydraulic fracturing, which utilizes large amounts of water, proppants, and chemical additives to stimulate sequestered hydrocarbons from impermeable subsurface strata. This process also produces large amounts of heterogeneous flowback and formation waters, the subsurface disposal of which has most recently been linked to the induction of anthropogenic earthquakes. As such, the management of these waste streams has provided a newfound impetus to explore recycling alternatives to reduce the reliance on subsurface disposal and fresh water resources. However, the biogeochemical characteristics of produced oilfield waste render its recycling and reutilization for production well stimulation a substantial challenge. Here we present a comprehensive analysis of produced waste from the Eagle Ford shale region before, during, and after treatment through adjustable separation, flocculation, and disinfection technologies. The collection of bulk measurements revealed significant reductions in suspended and dissolved constituents that could otherwise preclude untreated produced water from being utilized for production well stimulation. Additionally, a significant step-wise reduction in pertinent scaling and well-fouling elements was observed, in conjunction with notable fluctuations in the microbiomes of highly variable produced waters. Collectively, these data provide insight into the efficacies of available water treatment modalities within the shale energy sector, which is currently challenged with improving the environmental stewardship of produced water management.

Abstract:
The list of iodinated disinfection byproducts (iodo-DBPs) includes some of the most genotoxic and cytotoxic DBPs discovered to date. Therefore, human exposure should be minimized by reducing their presence in drinking water. This manuscript reviews the main iodo-DBP formation pathways during water disinfection, with focus on the advances reported in the last two years. We discuss the effect of iodine sources other than iodine salts, e.g., iodinated contrast media and iodate, on iodo-DBP formation. In addition, we review the anthropogenic activities (like oil and gas extraction, dairy industry, seawater desalination or advanced oxidation treatments with persulfate) that may release iodo-DBPs to the aquatic environment or increase the potential of source waters to generate these compounds when disinfected.

Abstract:
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.

Abstract:
To assess the risk of underground sources of drinking water contamination by barium (Ba) present in petroleum produced water disposed into deep saline aquifers, we examined the effect of salinity (NaCl), competition of cations (Ca, Mg), temperature (22 and 60°C), and organic fracturing additives (guar gum) on the sorption and transport of Ba in dolomites and sandstones. We found that at typical concentration levels of NaCl, Ca, and Mg in petroleum produced water, Ba sorption in both dolomites and sandstones is inhibited by the formation of Ba(Cl)+ complexes in solution and/or the competition of cations for binding sites of minerals. The inhibition of Ba sorption by both mechanisms is greater in dolomites than in sandstones. This is reflected by a larger decrease in the breakthrough times of Ba through dolomites than through sandstones. We found that the presence of guar gum has little influence on the sorption and thus the transport of Ba in both dolomites and sandstones. Contrary to most heavy metals, Ba sorption in both dolomites and sandstones decreases with increasing temperature, however the reducing effect of temperature on Ba sorption is relevant only at low salinity conditions. Higher inhibition of Ba sorption in dolomites than in sandstones is due to the greater reactivity of dolomite over sandstone. The results of this study which includes the formulation of a reactive transport model and estimation of partition coefficients of Ba in dolomites and sandstones have significant implications in understanding and predicting the mobility and transport of Ba in deep dolomite and sandstone saline aquifers.

Abstract:
On-site flowback treatment systems are typically rated and selected based on three fundamental categories: satisfying customer needs (e.g. meeting effluent quality, capacity, delivery time and time required to reach stable and steady effluent quality), common features comparison (e.g. treatment costs, stability of operation, scalability, logistics, and maintenance frequency) and through substantial product differentiation such as better service condition, overcoming current market limitations (e.g. fouling, salinity limit), and having lower environmental footprints and emissions. For treatment of flowback, multiple on-site treatment systems are available for primary separation (i.e. reducing TSS concentrations and particle size below 25 μm for disposal), secondary separation (i.e. removing TSS, iron and main scaling ions, and reducing particle size up to 5 μm for reuse), or tertiary treatment (i.e. reducing TDS concentration in the permeate/distillate to below 500 mg/L) for recycling or discharge. Depending on geographic features, frac-fluid characteristics, and regulatory aspects, operators may choose disposal or reuse of flowback water. Among these approaches, desalination is the least utilized option while in the majority of cases on-site basic separation is selected which can result in savings up to $306,800 per well. Compared to desalination systems, basic separation systems (e.g. electrocoagulation, dissolved air floatation) have higher treatment capacity (159–4133 m3/d) and specific water treatment production per occupied space (8.9–58.8 m3/m2), lower treatment costs ($2.90 to $13.30 per m3) and energy demand, and finally generate less waste owing to their high recovery of 98–99.5%, which reduces both operator costs and environmental burdens.

Abstract:
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:
The application of horizontal drilling and hydraulic fracturing has enabled access to previously unrecoverable gas reservoirs. This method uses large quantities of water and the likely presence of NORM in the water that flows up to the wells have caused some concerns. In this study, a new cation resin, RSM-25HP, was compared to Dowex 50W-X8 resin for its ability to separate radium from produced water. Our results show that the RSM resin was able to retain barium and radium at higher acidities compared to the Dowex resin and could provide a higher degree of separation in the flowback water.