Repository for Oil and Gas Energy Research (ROGER)

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Despite growing concerns over the potential for hydraulic fracturing to impact drinking water resources, there are limited data available to identify chemicals used in hydraulic fracturing fluids that may pose public health concerns. In an effort to explore these potential hazards, a multi-criteria decision analysis (MCDA) framework was employed to analyze and rank selected subsets of these chemicals by integrating data on toxicity, frequency of use, and physicochemical properties that describe transport in water. Data used in this analysis were obtained from publicly available databases compiled by the United States Environmental Protection Agency (EPA) as part of a larger study on the potential impacts of hydraulic fracturing on drinking water. Starting with nationwide hydraulic fracturing chemical usage data from EPA's analysis of the FracFocus Chemical Disclosure Registry 1.0, MCDAs were performed on chemicals that had either noncancer toxicity values (n=37) or cancer-specific toxicity values (n=10). The noncancer MCDA was then repeated for subsets of chemicals reported in three representative states (Texas, n=31; Pennsylvania, n=18; and North Dakota, n=20). Within each MCDA, chemicals received scores based on relative toxicity, relative frequency of use, and physicochemical properties (mobility in water, volatility, persistence). Results show a relative ranking of these chemicals based on hazard potential, and provide preliminary insight into chemicals that may be more likely than others to impact drinking water resources. Comparison of nationwide versus state-specific analyses indicates regional differences in the chemicals that may be of more concern to drinking water resources, although many chemicals were commonly used and received similar overall hazard rankings. Several chemicals highlighted by these MCDAs have been reported in groundwater near areas of hydraulic fracturing activity. This approach is intended as a preliminary analysis, and represents one possible method for integrating data to explore potential public health impacts.

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The objective of this study was to understand the adsorption ability of a surfactant and a non-surfactant chemical additive used in hydraulic fracturing onto shale and GAC. Experiments were performed at varying temperatures and sodium chloride concentrations to establish these impacts on the adsorption of the furfural (a non-surfactant) and 2-Butoxyethanol (2-BE) (a surfactant). Experiments were carried out in continuously mixed batch experiments with Langmuir and Freundlich isotherm modeling. The results of the experiments showed that adsorption of these compounds onto shale does not occur, which may allow these compounds to return to the surface in flowback and produced waters. The adsorption potential for these chemicals onto GAC follows the assumptions of the Langmuir model more strongly than those of the Freundlich model. The results show uptake of furfural and 2-BE occurs within 23 h in the presence of DI water, 0.1 mol L(-1) sodium chloride, and in lab synthesized hydraulic fracturing brine. Based on the data, 83% of the furfural and 62% of the 2-BE was adsorbed using GAC.

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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.

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The effect of pH changes on leachability of light and heavy metals from shale drill cuttings generated from unconventional shale gas production was investigated. Cuttings, being the primary byproduct generated from drilling operations, belong to the potentially hazardous type of wastes due to presence of heavy and radioactive elements and remains of drilling fluid. In this regard, assessment of potentially dangerous components (PDCs) from rock waste materials was performed by application of batch leaching tests, which has provided information on the sensitivity of leaching under externally imposed changes in pH (natural or caused by treatment) in specific scenarios. The description of shale rocks mineralogical and chemical properties was performed by means of X-ray fluorescence spectroscopy, diffractometry as well as scintillation spectrometry. The concentrations of released constituents due to the leaching tests were measured by atomic absorption spectrophotometry. Results were compared and discussed accordingly with the waste acceptable criteria of elution limits. Analysis of the substrate revealed that the elemental composition was dominated by light elements, whereas heavy metals were present in trace amounts. However, noticeable release of barium (2.0–4.6%) was also recorded, which has originated from not only rock material but also drill mud. Minor mobility was observed for transition elements such as Cr, Co, Fe, Mn, Ni, Zn, Cu and Pb. Results revealed that drill cuttings follow the requirements for other than hazardous and municipal type of deposition, with exception for barium. Moreover, content of radioactive isotopes fulfill the requirements range of acceptable concentrations.

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Unconventional oil and gas operations using hydraulic fracturing can contaminate surface and groundwater with endocrine-disrupting chemicals. We have previously shown that 23 of 24 commonly used hydraulic fracturing chemicals can activate or inhibit the estrogen, androgen, glucocorticoid, progesterone, and/or thyroid receptors in a human endometrial cancer cell reporter gene assay and that mixtures can behave synergistically, additively, or antagonistically on these receptors. In the current study, pregnant female C57Bl/6 dams were exposed to a mixture of 23 commonly used unconventional oil and gas chemicals at approximately 3, 30, 300, and 3000 μ g/kg·d, flutamide at 50 mg/kg·d, or a 0.2% ethanol control vehicle via their drinking water from gestational day 11 through birth. This prenatal exposure to oil and gas operation chemicals suppressed pituitary hormone concentrations across experimental groups (prolactin, LH, FSH, and others), increased body weights, altered uterine and ovary weights, increased heart weights and collagen deposition, disrupted folliculogenesis, and other adverse health effects. This work suggests potential adverse developmental and reproductive health outcomes in humans and animals exposed to these oil and gas operation chemicals, with adverse outcomes observed even in the lowest dose group tested, equivalent to concentrations reported in drinking water sources. These endpoints suggest potential impacts on fertility, as previously observed in the male siblings, which require careful assessment in future studies.

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One of the environmental risks associated with use of hydraulic fracturing stimulation technologies for oil and natural gas recovery is the potential release of used fluids into surface waters, soils, and groundwater that could contaminate drinking water resources. To better characterize biodegradability of organic additives, we developed a synthetic fracturing fluid (SFF) based on industry-disclosed formulas, compared its organic carbon composition to fluids used in Pennsylvania's Marcellus shale, and amended agricultural soil–groundwater microcosms with three different SFF concentrations to determine organic carbon degradation rates, changes in system biogeochemistry, and microbial community dynamics under aerobic and anaerobic conditions. Microorganisms indigenous to soils and groundwater were able to degrade between 70% and 92% of the amended dissolved organic carbon within 39 days, suggesting significant mineralization, transformation, or biomass assimilation of organic additives across anaerobic and aerobic redox conditions. Sequencing analysis of the 16S rRNA gene revealed a greater abundance of Pseudomonas in aerobic treatments and a higher relative portion of Desulfovibrio in anaerobic treatments amended with SFF, indicating that these taxa may be involved in SFF biodegradation processes under specific redox conditions. Results provide insight into biodegradability of hydraulic fracturing fluid organic additives in shallow agricultural soils and groundwater and biogeochemical processes that may attenuate their migration if accidentally released or spilled at the surface during hydraulic fracturing activities.

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Summary Recycling oilfield wastewater for hydraulic fracturing requires a good understanding of the water chemical characteristics and how these interact with the fracturing fluid. The viscosity and rheological properties of fracturing fluids affect

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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.

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Controlling microbial activity is a primary concern during the management of the large volumes of wastewater (produced water) generated during high-volume hydraulic fracturing. In this study we analyzed the transcriptional activity (metatranscriptomes) of three produced water samples from the Marcellus Shale. The goal of this study was to describe active metabolic pathways of industrial concern for produced water management and reuse, and to improve understanding of produced water microbial activity. Metatranscriptome analysis revealed active biofilm formation, sulfide production, and stress management mechanisms of the produced water microbial communities. Biofilm-formation and sulfate-reduction pathways were identified in all samples. Genes related to a diverse array of stress response mechanisms were also identified with implications for biocide efficacy. Additionally, active expression of a methanogenesis pathway was identified in a sample of produced water collected prior to holding pond storage. The active microbial community identified by metatranscriptome analysis was markedly different than the community composition as identified by 16S rRNA sequencing, highlighting the value of evaluating the active microbial fraction during assessments of produced water biofouling potential and evaluation of biocide application strategies. These results indicate biofouling and corrosive microbial processes are active in produced water and should be taken into consideration while designing produced water reuse strategies.

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Underground injection (UI) is an effective and efficient means of disposing of wastewater from shale gas production. However, the influence of UI on groundwater systems should be examined carefully to protect drinking groundwater sources. A regional hydrogeological model based on TOUGH2-MP/EOS7R of part of the Sichuan Basin is established to simulate pressure changes and solute transport in response to wastewater injection into deep aquifers. Wastewater is assumed to be injected through a well at a rate of 5.45 kg s−1 for 5 years and a post-injection period of 45 years. The simulation results indicate that UI will cause significant pressure buildup during the injection period, after which pressure will dissipate during the post-injection period. The mass fraction of solute increased over the entire simulation period. The draft regulation under the Safe Drinking Water Act and the level III groundwater quality standards regulated by the Chinese government is referenced as the criteria for evaluating the influence of UI on groundwater systems. It is found that maximum pressure levels caused by UI may exceed safe levels. Uncertainties with respect to permeability are analyzed from previous studies and injection test results. Lower levels of permeability incur higher degrees of pressure buildup when UI is implemented. Different injection schemes are discussed, and we verify that pressure buildup from time-variant injection schemes is less than that from constant injection schemes for the same total injection volume. Injection schemes should be carefully evaluated before implementing UI in a shale gas reservoir.

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Chemistry of flowback and produced waters from unconventional gas wells is controlled by reactions between fluids injected for well stimulation and the target geologic formation. Release of salts and metals from the formations are well documented, however, the fate of organic additives under down-hole conditions is not. One outcrop and six core samples of Marcellus Shale were obtained from locations throughout Pennsylvania and sequentially extracted to determine metal associations within various mineral matrices. Metal concentrations in different matrices varied significantly across the shale samples analyzed. In comparison to core samples, lower metal and salt concentrations were detected in the shale outcrop likely due to carbonate and salt dissolution during oxidative weathering processes. The shale outcrop was reacted with synthetic hydraulic fracturing fluids (SFFs) of high or low organic content to study the fate of organic additives and their influence on metal mobilization. The organic content of the fluid and high pressure and temperature (HPT; 1200 PSI and 80°C) conditions had little effect on metal dissolution. However, the organic composition changed significantly depending on the reaction conditions (pH and temperature effects). Major findings of this work include the following: (1) addition of oxidants to hydraulic fracturing fluids promotes degradation of organic additives in hydraulic fracturing fluids; (2) mineral composition of shale will effect solution pH, and low pH conditions will promote organic degradation and metal mobilization during hydraulic fracturing; and (3) surfactant additives are persistent under HPT conditions and will return in flowback waters.

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Unconventional natural gas development (UNGD) generates large volumes of wastewater, the detailed composition of which must be known for adequate risk assessment and treatment. In particular, transformation products of geogenic compounds and disclosed additives have not been described. This study investigated six Fayetteville Shale wastewater samples for organic composition using a suite of one- and two-dimensional gas chromatographic techniques to capture a broad distribution of chemical structures. Following the application of strict compound-identification-confidence criteria, we classified compounds according to their putative origin. Samples displayed distinct chemical distributions composed of typical geogenic substances (hydrocarbons and hopane biomarkers), disclosed UNGD additives (e.g., hydrocarbons, phthalates such as diisobutyl phthalate, and radical initiators such as azobis(isobutyronitrile)), and undisclosed compounds (e.g., halogenated hydrocarbons, such as 2-bromohexane or 4-bromoheptane). Undisclosed chloromethyl alkanoates (chloromethyl propanoate, pentanoate, and octanoate) were identified as potential delayed acids (i.e., those that release acidic moieties only after hydrolytic cleavage, the rate of which could be potentially controlled), suggesting they were deliberately introduced to react in the subsurface. In contrast, the identification of halogenated methanes and acetones suggested that those compounds were formed as unintended byproducts. Our study highlights the possibility that UNGD operations generate transformation products and underscores the value of disclosing additives injected into the subsurface.

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Management of Marcellus Shale flowback water is a rising concern in Pennsylvania. Due to limited capacity for wastewater disposal by deep-well injection, flowback water reuse is the dominant management option in PA. Microfiltration is a promising technology to be used in a mobile treatment system for solids removal from Marcellus Shale flowback water prior to reuse. It was found previously that early Marcellus Shale flowback water could cause severe membrane fouling due to the presence of stable submicron colloids. Bench-scale cross-flow filtration system was used in this study to evaluate the feasibility of microfiltration for treatment of Marcellus Shale flowback water that does not contain these submicron colloids. The performance of alumina (Al2O3) and silicon carbide (SiC) ceramic membranes that have distinct surface charge properties was evaluated in this system using a constant transmembrane pressure. The difference in the isoelectric point of these membranes suggested possible differences in fouling behavior, but extremely high salinity of the flowback water screened the electrostatic interactions and minimized these differences. For the two flowback waters tested in this study, the one with lower TDS caused more severe fouling of both SiC and Al2O3 membranes during the first 15 min of filtration. The flux decline analysis revealed that intermediate pore blocking was the dominant fouling mechanism in the early filtration stage. Such behavior was due to the fact that the particulate matter in this flowback water was in the aggregate form and the flocs were prone to breakup at elevated shear stress caused by high pumping rate. Despite having much higher TSS, the other flowback water did not cause excessive membrane fouling due to stability and strength of its original particles.

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Pennsylvania's rapid unconventional oil and gas (UOG) development-from a single well in 2004 to more than 6700 wells in 2013-has dramatically increased UOG waste transport by heavy trucks. This study quantified the amount of UOG waste and the distance it traveled between wells and disposal facilities on each type of road in each county between July 2010 and December 2013. In addition, the study estimated the associated financial costs to each county's road infrastructure over that period. We found that UOG wells produced a median wastewater volume of 1294 m(3) and a median of 89,267 kg of solid waste. The median number of waste-transport truck trips per well was 122. UOG wells existed in 38 Pennsylvania counties, but we estimated trucks transporting well waste traveled through 132 counties, including counties in West Virginia, Ohio, and New York. Median travel distance varied by disposal type, from 106 km to centralized treatment facilities up to 237 km to injection wells. Local roads experienced the greatest amount of truck traffic and associated costs ($1.1-6.5 M) and interstates, the least ($0.3-1.6 M). Counties with oil and gas development experienced the most truck traffic and incurred the highest associated roadway costs. However, many counties outside the active development area also incurred roadway repair costs, highlighting the extension of UOG development's spatial footprint beyond the active development area. An online data visualization tool is available here: www.nicholasinstitute.duke.edu/transportation-of-hydraulic-fracturing-waste.

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Formation of barite (BaSO4) scale is a potential problem for unconventional (shale) gas extraction, as the excessive scale can reduce well productivity by plugging the proppant pack. This study was designed to evaluate the impact of antiscalants on the formation and transport of barite particles through proppant sand under well-controlled laboratory conditions using batch and column experiments. Extensive attachment of BaSO4 particles to proppant sand was observed at typical background salinity and in the absence of antiscalants due to relatively large barite particle size and screened electrostatic interaction. Presence of polymeric antiscalants can enhance the mobility of BaSO4 particles by decreasing their size and providing electrosteric repulsion. Ethylene glycol that may be added to hydraulic fracturing fluid to prevent scale deposition can reduce the size of BaSO4 precipitates but has no impact on the deposition of BaSO4 particles during transport through proppant sand. Polymaleic acid and sulfonated poly-phosphino-carboxylic acid that are generally considered when the goal is to inhibit formation of mineral scales are unlikely to prevent barite formation at high supersaturation conditions that are typical for unconventional gas industry. However, they can reduce the size and alter the morphology of barite particles as well as inhibit the deposition of bulk precipitates onto proppant sand surface by inducing stronger repulsive interactions.

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Unconventional resource extraction from shale plays involves complex operations for water and wastewater management. These water management operations are expensive for companies and emit significant quantities of criteria air pollutants and greenhouse gases that impact human health and the environment (HHE). We present a multiobjective mixed integer linear programming (MILP) framework for assessing the trade-offs between financial cost and HHE costs for shale gas water acquisition, transport, storage, and treatment under realistic scheduling, operational, and regulatory constraints. We formulate objective functions to identify water management strategies that minimize financial cost, minimize HHE cost, and minimize combined financial and HHE costs. The model was applied to a 14 wellpad case study that is representative of shale gas extraction in the Marcellus Play. We observe significant variation in the financial and HHE costs under different objective functions and regulatory scenarios.

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Currently, > 95% of end disposal of hydraulic fracturing wastewater from unconventional oil and gas operations in the US occurs via injection wells. Key data gaps exist in understanding the potential impact of underground injection on surface water quality and environmental health. The goal of this study was to assess endocrine disrupting activity in surface water at a West Virginia injection well disposal site. Water samples were collected from a background site in the area and upstream, on, and downstream of the disposal facility. Samples were solid-phase extracted, and extracts assessed for agonist and antagonist hormonal activities for five hormone receptors in mammalian and yeast reporter gene assays. Compared to reference water extracts upstream and distal to the disposal well, samples collected adjacent and downstream exhibited considerably higher antagonist activity for the estrogen, androgen, progesterone, glucocorticoid and thyroid hormone receptors. In contrast, low levels of agonist activity were measured in upstream/distal sites, and were inhibited or absent at downstream sites with significant antagonism. Concurrent analyses by partner laboratories (published separately) describe the analytical and geochemical profiling of the water; elevated conductivity as well as high sodium, chloride, strontium, and barium concentrations indicate impacts due to handling of unconventional oil and gas wastewater. Notably, antagonist activities in downstream samples were at equivalent authentic standard concentrations known to disrupt reproduction and/or development in aquatic animals. Given the widespread use of injection wells for end-disposal of hydraulic fracturing wastewater, these data raise concerns for human and animal health nearby.

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Gas shale fracturing relies on a method known as horizontal fracturing to remove gas trapped within the impermeable facies. Conventional vertical and unconventional horizontal fracturing requires a large amount of water to be injected downhole under high pressure. These fracturing fluids can contain high concentrations of petroleum hydrocarbons with known adverse health effects. The development of reuse technologies that reduce the need of potable water requires an accurate understanding of petroleum hydrocarbon loading during key points in the fracturing process. In this study, flowback water quality from both horizontally and vertically fractured wells within the Marcellus Shale region in Pennsylvania and West Virginia were analyzed. Flowback data made available by the Shale Network were collected using geographic information systems. Flowback sample analytes of interest were diesel range organic (DRO) and gasoline range organic (GRO) compounds. Noticeable patterns were present in DRO and GRO flowback data. Flowback water results showed differences between horizontally and vertically fractured well DRO patterns. Vertically fractured wells showed a sharp decrease in DRO concentrations following fracture events. Horizontally fractured wells exhibited a peak in loading when flowback water shifted to produced water. This pattern suggests the method of completion may affect DRO loading. GRO loadings appeared to not be effected by the method of completion. A horizontally fractured well and vertically fractured well within 16 km showed similar loading patterns. GRO data suggest factors such as geographic location may be responsible for VOC loading trends.

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Microbial activity associated with produced water from hydraulic fracturing operations can lead to gas souring and corrosion of carbon-steel equipment. We examined the microbial ecology of produced water and the prospective role of the prevalent microorganisms in corrosion in a gas production field in the Barnett Shale. The microbial community was mainly composed of halophilic, sulfidogenic bacteria within the order Halanaerobiales, which reflected the geochemical conditions of highly saline water containing sulfur species (S2O32-, SO42-, and HS-). A predominant, halophilic bacterium (strain DL-01) was subsequently isolated and identified as belonging to the genus Halanaerobium. The isolate could degrade guar gum, a polysaccharide polymer used in fracture fluids, to produce acetate and sulfide in a 10% NaCl medium at 37°C when thiosulfate was available. To mitigate potential deleterious effects of sulfide and acetate, a quaternary ammonium compound was found to be an efficient biocide in inhibiting the growth and metabolic activity of strain DL-01 relative to glutaraldehyde and tetrakis (hydroxymethyl) phosphonium sulfate. Collectively, our findings suggest that predominant halophiles associated with unconventional shale gas extraction could proliferate and produce sulfide and acetate from the metabolism of polysaccharides used in hydraulic fracturing fluids. These metabolic products might be returned to the surface and transported in pipelines to cause pitting corrosion in downstream infrastructure.

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2,2-Dibromo-3-nitrilopropionamide (DBNPA) is a major biocide in hydraulic fracturing fluids. Most biocides in fracturing fluids are considered to have low acute toxicity to mammals, but little information is available in the literature regarding the toxic actions of DBNPA on mammalian cells. This information is important to suggest the DBNPA toxicity on wild mammals. In this study, the effects of DBNPA on rat thymocytes were studied using flow cytometric techniques in order to further characterize the cytotoxicity of DBNPA for its safe use. DBNPA at 3–7.5 μM produced a steep concentration-dependent increase in cell lethality. At 5 μM, DBNPA significantly depolarized the membranes with a disturbance of the asymmetrical distribution of membrane phospholipids. The lethal effect of DBNPA was completely abolished under cold conditions, and was augmented in the presence of ethanol. It is suggested that the lethal action of DBNPA is linked to changes in membrane fluidity. Because the concentration-dependent change of DBNPA-induced lethal action was very steep under in vitro conditions, the adverse actions of DBNPA on wild mammals are concerning, even though such reports have not yet surfaced.

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Hydraulic fracturing frequently occurs on agricultural land. Yet the extent of sorption, transformation, and interactions among the numerous organic frac fluid and oil and gas wastewater constituents upon environmental release is hardly known. Thus, this study aims to advance our current understanding of processes that control the environmental fate and toxicity of commonly used hydraulic fracturing chemicals. Poly(ethylene glycol) surfactants were completely biodegraded in agricultural topsoil within 42-71 days, but their transformation was impeded in the presence of the biocide glutaraldehyde and was completely inhibited by salt at concentrations typical for oil and gas wastewater. At the same time, aqueous glutaraldehyde concentrations decreased due to sorption to soil and were completely biodegraded within 33-57 days. While no aqueous removal of polyacrylamide friction reducer was observed over a period of 6 months, it cross-linked with glutaraldehyde, further lowering the biocide's aqueous concentration. These findings highlight the necessity to consider co-contaminant effects when we evaluate the risk of frac fluid additives and oil and gas wastewater constituents in agricultural soils in order to fully understand their human health impacts, likelihood for crop uptake, and potential for groundwater contamination.

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The rapid rise of unconventional oil production during the past decade in the Bakken region of North Dakota raises concerns related to water contamination associated with the accidental release of oil and gas wastewater to the environment. Here, we characterize the major and trace element chemistry and isotopic ratios (87Sr/86Sr, δ18O, δ2H) of surface waters (n = 29) in areas impacted by oil and gas wastewater spills in the Bakken region of North Dakota. We establish geochemical and isotopic tracers that can identify Bakken brine spills in the environment. In addition to elevated concentrations of dissolved salts (Na, Cl, Br), spill waters also consisted of elevated concentrations of other contaminants (Se, V, Pb, NH4) compared to background waters, and soil and sediment in spill sites had elevated total radium activities (228Ra + 226Ra) relative to background, indicating accumulation of Ra in impacted soil and sediment. We observed that inorganic contamination associated with brine spills in North Dakota is remarkably persistent, with elevated levels of contaminants observed in spills sites up to 4 years following the spill events.

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Produced and flowback waters are the largest byproducts associated with unconventional oil and gas exploration and production. Sustainable and low cost technologies are needed to treat and reuse this wastewater to avoid the environmental problems associated with current management practices (i.e., deep well injection). This study presents a new process to integrate AC-powered electrocoagulation (EC) with granular biochar to dramatically reduce energy use and electrode passivation while achieving high treatment efficiency. Results show achieving a 99% turbidity and TSS removal for the AC-EC-biochar system only used 0.079 kWh/m3 or 0.15 kWh/kg TSS, which is 70% lower than traditional DC-EC systems and orders of magnitude lower than previous studies. The amount of biochar added positively correlates with energy saving, and further studies are needed to improve organic carbon and salt removal through system integration.

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The United States Environmental Protection Agency (EPA) identified 1,173 chemicals associated with hydraulic fracturing fluids, flowback, or produced water, of which 1,026 (87%) lack chronic oral toxicity values for human health assessments. To facilitate the ranking and prioritization of chemicals that lack toxicity values, it may be useful to employ toxicity estimates from quantitative structure-activity relationship (QSAR) models. Here we describe an approach for applying the results of a QSAR model from the TOPKAT program suite, which provides estimates of the rat chronic oral lowest-observed-adverse-effect level (LOAEL). Of the 1,173 chemicals, TOPKAT was able to generate LOAEL estimates for 515 (44%). To address the uncertainty associated with these estimates, we assigned qualitative confidence scores (high, medium, or low) to each TOPKAT LOAEL estimate, and found 481 to be high-confidence. For 48 chemicals that had both a high-confidence TOPKAT LOAEL estimate and a chronic oral reference dose from EPA’s Integrated Risk Information System (IRIS) database, Spearman rank correlation identified 68% agreement between the two values (permutation p-value = 1x10-11). These results provide support for the use of TOPKAT LOAEL estimates in identifying and prioritizing potentially hazardous chemicals. High-confidence TOPKAT LOAELs were available for 389 of 1,026 hydraulic fracturing-related chemicals that lack chronic oral RfVs and OSFs from EPA-identified sources, including a subset of chemicals that are frequently used in hydraulic fracturing fluids.

Abstract:
The development of unconventional oil and gas (UOG) resources has rapidly increased in recent years; however, the environmental impacts and risks are poorly understood. A single well can generate millions of liters of wastewater, representing a mixture of formation brine and injected hydraulic fracturing fluids. One of the most common methods for wastewater disposal is underground injection; we are assessing potential risks of this method through an intensive, interdisciplinary study at an injection disposal facility in West Virginia. In June 2014, waters collected downstream from the site had elevated specific conductance (416 µS/cm) and Na, Cl, Ba, Br, Sr and Li concentrations, compared to upstream, background waters (conductivity, 74 µS/cm). Elevated TDS, a marker of UOG wastewater, provided an early indication of impacts in the stream. Wastewater inputs are also evident by changes in 87Sr/86Sr in stream water adjacent to the disposal facility. Sediments downstream from the facility were enriched in Ra and had high bioavailable Fe(III) concentrations relative to upstream sediments. Microbial communities in downstream sediments had lower diversity and shifts in composition. Although the hydrologic pathways were not able to be assessed, these data provide evidence demonstrating that activities at the disposal facility are impacting a nearby stream and altering the biogeochemistry of nearby ecosystems.

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Summary Natural-gas recovery from low-permeability unconventional reservoirs--enabled by advanced horizontal drilling and multistage hydraulic-fracture treatment--has become a very important energy resource in the past decade. While evaluation of ea

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This article presents a mathematical programing formulation for the optimal management of flowback water in shale gas wells. The formulation accounts for the time-based generation of the flowback water, the options for treatment, storage, reuse, and disposal. The economic and environmental objectives are considered. The economic objective function is aimed at determining the minimum cost for the fresh water, treatment, storage, disposals, and transportation. The environmental objectives account for the fresh water usage and wastewater discharge. To carry out the water integration, a reuse network including treatment is proposed. Additionally, the model considers seasonal fluctuations in the fresh water availability. A given scheduling for the completion phases of the wells is required to implement the methodology. Finally, an example problem is presented to show the applicability of the proposed methodology. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1634–1645, 2016

Abstract:
Spills from oil and gas operations can contaminate water resources, sediment, and soil, but in many cases, information about spill sources and environmental impacts is not available. Here we present age dating methods to estimate the time since the accumulation of radium in impacted soils and sediments from oil and gas wastewater spills. The retention of unsupported Ra-226 and Ra-228 from spill water to soil and sediment and the ingrowth of Ra progeny result in three independent age dating methods using the Th-228/Ra-228, Pb-210/Ra-226 and Ra-228/Ra-226 activity ratios. We tested the Th-228/Ra-228 method on spill sites in North Dakota and West Virginia, where the dates of the spills are known. The Th-228/Ra-228 method yields ages similar to the documented spill ages and can reveal the initial Ra-228/Ra-226 ratios of the spill waters, validating the notion that Ra isotopes and their decay products in contaminated soils and sediments can reveal the ages and origins of spills.

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There is growing interest in possible options for treatment or reuse of flowback and produced waters from natural gas processing. Here we investigated the fouling characteristics during microfiltration of different flowback and produced waters from hydraulic fracturing sites in the Marcellus shale. All samples caused severe and highly variable fouling, although there was no direct correlation between the fouling rate and total suspended solids, turbidity, or total organic carbon. Furthermore, the fouling of water after prefiltration through a 0.2 μm membrane was also highly variable. Low fouling seen with prefiltered water was mainly due to removal of submicron particles 0.4-0.8 μm during prefiltration. High fouling seen with prefiltered water was mainly caused by a combination of hydrophobic organics and colloidal particles <100 nm in size (quantified by transmission electron microscopy) that passed through the prefiltration membranes. The small colloidal particles were highly stable, likely due to the surfactants and other organics present in the fracking fluids. The colloid concentration was as high as 10(11) colloids/ml, which is more than 100 times greater than that in typical seawater. Furthermore, these colloids were only partially removed by MF, causing substantial fouling during a subsequent ultrafiltration. These results clearly show the importance of organics and colloidal material in membrane fouling caused by flowback and produced waters, which is of critical importance in the development of more sustainable treatment strategies in natural gas processing.

Abstract:
Concerns have been raised about potential public health effects that may arise if hydraulic fracturing-related chemicals were to impact drinking water resources. This study presents an overview of the chronic oral toxicity values?specifically, chronic oral reference values (RfVs) for noncancer effects, and oral slope factors (OSFs) for cancer?that are available for a list of 1,173 chemicals that the United States (US) Environmental Protection Agency (EPA) identified as being associated with hydraulic fracturing, including 1,076 chemicals used in hydraulic fracturing fluids, and 134 chemicals detected in flowback or produced waters from hydraulically fractured wells. EPA compiled RfVs and OSFs using six governmental and intergovernmental data sources. 90 (8%) of the 1,076 chemicals reported in hydraulic fracturing fluids and 83 (62%) of the 134 chemicals reported in flowback/produced water had a chronic oral RfV or OSF available from one or more of the six sources. Furthermore, of the 36 chemicals reported in hydraulic fracturing fluids in at least 10% of wells nationwide (identified from EPA?s analysis of the FracFocus Chemical Disclosure Registry 1.0), 8 chemicals (22%) have an available chronic oral RfV. The lack of chronic oral RfVs and OSFs for the majority of these chemicals highlights the significant knowledge gap that exists to assess the potential human health hazards associated with hydraulic fracturing.

Abstract:
Naturally-occurring radioactive materials (NORM) associated with unconventional drilling produced fluids from the Marcellus Shale have raised environmental concerns. However, few investigations into the fundamental chemistry of NORM in Marcellus Shale produced fluids have been performed. Thus, we performed radiochemical experiments with Marcellus Shale produced fluids to understand the partitioning behavior of major radioelements of environmental health concern (uranium (U), thorium (Th), radium (Ra), lead (Pb), and polonium (Po)). We applied a novel radiotracer, 203Pb, to understand the behavior of trace-levels of 210Pb in these fluids. Ultrafiltration experiments indicated U, Th, and Po are particle reactive in Marcellus Shale produced fluids and Ra and Pb are soluble. Sediment partitioning experiments revealed that >99% of Ra does not adsorb to sediments in the presence of Marcellus Shale produced fluids. Further experiments indicated that although Ra adsorption is related to ionic strength, the concentrations of heavier alkaline earth metals (Ba, Sr) are stronger predictors of Ra solubility.

Abstract:
Waters that return to the surface after injection of a hydraulic fracturing fluid for gas and oil production contain elements, including regulated metals and metalloids, which are mobilized through interactions between the fracturing fluid and the shale formation. The rate and extent of mobilization depends on the geochemistry of the formation and the chemical characteristics of the fracturing fluid. In this work, laboratory scale experiments investigated the influence of water chemistry on element mobilization from core samples taken from the Bakken formation, one of the most productive shale oil plays in the US. Fluid properties were systematically varied and evaluated with regard to pH, oxidant level, solid:water ratio, temperature, and chemical additives. Element mobilization strongly depended on solution pH and redox conditions and to a lesser extent on the temperature and solid:water ratio. The presence of oxygen and addition of hydrogen peroxide or ammonium persulfate led to pyrite oxidation, resulting in elevated sulfate concentrations. Further, depending on the mineral carbonates available to buffer the system pH, pyrite oxidation could lower the system pH and enhance the mobility of several metals and metalloids.

Abstract:
Growth in unconventional oil and gas has spurred concerns on environmental impact and interest in beneficial uses of produced water (PW), especially in arid regions such as the Permian Basin, the largest U.S. tight-oil producer. To evaluate environmental impact, treatment, and reuse potential, there is a need to characterize the compositional variability of PW. Although hydraulic fracturing has caused a significant increase in shale-oil production, there are no high-resolution organic composition data for the shale-oil PW from the Permian Basin or other shale-oil plays (Eagle Ford, Bakken, etc.). PW was collected from shale-oil wells in the Midland sub-basin of the Permian Basin. Molecular characterization was conducted using high-resolution solid phase micro extraction gas chromatography time-of-flight mass spectrometry. Approximately 1400 compounds were identified, and 327 compounds had a >70% library match. PW contained alkane, cyclohexane, cyclopentane, BTEX (benzene, toluene, ethylbenzene, and xylene), alkyl benzenes, propyl-benzene, and naphthalene. PW also contained heteroatomic compounds containing nitrogen, oxygen, and sulfur. 3D van Krevelen and double bond equivalence versus carbon number analyses were used to evaluate molecular variability. Source composition, as well as solubility, controlled the distribution of volatile compounds found in shale-oil PW. The salinity also increased with depth, ranging from 105 to 162 g/L total dissolved solids. These data fill a gap for shale-oil PW composition, the associated petroleomics plots provide a fingerprinting framework, and the results for the Permian shale-oil PW suggest that partial treatment of suspended solids and organics would support some beneficial uses such as onsite reuse and bio-energy production.

Abstract:
A new method that rapidly pre-concentrates and measures 226Ra from hydraulic fracturing wastewater samples was developed in the Savannah River Environmental Laboratory. The method improves the quality of 226Ra measurements using gamma spectrometry by providing up to 100 × pre-concentration of 226Ra from this difficult sample matrix, which contains very high levels of calcium, barium, strontium, magnesium and sodium. The high chemical yield, typically 80–90 %, facilitates a low detection limit, important for lower level samples, and indicates method ruggedness. Ba-133 tracer is used to determine chemical yield and correct for geometry-related counting issues. The 226Ra sample preparation takes <2 h.

Abstract:
During oil and natural gas production, so-called “produced water” comprises the largest byproduct stream. In addition, many oil and gas operations are augmented via injection of hydraulic fracturing (HF) fluids into the formation. Both produced water and HF fluids may contain hundreds of individual chemicals, some known to be detrimental to public health and the environment. Oil and gas production wastewater may serve a range of beneficial purposes, particularly in arid regions, if managed correctly. Numerous treatment technologies have been developed that allow for injection, discharge to the land surface, or beneficial reuse. Although many papers have addressed the effects of oil and gas production wastewater (OGPW) on groundwater and surface water quality, significantly less information is available on the effects of these fluids on the soil resource. This review paper compiles fundamental information on numerous chemicals used and produced during oil and gas development and their effects on the soil environment. Additionally, pollution prevention technologies relating to OGPW are presented. An understanding of the effects of OGPW on soil chemical, physical, and biological properties can provide a foundation for effective remediation of OGPW-affected soils; additionally, sustainable reuse of oil and gas water for irrigation and industrial purposes may be enhanced.

Abstract:
Wastewater produced by hydraulic fracturing for oil and gas production is characterized by high salinity and high chemical oxygen demand (COD). We applied a combination of flocculation and wet air oxidation technology to optimize the reduction of COD in the treatment of hydraulic fracturing wastewater. The experiments used different values of flocculant, coagulant, and oxidizing agent added to the wastewater, as well as different reaction times and treatment temperatures. The use of flocculants for the pretreatment of fracturing wastewater was shown to improve treatment efficiency. The addition of 500 mg/L of polyaluminum chloride (PAC) and 20 mg/L of anionic polyacrylamide (APAM) during pretreatment resulted in a COD removal ratio of 8.2% and reduced the suspended solid concentration of fracturing wastewater to 150 mg/L. For a solution of pretreated fracturing wastewater with 12 mL of added H2O2, the COD was reduced to 104 mg/L when reacted at 300 °C for 75 min, and reduced to 127 mg/L when reacted at the same temperature for 45 min while using a 1 L autoclave. An optimal combination of these parameters produced treated wastewater that met the GB 8978-1996 'Integrated Wastewater Discharge Standard' level I emission standard.

Abstract:
Much interest is directed at the chemical structure of hydraulic fracturing (HF) additives in unconventional gas exploitation. To bridge the gap between existing alphabetical disclosures by function / CAS number and emerging scientific contributions on fate and toxicity, we review the structural properties which motivate HF applications, and which determine environmental fate and toxicity. Our quantitative overview relied on voluntary U.S. disclosures evaluated from the FracFocus registry by different sources and on a House of Representatives (?Waxman?) list. Out of over 1000 reported substances, classification by chemistry yielded succinct subsets able to illustrate the rationale of their use, and physicochemical properties relevant for environmental fate, toxicity and chemical analysis. While many substances were non-toxic, frequent disclosures also included notorious groundwater contaminants like petroleum hydrocarbons (solvents), precursors of endocrine disruptors like nonylphenols (non-emulsifiers), toxic propargyl alcohol (corrosion inhibitor), tetramethyl ammonium (clay stabilizer), biocides or strong oxidants. Application of highly oxidizing chemicals, together with occasional disclosures of putative delayed acids and complexing agents (i.e., compounds designed to react in the subsurface) suggests that relevant transformation products may be formed. To adequately investigate such reactions, available information is not sufficient, but instead a full disclosure of HF additives is necessary.

Abstract:
The Marcellus Shale formation contains large natural gas reserves, which are increasingly being extracted using horizontal drilling techniques. Concerns about environmental effects have prompted studies regarding Marcellus operations, including the safety of pits and impoundments containing frac fluids and freshwater. A subset of these structures in West Virginia was evaluated using a risk-based field data collection tool, which revealed recurring problems. A probability-based method was developed to determine the likelihood of these problems occurring in larger sample sizes. Applying this method to portfolios of pits and impoundments would benefit the industry by identifying areas of improvement for construction and inspection.

Abstract:
This paper presents a mathematical programing formulation for synthesizing water networks associated with shale gas hydraulic fracturing operations while accounting for the system uncertainty. The proposed formulation yields strategic planning that minimizes the cost considering water requirements as well as equipment capacities for treatment technologies, storage units, and disposals. The key uncertainties pertain to the water usage for fracturing and the time-based return of flowback water. The objective function is aimed at the minimization of the total annual cost, which accounts for the operating and capital costs associated with the water network. The developed model addresses the scheduling problem associated with shale gas production, which provides as output the completion phases for all the projected wells. This information is used in estimating the periods with water requirements and where flowback water can be collected. The proposed methodology includes an analysis of the optimal equipment size. An illustrative example is presented to show the capabilities of the proposed methodology.

Abstract:
Hydraulic fracturing is an important technological advance in the extraction of natural gas and petroleum from black shales, but water injected into shale formations in the fracturing process returns with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium, Ba. It is generally assumed that high TDS comes from the mixing of surface water (injected fluid) with Na–Ca–Cl formation brines containing elevated Ba, but the mechanisms by which such mixing might occur are disputed. Here we show that Ba in water co-produced with gas could originate from water-rock reactions, with Ba levels observed in produced waters reached on a time scale relevant to hydraulic fracturing operations. We examined samples from three drill cores from the Marcellus Shale in Pennsylvania and New York to determine the possible water-rock reactions that release barium during hydraulic fracturing. Two samples, one containing microcrystalline barite (BaSO4) and one without barite, contain elevated concentrations of Ba relative to the crustal average for shale rocks. A third sample is slightly depleted in Ba relative to the crustal average. Micro-XRF measurements and SEM/EDS analysis combined with chemical sequential extraction methods reveal that a majority of the Ba in all samples (55–77 wt.%) is present in clays and can only be leached from the rock by dissolution in hydrofluoric acid. Thus, a majority of barium in our samples is relatively inaccessible to leaching under hydraulic fracturing conditions. However, the balance of Ba in the rocks is contained in phases that are potentially leachable during hydraulic fracturing (e.g., soluble salts, exchangeable sites on clays, carbonates, barite, organics). We next studied how shale reacts with water at elevated temperatures (80 °C), low Eh (−100 to −200 mV), and a range of ionic strengths (IS = 0.85–6.4) that emulate conditions prevalent at depth during hydraulic fracturing. Our experimental results indicate that the amount of Ba released from the bulk rock has a positive correlation with the ionic strength of the reacting fluid. Between 5 and 25% of the total Ba in the rock can be leached from shale under ionic strength conditions and leachate compositions typical of produced waters over a contact time of just 7 days. We suggest that reductive weathering of black shale occurs during hydraulic fracturing due to: 1) Ba2+ in clays exchanging with Na+ and Ca2+ ions that are present in high concentrations in produced water, and 2) increased solubility and dissolution kinetics of barite under high ionic strength conditions. At the low Eh conditions prevalent during hydraulic fracturing the sulfate deficient water allows Ba to be dissolved into the produced water. Based on Ba yields determined from laboratory leaching experiments of Marcellus Shale and a reasonable estimate of the water/rock mass ratio during hydraulic fracturing, we suggest that all of the Ba in produced water can be reconciled with leaching directly from the fractured rock.

Abstract:
Objectives. To investigate race and poverty in areas where oil and gas wastewater disposal wells, which are used to permanently inject wastewater from hydraulic fracturing (fracking) operations, are permitted.Methods. With location data of oil and gas disposal wells permitted between 2007 and 2014 in the Eagle Ford area, a region of intensive fracking in southern Texas, we analyzed the racial composition of residents living less than 5 kilometers from a disposal well and those farther away, adjusting for rurality and poverty, using a Poisson regression.Results. The proportion of people of color living less than 5 kilometers from a disposal well was 1.3 times higher than was the proportion of non-Hispanic Whites. Adjusting for rurality, disposal wells were 2.04 times (95% confidence interval = 2.02, 2.06) as common in areas with 80% people of color or more than in majority White areas. Disposal wells are also disproportionately sited in high-poverty areas.Conclusions. Wastewater disposal wells in southern Texas are disproportionately permitted in areas with higher proportions of people of color and residents living in poverty, a pattern known as “environmental injustice.” (Am J Public Health. Published online ahead of print January 21, 2016: e1–e7. doi:10.2105/AJPH.2015.303000)

Abstract:
In 2010, a dramatic increase in the levels of total trihalomethane (THM) and the relative proportion of brominated species was observed in finished water at several Pennsylvania water utilities (PDW) using the Allegheny River as their raw water supply. An increase in bromide (Br−) concentrations in the Allegheny River was implicated to be the cause of the elevated water disinfection byproducts. This study focused on quantifying the contribution of Br− from a commercial wastewater treatment facility (CWTF) that solely treats wastes from oil and gas producers and discharges into the upper reaches of the Allegheny River, and impacts on two downstream PDWs. In 2012, automated daily integrated samples were collected on the Allegheny River at six sites during three seasonal two-week sampling campaigns to characterize Br− concentrations and river dispersion characteristics during periods of high and low river discharges. The CWTF discharges resulted in significant increases in Br− compared to upstream baseline values in PDW raw drinking water intakes during periods of low river discharge. During high river discharge, the assimilative dilution capacity of the river resulted in lower absolute halide concentrations, but significant elevations Br− concentrations were still observed at the nearest downstream PDW intake over baseline river levels. On days with active CWTF effluent discharge the magnitude of bromide impact increased by 39 ppb (53%) and 7 ppb (22%) for low and high river discharge campaigns, respectively. Despite a declining trend in Allegheny River Br− (2009–2014), significant impacts from CWTF and coal-fired power plant discharges to Br− concentrations during the low river discharge regime at downstream PDW intakes was observed, resulting in small modeled increases in total THM (3%), and estimated positive shifts (41–47%) to more toxic brominated THM analogs. The lack of available coincident measurements of THM, precursors, and physical parameters limited the interpretation of historical trends.

Abstract:
Hydraulic-fracturing fluids and wastewater from unconventional oil and natural gas development contain hundreds of substances with the potential to contaminate drinking water. Challenges to conducting well-designed human exposure and health studies include limited information about likely etiologic agents. We systematically evaluated 1021 chemicals identified in hydraulic-fracturing fluids (n=925), wastewater (n=132), or both (n=36) for potential reproductive and developmental toxicity to triage those with potential for human health impact. We searched the REPROTOX database using Chemical Abstract Service registry numbers for chemicals with available data and evaluated the evidence for adverse reproductive and developmental effects. Next, we determined which chemicals linked to reproductive or developmental toxicity had water quality standards or guidelines. Toxicity information was lacking for 781 (76%) chemicals. Of the remaining 240 substances, evidence suggested reproductive toxicity for 103 (43%), developmental toxicity for 95 (40%), and both for 41 (17%). Of these 157 chemicals, 67 had or were proposed for a federal water quality standard or guideline. Our systematic screening approach identified a list of 67 hydraulic fracturing-related candidate analytes based on known or suspected toxicity. Incorporation of data on potency, physicochemical properties, and environmental concentrations could further prioritize these substances for future drinking water exposure assessments or reproductive and developmental health studies.

Abstract:
This work presents an optimization framework for evaluating different wastewater treatment/disposal options for water management during hydraulic fracturing (HF) operations. This framework takes into account both cost-effectiveness and system uncertainty. HF has enabled rapid development of shale gas resources. However, wastewater management has been one of the most contentious and widely publicized issues in shale gas production. The flowback and produced water (known as FP water) generated by HF may pose a serious risk to the surrounding environment and public health because this wastewater usually contains many toxic chemicals and high levels of total dissolved solids (TDS). Various treatment/disposal options are available for FP water management, such as underground injection, hazardous wastewater treatment plants, and/or reuse. In order to cost-effectively plan FP water management practices, including allocating FP water to different options and planning treatment facility capacity expansion, an optimization model named UO-FPW is developed in this study. The UO-FPW model can handle the uncertain information expressed in the form of fuzzy membership functions and probability density functions in the modeling parameters. The UO-FPW model is applied to a representative hypothetical case study to demonstrate its applicability in practice. The modeling results reflect the tradeoffs between economic objective (i.e., minimizing total-system cost) and system reliability (i.e., risk of violating fuzzy and/or random constraints, and meeting FP water treatment/disposal requirements). Using the developed optimization model, decision makers can make and adjust appropriate FP water management strategies through refining the values of feasibility degrees for fuzzy constraints and the probability levels for random constraints if the solutions are not satisfactory. The optimization model can be easily integrated into decision support systems for shale oil/gas lifecycle management. (C) 2015 Elsevier Ltd. All rights reserved.

Abstract:
The objective of this paper is to review different risk assessment techniques applicable to onshore unconventional oil and gas production to determine the risks to water quantity and quality associated with hydraulic fracturing and produced water management. Water resources could be at risk without proper management of water, chemicals, and produced water. Previous risk assessments in the oil and gas industry were performed from an engineering perspective leaving aside important social factors. Different risk assessment methods and techniques are reviewed and summarized to select the most appropriate one to perform a holistic and integrated analysis of risks at every stage of the water life cycle. Constraints to performing risk assessment are identified including gaps in databases, which require more advanced techniques such as modeling. Discussions on each risk associated with water and produced water management, mitigation strategies, and future research direction are presented. Further research on risks in onshore unconventional oil and gas will benefit not only the U.S. but also other countries with shale oil and gas resources.

Abstract:
Elevated levels of bromide have been shown to contribute to increased formation of disinfection byproducts (DBPs). Both produced water from unconventional oil and gas wells, which are hydraulically fractured using high volumes of fluids, and produced water from conventional oil and gas wells, which are also typically hydraulically fractured but with lower volumes of fluids, can contain high levels of bromide. If these produced waters are treated in conventional commercial wastewater treatment plants, bromide may not be removed from the effluent and is discharged to receiving water bodies. Elevated bromide levels at drinking water plant intakes is a concern for public health reasons if elevated bromide levels cause elevated levels of DBPs. This study used data from commercial wastewater treatment plants and river flow data in western Pennsylvania to construct generic discharge scenarios that illustrate the potential impacts from disposal of five classes of water that were developed from flowback and produced water bromide concentrations. Months with the historical high and low flows in the Allegheny River (Pennsylvania) and Blacklick Creek (Pennsylvania) were chosen for simulation, and treatment plant discharge rates were set at 100, 50, 33, and 25% of the permitted value for the purpose of varying the mass loading. Steady-state simulation results showed the highest probably of impact, defined as concentrations above target levels of 0.02 and 0.10 mg/L, for produced water in the creek at both high and low flows (100%), and produced water in the river at low flows (>75%). High probability of impact (>50%) occurred in the river at low flows and all flows in the creek with treated mixed/flowback water discharge. Modeled reduction in the effluent discharge rate reduced downstream impacts proportionally. Transient simulation showed that transient peak concentrations may exceed time-averaged concentration by up to a factor of four when mixing conditions are met.

Abstract:
Twenty-eight states require disclosure of hydraulic fracturing chemicals. Twenty-three states direct reporting to FracFocus; additionally, companies in other states use this registry. FracFocus contains the most comprehensive dataset on fracturing chemicals but faces data quality and transparency criticisms. In response, FracFocus announced upgrades, and since May 2015, publishes aggregated data. We used Linux and R version 3.2.0 to clean and analyze 96,449 forms submitted between March 9, 2011 and April 13, 2015 for accuracy, completeness, and timeliness. We characterize data, and compare results to state law and industry practice, to suggest how to induce more accurate and complete disclosures. We find that rates of withheld chemical information have increased since 2013, and appear unaffected by different legal requirements. However, when companies report fracturing chemicals without attribution to the specific products in the fracturing fluid (a “systems approach” to reporting), withholding rates drop four-fold. State deadlines shortened reporting timelines, but compliance rates are low absent indication states will enforce. Automatic field population and prompts in FracFocus can reduce data error, while enforcement signals, education, and harmonized requirements may boost compliance and enhance disclosure. Systems reporting should occur, with states retaining authority to request product-specific ingredient lists.

Abstract:
Hydraulic fracturing has advanced the development of shale gas extraction, while inadvertent spills of flowback water may pose a risk to the surrounding environment due to its high salt content, metals/metalloids (As, Se, Fe and Sr), and organic additives. This study investigated the potential impact of flowback water on four representative soils from shale gas regions in Northeast China using synthetic flowback solutions. The compositions of the solutions were representative of flowback water arising at different stages after fracturing well establishment. The effects of solution composition of flowback water on soil ecosystem were assessed in terms of metal mobility and bioaccessibility, as well as biological endpoints using Microtox bioassay (Vibrio fischeri) and enzyme activity tests. After one-month artificial aging of the soils with various flowback solutions, the mobility and bioaccessibility of As(V) and Se(VI) decreased as the ionic strength of the flowback solutions increased. The results inferred a stronger binding affinity of As(V) and Se(VI) with the soils. Nevertheless, the soil toxicity to Vibrio fischeri only presented a moderate increase after aging, while dehydrogenase and phosphomonoesterase activities were significantly suppressed with increasing ionic strength of flowback solutions. On the contrary, polyacrylamide in the flowback solutions led to higher dehydrogenase activity. These results indicated that soil enzyme activities were sensitive to the composition of flowback solutions. A preliminary human health risk assessment related to As(V) suggested a low level of cancer risk through exposure via ingestion, while holistic assessment of environmental implications is required.