Repository for Oil and Gas Energy Research (ROGER)

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The data in this report are associated with “Characterization of Produced Water and Surrounding Surface Water in the Permian Basin, the United States” (Jiang et al. 2022) and include raw data on produced water (PW) quality and Pecos River water quality in the Permian Basin, which is one of the major oil and gas producing areas in the U.S. The data include 46 samples for PW and 10 samples for Pecos River water. The data include wet chemistry, mineral salts, metals, oil and grease, volatile and semi-volatile organic compounds, radionuclides, ammonia, hydraulic fracturing additives, and per- and polyfluoroalkyl substances. The PW samples were collected from five different locations in the Permian Basin. Twenty-four of the PW samples and the ten Pecos River samples were analyzed by the authors. The information for the rest of PW samples (22 samples) was provided by industrial collaborators in the Permian Basin. Statistical analyses were performed on the combined data to obtain Mean, Max, Min, 25th percentile, 50th percentile, and 75th percentile of each analyte.

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Shale gas wastewater (SGW) has great potential for the recovery of valuable elements, but it also poses risks in terms of environmental pollution, with heavy metals and naturally occurring radioactive materials (NORM) being of major concerns. However, many of these species have not been fully determined. For the first time, we identify the elements present in SGW from the Sichuan Basin and consequently draw a comprehensive periodic table, including 71 elements in 15 IUPAC groups. Based on it, we analyze the elements possessing recycling opportunities or with risk potentials. Most of the metal elements in SGW exist at very low concentrations (< 0.2 mg/L), including rare earth elements, revealing poor economic feasibility for recovery. However, salts, strontium (Sr), lithium (Li), and gallium (Ga) are in higher concentrations and have impressive market demands, hence great potential to be recovered. As for environmental burdens related to raw SGW management, salinity, F, Cl, Br, NO3−, Ba, B, and Fe, Cu, As, Mn, V, and Mo pose relatively higher threats in view of the concentrations and toxicity. The radioactivity is also much higher than the safety range, with the gross α activity and gross β activity in SGW ranging from 3.71–83.4 Bq/L, and 1.62–18.7 Bq/L, respectively and radium-226 as the main component. The advanced combined process “pretreatment-disk tube reverse osmosis (DTRO)” with pilot-scale is evaluated for the safe reuse of SGW. This process has high efficiency in the removal of metals and total radioactivity. However, the gross α activity of the effluent (1.3 Bq/L) is slightly higher than the standard for discharge (1 Bq/L), which is thus associated with potential long-term environmental hazards.

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Environmental concerns with unconventional oil and gas development are frequently centered on elevated water usage and the induction of seismic events during waste disposal. Reuse of produced water for subsequent production well stimulation can effectively address these concerns, but the variability among such samples must be well understood. Twenty-four samples of wastewater from unconventional oil and gas development were collected from south and west Texas to assess their variability and feasibility for direct reuse. Bulk metrics were collected, including total organic carbon, total nitrogen, as well as total dissolved and suspended solids. The profiles of pertinent inorganic constituents were also evaluated. Variations were not only seen between regions but also among samples collected from the same region. For example, the average total organic carbon for Eagle Ford samples collected was 700 ± 500 mg/L, while samples collected from the Per-mian Basin featured an average total organic carbon concentration of 600 ± 900 mg/L. The Permian Basin total organic carbon ranged from 38 to 2600 mg/L. The total dissolved solids levels had the same variability between regions, with an average value for Eagle Ford of 20,000 ± 10,000 mg/L and a Permian Basin value of 150,000 ± 40,000 mg/L. However, samples were more reproducible within a given region. Collectively, the data indicate that the direct reuse of raw produced water for subsequent production well development without treatment is not feasible based on the reported reuse thresholds. Unconventional development wastewater samples from the Permian Basin were also compared to produced water values from conventional oil and gas wells in the same region, as reported by the United States Geological Survey. Samples collected in the Permian Basin consistently demonstrated lower ionic strength compared to conventional produced water data.

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Although shale gas has shown promising potential to alleviate energy crisis as a clean energy resource, more attention has been paid to the harmful environmental impacts during exploitation. It is a critical issue for the management of shale gas wastewater (SGW), especially the organic compounds. This review focuses on analytical methods and corresponding treatment technologies targeting organic matters in SGW. Firstly, detailed information about specific shale-derived organics and related organic compounds in SGW were overviewed. Secondly, the state-of-the art analytical methods for detecting organics in SGW were summarized. The gas chromatography paired with mass spectrometry was the most commonly used technique. Thirdly, relevant treatment technologies for SGW organic matters were systematically explored. Forward osmosis and membrane distillation ranked the top two most frequently used treatment processes. Moreover, quantitative analyses on the removal of general and single organic compounds by treatment technologies were conducted. Finally, challenges for the analytical methods and treatment technologies of organic matters in SGW were addressed. The lack of effective trace organic detection techniques and high cost of treatment technologies are the urgent problems to be solved. Advances in the extraction, detection, identification and disposal of trace organic matters are critical to address the issues.

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Water, water, everywhere, Nor any drop to drink!—The Rime of the Ancient Mariner, Samuel Taylor ColeridgeThis study shows that Wolfcamp-produced waters in the Permian Delaware Basin are predominantly in situ Wolfcamp shale formation water with δ18O ∼6.5 ± 0.5‰ (standard mean ocean water) and a salinity as low as 20,000 ppm, consistent with illite-water equilibrium at peak burial conditions.Produced waters in the Delaware Basin have highly radiogenic 87/86Sr ratios of ∼0.7085–0.7095 believed to be sourced from evaporative brines in the Salado salts and overlying shallow Ochoan evaporites. Despite Wolfcamp-produced waters in the Midland Basin routinely having total dissolved solids of up to ∼250,000 ppm, which is double that in the Delaware Basin, chloride-bromide systematics of produced waters show that only minimal halite dissolution was involved in both basins.High-salinity produced waters in the Bone Spring Formation and the upper Wolfcamp formation from the Delaware Basin (∼50,000–125,000 ppm) are mixtures of Wolfcamp formation water and Ochoan evaporative brines that have mixed with local meteoric water. These brines infiltrated deep into the Delaware Basin during uplift of the western edge of the Delaware Basin via permeable Guadalupian and Leonardian sandstone and siltstones.Due to the high illite content in the Wolfcamp shale, the shale-siltstone interface likely behaved as a clay membrane. Salinity differences of up to approximately 100,000 ppm across this interface created potential gradients in ion and water activity (aw), producing an osmotic pressure gradient.Ion diffusion into the shales results in the flow of water out of the shales (high aw) into high-salinity siltstones (low aw). The coupled osmosis–diffusion model predicts high absolute osmotic pressures of up to ∼1680 psi and cocurrent flow of oil and water out of the shale. However, the flow of water out of the shale into adjacent siltstone faces an opposing osmotic pressure. This may explain the high fluid pressures encountered in the Wolfcamp shale and why oil production in the Delaware Basin produces so much water.

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A thorough understanding of produced water (PW) quality is critical to advance the knowledge and tools for effective PW management, treatment, risk assessment, and feasibility for beneficial reuse outside the oil and gas industry. This study provides the first step to better understand PW quality to develop beneficial reuse programs that are protective of human health and the environment. In total, 46 PW samples from unconventional operations in the Permian Basin and ten surface water samples from the Pecos River in New Mexico were collected for quantitative target analyses of more than 300 constituents. Water quality analyses of Pecos River samples could provide context and baseline information for the potential discharge and reuse of treated PW in this area. Temporal PW and river water quality changes were monitored for eight months in 2020. PW samples had total dissolved solids (TDS) concentrations ranging from 100,800–201,500 mg/L. Various mineral salts, metals, oil and grease, volatile and semi-volatile organic compounds, radionuclides, ammonia, hydraulic fracturing additives, and per- and polyfluoroalkyl substances were detected at different concentrations. Chemical characterization of organic compounds found in Pecos River water showed no evidence of PW origin. Isometric log-ratio Na-Cl-Br analysis showed the salinity in the Pecos River samples appeared to be linked to an increase in natural shallow brine inputs. This study outlines baseline analytical information to advance PW research by describing PW and surrounding surface water quality in the Permian Basin that will assist in determining management strategies, treatment methods, potential beneficial reuse applications, and potential environmental impacts specific to intended beneficial use of treated PW.

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Here, we report the draft genome sequence of three glutaraldehyde-resistant isolates from produced water from hydraulic fracturing operations. The three strains were identified as Marinobacter sp. strain G11, Halomonas sp. strain G15, and Bacillus sp. ...

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Over the last decade, there has been a rapid growth in the use of hydraulic fracturing (fracking) to recover unconventional oil and gas in the Permian Basin of southeastern New Mexico (NM) and western Texas. Fracking generates enormous quantities of wastes that contain technologically enhanced naturally occurring radioactive materials (TENORM), which poses risks to human health and the environment because of the relatively high doses of radioactivity. However, very little is known about the chemical composition and radioactivity levels of Permian Basin fracking wastes. Here, we report chemical as well as radiochemical compositions of hydraulic fracking wastes from the Permian Basin. Radium, the major TENORM of interest in unconventional drilling wastes, varied from 19.1 ± 1.2 to 35.9 ± 3.2 Bq/L for 226Ra, 10.3 ± 0.5 to 21.5 ± 1.2 Bq/L for 228Ra, and 2.0 ± 0.05 to 3.7 ± 0.07 Bq/L for 224Ra. In addition to elevated concentrations of radium, these wastewaters also contain elevated concentrations of dissolved salts and divalent cations such as Na+ (31,856–43,000 mg/L), Ca2+ (668–4123 mg/L), Mg2+ (202–2430 mg/L), K+ (148–780 mg/L), Sr2+ (101–260 mg/L), Cl− (5160–66,700 mg/L), SO42− (291–1980 mg/L), Br− (315–596 mg/L), SiO2 (20–32 mg/L), and high total dissolved solid (TDS) of 5000–173,000 mg/L compared to background waters. These elevated levels are of radiological significance and represent a major source of Ra in the environment. The recent discovery of large deposits of recoverable oil and gas in the Permian Basin will lead to more fracking, TENORM generation, and radium releases to the environment. This paper evaluates the potential radiation risks associated with TENORM wastes generated by the oil and gas recovery industry in the Permian Basin.

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The effectiveness of oil and gas produced water (OGPW) applied to unpaved roads to reduce particulate matter (PM10) generation has not been well-characterized. Here we quantify the efficacy of OGPW compared to commercial and alternative byproducts as dust suppressants applied to unpaved roads and estimate efficacy of a dust suppressant extrapolated from both lab experiments and published data for OGPW across U.S. states. Both treated and untreated OGPW, simulated brines, and commercial dust suppressants were characterized by major and trace element composition and then applied to road aggregate in the laboratory. PM10 generation after treatment was quantified, both before and after simulated rain events to assess the need for multiple applications. We found the dust suppression efficacy of all OGPW to be less than commercial products and alternative byproducts such as waste soybean oil. In addition, OGPW lost efficacy following simulated rain events, which would require repeated applications of OGPW to maintain dust suppression. The dust suppression efficacy of OGPW can be estimated based on two chemical measurements, the sodium absorption ratio (SAR) and the total dissolved solids (TDS). OGPW with the lowest SAR and highest TDS performed best as dust suppressants while high SAR and lower TDS led to greater dust generation.

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Pressure-retarded osmosis (PRO) is a promising membrane technology for harnessing the osmotic energy of saline solutions. PRO is typically considered with seawater/river water pairings however greater energy can be recovered from hypersaline solutions including produced water (PW) from the petroleum industry. One of the major challenges facing the utilization of hypersaline PW is its high fouling propensity on membranes. In this unique experimental evaluation, real PW from different sites was pretreated to varying degrees: i) minimal, ii) intermediate, and iii) extensive. The treated effluent was subsequently used for PRO testing and fouling rates were assessed for different membrane configurations over multiple cycles. Commercial grade flat sheet (FLS) coupons and novel hollow fiber (HF) modules were compared to validate the lower fouling propensity of HF membranes in PRO application. When minimally pretreated PW (10-micron cartridge filtration (CF)) was tested in FLS mode, severe membrane fouling occurred and the PRO flux decreased by 60%. In contrast, HF modules showed <1% flux decrease under both minimal and intermediate pretreatment schemes. Extensive pretreatment (1-micron CF, dissolved air flotation (DAF), powdered activated carbon, and microfiltration) reduced FLS PRO flux decline to <1%. These results confirm that PW can be treated to suitable levels for PRO application to avoid membrane fouling. Further validation of these pretreatment methods requires long term pilot testing and techno-economic assessment.

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A large amount of shale gas fracturing flowback fluid (FFBF) from the process of shale gas exploitation causes obvious ecological harm to health of soil and water. However, biological hazard of soil microbial populations by fracturing flowback fluid remains rarely reported. In this study, the microbiological compositions were assessed via analyzing diversity of microbial populations. The results showed significant differences between polluted soil by fracturing flowback fluid and unpolluted soil in different pH and temperature conditions. And then, the microbe-index of biological integrity (M-IBI) was used to evaluate the toxicity of the fracturing flowback fluid based on analysis of microbial integrity. The results showed that polluted soil lacks key microbial species known to be beneficial to soil health, including denitrifying bacteria and cellulose-decomposing bacteria, and 35 °C is a critical value for estimating poor and sub-healthy level of damage to microbial integrity by fracturing flowback fluid. Our results provide a valuable reference for the evaluation of soil damage by fracturing flowback fluid.

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Abstract The resurgence of oil and gas extraction in the Appalachian Basin has resulted in an excess of oil and gas brines in Pennsylvania, West Virginia, and Ohio. Primarily driven by unconventional development, this expansion has also impacted conventional wells and consequently, created economic pressure to develop effective and cheap disposal options. Using brine as a road treatment, directly or as a processed deicer, however, creates substantial concern that naturally occurring radioactive material in the brines can contaminate roads and road-side areas. Current decision making is based on risk exposure scenarios developed by regulatory agencies based on recreational users in rural areas and exposures to drivers during a typical commute. These scenarios are not appropriate for evaluating exposures to residential deicer users or people living near treated streets. More appropriate exposure scenarios were developed in this work and exposures predicted with these models based on laboratory measurements and literature data. Exposure scenarios currently used for regulatory assessment of brine road treatment result in predicted exposures of 0.4-0.6 mrem/year. Residential exposures predicted by the scenarios developed in this work are 4.6 mrem/year. If the maximum range of near-road soil radium concentrations observed in the region is used in this residential scenario (60 pCi/g 226 Ra, 50 pCi/g 228 Ra), residents living near these roads would be exposed to an estimated 296 mrems/year, above regulatory exposure thresholds used in nuclear facility siting assessments. These results underline the urgent need to clarify exposure risks from the use of oil and gas brines as a road treatment, particularly given the existing disparities in the distribution of road impacts across socioeconomic status.

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As hydraulic fracturing (HF) practices keep expanding in China, a comparative understanding of biological characteristics of flowback and produced waters (FPW) and sludge in impoundments for FPW reserve will help propose appropriate treatment strategies. Therefore, in this study, the microbial communities and functions in impoundments that collected wastewaters from dozens of wells were characterized. The results showed that microbial richness and diversity were significantly increased in sludge compared with those in FPW. The vast majority of microorganisms found in FPW and sludge are organic degraders, providing the possibility of using these indigenous microorganisms to biodegrade organic compounds. Our laboratory findings first show that wastewater pretreatment using these microorganisms was effective, and organic compounds in FPW from different shale formations were removed by 35–68% within 72 h in a wide temperature range (8 – 30 ℃). Meanwhile, highly toxic compounds such as phthalate esters (PAEs), polycyclic aromatic hydrocarbons (PAHs), and petroleum hydrocarbons were effectively eliminated in reactors. The main microorganisms, key functional genes, and putative pathways for alkanes, PAHs, and PAEs degradation were also identified.

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Large stores of previously inaccessible hydrocarbons have become available due to the development of hydraulic fracturing technologies. During the hydraulic fracturing process, a mixture of water and proprietary additives is injected into geologic formations to release trapped hydrocarbons. After fracturing, injected water and fluid from the target formation return to the surface as flowback and produced water (FPW), a potentially toxic byproduct of hydraulic fracturing activities. FPW is a complex mixture that contains chemical additives present in the initial injection fluid as well as salts, metals, and a variety of organic compounds. As a result, FPW composition can be highly variable across wells from different geological formations, methods of fracturing and well development, and well age. The present study sought to determine if FPW sourced from four wells (O, P, U, V) located on the same well pad within the Montney Formation have similar levels of acute and chronic toxicity to the freshwater invertebrate, Daphnia magna. Minimal differences in the estimated 48 h LC50 concentrations were observed among the studied wells. Long-term, 21 d exposures to ≤2% FPW revealed differences in the level of lethality between wells, including complete mortality in daphnids exposed to 2% well O by day 9. No sublethal effects were observed as a result of exposure to FPW from wells P, U or V; however, a large impairment of reproductive traits and molting behaviour were detected after exposure to 0.75% well O FPW. These results indicate that FPW sourced from wells on the same well pad cannot be considered the same in terms of chemical composition or toxicity, an important distinction to make for risk assessment practices.

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In many basins across the United States, oil and gas (O&G) wastewater high in alkaline earth metals (such as Ba, Sr, and Ca) and radioactivity is discharged to surface waters. Freshwater mussels have experienced high mortality rates downstream of O&G discharges despite significant dilution. 87Sr/86Sr and Sr/Ca measured in mussel soft tissue could prove to be an inexpensive, efficient biomonitoring tool if tissue concentrations show O&G produced water signatures similar to those of shells. O&G-derived 226Ra/228Ra has not previously been studied in freshwater mussels. Additionally, accumulation of O&G-derived metals in mussel tissue may impact bioaccumulation in higher-trophic level organisms. A tank study using freshwater mussels (Elliptio complanata) was completed using Marcellus Shale-produced water diluted with regional surface water to realistic dilution levels (100–600-fold dilution). Results from the three-month study suggest Sr/Ca and 87Sr/86Sr robustly trace O&G pollution in mussel soft tissue. The high-dose tank soft tissue average 87Sr/86Sr [0.709502 ± (7.68 × 10–5)] was significantly more radiogenic than average control tank soft tissue [0.706808 ± (4.23 × 10–5)]. Radium concentrations in soft tissue were not significantly different between tanks. Changes in the soft tissue chemistry of mussel species from relatively low doses of O&G wastewater suggest surface water disposal volumes may require re-evaluation to prevent further impacts.

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Appropriate produced water (PW) management is critical for oil and gas industry. Understanding PW quantity and quality trends for one well or all similar wells in one region would significantly assist operators, regulators, and water treatment/disposal companies in optimizing PW management. In this research, historical PW quantity and quality data in the New Mexico portion (NM) of the Permian Basin from 1995 to 2019 was collected, pre-processed, and analyzed to understand the distribution, trend, and characteristics of PW production for potential beneficial use. Various machine learning algorithms were applied to predict PW quantity for different types of oil and gas wells. Both linear and non-linear regression approaches were used to conduct the analysis. The prediction results from five-fold cross-validation showed that the Random Forest Regression model reported high prediction accuracy. The AutoRegressive Integrated Moving Average model showed good results for predicting PW volume in time series. The water quality analysis results showed that the PW samples from the Delaware and Artesia Formations (mostly from conventional wells) had the highest and the lowest average total dissolved solids concentrations of 194,535 mg/L and 100,036 mg/L, respectively. This study is the first research that comprehensively analyzed and predicted PW quantity and quality in the NM-Permian Basin. The results can be used to develop a geospatial metrics analysis or facilitate system modeling to identify the potential opportunities and challenges of PW management alternatives within and outside oil and gas industry. The machine learning techniques developed in this study are generic and can be applied to other basins to predict PW quantity and quality.

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Hydraulic fracturing creates large volumes of flowback and produced water (FPW). The waste is a complex mixture of organic and inorganic constituents. Although the acute toxicity of FPW to freshwater organisms has been studied, few have attempted to discern the interaction between organic and inorganic constituents within this matrix and its role in toxicity. In the present study, bioaccumulation assays (7-d uptake and 7-d elimination period) with FPW (1% dilution) were conducted with the freshwater oligochaete, Lumbriculus variegatus, to evaluate the toxicokinetics of inorganic elements. To evaluate the interacting role of organics, bioaccumulation of elements in unmodified FPW was compared to activated carbon treated FPW (AC-modified). Differences in uptake and elimination rates as well as elimination steady state concentrations between unmodified and AC-modified treatments indicated that the organics play an important role in the uptake and depuration of inorganic elements in FPW. These differences in toxicokinetics between treatments aligned with observed growth rates in the worms which were higher in the AC-modified treatment. Whether growth differences resulted from increased accumulation and changes in toxicokinetic rates of inorganics or caused by direct toxicity from the organic fraction of FPW itself is still unknown and requires further research.

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

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This study investigated the removal of organic compounds from shale gas fracturing flowback water (FFW) by an integrated electro-coagulation and electro-peroxone (EC-EP) process in a divided electrochemical reactor. During the EC-EP process, electricity was efficiently utilized to produce both aluminum ion (Al3+) from electrochemical oxidation of an aluminum anode in the anodic compartment and hydrogen peroxide (H2O2) from oxygen reduction at a carbon-based cathode in the cathodic compartment. The in-situ generated H2O2 then reacted with ozone (O3) sparged in the cathodic compartment to produce hydroxyl radicals (•OH) for pollutant oxidation. The results showed that by sequentially treating the selected FFW by the EC and EP process in the anodic and cathodic compartment for 30 min, respectively, the EC-EP process effectively removed ~95% of total organic carbon (TOC) from the FFW, meeting the wastewater discharge standard for TOC (≤30 mg/L) with a low specific energy consumption of 0.11–0.21 kWh/g TOC removed. In contrast, individual EC and EP process, as well as the previously investigated ECP process that combined the EC and EP process in an undivided reactor, removed only ~76%, 32%, and 80% TOC from the FFW under similar reaction conditions, and thus could not meet the wastewater discharge standard. These results demonstrate that the EC-EP process successfully integrates the merit of the EC and EP process and may thus provide a cost-effective way to remove organic compounds for FFW disposal and reuses.

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Understanding the speciation and fate of radium during operational discharge from the offshore oil and gas industry into the marine environment is important in assessing its long term environmental impact. In the current work, 226Ra concentrations in marine sediments contaminated by produced water discharge from a site in the UK were analysed using gamma spectroscopy. Radium was present in field samples (0.1–0.3 Bq g−1) within International Atomic Energy Agency activity thresholds and was found to be primarily associated with micron sized radiobarite particles (≤2 μm). Experimental studies of synthetic/field produced water and seawater mixing under laboratory conditions showed that a significant proportion of radium (up to 97%) co-precipitated with barite confirming the radiobarite fate pathway. The results showed that produced water discharge into the marine environment results in the formation of radiobarite particles which incorporate a significant portion of radium and can be deposited in marine sediments.

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The oilfield produced water is a major waste stream in places where shale-gas production is growing rapidly. The reuse of produced water merits consideration because this practice helps reduce freshwater demand for fracking and moderates water pollution. Knowledge about the chemistry of produced water is needed to develop sustainable treatment/reuse strategies and set standards for acceptable levels of treatment of produced water. Thus, the author performed the first comprehensive analysis of oilfield produced water collected from the Bakken shale play in the U.S. state of North Dakota that represents the nation's third-largest net increase in proven crude oil reserves. The concentrations of a total of 36 elements in 13 IUPAC groups were determined. Among them, a few metals that are critical to the economy of the United States were detected at elevated concentrations (median, mg/L): K (7,620), Mg (2780), Sr (1610), Li (69), and Mn (33). Heavy metals essential for plants and animals, including Cu, Zn, and Mn, were detected at ppm levels. Measurable concentrations of highly toxic metal ions such as Cd and Pb were not detected. Concentrations of rare earth elements and platinum group metals were below respective detection limits. The produced water samples had very high total dissolved solids (237,680 ± 73,828 mg/L) and total hardness (>31,000 mg/L as CaCO3) but an extremely low alkalinity (152.4 ± 184.9 mg/L as CaCO3); therefore, softening by lime and soda was ineffective. Softening by caustic soda removed 99.5% hardness ions (Ca and Mg) under alkaline conditions. This study provides vital insight into the chemistry and treatability of produced water containing various metals.

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Diluted bitumen, also known as dilbit, is transported by rail and pipeline across Canada and the United States. Due to the fewer number of studies characterizing the toxicity of dilbit, a dilbit spill poses an unknown risk to freshwater aquatic ecosystems. In the following study, we compared the impact of early-life exposure to conventional and unconventional crude oils on the optomotor behavior, reproductive success, and transgenerational differences in gene expression in zebrafish and their progeny. For exposures, water accommodated fractions (WAFs) of crude oil were generated using a 1:1000 oil to water ratio for 3 different crudes; mixed sweet blend (MSB), medium sour composite (MSC) and dilbit. All three oils generated unique volatile organic compound (VOC) and polycyclic aromatic compound (PAC) profiles. Of the WAFs tested, only dilbit decreased the eye size of 2 dpf larvae, and only MSB exposed larvae had an altered behavioral response to a visual simulation of a predator. Early-life exposure to crude oil had no lasting impact on reproductive success of adult fish; however, each oil had unique impacts on the basal gene expression of the somatically exposed offspring. In this study, the biological effects differed between each of the oils tested, which implied chemical composition plays a critical role in determining the sublethal toxicity of conventional and unconventional crude oils in freshwater ecosystems.

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Despite the growing body of studies on the various fracturing phrases, the research on the differences between subterranean and surface microorganisms at shale gas drilling sites is still limited. Generally, shale gas development and the production process are divided into drilling and fracturing. The distribution of microbial communities in the latter has been paid some attention, but a deficit remains in terms of our understanding of the microbial community in the former, especially for the phase of drilling flowback and drilling flowback surface. In this study, four drilling flowback fluids (DFFs) (H230-flowback drilling cuttings, H23G-flowback drilling mud, H240-flowback drilling sediment, and H21F-flowback drilling water) from the outlet of subterranean pipeline to the inlet of storage tank were successively collected from H2 shale gas field during its initial drilling in Sichuan, China. Natural mountain water (H10W) used as the injection water of H2 was also sampled. Illumina MiSeq 16S rRNA gene sequencing revealed a total of 8 phyla, 17 classes, 35 orders, 61 families, and 98 genera that were recovered from these samples with uneven distribution. The majority of the obtained sequences belonged to the phyla Proteobacteria (75.36%), Bacteroidetes (10.75%), and Firmicutes (5.64%), with significant differences found in DFFs and injection water. The richness of microorganisms gradually increased with the increasing flowback flowing distance (H230< H23G< H240< H21F< H10W), which was employed to reveal a rapid change in microbiota that was evident in samples along the flow path aboveground from a depth of 3548 m. The findings of this study could expand our understanding of the ecological role of microorganisms during the shale gas drilling phase. Furthermore, the study highlights the temporal-spatial trajectory of microbial communities from subterranean environments to the surface in a short period of 30 days.

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Hydraulic fracturing of deep shale formations generates large volumes of wastewater that must be managed through treatment, reuse, or disposal. Produced wastewater liberates formation-derived radionuclides and contains previously uncharacterized organohalides thought to be generated within the shale well, both posing unknown toxicity to human and ecological health. Here, we assess the toxicity of 42 input media and produced fluid samples collected from four wells in the Utica formation and Marcellus Shale using two distinct endpoint screening assays. Broad spectrum acute toxicity was assessed using a bioluminescence inhibition assay employing the halotolerant bacterium Aliivibrio fischeri, while predictive mammalian cytotoxicity was evaluated using a N-acetylcysteine (NAC) thiol reactivity assay. The acute toxicity and thiol reactivity of early-stage flowback was higher than later produced fluids, with levels diminishing through time as the natural gas wells matured. Acute toxicity of early stage flowback and drilling muds were on par with the positive control, 3,5-dichlorophenol (6.8 mg L−1). Differences in both acute toxicity and thiol reactivity between paired natural gas well samples were associated with specific chemical additives. Samples from wells containing a larger diversity and concentration of organic additives resulted in higher acute toxicity, while samples from a well applying a higher composition of ammonium persulfate, a strong oxidizer, showed greater thiol reactivity, predictive of higher mammalian toxicity. Both acute toxicity and thiol reactivity are consistently detected in produced waters, in some cases present up to nine months after hydraulic fracturing. These results support that specific chemical additives, the reactions generated by the additives, or the constituents liberated from the formation by the additives contribute to the toxicity of hydraulic fracturing produced waters and reinforces the need for careful consideration of early produced fluid management.

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Understanding the behavior and composition of fracturing flowback water (FFW) can provide insight into in situ water–rock interactions, assessment of the success of the fracturing operations. FFW was collected from three wells (Z202-H1, Z203, and Z205) for up to 108 days after fracturing in the same area of western Chongqing, China. The samples were analyzed for the concentrations of various ions (Na+, K+, Ca2+, Mg2+, Ba2+, Sr2+, Cl−, SO42−, Br−, HCO3−, etc.) and for the stable isotope composition (δD and δ18O) of water. With increasing flowback time, the ionic concentration and total salinity increased (e.g., from 315 mg/L to 37117 mg/L after 38 days for well Z203), stable isotopic ratios became heavier (e.g., δD values changed from −23.59‰ to −14.32‰, δ18O values changed from −3.91‰ to −1.92‰). The total salinity of the FFW is shown to be the result of mixing of the highly saline formation water and the low-salinity fracturing water. FFW from Z205 had higher concentrations of Li+ and NO3−, heavier stable isotope compositions, larger Na+/Cl− ratio, smaller (Cl−-Na+)/Mg2+ ratio, and larger SO42− × 100/Cl− ratio compared to the other two wells. All these phenomena revealed that Z205 is more likely to contact with active aquifers which is not conducive to natural gas preservation, because Z205 is close to (less 300 m from) a grade II fault. The RITS and RSIH with flowback time in Z203 were higher than Z202-H1, which shows that FFW from Z203 contained a greater fraction of formation water released from pores or fractures due to complex the network fractures formed by fracturing. Therefore, the fracturing operations of Z203 is better than Z202-H1. This result can reveal the reason for the production difference of adjacent wells, which is difficult to explain by similar total SRV.

Abstract:
Flowback/Produced fluid samples were collected from several wells from two Utica/Point Pleasant (UPP) sites (UPPW and UPPS) in Ohio, and one Marcellus (Marcellus Shale Energy and Environment Laboratory (MSEEL)) site in West Virginia over a period of approximately two years. Although these formations have different ages, depositional environments, diagenetic histories, and geochemical and mineralogical compositions (i.e. the UPP is significantly more carbonate rich than the Marcellus which is more siliceous), analysis of trends in fluid species over time shows that, overall, the TDS and major solubilized elements (Na, Ca, Cl) in the UPP and Marcellus brines are remarkably similar. Total dissolved solutes (TDS) in these brines ranged from approximately 40 to 250 g/L salt, and in general, concentrations increased with time elapsed since natural gas well completion and stimulation. The behavior of Na, Br, and Cl suggests that the produced water signatures from these formations are largely derived from the native formational brines which display evidence of originating from evaporated seawater. There is a strong correlation between Cl and Br, indicating that both species behave conservatively, and the similarity among each of these brines suggests no appreciable contribution of salt from halite dissolution because Br is excluded from the halite structure. Cl/Br ratios in the brines range from ~80 to 120 (mg/L/mg/L). Other elements, such as K, which readily reacts between fluids and ion exchange sites on clays, generally exhibit conservative behavior for an individual site, but show significant variations among each of the different well pads. The concentrations of Sr and Ba vary dramatically among well sites, and increase with respect to Cl− over time, suggesting increasing solubilization, presumably from desorption from clay minerals or dissolution of carbonates or sulfates from the source formation(s). The UPPW well site has very low Ba due to high-sulfate input fluid, which resulted in precipitation of barite/celestite in the brines. In contrast the UPPS well site had elevated Sr (~ 3500 mg/L), presumably due to the use of Sr-rich recycled brine used in hydraulic fracturing. The Marcellus site had the highest Ba concentrations (up to 10 g/L) and highest Ba/Sr ratios in the fluids, due to the high concentration of barium in the Marcellus target (~ 1000 ppm, as compared to ~200 ppm in the UPP). These observations suggest that solutes in the FP fluids are derived from native brines, water-rock interactions that have occurred over geologic time scales, as well as some contribution from contemporaneous reactions in the subsurface. The results also show that the composition of the injected fluid can influence flowback fluid chemistry and possibly production efficiency.

Abstract:
Oilfield flowback and produced water (FPW) is a waste stream that may offer an alternative source of water for multiple beneficial uses. One practice gaining interest in several semi-arid states is the reuse of FPW for agricultural irrigation. However, it is unknown if the reuse of FPW on edible crops could increase health risks from ingestion of exposed food, or impact crop growth. A greenhouse experiment was conducted using wheat (Triticum aestivum) to investigate the uptake potential of select hydraulic fracturing additives known to be associated with health risks. The selected chemicals included acrylamide, didecyldimethylammonium chloride (DDAC), diethanolamine, and tetramethylammonium chloride (TMAC). Mature wheat grain was extracted and analyzed by liquid chromatography-triple quadrupole mass spectrometry (LC-QQQ) to quantify chemical uptake. Plant development observations were also documented to evaluate impacts of the chemicals on crop yield. Analytical results indicated that TMAC and diethanolamine had significantly higher uptake into both wheat grain and stems than control plants which were not exposed to the four chemicals under investigation. Acrylamide was measured in statistically higher concentrations in the stems only, while DDAC was not detected in grain or stems. Growth impacts included lodging in treated wheat plants due to increased stem height and grain weight, potentially resulting from increased nitrogen application. While analytical results show that uptake of select hydraulic fracturing chemicals in wheat grain and stems is measurable, reuse of FPW for irrigation in real world scenarios would likely result in less uptake because water would be subject to natural degradation, and often treatment and dilution practices. Nonetheless, based on the outstanding data gaps associated with this research topic, chemical specific treatment and regulatory safeguards are still recommended.

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

Abstract:
This research assessed the efficacy of UV and UV advanced oxidation processes (UV/AOPs) to reduce dissolved organic carbon (DOC), total petroleum hydrocarbons (TPH), and microorganisms in hydraulic fracturing produced water. To improve water quality conditions before UV treatment with and without added hydrogen peroxide (UV/H2O2), produced water was treated with coagulation, flocculation, and sedimentation (CFS) and biologically activated carbon filtration (BACF). BACF was more effective than CFS as a pre-UV and UV/AOP treatment strategy and reduced DOC, TPH, and absorbing species by over 70% which, subsequently, resulted in the highest hydroxyl radical steady-state concentrations during UV and UV/H2O2 experiments. UV alone minimally degraded DOC, while UV/H2O2 improved DOC and TPH degradation by 9% to 36%. Interestingly, UV without added H2O2 created an in situ AOP by generating hydroxyl radicals with similar steady-state concentrations to that of UV/H2O2. UV was found to be highly effective for the inactivation of microorganisms that were cultured in produced water by reducing microbial communities dominated by Citrobacter by 4 logs after only 30 mJ/cm2. Together, these results demonstrate UV/AOP as a potential strategy to not only improve the treatment and reuse of produced water but also reduce biocide use in fracturing fluids.

Abstract:
This review focuses on recent developments in electrochemical technology (with special emphasis on electrocoagulation, electro-oxidation, and electro-Fenton) to treat petroleum industry effluents (offshore and hydraulic fracturing extraction, as well as refinery effluents). In addition, an overview is given of what these processes face to position themselves as consolidated technologies.

Abstract:
Hydraulic fracturing of unconventional hydrocarbon resources involves the sequential injection of a high-pressure, particle-laden fluid with varying pH’s to make commercial production viable in low permeability rocks. This process both requires and produces extraordinary volumes of water. The water used for hydraulic fracturing is typically fresh, whereas “flowback” water is typically saline with a variety of additives which complicate safe disposal. As production operations continue to expand, there is an increasing interest in treating and reusing this high-salinity produced water for further fracturing. Here we review the relevant transport and geochemical properties of shales, and critically analyze the impact of water chemistry (including produced water) on these properties. We discuss five major geochemical mechanisms that are prominently involved in the temporal and spatial evolution of fractures during the stimulation and production phase: shale softening, mineral dissolution, mineral precipitation, fines migration, and wettability alteration. A higher salinity fluid creates both benefits and complications in controlling these mechanisms. For example, higher salinity fluid inhibits clay dispersion, but simultaneously requires more additives to achieve appropriate viscosity for proppant emplacement. In total this review highlights the nuances of enhanced hydrogeochemical shale stimulation in relation to the choice of fracturing fluid chemistry.

Abstract:
Produced water (PW) generation has been increasing recently due to the expansion of fossil fuel extraction and the aging of oil wells worldwide and especially in the United States (US). The adverse health risks, seismicity, and environmental impacts associated with PW have become a challenging concern. Therefore, there is increased demand for improved PW treatment and reuse management options. There are multiple methods for treating PW; this article focuses on treatment through membrane filtration. Moreover, this mini review aims to summarize statistics on PW abundance, trends in PW generation over time, to briefly call attention to health-related issues, highlight some treatment challenges, and mention potential purposes for reuse with an emphasis on the US, the largest generator of PW worldwide.

Abstract:
Hydraulic fracturing has become widely used in recent years to access vast global unconventional sources of oil and gas. This process involves the injection of proprietary mixtures of water and chemicals to fracture shale formations and extract the hydrocarbons trapped within. These injection fluids, along with minerals, hydrocarbons, and saline waters present within the formations being drilled into, return to the surface as flowback and produced water (FPW). FPW is a highly complex mixture, containing metals, salts and clay, as well as many organic chemicals, including polycyclic aromatic hydrocarbons such as phenanthrene. The present study sought to determine the effects of temperature on the accumulation of phenanthrene in rainbow trout (Oncorhynchus mykiss). This model organism resides in rivers overlapping the Montney and Duvernay formations, both highly developed formations for hydraulic fracturing. Rainbow trout acclimated to temperatures of 4, 13 and 17°C were exposed to either 5% or 20% FPW, as well as saline mixtures representing the exact ionic content of FPW to determine the accumulation of radiolabelled 14C phenanthrene within the gill, gut, liver and gallbladder. FPW exposure reduced the overall accumulation of phenanthrene in a manner most often similar to high salinity exposure, indicating that the high ionic strength of FPW is the primary factor affecting accumulation. Accumulation was different at the temperature extremes (4 and 17°C), although no consistent relationship was observed between temperature and accumulation across the observed tissues. These results indicate that several physiological responses occur as a result of FPW exposure and water temperature change which dictate phenanthrene uptake, particularly in the gills. Temperature (and seasonality) alone cannot be used to model the potential accumulation of polycyclic aromatic hydrocarbons after FPW spills.

Abstract:
Releases of oil and gas (OG) wastewaters can have complex effects on stream-water quality and downstream organisms, due to sediment-water interactions and groundwater/surface water exchange. Previously, elevated concentrations of sodium (Na), chloride (Cl), barium (Ba), strontium (Sr), and lithium (Li), and trace hydrocarbons were determined to be key markers of OG wastewater releases when combined with Sr and radium (Ra) isotopic compositions. Here, we assessed the persistence of an OG wastewater spill in a creek in North Dakota using a combination of geochemical measurements and modeling, hydrologic analysis, and geophysical investigations. OG wastewater comprised 0.1 to 0.3% of the stream-water compositions at downstream sites in February and June 2015, but could not be quantified in 2016 and 2017. However, OG-wastewater markers persisted in sediments and pore water for 2.5 years after the spill and up to 7.2-km downstream from the spill site. Concentrations of OG wastewater constituents were highly variable depending on the hydrologic conditions. Electromagnetic measurements indicated substantially higher electrical conductivity in groundwater seeps below the streambed 7.2 km downstream from the spill site. Geomorphic investigations revealed mobilization of sediment is an important contaminant transport process. Labile Ba, Ra, Sr, and ammonium (NH4) concentrations extracted from sediments indicated sediments are a long-term reservoir of these constituents, both in the creek and on the floodplain. Using the drivers of ecological effects identified at this intensively studied site we identified 41 watersheds across the North Dakota landscape that may be subject to similar episodic inputs from OG wastewater spills. Effects of contaminants released to the environment during OG waste management activities remain poorly understood; however, analyses of Ra and Sr isotopic compositions, as well trace inorganic and organic compound concentrations at these sites in pore-water provide insights into potentials for animal and human exposures well outside source remediation zones.

Abstract:
Hydraulic fracturing flowback and produced water (FPW) is a highly complex and heterogenous wastewater by-product of hydraulic fracturing practices. To date, no research has examined how FPW exposure to freshwater biota may affect energetic homeostasis following subsequent induction of detoxification processes. Rainbow trout (Oncorhynchus mykiss) were acutely exposed for 48 h to either 2.5% or 7.5% FPW, and hepatic metabolism was assessed either immediately or following a 3-week recovery period. Induction of xenobiotic metabolism was observed with an 8.8-fold increase in ethoxyresorufin-O-deethylase (EROD) activity after 48 h exposure to 7.5% FPW, alongside a 10.3-fold increase in the mRNA abundance of cyp1a, both of which returned to basal level after three weeks. Glucose uptake capacity was elevated by 6.8- and 12.9-fold following 2.5% and 7.5% FPW exposure, respectively, while alanine uptake was variable. Activity measurements and mRNA abundance of key enzymes involved in hepatic metabolism indicated that aerobic metabolism was maintained with exposure, as was glycolysis. Gluconeogenesis, as measured by phosphoenolpyruvate carboxykinase (PEPCK) activity, decreased by ~30% 48 h following 2.5% FPW exposure and ~20% 3 weeks after 7.5% FPW exposure. The abundance of pepck mRNA activity followed similar, yet non-significant, trends. Finally, a delayed increase in amino acid catabolism was observed, as glutamate dehydrogenase (GDH) activity was increased 2-fold in 7.5% FPW exposed fish when compared to saline control fish at the 3-week time point. We provide evidence to suggest that although hepatic metabolism is altered following acute FPW exposure, metabolic homeostasis generally returns 3-weeks post-exposure.

Abstract:
The Utica and Marcellus Shale Plays in the Appalachian Basin are the fourth and first largest natural gas producing plays in the United States, respectively. Hydrocarbon production generates large volumes of brine (“produced water”) that must be disposed of, treated, or reused. Though Marcellus brines have been studied extensively, there are few studies from the Utica Shale Play. This study presents new brine chemical analyses from 16 Utica Shale Play wells in Ohio and Pennsylvania. Results from Na–Cl–Br systematics and stable and radiogenic isotopes suggest that the Utica Shale Play brines are likely residual pore water concentrated beyond halite saturation during the formation of the Ordovician Beekmantown evaporative sequence. The narrow range of chemistry for the Utica Shale Play produced waters (e.g., total dissolved solids = 214–283 g/L) over both time and space implies a consistent composition for disposal and reuse planning. The amount of salt produced annually from the Utica Shale Play is equivalent to 3.4% of the annual U.S. halite production. Utica Shale Play brines have radium activities 580 times the EPA maximum contaminant level and are supersaturated with respect to barite, indicating the potential for surface and aqueous radium hazards if not properly disposed of.

Abstract:
Hydraulic fracturing is often criticized due in part to the potential degradation of ground and surface water quality by high-salinity produced water generated during well stimulation and production. This preliminary study evaluated the response of the freshwater mussel, Elliptio complanata, after exposure to produced water. A limited number of adult mussels were grown over an 8-week period in tanks dosed with produced water collected from a hydraulically fractured well. The fatty tissue and carbonate shells were assessed for accumulation of both inorganic and organic pollutants. Ba, Sr, and cyclic hydrocarbons indicated the potential to accumulate in the soft tissue of freshwater mussels following exposure to diluted oil and gas produced water. Exposed mussels showed accumulation of Ba in the soft tissue several hundred times above background water concentrations and increased concentrations of Sr. Cyclic hydrocarbons were detected in dosed mussels and principle component analysis of gas chromatograph time-of-flight mass spectrometer results could be a novel tool to help identify areas where aquatic organisms are impacted by oil and gas produced water, but larger studies with greater replication are necessary to confirm these results.

Abstract:
Unconventional shale gas production in the United States has been largely improved due to the development of hydraulic fracturing technology and is projected to rapidly grow in the coming years. However, the acquisition of freshwater and management of flowback and produced (FP) water associated with hydraulic fracturing operation are two of the greatest challenges in shale gas development, especially in arid regions. For efficient and sustainable water management, a better understanding of freshwater consumption and FP water production for shale gas wells is necessary to appropriately expand and upgrade the existing water network and shale gas network. To achieve this, we first collected water-use volume and monthly FP water production volume data for shale gas wells drilled in the Eagle Ford and Marcellus shale regions. Next, after integrating the data from multiple database sources, the water recovery ratio was calculated as the ratio of cumulative FP water volume to water-use volume and used as a metric to characterize the wells in these two shale regions. Then, we analyzed the obtained water recovery ratio data according to the location and production history to study the spatiotemporal variations across multiple counties and time periods. It shows that around 30% of the collected wells drilled in the Eagle Ford region have the water recovery ratio greater than 1; however, only 1% of the collected wells drilled in the Marcellus region have the water recovery ratio greater than 1. Besides, the water recovery ratios vary significantly across the counties in each shale region. To demonstrate how different water recovery ratio may affect shale gas development, a shale gas supply chain network (SGSCN) optimization model from the literature was utilized to perform two case studies in the Marcellus region. The optimal results suggest that different configurations of SGSCN are required for economically desirable and practically feasible management of shale gas wells with different water recovery ratios.

Abstract:
Fertilizer drawn forward osmosis (FDFO) was proposed to extract fresh water from flowback and produced water (FPW) from shale gas extraction for irrigation, with fertilizer types and membrane orientations assessed. Draw solution (DS) with NH4H2PO4 displayed the best performance, while DS with (NH4)2HPO4 resulted in the most severe membrane fouling. DS with KCl and KNO3 led to substantial reverse solute fluxes. FDFO operation where the active layer of the membrane was facing the feed solution outperformed that when the active layer was facing the DS. Diluted DS and diluted FPW samples were used for irrigation of Cherry radish and Chinese cabbage. Compared to deionized water, irrigation with diluted DS (total dissolved solid (TDS) = 350 mg·L-1) promoted plant growth. In contrast, inhibited plant growth was observed when FPW with high salinity (TDS = 5000 mg·L-1) and low salinity (TDS = 1000 mg·L-1) was used for irrigation of long-term (8-week) plant cultures. Finally, upregulated genes were identified to illustrate the difference in plant growing. The results of this study provide a guide for efficient and safe use of FPW after FDFO treatment for agricultural application.

Abstract:
The increased water consumption for hydraulic fracturing and the volume of wastewater generated from shale gas and tight oil exploration are major environmental challenges associated with unconventional energy development. Recycling of the flowback and produced water for hydraulic fracturing is one of the solutions for reducing the water footprint of hydraulic fracturing and removing highly saline oil and gas wastewater. Here we investigated the implications of recycling saline wastewater for hydraulic fracturing by monitoring the natural gas production, flowback water volume, and the water quality of generated flowback water in shale gas wells from Changning gas field in Sichuan Basin, China. A comparison of two sets of shale gas wells, with six wells in each sub-group, from the same location in Changning gas field shows lower (~20%) natural gas production and higher flowback water volume (~18%) in wells that were fracked with recycled saline wastewater relative to wells that were fracked with fresh water after a year of production. Geochemical analysis suggests that hydraulic fracturing with saline wastewater increases the salinity of the wastewater and reduces the magnitude of water-shale rock interactions. In spite of the direct economic consequences in reduction in natural gas production from recycling of wastewater for hydraulic fracturing, in areas where water scarcity could become a limiting factor for future large-scale shale gas development, hydraulic fracturing with recycled flowback water can be more beneficial than utilization of limited freshwater resources, as long as the higher saline flowback water is fully recycled.

Abstract:
A linear programming (LP) model is presented to investigate optimal shale gas wastewater management strategies for Marcellus shale play in Pennsylvania (PA) focusing on membrane distillation (MD) as the treatment technology. The optimization framework established in this study incorporates (1) detailed treatment cost obtained from techno-economic assessment (TEA) of MD, (2) cost of wastewater transportation from shale gas sites to treatment or disposal facilities, and (3) cost of injection into salt water disposal (SWD) wells. The optimization model is applied to four case study areas with significant shale gas extraction: Greene and Washington counties in Southwest PA and Susquehanna and Bradford counties in Northeast PA. The results reveal that onsite treatment in combination with shale gas wastewater treatment at natural gas compressor stations (NG CS) where available waste heat can be utilized for the treatment process are the most economically advantageous management options. The optimal solution could result in over 60% benefit over direct disposal in SWD, which translates to over $16 million/year savings in the counties in Northeast PA. Furthermore, the results of sensitivity analysis indicate that transportation cost is a major contributor to the overall cost of shale gas wastewater management.

Abstract:
Produced water (PW) is a major waste-product of oil and gas production that some consider a viable agricultural irrigation water source. However, the presence of petroleum hydrocarbons, toxic metals and potentially high salinity of PW may be deleterious for soil health. Thus, we irrigated wheat with minimally treated PW to investigate effects on soil health, wheat growth, and the soil microbiome. Irrigation treatments included control irrigation water (IW), 1% and 5% PW dilutions (1% PW, 5% PW), and a saltwater solution with salinity equivalent to the 5% PW dilution (SW). Wheat was irrigated three times a week, for a total of 2.1 L per pot by harvest. During wheat growth, we measured plant physiological parameters, soil electrical conductivity, as well as profiled soil microbial diversity by performing 16S ribosomal ribonucleic acid (rRNA) gene analysis. Soil health parameters were measured after harvest, including chemical, biological, physical, and nutrient properties that were used to calculate an overall soil health index (SQI). SQI analysis revealed that the SW and 5% PW treatments had significantly reduced soil health as compared to the control. Furthermore, the 16S rRNA gene analysis showed that the microbial community membership and structure was significantly different between irrigation treatments, highlighting shifts in the soil microbiome which may impact soil biochemical cycling. Both the SW- and 5% PW-treated wheat had reduced yields as compared to the control. Our results indicate that irrigating wheat with minimally treated PW may result in yield decreases, as well as reducing both overall soil health and soil microbial community diversity. Future large-scale field studies are needed to determine the long-term soil health effects of PW on different soil types and crops.

Abstract:
As global exploration of shale gas reserves increases, there is a need for accurate and efficient approach to proper water management, which is one of the vital problems related to shale gas production. This study looks at the effect of using multiple or hybrid treatment technologies in maximizing hydraulic fracturing wastewater reuse, whilst ensuring sustainability of the process in terms of energy and associated cost. The study considers ultrafiltration and membrane distillation processes as possible pre-treatment and desalination technologies for flowback water management. It also considers the possibility of supplying the electrical and thermal energy requirements of these regenerators using flared gas. Two different scenarios are considered based on flowback water composition in hydraulic fracturing in terms of salinity. Application of the proposed model to a case study leads to 24.13 % reduction in the quantity of water needed for fracturing. In terms of energy requirements, the approach yields 31.6 % reduction in the required thermal energy in membrane distillation and 8.62 % in energy requirement for ultrafiltration. For flowback water with moderate total dissolved solids concentration, 93.6 % of wastewater reuse comes from pre-treated water by ultrafiltration and 6.4 % from membrane distillation. However, as the flowback water salinity becomes higher, the percentage of pre-treated reusable water reduces to 81.1 % and the percentage supply through membrane distillation increases to 18.9 %. In all cases, the results indicate that the decision to allow the pre-treated water to pass through desalination technology strictly depends on the quantity of water required by a wellpad and the salinity of the wastewater.

Abstract:
Uranium and other radionuclides are prominent in many unconventional oil/gas shales and is a potential contaminant in flowback/produced waters due to the large volumes/types of chemicals injected into the subsurface during stimulation. To understand the stability of U before and after stimulation, a geochemical study of U speciation was carried out on three shales (Marcellus, Green River, and Barnett). Two types of samples for each shale were subjected to sequential chemical extractions: unreacted and shale reacted with synthetic hydraulic fracture fluid. A significant proportion of the total U (20-57%) was released from these three shales after reaction with fracture fluid, indicating that U is readily leachable. The total U released exceeds labile water soluble and exchangeable fractions in unreacted samples, indicating that fluids leach more recalcitrant phases in the shale. Radiographic analysis of unreacted Marcellus shale thin sections shows U associated with detrital quartz and the clay matrix in the shale. Detrital zircon and TiO2 identified by electron microprobe could account for the hotspots. This study shows that significant proportions of U in three shales are mobile upon stimulation. In addition, the extent of mobilization of U depends on the U species in these rocks.

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

Abstract:
Produced water is the largest waste stream associated with oil and gas operations. This complex fluid contains petroleum hydrocarbons, heavy metals, salts, naturally occurring radioactive materials and any remaining chemical additives. In the United States, west of the 98th meridian, the federal National Pollutant Discharge Elimination System (NPDES) exemption allows release of produced water for agricultural beneficial reuse. The goal of this study was to quantify mutagenicity of a produced water NPDES release and discharge stream. We used four mutation assays in budding yeast cells that provide rate estimates for copy number variation (CNV) duplications and deletions, as well as forward and reversion point mutations. Higher mutation rates were observed at the discharge and decreased with distance downstream, which correlated with the concentrations of known carcinogens detected in the stream (e.g., benzene, radium), described in a companion study. Mutation rate increases were most prominent for CNV duplications and were higher than mutations observed in mixtures of known toxic compounds. Additionally, the samples were evaluated for acute toxicity in Daphnia magna and developmental toxicity in zebrafish. Acute toxicity was minimal, and no developmental toxicity was observed. This study illustrates that chemical analysis alone (McLaughlin et al., 2020) is insufficient for characterizing the risk of produced water NPDES releases and that a thorough evaluation of chronic toxicity is necessary to fully assess produced water for beneficial reuse.

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

Abstract:
Unconventional methods of oil and natural gas extraction have been a growing part of North America's energy sector for the past 20-30 years. Technologies such as horizontal hydraulic fracturing have facilitated the exploitation of geologic reserves that were previously resistant to standard drilling approaches. However, the environmental risks associated with hydraulic fracturing are relatively understudied. One such hazard is the wastewater by-product of hydraulic fracturing processes: flowback and produced water (FPW). During FPW production, transport, and storage, there are many potential pathways for environmental exposure. In the current review, toxicological hazards associated with FPW surface water contamination events and potential effects on freshwater biota are assessed. This review contains an extensive survey of chemicals commonly associated with FPW samples from shale formations across North America and median 50% lethal concentration values (LC50) of corresponding chemicals for many freshwater organisms. We identify the characteristics of FPW which may have the greatest potential to be drivers of toxicity to freshwater organisms. Notably, components associated with salinity, the organic fraction, and metal species are reviewed. Additionally, we examine the current state of FPW production in North America and identify the most significant obstacles impeding proper risk assessment development when environmental contamination events of this wastewater occur. Findings within this study will serve to catalyze further work on areas currently lacking in FPW research, including expanded whole effluent testing, repeated and chronic FPW exposure studies, and toxicity identification evaluations.