Repository for Oil and Gas Energy Research (ROGER)

Abstract:
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.

Abstract:
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.

Abstract:
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.

Abstract:
Oil and gas (O&G) extraction generates large volumes of produced water (PW) in regions that are often water-stressed. In Wyoming, generators are permitted under the National Pollutant Discharge Elimination System (NPDES) program to discharge O&G PW for beneficial use. In one Wyoming study region, downstream of the NPDES facilities exist naturally occurring wetlands referred to herein as produced water retention ponds (PWRPs). Previously, it was found that dissolved radium (Ra) and organic contaminants are removed within 30 km of the discharges and higher-resolution sampling was required to understand contaminant attenuation mechanisms. In this study, we sampled three NPDES discharge facilities, five PWRPs, and a reference background wetland not impacted by O&G PW disposal. Water samples, grab sediments, sediment cores and vegetation were collected. No inorganic PW constituents were abated through the PWRP series but Ra was shown to accumulate within PWRP grab sediments, upwards of 2721 Bq kg−1, compared to downstream sites. Ra mineral association with depth in the sediment profile is likely controlled by the S cycle under varying microbial communities and redox conditions. Under anoxic conditions, common in wetlands, Ra was available as an exchangeable ion, similar to Ca, Ba and Sr, and S was mostly water-soluble. 226Ra concentration ratios in vegetation samples, normalizing vegetation Ra to sediment Ra, indicated that ratios were highest in sediments containing less exchangeable 226Ra. Sequential leaching data paired with redox potentials suggest that oxic conditions are necessary to contain Ra in recalcitrant sediment minerals and prevent mobility and bioavailability.

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:
Carboxymethyl cellulose (CMC) is a polymer used in many different industrial sectors. In the oil and gas industry, CMC is often used during hydraulic fracturing (fracking) operations as a thickening agent for effective proppant delivery. Accumulations of CMC at fracture faces (known as filter cakes) can impede oil and gas recovery. Although chemical oxidizers are added to disrupt these accumulations, there is industrial interest in developing alternative, enzyme-based treatments. Little is known about CMC biodegradation under fracking conditions. Here, we enriched a methanogenic CMC-degrading culture and demonstrated its ability to enzymatically utilize CMC under the conditions that typify oil fields. Using the extracellular enzyme fraction from the culture, significant CMC viscosity reduction was observed between 50 and 80˚C, at salinities up to 20% (w/v) and at pH 5-8 compared to controls. Similar levels of viscosity reduction by extracellular enzymes were observed under oxic and anoxic conditions. This proof-of-concept study demonstrates that enzyme biotechnology holds great promise as a viable approach to treating CMC filter cakes under oilfield conditions.

Abstract:
Arsenic (As) is a toxic trace element with many sources, including hydrocarbons such as oil, natural gas, oil sands, and oil- and gas-bearing shales. Arsenic from these hydrocarbon sources can be released to the environment through human activities of hydrocarbon production, storage, transportation and use. In addition, accidental release of hydrocarbons to aquifers with naturally occurring (geogenic) As can induce mobilization of As to groundwater through biogeochemical reactions triggered by hydrocarbon biodegradation. In this paper, we review the occurrence of As in different hydrocarbons and the release of As from these sources into the environment. We also examine the occurrence of As in wastes from hydrocarbon production, including produced water and sludge. Last, we discuss the potential for As release related to waste management, including accidental or intentional releases, and recycling and reuse of these wastes.

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 most massive waste stream generated by conventional and unconventional hydrocarbon exploration is the produced water (PW). The costs and environmental issues associated with the management and disposal of PW, which contains high concentrations of inorganic and organic pollutants, is one of the most challenging problems faced by the oil and gas industry. Many of the current strategies for the reuse and recycling of PW are inefficient because of varying water demand and the spatial and temporal variations in the chemical composition of PW. The chemical composition of PW is controlled by a multitude of factors and can vary significantly over time. This study aims to understand different parameters and processes that control the quality of PW generated from hydrocarbon-bearing Formations by analyzing relationships between their major ion concentrations, O, H, and Sr isotopic composition. We selected PW data sets from three conventional (Trenton, Edwards, and Wilcox Formations) and four unconventional (Lance, Marcellus, Bakken, and Mesaverde Formations) oil and gas Formations with varying lithology and depositional environment. Using comparative geochemical data analysis, we determined that the geochemical signature of PW is controlled by a complex interplay of several factors, including the original source of water (connate marine vs. non-marine), migration of the basinal fluids, the nature and degree of water-mineral-hydrocarbon interactions, water recharge, and processes such as evaporation and ultrafiltration processes, and production techniques (conventional vs. unconventional). The design of efficient PW recycle and reuse strategies requires a holistic understanding of the geological and hydrological history of each Formation and an account of temporal and spatial heterogeneities.

Abstract:
Leveraging waste heat has been considered to have significant potential for promoting the economic feasibility of wastewater treatment in unconventional oil and gas (UOG) production. However, its availability near well sites has not been fully understood and other energy sources may be also feasible. In this work, we quantitatively investigate the viability of using waste heat and well-pad natural gas to power on-site wastewater treatment by membrane distillation (MD) for twenty randomly selected wells located in the Denver-Julesburg (DJ) Basin, U.S. Results show that waste heat produced from on-site electrical loads is insufficient for MD treatment of all the wastewater generated during UOG production (2.2–24.3% of thermal energy required for MD treatment). Waste heat from hydraulic fracturing, which persists only for a short timeframe, is able to meet the full or partial energy requirement during the peak period of wastewater production (17–1005% of thermal energy required for MD treatment within the first two months of production), but this scenario varies among wells and is dependent on the energy efficiency of MD. Compared to waste heat, natural gas is a more consistent energy source. The treatment capacity of MD powered by natural gas at the well pad exceeds full wastewater treatment demands for all the twenty wells, with only two wells requiring short-term wastewater storage. Our work indicates that although waste heat has the potential to reduce the electricity consumption and cost of UOG wastewater treatment, it is unlikely to supply sufficient thermal energy required by MD for long-term treatment. Natural gas can serve as an alternative or complementary energy resource. Further investigations, in particular techno-economic analyses, are needed to identify the best suitable energy source or combination for on-site UOG wastewater treatment.

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:
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:
Key technological breakthroughs, such as hydraulic fracturing (HF) and horizontal drilling, have facilitated the extraction of shale gas. The boost of the shale gas industry has changed global energy markets and led to a decline in natural gas and oil price. Endowed with massive shale gas resources, China is ambitious to develop its shale gas industry, driven by growing energy demand and critical environmental conditions. However, an increasing number of pollution problems coming along with extraction has threatened our environment with atmospheric pollution, water risk, induced seismicity, occupational health, safety, and so on. Because HF needs millions of tons of water and produces a large quantity of effluents, water management becomes one of the most threatened problems. Also, wastewater treatment has become a key factor restricting the development of China’s shale gas industry. In response, international and domestic enterprises have developed a variety of management processes, which are divided into three categories: reinjection, reuse in hydraulic fracturing, and discharge after treatment. In this paper we first summarize Chinese shale gas development, then analyze the production of shale gas wastewater through major extraction techniques. Finally, a review was conducted on current wastewater treatments utilized in China, and advice is offered for future treatment techniques.

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:
Wastewater discharges from cities and industries, especially megacities, and intensive livestock can be considered as main sources of pollution of our rivers and groundwater. Water pollution, therefore, constitutes a major threat to both aquatic ecosystems and human health. Here we address the influence of chemical pollution in waste- and drinking water, their associated potential toxicological effects, as well as, the available technologies for their removal. This opinion paper provides illustrative selected examples covering a broad range for both drinking water and wastewater treatment processes, for which a battery of toxicity tests is applied for their risk assessment. The examples are classified based on five hot topics: (i) Bioassays for toxicity evaluation, (ii) Toxicity of municipal wastewaters, (iii) Toxicity of pharmaceutical residues and hospital wastewaters, (iv) Toxicity of other non-urban effluent examples, and (v) Drinking water treatment processes and toxicity evaluation. 'Chemical analysis combined with batteries of bioassays covering a broad range of endpoints: cytotoxicity, endocrine disruption, genotoxicity, and other types seem to be good way to assess performance/efficiency of the water treatment processes when removing chemical contaminants.. Altogether, while recognizing that water treatment is a cornerstone for water pollution reduction, providing safe water for both human use and its return back to the aquatic environment will be undoubtedly enhanced with the use of ecotoxicity biomonitoring.

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:
This study models emissions quantities and neighboring exposure concentrations of six airborne pollutants, including PM10, PM2.5, crystalline silica, arsenic, uranium, and barium, that result from the disposal of Marcellus shale drill cuttings waste during the 2011-to-2017 period. Using these predicted exposures, this study evaluates current setback distances required in Pennsylvania from waste facilities. For potential residents living at the perimeter of the current setback distance, 274 m (900 ft), a waste disposal rate of 612.4 metric tons per day at landfills (the 99th percentile in record) does not result in exceedances of the exposure limits for any of the six investigated pollutants. However, the current setback distance can result in exceedance with respect to the 24-hr daily concentration standards for PM10 and PM2.5 established in the National Air Ambient Quality Standards (NAAQS), if daily waste disposal rate surpasses 900 metric tons per day. Dry depositions of barium-containing and uranium-containing particulate matter should not be a danger to public health based on these results. To investigate the air quality impacts of waste transportation and the potential for reductions, this paper describes an optimization of landfill locations in Pennsylvania indicating the potential benefits in reduced environmental health hazard level possible by decreasing the distance traveled by waste disposal trucks. This strategy could reduce annual emissions of PM10 and PM2.5 by a mean of 64% and reduce the expected number of annual fatal accidents by nearly half and should be considered a potential risk management goal in the long run. Therefore, policy to limit or encourage reduction of distances traveled by waste removal trucks and manage setback distances as a function of delivered waste quantities is merited. Implications This study shows the necessity of reviewing current setback distance required in Pennsylvania, which might not ensure 24-hr mean PM10 and PM2.5 levels below the values stated in National Ambient Air Quality Standards for the residents living at the perimeter. Furthermore, this study also reveals potential tremendous benefits from optimizing location of landfills accepting drill cuttings within Pennsylvania, with PM10 and PM2.5 emission, total distance traveled shrinking, and number of fatal accidents shrinking by nearly half.

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:
Managing produced water from oil and gas wells constitutes a significant portion of the costs of operating a well. In this work, we have designed two different centralized water treatment facilities capable of managing produced water from oil and gas wells in Texas and Louisiana, both of which convert the produced water into the following valuable resources: ten-pound brine and fresh water. The two main designs each use commercially available technology with varying levels of establishment in treating produced water. Both treatment processes remove oil and grease and suspended solids, reduce the divalent ion concentrations, and concentrate the brines to a near-saturation state. The baseline design uses chemical precipitation to remove the divalent ions to meet the reuse specifications, whereas the advanced design uses nanofiltration (NF) membranes to separate divalent ions and uses reserve osmosis (RO) membranes to partially concentrate the brine. Both models use mechanical vapor recompression to concentrate the brine up to NaCl saturation. The baseline process is shown to be cost-effective for low-hardness brines. In the case of high hardness, the chemical precipitation step is cost-prohibitive. We find that NF membranes are a promising alternative to chemical precipitation as a means of separating monovalent and divalent ions.

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:
Mixing of acid mine drainage (AMD) and hydraulic fracturing flowback fluids (HFFF) could represent an efficient management practice to simultaneously manage two complex energy wastewater streams while reducing freshwater resource consumption. AMD discharges offer generally high sulfate concentrations, especially from the bituminous coal region of Pennsylvania; unconventional Marcellus shale gas wells generally yield HFFF enriched in alkaline earth metals such as Sr and Ba, known to cause scaling issues in oil and gas (O&G) production. Mixing the two waters can precipitate HFFF-Ba and -Sr with AMD-SO4, therefore removing them from solution. Four AMD discharges and HFFF from two unconventional Marcellus shale gas wells were characterized and mixed in batch reactors for 14 days. Ba could be completely removed from solution within 1 day of mixing in the form BaxSr1–xSO4 and no further significant precipitation occurred after 2 days. Total removal efficiencies of Ba + Sr + SO4 and the proportion of Ba and Sr in BaxSr1–xSO4 depended upon the Ba/Sr ratio in the initial HFFF. A geochemical model was calibrated from batch reactor data and used to identify optimum AMD–HFFF mixing ratios that maximize total removal efficiencies (Ba + Sr + SO4) for reuse in O&G development. Increasing Ba/Sr ratios can enhance total removal efficiency but decrease the efficiency of Ra removal. Thus, treatment objectives and intended beneficial reuse need to be identified prior to optimizing the treatment of HFFF with AMD.

Abstract:
Shale gas extraction processes generate a large amount of hypersaline wastewater, whose spills or discharges may significantly increase the bromide levels in downstream water supplies and result in the formation of brominated disinfection byproducts (DBPs) upon chlorination. Although a few studies have investigated selective bromide removal from produced water, the low removal efficiencies and complex system setups are not desirable. In this study, we examined a simple cost-effective approach for selective bromide removal from produced water relying on the oxidation by un-activated peroxymonosulfate (PMS). More than 95% of bromide was removed as Br2(g) in less than 10 min under weakly acidic conditions without significant formation of Cl2(g) even when the chloride concentration was more than two orders of magnitude higher. A kinetic model considering the involved reactions was then developed to describe the process well under various reaction conditions. The organic compounds in produced water neither noticeably lowered bromide removal efficiency nor reacted with the halogen species to form halogenated byproducts. The tests in batch and continuously-stirred tank reactor systems suggested that it was feasible to achieve both high bromide removal and neutral effluent pH such that further pH adjustment was not necessary before discharge. After the treatment, the effect of the produced water on DBP formation was largely eliminated.

Abstract:
The data in this report are associated with https://doi.org/10.1016/j.scitotenv.2020.137085 and include data on water volumes and water quality related to the major unconventional oil and gas plays in the U.S.. The data include volumes of water co-produced with oil and gas production, county-level estimates of annual water use volumes by various sectors, including hydraulic fracturing water use, and the quality of produced water. The data on volumes of produced water and hydraulic fracturing water volumes were obtained from the IHS Enerdeq and FracFocus databases. Water use in other sectors were obtained from the U.S. Geological Survey water use database. Data on produced water quality were obtained from the USGS produced waters database.

Abstract:
Membrane-based desalination system under consideration for shale gas fracturing flowback wastewater treatment involves ultrafiltration (UF), reverse osmosis (RO) and storage tanks. The membrane unit (UF, RO) consists of online washing, operation and offline chemical washing sub-units. These sub-units operate in semi-continuous mode and have the similar characteristics as batch water-using processes. Based on their semi-continuous behaviors, the models of UF and RO sub-units are developed. The objective is to maximize the total water production ratio and profit while minimize storage tank capacity. Three nonlinear programming optimization models are developed for optimal design of UF-RO treatment system for shale gas fracturing flowback wastewater. Two scenarios – fixed schedule and fixed operating period for UF/RO treatment sub-units are investigated. Results show that with the increasing the operation duration of treatment sub-units, the water production ratio and profit will increase. The schedule of treatment sub-units has significant impact on the water-storage profiles, without adversely affecting the water production ratio. The proposed approach can guide the design of UF-RO desalination system.

Abstract:
Unconventional shale gas exploitation presents complex problems in terms of radioactive waste disposal. Large volumes of saline produced water resulting from hydraulic fracturing are typically enriched in radium isotopes, up to several hundred Bq/dm3, orders of magnitude above national discharge limits. There is a need, therefore, to decontaminate the fluid prior to discharge, preferably by creating a less problematic radium-containing, solid waste form. Barite (barium sulphate) co-precipitation is a cost-effective method for achieving these objectives, provided the process can be controlled. In this work, radium recovery of ~90% has been achieved for simulant produced waters containing 100 Bq/dm3, using a single, optimised co-precipitation step. However, salinity has a significant effect on the efficiency of the process; higher salinity solutions requiring substantially more reagent to achieve the same recovery. If >90% radium removal is sought, multiple co-precipitation steps provide a much faster alternative than post-precipitation recrystallization of the barite solid phase, albeit at higher cost. The resulting solid waste has a relatively high specific radium activity but a much smaller volume, which presents a less intractable disposal problem for site operators than large volumes of radium-contaminated fluid.

Abstract:
Produced water is the largest volume of waste product generated during oil and natural gas exploration and production. The traditional method to dispose of produced water involves deep well injection, but this option is becoming more challenging due to high operational cost, limited disposal capacity, and more stringent regulations. Meanwhile, large volumes of freshwater are used for hydraulic fracturing. The goal of this study is to develop cost-effective technologies, and optimize system design and operation to treat highly saline produced water (120–140 g/L total dissolved solids) for hydraulic fracturing. Produced water was collected from a salt water disposal facility in the Permian Basin, New Mexico. Chemical coagulation (CC) using ferric chloride and aluminum sulfate as coagulants was compared with electrocoagulation (EC) with aluminum electrodes for removal of suspended contaminants. The effects of coagulant dose, current density, and hydraulic retention time during EC on turbidity removal were investigated. Experimental results showed that aluminum sulfate was more efficient and cost-effective than ferric chloride for removing turbidity from produced water. The optimal aluminum dose was achieved at operating current density of 6.60 mA/cm2 and 12 min contact time during EC treatment, which resulted in 74% removal of suspended solids and 53%–78% removal of total organic carbon (TOC). The energy requirement of EC was calculated 0.36 kWh/m3 of water treated. The total operating cost of EC was estimated $0.44/m3 of treated water, which is 1.7 or 1.2 times higher than CC using alum or ferric chloride as the coagulant, respectively. The EC operating cost was primarily associated with the consumption of aluminum electrode materials due to faradaic reactions and electrodes corrosions. EC has the advantage of shorter retention time, in situ production of coagulants, less sludge generation, and high mobility for onsite produced water treatment. The fine particles and other contaminants after coagulation were further treated in continuous-flow columns packed with different filter media, including agricultural waste products (pecan shell, walnut shell, and biochar), and new and spent granular activated carbon (GAC). Turbidity, TOC, metals, and electrical conductivity were monitored to evaluate the performance of the treatment system and the adsorption capacities of different media. Biochar and GAC showed the greatest removal of turbidity and TOC in produced water. These treatment technologies were demonstrated to be effective for the removal of suspended constituents and iron, and to produce a clean brine for onsite reuse, such as hydraulic fracturing.

Abstract:
This work addresses three significant issues associated with hydraulic fracturing in US shale fields: flaring/venting of excess natural gas, disposal of flowback water and freshwater procurement. Flaring/venting of excess gas is a significant contributor to global emissions. This work presents a novel utilization concept, wherein excess gas is used onsite to power reverse osmosis (RO)-based treatment of flowback water to supply freshwater for oilfield operations. This study details technical and techno-economic analyses of the above concept. An analytical model is extended and improved to quantify RO-based freshwater production for flowback water of different salinities. The technical performance of RO systems is analyzed and compared with two competing gas utilization technologies (thermal desalination, atmospheric water harvesting). The use of these technologies in the top eight US shale fields is analyzed, and a techno-economic analysis of RO-based water treatment is conducted. Results indicate that this concept will significantly benefit the Eagle Ford and Niobrara shales. It can meet 200% of water requirements and reduce wastewater disposal by 60% in the Eagle Ford. Furthermore, such RO-based projects can have favorable payback periods of as low as one year. Importantly, this waste-to-value concept has worldwide relevance since the underlying issues are present globally.

Abstract:
Hydraulic fracturing of shale gas extraction generates numerous flowback and produced water (FPW), which will cause huge pollution if not properly treated. Gravity-driven membrane with economic advantages was applied as a pretreatment for desalinating this wastewater. The effects of membrane materials (polyvinylidene fluoride (PVDF) and polyvinylchloride (PVC)) with different mean pore sizes, porosities, contact angles, and pure water permeabilities and hydrostatic pressures (40 and 120 mbar) were investigated. The setups were operated for 90 days and the fluxes stabilized at about 0.87–1.00 L/(m2 h). PVDF membranes with higher price, had 6 % higher stable fluxes than PVC membranes, and the extracellular polymeric substances (EPS) contents in fouling layer of PVDF membranes were 10 %–20 % lower than those of PVC membranes. At higher pressures, the stable fluxes increased by only 8 %, but the total resistances increased by nearly 180 %, and there were more EPS, dissolved organic carbon, Na+, Ca2+, Mg2+, Cl− and NO3− on the fouling layer at 120 mbar. A denser cake layer was formed at a higher hydrostatic pressure, as observed by a scanning electron microscope and energy dispersive spectroscopy. Membrane properties and pressures had no significant effect on permeate quality (p > 0.05).

Abstract:
Salinization of global freshwater resources is a concerning health and economic issue of the 21st century and requires serious management and study to understand how, and by what mechanism, Total Dissolved Solids (TDS) is changing in major watersheds. Oil and gas (O&G) produced water is a complex and saline (10–300 g/L TDS) wastewater often disposed to surface waters post-treatment. However, in western U.S. states, beneficial use of minimally treated O&G produced water discharged to ephemeral streams is permitted through the EPA National Pollutant Discharge Elimination System (NPDES) for agriculture and wildlife propagation. In a remote Wyoming study region, beneficial use of O&G NPDES effluents annually contributes 13 billion L of water to surface water resources. The primary O&G TDS constituents are sulfate and sodium followed by chloride and calcium. Significant TDS increases from 2013 to 2016 in a large perennial river (River C) impacted by O&G effluent disposal, slight TDS increases in a perennial river (River B) and chronically elevated TDS (upwards of 2500 mg/L) in a smaller tributary (Tributary A) comprised mainly of O&G effluents led to an investigation of O&G impacts to surface waters in the region. Chloride-normalized metal ratios such as Br/Cl and δ2H and δ18O distinguished evaporation as the mechanism for increasing TDS derived from O&G on Tributary A, which is causing O&G effluents that meet NPDES regulations to not only exceed outfall regulations downstream where it is beneficially used mainly for irrigation and drinking water but also exceed aquatic life and livestock recommended limits. 87Sr/86Sr and δ34SSO4 suggested minor impacts from O&G TDS loading on River C but also support an additional salinity source, such as streambed geological controls, the cause of significantly increasing TDS. While lithium isotopes provided insight into the O&G effluent origin (δ7Li ranged 9–10‰) and water-sediment interactions along O&G effluent streams, they did not function as distinct salinity tracers in the larger downstream rivers. This study suggests a multi-isotope (87Sr/86Sr and δ34SSO4) approach is often necessary for fingerprinting salinization sources and determining best management practices because multiple salinity sources and environmental mechanisms may need to be identified to protect water quality.

Abstract:
Hydraulic fracturing (HF), or “fracking,” is the driving force behind the “shale gas revolution,” completely transforming the United States energy industry over the last two decades. HF requires that 4–6 million gallons per well (15,000–24,000 m3/well) of water be pumped underground to stimulate the release of entrapped hydrocarbons from unconventional (i.e., shale or carbonate) formations. Estimated U.S. production volumes exceed 150 billion gallons/year across the industry from unconventional wells alone and are projected to grow for at least another two decades. Concerns over the environmental impact from accidental or incidental release of produced water from HF wells (“U-PW”), along with evolving regulatory and economic drivers, has spurred great interest in technological innovation to enhance U-PW recycling and reuse. In this review, we analyze U-PW quantity and composition based on the latest U.S. Geographical Survey data, identify key contamination metrics useful in tracking water quality improvement in the context of HF operations, and suggest “fit-for-purpose treatment” to enhance cost-effective regulatory compliance, water recovery/reuse, and resource valorization. Drawing on industrial practice and technoeconomic constraints, we further assess the challenges associated with U-PW treatment for onshore U.S. operations. Presented are opportunities for targeted end-uses of treated U-PW. We highlight emerging technologies that may enhance cost-effective U-PW management as HF activities grow and evolve in the coming decades.

Abstract:
Membrane-based processes are increasingly applied in shale gas flowback and produced water (SGFPW) reuse. However, severe membrane fouling remains a big challenge for maintaining long-term operation. The present paper investigates for the first time the performance of the integrated ozonation-ultrafiltration (UF)-reverse osmosis (RO) process to treat SGFPW for water reuse. Results showed that pre-ozonation could efficiently mitigate membrane fouling. The integrated process removed more than 98% of total dissolved solids (TDS), 96% of dissolved organic carbon (DOC), and 96% of all ionic constituents in SGFPW. Significantly, the effluent could meet the water quality standards of irrigation, livestock water, and surface discharge. Removal of targeted pollutants is negatively influenced by the high concentrations of chloride and bromide because of their high reactivity with ozone and hydroxyl radicals (HO·). Through pre-ozonation, the total fouling index and the hydraulically irreversible fouling index decreased by more than 85% and 47%, respectively. The variation of particle sizes in SGFPW by pre-ozonation manifested the mechanism of UF membrane fouling mitigation, i.e., the pre-ozonation decomposed macromolecular organics into low fractions. The optimal ozone flow rate is 0.4 L/min. Results demonstrated that a sustainable SGFPW reuse could be achieved by the current integrated process.

Abstract:
Reusing produced water for hydraulic fracturing simultaneously satisfies challenges of fresh water sourcing and the installation/operation of an extensive disposal well infrastructure. Herein, we systematically and rigorously investigate produced water treatment for reuse during hydraulic fracturing. Highly saline and turbid produced water from the Permian Basin was treated by adding chlorine as an oxidant, FeCl3 as the primary coagulant, and an anionic polymer to induce high rate sedimentation to generate “clean brine” by removing suspended solids and iron over a range of environmentally relevant temperatures. Mobile phone video capture, optical microscopy, and digital image/video analysis were employed to characterize floc morphology and measure its size and settling velocity. Conformational changes of the polymeric coagulant between 4 and 44 °C were inferred from viscosity and dynamic light scattering measurements providing clues to its performance characteristics. Floc settling velocities measured over the entire range of polymer dosages and temperatures were empirically modelled incorporating their fractal nature, average size, and the viscosity of the produced water using only a single fitting parameter. Juxtaposing the anionic polymer with the hydrolyzing metal-ion coagulant effectively destabilized the suspension and caused floc growth through a combination of enmeshment, adsorption and charge neutralization and inter-particle bridging as evidenced by Fourier transform infrared spectroscopy and thermogravimetric analysis. Very high turbidity (≥98%) and total iron (≥97%) removals were accomplished even with very short flocculation and sedimentation times of only 6 min each suggesting the feasibility of this approach to reuse produced water for hydraulic fracturing.

Abstract:
Membrane filtration is a technique that can be successfully applied to remove oil from stable oil-in-water emulsions. This is especially interesting for the re-use of produced water (PW), a water stream stemming from the petrochemical industry, which contains dispersed oil, surface-active components and often has a high ionic strength. Due to the complexity of this emulsion, membrane fouling by produced water is more severe and less understood than membrane fouling by more simple oil-in-water emulsions. In this work, we study the relation between surfactant type and the effect of the ionic strength on membrane filtration of an artificial produced water emulsion. As surfactants, we use anionic sodium dodecyl sulphate (SDS), cationic hexadecyltrimethylammonium bromide (CTAB), nonionic Triton TMX-100 (TX) and zwitterionic N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDAPS), at various ionic strengths (1, 10, 100 mM NaCl). Filtration experiments on a regenerated cellulose ultrafiltration (UF) membrane showed a pronounced effect of the ionic strength for the charged surfactants SDS and CTAB, although the nature of the effect was quite different. For anionic SDS, an increasing ionic strength leads to less droplet-droplet repulsion, allowing a denser cake layer to form, resulting in a much more pronounced flux decline. CTAB, on the other hand leads to a lower interfacial tension than observed for SDS, and thus more deformable oil droplets. At high ionic strength, increased surfactant adsorption leads to such a low oil-water surface tension that the oil droplets can permeate through the much smaller membrane pores. For the nonionic surfactant TX, no clear effect of the ionic strength was observed, but the flux decline is very high compared to the other surfactants. For the zwitterionic surfactant DDAPS, the flux decline was found to be very low and even decreased with increasing ionic strength, suggesting that membrane fouling decreases with increasing ionic strength. Especially promising is that at lower surfactant concentration (0.1 CMC) and high ionic strength no flux decline was observed, while a high oil retention (85%) was obtained. From our results, it becomes clear that the type of the surfactant used is crucial for a successful application of membrane filtration for PW treatment, especially at high ionic strengths. In addition, they point out that the application of zwitterionic surfactants can be highly beneficial for PW treatment with membranes.

Abstract:
The shale gas flowback and produced water (FPW) from hydraulic fracturing in the Sichuan province of China has relatively low to moderate levels of total dissolved solids (<20 g/L) and organics (<50 mg/L of dissolved organic carbon). As such, a combined ultrafiltration (UF), reverse osmosis (RO) system can be successfully applied to desalinate this feed water with the goal of reuse. However, the concentration of influent organic matter and particulates in the UF and RO stage is high, and the overall ionic and organics composition is highly complex, so that the membrane processes do not perform well, also due to fouling. To ensure the long-term and efficient operation of the UF-RO stages, a combined pretreatment of the FPW with coagulation and adsorption was investigated. The effect of different parameters on the performance on the system was studied in detail. Overall, the coagulation-adsorption pre-treatment greatly reduced fouling of the membrane processes, thanks to the high removal rate of turbidity (98.8%) and dissolved organic carbon (86.3%). The adsorption of organic matter by powdered activated carbon was best described by the Freundlich equilibrium model, with a pseudo second-order model representing the adsorption kinetics. Also, the various ions had competitive removal rates during the adsorption step, a phenomenon reported for the first time for FPW treatment. Also, an optimal dose of activated carbon existed to maximize fouling reduction and effluent quality. The overall treatment system produced a high-quality water streams, suitable for reuse.

Abstract:
Oil and gas (O&G) production in the United States is expected to grow at a substantial rate over the coming decades. Environmental sustainability related to water consumption during O&G extraction can be addressed through treatment and reuse of water returning to the surface after well completion. Water quality is an important factor in reuse applications, and specific treatment technologies must be utilized to remove different contaminants. Among others, biological active filtration can remove dissolved organic matter as a pre-treatment for surface discharge or to facilitate reuse in such applications as hydraulic fracturing, dust suppression, road stabilization, and crop irrigation. Yet, the formation of byproducts during treatment of O&G wastewater remains a concern when evaluating reuse applications. In this study, we investigated the previously unnoticed biotic formation of iodinated organic compounds (IOCs) such as triiodomethane during biological treatment of O&G wastewater for beneficial reuse. Iodide and several IOCs were quantified in O&G produced water before and after treatment in biological active filters filled with different media types over 13 weeks of operation. While iodide and total IOCs were measured at concentrations <53 mg/L and 147 μg/L, respectively, before biological treatment, total IOCs were measured at concentrations close to 4 mg/L after biological treatment. Triiodomethane was the IOC that was predominantly present. IOC formation had a negative strong correlation (r = −0.7 to −0.8, p < 0.05, n = 9) with iodide concentration in the treated O&G wastewater, indicating that iodide introduced to the biological active filter system was utilized in various reactions, including biologically mediated halogenation of organic matter. Additionally, iodide-oxidizing bacteria augmented in the treated produced water pointed towards potential negative environmental implications when releasing biologically treated halide-rich wastewater effluents to the aquatic environment.

Abstract:
Produced water (PW) is the largest by-product of the oil and gas industry. Its management is both economically and environmentally costly. PW reuse for irrigation offers an alternative to current disposal practices while providing water to irrigators in drylands. The aim of this investigation was to evaluate the environmental effects of irrigation with PW. The SALTIRSOIL_M model was used to simulate the irrigation of sugar beet with 15 PWs of a wide range of qualities in four climates of different aridity and on four contrasting soil types. The impacts on soil salinity, sodicity and pH as well as on crop yield and drainage water salinity were estimated. Well-drained soils with low water content at field capacity (Arenosol) are less sensitive to salinisation while a relatively high gypsum content (Gypsisol) makes the soil less vulnerable to both sodification and salinisation. On the contrary, clayey soils with higher water content at field capacity and lower gypsum content must be avoided as the soil structural stability as well as a tolerable soil electrical conductivity for the crop cannot be maintained on the long-term. Soil pH was not found to be sensitive to PW quality. Drainage water quality was found to be closely linked to PW quality although it is also influenced by the soil type. The impact of drainage water on the aquifer must be considered and reuse or disposal implemented accordingly for achieving sustainable irrigation. Finally, increasing aridity intensifies soil and drainage water salinity and sodicity. This investigation highlights the importance of adapting the existing irrigation water quality guidelines through the use of models to include relevant parameters related to soil type and aridity. Indeed, it will support the petroleum industry and irrigators, to estimate the risks due to watering crops with PW and will encourage its sustainable reuse in water-scarce areas.

Abstract:
Unconventional oil and gas extraction is on the rise across the United States and comprises an integral component in meeting the nation’s energy needs. The primary by-product of this industrious process is produced water, which is a challenging matrix to remediate because of its complex physical and chemical composition. Forward osmosis is a viable option to treat high-salinity produced water; however, fouling has been an issue. This study aimed to treat produced water before using forward osmosis as a remediation option. Trials consisted of a series of five experiments in order to evaluate the performance of the membrane. Samples were treated by centrifugation, activated carbon, filtration, ferric chloride, as well as coagulants and a polymer. It can be concluded that forward osmosis can be used to extract water from high-salinity oil field brines and produced water, and that pretreating the produced water decreased the tendency for fouling. The pretreatment with the overall best performance was activated carbon, which also yielded the lowest total organic carbon concentrations of 1.9 mg/L. During remediation trials using produced water pretreated with activated carbon as the feed solution, there was a 14% decrease in flux over the course of the 7 h trials. The membrane performance was restored after washing.

Abstract:
Shale oil and gas exploitation not only consumes substantial amounts of freshwater but also generates large quantities of hazardous wastewater. Tremendous research efforts have been invested in developing membrane-based technologies for the treatment of shale oil and gas wastewater. Despite their success at the laboratory scale, membrane processes have not been implemented at full scale in the oil and gas fields. In this article, we analyze the growing demands of wastewater treatment in shale oil and gas production, and then critically review the current stage of membrane technologies applied to the treatment of shale oil and gas wastewater. We focus on the unique niche of those technologies due to their advantages and limitations, and use mechanical vapor compression as the benchmark for comparison. We also highlight the importance of pretreatment as a key component of integrated treatment trains, in order to improve the performance of downstream membrane processes and water product quality. We emphasize the lack of sufficient efforts to scale up existing membrane technologies, and suggest that a stronger collaboration between academia and industry is of paramount importance to translate membrane technologies developed in the laboratory to the practical applications by the shale oil and gas industry.Open image in new window

Abstract:
Shale gas fracturing flowback water (SGFFW) contained high concentration of colloids and organics which can cause severe fouling for membrane distillation (MD). It is desirable to identify the key foulants for MD fouling for real SGWWFs treatment. In this study, coagulation and membrane filtrations with different molecular weight cut-off (MWCO) were applied to try to separate the different fractions and identify the key fouling/wetting component and evaluate the efficacy in alleviating MD fouling for real SGWWFs treatment. The organics with molecular weight of 20 kDa, which also belongs to humic acid-like components, protein-like components and fulvic acid-like components removed by coagulation can effectively mitigated MD fouling. However, the rest fraction of high molecular weight components of 20 kDa and low molecular weight components (i.e., 200 Da) removed by UF membrane, has less significant effect on the water flux of MD. Despite the further removal of small MW compounds, and even the removal of Ca2+ and Mg2+by NF slightly affect the water flux, indicating that the aromatic protein (21.2%) could cause severe wetting of the MD membrane. However, SEM-EDS demonstrated that the combination of organic fouling and crystallization of Ca and Ba contribute to the fouling of MD membrane. These studies demonstrated the removal of high molecular weight colloids by coagulation and aromatic protein with the molecular weight of 200Da might be vital for MD fouling and wetting, respectively.

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

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

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

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

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

Abstract: