Challenges and Solutions to Manage Flowback Water in Shale Gas Industry Yuanqing Zhu 1.

ABSTRACT Development of shale gas has rapidly expanded in the past few years to meet global energy demands. However, a significant drawback is that the waste water produced after hydraulic fracturing, known as flowback water, has become a local water problem. Based on our understanding of the formation and properties of flowback water, this paper focuses on analyzing four major options currently available for the treatment of flowback water: underground injection, discharge to wastewater plants, on-site water reuse and total dissolved solids (TDS) removal technologies. Among these technologies, the most promising one is on-site water reuse, but additional research and development of the technology is needed. 2. INTRODUCTION With the limitation of conventional natural gas resources, shale gas has become a rapidly increasing source of U.S. gas supplies and has experienced an exponential growth since 2000 (Continental Economics, Inc., 2012). Shale gas production is expected to grow more than threefold and to eventually represent 24% of the total natural gas production in the United States (EIA, 2011). However, natural gas extraction from shale will have to become environmentally sustainable and economically feasible to develop this vast energy source in the future. Compared to conventional oil/gas production or coal, the shale gas tends to require more water, which may lead to water pollution, when hydraulic fracturing is used to liberate the gas. After hydraulic fracturing, large volumes of water, also known as flowback water or produced water, which contains very high concentrations of TDS return to the surface. The owback water has increased levels of salinity as well as some metals such as barium and strontium, low level of radionuclides, and some volatiles (Jenner et al., 2013), which may lead to health and environmental problems in surface water and groundwater resources. As the amount of flowback water generated in the US keeps increasing, (It is currently about 2.0 million gallons per day (Benko et al., 2008)), wise water management solutions are critical in order to maintain responsible stewardship of the natural environment while pursuing the favorable economics of shale gas production. In this paper, current and prospective treatment technologies are discussed and compared based on case studies and literature review. 3. POLLUTANTS TO BE REMOVED The flowback water, which before being used in gas extraction is called frac water, is typically more than 98 percent fresh water and sand by volume. After hydraulic fracturing, the flowback water goes back to the ground as a brine solution that includes high concentrations of salts, metals, oils, greases, and soluble organic compounds, both volatile and semi volatile, as shown in table 1. Although the constituents of flowback water vary from one basin to another, generally speaking, the flowback water contains three main pollutants: a. High concentration of TDS, which is nearly five times that of seawater (TDS~36,000mg/L); b. High concentration of metals that can cause scaling, such as Barium, Strontium;

c. Hydrocarbon products and volatile organic compounds, such as oils, greases, and benzene. Other possible pollutants are naturally occurring radioactive material (radium, thorium, uranium). Chemical additives to frac water include potassium chloride, guar gum, ethylene glycol, and sodium carbonate (Rahm et al., 2011). During the flowback period, which usually lasts up to two weeks, approximately 10 to 40% of the fracturing water returns to the surface (Arthur et al., 2008) with a typical volumetric flow rate of 1000 m3/d (Gregory et al., 2011). The flowback water is usually impounded at the surface for further subsequent disposal, treatment, or reuse. Table 1 (Gregory et al., 2011). Typical range of concentrations for some common constituents of flowback water from natural gas development in the Marcellus Shale Low concentrations are from early flowback at one well. Medium concentrations are from late flowback at the same well for which the low concentrations are reported.

4. CURRENT MANAGEMENT OF FLOWBACK WATER 4.1 Underground Injection Currently, deep-well injection is the primary means for flowback water disposal, as regulated by the EPA in its direction for Class II (disposal) underground injection control. However, in many areas where shale gas production will be abundant, deep-well injection sites are not available. For example, in 2008 there were over 11,000 Class II disposal wells in Texas whereas only seven wells were available for receiving flowback water in the whole state of Pennsylvania (Gregory et al., 2011). Moreover, the suggestion that injection of gas-drilling

wastewater regulators led to a dozen earthquakes in the northeast of Ohio (Smyth, 2012) also makes the well injection solution less attractive. 4.2 Discharge to Wastewater Treatment facilities Another off-site treatment to flowback water is to haul it to publicly own municipal wastewater treatment plants (POTWs) or commercial wastewater disposal facilities. Before blending the produced water with other municipal wastewater, some general pretreatment steps are required to remove particular pollutants in flowback water. Taking the various wastewater disposal facilities in the case of Marcellus Shale (Kargbo et al., 2010) as an example, after first passing through a strainer to remove large debris, the water is settled in tanks to allow removal of solids and any free oil. Then the water is sent to treatment tanks where the pH is raised using sodium sulfate (Na2SO4) or lime to facilitate the removal of dissolved barium and other metals. From there, the water flows to clarifiers to settle with the help of certain coagulants. The current process removes metals, but it does not remove TDS. This causes certain problems when the treated water was discharged to the municipal sewer system and sent to the citys wastewater treatment plant. The proper daily operation of POTWs requires the flowback to occupy only 5% of all threated water. Since the TDS in the current flowback water is too high, the daily treatment amount is limited, making this process an inadequate approach. 4.3 On-Site Water Reuse One of the most promising technologies for management of flowback water is its reuse in subsequent hydraulic fracturing operations, with the benefit of minimizing the volume of water needed as well disposed. In practice, some of the operators are trying to recycle some, to all, of their flowback water (Kargbo et al., 2010) by blending it with freshwater without treating it. The challenges of this lie mainly in two areas: the quality of reuse water and the flowback water recovery rate. The three main adverse effects of pollutants in flowback water regarding the quality of water reuse are a. The effectiveness of friction reducers, which is the key component in fracturing water, may be decreased at high TDS concentrations (Kamel and Shah 2009); b. The divalent cations in the flowback water can form stable carbonate and sulfate precipitates in the wellbore if the flowback water is reinjected. In particular, barium and strontium form very low-solubility solids with sulfate, while high calcium concentrations may lead to calcite formation (Gregory et al., 2011); c. Microorganisms can corrode the pipe and block the well pores. These drawbacks of flowback water can greatly reduce the water recovery rate in a closed-loop water plan. It is estimated that only 5% of flowback water could be used in the final blend without pre-conditioning or remediation (Blauch, 2010), indicating effective treatments before flowback water reuse are needed to minimize the amount of fresh water needed. 4.4 TDS Removal Technologies The extremely high concentration of TDS in flowback water is the main challenge in its treatment. There are currently two viable options for TDS removal: membrane filtration and thermal distillation (Waterworld, 2012).

For the membrane approach, a commonly-deployed method is an integrated three-stage mobile reverse osmosis (RO) system. The first stage is pre-treatment using chemical flocculation, clarification and oil removal; the second stage is cold lime softening; and the third stage uses micro-, ultra- and nano-filtration, as well as reverse osmosis (Waterworld, 2012). However, stricter pre-treatment requirements must be met in order to avoid significant fouling and scaling leading to costly membrane replacement. More importantly, experiments have shown that the treatment of flowback water using RO is considered to be economically infeasible for waters containing more than 40,000 mg/L TDS (Cline et al., 2009). The most suitable method to deal with TDS higher than 40,000 mg/L is thermal distillation via a mechanical vapor recompression (MVR) evaporator unit (Gregory et al., 2011). Here, the incoming flowback water is boiled to produce steam, while all dissolved solids remain in the concentrate. The resulting steam is then condensed into pure water. Though partial energy has been saved in MVR units by using compressed vapor to preheat the influent, the total energy costs are still the highest among all the available treatment technologies, and the treatable flow rates (300m3/d) are quite limited (Veil et al., 2008). Several other technologies have been or are being developed for treating flowback water, including ion exchange and capacitive deionization (Gregory et al., 2011), but each has its limitations, mainly regarding the acceptable TDS treatment level or the daily operation volume. 5. PROSPECTIVE TECHNOLOGIES IN FLOWBACK WATER TREATMENT My review of current available technologies revealed that while underground injection and discharge into municipal wastewater treatment plant are not long-term strategies, a combination of physical and chemical treatment methods to increase the water quality and efficiency in on-site water use is the most promising approach to address flowback water problem. The prospective solutions should take into account the three main challenges in water reuse of flowback water: a. TDS in flowback water can greatly reduce the effectiveness of friction reducers. New kinds of salt compatible reducers, such as liquid-polymer emulsions made of nontoxic, inert silica particles ranging in size from nano- to micro-scale emulsifiers (Blauch et al., 2010), were developed, and they are currently under further environmental and ecoctoxicity tests. b. Divalent cation concentration results in geochemical precipitation. To reduce this concentration, pretreatment with a neutral pH iron-control agent was found (Blauch et al., 2010) suitable for reducing the metal concentration in flowback water. Sodium carbonate and sodium hydroxide were also applied for this target. c. Microorganisms pose a threat to the pipeline and environment. An environmentally sound quick-kill of microorganisms should be developed for aqueous biomass control, such as dibrominated nitrilopropionamide (Blauch et al., 2010) to decrease H2S sourcing and equipment erosion. Keys to successful reuse of flowback water are development of chemical additives and processes involving analysis of water chemistry, flow-loop testing, and geochemical modeling in the establishment of treatment and fresh water dilution standards to enable fracturing fluid reuse. Although each of the additives or treatment technologies deals with only one challenge, the

combination of the traditional treatment pathway and the newly developed methods makes it possible to craft a satisfying flowback water reuse plan. An example of such a plan might be to add the pre-treatment steps of POTWs to the water reuse loop and to use membrane filtration and thermal distillation for the final wastewater treatment after cycles of reuse. 6. MONITORING AND REGULATION SYSTEM Robust regulatory oversight will be an important element to assure environmental and public protection from the polluting effects of shale gas extraction. Under current U.S. laws, some aspects of hydraulic fracturing are regulated by the Clean Water Act, the Clean Air Act, and the Safe Drinking Water Act, but no regulation regarding flowback water has been crafted (Arthur et al., 2008). Moreover, as the flowback water is usually impounded in open space for 35 months before proper treatment is applied, the potential leakage and pollution should also be taken into account. For example, there are worries about the formation of Naturally Occurring Radioactive Materials (NORM), such as 226Ra and 228Ra in the flowback and its radioactive hazards due to the temperature and pressure changes during oil and gas production. Potential disposal options for radioactive wastewater are currently unclear (Kargbo et al., 2010). One approach is for the drilling companies to survey all wastewater for radioactivity before it is allowed to leave the well site. This will require the improvement of monitoring technology for contaminants such as NORM. 7. CONCLUSION AND OUTLOOK While many options are available for the treatment of flowback to meet the challenge of exponentially growing hydraulic fracturing residue wastewater, some traditional treatment paths such as deep-well injection and treatment in POTWs cannot keep up with the ever-growing flowback water treatment needs. Membrane filtration and thermal distillation are the suitable methods for high TDS removal, but the treatment capacity is not keeping up with intensive energy demand. As on-site flowback water reuse is the most promising approach, further investigation of new chemical additives and treatment steps is important to increase the reuse water quality and efficiency. Besides, the huge differences of flowback water at different sites contribute to the complexity of the problem as the optimized strategies for one basin or locality may not apply for others. Analysis of water chemistry, flow-loop testing, and geochemical modeling based on the nature of the sites will therefore be important in devising new water reuse solutions. 8. REFERENCES Arthur JD, Bohm B, Layne M. 2008. Hydraulic Fracturing Considerations for Natural Gas Wells of the Marcellus Shale. The Ground Water Protection Council 2008 Annual Forum, Cincinnati, OH, September 2124, 2008, 16 pp Benko KL, Drewes JE. 2008. Produced Water in the Western United States: Geographical Distribution, Occurrence, and Composition. Environmental Engineering Science, Vol 25(2): 239-246

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