THE DEVELOPING PROBLEM OF BROMINATED ORGANICS OF THE PUBLIC DRINKING WATER SUPPLY IN SOUTH WESTERN PENNSYLVANIA by David Karl Schultise Bachelor of Science, University of Pittsburgh, 2005 Submitted to the Graduate Faculty of Graduate School of Public Health in partial fulfillment of the requirements for the degree of Master of Public Health University of Pittsburgh 2013 i UNIVERSITY OF PITTSBURGH Graduate School of Public Health This essay is submitted by David Karl Schultise on April 17, 2013 and approved by Essay Advisor: Aaron Barchowsky, PhD _______________________________________ Professor Department of Environmental and Occupational Health Graduate School of Public Health University of Pittsburgh Essay Reader: Leonard Casson, PhD, P.E. _______________________________________ Associate Professor Department of Civil and Environmental Engineering Swanson School of Engineering University of Pittsburgh ii Copyright © by David Karl Schultise 2013 iii Aaron Barchowsky, PhD THE DEVELOPING PROBLEM OF BROMINATED ORGANICS OF THE PUBLIC DRINKING WATER SUPPLY IN SOUTH WESTERN PENNSYLVANIA David Karl Schultise, MPH University of Pittsburgh, 2013 ABSTRACT Shale found in the United States and globally represents a source of energy and economic impact too enormous to ignore. However, there are potential environmental impacts that have been discovered utilizing the unconventional drilling methods needed to extract gas from shale. In the U.S., there are environmental concerns involving to air and water quality as well as other factors such as impacts on communities. In Wyoming, where air quality is normally quite good, has seen extremely high levels of ozone since the gas extraction has begun. In other areas such as Pennsylvania there have been concerns of shale drilling and the contamination of private drinking water wells. Many research studies have focused on methane migration in shallow ground water wells. Additionally, in western Pennsylvania there has been an association with shale gas wastewater and elevated levels of bromide in rivers which is a major resource for drinking water. Bromide itself is not harmful and had not been tracked or regulated in Pennsylvania and therefore there are no historical records to reference. Bromide is a significant public health risk because bromide reacts with chlorinated organics to form disinfection by-products called trihalomethanes (THMs) in chlorinated drinking water. Local water quality experts observed higher than normal levels of brominated species of THMs iv since unconventional drilling in the Marcellus shale began in the region. Brominated species of disinfection by-products have been described by toxicologists as probable carcinogens and are more toxic then the chlorinated species. The numbers of violations for THMs in South Western PA correspond with the increases in drilling activity and shale gas waste-water. Additional research and policies regarding unconventional drilling and waste-water management are needed. v TABLE OF CONTENTS 1.0 INTRODUCTION ........................................................................................................ 1 1.1 MARCELLUS SHALE AND HYDRAULIC FRACTURING ........................ 2 1.2 TRIHALOMETHANE TOXICOLOGY ........................................................... 5 2.0 WATER CHEMISTRY AND BROMIDE CONCERNS ......................................... 7 2.1 PWSA AND UNIVERSITY OF PITTSBURGH STUDY ................................ 8 2.2 SAFE DRINKING WATER COMPLIANCE ISSUES.................................... 9 2.3 CONVENTIONAL TREATMENT INADEQUATE ..................................... 11 3.0 POTENTIAL SOURCES OF BROMIDE AND WATER MANAGEMENT ...... 14 4.0 SUSTAINABILITY ................................................................................................... 17 5.0 POLICY ...................................................................................................................... 18 6.0 SUMMARY AND CONCLUSION........................................................................... 20 APPENDIX: SUPPLEMENTAL INFORMATION ................................................................ 21 BIBLIOGRAPHY ....................................................................................................................... 25 vi LIST OF TABLES Table 1. The Maximum Contaminant Levels (MCL) and MCL Goals (MCLG) for Regulated THMs .............................................................................................................................................. 5 Table 2. Shale Gas Wastewater Bromide Concentrations ............................................................ 10 Table 3. Distribution of Wastewater Disposal Methods ............................................................... 15 vii LIST OF FIGURES Figure 1. Shale Plays in the Lower 48 States................................................................................ 21 Figure 2. THM Violations in Pennsylvania by Region................................................................. 22 Figure 3. Bromide Concentration in the Monongahela River....................................................... 22 Figure 4. Number of Treatment Plants by Region Utilizing Surface or GUDI Sources .............. 23 Figure 5. Number of Unconventional Wells Spud in Pennsylvania ............................................. 23 Figure 6. Number of THM Violations in South Western Pennsylvania ....................................... 24 viii 1.0 INTRODUCTION Shale found in the United States represents a source of energy and economic impact too enormous to ignore, see Figure 1. Natural gas has become the fossil fuel of choice both environmentally and politically because it is cleaner burning than other fossil fuels such as coal, it can be produced domestically, and it is relatively inexpensive (Rozell, 2012). In the US there are many large shale plays; among the largest is the Marcellus in the northeast. However, there are potential environmental impacts that have been discovered due to the use of the newly developed unconventional drilling methods needed to extract gas from the shale. In the US, there are environmental concerns mostly involving to air and water quality, as well as other factors such as impacts on communities. Wyoming, where air quality is normally quite good, has seen extremely high levels of ozone since the gas extraction has begun. Gas well sites have been known to increase ozone precursors such as NOx and VOCs, which contributed to ozone levels exceeding the national ambient air quality standard (NAAQS) (Fields, 2010). In Pennsylvania, there is increased alarm of shale drilling and contamination of private drinking water wells from methane migration. Many studies have been conducted to determine the fate and transport of the methane, but less attention has been on surface waters and water resource management. In Southwestern Pennsylvania there has been an association with drilling wastewater and increased levels of bromide in rivers which is a major source of drinking water. Bromide is a significant public health risk because bromide reacts with chlorinated organics to form disinfection by-products called trihalomethanes. Water quality experts at Pittsburgh Water and Sewer 1 Authority, University of Pittsburgh, Pennsylvania American Water Company, and Carnegie Mellon University have found higher than normal levels of brominated species in the local rivers since unconventional drilling started in Southwestern Pennsylvania. 1.1 MARCELLUS SHALE AND HYDRAULIC FRACTURING The Marcellus play occurs in Ohio, New York, West Virginia, Pennsylvania, and parts of Maryland (Kappel, 2009). The Marcellus shale is a Devonian age layer of sedimentary rock located in the Appalachian Basin (Kappel, 2009). This relatively thin layer of black shale formed from an ancient seabed, which over time and high pressure caused this layer to be abundant in hydrocarbons. Marcellus shale covers approximately 31 million acres and ranges from 4,000-7,000 feet below the Earth’s surface (Kappel, 2009). The Marcellus formation consists of wet and dry gases. Wet gas has greater value in the petrochemical industry than the energy industry. Some of the components of wet gas include ethane, benzene, tolulene, ethylbenzene, and xylene (a group called BTEX), hydrogen sulfide (H2S) and others which can be broken down or “cracked” into smaller chemical building blocks. Shell Chemical intends to build an ethane cracker in Beaver County Pennsylvania as a result of the abundant source of raw chemical materials. The chemical cracking and other spin-off jobs extend the economic impacts of this formation. Dry gas is predominantly methane, used as a fuel source for home heating, electrical power generation, and transportation among other uses. This resource has become significant recently and was estimated in 2008 to have recoverable natural gas of 363 trillion cubic feet (TCF) (Kappel, 2009). The total annual US consumption of natural gas is about 25 TCF (US Energy Information Administration, 2013). The oil and gas industry is not new to Pennsylvania, in fact, oil exploration began in Venango County, PA in 1859. Since then, over 350,000 2 wells have been drilled in PA (Boyer, 2012). Increased interest in the Marcellus shale began in the 1990s is a result of two factors. First, wellhead prices increased from $2.00 per million cubic feet (MCF) in the 1980s to a peak of $10.82 per MCF in 2008. Second, is due to the advent of directional drilling which is now used in conjunction with hydraulic fracturing (Kappel, 2009). Directional drilling allows for drillers to drill down to the shale layer and then turn to follow the horizontal shale seam. The existing technique of hydraulic fracturing is incorporated to fracture the shale which then allows for the gas to flow to the surface. The hydraulic fracturing process requires large volumes of water (3-5 million gallons), high pressure, proppant, about 0.5% chemicals, many of which are toxic to humans and wildlife (Colborn, 2011). Proppant is a material that holds open fractures in the formation to allow for the gas to flow freely, this is usually sand. The Pennsylvania Department of Environmental Protection has defined this new hydraulic fracturing process as such: Unconventional Drilling – “An unconventional gas well is a well that is drilled into an unconventional formation, which is defined as a geologic shale formation below the base of the Elk Sandstone or its geologic equivalent where natural gas generally cannot be produced except by horizontal or vertical well bores stimulated by hydraulic fracturing” (PA DEP). Some of the water from this process (10-25%) returns to the surface is called “flowback” and occurs after 10-14 days, over time up to 80% of water returns to the surface (Hayes, 2009; Kirby, 2010). Once production begins, produced water that returns to the surface contains chemicals from the Marcellus formation itself in addition to the chemicals in the slick water. Some of the chemicals returning to the surface are total dissolved solids (TDS), sodium, calcium, chloride, bromide, potassium, barium, strontium, radium, uranium, and hydrocarbons such as benzene (Kirby, 2010; Kappel, 2009; Vanbriesen, 2012). The concentrations of these chemicals in the produced water generally increase over time spent in 3 the formation (Hayes, 2009). TDS ranges from 3,010-261,000mg/L, bromide ranges from 1851,600mg/L, chloride ranges from 1,670-181,000mg/L, sulfate ranges from 10-89.3mg/L (VanBriesen, 2012). Despite all the benefits of the energy and chemical components, it is not hard to see there may be health and environmental consequences to this method of exploration. Surface water treatment plants in the South Western Region of Pennsylvania have experienced challenging source water conditions, possibly from shale wastewater, that have increased the brominated species of trihalomethanes (THMs) in drinking water. Many treatment works are failing or struggled to meet the disinfection by-products (DBPs) regulatory requirements that EPA establishes for public health. The Stage 1 and 2 Disinfectants and Disinfection By-products Rules are the regulatory framework, which is designed to maintain safe drinking water. Figure 2 illustrates most violations are in the South West compared to other regions in Pennsylvania. Stage 2 was implemented on April 1, 2012 for water systems serving a population greater than 100,000 and is more stringent than Stage 1. Stage 2 required samples to be collected in the distribution system and compliance calculated on a locational running annual average (LRAA) rather than averaging all sites so additional violations could be expected as more systems comply with the Stage 2 rule. This paper’s primary focus is on the trihalomethane (THM) class of disinfection by-products as a result of chlorinated drinking water. Haloacetic Acids are also a by-product of chlorinated water but remain low in South Western Pennsylvania. 4 Table 1. The Maximum Contaminant Levels (MCL) and MCL Goals (MCLG) for Regulated THMs Species of THM MCL Bromodichloromethane Bromoform Dibromochloromethane Chloroform 1.2 MCLG 80µg/L (Sum of the Zero concentrations all four Zero trihalomethanes) as an 60µg/L annual average 70µg/L TRIHALOMETHANE TOXICOLOGY DBPs were first discovered in chlorinated drinking water in the 1970s (Bellar, 1974 and Rook, 1974). THMs are a class of regulated disinfection by-products comprising of four species which are listed above. The EPA Integrated Risk Information System (IRIS) has classified these THMs as being B2, probable human carcinogens with the exception of dibromochloromethane, which is a C, possible human carcinogen, over a lifetime exposure. The brominated species (bromoform and dibromochlormethane) were found to develop cancers of the bladder, rectal, or colon in mice or rats. The chlorinated species (chloroform and bromodichloromethane) were found to cause liver and kidney tumors in mice or rats. There was inadequate support for humans but there was a positive correlation between drinking chlorinated water and several human cancers. This information lacked control for risk factors such as diet, smoking, and alcohol consumption. Toxicologists have described the brominated species of haloacetic acids to be more toxic than chlorinated species (Plewa, 2004). Richardson also describes brominated DBPs as having a greater toxicological effect than chlorinated (Richardson, 2007). Humans are exposed to THMs when they use chlorinated municipal water. According to the EPA, a family of four uses an average of 400 gallons of water per day, 70% of this is used indoors for activities such as cooking, 5 bathing, drinking. Routes of exposure include ingestion, dermal absorption, and inhalation (EPA). Due to multiple routes of exposure drinking bottled water may not have a significant reduction in exposure. As a result of THM toxicity and exposure it is important to find methods to reduce the levels of long term exposure and risk of cancer. 6 2.0 WATER CHEMISTRY AND BROMIDE CONCERNS The first unconventional hydraulically fractured well was drilled in 2006, since then surface water treatment works began to see an increase in DBP formation. Historically, many of the DBPs were predominantly chlorinated species of trihalomethanes, but have shifted more to the brominated species. In 2008-09 the PA DEP conducted a study of water systems whose source is the Monongahela and Ohio Rivers. These rivers had unusually high levels of sulfate and total dissolved solids (TDS) (Handke, 2009). DEP concluded that water systems in the DEP study were found to have THM concentrations that were impacted by bromide in the source water at varying times of the year (Handke, 2009). Two years later, Pittsburgh Water and Sewer Authority (PWSA) documented higher brominated species as a result of increased bromide levels in the neighboring Allegheny River (States, 2012). Natural Organic Matter (NOM) + Cl2 + Br- ----- Trihalomethanes: (CHCl3), (CHCl2Br), (CHClBr2), (CHBr3) Components of NOM include humic and fulvic acids from decaying plants and are identified as DBP precursors. A 2002 EPA study has shown that increases in bromide concentration in source water increases THMs and causes a shift in speciation (EPA, 2002). Even at low bromide concentrations mixed bromochloro and brominated species increased (Chang, 2001). Hypobromous acid and hypobromite are generated by the reaction with chlorine and bromide. Hypobromous acid reacts with NOM more quickly than hypochlorous acid. Therefore, when bromide is present increased brominated species of DBPs are expected (Chang, 2001). The observed shift within the THMs to more brominated species is partially due to the molecular mass being greater in the brominated than chlorinated species (Handke, 2009). Bromide 7 is common in seawater and the brominated DBPs predominate as expected. Known sources of bromide in South Western Pennsylvania may include, but are not limited to coal fired power plant air scrubbers, steel mills, publically owned treatment works (POTWs), and industrial waste water facilities. Because bromide by itself is not harmful, there is not a regulatory discharge limit and therefore is not measured or reported. However, it can be concluded that the increased presence of brominated THMs demonstrates an increase of bromide in the source water. 2.1 PWSA AND UNIVERSITY OF PITTSBURGH STUDY Due to limited or no data, the natural levels of bromide in Western Pennsylvania rivers systems are not clear. PWSA and the University of Pittsburgh studied the raw water in the Allegheny River and its tributaries and estimated the natural concentration to be less than 50µg/L. Their study found bromide levels at the water treatment plant intakes in Pittsburgh tend to vary by season and rainfall, but were often measured around 150-175µg/L in dryer months during 2010 and 2011. Peak levels have been measured as high as 241µg/L in 2010 and 299µg/L in 2011. In a 2002 EPA study which included all regions in the United States found source water bromide concentration ranges of 400µg/L, 150µg/L, and 20µg/L which were classified as high, moderate, and low concentrations, respectively. The source water that was 400µg/L was influenced by seawater intrusion (EPA, 2002). The PWSA study focused on several factors including the sources of bromide, effectiveness of bromide removal by the PWSA plant, and the natural levels of bromide in the Allegheny system. Known contributors of bromide on the Allegheny River system are coal power plants, POTWs receiving shale waste-water, steel mills, and industrial treatment facilities treating shale waste water. Data indicates industrial plants treating Marcellus shale waste-water has the most significant impact on water quality. For example, industrial waste plant C contributed a 21 fold increase (116 to 2,400µg/L) in bromide 8 concentration in July 2011 (States, 2012). A mass balance analysis in 2011 found that the industrial sites contributed to -30-130% mass contribution of bromide. Six of the twelve months in 2011 were more than 50% bromide contribution by mass (States, 2012). Coal fired power plants and POTWs treating Marcellus waste water also contributed to increases in bromide, particularly, power plants in the summer months (States, 2012). Overall, bromide levels increase downstream. There is a seasonal effect which can be seen in the bromide data from the Monongahela River in Figure 3. The drier seasons result in low river flows and thus increase the concentration of bromides. The Monongahela River was also researched by Dr. VanBriesen of CMU. Unfortunately, data from her studies have not been published. However, Dr. Vanbriesen has indicated to the media that shale waste water and new smokestack scrubbers at coal-fired power plants are likely sources of bromide on the Monongahela River (Hopey, 2011). 2.2 SAFE DRINKING WATER COMPLIANCE ISSUES Many surface water treatment plants are or have been in violation of the Stage 1 DBP rule. The water systems seem to believe the Marcellus Shale produced water causes the high DBPs in their water because it is the only new potential pollution source in the area. The general manager for the Beaver Falls Water Authority (BFWA) reported high THMs and cites Marcellus shale waste-water as a possible cause. BFWA was one the first water systems to be in violation for THMs. On January 31, 2013 a man was charged with dumping an estimated quarter million gallons of brine and drilling mud into a storm drain that empties into the Mahoning River in Youngstown, Ohio and then flows into the Beaver River, which the source for BFWA (Morgan, 2013). Brackenridge Water Authority was also out of compliance for THMs. Fawn-Frazier Water Authority, which purchases bulk water from Brackenridge Water Authority 9 on the Allegheny, has been out of compliance for THMs for 5 of 8 quarters in 2011-12. Carmichaels Municipal Water Authority, source is the Monongahela, also failed to meet regulatory compliance for THMs in late 2010, early 2011 (Niedbala, 2013). West View Water Authority exceeded the lead action level after switching to chloramines to help maintain compliance for THMs in 2010. Chloramines are an alternative disinfectant that slows THM formation, but can be corrosive to household plumbing. In addition to the potential health effects of THMs, there is increased stress and fear as well as reduced consumer confidence when the public is informed their water is failing standards for safe water. The cause for this problem that is unique to South Western Pennsylvania is unknown. The North Central region of Pennsylvania where drilling activities are also flourishing does not appear to have water quality problems related to THM formation as seen in Figure 2. The bromide concentration in produced water from both regions is equivalent, Table 2. There is twice as many water treatment plants (Figure 4) in the South Western region than the North Central region, but there are 97% more THM violations. Table 2. Shale Gas Wastewater Bromide Concentrations County No. of Samples North Central Bradford Tioga Susquehanna Lycoming Cammeron Centre South West Butler Washington Greene Westmoreland Fayette Avg. [Br-] mg/l St. Dev. 13 7 5 6 3 3 37 476 460 411 382 716 520 494 269 322 422 199 417 187 7 7 8 11 2 35 347 945 515 719 183 542 255 434 487 608 70 Source: Data obtained from PA DEP. 10 2.3 CONVENTIONAL TREATMENT INADEQUATE Through the conventional treatment process of surface water through flocculation, coagulation, sedimentation, and filtration, organic matter and chlorine react to form disinfection by-products (DBPs), trihalomethanes and haloacetic acids, as well as unregulated DBPs. As the bromide levels increase in the source water so do the brominated species of DBPs (Chang, 2001). Chlorine is widely used as a primary disinfectant because it is effective and relatively inexpensive therefore, removing chlorination is not a practical solution for water systems. Water systems are challenged with meeting all of the regulatory requirements and must balance acute and chronic health risks. Compliance with the Stage 1 and Stage 2 D/DBPR is difficult to achieve while also complying with the following regulations: Surface Water Treatment Rule (SWTR), Interim Enhanced Surface Water Treatment Rule (IESWTR), Long Term 1 Enhanced Surface Water Treatment Rule (LT1), Long Term 2 Enhanced Surface Water Treatment Rule (LT2), Lead and Copper Rule (LCR), and Total Coliform Rule (TCR). For example, reducing the level of chlorine disinfectant will decrease DBP formation but it also increases microbial risk that results in an acute waterborne disease outbreak. LeChevallier recommends a free chlorine residual of 0.2-0.5 mg/l in all areas of the distribution system to maintain a safe barrier to protect public health. Each rule has stature in law and requires simultaneous compliance, so the goal of one rule cannot be undermined in favor of the goal of another. The concentration of DBP precursors (NOM), chlorine dose and residual, time, temperature and pH affect the formation of DBPs (Handke, 2009). Temperature is easily identified because higher THM levels are observed during the warmer months because of faster reaction rates. Water age is identified as a factor because the samples collected from the distal locations in a distribution system are generally greater than fresher water. Chlorine influences THM formation, as chlorine reacts with organics, the concentration of THMs increase while chlorine decreases. Decreasing NOM during the treatment process also decreased THM formation (Teksoy, Alkan, 2008). 11 Researchers at Pittsburgh Water and Sewer Authority and University of Pittsburgh began to study the overall impact of bromide on DBP formation, identify sources of bromide, and the ability of the plant to remove bromide. They have identified several sources of bromide in the Allegheny River watershed. PWSA and other researchers have demonstrated there is a correlation between increased bromide and increased THM formation, brominated species of THMs also increased with bromide concentration (Chang and States). Dr. States of PWSA determined in October 2010 their treatment plant was only able to remove about 28.7% of the bromide. Unfortunately, conventional filtration is not efficient in reducing salts such as bromide. There are a few chemical or operational changes that can help to reduce the amount of THMs in the drinking water supply: 1. Change treatment plant operations ie: decrease pre-oxidant chlorine and increase post-oxidant chlorine. Oxidation of metals can be achieved by feeding potassium permanganate in lieu of prechlorine. However, these process changes will need to consider the Surface Water Treatment Rule which requires 1 log inactivation of Giardia cysts by chlorination. 2. Enhanced coagulation, which increases total organic carbon (TOC) removal and therefore reduces DBP precursors. Enhanced coagulation is a process of obtaining increased removal of DBP precursors by conventional treatment. This requires a certain percentage reduction in NOM using TOC as a surrogate for NOM. This treatment technique removes additional NOM measured as TOC. Since the removal is dependent on alkalinity there are “easy to treat” and “difficult to treat” waters. Step one measures TOC removal performance and step 2 requires an alternative removal protocol if the water is “difficult to treat”. 3. Changing from free chlorine to chloramines as a secondary disinfectant. Chlorine combined with ammonia yields a less reactive disinfectant which slows DBP formation. Chloramines do have DBPs as well and are being evaluated for regulatory change. Nitrosamines are currently under review under EPAs Unregulated Contaminant Monitoring Rule 3 (UCMR3). 12 4. Membrane filtration is ideal for removing salts and DBP precursors. However, membrane technology is maintenance intensive and has high energy demands. 5. Since DBPs form with increasing water age, DBPs can also increase throughout the distribution system. Distribution system optimization is being studied by the USEPA in the twelve area wide optimization program (AWOP) states. Optimization includes methods to increased water storage tank turnover, looping dead end lines, water quality sampling to identify areas of poor water quality. Parameters include chlorine concentration, pH, temperature, and DBPs. 6. Water storage facility mixing or aeration systems can also be effective. Mixing systems prevent stratification of water temperature gradients which can lead to poor water quality. Some aeration systems involve fans that strip off the DBPs which improves water quality. These systems can be expensive and may have energy needs. Given these potential solutions there is no guarantee these methods will always work. There is also a consequence to each method. Therefore, the most viable solution to this environmental problem is to minimize impacts of source water bromide through produced water management. 13 3.0 POTENTIAL SOURCES OF BROMIDE AND WATER MANAGEMENT Bromide concentration in source water has been correlated to brominated THMs at PWSA (States, 2012) There has also been an association with produced water and high levels of TDS and elevated levels of bromide when compared to other waters and wastewaters in Pennsylvania (VanBriesen, 2012). Unconventional wells require considerably more water for fracturing than conventional. Since 2005, the number of wells spud has increased exponentially with a slight decrease in 2012 largely due to oversaturation of supply of natural gas, Figure 5. There has been a marked increase in produced water in Pennsylvania from 2006-11 from this rapidly expanding industry. For example, from 2001-2006 there were 6.3 million barrels a year of produced water which increased dramatically in 2008-2011 to 26 million barrels (VanBriesen, 2012). This increase and the lack of adequate waste-water facilities in the region raise questions about where all this salty water is going. Increased produced water discharges seem to be increasing the salinity of fresh water resources. TDS in produced water from oil and gas wells in Pennsylvania is about 68,000-354,000mg/L (VanBriesen, 2012). The Marcellus formation TDS is about 3,010-261,000mg/L (Hayes, 2009). Freshwater should be less than 1,500mg/L TDS (Vanbriesen, 2012). The following are five methods for this waste-water; reuse, injection wells, brine treatment plants (CWT), municipal sewerage treatment works (POTW), other such as road application. 14 Table 3. Distribution of Wastewater Disposal Methods Disposal Method Percent of Total Disposed Industrial Water Water Treatment 77.5% Reuse in Other Wells 16% Municipal Waste Water Treatment Facilities(POTW) 5% Unknown Disposal 1% Injection Wells 0.5% Road Spreading 0.007% (Rozell, 2012) In the fall of 2008, the Monongahela River exceeded the drinking water standards for total dissolved solids (TDS), 500mg/L, and sulfate, 250mg/L (VanBriesen, 2012). Significant increases of TDS, sulfate, and increases of brominated THMs prompted the Pennsylvania Department of Environmental Protection (PA DEP) to request POTWs to stop accepting shale gas wastewater for treatment in May 19, 2011. However, industrial waste water plants are still permitted to accept the waste water despite high bromide, TDS and other chemicals in the effluent. In November 2012 Dr. Vanbriesen reported that “Bromide concentrations have declined (In the Monongahela), and there are reduced loads entering the river. We don’t know why, but the decline corresponds to the DEP’s request that treatment plants stop accepting drilling waste-water” (Hopey, 2012). As of November 2012, the bromide levels in the Allegheny remained elevated. A probability bounds analysis, which is well suited for when data is sparse and parameters are highly uncertain analyzed five pathways for the contamination of water from shale gas operations. The five pathways identified in the study were; transportation spills, well casing leaks, leaks through fractured rock, drilling site discharge, and waste-water disposal. Overwhelmingly, waste-water disposal was identified to be the most important area for additional research (Rozell et al., 2012). This conclusion and 15 other work support the need to eliminate surface waste-water discharges to protect the environment and drinking water sources. Several other areas in the United States where unconventional drilling is occurring are Texas, Colorado, and Wyoming. These locations do not appear to have the same problems with surface water treatment and disinfection by-products. Produced water management disposal methods can vary as a result of geology, climate, location, or other factors. In arid climates evaporation can be used. Wet and humid weather does not lend to efficient evaporation in Pennsylvania. Evaporation reduces the need to haul water to treatment plants which reduces the likelihood of spills. Some of the solids left behind like Barium may be at hazardous waste levels (Keister, 2010). EPA class II injection wells can be used in locations where the geology permits such as Texas and Ohio, but the geology in Pennsylvania does not allow for this disposal method. In Youngstown, OH a 4.0 magnitude earthquakes epicenter was near a 9,000 foot injection well where produced water was disposed. This and a series of smaller earthquakes in the area have been attributed to shale gas produced water injection as the probable cause. In Ohio, Senate Bill 315 was passed on June 11, 2012, which requires electronic submission of quarterly brine reports and a host of additional environmental health and safety measures (ODNR). 16 4.0 SUSTAINABILITY Water resources are limited. 2012 was the 3rd hottest summer on record in the continental U.S. resulting in strong winds, devastating storms, and wildfires. The Palmer Drought Index indicated 55.1% of the lower 48 states were moderate to extreme drought, with 39% experiencing severe to extreme drought (The Aquifer, 2012). With this in mind it simply does not make sense to use fresh water resources for hydraulic fracturing, because much of this water is unrecoverable especially when disposed via injection wells. PA DEP has proposed to utilize mine influenced water (MIW) or partially treated MIW for hydraulic fracturing operations. DEP produced a white paper outlining the process for the voluntary use of MIW which obviously reduces the impact of water resources for consumption, recreation, and the environment. This process also helps to reduce widespread legacy pollution, MIW (PA DEP). Overall, reusing, recycling and treating the waste-water seem to be the only sustainable methods to waste water disposal in the north eastern region of the United States. The pollution of water resources is expensive. The American Water Works Association reports the average cost of tap water to be $0.0048/gallon, pollution and unsustainable use of this resource is likely to increase the cost of water to each consumer (AWWA, 2012). Removal of salts and other constituents is important prior to discharging into streams, rivers, lakes, etc. because it can affect aquatic life and alter the ecosystem (VanBriesen, 2012). Alternative methods for hydraulic fracturing may have less environmental consequences such as using nitrogen gas, nitrogen based foams, carbon dioxide which could help carbon sequestering, and liquefied petroleum gas (LPG) (Rozell, 2012). 17 5.0 POLICY There is a need for national policies regarding oil and gas produced water management. The incidence of increased brominated THMs may become widespread throughout the country if produced water from shale gas operations continues to be unregulated. There are several potential policy solutions to consider. 1. A system for documenting water withdrawals, flowback, and produced water will be necessary to help prevent drillers or rogue water haulers from illegally dumping waste water into streams or sewers. A cradle to grave system similar to the Resource Conservation and Recovery Act (RCRA) would need to be developed in order to assure illegal dumping and falsification of records is greatly reduced. 2. Develop a plan to build infrastructure for brine water treatment for this expanding industry like stationary or mobile membrane plants or other proven technologies. Additional research is necessary to determine if there are acceptable levels of bromide and other chemicals that can be discharged to surface waters. Subsequently, changes to the national pollutant discharge elimination system (NPDES) requirements could be recommended. 3. Communicating accidental spills to the appropriate authorities is pertinent for source water protection and to assuring safe drinking water. The water systems already use communication networks, such as the River Alert Information Network (RAIN) and the Ohio River Water Basin Sanitation Commission (ORSANCO), to alert downstream water suppliers of chemical spills. The intentional spill in Youngstown, OH was never communicated to the public water systems and 18 later entered the BFWA water system. A communication plan could have prevented this exposure. 4. Research is needed to address human and ecological effects when developing new regulations regarding oil and gas waste-water management. 5. Developing a surrogate for bromide levels would be a useful tool for water systems. Conductivity varies by flow so it is not a good indicator of bromide (Kirby, 2010). TDS seemed to be a good indicator on the Monongahela River but not Allegheny River (States, VanBriesen). 6. Abandoning wells afterwards will need to be considered to prevent a legacy pollution problem. Currently underway are two EPA studies. The first is “EPA’s Study of Hydraulic Fracturing and its Potential Impact on Drinking Water”, a final draft is due in 2014. The second is a two-year study that will help to understand DBP formation in water treatment plants with a goal of producing a predictive model of DBP formation based on a set of measurable parameters. It is essential that policies need to be easily amended, due to an evolving industry. The Pittsburgh Tribune-Review reported that oil drillers have begun to hydraulic fracture on shallow oil formations between 1,000-3,000 feet, which already makes the new PA DEP regulations obsolete (Puko, 2013). 19 6.0 SUMMARY AND CONCLUSION The Marcellus Shale formation is a significant economic resource for the petrochemical industry and an abundant energy source, but it is important to use as much information that is available to make the necessary regulatory framework to ensure a safe environment and to protect public health. Although the connection between shale gas waste-water and the increase of brominated species of THMs has not been confirmed, there is information that suggests a cause and effect relationship. Increased gas well drilling (Figure. 5) and shale gas production water both correspond to the number of water system violations for THMs in Southwestern PA, Figure 6. Gas well drilling in Pennsylvania has been around for more than 150 years, but the elevated bromide levels have not been a noticeable problem for public water systems until the use of unconventional methods began. It is unclear why the bromide appears to have such a significant impact on the South Western region. The North Central region, also a hot spot for unconventional drilling in the Marcellus formation, does not seem to experience the same water quality consequences. There is a need to identify the source of the bromide and take action to prevent pollution of surface water sources. Poor water quality has negative impacts on the environment and public health. Rigorous national standards regulations and significant penalties for bad operators and rouge haulers are necessary to ensure uniformity throughout the industry. Fresh water sources are becoming increasingly limited and just might emerge as having more value than the gas it is used to extract. 20 APPENDIX SUPPLEMENTAL INFORMATION Figure 1. Shale Plays in the Lower 48 States Source: Provided by U.S. Energy Information Administration 21 Figure 2. THM Violations in Pennsylvania by Region Source: Data obtained from PA DEP Figure 3. Bromide Concentration in the Monongahela River Source: Pennsylvania American Water Company, January 2013 22 Figure 4. Number of Treatment Plants by Region Utilizing Surface or GUDI Sources Source: Data obtained from PA DEP Figure 5. Number of Unconventional Wells Spud in Pennsylvania Source: Data obtained from PA DEP 23 Figure 6. Number of THM Violations in South Western Pennsylvania Source: Data obtained from PA DEP 24 BIBLIOGRAPHY Bellar, T.A., Lichtenberg, J.J., Kroner, R.C., 1974. “The Occurrence of Organohalides inChlorinated Drinking Water.” Jour. AWWA, 66:12:703. 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