Regional Baseline Groundwater Quality Report for Athens, Belmont and Surrounding Counties

Transcription

1 Regional Baseline Groundwater Quality Report for Athens, Belmont and Surrounding Counties Funded in part by the Sugarbush Foundation, Ohio University s Voinovich School of Leadership and Public Affairs, and the Russ College of Engineering s Institute for Sustainable Energy and the Environment Laboratory June 14, 2013 Produced by: Ohio University s Voinovich School of Leadership and Public Affairs Jennifer Bowman, Dr. Natalie Kruse, Elizabeth Migliore, and Ryan Gilliom

2 Table of Contents 1.0 Introduction Purpose Background Previous Studies Methods Results and Discussion Groundwater Quality Mine Drainage Quality Conclusions References Appendices Appendix A. Range of values found at all regional groundwater data sites (MRL and MCL included).. 21 Appendix B. Range of values found at all deep coal mine discharge sites (MRL and MCL included) Appendix C. Groundwater and coal mine drainage chemical data parameters Acknowledgements I would like to thank the Sugarbush Foundation for providing the resources to initiate this important collaborative project filling a need in the region. Other entities that provided direct and indirect resources include: Ohio University s Voinovich School and Russ College of Engineers ISEE laboratory and the Ohio Environmental Protection Agency.

3 1.0 Introduction Environmental degradation is often difficult to determine due to lack of robust scientific data prior to an environmental impact. In late 2011, citizens of Athens County were alarmed by the unnatural increase in out of state and in state oil and gas companies contacting citizens to lease their mineral rights. While this interest was welcomed by some citizens, others were skeptical. As a result of the pending onslaught of new oil and gas drilling in the area, it was important to collect baseline data to document current conditions of regional shallow aquifer groundwater quality conditions. This study was conducted from January to April 2012 at sample locations in the following counties: Athens, Belmont, Guernsey, Hocking, Meigs, and Perry (Figures 1.1 and 1.2). Sample Locations in Athens, Hocking and Perry County Sample Type Mine Well Spring Streams Miles Figure 1.1 Athens, Hocking, Perry, and Meigs County sites

4 Sample Locations in Belmont and Guernsey County Sample Type Mine Well Spring Streams Miles Figure 1.2 Belmont and Guernsey County sites 2.0 Purpose Ohio University s Voinovich School for Leadership and Public Affairs partnered with the Institute for Sustainable Energy and the Environment Laboratory (ISEE), The Sugarbush Foundation, and Ohio Environmental Protection Agency to conduct a regional shallow aquifer groundwater study. This study measured baseline water quality parameters prior to the commencement of controversial high volume horizontal hydraulic fracturing drilling activities in and around Athens and Belmont Counties. This research was conducted by Voinovich School staff, faculty, and students, as well as personnel from Ohio Environmental Protection Agency and Analytical Associates. Funding for this research came from the the Sugarbush Foundation, Ohio University s Voinovich School and the Russ College of Engineering.

5 3.0 Background The recent rise in high volume horizontal hydraulic fracturing activity for natural gas and oil extraction from shale deposits brings new concerns to water quality in this region. This process uses a mixture of water, sand, and chemicals under high pressure to create fractures in the rock structure, releasing the trapped natural gas or oil, and allowing for the horizontal expansion of wells, which increases the volume of gas produced (USEPA 2012b). The technological advances of this procedure have allowed for the profitable extraction of natural gas and oil from tight geological formations such as shale (USEPA 2012b). This form of unconventional production began to be used at a commercial scale in shale formations during the 1990s, with development rapidly increasing over the past decade (USEPA 2012b). According to the U.S. Energy Information Administration (EIA), natural gas production in the United States is projected to increase 44 percent by 2040, to 33.1 trillion cubic feet of natural gas, with the majority of this from shale gas (2012). Crude oil production is also projected to increase through 2020, with tight oil production (from shale or chalk formations) making up 51 percent of onshore oil production by 2040 (EIA 2012). According to Waples, the process of fracturing rock to release trapped gas or oil has been used by the energy industry for decades within vertical wells (2012). Horizontal drilling, first developed in the 1930s, has been experimented with in shale formations by the Department of Energy since the 1970s. Mitchel Energy and Development began experimenting with deep shale gas formations in 1981 with the Barnett Shale in Texas. Eventually the company found the mixture of water and chemicals used in highvolume horizontal hydraulic fracturing today, and merged with Devon Energy Corporation in The Barnett Shale produced gas throughout the 1990s. Beginning in 2004, high volume horizontal shale drilling moved to new formations, including the Marcellus Shale and Utica in the Appalachian Basin (Waples 2012). Horizontal drilling begins in the same manner as vertical wells, with drilling to a depth below the deepest groundwater aquifer. Then, steel pipe is inserted down the drilled hole in several layers of casing in order to protect groundwater. Multiple layers of cement are then pumped into the well, forced under high pressure up the outside of the steel casing to the surface, which provides further protection for groundwater. The drill bit then begins to turn horizontally along a long radius. This horizontal pipe can stretch over a mile. According to Waples (2012), Multiple wells only a dozen feet apart can be drilled on the same well pad to offshoot into multiple horizontal directions to eventually cover a square mile of shale, vastly reducing the overall environmental footprint of the wells (Waples 2012). After the horizontal well is drilled, the process of hydraulic fracturing is conducted over two main phases: perforation (perfed) and fracturing (fracking). Perforation begins with a perforating gun that is inserted at the end of the horizontal drill pipe and set off with electric charges to create holes in the casing and surrounding shale. Then fracturing is conducted over four stages: an acid stage to clear an opening for the fracturing fluids;

6 a pad stage with slickwater to fracture the shale; a prop stage using water and proppants to hold the fractures open; and a flushing stage to eject excess proppant. Fracturing fluids are typically composed of 90 percent water, 9.5 percent sand, and up to 0.5 percent chemicals, and are pumped into the well at around 8,000 psi. Marcellus and/or Utica wells uses on average three to four million gallons of water per well, as compared to 100,000 gallons used for conventional well drilling (ODNR 2012). A well is perfed and fracked up to 12 times, with a heavy plug placed between each stage. After fracturing, the well needs to be shut until the fractures are stable, and then flowback fracturing fluid returns to the surface (Waples 2012). Various hazardous chemicals are used in this process, many of which are still unknown due to company proprietary information protections (Earth Works 2005). Flowback water typically includes surfactants, biocides, scale inhibitors, friction reducers, and proppants in order to make the water thick and slick enough to suspend the proppants and quicken flow through the drill pipe (Waples 2012). Chemicals used in the process typically include hydrochloric acid, acetaldehyde, sodium chloride, polyacrylamide, sodium polycarboxylate, ethylene glycol, borate salts, and isopropanol, along with many others (Waples 2012, Frac Focus 2013). The Marcellus shale gas play includes 60 million acres of Appalachia, with the fairway (area of economic extraction) from 4,000 to 8,500 feet below the surface within Pennsylvania, Ohio, West Virginia, Virginia, Maryland, Kentucky, and Tennessee (Waples 2012). The Utica Shale is more widespread than the Marcellus Shale, stretching from Canada down into Tennessee and Virginia, and is also older and deeper than the Marcellus Shale formation. The Utica Shale is currently the most produced shale in Ohio, with leasing concentrated in the eastern part of the state where the shale averages depths of 11,000 feet below the surface. The upper Devonian Shale also has the potential to be developed, which would include the northwestern portion of Ohio (Waples 2012). Between 2011 and 2012, Ohio saw a rapid increase in the number of producing, drilled, and permitted wells (Figure 3.1). At the end of 2011 there were 7 wells for which production was reported, 27 wells reported drilling activity but no production, and 53 wells that have been issued permits but have not been drilled. At the end of 2012, there were 44 wells for which production was reported, 148 wells reported drilling activity but no production, and 248 wells that have been issued permits but have not been drilled (ODNR 2013). Figure 3.2 shows the number of permitted or drilled injection wells in 2011 and 2012.

7 Figure 3.1 Number of oil and gas wells permitted, drilled, and/or producing in Ohio during 2011 and 2012 (ODNR 2013). Injection Wells Permitted or Drilled GEA 2 CUY 0 TRU 9 MED 1 POR 17 SUM 1 MAH 5 WAY 3 STA 17 COL 4 HOL 5 CAR 3 TUS 5 JEF 1 COS 4 HAS 0 MUS 5 GUE 3 BEL 2 Miles SCI 14 HOC 2 VIN 5 JAC 0 NOB 4 MOE 0 PER 3 MRG 8 GAL 2 WAS 9 ATH 4 MEG 10 LAW 0 Figure 3.2 Number of injection wells permitted and drilled in Ohio in 2011 and 2012.

8 4.0 Previous Studies Gillis s thesis Detection and Modeling of Tetrachloroethylene Contamination in Athens Well Fields (1994) involved data collection and the use of historical data from Sampling was centered in the City of Athens, with analysis performed by Watercheck Nation Testing Laboratories Inc. in Cleveland, Ohio. The majority of volatile organic chemicals and trihalomethanes were below detection levels. Historical data shows exceedance of maximum contaminant level (MCL) for tetrachloroethylene (TCE) and Cis 1,2 Dichloroethylene. TCE exceedance occurred near a municipal township garage, which may be explained by the fact that this chemical is a common component of degreasers. While banned from food and cosmetics in 1977, TCE is still allowed for industrial use (ATSDR 1997). Cis 1,2 Dichloroethylene is used in waxes and resins, rubber extraction, pharmaceuticals, meat oil and fat extraction, and as a refrigerant. The major source in drinking water is from industrial chemical factory discharge. It has been regulated under the SDWA since 1992 (USEPA 2012). Weatherby s thesis A Practical Approach to Wellhead Protection of the City of Athens Water Well Field (1992) involved a well field protection plan for the Armitage well field, which is a primary source for City of Athens water and the well field most at risk for contamination from upstream and surrounding factors. Sampling occurred in 1990 at abandoned wells in the Armitage and West State Street well fields, with analysis performed by Watercheck National Testing Laboratories of Cleveland, Ohio, and Fire and Environmental Consulting Laboratories of East Lansing, Michigan. The majority of data results were below detection level for all tested organic chemicals in Methods Water quality samples were drawn during sixteen separate sampling events from January through April of 2012 from a variety of sites. Most sites were sampled from plumbed and unplumbed groundwater sources, some sites were collected from free flowing deep coal mine surface discharges, others from municipal water treatment plants, and a few from emergent springs. Figures 1.1 and 1.2 show the locations of the 32 sites sampled (the star on the Dysart Wood site in Belmont County represents two sampling locations, these two wells are approximately 25 feet apart). The sites were distributed across Athens and its surrounding counties with a few sites located on and around Ohio University s Eastern Campus in Belmont County. Three separate laboratories with varying levels of certifications were chosen to perform the analyses (Table 5.1). As part of our quality control and quality assurance measures a duplicate sample was collected at each site and split between ISEE laboratory and either AA or EPA laboratories for some analytes (Appendix A raw chemical data).

9 Laboratory Table 5.1 List of Laboratories used to conduct water quality analysis. Certification during January April, 2012 Non EPA certified laboratory Institute for Sustainable Energy and the Environment Laboratory (ISEE) Ohio University 152 Biochemistry Building 350 West State Street Athens, OH Tel: (740) Analytical Associates Laboratory (AA) State Route 7 Proctorville, OH Tel: (740) Ohio Environmental Protection Agency Laboratory (EPA) Division of Environmental Services 8955 E. Main St. Reynoldsburg, Ohio Tel: (614) Voluntary Action Program (VAP) certified laboratory EPA certified Both the Ohio EPA and Analytical Associates Laboratories follow the methods described in the Manual of Ohio EPA Surveillance Methods and Quality Assurance Practices (Ohio EPA 2008) for the collection, transport and quality control of potable water samples. All samples were collected by personnel from these two laboratories. Data results from these laboratories are intended to provide a baseline of groundwater water quality for a specific well or regionally when looking at the collectively. Data analyzed at ISEE laboratory was collected by Voinovich School personnel and are intended for research purposes only. ISEE data was obtained to gather a general knowledge of background water quality in and around the groundwater aquifers of Athens and Belmont Counties. This data is not intended for regulatory compliance. The methods followed for sample collection are detailed below. Plumbed sites: Water was run for five minutes from faucet (w/o faucet aerator) (Figure 5.1), two glass volatile organic compound (VOC) vials with Teflon lined caps were filled from facet at low flow, one vial was pre acidified with an HCL preservative and the other was non acidified. Both vials were completely filled to form a meniscus then capped, stored in an iced cooler at 4 degrees Celsius, and delivered to the ISEE lab within hours. If the spigot was outside the house, a hose was used while the water was running for five minutes to direct the water away from the foundation of the house (Figure 5.2), the hose was then removed and vials were filled in the similar manner as described above. Figure 5.1 Plumbed site at inside faucet house Figure 5.2 Plumbed spigot outside

10 Unplumbed sites: A water level indicator was used to record the height of well water and bottom of the well (Figure 5.3), a submersible pump was used to pump the well water for minutes (Figure 5.4). Temperature, ph, and conductivity values were monitored while steady state of the water was achieved. Once steady state was achieved a disposable single use bailer was lowered into the well to retrieve a sample, a VOC tip was inserted on the end of the bailer to fill both glass VOC vials as described above, vials were then capped, stored in an iced cooler at 4 degrees Celsius, and delivered to the ISEE lab within hours. Figure 5.3 Submersible pump Figure 5.4 Water level indicator tape Deep mine discharges: The non acidified VOC bottle was submerged into the surface flowing deep mine discharge water (Figure 5.5.), filled completely, capped under water, while the acidified VOC vial was filled using a triple rinsed beaker that was submerged in the mine water to retrieve the sample. Both vials were stored in an iced cooler at 4 degrees Celsius, and delivered to the ISEE lab within hours. Figure 5.5 Essex deep mine discharge Water treatment plant: Pre treated water was run forcibly for 5 minutes from production well spout; the flow was decreased to a slow steady stream to fill both glass VOC vials (Figure 5.6). The vials were filled completely to form a meniscus, capped, stored in an iced cooler at 4 degrees Celsius, and delivered to the ISEE lab within hours. Figure 5.6 Athens County production well Free flowing springs: The non acidified VOC bottle was submerged into the surface free flowing water (Figure 5.7), filled completely to form a meniscus, capped under water, while the acidified VOC vial was filled using a triple rinsed beaker that was submerged in the surface water to retrieve the sample. Both vials were stored in an iced cooler at 4 degrees Celsius, and delivered to the ISEE lab within hours. Figure 5.7 Free flowing emergent spring

11 Developed spring: At the concrete encased developed spring, a sample was retrieved using a triple rinsed telescoping cup (Figure 5.8). Sampling cup was rinsed three times before completely filling both VOC vials under a slow steady stream of sample water, capped, stored in an iced cooler at 4 degrees Celsius, and delivered to the ISEE lab within hours. Figure 5.8 Telescoping cup used to collect sample Table 5.2 List of field and laboratory parameters analyzed Field Parameters ph Chemical Oxygen Demand (COD) Conductivity Hardness, Total Total Dissolved Solids Total Suspended Solids Turbidity Major Ions Acidity Alkalinity Calcium Chloride Magnesium Nitrate + Nitrite Nitrite Potassium Sodium Sulfate Minor and Trace Elements Aluminum Ammonia Arsenic Barium Beryllium Boron Bromide Cadmium Chloride Chromium Chromium 2677 Chromium 2835 Cobalt Copper Iron Iron 2395 Iron 2599 Lead Manganese Manganese 2576 Manganese 2794 Nickel Selenium Strontium Titanium Total Kjeldahl Nitrogen (TKN) Total Phosphorus Vanadium Zinc Organic Chemicals 1,1,1,2 Tetrachloroethane 1,1,1 Trichloroethane 1,1,2,2 Tetrachloroethane 1,1,2 Trichloroethane 1,1 Dichloroethane 1,1 Dichloroethene 1,1 Dichloropropene 1,2,3 Trichlorobenzene 1,2,3 Trichloropropane 1,2,4 Trichlorobenzene 1,2,4 Trimethylbenzene 1,2 Dibromo 3 chloropropane 1,2 Dibromoethane 1,2 Dichlorobenzene 1,2 Dichloroethane 1,2 Dichloropropane 1,3,5 Trimethylbenzene 1,3 Dichlorobenzene 1,3 Dichloropropane 1,4 Dichlorobenzene 1,4 Dioxane 1 Butanol 1 Propanol 2,2 Dichloropropane 2 Butanone 2 Chlorotoluene 2 Hexanone 2 Pentanone 4 Chlorotoluene 4 Isopropyltoluene 4 Methyl 2 pentanone Acetone Acetonitrile Acrolein Acrylonitrile Benzene Bromobenzene Bromochloromethane Bromodichloromethane Bromoform Bromomethane Carbon disulfide

12 Carbon tetrachloride Chlorobenzene Chloroethane Chloroform Chloromethane cis 1,2 Dichloroethene cis 1,3 Dichloropropene Dibromochloromethane Dibromomethane Dichlorodifluoromethane Ethanol Ethyl Acetate Ethylbenzene Ethylene Oxide Hexachlorobutadiene Iodomethane Isobutyl Alcohol Isopropyl Alcohol Isopropylbenzene Methane Methanol Methylene chloride Methyl Isobutyl Ketone Naphthalene n Butylbenzene n decane n docosane n dodecane n dotriaoctane n eicosane n hexacosane n hexadecane n octacosane n octadecane n Propylbenzene n tetracosane n tetradecane n triacontrane o Xylene Propionitrile Pyridine sec Butylbenzene Styrene t Butyl alcohol tert Butylbenzene Tetrachloroethene Toluene Total m&p xylenes trans 1,2 Dichloroethene trans 1,3 Dichloropropene trans 1,4 Dichloro 2 butene Trichloroethene Trichlorofluoromethane Vinyl acetate Vinyl chloride Xylene(s) 6.0 Results and Discussion Water samples were analyzed from groundwater wells, springs and mines. The results have been grouped by source: groundwater including springs and mine discharges. Analyses from all laboratories have been combined for interpretation; individual MRLs (method reporting limit) are reported in Appendix A. The following sections present the water quality results for groundwater samples, followed by results for mine water samples. Appendix A presents all data with method detection limit (MDL) and maximum contaminant limit (MCL) where applicable. 6.1 Groundwater Quality Analysis of samples taken from groundwater sources created a picture of the character of the groundwater quality across the counties sampled. Almost all organic analytes were below the detection level; Table 6.1 lists the analytes that were below detection in all groundwater samples. No organic contaminants were detected above MCL in the groundwater samples in the study. Although there is a long history of resource extraction in Appalachian Ohio, there are also many low permeability geologic strata including intact shale and coal layers which may have limited transport of organic pollutants into drinking water. Acetone was found above detection limit in groundwater samples. As shown in Figure 6.1, acetone was detected in concentrations varying from approximately 5 ug/l to over 18 ug/l. Acetone is a common laboratory contaminant; this is the likely source for the detected acetone concentrations and could be an area of future study.

13 Acetone 19 Acetone ug/l Figure 6.1. Acetone concentrations in all groundwater samples varied from approximately 5 ug/l to over 18 ug/l. Lab contamination is a likely source of acetone. Table 6.1. List of chemical parameters at or below detection level at groundwater sites Field Parameters Total Suspended Solids Minor and Trace Elements Titanium Vanadium Organic Chemicals Acrylonitrile n decane 1 Butanol Benzene n docosane 1 Propanol Bromobenzene n dodecane 1,1,1,2 Tetrachloroethane Bromochloromethane n dotriaoctane 1,1,1 Trichloroethane Bromodichloromethane n eicosane 1,1,2,2 Tetrachloroethane Bromoform n hexacosane 1,1,2 Trichloroethane Bromomethane n hexadecane 1,1 Dichloroethane Carbon disulfide n octacosane 1,1 Dichloroethene Carbon tetrachloride n octadecane 1,1 Dichloropropene Chlorobenzene n Propylbenzene 1,2,3 Trichlorobenzene Chloroethane n tetracosane 1,2,3 Trichloropropane Chloroform n tetradecane 1,2,4 Trichlorobenzene Chloromethane n triacontrane 1,2,4 Trimethylbenzene cis 1,2 Dichloroethene o Xylene 1,2 Dibromo 3 chloropropane cis 1,3 Dichloropropene Phenolics 1,2 Dibromoethane Dibromochloromethane Propionitrile 1,2 Dichlorobenzene Dibromomethane Pyridine 1,2 Dichloroethane Dichlorodifluoromethane sec Butylbenzene 1,2 Dichloropropane Ethanol Styrene 1,3,5 Trimethylbenzene Ethyl Acetate t Butyl alcohol 1,3 Dichlorobenzene Ethylbenzene tert Butylbenzene 1,3 Dichloropropane Ethylene Oxide Tetrachloroethene 1,4 Dichlorobenzene Hexachlorobutadiene Toluene

14 1,4 Dioxane 2,2 Dichloropropane 2 Chlorotoluene 2 Hexanone 2 Pentanone 4 Chlorotoluene 4 Isopropyltoluene 4 Methyl 2 pentanone Acetonitrile Acrolein Iodomethane Isobutyl Alcohol Isopropyl Alcohol Isopropylbenzene Methane Methanol Methylene chloride Methyl Isobutyl Ketone Naphthalene n Butylbenzene Total m&p xylenes trans 1,2 Dichloroethene trans 1,3 Dichloropropene trans 1,4 Dichloro 2 butene Trichloroethene Trichlorofluoromethane Vinyl acetate Vinyl chloride Xylene(s) Inorganic analytes showed the geologic origin of the various groundwater samples. As shown in Figure 6.2, the majority of groundwater samples plotted on a Piper diagram are dominated by calcium, carbonate and sulfate. This reflects limestone or calcite dominated sandstone sources for most groundwater in the study. A few outliers are dominated by sodium and potassium and carbonate; suggesting a clay mineral origin (e.g. feldspar, shale, etc) Calcium(Ca) Chloride(Cl) Figure 6.2. Piper diagram of all groundwater samples showing calcium and magnesium as the dominant cations and sulfate and carbonate as the dominant anions.

15 Several key analytes were detected above the EPA mandated MCL (maximum contaminant limit). As shown in Figure 6.3, one sample exceeded the MCL for lead of 15 ug/l with a measured value of 17.2 ug/l. In addition, arsenic was detected in many groundwater samples, but only one exceeded the MCL of 10 ug/l (see Figure 6.4). Other notable inorganic constituents found in the groundwater samples analyzed for this study were aluminum (Figure 6.5) and chromium (Figure 6.6). Both are resultant from the geologic origin of the groundwater and were detected below MCL, although increases in either constituent from anthropogenic sources could lead to an exceedence of MCL. Lead 20 Arsenic Lead ug/l Arsenic ug/l Figure 6.3 Box plot of detected concentrations of aluminum, most samples had low concentrations, although a few approached the MCL of 900 ug/l. 0 Figure 6.4 Box plot of detected concentrations of arsenic; many samples had detectable arsenic at concentrations below the MCL of 10 ug/l. One sample exceeded the MCL before the water is treated for consumption. Aluminum ug/l Aluminum Chromium ug/l Chromium 200 Figure 6.5 Box plot showing the conc. of Cr detected in several samples; none exceed MCL, although additional anthropogenic sources should be limited to avoid an exceedence. 2 Figure 6.6 Box plot of lead concentrations, most samples had either no detectable lead or the concentration was below the MCL. One sample exceeded the MCL.

16 6.2 Mine Drainage Quality While the chemistry of coal mine drainage is well understood and documented in Appalachian Ohio, the discharges have not been analyzed for organic chemicals. In the event of a spill or leaking well casing, high flow mine pools may be the quickest paths for contaminants to reach surface waters. Not surprisingly, the dominant anion in the mine water samples was sulfate with two outliers that were dominated by chloride, which are likely due to analytical error. Calcium and magnesium were the dominant cations, most likely from limestone in the strata surrounding the mines (Figure 6.7) Calcium(Ca) Chloride(Cl) Figure 6.7 Piper diagram of all mine water samples. Samples are dominated by calcium, magnesium and sulfate due to both the sulfur rich coal and the limestone geology that is coincident with coal. Two samples are outliers and are dominated by chloride rather than sulfate, although this may be an analytical error. Coal mine drainage site data analysis found aluminum levels up to 39.1 mg/l (Figure 6.8), exceeding the EPA MCL of 0.9 mg/l. Arsenic levels were detected as high as 39.9 ug/l (Figure 6.9), exceeding the EPA MCL of 10 ug/l. Like the groundwater samples, chromium (Figure 6.10) and lead (Figure 6.11) were detected in many samples as a result of the regional geology, although concentrations were lower than those detected in groundwater samples. Methane was the key

17 detectable organic chemical detected in mine water samples as shown in Figure Methane is commonly associated with coal (the cause of mine explosions) and should be expected in mine drainage. This demonstrates the necessity of baseline measurements since dissolved organic constituents may have various origins. Parameters found at or below the detection limit at deep mine discharge sites is found in Table Aluminum 40 Arsenic Aluminum ug/l Arsenic ug/l Figure 6.8. Box plot of detected concentrations of aluminum, samples contained higher concentrations than the groundwater samples due to the mining origin. 0 Figure 6.9. Box plot of arsenic concentrations in mine drainage samples. Arsenic has traditionally been mobilized in the acidic conditions prevalent in mine drainage and is expected at the concentrations present; significant increases may indicate a different source. Chromium ug/l Chromium Figure Box plot of chromium concentrations in mine drainage samples. Chromium concentrations were lower, on average, than those found in the groundwater samples. Lead ug/l Lead Figure Box plot of lead concentrations in mine water samples. Lead was found at lower concentrations, on average, in mine water than in groundwater.

18 Methane Methane mg/l Figure Box plot of methane concentrations detected in mine water samples. All values exceeded the USEPA action level of mg/l (4 ug/l). Table 6.2 List of chemical parameters at or below detection level at coal mine discharge sites Field Parameters COD Major Ions Nitrate/Nitrite Minor and Trace Elements Selenium Total Phosphorus Titanium Vanadium Organic Chemicals Acetonitrile n Butylbenzene 1 Butanol Acrolein n decane 1 Propanol Acrylonitrile n docosane 1,1,1,2 Tetrachloroethane Benzene n dodecane 1,1,1 Trichloroethane Bromobenzene n dotriaoctane 1,1,2,2 Tetrachloroethane Bromochloromethane n eicosane 1,1,2 Trichloroethane Bromodichloromethane n hexacosane 1,1 Dichloroethane Bromoform n hexadecane 1,1 Dichloroethene Bromomethane n octacosane 1,1 Dichloropropene Carbon disulfide n octadecane 1,2,3 Trichlorobenzene Carbon tetrachloride n Propylbenzene 1,2,3 Trichloropropane Chlorobenzene n tetracosane 1,2,4 Trichlorobenzene Chloroethane n tetradecane 1,2,4 Trimethylbenzene Chloroform n triacontrane 1,2 Dibromo 3 chloropropane Chloromethane o Xylene 1,2 Dibromoethane cis 1,2 Dichloroethene Propionitrile 1,2 Dichlorobenzene cis 1,3 Dichloropropene Pyridine 1,2 Dichloroethane Dibromochloromethane sec Butylbenzene 1,2 Dichloropropane Dibromomethane Styrene 1,3,5 Trimethylbenzene Dichlorodifluoromethane t Butyl alcohol

19 1,3 Dichlorobenzene Ethanol tert Butylbenzene 1,3 Dichloropropane Ethyl Acetate Tetrachloroethene 1,4 Dichlorobenzene Ethylbenzene Toluene 1,4 Dioxane Ethylene Oxide Total m&p xylenes 2,2 Dichloropropane Hexachlorobutadiene trans 1,2 Dichloroethene 2 Butanone Iodomethane trans 1,3 Dichloropropene 2 Chlorotoluene Isobutyl Alcohol trans 1,4 Dichloro 2 butene 2 Hexanone Isopropyl Alcohol Trichloroethene 2 Pentanone Isopropylbenzene Trichlorofluoromethane 4 Chlorotoluene Methanol Vinyl acetate 4 Isopropyltoluene Methylene chloride Vinyl chloride 4 Methyl 2 pentanone Methyl Isobutyl Ketone Xylene(s) Acetone Naphthalene 7.0 Conclusions This study aimed to establish baseline groundwater quality in and surrounding Athens and Belmont Counties prior to drilling for shale oil and gas. Samples were collected on three separate dates at most sites and were analyzed by three laboratories: Ohio University s Institute for Sustainable Energy and the Environment, Ohio Environmental Protection Agency and Analytical Associates. Data was analyzed separately for groundwater samples and samples taken from abandoned underground mines. In the groundwater samples, acetone was the only detectable organic analyte. While the origin is unknown, it is likely that the acetone was a contaminant from the laboratory. Analysis using a piper diagram shows that calcium and magnesium are the dominant cations, while sulfate and carbonate/bicarbonate are the dominant anions in the region. Other inorganic analytes of note include aluminum, arsenic, chromium and lead which were detected in several samples; most did not exceed the MCL. In the mine water, dissolved methane was detected in several samples; the origin is likely the coal itself. As expected, the dominant anions in the mine water samples were sulfate while calcium and magnesium were the dominant cations. Due to the metal rich nature of mine water, many metals and metalloids, including iron, aluminum, arsenic, chromium and lead, were detected in the mine water samples. The baseline establishment suggests that there is not widespread organic groundwater pollution in Athens and Belmont counties, despite a long history of coal mining and oil and gas extraction. The samples taken during this study may serve as a baseline for the sites sampled, but it is recommended that landowners establish pre drilling water quality on their drinking water source using a third party laboratory certified by the Ohio Environmental Protection Agency and a qualified sampler following established quality assurance and quality control procedures.

20 References ATSDR. (1997). Toxic Substances Portal Trichloroethylene (TCE). Sept Earth Works: Oil and Gas Accountability Project. (2005). Our drinking water at risk: What EPA and the Oil and Gas Industry don t want us to know about hydraulic fracturing. Washington, D.C.: Sumi, L. Frac Focus: Chemical Disclosure Registry. (2013). Retrieved from chemicals are used Gillis, Ian A. (1994) Detection and Modeling of Tetrachloroethylene Contamination in Athens Well Fields. Thesis. Ohio University, Athens, Ohio, Print. Ohio Department of Natural Resources (ODNR) Division of Oil and Gas Resources. (2013) Retrieved from the oil and gas well RBDMS database. Information/Oil Gas Well Database.aspx U.S. Energy Information Administration (EIA). U.S. Department of Energy, Office of Oil and Gas. (1993). Drilling sideways a review of horizontal well technology and its domestic application. U.S. Government Printing: Washington, D.C. U.S. Energy Information Administration (EIA). (2012). Annual Energy Outlook 2013 Early Release. U.S. Energy Information Administration (EIA). (2010). Summary maps: Natural gas. Retrieved from USEPA. (2012c, May). Basic Information about cis 1,2 Dichloroethylene, retrieved from dichloroethylene.cfm#four USEPA. (2012a, March 14). Key documents about mid atlantic oil and gas extraction. Retrieved from USEPA. (2012b, para. 4, February 15). Retrieved from Waples, D. A. (2012). The Natural Gas Industry in Appalachia: A History from the First Discovery to the Tapping of the Marcellus Shale. Second Edition. Jefferson, N.C.: McFarland & Company, Inc., Publishers. Weatherby, Michael L. (1992). A Practical Approach to Wellhead Protection of the City of Athens Water Well Field. Thesis. Ohio University, Athens, Ohio, Print

21 Appendices Appendix A. Range of values found at all regional groundwater data sites (MRL and MCL included). Groundwater Data Parameter Lab MRL Low High MCL ph AA Acidity (mg/l) EPA Alkalinity (mg/l) EPA AA Aluminum (ug/l) EPA Ammonia (mg/l) EPA 0.05 ISEE Arsenic (ug/l) EPA ISEE Barium (ug/l) EPA AA ISEE Beryllium (ug/l) EPA Boron (ug/l) EPA Bromide (ug/l) EPA AA Cadmium (ug/l) EPA Calcium (mg/l) EPA AA ISEE Chloride (mg/l) EPA AA Chromium (ug/l) EPA

22 Cobalt (ug/l) EPA Conductivity (umhos/cm) EPA 2 AA Copper (ug/l) EPA Hardness, Total (mg/l) EPA AA Iron (ug/l) EPA AA Lead (ug/l) EPA Magnesium (mg/l) EPA AA ISEE Manganese (ug/l) EPA AA Nickel (ug/l) EPA Phenolics (ug/l) EPA Potassium (mg/l) EPA AA ISEE Selenium (ug/l) EPA Sodium (mg/l) EPA AA ISEE Strontium (ug/l) EPA AA ISEE Sulfate (mg/l) EPA

23 AA Titanium (ug/l) EPA Total Dissolved Solids (mg/l) EPA AA Total Phosphorus (mg/l) EPA 0.01 ISEE Total Suspended Solids (mg/l) EPA 5 AA Vanadium (ug/l) EPA Zinc (ug/l) EPA ,1,1,2 Tetrachloroethane (ug/l) EPA ,1,1 Trichloroethane (ug/l) EPA ,1,2,2 Tetrachloroethane (ug/l) EPA ,1,2 Trichloroethane (ug/l) EPA ,1 Dichloroethane (ug/l) EPA ,1 Dichloroethene (ug/l) EPA ,1 Dichloropropene (ug/l) EPA ,2,3 Trichlorobenzene (ug/l) EPA ,2,3 Trichloropropane (ug/l) EPA ,2,4 Trichlorobenzene (ug/l) EPA ,2,4 Trimethylbenzene(ug/L) EPA ,2 Dibromo 3 chloropropane (ug/l) EPA ,2 Dibromoethane (ug/l) EPA ,2 Dichlorobenzene (ug/l) EPA ,2 Dichloroethane (ug/l) EPA ,2 Dichloropropane (ug/l) EPA

24 1,3,5 Trimethylbenzene (ug/l) EPA ,3 Dichlorobenzene (ug/l) EPA ,3 Dichloropropane (ug/l) EPA ,4 Dichlorobenzene (ug/l) EPA ,4 Dioxane (ug/l) AA Butanol (ug/l) AA Propanol (ug/l) AA ,2 Dichloropropane (ug/l) EPA Butanone (ug/l) EPA Chlorotoluene (ug/l) EPA Hexanone (ug/l) EPA Pentanone (ug/l) AA Chlorotoluene (ug/l) EPA Isopropyltoluene (ug/l) EPA Methyl 2 pentanone (ug/l) EPA Acetone (ug/l) EPA AA Acetonitrile (ug/l) AA Acrolein (ug/l) AA Acrylonitrile (ug/l) EPA AA Benzene (ug/l) EPA AA Bromobenzene (ug/l) EPA Bromochloromethane (ug/l) EPA Bromodichloromethane (ug/l) EPA (sum of TTHMs ann. ave.)

25 Bromoform (ug/l) EPA (sum of TTHMs ann. ave.) Bromomethane (ug/l) EPA Carbon disulfide (ug/l) EPA Carbon tetrachloride (ug/l) EPA Chlorobenzene (ug/l) EPA Chloroethane (ug/l) EPA Chloroform (ug/l) EPA Chloromethane (ug/l) EPA cis 1,2 Dichloroethene (ug/l) EPA cis 1,3 Dichloropropene (ug/l) EPA Dibromochloromethane (ug/l) EPA (sum of TTHMs ann. ave.) Dibromomethane (ug/l) EPA Dichlorodifluoromethane (ug/l) EPA Ethanol (ug/l) AA Ethyl Acetate (ug/l) AA Ethylbenzene (ug/l) EPA Ethylene Oxide(ug/L) AA Hexachlorobutadiene (ug/l) EPA Iodomethane (ug/l) EPA Isobutyl Alcohol (ug/l) AA Isopropyl Alcohol (ug/l) AA Isopropylbenzene (ug/l) EPA Methane (mg/l) AA Methanol (ug/l) AA Methyl Isobutyl Ketone (ug/l) AA

26 Methylene chloride (ug/l) EPA Naphthalene (ug/l) EPA n Butylbenzene (ug/l) EPA n decane (ug/l) AA n docosane (ug/l) AA n dodecane (ug/l) AA n dotriaoctane (ug/l) AA n eicosane (ug/l) AA n hexacosane (ug/l) AA n hexadecane (ug/l) AA n octacosane (ug/l) AA n octadecane (ug/l) AA n Propylbenzene (ug/l) EPA n tetracosane (ug/l) AA n tetradecane (ug/l) AA n triacontrane (ug/l) AA o Xylene (ug/l) EPA Propionitrile (ug/l) AA Pyridine (ug/l) AA sec Butylbenzene (ug/l) EPA Styrene (ug/l) EPA tert Butylbenzene (ug/l) EPA Tetrachloroethene (ug/l) EPA Toluene (ug/l) EPA AA Total m&p xylenes (ug/l) EPA ,000 trans 1,2 Dichloroethene (ug/l) EPA

27 trans 1,3 Dichloropropene (ug/l) trans 1,4 Dichloro 2 butene (ug/l) EPA EPA t Butyl alcohol (ug/l) AA Trichloroethene (ug/l) EPA Trichlorofluoromethane (ug/l) EPA Vinyl acetate (ug/l) EPA Vinyl chloride (ug/l) EPA Xylene(s) (ug/l) EPA AA ,000 Note: MRL Minimum Reporting Level The minimum concentration that can be reported as a quantitated value for a target analyte in a sample following analysis. This defined concentration can be no lower than the concentration of the lowest calibration standard for that analyte, and can only be used if acceptable quality control criteria for the analyte at this concentration are met. (EPA Note: MCL Maximum Contaminant Level MCLs are federally enforceable limits for contaminants in drinking water established as EPA National Primary Drinking Water Regulations (NPDWR)s. MCLs defines the highest level of a contaminant that is allowed in drinking water. MCLs are set as close to health based limits (Maximum Contaminant Level Goals, or MCLGs) as feasible using the best available analytical and treatment technologies and taking cost into consideration. (U.S. Environmental Protection Agency) Note: Trihalomethane (TTHMs) includes: bromoform, chloroform, bromodichloromethane, dibromochloremethane

28 Appendix B. Range of values found at all deep coal mine discharge sites (MRL and MCL included). Mine Drainage Data Parameter Lab MRL Low High MCL ph AA Acidity (mg/l) EPA Alkalinity (mg/l) EPA Aluminum (ug/l) EPA ISEE Ammonia (mg/l) EPA Arsenic (ug/l) EPA ISEE Barium (ug/l) EPA AA ISEE Beryllium (ug/l) EPA Boron (ug/l) EPA 2 ISEE Bromide (ug/l) EPA AA Cadmium (ug/l) EPA Calcium (mg/l) EPA AA ISEE Chloride (mg/l) EPA Chromium (ug/l) EPA Cobalt (ug/l) EPA COD EPA Conductivity (umhos/cm) EPA AA Copper (ug/l) EPA Hardness, Total (mg/l) EPA Iron (ug/l) EPA AA Lead (ug/l) EPA Magnesium (mg/l) EPA AA ISEE Manganese (ug/l) EPA AA Nickel (ug/l) EPA Nitrate+nitrite (mg/l) EPA Nitrite (mg/l) EPA Phenolics (ug/l) EPA Potassium (mg/l) EPA AA ISEE Selenium (ug/l) EPA Sodium (mg/l) EPA AA ISEE Strontium (ug/l) EPA AA ISEE Sulfate (mg/l) EPA

29 AA >1000 Titanium (ug/l) EPA TKN EPA Total Dissolved Solids (mg/l) EPA AA Total Phosphorus (mg/l) EPA ISEE Total Suspended Solids (mg/l) EPA AA Vanadium (ug/l) EPA Zinc (ug/l) EPA ,1,1,2 Tetrachloroethane (ug/l) EPA ,1,1 Trichloroethane (ug/l) EPA ,1,2,2 Tetrachloroethane (ug/l) EPA ,1,2 Trichloroethane (ug/l) EPA ,1 Dichloroethane (ug/l) EPA ,1 Dichloroethene (ug/l) EPA ,1 Dichloropropene (ug/l) EPA ,2,3 Trichlorobenzene (ug/l) EPA ,2,3 Trichloropropane (ug/l) EPA ,2,4 Trichlorobenzene (ug/l) EPA ,2,4 Trimethylbenzene (ug/l) EPA ,2 Dibromo 3 chloropropane EPA (ug/l) 1,2 Dibromoethane (ug/l) EPA ,2 Dichlorobenzene (ug/l) EPA ,2 Dichloroethane (ug/l) EPA ,2 Dichloropropane (ug/l) EPA ,3,5 Trimethylbenzene (ug/l) EPA ,3 Dichlorobenzene EPA ,3 Dichloropropane (ug/l) EPA ,4 Dichlorobenzene (ug/l) EPA ,4 Dioxane (ug/l) AA Butanol (ug/l) AA Propanol (ug/l) AA ,2 Dichloropropane (ug/l) EPA Butanone (ug/l) EPA Chlorotoluene (ug/l) EPA Hexanone (ug/l) EPA Pentanone (ug/l) AA Chlorotoluene (ug/l) EPA Isopropyltoluene (ug/l) EPA Methyl 2 pentanone (ug/l) EPA Acetone (ug/l) EPA AA Acetonitrile (ug/l) AA Acrolein (ug/l) AA Acrylonitrile (ug/l) EPA AA Benzene (ug/l) EPA AA Bromobenzene (ug/l) EPA Bromochloromethane (ug/l) EPA Bromodichloromethane (ug/l) EPA (sum of TTHMs ann. ave.) Bromoform (ug/l) EPA (sum of TTHMs ann. ave.) Bromomethane (ug/l) EPA

30 Carbon disulfide (ug/l) EPA Carbon tetrachloride (ug/l) EPA Chlorobenzene (ug/l) EPA Chloroethane (ug/l) EPA Chloroform (ug/l) EPA Chloromethane (ug/l) EPA cis 1,2 Dichloroethene (ug/l) EPA cis 1,3 Dichloropropene (ug/l) EPA Dibromochloromethane (ug/l) EPA (sum of TTHMs ann. ave.) Dibromomethane (ug/l) EPA Dichlorodifluoromethane (ug/l) EPA Ethanol (ug/l) AA Ethyl Acetate (ug/l) AA Ethylbenzene (ug/l) EPA Ethylene Oxide (ug/l) AA Hexachlorobutadiene (ug/l) EPA Iodomethane (ug/l) EPA Isobutyl Alcohol (ug/l) AA Isopropyl Alcohol (ug/l) AA Isopropylbenzene (ug/l) EPA Methane (mg/l) AA Methanol (ug/l) AA Methyl Isobutyl Ketone (ug/l) AA Methylene chloride (ug/l) EPA Naphthalene (ug/l) EPA n Butylbenzene (ug/l) EPA n decane (ug/l) AA n docosane (ug/l) AA n dodecane (ug/l) AA n dotriaoctane (ug/l) AA n eicosane (ug/l) AA n hexacosane (ug/l) AA n hexadecane (ug/l) AA n octacosane (ug/l) AA n octadecane (ug/l) AA n Propylbenzene (ug/l) EPA n tetracosane (ug/l) AA n tetradecane (ug/l) AA n triacontrane (ug/l) AA o Xylene (ug/l) EPA Propionitrile (ug/l) AA Pyridine (ug/l) AA sec Butylbenzene (ug/l) EPA Styrene (ug/l) EPA tert Butylbenzene (ug/l) EPA Tetrachloroethene (ug/l) EPA Toluene (ug/l) EPA AA Total m&p xylenes (ug/l) EPA ,000 trans 1,2 Dichloroethene (ug/l) EPA trans 1,3 Dichloropropene (ug/l) EPA trans 1,4 Dichloro 2 butene EPA (ug/l) t Butyl alcohol (ug/l) AA Trichloroethene (ug/l) EPA Trichlorofluoromethane (ug/l) EPA

31 Vinyl acetate (ug/l) EPA Vinyl chloride (ug/l) EPA Xylene(s) (ug/l) EPA AA ,000 Note: MRL Minimum Reporting Level The minimum concentration that can be reported as a quantitated value for a target analyte in a sample following analysis. This defined concentration can be no lower than the concentration of the lowest calibration standard for that analyte, and can only be used if acceptable quality control criteria for the analyte at this concentration are met. (EPA Note: MCL Maximum contaminant level MCLs are federally enforceable limits for contaminants in drinking water established as EPA National Primary Drinking Water Regulations (NPDWR)s. MCLs defines the highest level of a contaminant that is allowed in drinking water. MCLs are set as close to health based limits (Maximum Contaminant Level Goals, or MCLGs) as feasible using the best available analytical and treatment technologies and taking cost into consideration. (U.S. Environmental Protection Agency) Note: Trihalomethane (TTHMs) includes: bromoform, chloroform, bromodichloromethane, dibromochloremethane

32 Appendix C. Groundwater and coal mine drainage chemical data parameters

33 Appendix C - Groundwater Water Quality Data Field AA Field Field Field Field EPA Field EPA AA Field ISEE EPA EPA ISEE EPA ISEE EPA AA EPA ISEE EPA AA EPA ISEE Dissolved Oxygen Dissolved Oxygen (%) ORP Acidity Acidity Alkalinity Alkalinity Alkalinity Aluminum Aluminum Ammonia Arsenic Arsenic Barium Barium Barium Beryllium Boron Bromide Bromide Cadmium Calcium Site Number Date ph ph Temp ( C) mg/l mg/l mg/l mg/l mg/l mg/l ug/l ug/l mg/l ug/l ug/l ug/l ug/l ug/l ug/l ug/l ug/l ug/l ug/l mg/l Ath_001_AC 1/24/ Ath_001_AC 2/13/ Ath_001_AC 3/26/ Ath_002_AC 1/24/ Ath_002_AC 2/13/ Ath_002_AC 3/26/ Ath_003_AC 1/24/ Ath_003_AC 2/13/ Ath_003_AC 3/26/ Ath_004_OU 1/24/ Ath_004_OU 2/13/ Ath_004_OU 3/13/ Ath_005_MI 1/24/ >4, Est. > Ath_005_MI 2/13/ Ath_005_MI 3/13/ Ath_006_MI 2/22/ Ath_006_MI 4/11/ Ath_007_MI 1/25/ Ath_007_MI 3/1/ >10, Ath_007_MI 3/12/ Ath_008_TB 1/25/ Ath_008_TB 3/1/ Ath_008_TB 3/12/ Ath_009_MW 1/25/ Ath_009_MW 3/1/ Ath_009_MW 3/12/ Ath_010_MS 1/25/ Ath_010_MS 3/1/ Ath_010_MS 3/12/ Ath_011_HK 2/1/ Ath_011_HK 2/13/ Ath_011_HK 3/13/ Ath_011_HK 3/15/ Ath_012_SS 1/25/ Ath_012_SS 3/1/ Ath_012_SS 3/12/ Ath_013_RH 1/25/ Ath_013_RH 3/1/ Ath_013_RH 3/12/ Ath_014_CB 1/24/ Ath_014_CB 3/1/ Ath_014_CB 3/12/ Ath_015_KR 1/25/ Ath_015_KR 3/1/ Ath_015_KR 3/12/ Ath_016_CL 1/25/ Ath_016_CL 3/1/ Ath_016_CL 3/12/ Ath_017_MF 1/25/ Ath_017_MF 3/1/